Effect of metal ions on the hydrolytic and transesterification activities of Candida rugosa lipase.

PubMed

Katiyar, Madhu; Ali, Amjad

2013-01-01

In order to study the effect of metal ions on lipase activity, hydrolytic and transesterification activities of Candida rugosa lipase were investigated in presence of alkali (Na⁺ and K⁺), alkaline earth (Ca⁺² and Ba⁺²) and transition (Cr⁺³, Fe⁺³, Co⁺², Cu⁺² and Ni⁺²) metal ions. Maximum enhancement in hydrolytic activity of lipase was observed by Ca⁺², and in transesterification activity by Cr⁺³ and Co⁺². The kinetics of the lipase catalyzed transesterification (methanolysis and ethanolysis) reactions were also studied, and the activation energies of methanolysis and ethanolysis were reduced from 10.16 and 10.24 kcal mol⁻¹, respectively, to 5.41 and 7.55 kcal mol⁻¹, respectively, when reactions were performed in presence of Co⁺². Thus, in lipase catalyzed transesterification Cr⁺³ or Co⁺² could be added to the assay in order to produce the biodiesel in relatively shorter reaction duration.

Efficient solvothermal wet in situ transesterification of Nannochloropsis gaditana for biodiesel production.

PubMed

Kim, Bora; Chang, Yong Keun; Lee, Jae W

2017-05-01

In situ transesterification of wet microalgae is a promising, simplified alternative biodiesel production process that replaces multiple operations of cell drying, extraction, and transesterification reaction. This study addresses enhanced biodiesel production from Nannochloropsis gaditana at elevated temperatures. Compared with the previously reported in situ transesterification process of conducting the reaction at a temperature ranging from 95 to 125 °C, the present work employs higher temperatures of at least 150 °C. This relatively harsh condition allows much less acid catalyst with or without co-solvent to be used during this single extraction-conversion process. Without any co-solvent, 0.58% (v/v) of H 2 SO 4 in the reaction medium can achieve 90 wt% of the total lipid conversion to biodiesel at 170 °C when the moisture content of wet algal paste is 80 wt%. Here, the effects of temperature, acid catalyst, and co-solvent on the FAEE yield and specification were scrutinized, and the reaction kinetic was investigated to understand the solvothermal in situ transesterification reaction at the high temperature. Having a biphasic system (water/chloroform) during the reaction also helped to meet biodiesel quality standard EN 14214, as Na + , K + , Ca 2+ , Mg 2+ cations and phosphorus were detected only below 5 ppm. With highlights on the economic feasibility, wet in situ transesterification at the high temperature can contribute to sustainable production of biodiesel from microalgae by reducing the chemical input and relieve the burden of extensive post purification process, therefore a step towards green process.

The study of CaO and MgO heterogenic nano-catalyst coupling on transesterification reaction efficacy in the production of biodiesel from recycled cooking oil.

PubMed

Tahvildari, Kambiz; Anaraki, Yasaman Naghavi; Fazaeli, Reza; Mirpanji, Sogol; Delrish, Elham

2015-01-01

Fossil fuels' pollution and their non-renewability have motivated the search for alternative fuels. Some common example of seed oils are sunflower oil, date seed oil, soy bean oil. For instance, soy methyl and soy-based biodiesel are the main biodiesel. Biodiesel is a clean diesel fuel that can be produced through transesterification reaction. Recycled cooking oil, on the other hand, is one of the inexpensive, easily available sources for producing biodiesel. This article is aimed at production of biodiesel via trans-esterification method, Nano CaO synthesis using sol-gel method, and Nano MgO synthesis using sol-gel self-combustion. Two catalysts' combination affecting the reaction's efficacy was also discussed. Optimum conditions for the reaction in the presence of Nano CaO are 1.5 % weight fracture, 1:7 alcohol to oil proportion and 6 h in which biodiesel and glycerin (the byproduct) are produced. Moreover, the optimum conditions for this reaction in the presence of Nano CaO and Nano MgO mixture are 3 % weight fracture (0.7 g of Nano CaO and 0.5 g of Nano MgO), 1:7 alcohols to oil proportion and 6 h. Nano MgO is not capable of catalyzing the transesterification by itself, because it has a much weaker basic affinity but when used with Nano CaO due to its surface structure, the basic properties increase and it becomes a proper base for the catalyst so that CaO contact surface increases and transesterification reaction yield significantly increases as well. This study investigates the repeatability of transesterification reaction in the presence of these Nano catalysts as well.

Ionic liquids as transesterification catalysts: applications for the synthesis of linear and cyclic organic carbonates

PubMed Central

Perosa, Alvise; Guidi, Sandro; Cattelan, Lisa

2016-01-01

Summary The use of ionic liquids (ILs) as organocatalysts is reviewed for transesterification reactions, specifically for the conversion of nontoxic compounds such as dialkyl carbonates to both linear mono-transesterification products or alkylene carbonates. An introductory survey compares pros and cons of classic catalysts based on both acidic and basic systems, to ionic liquids. Then, innovative green syntheses of task-specific ILs and their representative applications are introduced to detail the efficiency and highly selective outcome of ILs-catalyzed transesterification reactions. A mechanistic hypothesis is discussed by the concept of cooperative catalysis based on the dual (electrophilic/nucleophilic) activation of reactants. PMID:27829898

Kinetics of acid base catalyzed transesterification of Jatropha curcas oil.

PubMed

Jain, Siddharth; Sharma, M P

2010-10-01

Out of various non-edible oil resources, Jatropha curcas oil (JCO) is considered as future feedstock for biodiesel production in India. Limited work is reported on the kinetics of transesterification of high free fatty acids containing oil. The present study reports the results of kinetic study of two-step acid base catalyzed transesterification process carried out at an optimum temperature of 65 °C and 50 °C for esterification and transesterification respectively under the optimum methanol to oil ratio of 3:7 (v/v), catalyst concentration 1% (w/w) for H₂SO₄ and NaOH. The yield of methyl ester (ME) has been used to study the effect of different parameters. The results indicate that both esterification and transesterification reaction are of first order with reaction rate constant of 0.0031 min⁻¹ and 0.008 min⁻¹ respectively. The maximum yield of 21.2% of ME during esterification and 90.1% from transesterification of pretreated JCO has been obtained. Copyright © 2010 Elsevier Ltd. All rights reserved.

Biodiesel Production from Chlorella protothecoides Oil by Microwave-Assisted Transesterification

PubMed Central

Gülyurt, Mustafa Ömer; Özçimen, Didem; İnan, Benan

2016-01-01

In this study, biodiesel production from microalgal oil by microwave-assisted transesterification was carried out to investigate its efficiency. Transesterification reactions were performed by using Chlorella protothecoides oil as feedstock, methanol, and potassium hydroxide as the catalyst. Methanol:oil ratio, reaction time and catalyst:oil ratio were investigated as process parameters affected methyl ester yield. 9:1 methanol/oil molar ratio, 1.5% KOH catalyst/oil ratio and 10 min were optimum values for the highest fatty acid methyl ester yield. PMID:27110772

Biodiesel Production from Chlorella protothecoides Oil by Microwave-Assisted Transesterification.

PubMed

Gülyurt, Mustafa Ömer; Özçimen, Didem; İnan, Benan

2016-04-22

In this study, biodiesel production from microalgal oil by microwave-assisted transesterification was carried out to investigate its efficiency. Transesterification reactions were performed by using Chlorella protothecoides oil as feedstock, methanol, and potassium hydroxide as the catalyst. Methanol:oil ratio, reaction time and catalyst:oil ratio were investigated as process parameters affected methyl ester yield. 9:1 methanol/oil molar ratio, 1.5% KOH catalyst/oil ratio and 10 min were optimum values for the highest fatty acid methyl ester yield.

Heterobimetallic dinuclear lanthanide alkoxide complexes as acid-base difunctional catalysts for transesterification.

PubMed

Zeng, Ruijie; Sheng, Hongting; Zhang, Yongcang; Feng, Yan; Chen, Zhi; Wang, Junfeng; Chen, Man; Zhu, Manzhou; Guo, Qingxiang

2014-10-03

A practical lanthanide(III)-catalyzed transesterification of carboxylic esters, weakly reactive carbonates, and much less-reactive ethyl silicate with primary and secondary alcohols was developed. Heterobimetallic dinuclear lanthanide alkoxide complexes [Ln2Na8{(OCH2CH2NMe2)}12(OH)2] (Ln = Nd (I), Sm (II), and Yb (III)) were used as highly active catalysts for this reaction. The mild reaction conditions enabled the transesterification of various substrates to proceed in good to high yield. Efficient activation of transesterification may be endowed by the above complexes as cooperative acid-base difunctional catalysts, which is proposed to be responsible for the higher reactivity in comparison with simple acid/base catalysts.

Alkaline in situ transesterification of Aurantiochytrium sp. KRS 101 using potassium carbonate.

PubMed

Sung, Mina; Han, Jong-In

2016-04-01

The aims of this work were to evaluate K2CO3 as a potent alkaline catalyst for in situ transesterification of Aurantiochytrium sp. KRS 101, one step process in which oil extraction and conversion take place together. This K2CO3-based in situ transesterification was optimized in terms of recovery yield of fatty acid methyl esters (FAMEs) by way of varying biomass concentration, reaction temperature, reaction time, and catalyst concentration. The optimal condition was achieved at 50g/L of biomass concentration and 1% of K2CO3 in the methanol, 25°C of reaction temperature, and 5min of reaction time, resulting in the FAME recovery yield over 90%. It was found that K2CO3 performed better than any other tested catalysts including acids, supporting the notion that K2CO3 is a promising catalyst, especially for in situ transesterification. Copyright © 2016. Published by Elsevier Ltd.

Pentynyl dextran as a support matrix for immobilization of serine protease subtilisin Carlsberg and its use for transesterification of N-acetyl-L-phenylalanine ethyl ester in organic media.

PubMed

Tahir, Muhammad Nazir; Cho, Eunae; Mischnick, Petra; Lee, Jae Yung; Yu, Jae-Hyuk; Jung, Seunho

2014-04-01

In this study, serine protease (subtilisin Carlsberg) was immobilized on pentynyl dextran (PyD, O-alkynyl ether of dextran, 1) and used for the transesterification of N-acetyl-L-phenylalanine ethyl ester (2) with different aliphatic (1-propanol, 1-butanol, 1-pentanol, 1-hexanol) and aromatic (benzyl alcohol, 2-phenyl ethanol, 4-phenyl-1-butanol) alcohols in tetrahydrofuran (THF). The effect of carbon chain length in aliphatic and aromatic alcohols on initial and average transesterification rate, transesterification activity of immobilized enzyme and yield of the reaction under selected reaction conditions was investigated. The transesterification reactivity of the enzyme and yield of the reaction increased as the chain length of the alcohols decreased. Furthermore, almost no change in yield was observed when the immobilized enzyme was repeatedly used for selected alcohols over six cycles. Intrinsic fluorescence analysis showed that the catalytic activity of the immobilized enzyme in THF was maintained due to retention of the tertiary structure of the enzyme after immobilization on PyD (1).

Establishing a green platform for biodiesel synthesis via strategic utilization of biochar and dimethyl carbonate.

PubMed

Lee, Jechan; Jung, Jong-Min; Oh, Jeong-Ik; Sik Ok, Yong; Kwon, Eilhann E

2017-10-01

To establish a green platform for biodiesel production, this study mainly investigates pseudo-catalytic (non-catalytic) transesterification of olive oil. To this end, biochar from agricultural waste (maize residue) and dimethyl carbonate (DMC) as an acyl acceptor were used for pseudo-catalytic transesterification reaction. Reaction parameters (temperature and molar ratio of DMC to olive oil) were also optimized. The biodiesel yield reached up to 95.4% under the optimal operational conditions (380°C and molar ratio of DMC to olive oil (36:1)). The new sustainable environmentally benign biodiesel production introduced in this study is greener and faster than conventional transesterification reactions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Analysis of parameter and interaction between parameter of the microwave assisted transesterification process of coconut oil using response surface methodology

NASA Astrophysics Data System (ADS)

Hidayanti, Nur; Suryanto, A.; Qadariyah, L.; Prihatini, P.; Mahfud, Mahfud

2015-12-01

A simple batch process was designed for the transesterification of coconut oil to alkyl esters using microwave assisted method. The product with yield above 93.225% of alkyl ester is called the biodiesel fuel. Response surface methodology was used to design the experiment and obtain the maximum possible yield of biodiesel in the microwave-assisted reaction from coconut oil with KOH as the catalyst. The results showed that the time reaction and concentration of KOH catalyst have significant effects on yield of alkyl ester. Based on the response surface methodology using the selected operating conditions, the time of reaction and concentration of KOH catalyst in transesterification process were 150 second and 0.25%w/w, respectively. The largest predicted and experimental yield of alkyl esters (biodiesel) under the optimal conditions are 101.385% and 93.225%, respectively. Our findings confirmed the successful development of process for the transesterification reaction of coconut oil by microwave-assisted heating, which is effective and time-saving for alkyl ester production.

Synthesis of L-Ascorbyl Flurbiprofenate by Lipase-Catalyzed Esterification and Transesterification Reactions

PubMed Central

Sun, Li-rui; Wang, Yan; Xia, Chun-gu

2017-01-01

The synthesis of L-ascorbyl flurbiprofenate was achieved by esterification and transesterification in nonaqueous organic medium with Novozym 435 lipase as biocatalyst. The conversion was greatly influenced by the kinds of organic solvents, speed of agitation, catalyst loading amount, reaction time, and molar ratio of acyl donor to L-ascorbic acid. A series of solvents were investigated, and tert-butanol was found to be the most suitable from the standpoint of the substrate solubility and the conversion for both the esterification and transesterification. When flurbiprofen was used as acyl donor, 61.0% of L-ascorbic acid was converted against 46.4% in the presence of flurbiprofen methyl ester. The optimal conversion of L-ascorbic acid was obtained when the initial molar ratio of acyl donor to ascorbic acid was 5 : 1. kinetics parameters were solved by Lineweaver-Burk equation under nonsubstrate inhibition condition. Since transesterification has lower conversion, from the standpoint of productivity and the amount of steps required, esterification is a better method compared to transesterification. PMID:28421196

Conversion of dried Aspergillus candidus mycelia grown on waste whey to biodiesel by in situ acid transesterification.

PubMed

Kakkad, Hardik; Khot, Mahesh; Zinjarde, Smita; RaviKumar, Ameeta; Ravi Kumar, V; Kulkarni, B D

2015-12-01

This study reports optimization of the transesterification reaction step on dried biomass of an oleaginous fungus Aspergillus candidus grown on agro-dairy waste, whey. Acid catalyzed transesterification was performed and variables affecting esterification, viz., catalyst methanol and chloroform concentrations, temperature, time, and biomass were investigated. Statistical optimization of the transesterification reaction using Plackett-Burman Design showed biomass to be the predominant factor with a 12.5-fold increase in total FAME from 25.6 to 320mg. Studies indicate that the transesterification efficiency in terms of conversion is favored by employing lower biomass loadings. A. candidus exhibited FAME profiles containing desirable saturated (30.2%), monounsaturated (31.5%) and polyunsaturated methyl esters (38.3%). The predicted and experimentally determined biodiesel properties (density, kinematic viscosity, iodine value, cetane number, TAN, water content, total and free glycerol) were in accordance with international (ASTM D6751, EN 14214) and national (IS 15607) standards. Copyright © 2015. Published by Elsevier Ltd.

Mathematical modeling of methyl ester concentration distribution in a continuous membrane tubular reactor and comparison with conventional tubular reactor

NASA Astrophysics Data System (ADS)

Talaghat, M. R.; Jokar, S. M.; Modarres, E.

2017-10-01

The reduction of fossil fuel resources and environmental issues made researchers find alternative fuels include biodiesels. One of the most widely used methods for production of biodiesel on a commercial scale is transesterification method. In this work, the biodiesel production by a transesterification method was modeled. Sodium hydroxide was considered as a catalyst to produce biodiesel from canola oil and methanol in a continuous tubular ceramic membranes reactor. As the Biodiesel production reaction from triglycerides is an equilibrium reaction, the reaction rate constants depend on temperature and related linearly to catalyst concentration. By using the mass balance for a membrane tubular reactor and considering the variation of raw materials and products concentration with time, the set of governing equations were solved by numerical methods. The results clearly show the superiority of membrane reactor than conventional tubular reactors. Afterward, the influences of molar ratio of alcohol to oil, weight percentage of the catalyst, and residence time on the performance of biodiesel production reactor were investigated.

Behavior of silica aerogel networks as highly porous solid solvent media for lipases in a model transesterification reaction.

PubMed

El Rassy, H; Perrard, A; Pierre, A C

2003-03-03

Highly porous silica aerogels with differing balances of hydrophobic and hydrophilic functionalities were studied as a new immobilization medium for enzymes. Two types of lipases from Candida rugosa and Burkholderia cepacia were homogeneously dispersed in wet gel precursors before gelation. The materials obtained were compared in a simple model reaction: transesterification of vinyl laurate by 1-octanol. To allow a better comparison of the hydrophobic/hydrophilic action of the solid, very open aerogel networks with traditional organic hydrophobic/hydrophilic liquid solvents, this reaction was studied in mixtures containing different proportions of 2-methyl-2-butanol, isooctane, and water. The results are discussed in relation to the porous and hydrophobic nature of aerogels, characterized by nitrogen adsorption. It was found that silica aerogels can be considered as "solid" solvents for the enzymes, able to provide hydrophobic/hydrophilic characteristics different from those prevailing in the liquid surrounding the aerogels. A simple mechanism of action for these aerogel networks is proposed.

Biodiesel transesterification kinetics monitored by pH measurement.

PubMed

Clark, William M; Medeiros, Nicholas J; Boyd, Donal J; Snell, Jared R

2013-05-01

Quantification of a pH change that was observed over the course of the transesterification reaction that converts vegetable oil to biodiesel may provide a simple method to monitor the reaction. Transesterification of canola oil at 6:1 methanol to oil ratio with 0.5 wt.% KOH as catalyst was studied at 25, 35, and 45 °C. Reaction conversion was correlated to pH measurements and the results were shown to be in agreement with an independent measure of conversion using an enzymatic assay for glycerol. Rate constants obtained from these measurements are consistent with those in the literature. The measured pH change appears to be related to dilution of OH(-) ions as the oil is converted to products rather than to depletion of OH(-) due to reaction. Copyright © 2013 Elsevier Ltd. All rights reserved.

On the tandem Morita-Baylis-Hillman/transesterification processes. Mechanistic insights for the role of protic solvents

NASA Astrophysics Data System (ADS)

Carpanez, Arthur G.; Coelho, Fernando; Amarante, Giovanni W.

2018-02-01

Despite the remarkable rate acceleration under protic solvents such as alcohols and water, the use of acrylates as activated alkenes places a problem due to the possibility of ester hydrolysis or transesterification. Therefore, the tandem transesterification/Morita-Baylis-Hillman (MBH) reactions were investigated by ESI(+)-MS/(MS) and 1H NMR techniques. For the first time, the MBH back-reaction was fully examined by ESI(+)-MS/(MS) using labelling reagents revealed the complex equilibrium involving the Michael-type addition step of DABCO to acrylate. C- and O-protonation were observed at this stage, showing the transesterification process occurs previous to the aldol step, which is the rate-determining step of the mechanism. At this stage, a short-lived tetrahedral intermediate might be involved and should be considered in these processes.

One step transesterification process of sludge palm oil (SPO) by using deep eutectic solvent (DES) in biodiesel production

NASA Astrophysics Data System (ADS)

Manurung, Renita; Ramadhani, Debbie Aditia; Maisarah, Siti

2017-06-01

Biodiesel production by using sludge palm oil (SPO) as raw material is generally synthesized in two step reactions, namely esterification and transesterification, because the free fatty acid (FFA) content of SPO is relatively high. However, the presence of choline chloride (ChCl), glycerol based deep eutectic solvent (DES), in transesterification may produce biodiesel from SPO in just one step. In this study, DES was produced by the mixture of ChCl and glycerol at molar ratio of 1:2 at a temperature of 80°C and stirring speed of 400 rpm for 1 hour. DES was characterized by its density and viscosity. The transesterification process was performed at reaction temperature of 70 °C, ethanol to oil molar with ratio of 9:1, sodium hydroxide as catalyst concentration of 1 % wt, DES as cosolvent with concentration of 0 to 5 % wt, stirring speed of 400 rpm, and one hour reaction time. The obtained biodiesel was then assessed with density, viscosity, and ester content as the parameters. FFA content of SPO as the raw material was 7.5290 %. In this case, DES as cosolvent in one step transesterification process of low feedstock could reduce the side reaction (saponification), decrease the time reaction, decrease the surface tension between ethanol and oil, and increase the mass transfer that simultaneously simplified the purification process and obtained the highest yield. The esters properties met the international standards of ASTM D 6751, with the highest yield obtained was 83.19% with 99.55% of ester content and the ratio of ethanol:oil of 9:1, concentration of DES of 4%, catalyst amount of 1%, temperature of reaction at 70°C and stirring speed of 400 rpm.

Biodiesel Production from Citrillus colocynthis Oil Using Enzymatic Based Catalytic Reaction and Characterization Studies.

PubMed

Nehdi, Imededdine Arbi; Sbihi, Hassen Mohamed; Blidi, Lahssen El; Rashid, Umer; Tan, Chin Ping; Al-Resayes, Saud Ibrahim

2018-01-01

Biodiesel is a green fuel consisting of long chain fatty acid monoalkyl esters, which can be blended with diesel or used alone which is usually produced from vegetable oils/fats by either lipasecatalyzed transesterification. In this investigation, an enzyme (Novozym 435) catalyzed process was optimized to prepare methyl esters from crude Citrullus colocynthis oil (CCO) by transesterification of CCO with methanol. However, as per our knowledge, lipase-catalyzed transesterification have not been used for biodiesel production from Citrullus colocynthis. The purpose of this work was to transesterify the CCO in the presence of Candida antarctica lipase as catalyst and methanol. Additionally, the physicochemical parameters/fuel properties of the Citrullus colocynthis methyl ester (CCME) were assessed and compared. Lipase-catalyzed reactions were carried out in three necked flask (50 mL) attached with reflux condenser and thermometer, immersed in oil bath at constant stirring speed (400 rpm). The reaction mixture was consisted of CCO and varying the calculated amount of methanol, tert-butyl alcohol, and Novozym 435. The experimental parameters reaction time, methanol/oil molar ratio, reaction temperature, tert-butanol content, Novozym 435 content and water content were optimized for the transesterification reaction. The CCME yield was measured using gas chromatograph. The fuel properties of the produced CCME were determined as per American Society for Testing and Materials (ASTM) and European (EN) biodiesel standard methods. In this study, an enzymatic catalyst was employed to synthesize the CCME from CCO via transesterification. Several variables affecting the CCME yield were optimized as lipase quantity (4%), water content (0.5%), methanol/oil molar ratio (5:1), reaction temperature (43 °C), reaction medium composition (80% tertbutanol/ oil), and reaction time (3.7 h). A CCME yield of 97.8% was achieved using enzyme catalyzed transesterification of CCO under optimal conditions. The significant biodiesel fuel properties of CCME, i.e. cloud point (0.70 °C); cetane number (49.07); kinematic viscosity (2.27 mm2/s); flash point (143 °C); sulfur content (2 ppm) density (880 kg/m3) and acid value (0.076 mg KOH/g) were appraised. CCME also exhibited long-term storage stability (4.80 h) and all the biodiesel fuel properties were within the range of standards (ASTM D6751 and EN 14214). The lipase-catalyzed transesterification produced better conversion than the base-catalyzed reaction. The fuel properties of CCME were within the limits of the ASTM D6751 and EN14214 standards. Furthermore, CCME showed good oxidative stability and a long shelf life due its high natural antioxidant content. CCME showed better fuel properties and long-term storage stability due to which it can be used as a potential alternative fuel. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

HPLC method for rapidly following biodiesel fuel transesterification reaction progress using a core-shell column.

PubMed

Allen, Samuel J; Ott, Lisa S

2012-07-01

There are a wide and growing variety of feedstocks for biodiesel fuel. Most commonly, these feedstocks contain triglycerides which are transesterified into the fatty acid alkyl esters (FAAEs) which comprise biodiesel fuel. While the tranesterification reaction itself is simple, monitoring the reaction progress and reaction products is not. Gas chromatography-mass spectrometry is useful for assessing the FAAE products, but does not directly address either the tri-, di-, or monoglycerides present from incomplete transesterification or the free fatty acids which may also be present. Analysis of the biodiesel reaction mixture is complicated by the solubility and physical property differences among the components of the tranesterification reaction mixture. In this contribution, we present a simple, rapid HPLC method which allows for monitoring all of the main components in a biodiesel fuel transesterification reaction, with specific emphasis on the ability to monitor the reaction as a function of time. The utilization of a relatively new, core-shell stationary phase for the HPLC column allows for efficient separation of peaks with short elution times, saving both time and solvent.

The Effect of Acetone Amount Ratio as Co-Solvent to Methanol in Transesterification Reaction of Waste Cooking Oil

NASA Astrophysics Data System (ADS)

Julianto, T. S.; Nurlestari, R.

2018-04-01

The production of biodiesel from waste cooking oil by transesterification reaction using acetone as co-solvent has been carried out. This research studied the optimal amount ratio of acetone as co-solvent to methanol in the transesterification process using homogeneous alkaline catalyst KOH 1% (w/w) of waste cooking oil at room temperature for 15 minutes of reaction time. Mole ratio of waste cooking oil to methanol is 1:12. Acetone was added as co-solvent in varied amount ratio to methanol are 1:4, 1:2, and 1:1, respectively. The results of fatty acid methyl esters (FAME) were analysed using GC-MS instrument. The results showed that the optimal ratio is 1:4 with 99.93% of FAME yield.

Microwave assisted alkali-catalyzed transesterification of Pongamia pinnata seed oil for biodiesel production.

PubMed

Kumar, Ritesh; Kumar, G Ravi; Chandrashekar, N

2011-06-01

In this study, microwave assisted transesterification of Pongamia pinnata seed oil was carried out for the production of biodiesel. The experiments were carried out using methanol and two alkali catalysts i.e., sodium hydroxide (NaOH) and potassium hydroxide (KOH). The experiments were carried out at 6:1 alcohol/oil molar ratio and 60°C reaction temperature. The effect of catalyst concentration and reaction time on the yield and quality of biodiesel was studied. The result of the study suggested that 0.5% sodium hydroxide and 1.0% potassium hydroxide catalyst concentration were optimum for biodiesel production from P. pinnata oil under microwave heating. There was a significant reduction in reaction time for microwave induced transesterification as compared to conventional heating. Copyright © 2011 Elsevier Ltd. All rights reserved.

Determination of physiochemical properties of palm oil methyl ester catalyzed by waste cockle shells

NASA Astrophysics Data System (ADS)

Nasir, Nurul Fitriah; Latif, Noradila Abdul; Bakar, Sharifah Adzila Syed Abu; Rahman, Mohd Nasrull Abdul; Selamat, Siti Norhidayah; Nasharudin, Nurul Nadirah

2017-04-01

Waste cockle shell can be used as a source of calcium oxide (CaO) in catalyzing a transesterification reaction to produce biodiesel or fatty acid methyl ester (FAME). This aim of this paper is to determine the physicochemical properties of (FAME) which utilize waste cockle shells in the transesterification reaction process. In this study, the catalyst was prepared using high temperature furnace (700°C) for 4 h. The molar ratio of methanol to oil was fixed at 9:1 and the reaction temperature and catalyst concentration were varied from 65 -70 °C, and 10-30 wt. %, respectively for transesterification reaction. The reaction time was also fixed at 3 h. The analyzed physicochemical properties were density, viscosity, flash point and net heat of combustion. The results obtained from the analysis found that reaction temperature 65°C with 30% of catalyst concentration has produced the physical properties of FAME that comply the biodiesel standards. The results suggest that reaction temperature and catalyst concentration have influence on the value of physicochemical properties of FAME produced.

Ultrasound assisted production of fatty acid methyl esters from transesterification of triglycerides with methanol in the presence of KOH catalyst: optimization, mechanism and kinetics.

PubMed

Thanh, Le Tu; Okitsu, Kenji; Maeda, Yasuaki; Bandow, Hiroshi

2014-03-01

Ultrasound assisted transesterification of triglycerides (TG) with methanol in the presence of KOH catalyst was investigated, where the changes in the reactants and products (diglycerides (DG), monoglycerides (MG), fatty acid methyl esters (FAME) and glycerin (GL)) concentrations were discussed to understand the reaction mechanism and kinetics under ultrasound irradiation. The optimum reaction condition for the FAME production was the concentration of KOH 1.0 wt.%, molar ratio of TG to methanol of 1:6, and irradiation time of 25 min. The rate constants during the TG transesterification with methanol into GL and FAME were estimated by a curve fitting method with simulated curves to the obtained experimental results. The rate constants of [Formula: see text] were estimated to be 0.21, 0.008, 0.23, 0.005, 0.14 and 0.001 L mol(-1)min(-1), respectively. The rate determining step for the TG transesterification with methanol into GL and FAME was the reaction of MG with methanol into GL and FAME. Copyright © 2013 Elsevier B.V. All rights reserved.

Optimization of the isolation and quantitation of kahweol and cafestol in green coffee oil.

PubMed

Chartier, Agnes; Beaumesnil, Mathieu; de Oliveira, Alessandra Lopes; Elfakir, Claire; Bostyn, Stephane

2013-12-15

Kahweol and cafestol are two diterpenes that exist mainly as esters of fatty acids in green coffee oil. To recover them under their free form they have to be either saponified or trans-esterified. These two compounds are well known to be sensitive to heat, and reagents, therefore experimental conditions used in the transesterification reaction are critical. In this paper, a Doehlert experimental design plan is used to optimize the transesterification conditions using some key variables such as the temperature of the reaction, the reagent base concentration and the duration of the reaction. Therefore, the optimal parameters determined from the Doehlert design are equal to 70 °C, temperature of the reaction; 1.25 mol L(-1) concentration of the reagent base; and 60 min reaction time. The contour plots show that the extracted quantity of kahweol and cafestol can depend greatly from the experimental conditions. After transesterification, the free form of the diterpernes is extracted from the lipid fraction using liquid-liquid extraction and analyzed using GC-FID without prior derivatization. The amount of kahweol and cafestol obtained from green coffee oil obtained by cold mechanical press of Catuai coffee bean is equal to 33.2±2.2 and 24.3±2.4 g kg(-1)oil, respectively. In an attempt to streamline the process, the transesterification reaction is performed in an in-flow chemistry reactor using the optimal conditions obtained with the Doehlert experimental design. The amount of kahweol and cafestol obtained from the same green coffee oil is equal to 43.5 and 30.072 g kg(-1)oil, respectively. Results are slightly higher compared to the ones obtained with the batch procedure. This can be explained by a better mixing of the coffee oil with the reagents and a faster transesterification reaction. © 2013 Elsevier B.V. All rights reserved.

Effects of methanol-to-oil ratio, catalyst amount and reaction time on the FAME yield by in situ transesterification of rubber seeds (Hevea brasiliensis)

NASA Astrophysics Data System (ADS)

Abdulkadir, Bashir Abubakar; Uemura, Yoshimitsu; Ramli, Anita; Osman, Noridah B.; Kusakabe, Katsuki; Kai, Takami

2014-10-01

In this research, biodiesel is produced by in situ transesterification (direct transesterification) method from the rubber seeds using KOH as a catalyst. The influence of methanol to seeds mass ratio, duration of reaction, and catalyst loading was investigated. The result shows that, the best ratio of seeds to methanol is 1:6 (10 g seeds with 60 g methanol), 120 minutes reaction time and catalyst loading of 3.0 g. The maximum FAME yield obtain was 70 %. This findings support FAME production from the seeds of rubber tree using direct transesterifcation method from the seeds of rubber tree as an alternative to diesel fuel. Also, significant properties of biodiesel such as cloud point, density, pour point, specific gravity, and viscosity were investigated.

Biodiesel production via the transesterification of soybean oil using waste starfish (Asterina pectinifera).

PubMed

Jo, Yong Beom; Park, Sung Hoon; Jeon, Jong-Ki; Ko, Chang Hyun; Ryu, Changkook; Park, Young-Kwon

2013-07-01

Calcined waste starfish was used as a base catalyst for the production of biodiesel from soybean oil for the first time. A batch reactor was used for the transesterification reaction. The thermal characteristics and crystal structures of the waste starfish were investigated by thermo-gravimetric analysis and X-ray diffraction. The biodiesel yield was determined by measuring the content of fatty acid methyl esters (FAME). The calcination temperature appeared to be a very important parameter affecting the catalytic activity. The starfish-derived catalyst calcined at 750 °C or higher exhibited high activity for the transesterification reaction. The FAME content increased with increasing catalyst dose and methanol-over-oil ratio.

Transesterification of coconut oil for FAME production using ultrasound

NASA Astrophysics Data System (ADS)

Supriadi, Eko; Marlinda, Lenny; Prajitno, Danawati Hari; Mahfud, Mahfud

2017-05-01

To overcome energy crisis, the vegetable oils-derived biofuel can be chosen as an alternative to petroleum-based diesel. The transesterification of coconut oil in methanol with K/γ-Al2O3 catalyst using ultrasound-assisted to produce fatty acid methyl ester (FAME) as one of type biofuel was studied. The reaction occurred in batch reactor at a 9 : 1 molar ratio of methanol to coconut oil. The following reaction conditions were used in the catalytic test : concentration of catalyst to oil of 0.5, 1.0, 1.5, 2.0, and 2.5%, the reaction time of 10, 20, 30, 60, 90, 120, and 150 s, and the frequency ultrasonication of 20 and 40 KHz. At first, the preparation of K/γ-Al2O3 catalyst was done and followed by transesterification process. After reaction, the phase separation and purification from impurities were done. Finally, FAME was analized based on this parameters, i.e., yield, density, viscosity, and flash point. FAME yield of 93.76% was obtained at the frequency ultrasonication of 40 kHz with K/γ-Al2O3 catalyst concentration to oil of 2.5 wt.% for 150 s. It's the best conditions for FAME production by transesterification of coconut oil using ultrasound-assisted.

Production of biodiesel fuel by transesterification of different vegetable oils with methanol using Al₂O₃ modified MgZnO catalyst.

PubMed

Olutoye, M A; Hameed, B H

2013-03-01

An active heterogeneous Al2O3 modified MgZnO (MgZnAlO) catalyst was prepared and the catalytic activity was investigated for the transesterification of different vegetable oils (refined palm oil, waste cooking palm oil, palm kernel oil and coconut oil) with methanol to produce biodiesel. The catalyst was characterized by using X-ray diffraction, Fourier transform infrared spectra, thermo gravimetric and differential thermal analysis to ascertain its versatility. Effects of important reaction parameters such as methanol to oil molar ratio, catalyst dosage, reaction temperature and reaction time on oil conversion were examined. Within the range of studied variability, the suitable transesterification conditions (methanol/oil ratio 16:1, catalyst loading 3.32 wt.%, reaction time 6h, temperature 182°C), the oil conversion of 98% could be achieved with reference to coconut oil in a single stage. The catalyst can be easily recovered and reused for five cycles without significant deactivation. Copyright © 2013 Elsevier Ltd. All rights reserved.

Monitoring biodiesel reactions of soybean oil and sunflower oil using ultrasonic parameters

NASA Astrophysics Data System (ADS)

Figueiredo, M. K. K.; Silva, C. E. R.; Alvarenga, A. V.; Costa-Félix, R. P. B.

2015-01-01

Biodiesel is an innovation that attempts to substitute diesel oil with biomass. The aim of this paper is to show the development of a real-time method to monitor transesterification reactions by using low-power ultrasound and pulse/echo techniques. The results showed that it is possible to identify different events during the transesterification process by using the proposed parameters, showing that the proposed method is a feasible way to monitor the reactions of biodiesel during its fabrication, in real time, and with relatively low- cost equipment.

Optimization of biodiesel production process using recycled vegetable oil

NASA Astrophysics Data System (ADS)

Lugo, Yarely

Petro diesel toxic emissions and its limited resources have created an interest for the development of new energy resources, such as biodiesel. Biodiesel is traditionally produced by a transesterification reaction between vegetable oil and an alcohol in the presence of a catalyst. However, this process is slow and expensive due to the high cost of raw materials. Low costs feedstock oils such as recycled and animal fats are available but they cannot be transesterified with alkaline catalysts due to high content of free fatty acids, which can lead to undesirable reactions such as saponification. In this study, we reduce free fatty acids content by using an acid pre-treatment. We compare sulfuric acid, hydrochloric acid and ptoluenesulfonic acid (PTSA) to pre-treat recycled vegetable oil. PTSA removes water after 60 minutes of treatment at room temperature or within 15 minutes at 50°C. The pretreatment was followed by a transesterification reaction using alkaline catalyst. To minimize costs and accelerate reaction, the pretreatment and transesterification reaction of recycle vegetable oil was conducted at atmospheric pressure in a microwave oven. Biodiesel was characterized using a GC-MS method.

A Multidimensional B-Spline Correction for Accurate Modeling Sugar Puckering in QM/MM Simulations.

PubMed

Huang, Ming; Dissanayake, Thakshila; Kuechler, Erich; Radak, Brian K; Lee, Tai-Sung; Giese, Timothy J; York, Darrin M

2017-09-12

The computational efficiency of approximate quantum mechanical methods allows their use for the construction of multidimensional reaction free energy profiles. It has recently been demonstrated that quantum models based on the neglect of diatomic differential overlap (NNDO) approximation have difficulty modeling deoxyribose and ribose sugar ring puckers and thus limit their predictive value in the study of RNA and DNA systems. A method has been introduced in our previous work to improve the description of the sugar puckering conformational landscape that uses a multidimensional B-spline correction map (BMAP correction) for systems involving intrinsically coupled torsion angles. This method greatly improved the adiabatic potential energy surface profiles of DNA and RNA sugar rings relative to high-level ab initio methods even for highly problematic NDDO-based models. In the present work, a BMAP correction is developed, implemented, and tested in molecular dynamics simulations using the AM1/d-PhoT semiempirical Hamiltonian for biological phosphoryl transfer reactions. Results are presented for gas-phase adiabatic potential energy surfaces of RNA transesterification model reactions and condensed-phase QM/MM free energy surfaces for nonenzymatic and RNase A-catalyzed transesterification reactions. The results show that the BMAP correction is stable, efficient, and leads to improvement in both the potential energy and free energy profiles for the reactions studied, as compared with ab initio and experimental reference data. Exploration of the effect of the size of the quantum mechanical region indicates the best agreement with experimental reaction barriers occurs when the full CpA dinucleotide substrate is treated quantum mechanically with the sugar pucker correction.

Biodiesel from wet microalgae: extraction with hexane after the microwave-assisted transesterification of lipids.

PubMed

Cheng, Jun; Huang, Rui; Li, Tao; Zhou, Junhu; Cen, Kefa

2014-10-01

A chloroform-free novel process for the efficient production of biodiesel from wet microalgae is proposed. Crude biodiesel is produced through extraction with hexane after microwave-assisted transesterification (EHMT) of lipids in wet microalgae. Effects of different parameters, including reaction temperature, reaction time, methanol dosage, and catalyst dosage, on fatty acids methyl esters (FAMEs) yield are investigated. The yield of FAME extracted into the hexane from the wet microalgae is increased 6-fold after the transesterification of lipids. The yield of FAME obtained through EHMT of lipids in wet microalgae is comparable to that obtained through direct transesterification of dried microalgae biomass with chloroform; however, FAME content in crude biodiesel obtained through EHMT is 86.74%, while that in crude biodiesel obtained through the chloroform-based process is 75.93%. EHMT ensures that polar pigments present in microalgae are not extracted into crude biodiesel, which leads to a 50% reduction in nitrogen content in crude biodiesel. Copyright © 2014 Elsevier Ltd. All rights reserved.

The feasibility study of crude palm oil transesterification at 30 °C operation.

PubMed

Sim, Jia Huey; Kamaruddin, Azlina Harun; Bhatia, Subhash

2010-12-01

The objective of this research is to investigate the potential of transesterification of crude palm oil (CPO) to biodiesel at 30 degrees C. The mass transfer limitations problem crucial at 30 degrees C due to the viscosity of CPO has been addressed. The process parameters that are closely related to mass transfer effects like enzyme loading, agitation speed and reaction time were optimized. An optimum methanol to oil substrate molar ratio at 6.5:1 was observed and maintained throughout the experiments. The optimum operating condition for the transesterification process was found at 6.67 wt% of enzyme loading and at 150 rpm of agitation speed. The corresponding initial reaction and FAME yield obtained at 6 h were 89.29% FAME yield/hr and 85.01%, respectively. The 85% FAME yield obtained at 30 degrees C operation of CPO transesterification shows that the process is potentially feasible for the biodiesel synthesis. 2010 Elsevier Ltd. All rights reserved.

Boosting the value of biodiesel byproduct by the non-catalytic transesterification of dimethyl carbonate via a continuous flow system under ambient pressure.

PubMed

Kwon, Eilhann E; Yi, Haakrho; Jeon, Young Jae

2014-10-01

Transformation of coconut oil into biodiesel by using dimethyl carbonate (DMC) via a non-catalytic transesterification reaction under ambient pressure was investigated in this study. The non-catalytic transformation to biodiesel was achieved by means of a heterogeneous reaction between liquid triglycerides and gas phase DMC. The reaction was enhanced in the presence of porous material due to its intrinsic physical properties such as tortuosity and absorption/adsorption. The numerous pores in the material served as micro reaction chambers and ensured that there was enough contact time between the liquid triglycerides and the gaseous DMC, which enabled the completion of the transesterification. The highest fatty acid methyl esters (FAMEs) yield achieved was 98±0.5% within 1-2min at a temperature of 360-450°C under ambient pressure. The fast reaction rates made it possible to convert the lipid feedstock into biodiesel via a continuous flow system without the application of increased pressure. This suggested that the commonly used supercritical conditions could be avoided, resulting in huge cost benefits for biodiesel production. In addition, the high value of the byproduct from the transesterification of the lipid feedstock with DMC suggested that the production biodiesel using this method could be more economically competitive. Finally, the basic properties of biodiesel derived from the non-catalytic conversion of rapeseed oil with DMC were summarised. Copyright © 2014 Elsevier Ltd. All rights reserved.

Optimization of transesterification of rubber seed oil using heterogeneous catalyst calcium oxide

NASA Astrophysics Data System (ADS)

Inggrid, Maria; Kristanto, Aldi; Santoso, Herry

2015-12-01

Biodiesel is an alternative fuel manufactured with the help of alkali hydroxide catalyst through transesterification reaction of vegetable oil. This study aims to examine methods and the most suitable conditions for transesterification reaction producing biodiesel from crude rubber seed oil by varying process parameters such as the molar ratio of alcohol, CaO amount as the alkaline catalyst, and reaction time. The rubber seed oil has a high level of free fatty acid content, which means the use of homogenous alkaline catalyst gives some technological problems such as soap formation which leaded in difficulty in the separation and purification of the product. Calcium oxide (CaO) is one of the most favorable heterogeneous base catalysts because it's reusable, noncorrosive, and low cost. Pre-treatment was performed by acid esterification with H2SO4 as the catalyst to decrease the content of free fatty acid in the rubber seed oil, in this pretreatment process the 12% FFA of crude oil could be reduced to below 3% FFA. The product after esterification process was then transesterified by alkaline transesterification by varying process parameters to convert triglyceride into biodiesel. The study found that maximum curvature for biodiesel yield occurred at 9:1 molar ratio of alcohol, 5%w catalyst loading, and 3 hours reaction time. Design expert software is used to determine the optimum point from experimental data. The result showed that the optimum yield of methyl ester from transesterification was 73.5 % by mass with 0.69 degree of desirability. The yielded methyl ester was tested for its density, viscosity, acid number, and solubility to meet SNI requirement standards.

Key role of temperature monitoring in interpretation of microwave effect on transesterification and esterification reactions for biodiesel production.

PubMed

Mazubert, Alex; Taylor, Cameron; Aubin, Joelle; Poux, Martine

2014-06-01

Microwave effects have been quantified, comparing activation energies and pre-exponential factors to those obtained in a conventionally-heated reactor for biodiesel production from waste cooking oils via transesterification and esterification reactions. Several publications report an enhancement of biodiesel production using microwaves, however recent reviews highlight poor temperature measurements in microwave reactors give misleading reaction performances. Operating conditions have therefore been carefully chosen to investigate non-thermal microwave effects alone. Temperature is monitored by an optical fiber sensor, which is more accurate than infrared sensors. For the transesterification reaction, the activation energy is 37.1kJ/mol (20.1-54.2kJ/mol) in the microwave-heated reactor compared with 31.6kJ/mol (14.6-48.7kJ/mol) in the conventionally-heated reactor. For the esterification reaction, the activation energy is 45.4kJ/mol (31.8-58.9kJ/mol) for the microwave-heated reactor compared with 56.1kJ/mol (55.7-56.4kJ/mol) for conventionally-heated reactor. The results confirm the absence of non-thermal microwave effects for homogenous-catalyzed reactions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Ionic Liquid Droplet Microreactor for Catalysis Reactions Not at Equilibrium.

PubMed

Zhang, Ming; Ettelaie, Rammile; Yan, Tao; Zhang, Suojiang; Cheng, Fangqin; Binks, Bernard P; Yang, Hengquan

2017-12-06

We develop a novel strategy to more effectively and controllably process continuous enzymatic or homogeneous catalysis reactions based on nonaqueous Pickering emulsions. A key element of this strategy is "bottom-up" construction of a macroscale continuous flow reaction system through packing catalyst-containing micron-sized ionic liquid (IL) droplet in oil in a column reactor. Due to the continuous influx of reactants into the droplet microreactors and the continuous release of products from the droplet microreactors, catalysis reactions in such a system can take place without limitations arising from establishment of the reaction equilibrium and catalyst separation, inherent in conventional batch reactions. As proof of the concept, enzymatic enantioselective trans-esterification and CuI-catalyzed cycloaddition reactions using this IL droplet-based flow system both exhibit 8 to 25-fold enhancement in catalysis efficiency compared to their batch counterparts, and a durability of at least 4000 h for the enantioselective trans-esterification of 1-phenylethyl alcohol, otherwise unattainable in their batch counterparts. We further establish a theoretical model for such a catalysis system working under nonequilibrium conditions, which not only supports the experimental results but also helps to predict reaction progress at a microscale level. Being operationally simple, efficient, and adaptive, this strategy provides an unprecedented platform for practical applications of enzymes and homogeneous catalysts even at a controllable level.

Effect of supercritical carbon dioxide on the enzymatic production of biodiesel from waste animal fat using immobilized Candida antarctica lipase B variant.

PubMed

Pollardo, Aldricho Alpha; Lee, Hong-Shik; Lee, Dohoon; Kim, Sangyong; Kim, Jaehoon

2017-09-09

Waste animal fat is a promising feedstock to replace vegetable oil that widely used in commercial biodiesel process, however the high content of free fatty acid in waste fat makes it unfeasible to be processed with commercial base-catalytic process. Enzymatic process is preferable to convert waste fat into biodiesel since enzyme can catalyze both esterification of free fatty acid and transesterification of triglyceride. However, enzymatic reaction still has some drawbacks such as lower reaction rates than base-catalyzed transesterification and the limitation of reactant concentration due to the enzyme inhibition of methanol. Supercritical CO 2 is a promising reaction media for enzyme-catalyzed transesterification to overcome those drawbacks. The transesterification of waste animal fat was carried out in supercritical CO 2 with varied concentration of feedstock and methanol in CO 2 . The CO 2 to feedstock mass ratio of 10:1 showed the highest yield compared to other ratios, and the highest FAME yield obtained from waste animal fat was 78%. The methanol concentration effect was also observed with variation 12%, 14%, and 16% of methanol to feedstock ratio. The best yield was 87% obtained at the CO 2 to feedstock ratio of 10: 1 and at the methanol to feedstock ratio of 14% after 6 h of reaction. Enzymatic transesterification to produce biodiesel from waste animal fat in supercritical fluid media is a potential method for commercialization since it could enhance enzyme activity due to supercritical fluid properties to remove mass transfer limitation. The high yield of FAME when using high mass ratio of CO 2 to oil showed that supercritical CO 2 could increase the reaction and mass transfer rate while reducing methanol toxicity to enzyme activity. The increase of methanol concentration also increased the FAME yield because it might shift the reaction equilibrium to FAME production. This finding describes that the application of supercritical CO 2 in the enzymatic reaction enables the application of simple process such as a packed-bed reactor.

Data set for extraction and transesterification of bio-oil from Stoechospermum marginatum, a brown marine algae.

PubMed

Venkatesan, Hariram; Godwin, John J; Sivamani, Seralathan

2017-10-01

The article presents the experimental data on the extraction and transesterification of bio-oil derived from Stoechospermum marginatum, a brown macro marine algae. The samples were collected from Mandapam region, Gulf of Mannar, Tamil Nadu, India. The bio-oil was extracted using Soxhlet technique with a lipid extraction efficiency of 24.4%. Single stage transesterification was adopted due to lower free fatty acid content. The yield of biodiesel was optimized by varying the process parameters. The obtained data showed the optimum process parameters as reaction time 90 min, reaction temperature 65 °C, catalyst concentration 0.50 g and 8:1 M ratio. Furthermore, the data pertaining to the physio-chemical properties of the derived algal biodiesel were also presented.

Pyrogenic transformation of Nannochloropsis oceanica into fatty acid methyl esters without oil extraction for estimating total lipid content.

PubMed

Kim, Jieun; Jung, Jong-Min; Lee, Jechan; Kim, Ki-Hyun; Choi, Tae O; Kim, Jae-Kon; Jeon, Young Jae; Kwon, Eilhann E

2016-07-01

This study fundamentally investigated the pseudo-catalytic transesterification of dried Nannochloropsis oceanica into fatty acid methyl esters (FAMEs) without oil extraction, which was achieved in less than 5min via a thermo-chemical pathway. This study presented that the pseudo-catalytic transesterification reaction was achieved in the presence of silica and that its main driving force was identified as temperature: pores in silica provided the numerous reaction space like a micro-reactor, where the heterogeneous reaction was developed. The introduced FAME derivatization showed an extraordinarily high tolerance of impurities (i.e., pyrolytic products and various extractives). This study also explored the thermal cracking of FAMEs derived from N. oceanica: the thermal cracking of saturated FAMEs was invulnerable at temperatures lower than 400°C. Lastly, this study reported that N. oceanica contained 14.4wt.% of dried N. oceanica and that the introduced methylation technique could be applicable to many research fields sharing the transesterification platform. Copyright © 2016 Elsevier Ltd. All rights reserved.

Biodiesel production by transesterification using immobilized lipase.

PubMed

Narwal, Sunil Kumar; Gupta, Reena

2013-04-01

Biodiesel can be produced by transesterification of vegetable or waste oil catalysed by lipases. Biodiesel is an alternative energy source to conventional fuel. It combines environmental friendliness with biodegradability, low toxicity and renewability. Biodiesel transesterification reactions can be broadly classified into two categories: chemical and enzymatic. The production of biodiesel using the enzymatic route eliminates the reactions catalysed under acid or alkali conditions by yielding product of very high purity. The modification of lipases can improve their stability, activity and tolerance to alcohol. The cost of lipases and the relatively slower reaction rate remain the major obstacles for enzymatic production of biodiesel. However, this problem can be solved by immobilizing the enzyme on a suitable matrix or support, which increases the chances of re-usability. The main factors affecting biodiesel production are composition of fatty acids, catalyst, solvents, molar ratio of alcohol and oil, temperature, water content, type of alcohol and reactor configuration. Optimization of these parameters is necessary to reduce the cost of biodiesel production.

Biodiesel synthesis by direct transesterification of microalga Botryococcus braunii with continuous methanol reflux.

PubMed

Hidalgo, Pamela; Ciudad, Gustavo; Schober, Sigurd; Mittelbach, Martin; Navia, Rodrigo

2015-04-01

Direct transesterification of Botryococcus braunii with continuous acyl acceptor reflux was evaluated. This method combines in one step lipid extraction and esterification/transesterification. Fatty acid methyl esters (FAME) synthesis by direct conversion of microalgal biomass was carried out using sulfuric acid as catalyst and methanol as acyl acceptor. In this system, once lipids are extracted, they are contacted with the catalyst and methanol reaching 82%wt of FAME yield. To optimize the reaction conditions, a factorial design using surface response methodology was applied. The effects of catalyst concentration and co-solvent concentration were studied. Hexane was used as co-solvent for increasing lipid extraction performance. The incorporation of hexane in the reaction provoked an increase in FAME yield from 82% (pure methanol) to 95% when a 47%v/v of hexane was incorporated in the reaction. However, the selectivity towards non-saponifiable lipids such as sterols was increased, negatively affecting biodiesel quality. Copyright © 2015 Elsevier Ltd. All rights reserved.

Transesterification of Waste Olive Oil by "Candida" Lipase

ERIC Educational Resources Information Center

Shen, Xiangping; Vasudevan, Palligarnai T.

2008-01-01

Biodiesel was produced by transesterification of waste olive oil with methanol and Novozym [R] 435. The effect of the molar ratio of methanol to triolein, mode of methanol addition, reaction temperature, and mixing speed on biodiesel yield was determined. The effect of different acyl acceptors and/or solvents on biodiesel yield was also evaluated.…

Production of biodiesel via the in situ transesterification of grain sorghum bran and DDGS

USDA-ARS?s Scientific Manuscript database

The acylglycerides in sorghum bran and distiller’s dried grains and solubles (DDGS) from sorghum post-fermentation stillage have been converted to fatty acid methyl esters (FAMEs) using an in-situ transesterification (IST) method. The reactions were conducted at 25 deg C or 40 deg C in the presence...

Effect of sub- and supercritical CO2 treatment on the properties of Pseudomonas cepacia lipase.

PubMed

Chen, Dawei; Zhang, Houjin; Xu, Jing; Yan, Yunjun

2013-07-10

In this work, we have investigated the influences of sub- and supercritical CO2 treatment on the properties of Pseudomonas cepacia lipase (PCL), including its esterification and transesterification activities, structural changes and stability. Results demonstrated that exposure time to subcritical CO2 treatment had a negative effect on PCL transesterification activity whereas exposure time to supercritical CO2 treatment had a positive effect. But generally, most compressed treatments significantly enhanced PCL esterification activity. Conformational analysis by FT-IR and fluorescence emission spectra revealed that enhanced activities after supercritical CO2 treatment were correlated with the secondary and tertiary structural changes of PCL. Secondary structure changes also appeared to be responsible for enhancement of PCL activities by subcritical CO2 treatment. Compared to native PCL, treated PCL's esterification activity significantly decreased in hydrophilic organic media, while transesterification activity significantly increased in tert-amyl alcohol and acetone. After supercritical treatment, the thermal stability of PCL significantly decreased in esterification reactions, however, there was no significant difference in transesterification reactions. Copyright © 2013 Elsevier Inc. All rights reserved.

Detergent assisted ultrasonication aided in situ transesterification for biodiesel production from oleaginous yeast wet biomass.

PubMed

Yellapu, Sravan Kumar; Kaur, Rajwinder; Tyagi, Rajeshwar D

2017-01-01

In situ transesterification of oleaginous yeast wet biomass for fatty acid methyl esters (FAMEs) production using acid catalyst, methanol with or without N-Lauroyl sarcosine (N-LS) treatment was performed. The maximum FAMEs yield obtained with or without N-LS treatment in 24h reaction time was 96.1±1.9 and 71±1.4% w/w, respectively. The N-LS treatment of biomass followed by with or without ultrasonication revealed maximum FAMEs yield of 94.3±1.9% and 82.9±1.8% w/w using methanol to lipid molar ratio 360:1 and catalyst concentration 360mM (64μL H 2 SO 4 /g lipid) within 5 and 25min reaction time, respectively. The FAMEs composition obtained in in situ transesterification was similar to that obtained with conventional two step lipid extraction and transesterification process. Biodiesel fuel properties (density, kinematic viscosity, cetane number and total glycerol) were in accordance with international standard (ASTM D6751), which suggests the suitability of biodiesel as a fuel. Copyright © 2016 Elsevier Ltd. All rights reserved.

Optimization of bio-diesel production from soybean and wastes of cooked oil: combining dielectric microwave irradiation and a SrO catalyst.

PubMed

Koberg, Miri; Abu-Much, Riam; Gedanken, Aharon

2011-01-01

This work offers an optimized method in the transesterification of pristine (soybean) oil and cooked oil to bio-diesel, based on microwave dielectric irradiation as a driving force for the transesterification reaction and SrO as a catalyst. This combination has demonstrated excellent catalytic activity and stability. The transesterification was carried out with and without stirring. According to 1H NMR spectroscopy and TLC results, this combination accelerates the reaction (to less than 60 s), maintaining a very high conversion (99%) and high efficiency. The catalytic activity of SrO under atmospheric pressure in the presence of air and under the argon atmosphere is demonstrated. The optimum conversion of cooked oil (99.8%) is achieved under MW irradiation of 1100 W output with magnetic stirring after only 10 s. The optimum method decreases the cost of bio-diesel production and has the potential for industrial application in the transesterification of cooked oil to bio-diesel. Copyright © 2010 Elsevier Ltd. All rights reserved.

Biodiesel production process intensification using a rotor-stator type generator of hydrodynamic cavitation.

PubMed

Crudo, Daniele; Bosco, Valentina; Cavaglià, Giuliano; Grillo, Giorgio; Mantegna, Stefano; Cravotto, Giancarlo

2016-11-01

Triglyceride transesterification for biodiesel production is a model reaction which is used to compare the conversion efficiency, yield, reaction time, energy consumption, scalability and cost estimation of different reactor technology and energy source. This work describes an efficient, fast and cost-effective procedure for biodiesel preparation using a rotating generator of hydrodynamic cavitation (HC). The base-catalyzed transesterification (methanol/sodium hydroxide) has been carried out using refined and bleached palm oil and waste vegetable cooking oil. The novel HC unit is a continuous rotor-stator type reactor in which reagents are directly fed into the controlled cavitation chamber. The high-speed rotation of the reactor creates micron-sized droplets of the immiscible reacting mixture leading to outstanding mass and heat transfer and enhancing the kinetics of the transesterification reaction which completes much more quickly than traditional methods. All the biodiesel samples obtained respect the ASTM standard and present fatty acid methyl ester contents of >99% m/m in both feedstocks. The electrical energy consumption of the HC reactor is 0.030kWh per L of produced crude biodiesel, making this innovative technology really quite competitive. The reactor can be easily scaled-up, from producing a few hundred to thousands of liters of biodiesel per hour while avoiding the risk of orifices clogging with oil impurities, which may occur in conventional HC reactors. Furthermore it requires minimal installation space due to its compact design, which enhances overall security. Copyright © 2016 Elsevier B.V. All rights reserved.

Biodiesel production using waste frying oil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Charpe, Trupti W.; Rathod, Virendra K., E-mail: vk.rathod@ictmumbai.edu.in

2011-01-15

Research highlights: {yields} Waste sunflower frying oil is successfully converted to biodiesel using lipase as catalyst. {yields} Various process parameters that affects the conversion of transesterification reaction such as temperature, enzyme concentration, methanol: oil ratio and solvent are optimized. {yields} Inhibitory effect of methanol on lipase is reduced by adding methanol in three stages. {yields} Polar solvents like n-hexane and n-heptane increases the conversion of tranesterification reaction. - Abstract: Waste sunflower frying oil is used in biodiesel production by transesterification using an enzyme as a catalyst in a batch reactor. Various microbial lipases have been used in transesterification reaction tomore » select an optimum lipase. The effects of various parameters such as temperature, methanol:oil ratio, enzyme concentration and solvent on the conversion of methyl ester have been studied. The Pseudomonas fluorescens enzyme yielded the highest conversion. Using the P. fluorescens enzyme, the optimum conditions included a temperature of 45 deg. C, an enzyme concentration of 5% and a methanol:oil molar ratio 3:1. To avoid an inhibitory effect, the addition of methanol was performed in three stages. The conversion obtained after 24 h of reaction increased from 55.8% to 63.84% because of the stage-wise addition of methanol. The addition of a non-polar solvent result in a higher conversion compared to polar solvents. Transesterification of waste sunflower frying oil under the optimum conditions and single-stage methanol addition was compared to the refined sunflower oil.« less

The mechanism and thermodynamics of transesterification of acetate-ester enolates in the gas phase

NASA Astrophysics Data System (ADS)

Haas, George W.; Giblin, Daryl E.; Gross, Michael L.

1998-01-01

In solution, base-catalyzed hydrolysis and transesterification of esters are initiated by hydroxide- or alkoxide-ion attack at the carbonyl carbon. At low pressures in the gas phase, however, transesterification proceeds by an attack of the enolate anion of an acetate ester on an alcohol. Fourier transform mass spectrometry (FTMS) indicates that the reaction is the second-order process: -CH2-CO2-R + R'-OH --> - CH2-CO2-R' + R-OH and there is little to no detectable production of either alkoxide anion. Labeling studies show that the product and reactant enolate anion esters undergo exchange of hydrogens located [alpha] to the carbonyl carbon with the deuterium of R'-OD. The extent of the H/D exchange increases with reaction time, pointing to a short-lived intermediate. The alcoholysis reaction rate constants increase with increasing acidity of the primary, straight-chained alkyl alcohols, whereas steric effects associated with branched alcohols cause the rate constants to decrease. Equilibrium constants, which were determined directly from measurements at equilibrium and which were calculated from the forward and reverse rate constants, are near unity and show internal consistency. In the absence of steric effects, the larger enolate is always the favored product at equilibrium. The intermediate for the transesterification reaction, which can be generated at a few tenths of a torr in a tandem mass spectrometer, is tetrahedral, but other adducts that are collisionally stabilized under these conditions are principally loosely bound complexes.

Synthesis of fatty acid methyl ester from the transesterification of high- and low-acid-content crude palm oil (Elaeis guineensis) and karanj oil (Pongamia pinnata) over a calcium-lanthanum-aluminum mixed-oxides catalyst.

PubMed

Syamsuddin, Y; Murat, M N; Hameed, B H

2016-08-01

The synthesis of fatty acid methyl ester (FAME) from the high- and low-acid-content feedstock of crude palm oil (CPO) and karanj oil (KO) was conducted over CaO-La2O3-Al2O3 mixed-oxide catalyst. Various reaction parameters were investigated using a batch reactor to identify the best reaction condition that results in the highest FAME yield for each type of oil. The transesterification of CPO resulted in a 97.81% FAME yield with the process conditions of 170°C reaction temperature, 15:1 DMC-to-CPO molar ratio, 180min reaction time, and 10wt.% catalyst loading. The transesterification of KO resulted in a 96.77% FAME yield with the conditions of 150°C reaction temperature, 9:1 DMC-to-KO molar ratio, 180min reaction time, and 5wt.% catalyst loading. The properties of both products met the ASTM D6751 and EN 14214 standard requirements. The above results showed that the CaO-La2O3-Al2O3 mixed-oxide catalyst was suitable for high- and low-acid-content vegetable oil. Copyright © 2016 Elsevier Ltd. All rights reserved.

Electrochemical method for producing a biodiesel mixture comprising fatty acid alkyl esters and glycerol

DOEpatents

Lin, YuPo J; St. Martin, Edward J

2013-08-13

The present invention relates to an integrated method and system for the simultaneous production of biodiesel from free fatty acids (via esterification) and from triglycerides (via transesterification) within the same reaction chamber. More specifically, one preferred embodiment of the invention relates to a method and system for the production of biodiesel using an electrodeionization stack, wherein an ion exchange resin matrix acts as a heterogeneous catalyst for simultaneous esterification and transesterification reactions between a feedstock and a lower alcohol to produce biodiesel, wherein the feedstock contains significant levels of free fatty acid. In addition, because of the use of a heterogeneous catalyst, the glycerol and biodiesel have much lower salt concentrations than raw biodiesel produced by conventional transesterification processes. The present invention makes it much easier to purify glycerol and biodiesel.

Role of solid acid catalysts in bio diesel production.

PubMed

Shivayogimath, C B; Sunita, G; Manoj Kumar, B

2009-07-01

Biodiesel is gaining importance as an alternate source of attractive fuel because of depleting fossil fuel resources. It is produced by trans-esterification, in which oil or fat reacts with a monohydric alcohol in presence of a catalyst. In the present work, trans-esterification of sunflower oil with methanol is carried out by using zirconia supported isopoly and heteropoly tungstates (HPAs) as catalysts. Effects of reaction parameters, such as catalyst types and its concentration, molar ratio of sunflower oil to methanol, reaction temperature and time, have been optimized to get higher conversion of sunflower oil and the product distribution of fatty acid methyl esters (FAME) in the trans-esterfication reaction.

Concurrent extraction and reaction for the production of biodiesel from wet microalgae.

PubMed

Im, Hanjin; Lee, HanSol; Park, Min S; Yang, Ji-Won; Lee, Jae W

2014-01-01

This work addresses a reliable in situ transesterification process which integrates lipid extraction from wet microalgae, and its conversion to biodiesel, with a yield higher than 90 wt.%. This process enables single-step production of biodiesel from microalgae by mixing wet microalgal cells with solvent, methanol, and acid catalyst; and then heating them in one pot. The effects of reaction parameters such as reaction temperature, wet cell weight, reaction time, and catalyst volume on the conversion yield are investigated. This simultaneous extraction and transesterification of wet microalgae may enable a significant reduction in energy consumption by eliminating the drying process of algal cells and realize the economic production of biodiesel using wet microalgae. Copyright © 2013 Elsevier Ltd. All rights reserved.

Ultrasound assisted two-stage biodiesel synthesis from non-edible Schleichera triguga oil using heterogeneous catalyst: Kinetics and thermodynamic analysis.

PubMed

Sarve, Antaram N; Varma, Mahesh N; Sonawane, Shriram S

2016-03-01

Present work deals with the ultrasound-assisted biodiesel production from low cost, substantial acid value kusum (Schleichera triguga) oil using a two-step method of esterification in presence of acid (H2SO4) catalyst followed by transesterification using a basic heterogeneous barium hydroxide (Ba(OH)2) catalyst. The initial acid value of kusum oil was reduced from 21.65 to 0.84 mg of KOH/g of oil, by acid catalyzed esterification with 4:1 methanol to oil molar ratio, catalyst concentration 1% (v/v), ultrasonic irradiation time 20 min at 40 °C. Then, Ba(OH)2 concentration of 3% (w/w), methanol to oil molar ratio of 9:1, ultrasonic irradiation time of 80 min, and temperature of 50 °C was found to be the optimum conditions for transesterification step and triglyceride conversion of 96.8% (wt) was achieved. This paper also examined the kinetics as well as the evaluation of thermodynamic parameters for both esterification and transesterification reactions. The lower value of activation energy and higher values of kinetic constants indicated a fast rate of reaction, which could be attributed to the physical effect of emulsification, in which the microturbulence generated due to radial motion of bubbles, creates an intimate mixing of the immiscible reactants causing the increase in the interfacial area, giving faster reaction kinetics. The positive values of Gibbs-free energy (ΔG), enthalpy (ΔH) and negative value of entropy (ΔS) revealed that both the esterification and transesterification were non-spontaneous, endothermic and endergonic reactions. Therefore, the present work has not only established the escalation obtained due to ultrasonication but also exemplified the two-step approach for synthesis of biodiesel from non-edible kusum oil based on the use of heterogeneous catalyst for the transesterification step. Copyright © 2015 Elsevier B.V. All rights reserved.

Electrophilic assistance to the cleavage of an RNA model phopshodiester via specific and general base-catalyzed mechanisms.

PubMed

Corona-Martínez, David Octavio; Gomez-Tagle, Paola; Yatsimirsky, Anatoly K

2012-10-19

Kinetics of transesterification of the RNA model substrate 2-hydroxypropyl 4-nitrophenyl phosphate promoted by Mg(2+) and Ca(2+), the most common biological metals acting as cofactors for nuclease enzymes and ribozymes, as well as by Co(NH(3))(6)(3+), Co(en)(3)(3+), Li(+), and Na(+) cations, often employed as mechanistic probes, was studied in 80% v/v (50 mol %) aqueous DMSO, a medium that allows one to discriminate easily specific base (OH(-)-catalyzed) and general base (buffer-catalyzed) reaction paths. All cations assist the specific base reaction, but only Mg(2+) and Na(+) assist the general base reaction. For Mg(2+)-assisted reactions, the solvent deuterium isotope effects are 1.23 and 0.25 for general base and specific base mechanisms, respectively. Rate constants for Mg(2+)-assisted general base reactions measured with different bases fit the Brønsted correlation with a slope of 0.38, significantly lower than the slope for the unassisted general base reaction (0.77). Transition state binding constants for catalysts in the specific base reaction (K(‡)(OH)) both in aqueous DMSO and pure water correlate with their binding constants to 4-nitrophenyl phosphate dianion (K(NPP)) used as a minimalist transition state model. It was found that K(‡)(OH) ≈ K(NPP) for "protic" catalysts (Co(NH(3))(6)(3+), Co(en)(3)(3+), guanidinium), but K(‡)(OH) ≫ K(NPP) for Mg(2+) and Ca(2+) acting as Lewis acids. It appears from results of this study that Mg(2+) is unique in its ability to assist efficiently the general base-catalyzed transesterification often occurring in active sites of nuclease enzymes and ribozymes.

Biodiesel production from rice bran oil by transesterification using heterogeneous catalyst natural zeolite modified with K2CO3

NASA Astrophysics Data System (ADS)

Taslim; Iriany; Bani, O.; Parinduri, S. Z. D. M.; Ningsih, P. R. W.

2018-02-01

In the present study, an effort had been made to use natural zeolite from Tapanuli Utara, North Sumatera as a potential catalyst for biodiesel production. Biodiesel production is usuallythrough transesterification, and a catalyst is employed to improve reaction rate and yield. In this research rice bran oil (RBO) was used as feedstock. The objective of this work was to discover the effectiveness of natural zeolite modified by K2CO3 as catalysts in biodiesel production from RBO. K2CO3/natural zeolite catalyst modification was by impregnation method at various K2CO3 concentrations followed by drying and calcination. Transesterification was conducted at 65°C and 500 rpm. Effect of process variables such as the amount of catalyst, reaction time, and the molar ratio of methanol to RBO was investigated.The maximum yield of 98.18% biodiesel was obtained by using 10:1 molar ratio of methanol to RBO at a reaction time of 3 hours in the presence of 4 w% catalyst. The obtained biodiesel was then characterized by its density, viscosity and ester content. The biodiesel properties met the Indonesia standard (SNI).The results showed that natural zeolite modified by K2CO3 was suitable as a catalyst in the synthesis of biodiesel through transesterification from RBO.

Ohmic heating pretreatment of algal slurry for production of biodiesel.

PubMed

Yodsuwan, Natthawut; Kamonpatana, Pitiya; Chisti, Yusuf; Sirisansaneeyakul, Sarote

2018-02-10

Suspensions of the model microalga Chlorella sp. TISTR 8990 were pretreated by ohmic heating to facilitate release of lipids from the cells in subsequent extraction and lipase-mediated transesterification to biodiesel. After ohmic pretreatment, the moist biomass was suspended in a system of water, hexane, methanol and immobilized lipase for extraction of lipids and simultaneous conversion to biodiesel. The ohmic pretreatment was optimized using an experimental design based on Taguchi method to provide treated biomass that maximized the biodiesel yield in subsequent extraction-transesterification operation. The experimental factors were the frequency of electric current (5-10 5  Hz), the processing temperature (50-70 °C), the algal biomass concentration in the slurry (algal fresh weight to water mass ratio of 1-3) and the incubation time (1-3 min). Extraction-transesterification of the pretreated biomass was carried out at 40 °C for 24 h using a reaction systems of a fixed composition (i.e. biomass, hexane, methanol, water and immobilized enzyme). Compared to control (i.e. untreated biomass), the ohmic pretreatment under optimal conditions (5 Hz current frequency, 70 °C, 1:2 mass ratio of biomass to water, incubation time of 2-min) increased the rate of subsequent transesterification by nearly 2-fold. Copyright © 2017 Elsevier B.V. All rights reserved.

The utilization of leftover as acid catalyst to catalyse the transesterification and esterification reactions

NASA Astrophysics Data System (ADS)

Leung, K. K.; Yau, Y. H.

2017-08-01

Biodiesel (Fatty Acid Methyl Ester, FAME) is a green and renewable energy. It is carbon neutral and produces less air pollutants in combustion. In my project, the selected feedstock of biodiesel production is grease trap oil (GTO). It is extracted from restaurants, and needs pre-treatment. The triglycerides and free fatty acid (FFA) are the main components of GTO. Both triglycerides and free fatty acid can be converted to biodiesel (Fatty Acid Methyl Ester) by transesterification and esterification, through reaction with alcohol (methanol) and catalyst. In the processes, acidic catalyst is chosen to speed up the reactions. The catalyst used In the study, a heterogeneous solid acid is applied. It is waste cooked rice (WCR) collected from leftover. The WCR powder is pyrolysed in 400°C furnace 15 hours and blown with nitrogen gas (incomplete carbonization). The WCR black powder is then mixed with concentrated sulphuric acid and heat in 160°C furnace 15 hours and continuous blown with nitrogen gas (sulphonation). This heterogeneous solid acid is used in the both transesterification and esterification to produce FAME. Moreover, in the optimal reaction conditions, this catalyst offers a stable catalytic effect. After 20 times usage in optimal reaction condition, the catalytic activity remains unchanged.

In-situ transesterification of seeds of invasive Chinese tallow trees (Triadica sebifera L.) in a microwave batch system (GREEN(3)) using hexane as co-solvent: Biodiesel production and process optimization.

PubMed

Barekati-Goudarzi, Mohamad; Boldor, Dorin; Nde, Divine B

2016-02-01

In-situ transesterification (simultaneous extraction and transesterification) of Chinese tallow tree seeds into methyl esters using a batch microwave system was investigated in this study. A high degree of oil extraction and efficient conversion of oil to biodiesel were found in the proposed range. The process was further optimized in terms of product yields and conversion rates using Doehlert optimization methodology. Based on the experimental results and statistical analysis, the optimal production yield conditions for this process were determined as: catalyst concentration of 1.74wt.%, solvent ratio about 3 (v/w), reaction time of 20min and temperature of 58.1°C. H(+)NMR was used to calculate reaction conversion. All methyl esters produced using this method met ASTM biodiesel quality specifications. Copyright © 2015 Elsevier Ltd. All rights reserved.

CaO Nanocatalyst for Transesterification Reaction of Palm Oil to Biodiesel: Effect of Precursor’s Concentration on the Catalyst Behavior

NASA Astrophysics Data System (ADS)

Hassan, N.; Ismail, K. N.; Hamid, K. H. Ku; Hadi, Abdul

2018-05-01

Depletion of fossil fuel sources in a few decades due to industrialization and motorization has led to a keen interest in the production of alternative fuels like biodiesel. Research on the development and improvement of more efficient transesterification process for biodiesel production has attain great attention in the last decade. The using of low cost catalyst is one of the main focuses on the biodiesel production. As a basic heterogeneous catalyst, CaO has been examined in the transesterification of vegetable oils for biodiesel production. In this research, calcium oxide (CaO-X) catalysts were prepared by sol-gel method at different Ca2+ precursor concentration (X = 1.0, 1.5, 2.0 M). The crystalline structure and morphology of the synthesized catalysts were characterized by means of x-ray diffraction (XRD) and N2 adsorption-desorption analysis. All the synthesized catalysts were then applied to transesterification reaction of palm oil to produce biodiesel. The characterization by x-ray diffraction demonstrate CaO-1.0 was partially hydrated due to the incomplete reaction during synthesis. As a matter of fact, formation of H2O on the surface of CaO causes lower basic strength of the catalysts, thus responsible in lowering the catalytic activity. It is demonstrated that CaO-2.0 exhibits mesoporous structure with least chemisorb amount of H2O on the catalysts surface has a very active catalytic activity. It was found that 2.0M of calcium precursor has high catalytic activity and 81% FAME yield was obtained within 3h reaction.

Erratum to "The mechanism and thermodynamics of transesterification of acetate-ester enolates in the gas phase" : [Int. J. Mass Spectrom. Ion Process. 172 (1998) 25

NASA Astrophysics Data System (ADS)

Haas, George W.; Giblin, Daryl E.; Gross, Michael L.

1998-02-01

In solution, base-catalyzed hydrolysis and transesterification of esters are initiated by hydroxide- or alkoxide-ion attack at the carbonyl carbon. At low pressures in the gas phase, however, transesterification proceeds by an attack of the enolate anion of an acetate ester on an alcohol. Fourier transform mass spectrometry (FTMS) indicates that the reaction is the second-order process: -CH2-CO2-R+R'-OH-->-CH2-CO2-R'+R-OH and there is little to no detectable production of either alkoxide anion. Labeling studies show that the product and reactant enolate anion esters undergo exchange of hydrogens located [alpha] to the carbonyl carbon with the deuterium of R'--OD. The extent of the H/D exchange increases with reaction time, pointing to a short-lived intermediate. The alcoholysis reaction rate constants increase with increasing acidity of the primary, straight-chained alkyl alcohols, whereas steric effects associated with branched alcohols cause the rate constants to decrease. Equilibrium constants, which were determined directly from measurements at equilibrium and which were calculated from the forward and reverse rate constants, are near unity and show internal consistency. In the absence of steric effects, the larger enolate is always the favored product at equilibrium. The intermediate for the transesterification reaction, which can be generated at a few tenths of a torr in a tandem mass spectrometer, is tetrahedral, but other adducts that are collisionally stabilized under these conditions are principally loosely bound complexes.

Preparation and characterizaton of CaO nanoparticle for biodiesel production

NASA Astrophysics Data System (ADS)

Gupta, Jharna; Agarwal, Madhu

2016-04-01

Nanoparticle of CaO from calcium Nitrate (CaO/CaN) and Snail shell (CaO/SS) are successfully synthesized by method as described in the literature and used as an active and stable catalyst for the biodiesel production. These catalysts are characterized by Fourier-transform infrared spectra (FT-IR), X-ray diffraction (XRD), and thermal gravimetric analysis (TGA). The average crystalline size in nanometer was also calculated by Debye-Scherrer equation. The performance of the CaO/CaN and CaO/SS were tested for their catalytic activity via transesterification process and it was found that biodiesel yield has been increased from 93 to 96%. The optimum conditions for the highest yield were 8wt% catalyst loading, 65°C temperature, 12:1 methanol/oil molar ratio, and 6 h for reaction time. The nano catalyst from snail shell exhibits excellent catalytic activity and stability for the transesterification reaction, which suggested that this catalyst would be potentially used as a solid base nano catalyst for biodiesel production. In order to examine the reusability of catalyst developed from snail shell, five transesterification reaction cycles were also performed.

Biodiesel synthesis by TiO2-ZnO mixed oxide nanocatalyst catalyzed palm oil transesterification process.

PubMed

Madhuvilakku, Rajesh; Piraman, Shakkthivel

2013-12-01

Biodiesel is a promising alternating environmentally benign fuel to mineral diesel. For the development of easier transesterification process, stable and active heterogeneous mixed metal oxide of TiO2-ZnO and ZnO nanocatalysts were synthesized and exploited for the palm oil transesterification process. The synthesized catalysts were characterized by XRD, FT-IR, and FE-SEM studies for their structural and morphological characteristics. It was found that TiO2-ZnO nanocatalyst exhibits good catalytic activity and the catalytic performance was greatly depends on (i) catalyst concentration (ii) methanol to oil molar ratio (iii) reaction temperature and (iv) reaction time. A highest 98% of conversion was obtained at the optimum reaction parameters with 200 mg of catalyst loading and the biodiesel was analyzed by TLC and (1)H NMR techniques. The TiO2-ZnO nanocatalyst shows good catalytic performance over the ZnO catalyst, which could be a potential candidate for the large-scale biodiesel production from palm oil at the reduced temperature and time. Copyright © 2013. Published by Elsevier Ltd.

Microwave Energy Increases Fatty Acid Methyl Ester Yield in Human Whole Blood Due to Increased Sphingomyelin Transesterification.

PubMed

Metherel, Adam H; Aristizabal Henao, Juan J; Ciobanu, Flaviu; Taha, Ameer Y; Stark, Ken D

2015-09-01

Dried blood spots (DBS) by fingertip prick collection for fatty acid profiling are becoming increasingly popular due to ease of collection, minimal invasiveness and its amenability to high-throughput analyses. Herein, we assess a microwave-assisted direct transesterification method for the production of fatty acid methyl esters (FAME) from DBS. Technical replicates of human whole blood were collected and 25-μL aliquots were applied to chromatography strips prior to analysis by a standard 3-h transesterification method or microwave-assisted direct transesterification method under various power (variable vs constant), time (1-5 min) and reagent (1-10% H2SO4 in methanol) conditions. In addition, a standard method was compared to a 5-min, 30-W power microwave in 1% H2SO4 method for FAME yield from whole blood sphingomyelin, and sphingomyelin standards alone and spiked in whole blood. Microwave-assisted direct transesterification yielded no significant differences in both quantitative (nmol/100 µL) and qualitative (mol%) fatty acid assessments after as little as 1.5- and 1-min reaction times, respectively, using the variable power method and 5% H2SO4 in methanol. However, 30-W power for 5 min increased total FAME yield of the technical replicates by 14%. This increase appears largely due to higher sphingomyelin-derived FAME yield of up to 109 and 399% compared to the standard method when determined from whole blood or pure standards, respectively. In conclusion, microwave-assisted direct transesterification of DBS achieved in as little as 1-min, and 5-min reaction times increase total fatty acids primarily by significantly improving sphingomyelin-derived fatty acid yield.

CaFeAl mixed oxide derived heterogeneous catalysts for transesterification of soybean oil to biodiesel.

PubMed

Lu, Yongsheng; Zhang, Zaiwu; Xu, Yunfeng; Liu, Qiang; Qian, Guangren

2015-08-01

CaAl layered double oxides (LDO) were prepared by co-precipitation and calcined at 750°C, and then applied to biodiesel production by transesterification reaction between methanol and soybean oil. Compared with characteristics of CaFe/LDO and CaAl/LDO, CaFeAl/LDO had the best performance based on prominent catalytic activity and stability, and achieved over 90% biodiesel yield, which stayed stable (over 85%) even after 8 cycles of reaction. The optimal catalytic reaction condition was 12:1M-ratio of methanol/oil, reaction temperatures of 60°C, 270rpm stirring rate, 60min reaction time, and 6% weight-ratio of catalyst/oil. In addition, the CaFeAl/LDO catalyst is insoluble in both methanol and methyl esters and can be easily separated for further reaction, turning it into an excellent alternative for biodiesel synthesis. Copyright © 2015 Elsevier Ltd. All rights reserved.

Cavitation assisted synthesis of fatty acid methyl esters from sustainable feedstock in presence of heterogeneous catalyst using two step process.

PubMed

Dubey, Sumit M; Gole, Vitthal L; Gogate, Parag R

2015-03-01

The present work reports the intensification aspects for the synthesis of fatty acid methyl esters (FAME) from a non-edible high acid value Nagchampa oil (31 mg of KOH/g of oil) using two stage acid esterification (catalyzed by H₂SO₄) followed by transesterification in the presence of heterogeneous catalyst (CaO). Intensification aspects of both stages have been investigated using sonochemical reactors and the obtained degree of intensification has been established by comparison with the conventional approach based on mechanical agitation. It has been observed that reaction temperature for esterification reduced from 65 to 40 °C for the ultrasonic approach whereas there was a significant reduction in the optimum reaction time for transesterification from 4h for the conventional approach to 2.5h for the ultrasound assisted approach. Also the reaction temperature reduced marginally from 65 to 60 °C and yield increased from 76% to 79% for the ultrasound assisted approach. Energy requirement and activation energy for both esterification and transesterification was lower for the ultrasound based approach as compared to the conventional approach. The present work has clearly established the intensification obtained due to the use of ultrasound and also illustrated the two step approach for the synthesis of FAME from high acid value feedstock based on the use of heterogeneous catalyst for the transesterification step. Copyright © 2014 Elsevier B.V. All rights reserved.

21 CFR 172.270 - Sulfated butyl oleate.

Code of Federal Regulations, 2011 CFR

2011-04-01

... transesterification of an edible vegetable oil using 1-butanol. Following sulfation, the reaction mixture is washed... oleate reaction mixture meets the following specifications: (1) Not less than 90 percent butyl oleate. (2...

Production of Omega-3 Fatty Acid Ethyl Esters from Menhaden Oil Using Proteus vulgaris Lipase-Mediated One-Step Transesterification and Urea Complexation.

PubMed

Kim, Soo-Jin; Kim, Hyung Kwoun

2016-05-01

An organic solvent-stable lipase from Proteus vulgaris K80 was used to produce the omega-3 polyunsaturated fatty acid ethyl esters (ω-3 PUFA EEs). First, the lyophilized recombinant lipase K80 (LyoK80) was used to perform the transesterification reaction of menhaden oil and ethanol. LyoK80 produced the ω-3 PUFA EEs with a conversion yield of 82 % in the presence of 20 % water content via a three-step ethanol-feeding process; however, in a non-aqueous condition, LyoK80 produced only a slight amount of the ω-3 PUFA EEs. To enhance its reaction properties, the lipase K80 was immobilized on a hydrophobic bead to derive ImmK80; the biochemical properties and substrate specificity of ImmK80 are similar to those of LyoK80. ImmK80 was then used to produce ω-3 PUFA EEs in accordance with the same transesterification reaction. Unlike LyoK80, ImmK80 achieved a high ω-3 PUFA EE conversion yield of 86 % under a non-aqueous system via a one-step ethanol-feeding reaction. The ω-3 PUFA EEs were purified up to 92 % using a urea complexation method.

Inverse problem analysis for identification of reaction kinetics constants in microreactors for biodiesel synthesis

NASA Astrophysics Data System (ADS)

Pontes, P. C.; Naveira-Cotta, C. P.

2016-09-01

The theoretical analysis for the design of microreactors in biodiesel production is a complicated task due to the complex liquid-liquid flow and mass transfer processes, and the transesterification reaction that takes place within these microsystems. Thus, computational simulation is an important tool that aids in understanding the physical-chemical phenomenon and, consequently, in determining the suitable conditions that maximize the conversion of triglycerides during the biodiesel synthesis. A diffusive-convective-reactive coupled nonlinear mathematical model, that governs the mass transfer process during the transesterification reaction in parallel plates microreactors, under isothermal conditions, is here described. A hybrid numerical-analytical solution via the Generalized Integral Transform Technique (GITT) for this partial differential system is developed and the eigenfunction expansions convergence rates are extensively analyzed and illustrated. The heuristic method of Particle Swarm Optimization (PSO) is applied in the inverse analysis of the proposed direct problem, to estimate the reaction kinetics constants, which is a critical step in the design of such microsystems. The results present a good agreement with the limited experimental data in the literature, but indicate that the GITT methodology combined with the PSO approach provide a reliable computational algorithm for direct-inverse analysis in such reactive mass transfer problems.

Effect of reaction temperature on biodiesel production from waste cooking oil using lipase as biocatalyst

NASA Astrophysics Data System (ADS)

Istiningrum, Reni Banowati; Aprianto, Toni; Pamungkas, Febria Lutfi Udin

2017-12-01

This study aims to determine the effect of temperature on conversion of biodiesel from waste cooking oil enzymatically using lipase extracted from rice bran. The feedstock was simulated waste cooking oil and lipase enzyme was extracted with buffer pH variation. The enzyme activity was titrimetrically determined and the optimum pH buffer was used to study the effect of temperature on the transesterification reaction. Temperature effects were assessed in the range of 45-60 °C and the content of methyl esters in biodiesel was determined by GC-MS. The reaction temperature significantly influences the transesterification reaction with optimum biodiesel conversion occurred at 55 °C with methyl ester content of 81.19%. The methyl ester composition in the resulting biodiesel is methyl palmitate, methyl oleate and methyl stearate.

Optimization of biodiesel production in a hydrodynamic cavitation reactor using used frying oil.

PubMed

Ghayal, Dyneshwar; Pandit, Aniruddha B; Rathod, Virendra K

2013-01-01

The present work demonstrates the application of a hydrodynamic cavitation reactor for the synthesis of biodiesel with used frying oil as a feedstock. The synthesis involved the transesterification of used frying oil (UFO) with methanol in the presence of potassium hydroxide as a catalyst. The effect of geometry and upstream pressure of a cavitating orifice plate on the rate of transesterification reaction has been studied. It is observed that the micro level turbulence created by hydrodynamic cavitation somewhat overcomes the mass transfer limitations for triphasic transesterification reaction. The significant effects of upstream pressure on the rate of formation of methyl esters have been seen. It has been observed that flow geometry of orifice plate plays a crucial role in process intensification. With an optimized plate geometry of 2mm hole diameter and 25 holes, more than 95% of triglycerides have been converted to methyl esters in 10 min of reaction time with cavitational yield of 1.28 × 10(-3) (Grams of methyl esters produced per Joule of energy supplied). The potential of UFO to produce good quality methyl esters has been demonstrated. Copyright © 2012 Elsevier B.V. All rights reserved.

Catalytic activity of calcium-based mixed metal oxides nanocatalysts in transesterification reaction of palm oil

NASA Astrophysics Data System (ADS)

Hassan, Noraakinah; Ismail, Kamariah Noor; Hamid, Ku Halim Ku; Hadi, Abdul

2017-12-01

Nowadays, biodiesel has become the forefront development as an alternative diesel fuel derived from biological sources such as oils of plant and fats. Presently, the conventional transesterification of vegetable oil to biodiesel gives rise to some technological problem. In this sense, heterogeneous nanocatalysts of calcium-based mixed metal oxides were synthesized through sol-gel method. It was found that significant increase of biodiesel yield, 91.75 % was obtained catalyzed by CaO-NbO2 from palm oil compared to pure CaO of 53.99 % under transesterification conditions (methanol/oil ratio 10:1, reaction time 3 h, catalyst concentration 4 wt%, reaction temperature 60 °C, and mixing speed of 600 rpm). The phase structure and crystallinity as well as the texture properties of the prepared catalysts were characterized by X-ray Diffraction (XRD) and the textural properties were characterized by N2 adsorption-desorption analysis. Sol-gel method has been known as versatile method in controlling the structural and chemical properties of the catalyst. Calcium-based mixed oxide synthesized from sol-gel method was found to exist as smaller crystallite size with high surface area.

Preparation and characterizaton of CaO nanoparticle for biodiesel production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gupta, Jharna, E-mail: onlinejharna@gmail.com; Agarwal, Madhu, E-mail: madhunaresh@gmail.com

Nanoparticle of CaO from calcium Nitrate (CaO/CaN) and Snail shell (CaO/SS) are successfully synthesized by method as described in the literature and used as an active and stable catalyst for the biodiesel production. These catalysts are characterized by Fourier-transform infrared spectra (FT-IR), X-ray diffraction (XRD), and thermal gravimetric analysis (TGA). The average crystalline size in nanometer was also calculated by Debye–Scherrer equation. The performance of the CaO/CaN and CaO/SS were tested for their catalytic activity via transesterification process and it was found that biodiesel yield has been increased from 93 to 96%. The optimum conditions for the highest yield weremore » 8wt% catalyst loading, 65°C temperature, 12:1 methanol/oil molar ratio, and 6 h for reaction time. The nano catalyst from snail shell exhibits excellent catalytic activity and stability for the transesterification reaction, which suggested that this catalyst would be potentially used as a solid base nano catalyst for biodiesel production. In order to examine the reusability of catalyst developed from snail shell, five transesterification reaction cycles were also performed.« less

In-line near-infrared (NIR) and Raman spectroscopy coupled with principal component analysis (PCA) for in situ evaluation of the transesterification reaction.

PubMed

Fontalvo-Gómez, Miriam; Colucci, José A; Velez, Natasha; Romañach, Rodolfo J

2013-10-01

Biodiesel was synthesized from different commercially available oils while in-line Raman and near-infrared (NIR) spectra were obtained simultaneously, and the spectral changes that occurred during the reaction were evaluated with principal component analysis (PCA). Raman and NIR spectra were acquired every 30 s with fiber optic probes inserted into the reaction vessel. The reaction was performed at 60-70 °C using magnetic stirring. The time of reaction was 90 min, and during this time, 180 Raman and NIR spectra were collected. NIR spectra were collected using a transflectance probe and an optical path length of 1 mm at 8 cm(-1) spectral resolution and averaging 32 scans; for Raman spectra a 3 s exposure time and three accumulations were adequate for the analysis. Raman spectroscopy showed the ester conversion as evidenced by the displacement of the C=O band from 1747 to 1744 cm(-1) and the decrease in the intensity of the 1000-1050 cm(-1) band and the 1405 cm(-1) band as methanol was consumed in the reaction. NIR spectra also showed the decrease in methanol concentration with the band in the 4750-5000 cm(-1) region; this signal is present in the spectra of the transesterification reaction but not in the neat oils. The variations in the intensity of the methanol band were a main factor in the in-line monitoring of the transesterification reaction using Raman and NIR spectroscopy. The score plot of the first principal component showed the progress of the reaction. The final product was analyzed using (1)H nuclear magnetic resonance ((1)H NMR) spectroscopy and using mid-infrared spectroscopy, confirming the conversion of the oils to biodiesel.

Heterogeneous base catalysts for edible palm and non-edible Jatropha-based biodiesel production

PubMed Central

2014-01-01

Background Transesterification catalyzed by solid base catalyst is a brilliant technology for the noble process featuring the fast reaction under mild reacting condition in biodiesel production. Heterogeneous base catalysts are generally more reactive than solid acid catalysts which require extreme operating condition for high conversion and biodiesel yield. In the present study, synthesis of biodiesel was studied by using edible (palm) or non-edible (Jatropha) feedstock catalyzed by heterogeneous base catalysts such as supported alkali metal (NaOH/Al2O3), alkaline-earth metal oxide (MgO, CaO and SrO) and mixed metal oxides catalysts (CaMgO and CaZnO). Results The chemical characteristic, textural properties, basicity profile and leaching test of synthesized catalysts were studied by using X-ray diffraction, BET measurement, TPD-CO2 and ICP-AES analysis, respectively. Transesterification activity of solid base catalysts showed that > 90% of palm biodiesel and > 80% of Jatropha biodiesel yield under 3 wt.% of catalyst, 3 h reaction time, methanol to oil ratio of 15:1 under 65°C. This indicated that other than physicochemical characteristic of catalysts; different types of natural oil greatly influence the catalytic reaction due to the presence of free fatty acids (FFAs). Conclusions Among the solid base catalysts, calcium based mixed metal oxides catalysts with binary metal system (CaMgO and CaZnO) showed capability to maintain the transesterification activity for 3 continuous runs at ~ 80% yield. These catalysts render high durability characteristic in transesterification with low active metal leaching for several cycles. PMID:24812574

Transesterification of oil mixtures catalyzed by microencapsulated cutinase in reversed micelles.

PubMed

Badenes, Sara M; Lemos, Francisco; Cabral, Joaquim M S

2010-03-01

Recombinant cutinase from Fusarium solani pisi was used to catalyze the transesterification reaction between a mixture of triglycerides (oils) and methanol in reversed micelles of bis(2-ethylhexyl) sodium sulfosuccinate (AOT) in isooctane for the purposes of producing biodiesel. The use of a bi-phase lipase-catalyzed system brings advantages in terms of catalyst re-use and the control of water activity in the medium and around the enzyme micro-environment. Small-scale batch studies were performed to study the influence of the initial enzyme and alcohol concentrations, and the substrates molar ratio. Conversions in excess of 75 were obtained with reaction times under 24 h, which makes this enzymatic process highly competitive when compared to similar lipase catalyzed reactions for biodiesel production using methanol.

Transesterification of Waste Frying Oil and Soybean Oil by Combi-lipases Under Ultrasound-Assisted Reactions.

PubMed

Poppe, Jakeline Kathiele; Matte, Carla Roberta; Fernandez-Lafuente, Roberto; Rodrigues, Rafael C; Ayub, Marco Antônio Záchia

2018-04-21

This work describes the use of an ultrasound system for the enzymatic transesterification of oils using combi-lipases as biocatalyst. The reactions were carried out evaluating the individual use of waste oil and fresh soybean oil, and the immobilized lipases CALB, TLL, and RML were used as biocatalysts. It was performed in a mixture design of three factors to obtain the ideal mixture of lipases according to the composition of fatty acids present in each oil, and the main reaction variables were optimized. After 18 h of reaction, ultrasound provided a biodiesel yield of about 90% when using soybean oil and 70% using the waste oil. The results showed that ultrasound technology, in combination with the application of enzyme mixtures, known as combi-lipases, and the use of waste oil, could be a promising route to reduce the overall process costs of enzymatic production of biodiesel.

Graphene oxide for acid catalyzed-reactions: Effect of drying process

NASA Astrophysics Data System (ADS)

Gong, H. P.; Hua, W. M.; Yue, Y. H.; Gao, Z.

2017-03-01

Graphene oxides (GOs) were prepared by Hummers method through various drying processes, and characterized by XRD, SEM, FTIR, XPS and N2 adsorption. Their acidities were measured using potentiometric titration and acid-base titration. The catalytic properties were investigated in the alkylation of anisole with benzyl alcohol and transesterification of triacetin with methanol. GOs are active catalysts for both reaction, whose activity is greatly affected by their drying processes. Vacuum drying GO exhibits the best performance in transesterification while freezing drying GO is most active for alkylation. The excellent catalytic behavior comes from abundant surface acid sites as well as proper surface functional groups, which can be obtained by selecting appropriate drying process.

Mechanistic analysis of cavitation assisted transesterification on biodiesel characteristics.

PubMed

Sajjadi, Baharak; Abdul Aziz, A R; Ibrahim, Shaliza

2015-01-01

The influence of sonoluminescence transesterification on biodiesel physicochemical properties was investigated and the results were compared to those of traditional mechanical stirring. This study was conducted to identify the mechanistic features of ultrasonication by coupling statistical analysis of the experiments into the simulation of cavitation bubble. Different combinations of operational variables were employed for alkali-catalysis transesterification of palm oil. The experimental results showed that transesterification with ultrasound irradiation could change the biodiesel density by about 0.3kg/m(3); the viscosity by 0.12mm(2)/s; the pour point by about 1-2°C and the flash point by 5°C compared to the traditional method. Furthermore, 93.84% of yield with alcohol to oil molar ratio of 6:1 could be achieved through ultrasound assisted transesterification within only 20min. However, only 89.09% of reaction yield was obtained by traditional macro mixing/heating under the same condition. Based on the simulated oscillation velocity value, the cavitation phenomenon significantly contributed to generation of fine micro emulsion and was able to overcome mass transfer restriction. It was found that the sonoluminescence bubbles reached the temperature of 758-713K, pressure of 235.5-159.55bar, oscillation velocity of 3.5-6.5cm/s, and equilibrium radius of 17.9-13.7 times greater than its initial size under the ambient temperature of 50-64°C at the moment of collapse. This showed that the sonoluminescence bubbles were in the condition in which the decomposition phenomena were activated and the reaction rate was accelerated together with a change in the biodiesel properties. Copyright © 2014 Elsevier B.V. All rights reserved.

Preparation of Biodiesel from Microalgae and Palm Oil by Direct Transesterification in a Batch Microwave Reactor

NASA Astrophysics Data System (ADS)

Marwan; Suhendrayatna; Indarti, E.

2015-06-01

The present work was aimed to study the so-called direct transesterification of microalgae lipids to biodiesel in a batch microwave reactor. As a comparison, preparation of palm oil to biodiesel by alkaline catalyzed ethanolysis was also carried out. Palm oil biodiesel was recovered close to an equilibrium conversion (94-96% yield) under microwave heating for at least 6 min, while the conventional method required more than 45 minutes reaching the same yield. A very short reaction time suggests the benefit of microwave effect over conventional heating method in making biodiesel. FTIR analysis revealed the presence of fatty acid ethyl esters with no undesired chemical groups or compounds formed due to local heat generated by microwave effect, thus the conversion only followed transesterification route. Oil containing microalgae of Chlorella sp. isolated from the local brackish water pond was used as a potential source of biodiesel. High yield of biodiesel (above 0.6 g/g of dried algae) was also attainable for the direct transesterification of microalgae in the microwave reactor. Effect of water content of the algae biomass became insignificant at 11.9%(w/w) or less, related to the algae biomass dried for longer than 6 h. Fast transesterification of the algal oil towards equilibrium conversion was obtained at reaction time of 6 min, and at longer times the biodiesel yield remains unchanged. FAME profile indicates unsaturated fatty acids as major constituents. It was shown that microwave irradiation contributes not only to enhance the transeseterification, but also to assist effective release of fatty acid containing molecules (e.g. triacylglycerol, free fatty acids and phospholipids) from algal cells.

Evaluating the effectiveness of various biochars as porous media for biodiesel synthesis via pseudo-catalytic transesterification.

PubMed

Lee, Jechan; Jung, Jong-Min; Oh, Jeong-Ik; Ok, Yong Sik; Lee, Sang-Ryong; Kwon, Eilhann E

2017-05-01

This study focuses on investigating the optimized chemical composition of biochar used as porous material for biodiesel synthesis via pseudo-catalytic transesterification. To this end, six biochars from different sources were prepared and biodiesel yield obtained from pseudo-catalytic transesterification of waste cooking oil using six biochars were measured. Biodiesel yield and optimal reaction temperature for pseudo-catalytic transesterification were strongly dependent on the raw material of biochar. For example, biochar generated from maize residue exhibited the best performance, which yield was reached ∼90% at 300°C; however, the maximum biodiesel yield with pine cone biochar was 43% at 380°C. The maximum achievable yield of biodiesel was sensitive to the lignin content of biomass source of biochar but not sensitive to the cellulose and hemicellulose content. This study provides an insight for screening the most effective biochar as pseudo-catalytic porous material, thereby helping develop more sustainable and economically viable biodiesel synthesis process. Copyright © 2017 Elsevier Ltd. All rights reserved.

Biodiesel production from wet municipal sludge: evaluation of in situ transesterification using xylene as a cosolvent.

PubMed

Choi, O K; Song, J S; Cha, D K; Lee, J W

2014-08-01

This study proposes a method to produce biodiesel from wet wastewater sludge. Xylene was used as an alternative cosolvent to hexane for transesterification in order to enhance the biodiesel yield from wet wastewater sludge. The water present in the sludge could be separated during transesterification by employing xylene, which has a higher boiling point than water. Xylene enhanced the biodiesel yield up to 8.12%, which was 2.5 times higher than hexane. It was comparable to the maximum biodiesel yield of 9.68% obtained from dried sludge. Xylene could reduce either the reaction time or methanol consumption, when compared to hexane for a similar yield. The fatty acid methyl esters (FAMEs) content of the biodiesel increased approximately two fold by changing the cosolvent from hexane to xylene. The transesterification method using xylene as a cosolvent can be applied effectively and economically for biodiesel recovery from wet wastewater sludge without drying process. Copyright © 2014 Elsevier Ltd. All rights reserved.

Technical difficulties and solutions of direct transesterification process of microbial oil for biodiesel synthesis.

PubMed

Yousuf, Abu; Khan, Maksudur Rahman; Islam, M Amirul; Wahid, Zularisam Ab; Pirozzi, Domenico

2017-01-01

Microbial oils are considered as alternative to vegetable oils or animal fats as biodiesel feedstock. Microalgae and oleaginous yeast are the main candidates of microbial oil producers' community. However, biodiesel synthesis from these sources is associated with high cost and process complexity. The traditional transesterification method includes several steps such as biomass drying, cell disruption, oil extraction and solvent recovery. Therefore, direct transesterification or in situ transesterification, which combines all the steps in a single reactor, has been suggested to make the process cost effective. Nevertheless, the process is not applicable for large-scale biodiesel production having some difficulties such as high water content of biomass that makes the reaction rate slower and hurdles of cell disruption makes the efficiency of oil extraction lower. Additionally, it requires high heating energy in the solvent extraction and recovery stage. To resolve these difficulties, this review suggests the application of antimicrobial peptides and high electric fields to foster the microbial cell wall disruption.

[Column chromatography purification and analysis of biodiesel by transesterification].

PubMed

Liu, Yang; Yi, Huai-feng; Chen, Yu; Wu, Yu-long; Yang, Ming-de; Chen, Zeng; Tong, Jun-mao

2012-02-01

In the present paper, crude biodiesel prepared with sorbifolia oil as raw material by transesterification was purified by column chromatography, then the composition of biodiesel was analyzed by gas chromatography, FTIR, GC-MS and 1H NMR. Column chromatography can separate the crude biodiesel into two fractions: petroleum ether eluted fraction (A1) and methanol eluted fraction (A2). Petroleum ether eluted fraction was mainly biodiesel fraction, which was produced from sorbifolia oil by transesterification, including methyl linoleate, methyl cis-9-octadecenoate and so on; methanol eluted fraction was mainly glycerol fraction, which came from the side reaction of transesterification. The results show that the purity of refined biodiesel increased from 77.51% to 93.872, and the product recovery rate reached up to 91.04% after the purification by column chromatography. The results obtained by FTIR and 1H NMR further showed that the column chromatography can effectively improve the purity of biodiesel. This paper provides a basis for industrialization of purification of biodiesel.

Optimization of sodium loading on zeolite support for catalyzed transesterification of triolein with methanol.

PubMed

Wang, Yu-Yuan; Chou, Hsin-Yu; Chen, Bing-Hung; Lee, Duu-Jong

2013-10-01

Optimization of sodium loading on zeolite HY for catalyzed transesterification of triolein in excess methanol to biodiesel was studied. Zeolite HY catalyst was activated by loading sodium ions to their surface via an ion-exchange method. The effects of ion-exchange process parameters, including the temperature, the process time, the pH value, as well as concentrations and sources of Na(+) cations (NaOH, NaCl and Na2SO4), on the conversion yield of triolein to biodiesel were investigated. Most of these Na(+)-activated zeolite HY catalysts could really facilitate the catalyzed transesterification reaction of triolein to biodiesel at a lower temperature near 65°C. Consequently, a high conversion yield of triglycerides to biodiesel at 97.3% was obtained at 65°C. Moreover, the durability of zeolite catalysts was examined as well. Catalytic performance tests of these zeolite catalysts in transesterification did not show a significant decrease in catalysis at least for three batch cycles. Copyright © 2013 Elsevier Ltd. All rights reserved.

Ultrasound assisted transesterification of waste cooking oil using heterogeneous solid catalyst.

PubMed

Pukale, Dipak D; Maddikeri, Ganesh L; Gogate, Parag R; Pandit, Aniruddha B; Pratap, Amit P

2015-01-01

Transesterification based biodiesel production from waste cooking oil in the presence of heterogeneous solid catalyst has been investigated in the present work. The effect of different operating parameters such as type of catalyst, catalyst concentration, oil to methanol molar ratio and the reaction temperature on the progress of the reaction was studied. Some studies related to catalyst reusability have also been performed. The important physicochemical properties of the synthesized biodiesel have also been investigated. The results showed that tri-potassium phosphate exhibits high catalytic activity for the transesterification of waste cooking oil. Under the optimal conditions, viz. catalyst concentration of 3wt% K3PO4, oil to methanol molar ratio of 1:6 and temperature of 50°C, 92.0% of biodiesel yield was obtained in 90min of reaction time. Higher yield was obtained in the presence of ultrasound as compared to conventional approach under otherwise similar conditions, which can be attributed to the cavitational effects. Kinetic studies have been carried out to determine the rate constant at different operating temperatures. It was observed that the kinetic rate constant increased with an increase in the temperature and the activation energy was found to be 64.241kJ/mol. Copyright © 2014 Elsevier B.V. All rights reserved.

Dimethyl carbonate-mediated lipid extraction and lipase-catalyzed in situ transesterification for simultaneous preparation of fatty acid methyl esters and glycerol carbonate from Chlorella sp. KR-1 biomass.

PubMed

Jo, Yoon Ju; Lee, Ok Kyung; Lee, Eun Yeol

2014-04-01

Fatty acid methyl esters (FAMEs) and glycerol carbonate were simultaneously prepared from Chlorella sp. KR-1 containing 40.9% (w/w) lipid using a reactive extraction method with dimethyl carbonate (DMC). DMC was used as lipid extraction agent, acyl acceptor for transesterification of the extracted triglycerides, substrate for glycerol carbonate synthesis from glycerol, and reaction medium for the solvent-free reaction system. For 1g of biomass, 367.31 mg of FAMEs and 16.73 mg of glycerol carbonate were obtained under the optimized conditions: DMC to biomass ratio of 10:1 (v/w), water content of 0.5% (v/v), and Novozyme 435 to biomass ratio of 20% (w/w) at 70°C for 24h. The amount of residual glycerol was only in the range of 1-2.5mg. Compared to conventional method, the cost of FAME production with the proposed technique could be reduced by combining lipid extraction with transesterification and omitting the extraction solvent recovery process. Copyright © 2014 Elsevier Ltd. All rights reserved.

Enzymatic production of biodiesel from microalgal oil using ethyl acetate as an acyl acceptor.

PubMed

Alavijeh, Razieh Shafiee; Tabandeh, Fatemeh; Tavakoli, Omid; Karkhane, Aliasghar; Shariati, Parvin

2015-01-01

Microalgae have become an important source of biomass for biodiesel production. In enzymatic transesterification reaction, the enzyme activity is decreased in presence of alcohols. The use of different acyl acceptors such as methyl/ethyl acetate is suggested as an alternative and effective way to overcome this problem. In this study, ethyl acetate was used for the first time in the enzymatic production of biodiesel by using microalga, Chlorella vulgaris, as a triglyceride source. Enzymatic conversion of such fatty acids to biodiesel was catalyzed by Novozym 435 as an efficient immobilized lipase which is extensively used in biodiesel production. The best conversion yield of 66.71% was obtained at the ethyl acetate to oil molar ratio of 13:1 and Novozym 435 concentration of 40%, based on the amount of oil, and a time period of 72 h at 40℃. The results showed that ethyl acetate have no adverse effect on lipase activity and the biodiesel amount was not decreased even after seven transesterification cycles, so ethyl acetate has a great potential to be substituted for short-chain alcohols in transesterification reaction.

Ultrasound-enhanced rapid in situ transesterification of marine macroalgae Enteromorpha compressa for biodiesel production.

PubMed

Suganya, Tamilarasan; Kasirajan, Ramachandran; Renganathan, Sahadevan

2014-03-01

In situ transesterification of Enteromorpha compressa algal biomass was carried out for the production of biodiesel. The maximum methyl esters (ME) yield of 98.89% was obtained using ultrasonic irradiation. Tetra hydro furan (THF) and acid catalyst (H2SO4) was found to be an appropriate co-solvent and catalyst for high free fatty acids (FFA) content E. compressa biomass to increase the efficiency of the reactive in situ process. The optimization study was conducted to obtain the maximum yield and it was determined as 30vol% of THF as a co-solvent, 10wt% of H2SO4, 5.5:1 ratio of methanol to algal biomass and 600rpm of mixing intensity at 65°C for 90min of ultrasonic irradiation time. The produced biodiesel was characterized by (1)H nuclear magnetic resonance spectroscopy ((1)H NMR) analysis. Kinetic studies revealed that the reaction followed the first-order reaction mechanism. Rapid in situ transesterification was found to be suitable technique to produce biodiesel from marine macroalgae feedstock. Copyright © 2014 Elsevier Ltd. All rights reserved.

Beauveria bassiana Lipase A expressed in Komagataella (Pichia) pastoris with potential for biodiesel catalysis.

PubMed

Vici, Ana C; da Cruz, Andrezza F; Facchini, Fernanda D A; de Carvalho, Caio C; Pereira, Marita G; Fonseca-Maldonado, Raquel; Ward, Richard J; Pessela, Benevides C; Fernandez-Lorente, Gloria; Torres, Fernando A G; Jorge, João A; Polizeli, Maria L T M

2015-01-01

Lipases (EC 3.1.1.3) comprise a biotechnologically important group of enzymes because they are able to catalyze both hydrolysis and synthesis reactions, depending on the amount of water in the system. One of the most interesting applications of lipase is in the biofuel industry for biodiesel production by oil and ethanol (or methanol) transesterification. Entomopathogenic fungi, which are potential source of lipases, are still poorly explored in biotechnological processes. The present work reports the heterologous expression and biochemical characterization of a novel Beauveria bassiana lipase with potential for biodiesel production. The His-tagged B. bassiana lipase A (BbLA) was produced in Komagataella pastoris in buffered methanol medium (BMM) induced with 1% methanol at 30°C. Purified BbLA was activated with 0.05% Triton X-100 and presented optimum activity at pH 6.0 and 50°C. N-glycosylation of the recombinant BbLA accounts for 31.5% of its molecular weight. Circular dichroism and molecular modeling confirmed a structure composed of α-helix and β-sheet, similar to α/β hydrolases. Immobilized BbLA was able to promote transesterification reactions in fish oil, demonstrating potential for biodiesel production. BbLA was successfully produced in K. pastoris and shows potential use for biodiesel production by the ethanolysis reaction.

Beauveria bassiana Lipase A expressed in Komagataella (Pichia) pastoris with potential for biodiesel catalysis

PubMed Central

Vici, Ana C.; da Cruz, Andrezza F.; Facchini, Fernanda D. A.; de Carvalho, Caio C.; Pereira, Marita G.; Fonseca-Maldonado, Raquel; Ward, Richard J.; Pessela, Benevides C.; Fernandez-Lorente, Gloria; Torres, Fernando A. G.; Jorge, João A.; Polizeli, Maria L. T. M.

2015-01-01

Lipases (EC 3.1.1.3) comprise a biotechnologically important group of enzymes because they are able to catalyze both hydrolysis and synthesis reactions, depending on the amount of water in the system. One of the most interesting applications of lipase is in the biofuel industry for biodiesel production by oil and ethanol (or methanol) transesterification. Entomopathogenic fungi, which are potential source of lipases, are still poorly explored in biotechnological processes. The present work reports the heterologous expression and biochemical characterization of a novel Beauveria bassiana lipase with potential for biodiesel production. The His-tagged B. bassiana lipase A (BbLA) was produced in Komagataella pastoris in buffered methanol medium (BMM) induced with 1% methanol at 30°C. Purified BbLA was activated with 0.05% Triton X-100 and presented optimum activity at pH 6.0 and 50°C. N-glycosylation of the recombinant BbLA accounts for 31.5% of its molecular weight. Circular dichroism and molecular modeling confirmed a structure composed of α-helix and β-sheet, similar to α/β hydrolases. Immobilized BbLA was able to promote transesterification reactions in fish oil, demonstrating potential for biodiesel production. BbLA was successfully produced in K. pastoris and shows potential use for biodiesel production by the ethanolysis reaction. PMID:26500628

Butanolysis: Comparison of potassium hydroxide and potassium tert-butoxide as catalyst for biodiesel preparing from rapeseed oil.

PubMed

Musil, Martin; Skopal, Frantisek; Hájek, Martin; Vavra, Ales

2018-07-15

Biodiesel is a mixture of esters of fatty acids (most often palmitic, stearic and oleic) and lower alcohols (in our work butanol) produced by transesterification. It is a renewable source of energy, prepared from triacylglycerides, which are contained in vegetable oils and animal fats. This work focuses on alkaline catalyzed transesterification of rapeseed oil with butanol and comparison of two catalysts (potassium hydroxide and potassium tert-butoxide). In industry is usually transesterification of rapeseed oil carried out like reaction catalyzed by potassium hydroxide. Potassium hydroxide have high content of K 2 CO 3 , KHCO 3 and water. Moreover water is formed by neutralization of potassium hydroxide with free fatty acids contained in oil. In cause of tert-butoxide catalyzed reaction, it is not possible because tert-butoxide have not a OH - aniont, which is needed for water forming. The influence of various conditions (addition of water, temperature of separation, intensity of stirring and type of catalyst) on butanolysis process was studied for both catalysts. For both catalysts dependence of conversions on time were plotted. When tert-butoxide was used, satisfactory phase separation was not achieved. The only way was separation of hot crude reaction mixture without adding water. Ester formed by this method had high content of free glycerol and soaps, but reached higher conversion. The best results were obtained with KOH and subsequent separation of cold crude reaction mixture with the addition of water and slow stirring. The difference between reactions catalyzed by potassium hydroxide and potassium tert-butoxide was described. Copyright © 2018 Elsevier Ltd. All rights reserved.

Biodiesel production with special emphasis on lipase-catalyzed transesterification.

PubMed

Bisen, Prakash S; Sanodiya, Bhagwan S; Thakur, Gulab S; Baghel, Rakesh K; Prasad, G B K S

2010-08-01

The production of biodiesel by transesterification employing acid or base catalyst has been industrially accepted for its high conversion and reaction rates. Downstream processing costs and environmental problems associated with biodiesel production and byproducts recovery have led to the search for alternative production methods. Recently, enzymatic transesterification involving lipases has attracted attention for biodiesel production as it produces high purity product and enables easy separation from the byproduct, glycerol. The use of immobilized lipases and immobilized whole cells may lower the overall cost, while presenting less downstream processing problems, to biodiesel production. The present review gives an overview on biodiesel production technology and analyzes the factors/methods of enzymatic approach reported in the literature and also suggests suitable method on the basis of evidence for industrial production of biodiesel.

Transesterification reaction for synthesis of palm-based ethylhexyl ester and formulation as base oil for synthetic drilling fluid.

PubMed

Abdul Habib, Nor Saiful Hafiz; Yunus, Robiah; Rashid, Umer; Taufiq-Yap, Yun H; Abidin, Zurina Zainal; Syam, Azhari Muhammad; Irawan, Sonny

2014-01-01

The use of vegetable oil-based ester as a base fluid in synthetic drilling fluid has become a trend in drilling operations due to its environmental advantages. The transesterification reaction of palm oil methyl ester (POME) with 2-ethylhexanol (2EH) produced 98% of palm oil-based ethylhexyl ester in less than 30 minutes. Since the transesterification reaction of POME with 2EH is a reversible reaction, its kinetics was studied in the presence of excess EH and under vacuum. The POME-to-EH molar ratio and vacuum pressure were held constant at 1:2 and 1.5 mbar respectively and the effects of temperature (70 to 110°C) were investigated. Using excess of EH and continual withdrawal of methanol via vacuum promoted the reaction to complete in less than 10 minutes. The rate constant of the reaction (k) obtained from the kinetics study was in the range of 0.44 to 0.66 s⁻¹ and the activation energy was 15.6 kJ.mol⁻¹. The preliminary investigations on the lubrication properties of drilling mud formulated with palm oil-based 2EH ester indicated that the base oil has a great potential to substitute the synthetic ester-based oil for drilling fluid. Its high kinematic viscosity provides better lubrication to the drilling fluid compared to other ester-based oils. The pour point (-15°C) and flash point (204°C) values are superior for the drilling fluid formulation. The plastic viscosity, HPHT filtrate loss and emulsion stability of the drilling fluid had given acceptable values, while gel strength and yield point could be improved by blending it with proper additives.

Candida rugosa lipase LIP1-catalyzed transesterification to produce human milk fat substitute.

PubMed

Srivastava, Anita; Akoh, Casimir C; Chang, Shu-Wei; Lee, Guan-Chiun; Shaw, Jei-Fu

2006-07-12

Structured lipids (SLs) containing palmitic and oleic acids were synthesized by transesterification of tripalmitin with either oleic acid or methyl oleate as acyl donor. This SL with palmitic acid at the sn-2 position and oleic acid at sn-1,3 positions is similar in structure to human milk fat triacylglycerol. LIP1, an isoform of Candida rugosa lipase (CRL), was used as biocatalyst. The effects of reaction temperature, substrate molar ratio, and time on incorporation of oleic acid were investigated. Reaction time and temperature were set at 6, 12, and 24 h, and 35, 45, and 55 degrees C, respectively. Substrate molar ratio was varied from 1:1 to 1:4. The highest incorporation of oleic acid (37.7%) was at 45 degrees C with methyl oleate as acyl donor. Oleic acid resulted in slightly lesser (26.3%) incorporation. Generally, higher percentage incorporation of oleic acid was observed with methyl oleate (transesterification) than with oleic acid (acidolysis). In both cases percentage incorporation increased with reaction time. Incorporation decreased with increase in temperature above 45 degrees C. Initially, oleic acid incorporation increased with increase in substrate molar ratio up to 1:3. LIP1 was also compared with Lipozyme RM IM as biocatalysts. The tested reaction parameters were selected on the basis of maximum incorporation of C18:1 obtained during optimization of LIP1 reaction conditions. Reaction temperature was maintained at 45, 55, and 65 degrees C. Lipozyme RM IM gave highest oleic acid incorporation (49.4%) at 65 degrees C with methyl oleate as acyl donor. Statistically significant (P < 0.05) differences were observed for both enzymes. SL prepared using Lipozyme RM IM may be more suitable for possible use in human milk fat substitutes.

Novel 1H low field nuclear magnetic resonance applications for the field of biodiesel

PubMed Central

2013-01-01

Background Biodiesel production has increased dramatically over the last decade, raising the need for new rapid and non-destructive analytical tools and technologies. 1H Low Field Nuclear Magnetic Resonance (LF-NMR) applications, which offer great potential to the field of biodiesel, have been developed by the Phyto Lipid Biotechnology Lab research team in the last few years. Results Supervised and un-supervised chemometric tools are suggested for screening new alternative biodiesel feedstocks according to oil content and viscosity. The tools allowed assignment into viscosity groups of biodiesel-petrodiesel samples whose viscosity is unknown, and uncovered biodiesel samples that have residues of unreacted acylglycerol and/or methanol, and poorly separated and cleaned glycerol and water. In the case of composite materials, relaxation time distribution, and cross-correlation methods were successfully applied to differentiate components. Continuous distributed methods were also applied to calculate the yield of the transesterification reaction, and thus monitor the progress of the common and in-situ transesterification reactions, offering a tool for optimization of reaction parameters. Conclusions Comprehensive applied tools are detailed for the characterization of new alternative biodiesel resources in their whole conformation, monitoring of the biodiesel transesterification reaction, and quality evaluation of the final product, using a non-invasive and non-destructive technology that is new to the biodiesel research area. A new integrated computational-experimental approach for analysis of 1H LF-NMR relaxometry data is also presented, suggesting improved solution stability and peak resolution. PMID:23590829

Calcium Oxide Derived from Waste Shells of Mussel, Cockle, and Scallop as the Heterogeneous Catalyst for Biodiesel Production

PubMed Central

Chaiyut, Nattawut; Worawanitchaphong, Phatsakon

2013-01-01

The waste shell was utilized as a bioresource of calcium oxide (CaO) in catalyzing a transesterification to produce biodiesel (methyl ester). The economic and environmen-friendly catalysts were prepared by a calcination method at 700–1,000°C for 4 h. The heterogeneous catalysts were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM), and the Brunauer-Emmett-Teller (BET) method. The effects of reaction variables such as reaction time, reaction temperature, methanol/oil molar ratio, and catalyst loading on the yield of biodiesel were investigated. Reusability of waste shell catalyst was also examined. The results indicated that the CaO catalysts derived from waste shell showed good reusability and had high potential to be used as biodiesel production catalysts in transesterification of palm oil with methanol. PMID:24453854

Biosynthesis of glycerol carbonate from glycerol by lipase in dimethyl carbonate as the solvent.

PubMed

Lee, Kyung Hwa; Park, Chang-Ho; Lee, Eun Yeol

2010-11-01

Glycerol carbonate was synthesized from renewable glycerol and dimethyl carbonate using lipase in solvent-free reaction system in which excess dimethyl carbonate played as the reaction medium. A variety of lipases have been tested for their abilities to catalyze transesterification reaction, and Candida antartica lipase B and Novozyme 435 exhibited higher catalytic activities. The silica-coated glycerol with a 1:1 ratio was supplied to prevent two-phase formation between hydrophobic dimethyl carbonate and hydrophilic glycerol. Glycerol carbonate was successfully synthesized with more than 90% conversion from dimethyl carbonate and glycerol with a molar ratio of 10 using Novozyme 435-catalyzed transesterification at 70 °C. The Novozyme 435 [5% (w/w) and 20% (w/w)] and silica gel were more than four times recycled with good stability in a repeated batch operation for the solvent-free synthesis of glycerol carbonate.

A green recyclable SO(3)H-carbon catalyst derived from glycerol for the production of biodiesel from FFA-containing karanja (Pongamia glabra) oil in a single step.

PubMed

Prabhavathi Devi, B L A; Vijai Kumar Reddy, T; Vijaya Lakshmi, K; Prasad, R B N

2014-02-01

Simultaneous esterification and transesterification method is employed for the preparation of biodiesel from 7.5% free fatty acid (FFA) containing karanja (Pongamia glabra) oil using water resistant and reusable carbon-based solid acid catalyst derived from glycerol in a single step. The optimum reaction parameters for obtaining biodiesel in >99% yield by simultaneous esterification and transesterification are: methanol (1:45 mole ratio of oil), catalyst 20wt.% of oil, temperature 160°C and reaction time of 4h. After the reaction, the catalyst was easily recovered by filtration and reused for five times with out any deactivation under optimized conditions. This single-step process could be a potential route for biodiesel production from high FFA containing oils by simplifying the procedure and reducing costs and effluent generation. Copyright © 2013 Elsevier Ltd. All rights reserved.

Biodiesel synthesis using calcined layered double hydroxide catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schumaker, J. Link; Crofcheck, Czarena; TAckett, S. Adam

2008-01-01

The catalytic properties of calcined Li-Al, Mg-Al and Mg-Fe layered double hydroxides (LDHs) were examined in two transesterification reactions, namely, the reaction of glyceryl tributyrate with methanol, and the reaction of soybean oil with methanol. While the Li-Al catalysts showed high activity in these reactions at the reflux temperature of methanol, the Mg-Fe and Mg-Al catalysts exhibited much lower methyl ester yields. CO2 TPD measurements revealed the presence of sites of weak, medium and strong basicity on both Mg-Al and Li-Al catalysts, the latter showing higher concentrations of medium and strong base sites; by implication, these are the main sitesmore » active in transesterification catalyzed by calcined Li-Al LDHs. Maximum activity was observed for the Li-Al catalysts when a calcination temperature of 450-500 aC was applied, corresponding to decomposition of the layered double hydroxide to the mixed oxide without formation of crystalline lithium aluminate phases.« less

Production and Characterization of Ethyl Ester from Crude Jatropha curcas Oil having High Free Fatty Acid Content

NASA Astrophysics Data System (ADS)

Kumar, Rajneesh; Dixit, Anoop; Singh, Shashi Kumar; Singh, Gursahib; Sachdeva, Monica

2015-09-01

The two step process was carried out to produce biodiesel from crude Jatropha curcas oil. The pretreatment process was carried out to reduce the free fatty acid content by (≤2 %) acid catalyzed esterification. The optimum reaction conditions for esterification were reported to be 5 % H2SO4, 20 % ethanol and 1 h reaction time at temperature of 65 °C. The pretreatment process reduced the free fatty acid of oil from 7 to 1.85 %. In second process, alkali catalysed transesterification of pretreated oil was carried and the effects of the varying concentrations of KOH and ethanol: oil ratios on percent ester recovery were investigated. The optimum reaction conditions for transesterification were reported to be 3 % KOH (w/v of oil) and 30 % (v/v) ethanol: oil ratio and reaction time 2 h at 65 °C. The maximum percent recovery of ethyl ester was reported to be 60.33 %.

Synthesis of CaO-CeO2 catalysts by soft template method for biodiesel production

NASA Astrophysics Data System (ADS)

Zheng, Y. C.; Yu, X. H.; Yang, J.

2017-06-01

Biodiesel has recently gained extensive attention. Catalysts play an important role in producing biodiesel by transesterification reaction. In this study, CaO-CeO2 catalysts are developed as the solid base catalyst. Using PDMS-PEO as a structure-directing agent, the prepared CaO-CeO2 catalysts have a three-dimensional interconnected porous structure, which benefits the transesterification reaction. While the added Ce slightly decreases the catalytic activity, the stability of the catalyst shows remarkable improvement. Considering the catalytic activity and stability, the best catalyst is determined to be catalyst 0.15-1073 (Ce/Ca molar ratio of 0.15 and calcination temperature of 1073 K). Under optimum reaction conditions, the biodiesel yield reaches to 97.5% and metal leaching is 117.7 ppm. For catalyst 0.15-1073 regenerated after four reaction cycles, the biodiesel yield is 94.1%. The results reveal that the CaO-CeO2 catalyst has good potential for application in large-scale biodiesel production in the future.

Influence of the reaction conditions on the enzyme catalyzed transesterification of castor oil: A possible step in biodiesel production.

PubMed

Andrade, Thalles A; Errico, Massimiliano; Christensen, Knud V

2017-11-01

The identification of the influence of the reaction parameters is of paramount importance when defining a process design. In this work, non-edible castor oil was reacted with methanol to produce a possible component for biodiesel blends, using liquid enzymes as the catalyst. Temperature, alcohol-to-oil molar ratio, enzyme and added water contents were the reaction parameters evaluated in the transesterification reactions. The optimal conditions, giving the optimal final FAME yield and FFA content in the methyl ester-phase was identified. At 35°C, 6.0 methanol-to-oil molar ratio, 5wt% of enzyme and 5wt% of water contents, 94% of FAME yield and 6.1% of FFA in the final composition were obtained. The investigation was completed with the analysis of the component profiles, showing that at least 8h are necessary to reach a satisfactory FAME yield together with a minor FFA content. Copyright © 2017 Elsevier Ltd. All rights reserved.

Behaviors of rice straw two-step liquefaction with sub/supercritical ethanol in carbon dioxide atmosphere.

PubMed

Yang, Tianhua; Wang, Jian; Li, Bingshuo; Kai, Xingping; Xing, Wanli; Li, Rundong

2018-06-01

This study extended previous work investigating two-step liquefaction by supercritical ethanol of rice straw under CO 2 atmosphere at temperatures of 270-345 °C. Subcritical CO 2 -subcritical ethanol (SubCO 2 -SubEtOH) pretreatment decreased the content of lignin in the rice stalk from 22.94 to 21.43 wt%. The results showed that although oxygen-transfer reaction, transesterification, carbonylation, and other reactions may occur with the supercritical CO 2 -supercritical ethanol (ScCO 2 -ScEtOH) liquefaction reactions, transesterification was the main reaction. The "de-oxygen-transfer" reaction mainly comprised de-oxygenation and decarboxylation. For temperatures exceeding 320 °C, the bio-oil yield decreased because the effects of esters decreased. The residence time affected the H/C and O/C ratios to a minor extent. It was shown that the nucleophilic and hydrolytic functions of ethanol might be strengthened, generating higher amounts of ester, phenolic, acidic, and hydrocarbon derivatives in the bio-oil fraction. Copyright © 2018 Elsevier Ltd. All rights reserved.

Characterization of calcium oxide catalysts from natural sources and their application in the transesterification of sunflower oil.

PubMed

Correia, Leandro Marques; Saboya, Rosana Maria Alves; Campelo, Natália de Sousa; Cecilia, Juan Antonio; Rodríguez-Castellón, Enrique; Cavalcante, Célio Loureiro; Vieira, Rodrigo Silveira

2014-01-01

The catalytic activities of calcium oxide obtained from natural sources (crab shell and eggshell) were characterized and evaluated in the transesterification of vegetable oil. These catalysts are mainly composed of calcium carbonate, which is partially converted into CaO after calcination (900°C for 2h). The catalysts have some advantages, such as abundant occurrence, low cost, porous structure, and nontoxic. The materials were characterized by XRD, FTIR, TG/DTG, CO2-TPD, XPS, SEM, and BET methods. The thermal treatment produces small particles of CaCO3 and CaO that are responsible for the catalytic activity. The conversion from triglycerides to methyl ester was not observed in transesterification carried out using natural crab shell and eggshell. Under optimized reaction conditions, the conversions to YFAME using the calcined catalysts were: crab shell (83.10±0.27 wt.%) and eggshell (97.75±0.02 wt.%). These results, showed that these materials have promising viability in transesterification for biodiesel production. Copyright © 2013 Elsevier Ltd. All rights reserved.

Enhancement of biodiesel production from marine alga, Scenedesmus sp. through in situ transesterification process associated with acidic catalyst.

PubMed

Kim, Ga Vin; Choi, Woonyong; Kang, Dohyung; Lee, Shinyoung; Lee, Hyeonyong

2014-01-01

The aim of this study was to increase the yield of biodiesel produced by Scenedesmus sp. through in situ transesterification by optimizing various process parameters. Based on the orthogonal matrix analysis for the acidic catalyst, the effects of the factors decreased in the order of reaction temperature (47.5%) > solvent quantity (26.7%) > reaction time (17.5%) > catalyst amount (8.3%). Based on a Taguchi analysis, the effects of the factors decreased in the order of solvent ratio (34.36%) > catalyst (28.62%) > time (19.72%) > temperature (17.32%). The overall biodiesel production appeared to be better using NaOH as an alkaline catalyst rather than using H2SO4 in an acidic process, at 55.07 ± 2.18% (based on lipid weight) versus 48.41 ± 0.21%. However, in considering the purified biodiesel, it was found that the acidic catalyst was approximately 2.5 times more efficient than the alkaline catalyst under the following optimal conditions: temperature of 70 °C (level 2), reaction time of 10 hrs (level 2), catalyst amount of 5% (level 3), and biomass to solvent ratio of 1 : 15 (level 2), respectively. These results clearly demonstrated that the acidic solvent, which combined oil extraction with in situ transesterification, was an effective catalyst for the production of high-quantity, high-quality biodiesel from a Scenedesmus sp.

Enhancement of Biodiesel Production from Marine Alga, Scenedesmus sp. through In Situ Transesterification Process Associated with Acidic Catalyst

PubMed Central

Kim, Ga Vin; Choi, WoonYong; Kang, DoHyung; Lee, ShinYoung; Lee, HyeonYong

2014-01-01

The aim of this study was to increase the yield of biodiesel produced by Scenedesmus sp. through in situ transesterification by optimizing various process parameters. Based on the orthogonal matrix analysis for the acidic catalyst, the effects of the factors decreased in the order of reaction temperature (47.5%) > solvent quantity (26.7%) > reaction time (17.5%) > catalyst amount (8.3%). Based on a Taguchi analysis, the effects of the factors decreased in the order of solvent ratio (34.36%) > catalyst (28.62%) > time (19.72%) > temperature (17.32%). The overall biodiesel production appeared to be better using NaOH as an alkaline catalyst rather than using H2SO4 in an acidic process, at 55.07 ± 2.18% (based on lipid weight) versus 48.41 ± 0.21%. However, in considering the purified biodiesel, it was found that the acidic catalyst was approximately 2.5 times more efficient than the alkaline catalyst under the following optimal conditions: temperature of 70°C (level 2), reaction time of 10 hrs (level 2), catalyst amount of 5% (level 3), and biomass to solvent ratio of 1 : 15 (level 2), respectively. These results clearly demonstrated that the acidic solvent, which combined oil extraction with in situ transesterification, was an effective catalyst for the production of high-quantity, high-quality biodiesel from a Scenedesmus sp. PMID:24689039

Simultaneous production of oil enriched in ω-3 polyunsaturated fatty acids and biodiesel from fish wastes.

PubMed

Enascuta, Cristina Emanuela; Stepan, Emil; Bolocan, Ion; Bombos, Dorin; Calin, Catalina; Oprescu, Elena-Emilia; Lavric, Vasile

2018-05-01

The waste resulted from fish processing industries are discarded into the environment around the world, causing environmental pollution. The main problem of fish oil extracted from waste is the high content in free fatty acids (FFA) which decrease the yield in fatty acids esters during transesterification reactions. Therefore, to correct the fish-oil properties, a new environmentally friendly heterogeneous superacid catalyst (SO 4 2- /SnO 2 -ZrO 2 ) was tested in the esterification reaction of FFA with ethanol. The catalyst was characterized by different techniques (XRD, FT-IR, FT-IR of adsorbed pyridine, BET, SEM-EDX, TGA and acidity measurements). The reaction was found to follow a Langmuir-Hinshelwood (L-H) dual-site mechanism with the novelty that both Brönsted and Lewis acid centers participate equally in the esterification reaction. The pre-treated oil was subjected to transesterification reaction with ethanol over a heterogeneous base catalyst and then, the saturated and unsaturated fractions of fatty acid ethyl esters (FAEE) were separated using a vacuum rectification unit with falling film. The saturated content can be used as biofuel, while the unsaturated FAEE are further transesterified with glycerol in order to obtain oil with high content in polyunsaturated fatty acids (PUFA). A detailed study of the intrinsic kinetic process at the surface of the superacid catalyst and a thorough mathematical model of the fixed bed reactor were written and validated by an experimental program, designed according to the D-optimal methodology. Copyright © 2018 Elsevier Ltd. All rights reserved.

A review on production of biodiesel using catalyzed transesterification

NASA Astrophysics Data System (ADS)

Dash, Santosh Kumar; Lingfa, Pradip

2017-07-01

Biodiesel is arguably an important fuel for compression ignition engine as far as sustainability and environmental issues are concerned. It can be produced from both edible and non-edible vegetable oils and animal fats. Owing to higher viscosity, the utilization of crude vegetable oil is not advisable as it results engine failure. For reducing the viscosity and improving the other fuel characteristics comparable to that of diesel fuel, different approaches have been developed. However, transesterification process is very reliable, less costly and easy method compared to other methods. Due to more free fatty acids content in most of the non-edible vegetable oils, a pretreatment is employed to convert the acids to ester, then transesterified with suitable alcohol. Primarily yield of biodiesel depends upon the molar ratio of oil/alcohol, reaction temperature, reaction time, amount of catalyst, type of catalyst, stirring speed. Both homogeneous and heterogeneous catalysts are used for synthesis purposes. Heterogeneous catalysts are less costly, environmental benign and can be derived from natural resources. Enzymatic catalysts are more environmental benign than heterogeneous catalysts but are costly, which hinders its widespread research and utilization. This article reviews the results of prominent works and researches in the field of production of biodiesel via catalyzed transesterification process.

Developmentally programmed DNA deletion in Tetrahymena thermophila by a transposition-like reaction pathway.

PubMed Central

Saveliev, S V; Cox, M M

1996-01-01

We provide a molecular description of key intermediates in the deletion of two internal eliminated sequences (IES elements), the M and R regions, during macronuclear development in Tetrahymena thermophila. Using a variety of PCR-based methods in vivo, double-strand breaks are detected that are generated by hydrolytic cleavage and correspond closely to the observed chromosomal junctions left behind in the macronuclei. The breaks exhibit a temporal and structural relationship to the deletion reaction that provides strong evidence that they are intermediates in the deletion pathway. Breaks in the individual strands are staggered by 4 bp, producing a four nucleotide 5' extension. Evidence is presented that breaks do not occur simultaneously at both ends. The results are most consistent with a deletion mechanism featuring initiation by double-strand cleavage at one end of the deleted element, followed by transesterification to generate the macronuclear junction on one DNA strand. An adenosine residue is found at all the nucleophilic 3' ends used in the postulated transesterification step. Evidence for the transesterification step is provided by detection of a 3' hydroxyl that would be liberated by such a step at a deletion boundary where no other DNA strand ends are detected. Images PMID:8654384

Immobilization of Pseudomonas fluorescens lipase on hydrophobic supports and application in biodiesel synthesis by transesterification of vegetable oils in solvent-free systems.

PubMed

Lima, Lionete N; Oliveira, Gladson C; Rojas, Mayerlenis J; Castro, Heizir F; Da Rós, Patrícia C M; Mendes, Adriano A; Giordano, Raquel L C; Tardioli, Paulo W

2015-04-01

This work describes the preparation of biocatalysts for ethanolysis of soybean and babassu oils in solvent-free systems. Polystyrene, Amberlite (XAD-7HP), and octyl-silica were tested as supports for the immobilization of Pseudomonas fluorescens lipase (PFL). The use of octyl-silica resulted in a biocatalyst with high values of hydrolytic activity (650.0 ± 15.5 IU/g), immobilization yield (91.3 ± 0.3 %), and recovered activity (82.1 ± 1.5 %). PFL immobilized on octyl-silica was around 12-fold more stable than soluble PFL, at 45 °C and pH 8.0, in the presence of ethanol at 36 % (v/v). The biocatalyst provided high vegetable oil transesterification yields of around 97.5 % after 24 h of reaction using babassu oil and around 80 % after 48 h of reaction using soybean oil. The PFL-octyl-silica biocatalyst retained around 90 % of its initial activity after five cycles of transesterification of soybean oil. Octyl-silica is a promising support that can be used to immobilize PFL for subsequent application in biodiesel synthesis.

Purification of crude glycerol from transesterification reaction of palm oil using direct method and multistep method

NASA Astrophysics Data System (ADS)

Nasir, N. F.; Mirus, M. F.; Ismail, M.

2017-09-01

Crude glycerol which produced from transesterification reaction has limited usage if it does not undergo purification process. It also contains excess methanol, catalyst and soap. Conventionally, purification method of the crude glycerol involves high cost and complex processes. This study aimed to determine the effects of using different purification methods which are direct method (comprises of ion exchange and methanol removal steps) and multistep method (comprises of neutralization, filtration, ion exchange and methanol removal steps). Two crude glycerol samples were investigated; the self-produced sample through the transesterification process of palm oil and the sample obtained from biodiesel plant. Samples were analysed using Fourier Transform Infrared Spectroscopy, Gas Chromatography and High Performance Liquid Chromatography. The results of this study for both samples after purification have showed that the pure glycerol was successfully produced and fatty acid salts were eliminated. Also, the results indicated the absence of methanol in both samples after purification process. In short, the combination of 4 purification steps has contributed to a higher quality of glycerol. Multistep purification method gave a better result compared to the direct method as neutralization and filtration steps helped in removing most excess salt, fatty acid and catalyst.

Design and synthesis of multifunctional poly(ethylene glycol)s using enzymatic catalysis for multivalent cancer drug delivery

NASA Astrophysics Data System (ADS)

Seo, Kwang Su

The objective of this research was to design and synthesize multifunctional poly(ethylene glycol)s (PEG)s using enzyme-catalyzed reactions for multivalent targeted drug delivery. Based on computer simulation for optimum folate binding, a four-arm PEG star topology with Mn = 1000 g/mol was proposed. First, a four-functional core based on tetraethylene glycol (TEG) was designed and synthesized using transesterification and Michael addition reactions in the presence of Candida antarctica lipase B (CALB) as a biocatalyst. The four-functional core (HO)2-TEG-(OH)2 core was successfully prepared by the CALB-catalyzed transesterification of vinyl acrylate (VA) with TEG and then Michael addition of diethanolamine to the resulting TEG diacrylate with/without the use of solvent. The functional PEG arms with fluorescein isothiocyanate (FITC) and folic acid (FA) were prepared using both traditional organic chemistry and enzyme-catalyzed reactions. FITC was reacted with the amine group of H2N-PEG-OH in the presence of triethylamine via nucleophilic addition onto the isothiocyanate group. Then, divinyl adipate (DVA) was transesterified with the FITC-PEG-OH product in the presence of CALB to produce the FITC-PEG vinyl ester that will be attached to the four-functional core via CALC-catalyzed transesterification. For the synthesis of FA-PEG vinyl ester arm, DVA was first reacted with PEG-monobenzyl ether (BzPEG-OH) in bulk in the presence of CALB. The BzPEG vinyl ester was then transesterified with 12-bromo-1-dodecanol in the presence of CALB. Finally, BzPEG-Br was attached to FA exclusively in the gamma position using a new method. The thesis also discusses fundamental studies that were carried out in order to get better understanding of enzyme catalyzed transesterification and Michael addition reactions. First, in an effort to investigate the effects of reagent and enzyme concentrations in transesterification, vinyl methacrylate (VMA) was reacted with 2-(hydroxyethyl) acrylate (2HEA) in the presence of CALB. When the reaction was performed in tetrahydrofuran (THF) with a 2HEA concentration of 0.10 mol/L, only 19% conversion was observed within 4 hours, whereas complete conversion was achieved under solventless conditions. The effect of enzyme concentration in reactions with and without solvent was also studied. The effect of DVA concentration on the CALB-catalyzed transesterification with TEG was studied under solventless conditions. When 1.5 molar equivalent of DVA per OH in TEG was used, 42% divinyl-functionalized product was observed together with 56.5% oligomerized (di-, tri-, tetra- and pentamer) products. At 10 eq. of DVA, only 18.4% oligomerized products were obtained. The effect of diol molecular weight was also investigated. At 10.0 eq. DVA per OH only 2% dimer was observed with PEG Mn=1000 g/mol, and a single divinyl functionalized product was obtained with M n=2000 g/mol. The effects of polymer molecular weight and DVA concentration were also studied in the reaction of DVA with PEG monomethyl ether (MPEG-OH, Mn=1100 g/mol and 2000 g/mol). The extent of coupling decreased from 35% to 0.4% when the DVA concentration was increased from 1.5 to 10 per -OH in the MPEG-OH. No coupling was observed with MPEG-OH Mn=2000 g/mol at 5 eq. DVA per -OH. Following these fundamental studies, TEGs and PEGs were enzymatically functionalized. TEGs were transesterified with VMA and vinyl crotonate in the presence of CALB under solventless conditions within 4 hours of reaction time. Benzyl protected TEG-OHs were also successfully functionalized with VMA and vinyl crotonate in the presence of CALB under solventless conditions within 2 hours. An eight-functional molecule was also synthesized from (HO)2-TEG-(OH) 2. First an alpha-vinyl-o-acrylate linker was prepared by the transesterification of DVA with 2HEA. This linker was then transesterified with (HO)-TEG-(OH)2, followed by Michael addition of DEA to the tetra-acrylated TEG. (Abstract shortened by UMI.)

Evaluation of in-situ fatty acid extraction protocols for the analysis of staphylococcal cell membrane associated fatty acids by gas chromatography.

PubMed

Crompton, Marcus J; Dunstan, R Hugh

2018-05-01

The composition and integrity of the bacterial cytoplasmic membrane is critical to the survival of staphylococci in dynamic environments and it is important to investigate how the cell membrane responds to changes in the environmental conditions. The staphylococcal membrane differs from eukaryotic and many other bacterial cell membranes by having a high abundance of branch fatty acids and relatively few unsaturated fatty acids. The range of available methods for extraction and efficient analyses of staphylococcal fatty acids was initially appraised to identify the best potential procedures for appraisal. Staphylococcus aureus subsp. aureus Rosenbach (ATCC® 29213) was grown under optimal conditions to generate a cell biomass to compare the efficiencies of three approaches to extract and prepare methyl esters of the membrane fatty acids: (1) acidic direct transesterification of lipids, (2) modified basic direct transesterification of membrane lipids with adjusted reaction times and temperatures, and (3) base catalysed hydrolysis followed by acid catalysed esterification in two separate chemical reactions (MIDI process). All methods were able to extract fatty acids from the cell mass effectively where these lipids represented approximately 5% of the cellular dry mass. The acidic transesterification method had the least number of steps, the lowest coefficient of variation at 6.7% and good resistance to tolerating water. Basic transesterification was the least accurate method showing the highest coefficient of variation (26%). The MIDI method showed good recoveries, but had twice the number of steps and a coefficient of variation of 16%. It was also found that there was no need to use an anti-oxidant such as BHT for the protection of polyunsaturated fatty acids when the GC-MS injection liner was clean. It was concluded that the acidic transesterification procedures formed the most efficient and reproducible method for the analyses of staphylococcal membrane fatty acids. Crown Copyright © 2018. Published by Elsevier B.V. All rights reserved.

Comparing Ultrasound and Mechanical Steering in a Biodiesel Production Process

NASA Astrophysics Data System (ADS)

Costa-Felix, Rodrigo P. B.; Ferreira, Jerusa R. L.

The analysis of the kinetics of the transesterification reaction is crucial to compare different routes or routes with different catalysts or reaction accelerators. The use of ultrasound is considereda method for accelerating the biodiesel production. However, little effort has been done and is reported in the literature about how and under what conditions the use of ultrasound really speeds up the process, or the conditions under which its use is unnecessary or even harmful, burdening the process. Two dissimilar energy injections into a typical route were tested: ultrasound (@ 1 MHz and no heating) and mechanical steering (with heating), both applied in an 8:1 ratio of soybean oil and methanol, adding 1% of KOH as catalyzer. As results, during the first 10 minutes of reaction ultrasound showed unbearable effect on the transesterification, whilst mechanical steering and heating achieved almost 70% of conversion ratio. However, during the following 10 minutes, the mechanical steering and heating got nothing more than 80% of conversion, a considerable less efficient process than ultrasound assisted one, which achieved more than 90%. The straightforward explanation is that ultrasound continually inserts energy in a slower rate, what can result in a more stable conversion scenario. On the other hand, mechanical steering and heating provides more energy at a glance, but cannot push the final conversion rate beyond a limit, as the transesterification is a double-way chemical process. The instability mechanical steering and heating settles in the reaction medium pulls the components back to their original states more than pushes than to the converted equilibrium state of the matter.

Biodiesel production from vegetable oil and waste animal fats in a pilot plant.

PubMed

Alptekin, Ertan; Canakci, Mustafa; Sanli, Huseyin

2014-11-01

In this study, corn oil as vegetable oil, chicken fat and fleshing oil as animal fats were used to produce methyl ester in a biodiesel pilot plant. The FFA level of the corn oil was below 1% while those of animal fats were too high to produce biodiesel via base catalyst. Therefore, it was needed to perform pretreatment reaction for the animal fats. For this aim, sulfuric acid was used as catalyst and methanol was used as alcohol in the pretreatment reactions. After reducing the FFA level of the animal fats to less than 1%, the transesterification reaction was completed with alkaline catalyst. Due to low FFA content of corn oil, it was directly subjected to transesterification. Potassium hydroxide was used as catalyst and methanol was used as alcohol for transesterification reactions. The fuel properties of methyl esters produced in the biodiesel pilot plant were characterized and compared to EN 14214 and ASTM D6751 biodiesel standards. According to the results, ester yield values of animal fat methyl esters were slightly lower than that of the corn oil methyl ester (COME). The production cost of COME was higher than those of animal fat methyl esters due to being high cost biodiesel feedstock. The fuel properties of produced methyl esters were close to each other. Especially, the sulfur content and cold flow properties of the COME were lower than those of animal fat methyl esters. The measured fuel properties of all produced methyl esters met ASTM D6751 (S500) biodiesel fuel standards. Copyright © 2014 Elsevier Ltd. All rights reserved.

Biodiesel production from waste frying oils and its quality control.

PubMed

Sabudak, T; Yildiz, M

2010-05-01

The use of biodiesel as fuel from alternative sources has increased considerably over recent years, affording numerous environmental benefits. Biodiesel an alternative fuel for diesel engines is produced from renewable sources such as vegetable oils or animal fats. However, the high costs implicated in marketing biodiesel constitute a major obstacle. To this regard therefore, the use of waste frying oils (WFO) should produce a marked reduction in the cost of biodiesel due to the ready availability of WFO at a relatively low price. In the present study waste frying oils collected from several McDonald's restaurants in Istanbul, were used to produce biodiesel. Biodiesel from WFO was prepared by means of three different transesterification processes: a one-step base-catalyzed, a two-step base-catalyzed and a two-step acid-catalyzed transesterification followed by base transesterification. No detailed previous studies providing information for a two-step acid-catalyzed transesterification followed by a base (CH(3)ONa) transesterification are present in literature. Each reaction was allowed to take place with and without tetrahydrofuran added as a co-solvent. Following production, three different procedures; washing with distilled water, dry wash with magnesol and using ion-exchange resin were applied to purify biodiesel and the best outcome determined. The biodiesel obtained to verify compliance with the European Standard 14214 (EN 14214), which also corresponds to Turkish Biodiesel Standards. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Evaluation of malt spent rootlets biochar as catalyst for biodiesel production.

NASA Astrophysics Data System (ADS)

Pantiora, Dimitra

2014-05-01

Evaluation of malt spent rootlets biochar as catalyst for biodiesel production. Dimitra Pantiora1, Hrissi K. Karapanagioti1, Ioannis D. Manariotis2, Alexis Lycourghiotis1, Christos Kordulis1,3 (1) University of Patras, Department of Chemistry, GR 26500, Patras, Greece, (2) University of Patras, Department of Civil Engineering, Patras, Greece, (3) Institute of Chemical Engineering Science (FORTH/ ICE-HT), Stadiou Str., Platani, GR 26500, Patras, Greece Biodiesel is an attractive renewable fuel, environmentally friendly, and can readily be synthesized from the triglycerides found in animal fats and vegetable oils. It can be used in existing engines. Biodiesel consists of fatty acid alkyl esters. Conversion of triglycerides to biodiesel fuel is commonly achieved through a series of transesterification reactions involving the reaction of an alkoxy group of an ester (i.e., mono-, di-, or triglyceride) with that of a small alcohol (usually methanol). This reaction is traditionally catalyzed by homogeneous catalysts, such as bases or mineral acids. Basic catalysts have been proved to be much more active than acidic ones. However, due to environmental (waste water) and economic concerns (catalyst separation and product and by-product cleaning), heterogeneous catalysts are much more desirable. In the present study we have evaluated the use of biochar, produced from malt spent rootlets, as a potential basic catalyst, for transesterification of triglycerides using triacetin as a probe molecule. The biochar used in this study was prepared by heating malt spent rootlets in an oxygen-limited environment. It is a carbon rich material, containing 66% C, 22% O, 0.45% Mg, 0.86% Si, 5.7% K, 1.5% Cl, 0.61% Ca, and 2.4% P. Aqueous suspension of this material equilibrates at pH= 10. This is probably due to high K content. Furthermore, it exhibits high specific surface area (SSA= 183 m2g-1). The above described characteristics make this material very promising catalyst for transesterification reactions. Indeed, the corresponding catalytic tests showed that 100% transesterification of triacetin can be achieved into 0.5 hour. This activity was maintained at least for 4 successive catalytic runs.

Kinetics study of Jatropha oil esterification with ethanol in the presence of tin (II) chloride catalyst for biodiesel production

NASA Astrophysics Data System (ADS)

Kusumaningtyas, Ratna Dewi; Ratrianti, Naomi; Purnamasari, Indah; Budiman, Arief

2017-01-01

Jatropha oil is one of the promising feedstocks for biodiesel production. Jatropha oil is non-edible oil hence utilization of this oil would not compete with the needs of food. However, crude jatropha oil usually has high free fatty acid (FFA) content. Due to this fact, direct alkaline-catalyzed transesterification of crude jatropha oil for biodiesel production cannot be performed. FFA in crude jatropha oil will react with a base catalyst, resulting in soap as by product and hindering methyl ester (biodiesel) production. Therefore, prior to a transesterification reaction, it is crucial to run a pretreatment step of jatropha oil which can lower the FFA content in the oil. In this work, the pretreatment process was conducted through the esterification reaction of FFA contained in crude jatropha oil with ethanol over tin (II) chloride catalyst to reduce the acid value of the feedstock. The feedstock was Indonesia crude jatropha oil containing 12.03% of FFA. The esterification reaction was carried out in a batch reactor with a molar ratio of FFA to ethanol was 1:60 and total reaction time was 180 minutes. Tin (II) chloride catalyst was varied at 2.5, 5, 7.5, and 10% wt, whereas the effect of the reaction temperature was studied at 35, 34, 55, and 65 °C. The best reaction conversion was 71.55%, achieved at the following condition: a reaction temperature of 65 °C, catalyst concentration of 10% wt, the reaction time of 180 min, and the molar ratio of FFA to ethanol was 1:60. Kinetics study was also conducted in this work. It was found that esterification reaction of jatropha oil FFA with ethanol catalyzed by tin(II) chloride fitted the first-order pseudo-homogeneous kinetics model. It was also revealed that the frequency factor (A) and the activation energy (Ea) were 4.3864 × 106 min-1 and 56.2513 kJ/mole, respectively.

Economical and green biodiesel production process using river snail shells-derived heterogeneous catalyst and co-solvent method.

PubMed

Roschat, Wuttichai; Siritanon, Theeranun; Kaewpuang, Teadkait; Yoosuk, Boonyawan; Promarak, Vinich

2016-06-01

River snail shells-derived CaO was used as a heterogeneous catalyst to synthesize biodiesel via transesterification of palm oil with methanol. The shell materials were calcined in air at 600-1000°C for 3h. Physicochemical properties of the resulting catalysts were characterized by TGA-DTG, XRD, SEM, BET, XRF, FT-IR and TPD. CaO catalyzed transesterification mechanism of palm oil into biodiesel was verified. The effects of adding a co-solvent on kinetic of the reaction and %FAME yield were investigated. %FAME yield of 98.5%±1.5 was achieved under the optimal conditions of catalyst/oil ratio of 5wt.%; methanol/oil molar ratio of 12:1; reaction temperature of 65°C; 10%v/v of THF in methanol and reaction time of 90min. The results ascertained that river snail shells is a novel raw material for preparation of CaO catalyst and the co-solvent method successfully decreases the reaction time and biodiesel production cost. Copyright © 2016 Elsevier Ltd. All rights reserved.

Highly efficient extraction and lipase-catalyzed transesterification of triglycerides from Chlorella sp. KR-1 for production of biodiesel.

PubMed

Lee, Ok Kyung; Kim, Young Hyun; Na, Jeong-Geol; Oh, You-Kwan; Lee, Eun Yeol

2013-11-01

We developed a method for the highly efficient lipid extraction and lipase-catalyzed transesterification of triglyceride from Chlorella sp. KR-1 using dimethyl carbonate (DMC). Almost all of the total lipids, approximately 38.9% (w/w) of microalgae dry weight, were extracted from the dried microalgae biomass using a DMC and methanol mixture (7:3 (v/v)). The extracted triglycerides were transesterified into fatty acid methyl esters (FAMEs) using Novozyme 435 as the biocatalyst in DMC. Herein, DMC was used as the reaction medium and acyl acceptor. The reaction conditions were optimized and the FAMEs yield was 293.82 mg FAMEs/g biomass in 6 h of reaction time at 60 °C in the presence of 0.2% (v/v) water. Novozyme 435 was reused more than ten times while maintaining relative FAMEs conversion that was greater than 90% of the initial FAMEs conversion. Copyright © 2013 Elsevier Ltd. All rights reserved.

Transesterification reaction of the fat originated from solid waste of the leather industry.

PubMed

Işler, Asli; Sundu, Serap; Tüter, Melek; Karaosmanoğlu, Filiz

2010-12-01

The leather industry is an industry which generates a large amount of solid and liquid wastes. Most of the solid wastes originate from the pre-tanning processes while half of it comes from the fleshing step. Raw fleshing wastes which mainly consist of protein and fat have almost no recovery option and the disposal is costly. This study outlines the possibility of using the fleshing waste as an oil source for transesterification reaction. The effect of oil/alcohol molar ratio, the amount of catalyst and temperature on ester production was individually investigated and optimum reaction conditions were determined. The fuel properties of the ester product were also studied according to the EN 14214 standard. Cold filter plugging point and oxidation stability have to be improved in order to use the ester product as an alternative fuel candidate. Besides, this product can be used as a feedstock in lubricant production or cosmetic industry. Copyright © 2010 Elsevier Ltd. All rights reserved.

Selection of Lipases for the Synthesis of Biodiesel from Jatropha Oil and the Potential of Microwave Irradiation to Enhance the Reaction Rate

PubMed Central

2016-01-01

The present study deals with the enzymatic synthesis of biodiesel by transesterification of Jatropha oil (Jatropha curcas L.) with ethanol in a solvent-free system. Seven commercial lipase preparations immobilized by covalent attachment on epoxy-polysiloxane-polyvinyl alcohol composite (epoxy-SiO2-PVA) were tested as biocatalysts. Among them, immobilized lipases from Pseudomonas fluorescens (lipase AK) and Burkholderia cepacia (lipase PS) were the most active biocatalysts in biodiesel synthesis, reaching ethyl ester yields (FAEE) of 91.1 and 98.3% at 72 h of reaction, respectively. The latter biocatalyst exhibited similar performance compared to Novozym® 435. Purified biodiesel was characterized by different techniques. Transesterification reaction carried out under microwave irradiation exhibited higher yield and productivity than conventional heating. The operational stability of immobilized lipase PS was determined in repeated batch runs under conventional and microwave heating systems, revealing half-life times of 430.4 h and 23.5 h, respectively. PMID:27868060

Synthesis of methyl esters from waste cooking oil using construction waste material as solid base catalyst.

PubMed

Balakrishnan, K; Olutoye, M A; Hameed, B H

2013-01-01

The current research investigates synthesis of methyl esters by transesterification of waste cooking oil in a heterogeneous system, using barium meliorated construction site waste marble as solid base catalyst. The pretreated catalyst was calcined at 830 °C for 4h prior to its activity test to obtained solid oxide characterized by scanning electron microscopy/energy dispersive spectroscopy, BET surface area and pore size measurement. It was found that the as prepared catalyst has large pores which contributed to its high activity in transesterification reaction. The methyl ester yield of 88% was obtained when the methanol/oil molar ratio was 9:1, reaction temperature at 65 °C, reaction time 3h and catalyst/oil mass ratio of 3.0 wt.%. The catalyst can be reused over three cycles, offer low operating conditions, reduce energy consumption and waste generation in the production of biodiesel. Copyright © 2012 Elsevier Ltd. All rights reserved.

Data on calcium oxide and cow bone catalysts used for soybean biodiesel production.

PubMed

Ayodeji, Ayoola A; Blessing, Igho E; Sunday, Fayomi O

2018-06-01

Biodiesel was produced from soybean oil using calcium oxide and cow bone as heterogeneous catalysts, through transesterification process. The soybean oil used was characterized using gas chromatography mass spectrometer (GCMS) and the cow bone catalyst produced was characterized X-ray fluorescence (XRF) spectrometer. The effects of the variation of methanol/oil mole ratio, catalyst concentration and reaction temperature on biodiesel yield during the transesterification of soybean oil were investigated. Reaction time of 3 h and stirring rate of 500 rpm were kept constant. Using Response Optimizer (Minitab 17), the optimum conditions for biodiesel production were established. It was observed that the calcination of cow bone catalyst enhanced its conversion to apatite-CaOH. Also, the results obtained showed that the performance trends of calcined cow bone catalyst and the conventional CaO catalyst were similar.

Selection and Characterization of Biofuel-Producing Environmental Bacteria Isolated from Vegetable Oil-Rich Wastes

PubMed Central

Escobar-Niño, Almudena; Luna, Carlos; Luna, Diego; Marcos, Ana T.; Cánovas, David; Mellado, Encarnación

2014-01-01

Fossil fuels are consumed so rapidly that it is expected that the planet resources will be soon exhausted. Therefore, it is imperative to develop alternative and inexpensive new technologies to produce sustainable fuels, for example biodiesel. In addition to hydrolytic and esterification reactions, lipases are capable of performing transesterification reactions useful for the production of biodiesel. However selection of the lipases capable of performing transesterification reactions is not easy and consequently very few biodiesel producing lipases are currently available. In this work we first isolated 1,016 lipolytic microorganisms by a qualitative plate assay. In a second step, lipolytic bacteria were analyzed using a colorimetric assay to detect the transesterification activity. Thirty of the initial lipolytic strains were selected for further characterization. Phylogenetic analysis revealed that 23 of the bacterial isolates were Gram negative and 7 were Gram positive, belonging to different clades. Biofuel production was analyzed and quantified by gas chromatography and revealed that 5 of the isolates produced biofuel with yields higher than 80% at benchtop scale. Chemical and viscosity analysis of the produced biofuel revealed that it differed from biodiesel. This bacterial-derived biofuel does not require any further downstream processing and it can be used directly in engines. The freeze-dried bacterial culture supernatants could be used at least five times for biofuel production without diminishing their activity. Therefore, these 5 isolates represent excellent candidates for testing biofuel production at industrial scale. PMID:25099150

Synthesis of Transesterified Palm Olein-Based Polyol and Rigid Polyurethanes from this Polyol.

PubMed

Arniza, Mohd Zan; Hoong, Seng Soi; Idris, Zainab; Yeong, Shoot Kian; Hassan, Hazimah Abu; Din, Ahmad Kushairi; Choo, Yuen May

Transesterification of palm olein with glycerol can increase the functionality by introducing additional hydroxyl groups to the triglyceride structure, an advantage compared to using palm olein directly as feedstock for producing palm-based polyol. The objective of this study was to synthesize transesterified palm olein-based polyol via a three-step reaction: (1) transesterification of palm olein, (2) epoxidation and (3) epoxide ring opening. Transesterification of palm olein yielded approximately 78 % monoglyceride and has an hydroxyl value of approximately 164 mg KOH g -1 . The effect of formic acid and hydrogen peroxide concentrations on the epoxidation reaction was studied. The relationships between epoxide ring-opening reaction time and residual oxirane oxygen content and hydroxyl value were monitored. The synthesized transesterified palm olein-based polyol has hydroxyl value between 300 and 330 mg KOH g -1 and average molecular weight between 1,000 and 1,100 Da. On the basis of the hydroxyl value and average molecular weight of the polyol, the transesterified palm olein-based polyol is suitable for producing rigid polyurethane foam, which can be designed to exhibit desirable properties. Rigid polyurethane foams were synthesized by substituting a portion of petroleum-based polyol with the transesterified palm olein-based polyol. It was observed that by increasing the amount of transesterified palm olein-based polyol, the core density and compressive strength were reduced but at the same time the insulation properties of the rigid polyurethane foam were improved.

Application of kaolin-based catalysts in biodiesel production via transesterification of vegetable oils in excess methanol.

PubMed

Dang, Tan Hiep; Chen, Bing-Hung; Lee, Duu-Jong

2013-10-01

Biodiesel production from transesterification of vegetable oils in excess methanol was performed by using as-prepared catalyst from low-cost kaolin clay. This effective heterogeneous catalyst was successfully prepared from natural kaolin firstly by dehydroxylation at 800°C for 10h and, subsequently, by NaOH-activation hydrothermally at 90°C for 24h and calcined again at 500°C for 6h. The as-obtained catalytic material was characterized with instruments, including FT-IR, XRD, SEM, and porosimeter (BET/BJH analysis). The as-prepared catalyst was advantageous not only for its easy preparation, but also for its cost-efficiency and superior catalysis in transesterification of vegetable oils in excess methanol to produce fatty acid methyl esters (FAMEs). Conversion efficiencies of soybean and palm oils to biodiesel over the as-prepared catalysts reached 97.0±3.0% and 95.4±3.7%, respectively, under optimal conditions. Activation energies of transesterification reactions of soybean and palm oils in excess methanol using these catalysts are 14.09 kJ/mol and 48.87 kJ/mol, respectively. Copyright © 2012 Elsevier Ltd. All rights reserved.

Ethanesulfonic acid-based esterification of industrial acidic crude palm oil for biodiesel production.

PubMed

Hayyan, Adeeb; Mjalli, Farouq S; Hashim, Mohd Ali; Hayyan, Maan; AlNashef, Inas M; Al-Zahrani, Saeed M; Al-Saadi, Mohammed A

2011-10-01

An industrial grade acidic crude palm oil (ACPO) pre-treatment process was carried out using ethanesulfonic acid (ESA) as a catalyst in the esterification reaction. ESA was used in different dosages to reduce free fatty acid (FFA) to a minimum level for the second stage of biodiesel production via alkaline transesterification reaction. Different process operating conditions were optimized such as ESA dosage (0.25-3.5% wt/wt), methanol to ACPO molar ratio (1:1-20:1), reaction temperature (40-70 °C), and reaction time (3-150 min). This study revealed the potential use of abundant quantities of ACPO from oil palm mills for biodiesel production. The lab scale results showed the effectiveness of the pre-treatment process using ESA catalyst. Three consecutive catalyst recycling runs were achieved without significant degradation in its performance. Second and third reuse runs needed more reaction time to achieve the target level of FFA content. Esterification and transesterification using ESA and KOH respectively is proposed for biodiesel industrial scale production. The produced biodiesel meets the international standards specifications for biodiesel fuel (EN 14214 and ASTM D6751). Copyright © 2011 Elsevier Ltd. All rights reserved.

Biocatalytic Synthesis of Epoxy Resins from Fatty Acids as a Versatile Route for the Formation of Polymer Thermosets with Tunable Properties.

PubMed

Torron, Susana; Semlitsch, Stefan; Martinelle, Mats; Johansson, Mats

2016-12-12

The work herein presented describes the synthesis and polymerization of series of bio-based epoxy resins prepared through lipase catalyzed transesterification. The epoxy-functional polyester resins with various architectures (linear, tri-branched, and tetra-branched) were synthesized through condensation of fatty acids derived from epoxidized soybean oil and linseed oil with three different hydroxyl cores under bulk conditions. The selectivity of the lipases toward esterification/transesterification reactions allowed the formation of macromers with up to 12 epoxides in the backbone. The high degree of functionality of the resins resulted in polymer thermosets with T g values ranging from -25 to over 100 °C prepared through cationic polymerization. The determining parameters of the synthesis and the mechanism for the formation of the species were determined through kinetic studies by 1 H NMR, SEC, and molecular modeling studies. The correlation between macromer structure and thermoset properties was studied through real-time FTIR measurements, DSC, and DMA.

Comparative assessment of various lipid extraction protocols and optimization of transesterification process for microalgal biodiesel production.

PubMed

Mandal, Shovon; Patnaik, Reeza; Singh, Amit Kumar; Mallick, Nirupama

2013-01-01

Biodiesel, using microalgae as feedstocks, is being explored as the most potent form of alternative diesel fuel for sustainable economic development. A comparative assessment of various protocols for microalgal lipid extraction was carried out using five green algae, six blue-green algae and two diatom species treated with different single and binary solvents both at room temperature and using a soxhlet. Lipid recovery was maximum with chloroform-methanol in the soxhlet extractor. Pretreatments ofbiomass, such as sonication, homogenization, bead-beating, lyophilization, autoclaving, microwave treatment and osmotic shock did not register any significant rise in lipid recovery. As lipid recovery using chloroform-methanol at room temperature demonstrated a marginally lower value than that obtained under the soxhlet extractor, on economical point of view, the former is recommended for microalgal total lipid extraction. Transesterification process enhances the quality of biodiesel. Experiments were designed to determine the effects of catalyst type and quantity, methanol to oil ratio, reaction temperature and time on the transesterification process using response surface methodology. Fatty acid methyl ester yield reached up to 91% with methanol:HCl:oil molar ratio of 82:4:1 at 65 degrees C for 6.4h reaction time. The biodiesel yield relative to the weight of the oil was found to be 69%.

Synthesis of methyl ester sulfonate surfactant from crude palm oil as an active substance of laundry liquid detergent

NASA Astrophysics Data System (ADS)

Slamet, Ibadurrohman, Muhammad; Wulandari, Pangiastika Putri

2017-11-01

Liquid detergent with combination of MES surfactant and TiO2 nanoparticles to remove and degrade the dirt in the form of methylene blue and produce waste with the lowest surfactant residual concentration has been done. The formation of MES is carried out by esterification and transesterification of crude palm oil, sulfonation, refining, and neutralization. The photocatalyst TiO2 nanoparticles is added as an additive to improve surfactant performance in removing dirt and degrading organic compounds. MES formation is performed by varying the mole ratio of the reactants in the esterification and transesterification reactions, and the mole ratios between methyl esters and NaHSO3 during the sulfonation reaction. Variations of MES surfactant and TiO2 nanoparticles compositions were performed to obtain detergent stability. Data analysis technique in this research is characterization of methyl ester, MES surfactant, and detergent using UV-Vis spectrophotometer instrument, FTIR, GC-MS, and LC-MS. The optimum conditions in the esterification and transesterification process were each mole ratio of 1: 6 between CPO and methanol based on the highest conversion, 99%. The optimum condition of the sulfonation process is the 1: 1.5 mole ratio between methyl ester and NaHSO3 based on the lowest surface tension value, which is about 36 dyne/cm.

Kinetic studies and thermodynamics of oil extraction and transesterification of Chlorella sp. for biodiesel production.

PubMed

Ahmad, A L; Yasin, N H Mat; Derek, C J C; Lim, J K

2014-01-01

In this work, a mixture of chloroform and methanol (1:1, v/v) was applied to oil extraction from Chlorella sp. at 30, 40, 50 and 60 degrees C for 150 min extraction times. Kinetic studies revealed that the values of n and the rate constants were found to depend strongly on temperature. The activation energy was Ea = 38.893 kJ/mol, and the activation thermodynamic parameters at 60 degrees C were ΔS≠ = -180.190 J/mol , ΔH≠ = 36.124k J/mol and ΔG≠ = 96.128k J/mol. Both ΔH and ΔS yielded positive values, whereas ΔG was negative at 60 degrees C, indicating that this process is endothermic, irreversible and spontaneous. The acidic transesterification process was also investigated by gas chromatographic analysis of the microalgae fatty acid methyl esters (biodiesel) at different temperatures and reaction times. The fatty acid profile indicated that the main components were palmitic, linoleic and linolenic acids. The concentration of linolenic acid increased and oleic acid decreased as the temperature increased. Two-hour transesterification is the best reaction time for biodiesel production because it produces the highest percentage of unsaturated fatty acids (74%). These results indicate the potential of Chlorella sp. to produce biodiesel of good quality.

Optimization of lipase-catalyzed biodiesel by isopropanolysis in a continuous packed-bed reactor using response surface methodology.

PubMed

Chang, Cheng; Chen, Jiann-Hwa; Chang, Chieh-Ming J; Wu, Tsung-Ta; Shieh, Chwen-Jen

2009-10-31

Isopropanolysis reactions were performed using triglycerides with immobilized lipase in a solvent-free environment. This study modeled the degree of isopropanolysis of soybean oil in a continuous packed-bed reactor when Novozym 435 was used as the biocatalyst. Response surface methodology (RSM) and three-level-three-factor Box-Behnken design were employed to evaluate the effects of synthesis parameters, reaction temperature ( degrees C), flow rate (mL/min) and substrate molar ratio of isopropanol to soybean oil, on the percentage molar conversion of biodiesel by transesterification. The results show that flow rate and temperature have a significant effect on the percentage of molar conversion. On the basis of ridge max analysis, the optimum conditions for synthesis were as follows: flow rate 0.1 mL/min, temperature 51.5 degrees C and substrate molar ratio 1:4.14. The predicted value was 76.62+/-1.52% and actual experimental value was 75.62+/-0.81% molar conversion. Moreover, continuous enzymatic process for seven days did not show any appreciable decrease in the percent of molar conversion (75%). This work demonstrates the applicability of lipase catalysis to prepare isopropyl esters by transesterification in solvent-free system with a continuous packed-bed reactor for industrial production.

Study on production of biodiesel from Jatropha oil and the performance and emission of a diesel engine

NASA Astrophysics Data System (ADS)

Nor, N. F. M.; Hafidzal, M. H. M.; Shamsuddin, S. A.; Ismail, M. S.; Hashim, A. H.

2015-05-01

The use of nonedible oil as a feedstock is needed to replace edible oil as an alternative fuel for diesel engine. This nonedible oils in diesel engine however leads to low performance and higher emission due to its high viscosity. The characteristics of the fuel can be improved through transesterification process. The yield of biodiesel from Jatropha oil using potassium hydroxide catalyst concentration of 1%, reaction temperature 60°C, reaction time 40 minutes and molar ratio methanol to oil 6:1 was 70.1% from the lab scale. The experimental study on the performances and emissions of a diesel engine is carried out using the Jatropha biodiesel produced from the transesterification process and compared with pure diesel. Results show that B20 has closer performance to diesel and lower emission compared to B5 and diesel in terms of CO2 and HC.

Trimethylsulfonium hydroxide as derivatization reagent for the chemical investigation of drying oils in works of art by gas chromatography.

PubMed

Dron, Julien; Linke, Robert; Rosenberg, Erwin; Schreiner, Manfred

2004-08-20

A procedure for the determination of fatty acids (FA) and glycerol in oils has been developed. The method includes a derivatization step of the FAs into their methyl esters or a transesterification of the triacylglycerols with trimethylsulfonium hydroxide (TMSH), respectively. The analysis is carried out by gas chromatography with parallel flame ionization and mass spectrometric detection. The parameters involved in the transesterification reaction were optimized. Only the stoichiometric ratio of TMSH:total FA amount showed a significant influence on the reaction yield. Relative standard deviations for 10 replicates were below 3% for all FAs studied and their linearity range was 0.5-50 mmol/L, when using heptadecanoic acid as an internal standard. The final procedure was rapid and required little sample handling. It was then tested on fresh oil samples and presented satisfying results, in agreement with previous works.

Biodiesel production from used cooking oil by two-step heterogeneous catalyzed process.

PubMed

Srilatha, K; Prabhavathi Devi, B L A; Lingaiah, N; Prasad, R B N; Sai Prasad, P S

2012-09-01

The present study demonstrates the production of biodiesel from used cooking oil containing high free fatty acid by a two-step heterogeneously catalyzed process. The free fatty acids were first esterified with methanol using a 25 wt.% TPA/Nb(2)O(5) catalyst followed by transesterification of the oil with methanol over ZnO/Na-Y zeolite catalyst. The catalysts were characterized by XRD, FT-IR, BET surface area and CO(2)-TPD. In the case of transesterification the effect of reaction parameters, such as catalyst concentration, methanol to oil molar ratio and reaction temperature, on the yield of ester were investigated. The catalyst with 20 wt.% ZnO loading on Na-Y exhibited the highest activity among the others. Both the solid acid and base catalysts were found to be reusable for several times indicating their efficacy in the two-step process. Copyright © 2012 Elsevier Ltd. All rights reserved.

Functional Characterization of a Novel Marine Microbial GDSL Lipase and Its Utilization in the Resolution of (±)-1-Phenylethanol.

PubMed

Deng, Dun; Zhang, Yun; Sun, Aijun; Liang, Jiayuan; Hu, Yunfeng

2016-04-01

A novel GDSL lipase (MT6) was cloned from the genome of Marinactinospora thermotolerans SCSIO 00652 identified from the South China Sea. MT6 showed its maximum identity of 59 % with a putative lipase from Nocardiopsis dassonville. MT6 was heterologously expressed in E. coli BL21(DE3) and further functionally characterized. MT6 could efficiently resolve racemic 1-phenylethanol and generate (R)-1-phenylethanol with high enantiomeric excess (99 %) and conversion rate (54 %) through transesterification reactions after process optimization. Our report was the first one report about the utilization of one GDSL lipase in the preparation of chiral chemicals by transesterification reactions, and the optical selectivity of MT6 was interestingly opposite to those of other common lipases. GDSL lipases represented by MT6 possess great potential for the generation of valuable chiral chemicals in industry.

Production of Biodiesel from Thespesiapopulnea seed oil through rapid in situ transesterification - an optimization study and assay of fuel properties

NASA Astrophysics Data System (ADS)

Bhargavi, G.; Nageswara Rao, P.; Renganathan, S.

2018-03-01

Biodiesel production was carried out from Thespesia populnea seed oil through rapid insitu transesterification. Influence of reaction parameters such as catalyst type and concentration, methanol to biomass ratio, co-solvent volume, temperature and agitation speed on conversion of oil into methyl esters was investigated. The effect of different co-solvents on conversion was evaluated. Optimum methyl ester conversion of 97.80% was achieved at 1.5wt% of KOH catalyst, 5.5:1 (v/w) methanol to biomass ratio, 25vol%tetrahydrofuranco-solvent, 60°C and 500 rpm within 120min of reaction time. Fuel properties of produced methyl esters were well fitted within the limits of ASTMD 6751 standards. Considering the properties of produced biodiesel, Thespesia populnea seed derived biodiesel can be used as potential alternate to fossil diesel fuel.

Production of biodiesel by enzymatic transesterification of waste sardine oil and evaluation of its engine performance.

PubMed

Arumugam, A; Ponnusami, V

2017-12-01

Waste sardine oil, a byproduct of fish industry, was employed as a low cost feedstock for biodiesel production. It has relatively high free fatty acid (FFA) content (32 mg KOH/g of oil). Lipase enzyme immobilized on activated carbon was used as the catalyst for the transesterification reaction. Process variables viz. reaction temperature, water content and oil to methanol molar ratio were optimized. Optimum methanol to oil molar ratio, water content and temperature were found to be 9:1, 10 v/v% and 30 °C respectively. Reusability of immobilized lipase was studied and it was found after 5 cycles of reuse there was about 13% drop in FAME yield. Engine performance of the produced biodiesel was studied in a Variable Compression Engine and the results confirm that waste sardine oil is a potential alternate and low-cost feedstock for biodiesel production.

Ultrasonic-assisted continuous methanolysis of Jatropha curcas oil in the appearance of biodiesel used as an intermediate solvent.

PubMed

Kumar, Gajendra; Singh, Vidhi; Kumar, Dharmendra

2017-11-01

A environmental friendly system for fast transesterification of Jatropha curcas oil was developed for the production of biodiesel using an ultrasonic-assisted continuous tank reactor in the presence of fatty acid methyl ester (FAMEs) used as a green (intermediate) solvent with potassium hydroxide used as a catalyst. This research provide a new biodiesel production process, the optimal condition for the reaction were established: reaction temperature 25°C oil to methanol molar ratio was 1:5, catalyst concentration 0.75wt% of oil, solvent concentration 7.5%, flow rate 241.68±0.80ml/min, ultrasonic amplitude 60% and ultrasonic cycles 0.7s, transesterification was completed within 1.09min (residence time). The purity and conversion of biodiesel was 98.75±0.50% analyzed by the reverse phase HPLC method. Copyright © 2017 Elsevier B.V. All rights reserved.

Highly efficient conversion of plant oil to bio-aviation fuel and valuable chemicals by combination of enzymatic transesterification, olefin cross-metathesis, and hydrotreating.

PubMed

Wang, Meng; Chen, Mojin; Fang, Yunming; Tan, Tianwei

2018-01-01

The production of fuels and chemicals from renewable resources is increasingly important due to the environmental concern and depletion of fossil fuel. Despite the fast technical development in the production of aviation fuels, there are still several shortcomings such as a high cost of raw materials, a low yield of aviation fuels, and poor process techno-economic consideration. In recent years, olefin metathesis has become a powerful and versatile tool for generating new carbon-carbon bonds. The cross-metathesis reaction, one kind of metathesis reaction, has a high potential to efficiently convert plant oil into valuable chemicals, such as α-olefin and bio-aviation fuel by combining with a hydrotreatment process. In this research, an efficient, four-step conversion of plant oil into bio-aviation fuel and valuable chemicals was developed by the combination of enzymatic transesterification, olefin cross-metathesis, and hydrotreating. Firstly, plant oil including oil with poor properties was esterified to fatty acid methyl esters by an enzyme-catalyzed process. Secondly, the fatty acid methyl esters were partially hydrotreated catalytically to transform poly-unsaturated fatty acid such as linoleic acid into oleic acid. The olefin cross-metathesis then transformed the oleic acid methyl ester (OAME) into 1-decene and 1-decenoic acid methyl ester (DAME). The catalysts used in this process were prepared/selected in function of the catalytic reaction and the reaction conditions were optimized. The carbon efficiency analysis of the new process illustrated that it was more economically feasible than the traditional hydrotreatment process. A highly efficient conversion process of plant oil into bio-aviation fuel and valuable chemicals by the combination of enzymatic transesterification, olefin cross-metathesis, and hydrotreatment with prepared and selected catalysts was designed. The reaction conditions were optimized. Plant oil was transformed into bio-aviation fuel and a high value α-olefin product with high carbon utilization.

Chemoselective catalytic conversion of glycerol as a biorenewable source to valuable commodity chemicals.

PubMed

Zhou, Chun-Hui Clayton; Beltramini, Jorge N; Fan, Yong-Xian; Lu, G Q Max

2008-03-01

New opportunities for the conversion of glycerol into value-added chemicals have emerged in recent years as a result of glycerol's unique structure, properties, bioavailability, and renewability. Glycerol is currently produced in large amounts during the transesterification of fatty acids into biodiesel and as such represents a useful by-product. This paper provides a comprehensive review and critical analysis on the different reaction pathways for catalytic conversion of glycerol into commodity chemicals, including selective oxidation, selective hydrogenolysis, selective dehydration, pyrolysis and gasification, steam reforming, thermal reduction into syngas, selective transesterification, selective etherification, oligomerization and polymerization, and conversion of glycerol into glycerol carbonate.

Magnesium oxide prepared via metal-chitosan complexation method: Application as catalyst for transesterification of soybean oil and catalyst deactivation studies

NASA Astrophysics Data System (ADS)

Almerindo, Gizelle I.; Probst, Luiz F. D.; Campos, Carlos E. M.; de Almeida, Rusiene M.; Meneghetti, Simoni M. P.; Meneghetti, Mario R.; Clacens, Jean-Marc; Fajardo, Humberto V.

2011-10-01

A simple method to prepare magnesium oxide catalysts for biodiesel production by transesterification reaction of soybean oil with ethanol is proposed. The method was developed using a metal-chitosan complex. Compared to the commercial oxide, the proposed catalysts displayed higher surface area and basicity values, leading to higher yield in terms of fatty acid ethyl esters (biodiesel). The deactivation of the catalyst due to contact with CO2 and H2O present in the ambient air was verified. It was confirmed that the active catalytic site is a hydrogenocarbonate adsorption site.

The Phase Behavior Effect on the Reaction Engineering of Transesterification Reactions and Reactor Design for Continuous Biodiesel Production

NASA Astrophysics Data System (ADS)

Csernica, Stephen N.

The demand for renewable forms of energy has increased tremendously over the past two decades. Of all the different forms of renewable energy, biodiesel, a liquid fuel, has emerged as one of the more viable possibilities. This is in large part due to the fact that biodiesel can readily be used in modern day diesel engines with nearly no engine modifications. It is commonly blended with conventional petroleum-derived diesel but it can also be used neat. As a result of the continued growth of the industry, there has been a correspondingly large increase in the scientific and technical research conducted on the subject. Much of the research has been conducted on the feasibility of using different types of feedstocks, which generally vary with respect to geographic locale, as well as different types of catalysts. Much of the work of the present study was involved with the investigation of the binary liquid-liquid nature of the system and its effects on the reaction kinetics. Initially, the development of an analytical method for the analysis of the compounds present in transesterification reaction mixtures using high performance liquid chromatography (HPLC) was developed. The use of UV(205 nm) as well as refractive index detection (RID) were shown capable to detect the various different types of components associated with transesterification reactions. Reversed-phase chromatography with isocratic elution was primarily used. Using a unique experimental apparatus enabling the simultaneous analysis of both liquid phases throughout the reaction, an experimental method was developed for measuring the reaction rate under both mass transfer control and reaction control. The transesterification reaction rate under each controlling mechanism was subsequently evaluated and compared. It was determined that the reaction rate is directly proportional to the concentration of triglycerides in the methanol phase. Furthermore, the reaction rate accelerates rapidly as the system transitions from two phases to a single phase, or pseudo-single phase. The transition to a single phase or pseudo-single phase is a function of the methanol content. Regardless, the maximum observed reaction rate occurs at the point of the phase transition, when the concentration of triglycerides in the methanol phase is largest. The phase transition occurs due to the accumulation of the primary product, biodiesel methyl esters. Through various experiments, it was determined that the rate of the triglyceride mass transfer into the methanol phase, as well as the solubility of triglycerides in methanol, increases with increasing methyl ester concentration. Thus, there exists some critical methyl ester concentration which favors the formation of a single or pseudo-single phase system. The effect of the by-product glycerol on the reaction kinetics was also investigated. It was determined that at low methanol to triglyceride molar ratios, glycerol acts to inhibit the reaction rate and limit the overall triglyceride conversion. This occurs because glycerol accumulates in the methanol phase, i.e. the primary reaction volume. When glycerol is at relatively high concentrations within the methanol phase, triglycerides become excluded from the reaction volume. This greatly reduces the reaction rate and limits the overall conversion. As the concentration of methanol is increased, glycerol becomes diluted and the inhibitory effects become dampened. Assuming pseudo-homogeneous phase behavior, a simple kinetic model incorporating the inhibitory effects of glycerol was proposed based on batch reactor data. The kinetic model was primarily used to theoretically compare the performance of different types of continuous flow reactors for continuous biodiesel production. It was determined that the inhibitory effects of glycerol result in the requirement of very large reactor volumes when using continuous stirred tank reactors (CSTR). The reactor volume can be greatly reduced using tubular style plug flow reactors (PFR). Despite this fact, the use of CSTRs is more common than the use of PFRs. This is mostly due to the fact that the two initial reactant phases are relatively immiscible and significant agitation is generally supplied to initiate the reaction. Based on the theoretical results, however, the use of a packed-bed tubular flow reactor was investigated experimentally. A series of two tubular flow reactors was built in the laboratory. The first reactor was of the shell and tube variety and also functioned as a preheater. The second reactor was larger and contained a packed-bed. Two different flow configurations were invested, upflow-upflow and downflow-downflow. It was determined that the downflow-downflow configuration provided significantly better triglyceride conversions that the upflow-upflow configuration.

Trypsin-catalyzed tandem reaction: one-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones by in situ formed acetaldehyde.

PubMed

Xie, Zong-Bo; Wang, Na; Wu, Wan-Xia; Le, Zhang-Gao; Yu, Xiao-Qi

2014-01-20

A simple, mild, one-pot tandem method catalyzed by trypsin was developed for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones by the Biginelli reaction of urea, β-dicarbonyl compounds, and in situ-formed acetaldehyde. Trypsin was found to display dual promiscuous functions to catalyze transesterification and the Biginelli reaction in sequence. Copyright © 2013 Elsevier B.V. All rights reserved.

Optimization of experimental conditions for composite biodiesel production from transesterification of mixed oils of Jatropha and Pongamia

NASA Astrophysics Data System (ADS)

Yogish, H.; Chandrashekara, K.; Pramod Kumar, M. R.

2012-11-01

India is looking at the renewable alternative sources of energy to reduce its dependence on import of crude oil. As India imports 70 % of the crude oil, the country has been greatly affected by increasing cost and uncertainty. Biodiesel fuel derived by the two step acid transesterification of mixed non-edible oils from Jatropha curcas and Pongamia (karanja) can meet the requirements of diesel fuel in the coming years. In the present study, different proportions of Methanol, Sodium hydroxide, variation of Reaction time, Sulfuric acid and Reaction Temperature were adopted in order to optimize the experimental conditions for maximum biodiesel yield. The preliminary studies revealed that biodiesel yield varied widely in the range of 75-95 % using the laboratory scale reactor. The average yield of 95 % was obtained. The fuel and chemical properties of biodiesel, namely kinematic viscosity, specific gravity, density, flash point, fire point, calorific value, pH, acid value, iodine value, sulfur content, water content, glycerin content and sulfated ash values were found to be within the limits suggested by Bureau of Indian Standards (BIS 15607: 2005). The optimum combination of Methanol, Sodium hydroxide, Sulfuric acid, Reaction Time and Reaction Temperature are established.

(Trans)esterification of mannose catalyzed by lipase B from Candida antarctica in an improved reaction medium using co-solvents and molecular sieve.

PubMed

Nott, Katherine; Brognaux, Alison; Richard, Gaëtan; Laurent, Pascal; Favrelle, Audrey; Jérôme, Christine; Blecker, Christophe; Wathelet, Jean-Paul; Paquot, Michel; Deleu, Magali

2012-01-01

Four co-solvents (dimethylformamide [DMF], formamide, dimethyl sulfoxide [DMSO], and pyridine) were tested with tert-butanol (tBut) to optimize the initial rate (v₀) and yield of mannosyl myristate synthesis by esterification catalyzed by immobilized lipase B from Candida antarctica. Ten percent by volume of DMSO resulted in the best improvement of v₀ and 48-hr yield (respectively 115% and 13% relative gain compared to pure tBut). Use of molecular sieve (5% w/v) enhances the 48-hr yield (55% in tBut/DMSO [9:1, v/v]). Transesterification in tBut/DMSO (9:1, v/v) with vinyl myristate leads to further improvement of v₀ and 48-hr yield: a relative gain of 85% and 65%, respectively, without sieve and 25% and 10%, respectively, with sieve, compared to esterification. No difference in v₀ and 48-hr yield is observed when transesterification is carried out with or without sieve.

Transesterification of PHA to oligomers covalently bonded with (bio)active compounds containing either carboxyl or hydroxyl functionalities.

PubMed

Kwiecień, Iwona; Radecka, Iza; Kowalczuk, Marek; Adamus, Grażyna

2015-01-01

This manuscript presents the synthesis and structural characterisation of novel biodegradable polymeric controlled-release systems of pesticides with potentially higher resistance to weather conditions in comparison to conventional forms of pesticides. Two methods for the preparation of pesticide-oligomer conjugates using the transesterification reaction were developed. The first method of obtaining conjugates, which consist of bioactive compounds with the carboxyl group and polyhydroxyalkanoates (PHAs) oligomers, is "one-pot" transesterification. In the second method, conjugates of bioactive compounds with hydroxyl group and polyhydroxyalkanoates oligomers were obtained in two-step method, through cyclic poly(3-hydroxybutyrate) oligomers. The obtained pesticide-PHA conjugates were comprehensively characterised using GPC, 1H NMR and mass spectrometry techniques. The structural characterisation of the obtained products at the molecular level with the aid of mass spectrometry confirmed that both of the synthetic strategies employed led to the formation of conjugates in which selected pesticides were covalently bonded to PHA oligomers via a hydrolysable ester bond.

Transesterification of waste cooking oil by an organic solvent-tolerant alkaline lipase from Streptomyces sp. CS273.

PubMed

Mander, Poonam; Yoo, Hah-Young; Kim, Seung Wook; Choi, Yun Hee; Cho, Seung Sik; Yoo, Jin Cheol

2014-02-01

The aim of this present study was to produce a microbial enzyme that can potentially be utilized for the enzymatic transesterification of waste cooking oil. To that end, an extracellular lipase was isolated and purified from the culture broth of Streptomyces sp. CS273. The molecular mass of purified lipase was estimated to be 36.55 kDa by SDS PAGE. The optimum lipolytic activity was obtained at alkaline pH 8.0 to 8.5 and temperature 40 °C, while the enzyme was stable in the pH range 7.0 ∼ 9.0 and at temperature ≤40 °C. The lipase showed highest hydrolytic activity towards p-nitrophenyl myristate (C14). The lipase activity was enhanced by several salts and detergents including NaCl, MnSo₄, and deoxy cholic acid, while phenylmethylsulfonyl fluoride at concentration 10 mM inhibited the activity. The lipase showed tolerance towards different organic solvents including ethanol and methanol which are commonly used in transesterification reactions to displace alcohol from triglycerides (ester) contained in renewable resources to yield fatty acid alkyl esters known as biodiesel. Applicability of the lipase in transesterification of waste cooking oil was confirmed by gas chromatography mass spectrometry analysis.

Biodiesel Fuel Quality and the ASTM Biodiesel Standard

USDA-ARS?s Scientific Manuscript database

Biodiesel is usually produced from vegetable oils, animal fats and used cooking oils with alternative feedstocks such as algae receiving increasing interest. The transesterification reaction which produces biodiesel also produces glycerol and proceeds stepwise via mono- and diacylglycerol intermedi...

Biodiesel Fuel Quality and the ASTM Standard

USDA-ARS?s Scientific Manuscript database

Biodiesel is usually produced from vegetable oils, animal fats and used cooking oils with alternative feedstocks such as algae receiving increasing interest. The transesterification reaction which produces biodiesel also produces glycerol and proceeds stepwise via mono- and diacylglycerol intermedia...

Glymes as benign co-solvents for CaO-catalyzed transesterification of soybean oil to biodiesel.

PubMed

Tang, Shaokun; Zhao, Hua; Song, Zhiyan; Olubajo, Olarongbe

2013-07-01

The base (such as CaO)-catalyzed heterogeneous preparation of biodiesel encounters a number of obstacles including the need for CaO pretreatment and the reactions being incomplete (typically 90-95% yields). In this study, a number of glymes were investigated as benign solvents for the CaO-catalyzed transesterification of soybean oil into biodiesel with a high substrate loading (typically soybean oil >50% v/v). The triglyceride-dissolving capability of glymes led to a much faster reaction rate (>98% conversions in 4h) than in methanol alone (typically 24h) and minimized the saponification reaction when catalyzed by anhydrous CaO or commercial lime without pre-activation. The use of glyme (e.g. P2) as co-solvent also activates commercial lime to become an effective catalyst without calcination pretreatment. The SEM images suggest a dissolution-agglomeration process of CaO surface in the presence of P2, which could remove the CaCO3 and Ca(OH)2 layer coated on the surface of lime. Copyright © 2013 Elsevier Ltd. All rights reserved.

The Production of Biodiesel and Bio-kerosene from Coconut Oil Using Microwave Assisted Reaction

NASA Astrophysics Data System (ADS)

SAIFUDDIN, N.; SITI FAZLILI, A.; KUMARAN, P.; PEI-JUA, N.; PRIATHASHINI, P.

2016-03-01

Biofuels including biodiesel, an alternative fuel, is renewable, environmentally friendly, non-toxic and low emissions. The raw material used in this work was coconut oil, which contained saturated fatty acids about 90% with high percentage of medium chain (C8-C12), especially lauric acid and myristic acid. The purpose of this research was to study the effect of power and NaOH catalyst in transesterification assisted by microwave for production of biofuels (biodiesel and bio-kerosene) derived from coconut oil. The reaction was performed with oil and methanol using mole ratio of 1:6, catalyst concentration of 0.6% with microwave power at 100W, 180W, 300W, 450W, 600W, and 850W. The reaction time was set at of 3, 5, 7, 10 and 15 min. The results showed that microwave could accelerate the transesterification process to produce biodiesel and bio-kerosene using NaOH catalyst. The highest yield of biodiesel was 97.17 %, or 99.05 % conversion at 5 min and 100W microwave power. Meanwhile, the bio-kerosene obtained was 65% after distillation.

Evaluation of Biodiesel Production, Engine Performance, and Emissions

NASA Astrophysics Data System (ADS)

Gürü, Metin; Keskïn, Ali

2016-08-01

Nowadays, to decrease environmental pollution and dependence on fossil-based fuels, research on alternative renewable energy sources has been increasing. One such renewable energy source is biodiesel, which is used as an alternative fuel for diesel engines. Biodiesel is renewable, nontoxic, biodegradable, and environmentally friendly. Biodiesel is domestically produced from vegetable oil (edible or nonedible), animal fat, and used cooking oils. In the biodiesel production process, oil or fat undergoes transesterification reaction through use of simple alcohols such as methanol, ethanol, propanol, butanol, etc. Use of methanol is most feasible because of its low cost, and physical and chemical advantages. Acid catalysis, alkali catalysis, and enzyme catalysis are usually used to improve the reaction rate and yield. Glycerol is a byproduct of the reaction and can be used as an industrial raw material. In this study, biodiesel production methods (direct use, pyrolysis, microemulsion, transesterification, supercritical processes, ultrasound- assisted, and microwave-assisted) and types of catalyst (homogeneous, heterogeneous, and enzyme) have been evaluated and compared. In addition, the effects of biodiesel and its blends on diesel engine performance and exhaust emissions are described and reviewed.

Tailoring the Synergistic Bronsted-Lewis acidic effects in Heteropolyacid catalysts: Applied in Esterification and Transesterification Reactions.

PubMed

Tao, Meilin; Xue, Lifang; Sun, Zhong; Wang, Shengtian; Wang, Xiaohong; Shi, Junyou

2015-09-16

In order to investigate the influences of Lewis metals on acidic properties and catalytic activities, a series of Keggin heteropolyacid (HPA) catalysts, HnPW11MO39 (M = Ti(IV), Cu(II), Al(III), Sn(IV), Fe(III), Cr(III), Zr(IV) and Zn(II); for Ti and Zr, the number of oxygen is 40), were prepared and applied in the esterification and transesterification reactions. Only those cations with moderate Lewis acidity had a higher impact. Ti Substituted HPA, H5PW11TiO40, posse lower acid content compared with Ti(x)H(3-4x)PW12O40 (Ti partial exchanged protons in saturated H3PW12O40), which demonstrated that the Lewis metal as an addenda atom (H5PW11TiO40) was less efficient than those as counter cations (Ti(x)H(3-4x)PW12O40). On the other hand, the highest conversion reached 92.2% in transesterification and 97.4% in esterification. Meanwhile, a good result was achieved by H5PW11TiO40 in which the total selectivity of DAG and TGA was 96.7%. In addition, calcination treatment to H5PW11TiO40 make it insoluble in water which resulted in a heterogeneous catalyst feasible for reuse.

Tailoring the Synergistic Bronsted-Lewis acidic effects in Heteropolyacid catalysts: Applied in Esterification and Transesterification Reactions

PubMed Central

Tao, Meilin; Xue, Lifang; Sun, Zhong; Wang, Shengtian; Wang, Xiaohong; Shi, Junyou

2015-01-01

In order to investigate the influences of Lewis metals on acidic properties and catalytic activities, a series of Keggin heteropolyacid (HPA) catalysts, HnPW11MO39 (M = TiIV, CuII, AlIII, SnIV, FeIII, CrIII, ZrIV and ZnII; for Ti and Zr, the number of oxygen is 40), were prepared and applied in the esterification and transesterification reactions. Only those cations with moderate Lewis acidity had a higher impact. Ti Substituted HPA, H5PW11TiO40, posse lower acid content compared with TixH3−4xPW12O40 (Ti partial exchanged protons in saturated H3PW12O40), which demonstrated that the Lewis metal as an addenda atom (H5PW11TiO40) was less efficient than those as counter cations (TixH3−4xPW12O40). On the other hand, the highest conversion reached 92.2% in transesterification and 97.4% in esterification. Meanwhile, a good result was achieved by H5PW11TiO40 in which the total selectivity of DAG and TGA was 96.7%. In addition, calcination treatment to H5PW11TiO40 make it insoluble in water which resulted in a heterogeneous catalyst feasible for reuse. PMID:26374393

Tailoring the Synergistic Bronsted-Lewis acidic effects in Heteropolyacid catalysts: Applied in Esterification and Transesterification Reactions

NASA Astrophysics Data System (ADS)

Tao, Meilin; Xue, Lifang; Sun, Zhong; Wang, Shengtian; Wang, Xiaohong; Shi, Junyou

2015-09-01

In order to investigate the influences of Lewis metals on acidic properties and catalytic activities, a series of Keggin heteropolyacid (HPA) catalysts, HnPW11MO39 (M = TiIV, CuII, AlIII, SnIV, FeIII, CrIII, ZrIV and ZnII; for Ti and Zr, the number of oxygen is 40), were prepared and applied in the esterification and transesterification reactions. Only those cations with moderate Lewis acidity had a higher impact. Ti Substituted HPA, H5PW11TiO40, posse lower acid content compared with TixH3-4xPW12O40 (Ti partial exchanged protons in saturated H3PW12O40), which demonstrated that the Lewis metal as an addenda atom (H5PW11TiO40) was less efficient than those as counter cations (TixH3-4xPW12O40). On the other hand, the highest conversion reached 92.2% in transesterification and 97.4% in esterification. Meanwhile, a good result was achieved by H5PW11TiO40 in which the total selectivity of DAG and TGA was 96.7%. In addition, calcination treatment to H5PW11TiO40 make it insoluble in water which resulted in a heterogeneous catalyst feasible for reuse.

Green Synthesis of a Fluorescent Natural Product

ERIC Educational Resources Information Center

Young, Douglas M.; Welker, Jacob J. C.; Doxsee, Kenneth M.

2011-01-01

Synthesis of 4-methylumbelliferone via the acid-catalyzed Pechmann condensation introduces students to several types of organic reactions: transesterification, electrophilic aromatic substitution, and alcohol dehydration. Performed with a recyclable, solid catalyst and under solvent-free conditions, the experiment illustrates many of the…

Analysis of biodiesel

USDA-ARS?s Scientific Manuscript database

Biodiesel is a biogenic alternative to diesel fuel derived from petroleum. It is produced by a transesterification reaction from materials consisting largely of triacylglycerols such as vegetable and other plant oils, animal fats, used cooking oils, and “alternative” feedstocks such as algal oils. T...

Solid-phase organic synthesis of difluoroalkyl entities using a novel fluorinating cleavage strategy: part 2. Synthesis of three small gem-difluorinated compound libraries using a dithiane linker.

PubMed

Wiehn, Matthias S; Fürniss, Daniel; Bräse, Stefan

2009-01-01

Three small compound biaryl libraries featuring a novel fluorinating cleavage strategy for preparation of a difluoromethyl group were assembled on solid supports. The average reaction yield per step was up to 96% in a synthetic sequence over five to six steps. Key features were Suzuki coupling reactions, transesterification with potassium cyanide and amidation reaction with trimethyl aluminum on solid supports.

Use of Ceramic Material (cement Clinker) for the Production of Biodiesel

NASA Astrophysics Data System (ADS)

Soni, Sunny; Agarwal, Madhu

Biodiesel is a renewable liquid fuel made from natural, renewable biological sources such as edible and non edible oils. Over the last years, biodiesel has gained more market due to its benefits and because it appears as the natural substitute for diesel. Reasons for growing interest in biodiesel include its potential for reducing noxious emissions, potential contributions to rural economic development, as an additional demand center for agricultural commodities, and as a way to reduce reliance on foreign oil. Biodiesel was prepared from soybean oil by transesterification with methanol in the presence of cement clinker. Cement clinker was examined as a catalyst for a conversion of soybean oil to fatty acid methyl esters (FAMEs). It can be a promising heterogeneous catalyst for the production of biodiesel fuels from soybean oil because of high activity in the conversion and no leaching in the transesterification reaction. The reaction conditions were optimized. A study for optimizing the reaction parameters such as the reaction temperature, and reaction time, was carried out. The catalyst cement clinker composition was characterized by XRF. The results demonstrate that the cement clinker shows high catalytic performance & it was found that the yield of biodiesel can reach as high as 84.52% after 1 h reaction at 65°C, with a 6:1 molar ratio of methanol to oil, 21 wt% KOH/cement clinker as catalyst.

Acetyl diacylglycerol produced by modified camelina (Camelina sativa)

USDA-ARS?s Scientific Manuscript database

Acetyl diacylglyceride (Acetyl-TAG) is a component of a commercial product, ACETEM, manufactured by transesterification reaction of triglycerides, glycerol, and triacetin or by acetylation of mono- and diglycerides with acetic acid anhydride. ACETEM is commonly used as foaming agents and coatings in...

Georges Chavanne and the first biodiesel

USDA-ARS?s Scientific Manuscript database

This article discusses the first production and use of a fuel around 1937 now called biodiesel, which is obtained from a vegetable or plant oil through a straightforward chemical reaction called transesterification. Biodiesel has become an alternative or supplement to conventional diesel fuel derive...

Lipids for Health and Beauty: Enzymatic Modification of Vegetable Oil

USDA-ARS?s Scientific Manuscript database

Ferulic acid has been extensively investigated for its potential as a cosmetic and pharmaceutical agent. We have prepared lipophilic derivatives of ferulic acid by a simple, enzyme-catalyzed transesterification reaction of ethyl ferulate with vegetable oils. Immobilized Candida antarctica lipase B...

Transesterification of diethyl oxalate with phenol over sol-gel MoO(3)/TiO(2) catalysts.

PubMed

Kotbagi, Trupti; Nguyen, Duy Luan; Lancelot, Christine; Lamonier, Carole; Thavornprasert, Kaew-Arpha; Wenli, Zhu; Capron, Mickaël; Jalowiecki-Duhamel, Louise; Umbarkar, Shubhangi; Dongare, Mohan; Dumeignil, Franck

2012-08-01

The transesterification of diethyl oxalate (DEO) with phenol to form diphenyl oxalate (DPO) has been carried out in the liquid phase over very efficient MoO(3)/TiO(2) solid-acid sol-gel catalysts. A selectivity of 100 % with a remarkable maximum yield of 88 % were obtained, which opens the route to downstream phosgene-free processes for the synthesis of polycarbonates. Interpretation of the results of various acidity measurements (NH(3) and pyridine desorption, methanol oxidation as a probe reaction) allowed us to identify the catalytic sites as Lewis acid sites. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hierarchical Na-doped cubic ZrO{sub 2} synthesis by a simple hydrothermal route and its application in biodiesel production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lara-García, Hugo A.; Romero-Ibarra, Issis C.; Pfeiffer, Heriberto, E-mail: pfeiffer@iim.unam.mx

Hierarchical growth of cubic ZrO{sub 2} phase was successfully synthesized via a simple hydrothermal process in the presence of different surfactants (cationic, non-ionic and anionic) and sodium hydroxide. The structural and microstructural characterizations of different ZrO{sub 2} powders were performed using various techniques, such as X-ray diffraction, transmission electron microscopy, N{sub 2} adsorption–desorption, scanning electron microscopy and infrared. Results indicated that sodium addition stabilized the cubic ZrO{sub 2} phase by a Na-doping process, independently of the surfactant used. In contrast, microstructural characteristics varied as a function of the surfactant and sodium presence. In addition, water vapor (H{sub 2}O) and carbonmore » dioxide (CO{sub 2}) sorption properties were evaluated on ZrO{sub 2} samples. Results evidenced that sample surface reactivity changed as a function of the sodium content. Finally, this surface reactivity was evaluated on the biodiesel transesterification reaction using the different synthesized samples, obtaining yields of 93%. - Graphical abstract: Hierarchical growth of cubic Na-ZrO{sub 2} phase was synthesized by hydrothermal processes in the presence of surfactants and sodium. Sodium addition stabilized the cubic phase by a Na-doping process, while the microstructural characteristics varied with surfactants. Finally, this surface reactivity was evaluated on the biodiesel transesterification reaction. - Highlights: • Cubic-ZrO{sub 2} phase was synthesized via a simple hydrothermal process. • ZrO{sub 2} structure and microstructures changed as a function of the surfactant. • Cubic-ZrO{sub 2} phase was evaluated on the biodiesel transesterification reaction.« less

Bifunctional heterogeneous catalysts from oil palm empty fruit bunches ash and alum for biodiesel synthesis simultaneously

NASA Astrophysics Data System (ADS)

Astar, Ismail; Usman, Thamrin; Wahyuni, Nelly; Rudiyansyah, Alimuddin, Andi Hairil

2017-03-01

Free fatty acids (FFA) contained in crude palm oil (CPO) and sludge oil has been used as the base material of biodiesel with the aid of a catalyst in the transesterification and esterification reactions. This study aims to synthesize and characterize bifunctional catalysts were synthesized from the ashes of palm empty fruit bunches (EFB) and alum based on the analysis of XRD, XRF and acidity test. Bifunctional catalyst obtained was used as a catalyst to production of biodiesel with different levels of FFA. The optimum ratio alum added was 0.2 mol at 3 hours of reaction time and 3% of catalyst by the FFA samples were used 67,40%. The catalyst with optimum alum mole variations subsequently used on samples with varying levels of FFA, namely 1.29%, 4.98%, 29.21%, 67.40% and 74.47%. Optimum conversion of methyl ester in the esterification reaction occurs in the sample with 67.40% FFA content, which reached 86.17%, while the conversion of methyl ester transesterification process optimum amounted to 45.70% in the samples with 4.98% FFA content. Methyl ester produced has a refractive index of 1.448 (29.8 ° C), density of 0.883 g / mL (25 °C) and a viscosity of 8.933 cSt (25 ° C). The results of GC-MS analysis showed that the main composition of methyl ester result of esterification of sludge oil methyl palmitate (36.84%), while the CPO transesterification shows the main composition of methyl ester is methyl oleic (38.87%). Based on the research results, the catalyst synthesized from alum and EFB ash can be used as a Bifunctional catalysts for biodiesel synthesis.

Effect of reactive agent and transesterification catalyst on properties of PLA/PBAT blends

NASA Astrophysics Data System (ADS)

Pitivut, S.; Suttiruengwong, S.; Seadan, M.

2015-07-01

This research aimed to study the properties of poly (lactic acid) (PLA)/poly (butylene adipate-co-terephthalate) (PBAT) blends with two different reactive systems: free radical reaction through peroxide (Perkadox) and transesterification catalyst (tetrabutyl titanate; TBT). Two blends composed of PLA as a matrix phase with the composition of 80 and 70 percent by weight. PLA/PBAT blends with Perkadox were prepared in twin screw extruder, whereas PLA/PBAT blends with TBT were prepared in an internal mixer. The morphology of the blends was investigated by scanning electron microscope (SEM). Tensile and impact testingsof the blends were reported. In case of the blends with Perkadox, SEM micrographs revealed that the size of particles was substantially reduced when adding more Perkadox. Young's modulus and the tensile strength of all blend ratios were insignificantly changed, whereas the elongation at break was decreased when compared to non-reactive blends due to the possible crosslinking reaction as observed from melt flow index (MFI) values. When adding Perkadox, the impact strength of PLA/PBAT (80/20) remained almost unchanged. However, the impact strength of PLA/PBAT (70/30) was enhanced, increasing to 110% for 0.05 phr Perkadox. In case of the blends with TBT, SEM micrographs showed the decrease in the particle size of PBAT phase when adding TBT. Young's modulus and the tensile strength of all blend ratios were not different, but the elongation at break was improved when adding TBT owing to the transesterification reaction. For PLA/PBAT (80/20), the elongation at break was increased by 39%, whereas the elongation at break was increased by 15% for PLA/PLA (70/30). The impact strength of all blend ratios unaffected.

CFD simulation of fatty acid methyl ester production in bubble column reactor

NASA Astrophysics Data System (ADS)

Salleh, N. S. Mohd; Nasir, N. F.

2017-09-01

Non-catalytic transesterification is one of the method that was used to produce the fatty acid methyl ester (FAME) by blowing superheated methanol bubbles continuously into the vegetable oil without using any catalyst. This research aimed to simulate the production of FAME from palm oil in a bubble column reactor. Computational Fluid Dynamic (CFD) simulation was used to predict the distribution of fatty acid methyl ester and other product in the reactor. The fluid flow and component of concentration along the reaction time was investigated and the effects of reaction temperature (523 K and 563 K) on the non-catalytic transesterification process has been examined. The study was carried out using ANSYS CFX 17.1. The finding from the study shows that increasing the temperature leads to higher amount of fatty acid methyl ester can be produced in shorter time. On the other hand, concentration of the component such as triglyceride (TG), glycerol (GL) and fatty acid methyl ester (FAME) can be known when reaching the optimum condition.

Biodiesel Production using Heterogeneous Catalyst in CSTR: Sensitivity Analysis and Optimization

NASA Astrophysics Data System (ADS)

Keong, L. S.; Patle, D. S.; Shukor, S. R.; Ahmad, Z.

2016-03-01

Biodiesel as a renewable fuel has emerged as a potential replacement for petroleum-based diesels. Heterogeneous catalyst has become the focus of researches in biodiesel production with the intention to overcome problems associated with homogeneous catalyzed processes. The simulation of heterogeneous catalyzed biodiesel production has not been thoroughly studied. Hence, a simulation of carbon-based solid acid catalyzed biodiesel production from waste oil with high FFA content (50 weight%) was developed in the present work to study the feasibility and potential of the simulated process. The simulated process produces biodiesel through simultaneous transesterification and esterification with the consideration of reaction kinetics. The developed simulation is feasible and capable to produce 2.81kmol/hr of FAME meeting the international standard (EN 14214). Yields of 68.61% and 97.19% are achieved for transesterification and esterification respectively. Sensitivity analyses of FFA composition in waste oil, methanol to oil ratio, reactor pressure and temperature towards FAME yield from both reactions were carried out. Optimization of reactor temperature was done to maximize FAME products.

Soybean biodiesel methyl esters, free glycerin and acid number quantification by 1H nuclear magnetic resonance spectroscopy.

PubMed

Coral, Natasha; Rodrigues, Elizabeth; Rumjanek, Victor; Zamian, José Roberto; da Rocha Filho, Geraldo Narciso; da Costa, Carlos Emmerson Ferreira

2013-02-01

Production of alternative fuels, such as biodiesel, from transesterification of vegetable oil driven by heterogeneous catalysts is a promising alternative to fossil diesel. However, achieving a successful substitution for a new renewable fuel depends on several quality parameters. (1)H NMR spectroscopy was used to determine the amount of methyl esters, free glycerin and acid number in the transesterification of soybean oil with methanol in the presence of hydrotalcite-type catalyst to produce biodiesel. Reaction parameters, such as temperature and time, were used to evaluate soybean oil methyl esters rate conversion. Temperatures of 100 to 180 °C and times of 20 to 240 min were tested on a 1 : 12 molar ratio soybean oil/methanol reaction. At 180 °C/240 min conditions, a rate of 94.5 wt% of methyl esters was obtained, where free glycerin and free fatty acids were not detected. Copyright © 2012 John Wiley & Sons, Ltd.

Wet in situ transesterification of spent coffee grounds with supercritical methanol for the production of biodiesel.

PubMed

Son, Jeesung; Kim, Bora; Park, Jeongseok; Yang, Jeongwoo; Lee, Jae W

2018-07-01

This work introduces biodiesel production from wet spent coffee grounds (SCGs) with supercritical methanol without any pre-drying process. Supercritical methanol and subcritical water effectively produced biodiesel via in situ transesterification by inducing more porous SCG and enhancing the efficiency of lipid extraction and conversion. It was also found that space loading was one of the critical factors for biodiesel production. An optimal biodiesel yield of 10.17 wt% of dry SCG mass (86.33 w/w% of esterifiable lipids in SCG) was obtained at reaction conditions of 270 °C, 90 bars, methanol to wet SCG ratio 5:1, space loading 58.4 ml/g and reaction time 20 min. Direct use of wet SCG waste as feedstock for supercritical biodiesel production eliminates the conventional dying process and the need of catalyst and also reduces environmental problems caused by landfill accumulation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Encapsulated heterogeneous base catalysts onto SBA-15 nanoporous material as highly active catalysts in the transesterification of sunflower oil to biodiesel

NASA Astrophysics Data System (ADS)

Albayati, Talib M.; Doyle, Aidan M.

2015-02-01

Alkali metals and their hydroxides, Na, NaOH, Li, and LiOH, were encapsulated onto SBA-15 nanoporous material as highly active catalysts for the production of biodiesel fuel from sunflower oil. The incipient wetness impregnation method was adopted for the prepared catalysts. The characterization properties of the catalysts and unmodified SBA-15 were determined using X-ray diffraction, scanning electron microscopy, EDAX, nitrogen adsorption-desorption porosimetry (Brunauer-Emmett-Teller), Fourier-transform infrared spectroscopy, and transmission electron microscopy. Transesterification was conducted in a batch reactor at atmospheric pressure and 65 °C. The catalysts were highly active with yields of fatty acid methyl ester (FAME) in the range 96-99 %. Na/SBA-15 catalyst was reused for seven consecutive cycles under the same reaction conditions; the yield to FAME on the final cycle was 96 %. This study shows that the alkali metals and their hydroxides supported on SBA-15-based catalyst are excellent catalysts for the biodiesel reaction.

Synthesis of biodiesel from pongamia oil using heterogeneous ion-exchange resin catalyst.

PubMed

Jaya, N; Selvan, B Karpanai; Vennison, S John

2015-11-01

Biodiesel is a clean-burning renewable substitute fuel for petroleum. Biodiesel could be effectively produced by transesterification reaction of triglycerides of vegetable oils with short-chain alcohols in the presence of homogeneous or heterogeneous catalysts. Conventionally, biodiesel manufacturing processes employ strong acids or bases as catalysts. But, separation of the catalyst and the by-product glycerol from the product ester is too expensive to justify the product use as an automobile fuel. Hence heterogeneous catalysts are preferred. In this study, transesterification of pongamia oil with ethanol was performed using a solid ion-exchange resin catalyst. It is a macro porous strongly basic anion exchange resin. The process parameters affecting the ethyl ester yield were investigated. The reaction conditions were optimized for the maximum yield of fatty acid ethyl ester (FAEE) of pongamia oil. The properties of FAEE were compared with accepted standards of biodiesel. Engine performance was also studied with pongamia oil diesel blend and engine emission characteristics were observed. Copyright © 2015 Elsevier Inc. All rights reserved.

Electro-catalytic biodiesel production from canola oil in methanolic and ethanolic solutions with low cost stainless steel and hybrid ion-exchange resin grafted electrodes

NASA Astrophysics Data System (ADS)

Allioux, Francois-Marie; Holland, Brendan J.; Kong, Lingxue; Dumée, Ludovic F.

2017-07-01

Biodiesel is a growing alternative to petroleum fuels and is produced by the catalysed transesterification of fats in presence of an alcohol base. Transesterification processes using homogeneous catalysts are considered to be amongst the most efficient methods but rely on the feedstock quality and low water content in order to avoid undesirable saponification reactions. In this work, the electro-catalytic conversion of canola oil to biodiesel in a 1% aqueous methanolic and ethanolic reaction mixture was performed without the addition of external catalyst or co-solvent. An inexpensive stainless steel electrode and a hybrid stainless steel electrode coated with an ion-exchange resin catalyst were used as cathode materials while the anode was composed of a plain carbon paper. The cell voltages were varied from 10 to 40 V and the reaction temperature maintained at 20 or 40°C. The canola oil conversion rates were found to be superior at 40°C without saponification reactions for cell voltages below 30 V. The conversion rates were as high as 87% for the hybrid electrode and 81% for the plain stainless steel electrode. This work could inspire new process development for the conversion of high water content feedstock for the production of second-generation biodiesel.

Ultrasonic-assisted production of biodiesel from transesterification of palm oil over ostrich eggshell-derived CaO catalysts.

PubMed

Chen, Guanyi; Shan, Rui; Shi, Jiafu; Yan, Beibei

2014-11-01

In this study, waste ostrich eggshell-derived calcium oxide (denoted as CaO(OE)) particles were synthesized and explored as cost-effective catalysts for the ultrasonic-assisted transesterification of palm oil. The physicochemical properties of the resultant catalysts were characterized by XRD, N2 adsorption, XRF and Hammett indicator, while the catalytic activity was evaluated through transesterification of palm oil with methanol under ultrasonic conditions. More specifically, the CaO(OE) showed comparable catalytic activity to the one derived from commercial calcium carbonate (denoted as CaO(Lab)). Moreover, under ultrasonic conditions, the catalytic activity of CaO(OE) could be enhanced significantly. The maximum yield of fatty acid methyl esters could reach 92.7% under the optimal condition of reaction time of 60 min with ultrasonic power of 60% (120 W), methanol-to-oil ratio of 9:1, and catalyst loading of 8 wt.%. The results indicated that the CaO(OE) catalysts showed good catalytic performance and reusability, and may potentially reduce the cost of biodiesel production. Copyright © 2014 Elsevier Ltd. All rights reserved.

One-step production of biodiesel from rice bran oil catalyzed by chlorosulfonic acid modified zirconia via simultaneous esterification and transesterification.

PubMed

Zhang, Yue; Wong, Wing-Tak; Yung, Ka-Fu

2013-11-01

Due to the high content (25-50%) of free fatty acid (FFA), crude rice bran oil usually requires a two steps conversion or one step conversion with very harsh condition for simultaneous esterification and transesterification. In this study, chlorosulfonic acid modified zirconia (HClSO3-ZrO2) with strong acidity and durability is prepared and it shows excellent catalytic activity toward simultaneous esterification and transesterification. Under a relative low reaction temperature of 120 °C, HClSO3-ZrO2 catalyzes a complete conversion of simulated crude rice bran oil (refined oil with 40 wt% FFA) into biodiesel and the conversion yield keep at above 92% for at least three cycles. Further investigation on the tolerance towards FFA and water reveals that it maintains high activity even with the presence of 40 wt% FFA and 3 wt% water. It shows that HClSO3-ZrO2 is a robust and durable catalyst which shows high potential to be commercial catalyst for biodiesel production from low grade feedstock. Copyright © 2013 Elsevier Ltd. All rights reserved.

Cogeneration of biodiesel and nontoxic rapeseed meal from rapeseed through in-situ alkaline transesterification.

PubMed

Qian, Junfeng; Yang, Qiuhui; Sun, Fuan; He, Mingyang; Chen, Qun; Yun, Zhi; Qin, Lizhen

2013-01-01

In-situ alkaline transesterification of rapeseed oil with methanol for the production of biodiesel and nontoxic rapeseed meal was carried out. Water removal from milled rapeseed by methanol washing was more effective than vacuum drying. The conversion rate of rapeseed oil into FAME was 92%, FAME mass was 8.81 g, glucosinolates content in remaining rapeseed meal was 0.12% by methanol washing, while by vacuum drying the values were 46%, 4.44 g, 0.58%, respectively. In the presence of 0.10 mol/L NaOH in methanol, with methanol/oil molar ratio of 180:1 and a 3h reaction at 40 °C, a conversion rate of 98% was achieved, and the glucosinolates content was reduce to 0.07%, a value which below the GB/T 22514-2008 standard in China. Thus the rapeseed meal can be used as a source of protein in animal feed. The FAME prepared through in-situ alkaline transesterification met the ASTM specifications for biodiesel. Copyright © 2012 Elsevier Ltd. All rights reserved.

Biodiesel from Seeds: An Experiment for Organic Chemistry

ERIC Educational Resources Information Center

Goldstein, Steven W.

2014-01-01

Plants can store the chemical energy required by their developing offspring in the form of triglycerides. These lipids can be isolated from seeds and then converted into biodiesel through a transesterification reaction. This second-year undergraduate organic chemistry laboratory experiment exemplifies the conversion of an agricultural energy…

Direct conversion of wet algae to crude biodiesel under supercritical ethanol conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reddy, Harvind K.; Muppaneni, Tapaswy; Patil, Prafulla D.

This paper presents a single-step, environmentally friendly approach for the direct conversion of wet algae to crude biodiesel under supercritical ethanol conditions. Ethanol was used for the simultaneous extraction and transesterification of lipids in algae to produce fatty acid ethyl esters at supercritical conditions. In this work the effects of process parameters dry algae to ethanol (wt./vol.) ratio (1:6-1:15), reaction temperature (245-270 C), and reaction time (2-30 min.) on the yield of fatty acid ethyl esters (FAEE) were studied. 67% conversion was achieved at 265 C and 20 min of reaction time. The calorific value of a purified biodiesel samplemore » produced at optimum conditions was measured to be 43 MJ/kg, which is higher than that of fatty acid methyl esters produced from the same biomass. The purified fatty acid ethyl esters were analyzed using GC-MS and FTIR. TGA analysis of algal biomass and purified FAEE was presented along with TEM images of the biomass captured before and after supercritical ethanol transesterification. This green conversion process has the potential to provide an energy-efficient and economical route for the production of renewable biodiesel production.« less

Synthesis of solid catalyst from egg shell waste and clay for biodiesel production

NASA Astrophysics Data System (ADS)

Setiadji, S.; Sundari, C. D. D.; Munir, M.; Fitriyah, S.

2018-05-01

Until now, energy consumption in Indonesia is almost entirely fulfilled by fossil fuels, thus, its availability will be limited and continue to decrease. To overcome these problems, development and utilization of renewable energy are required, one of which is biodiesel. Biodiesel can be prepared through transesterification reaction of vegetable oil using catalyst. In this research, a solid catalyst for biodiesel synthesis was prepared from chicken egg shell waste and clay. Optimization of the transesterification reaction of coconut (Cocos nucifera) oil to obtain biodiesel was also carried out. The formation of CaO/kaolin catalyst was confirmed based on the results of XRD and SEM-EDS. This catalyst is suitable for biodiesel synthesis from vegetable oils with lower FFA (free fatty acid) levels, i.e. coconut oil with FFA level of 0.18%. Based on FTIR result, FFA level and flame tests, it was found that biodiesel was successfully formed. Synthesis of biodiesel has the optimum conditions on reaction time of 16 hours and temperature of 64 °C, with oil: methanol ratio of 1: 15 and CaO/kaolin catalyst concentration of 0.9% in a reflux system.

Solid Catalyst Nanoparticles derived from Oil-Palm Empty Fruit Bunches (OP-EFB) as a Renewable Catalyst for Biodiesel Production

NASA Astrophysics Data System (ADS)

Husin, H.; Asnawi, T. M.; Firdaus, A.; Husaini, H.; Ibrahim, I.; Hasfita, F.

2018-05-01

Solid nanocatalyst derived from oil-palm empty fruit bunches (OP-EFB) fiber was successfully synthesized and its application for biodiesel production was investigated. The OPEFB was treated by burning, milling and heating methods to generate ashes in a nanoparticle size. The nanoparticle palm-bunch ash was characterized by scanning electron microscopy (SEM) and x-ray diffraction (XRD). The effects of the calcination temperature and catalyst amounts for transesterification reactions were investigated. XRD analysis of palm bunch ash exhibited that the highest composition of peaks characteristic were potassium oxide (K2O). SEM analysis showed that the nano palm bunch ash have a particle size ranging of 150-400 nm. The highest conversion of palm-oil to biodiesel reach to 97.90% was observed by using of palm bunch ash nanocatalyst which heated at 600°C, 3 h reaction time and 1% catalyst amount. Reusability of palm bunch ash catalysts was also examined. It was found that of its high active sites, reusable solid catalyst was obtained by just heating of palm bunch ash. It has a capability to reduce not only the amount of catalyst consumption but also reduce the reaction time of transesterification process.

Chemical modification of nanocellulose with canola oil fatty acid methyl ester

Treesearch

Liqing Wei; Umesh P. Agarwal; Kolby C. Hirth; Laurent M. Matuana; Ronald C. Sabo; Nicole M. Stark

2017-01-01

Cellulose nanocrystals (CNCs), produced from dissolving wood pulp, were chemically functionalized by transesterification with canola oil fatty acid methyl ester (CME). CME performs as both the reaction reagent and solvent. Transesterified CNC (CNCFE) was characterized for their chemical structure, morphology, crystalline structure, thermal stability, and hydrophobicity...

The Depolymerization of Poly(Ethylene Terephthalate) (PET) Using N-Heterocyclic Carbenes from Ionic Liquids

ERIC Educational Resources Information Center

Kamber, Nahrain E.; Tsujii, Yasuhito; Keets, Kate; Waymouth, Robert M.; Pratt, Russell C.; Nyce, Gregory W.; Hedrick, James L.

2010-01-01

The depolymerization of the plastic polyethylene terephthalate (PET or PETE) is described in this laboratory procedure. The transesterification reaction used to depolymerize PET employs a highly efficient N-heterocyclic carbene catalyst derived from a commercially available imidazolium ionic liquid. N-heterocyclic carbenes are potent nucleophilic…

A glycerol-free process to produce biodiesel by supercritical methyl acetate technology: an optimization study via Response Surface Methodology.

PubMed

Tan, Kok Tat; Lee, Keat Teong; Mohamed, Abdul Rahman

2010-02-01

In this study, fatty acid methyl esters (FAME) have been successfully produced from transesterification reaction between triglycerides and methyl acetate, instead of alcohol. In this non-catalytic supercritical methyl acetate (SCMA) technology, triacetin which is a valuable biodiesel additive is produced as side product rather than glycerol, which has lower commercial value. Besides, the properties of the biodiesel (FAME and triacetin) were found to be superior compared to those produced from conventional catalytic reactions (FAME only). In this study, the effects of various important parameters on the yield of biodiesel were optimized by utilizing Response Surface Methodology (RSM) analysis. The mathematical model developed was found to be adequate and statistically accurate to predict the optimum yield of biodiesel. The optimum conditions were found to be 399 degrees C for reaction temperature, 30 mol/mol of methyl acetate to oil molar ratio and reaction time of 59 min to achieve 97.6% biodiesel yield.

RSM based optimization of chemical and enzymatic transesterification of palm oil: biodiesel production and assessment of exhaust emission levels.

PubMed

Mumtaz, Muhammad Waseem; Mukhtar, Hamid; Anwar, Farooq; Saari, Nazamid

2014-01-01

Current study presents RSM based optimized production of biodiesel from palm oil using chemical and enzymatic transesterification. The emission behavior of biodiesel and its blends, namely, POB-5, POB-20, POB-40, POB-50, POB-80, and POB-100 was examined using diesel engine (equipped with tube well). Optimized palm oil fatty acid methyl esters (POFAMEs) yields were depicted to be 47.6 ± 1.5, 92.7 ± 2.5, and 95.4 ± 2.0% for chemical transesterification catalyzed by NaOH, KOH, and NaOCH3, respectively, whereas for enzymatic transesterification reactions catalyzed by NOVOZYME-435 and A. n. lipase optimized biodiesel yields were 94.2 ± 3.1 and 62.8 ± 2.4%, respectively. Distinct decrease in particulate matter (PM) and carbon monoxide (CO) levels was experienced in exhaust emissions from engine operating on biodiesel blends POB-5, POB-20, POB-40, POB-50, POB-80, and POB-100 comparative to conventional petroleum diesel. Percentage change in CO and PM emissions for different biodiesel blends ranged from -2.1 to -68.7% and -6.2 to -58.4%, respectively, relative to conventional diesel, whereas an irregular trend was observed for NOx emissions. Only POB-5 and POB-20 showed notable reductions, whereas all other blends (POB-40 to POB-100) showed slight increase in NOx emission levels from 2.6 to 5.5% comparative to petroleum diesel.

RSM Based Optimization of Chemical and Enzymatic Transesterification of Palm Oil: Biodiesel Production and Assessment of Exhaust Emission Levels

PubMed Central

Mumtaz, Muhammad Waseem; Anwar, Farooq; Saari, Nazamid

2014-01-01

Current study presents RSM based optimized production of biodiesel from palm oil using chemical and enzymatic transesterification. The emission behavior of biodiesel and its blends, namely, POB-5, POB-20, POB-40, POB-50, POB-80, and POB-100 was examined using diesel engine (equipped with tube well). Optimized palm oil fatty acid methyl esters (POFAMEs) yields were depicted to be 47.6 ± 1.5, 92.7 ± 2.5, and 95.4 ± 2.0% for chemical transesterification catalyzed by NaOH, KOH, and NaOCH3, respectively, whereas for enzymatic transesterification reactions catalyzed by NOVOZYME-435 and A. n. lipase optimized biodiesel yields were 94.2 ± 3.1 and 62.8 ± 2.4%, respectively. Distinct decrease in particulate matter (PM) and carbon monoxide (CO) levels was experienced in exhaust emissions from engine operating on biodiesel blends POB-5, POB-20, POB-40, POB-50, POB-80, and POB-100 comparative to conventional petroleum diesel. Percentage change in CO and PM emissions for different biodiesel blends ranged from −2.1 to −68.7% and −6.2 to −58.4%, respectively, relative to conventional diesel, whereas an irregular trend was observed for NOx emissions. Only POB-5 and POB-20 showed notable reductions, whereas all other blends (POB-40 to POB-100) showed slight increase in NOx emission levels from 2.6 to 5.5% comparative to petroleum diesel. PMID:25162053

Ring-Opening Polymerization of Lactide to Form a Biodegradable Polymer

ERIC Educational Resources Information Center

Robert, Jennifer L.; Aubrecht, Katherine B.

2008-01-01

In this laboratory activity for introductory organic chemistry, students carry out the tin(II) bis(2-ethylhexanoate)/benzyl alcohol mediated ring-opening polymerization of lactide to form the biodegradable polymer polylactide (PLA). As the mechanism of the polymerization is analogous to that of a transesterification reaction, the experiment can be…

Evaluating Sustainability: Soap versus Biodiesel Production from Plant Oils

ERIC Educational Resources Information Center

Pohl, Nicola L. B.; Streff, Jennifer M.; Brokman, Steve

2012-01-01

Herein we describe a series of experiments for the undergraduate organic laboratory curriculum in which various plant oils (soybean, rapeseed, and olive) are subjected to saponification and transesterification reactions to create a set of compounds that can function as soaps or as fuels. The experiments introduce students to and asks them to…

Utilization of eggshell waste as low-cost solid base catalyst for biodiesel production from used cooking oil

NASA Astrophysics Data System (ADS)

Asri, N. P.; Podjojono, B.; Fujiani, R.; Nuraini

2017-05-01

A solid CaO-based catalyst of waste eggshell was developed for biodiesel production from used cooking oil. The waste eggshell powder was calcined in air at 90° C for 4 h to convert calcium species in the eggshells into active CaO catalysts. The characterization of CaO catalyst was done by XRD and BET analysis. The CaO catalyst was then introduced for transesterification of used cooking oil (UCO) for testing of its catalytic activity. The experiment was conducted in batch type reactor that consists of three-neck glass equipped by reflux condenser and magnetic stirrer. Before tranesterification process, the UCO was treated by coconut coir powder in order to reduce the free fatty acid content. The result showed that the catalyst was potentially use for transesterification of used cooking oil into biodiesel with relatively high yield of 75.92% was achieved at reaction temperature, reaction time, molar ratio UCO to methanol and catalyst amount of 65° C, 7 h, 1:15 and 6%, respectively.

Biodiesel Derive Bio-oil of Hermetia illucens Pre-pupae Catalysed by Sulphonated Biochar

NASA Astrophysics Data System (ADS)

Yoong Leong, Siew; Chong, Soo Shin; Chin, Kah Seng

2018-03-01

This study investigates the development of biochar catalyst from bamboo applied for biodiesel synthesis. A non-conventional biodiesel feedstock was used in the in-situ transesterification reaction. This non-conventional feedstock is obtained from an insect's fly, the Hermetia illucens fly. Biochar derived from bamboo has been investigated as a promising catalyst for biodiesel synthesis. The biochar acid catalysts were prepared by sulphonation via impregnation with concentrated sulphuric acid. The prepared catalysts were investigated for their performance to catalyse in-situ transesterification via ultra-sonication of Hermetia illucens bio-oil. The effects of carbonisation time (1 hour and 2 hour) and temperature (400°C, 500°C and 600°C) as well as catalyst loading (5-20 wt% on oil basis) on the transesterification yield were studied. Result showed that the highest yield of FAME obtained was 95.6% with catalyst loading of 15 wt% carbonized at 500°C for 2 hours. Sharp band of methyl ester functional groups were observed in the FTIR spectra at 1735-1750cm-1. The composition of this methyl ester was further deduced using gas chromatography and the fatty acid was predominantly lauric acid.

Development of a millimetrically scaled biodiesel transesterification device that relies on droplet-based co-axial fluidics

NASA Astrophysics Data System (ADS)

Yeh, S. I.; Huang, Y. C.; Cheng, C. H.; Cheng, C. M.; Yang, J. T.

2016-07-01

In this study, we investigated a fluidic system that adheres to new concepts of energy production. To improve efficiency, cost, and ease of manufacture, a millimetrically scaled device that employs a droplet-based co-axial fluidic system was devised to complete alkali-catalyzed transesterification for biodiesel production. The large surface-to-volume ratio of the droplet-based system, and the internal circulation induced inside the moving droplets, significantly enhanced the reaction rate of immiscible liquids used here - soybean oil and methanol. This device also decreased the molar ratio between methanol and oil to near the stoichiometric coefficients of a balanced chemical equation, which enhanced the total biodiesel volume produced, and decreased the costs of purification and recovery of excess methanol. In this work, the droplet-based co-axial fluidic system performed better than other methods of continuous-flow production. We achieved an efficiency that is much greater than that of reported systems. This study demonstrated the high potential of droplet-based fluidic chips for energy production. The small energy consumption and low cost of the highly purified biodiesel transesterification system described conforms to the requirements of distributed energy (inexpensive production on a moderate scale) in the world.

Practical method for the confirmation of authentic flours of different types of cereals and pseudocereals.

PubMed

Ačanski, Marijana M; Vujić, Djura N; Psodorov, Djordje B

2015-04-01

Gas chromatography with mass spectrometry was used to perform a qualitative analysis of the liposoluble flour extract of different types of cereals (bread wheat and spelt) and pseudocereals (amaranth and buckwheat). In addition to major fatty acids, the liposoluble extract also contained minor fatty acids with more than 20 carbon atoms, higher hydrocarbons and phytosterols. TMSH (trimethylsulfonium hydroxide, 0.2 mol/l in methanol) was used as a trans-esterification reagent. In a trans-esterification reaction, triglycerides esterified from acilglycerols to methyl-esters. SIM (selected ion monitoring) was applied to isolate fatty acid methyl esters on TIC (total ion current) chromatograms, using the 74 Da fragment ion, which originated from McLafferty rearrangement, and is typical for methyl-esters. GC-MS system was used for the trans-esterification of triglycerides to fatty acid methyl esters in the gas chromatographic injector. This eliminated laboratory preparation for fatty acid methyl esters. Cluster analysis was applied to compare the liposoluble flour extract from different types of cereals and pseudocereals. Statistical data showed the liposoluble extract analysis enabled determination of flour origin and, because the results were unambiguous, this approach could be used for quality control. Copyright © 2014 Elsevier Ltd. All rights reserved.

VR-SCOSMO: A smooth conductor-like screening model with charge-dependent radii for modeling chemical reactions.

PubMed

Kuechler, Erich R; Giese, Timothy J; York, Darrin M

2016-04-28

To better represent the solvation effects observed along reaction pathways, and of ionic species in general, a charge-dependent variable-radii smooth conductor-like screening model (VR-SCOSMO) is developed. This model is implemented and parameterized with a third order density-functional tight binding quantum model, DFTB3/3OB-OPhyd, a quantum method which was developed for organic and biological compounds, utilizing a specific parameterization for phosphate hydrolysis reactions. Unlike most other applications with the DFTB3/3OB model, an auxiliary set of atomic multipoles is constructed from the underlying DFTB3 density matrix which is used to interact the solute with the solvent response surface. The resulting method is variational, produces smooth energies, and has analytic gradients. As a baseline, a conventional SCOSMO model with fixed radii is also parameterized. The SCOSMO and VR-SCOSMO models shown have comparable accuracy in reproducing neutral-molecule absolute solvation free energies; however, the VR-SCOSMO model is shown to reduce the mean unsigned errors (MUEs) of ionic compounds by half (about 2-3 kcal/mol). The VR-SCOSMO model presents similar accuracy as a charge-dependent Poisson-Boltzmann model introduced by Hou et al. [J. Chem. Theory Comput. 6, 2303 (2010)]. VR-SCOSMO is then used to examine the hydrolysis of trimethylphosphate and seven other phosphoryl transesterification reactions with different leaving groups. Two-dimensional energy landscapes are constructed for these reactions and calculated barriers are compared to those obtained from ab initio polarizable continuum calculations and experiment. Results of the VR-SCOSMO model are in good agreement in both cases, capturing the rate-limiting reaction barrier and the nature of the transition state.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuechler, Erich R.; Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455-0431; Giese, Timothy J.

To better represent the solvation effects observed along reaction pathways, and of ionic species in general, a charge-dependent variable-radii smooth conductor-like screening model (VR-SCOSMO) is developed. This model is implemented and parameterized with a third order density-functional tight binding quantum model, DFTB3/3OB-OPhyd, a quantum method which was developed for organic and biological compounds, utilizing a specific parameterization for phosphate hydrolysis reactions. Unlike most other applications with the DFTB3/3OB model, an auxiliary set of atomic multipoles is constructed from the underlying DFTB3 density matrix which is used to interact the solute with the solvent response surface. The resulting method is variational,more » produces smooth energies, and has analytic gradients. As a baseline, a conventional SCOSMO model with fixed radii is also parameterized. The SCOSMO and VR-SCOSMO models shown have comparable accuracy in reproducing neutral-molecule absolute solvation free energies; however, the VR-SCOSMO model is shown to reduce the mean unsigned errors (MUEs) of ionic compounds by half (about 2-3 kcal/mol). The VR-SCOSMO model presents similar accuracy as a charge-dependent Poisson-Boltzmann model introduced by Hou et al. [J. Chem. Theory Comput. 6, 2303 (2010)]. VR-SCOSMO is then used to examine the hydrolysis of trimethylphosphate and seven other phosphoryl transesterification reactions with different leaving groups. Two-dimensional energy landscapes are constructed for these reactions and calculated barriers are compared to those obtained from ab initio polarizable continuum calculations and experiment. Results of the VR-SCOSMO model are in good agreement in both cases, capturing the rate-limiting reaction barrier and the nature of the transition state.« less

Conformation Analysis of T1 Lipase on Alcohols Solvent using Molecular Dynamics Simulation

NASA Astrophysics Data System (ADS)

Putri, A. M.; Sumaryada, T.; Wahyudi, S. T.

2017-07-01

Biodiesel usually is produced commercially via a transesterification reaction of vegetable oil with alcohol and alkali catalyst. The alkali catalyst has some drawbacks, such as the soap formation during the reaction. T1 Lipase enzyme had been known as a thermostable biocatalyst which is able to produce biodiesel through a cleaner process. In this paper the performance of T1 lipase enzyme as catalyst for transesterification reaction in pure ethanol, methanol, and water solvents were studied using a Molecular Dynamics (MD) Simulation at temperature of 300 K for 10 nanoseconds. The results have shown that in general the conformation of T1 lipase enzyme in methanol is more dynamics as shown by the value of root mean square deviation (RMSD), root mean squared fluctuation (RMSF), and radius of gyration. The highest solvent accessible surface area (SASA) total was also found in methanol due to the contribution of non-polar amino acid in the interior of the protein. Analysis of MD simulation has also revealed that the enzyme structure tend to be more rigid in ethanol environment. The analysis of electrostatic interactions have shown that Glu359-Arg270 salt-bridge pair might hold the key of thermostability of T1 lipase enzyme as shown by its strong and stable binding in all three solvents.

Lipase-catalyzed biodiesel production and quality with Jatropha curcas oil: exploring its potential for Central America.

PubMed

Bueso, Francisco; Moreno, Luis; Cedeño, Mathew; Manzanarez, Karla

2015-01-01

Extensive native Jatropha curcas L. (Jatropha) crop areas have been planted in Central America marginal lands since 2008 as a non-edible prospective feedstock alternative to high-value, edible palm oil. Jatropha biodiesel is currently exclusively produced in the region at commercial scale utilizing alkaline catalysts. Recently, a free, soluble Thermomyces lanuginosus (TL) 1,3 specific lipase has shown promise as biocatalyst, reportedly yielding up to 96 % ASTM D6751 compliant biodiesel after 24 h transesterification of soybean, canola oils and other feedstocks. Biodiesel conversion rate and quality of enzymatically catalyzed transesterification of Jatropha oil was evaluated. Two lipases: free, soluble TL and immobilized Candida antarctica (CA) catalyzed methanolic transesterification of crude Jatropha and refined palm oil. Jatropha yields were similar to palm biodiesel with NaOH as catalyst. After 24 h transesterification, Jatropha (81 %) and palm oil (86 %) biodiesel yields with TL as catalyst were significantly higher than CA (<70 %) but inferior to NaOH (>90 %). Enzymatic catalysts (TL and CA) produced Jatropha biodiesel with optimum flow properties but did not complied with ASTM D6751 stability parameters (free fatty acid content and oil stability index). Biodiesel production with filtered, degummed, low FFA Jatropha oil using a free liquid lipase (TL) as catalyst showed higher yielding potential than immobilized CA lipase as substitute of RBD palm oil with alkaline catalyst. However, Jatropha enzymatic biodiesel yield and stability were inferior to alkaline catalyzed biodiesel and not in compliance with international quality standards. Lower quality due to incomplete alcoholysis and esterification, potential added costs due to need of more than 24 h to achieve comparable biodiesel yields and extra post-transesterification refining reactions are among the remaining drawbacks for the environmentally friendlier enzymatic catalysis of crude Jatropha oil to become an economically viable alternative to chemical catalysis.

Propyl gallate synthesis using acidophilic tannase and simultaneous production of tannase and gallic acid by marine Aspergillus awamori BTMFW032.

PubMed

Beena, P S; Basheer, Soorej M; Bhat, Sarita G; Bahkali, Ali H; Chandrasekaran, M

2011-07-01

Marine Aspergillus awamori BTMFW032, recently reported by us, produce acidophilic tannase as extracellular enzyme. Here, we report the application of this enzyme for synthesis of propyl gallate by direct transesterification of tannic acid and in tea cream solubilisation besides the simultaneous production of gallic acid along with tannase under submerged fermentation by this fungus. This acidophilic tannase enabled synthesis of propyl gallate by direct transesterification of tannic acid using propanol as organic reaction media under low water conditions. The identity of the product was confirmed with thin layer chromatography and Fourier transform infrared spectroscopy. It was noted that 699 U/ml of enzyme could give 60% solubilisation of tea cream within 1 h. Enzyme production medium was optimized adopting Box-Behnken design for simultaneous synthesis of tannase and gallic acid. Process variables including tannic acid, sodium chloride, ferrous sulphate, dipotassium hydrogen phosphate, incubation period and agitation were recognized as the critical factors that influenced tannase and gallic acid production. The model obtained predicted 4,824.61 U/ml of tannase and 136.206 μg/ml gallic acid after 48 h of incubation, whereas optimized medium supported 5,085 U/ml tannase and 372.6 μg/ml of gallic acid production after 36 and 84 h of incubation, respectively, with a 15-fold increase in both enzyme and gallic acid production. Results indicated scope for utilization of this acidophilic tannase for transesterification of tannic acid into propyl gallate, tea cream solubilisation and simultaneous production of gallic acid along with tannase.

Metal ion-promoted cleavage of nucleoside diphosphosugars: a model for reactions of phosphodiester bonds in carbohydrates.

PubMed

Dano, Meisa; Elmeranta, Marjukka; Hodgson, David R W; Jaakkola, Juho; Korhonen, Heidi; Mikkola, Satu

2015-12-01

Cleavage of five different nucleoside diphosphosugars has been studied in the presence of Cu(2+) and Zn(2+) complexes. The results show that metal ion catalysts promote the cleavage via intramolecular transesterification whenever a neighbouring HO group can adopt a cis-orientation with respect to the phosphate. The HO group attacks the phosphate and two monophosphate products are formed. If such a nucleophile is not available, Cu(2+) complexes are able to promote a nucleophilic attack of an external nucleophile, e.g. a water molecule or metal ion coordinated HO ligand, on phosphate. With the Zn(2+) complex, this was not observed.

Charge-dependent non-bonded interaction methods for use in quantum mechanical modeling of condensed phase reactions

NASA Astrophysics Data System (ADS)

Kuechler, Erich R.

Molecular modeling and computer simulation techniques can provide detailed insight into biochemical phenomena. This dissertation describes the development, implementation and parameterization of two methods for the accurate modeling of chemical reactions in aqueous environments, with a concerted scientific effort towards the inclusion of charge-dependent non-bonded non-electrostatic interactions into currently used computational frameworks. The first of these models, QXD, modifies interactions in a hybrid quantum mechanical/molecular (QM/MM) mechanical framework to overcome the current limitations of 'atom typing' QM atoms; an inaccurate and non-intuitive practice for chemically active species as these static atom types are dictated by the local bonding and electrostatic environment of the atoms they represent, which will change over the course of the simulation. The efficacy QXD model is demonstrated using a specific reaction parameterization (SRP) of the Austin Model 1 (AM1) Hamiltonian by simultaneously capturing the reaction barrier for chloride ion attack on methylchloride in solution and the solvation free energies of a series of compounds including the reagents of the reaction. The second, VRSCOSMO, is an implicit solvation model for use with the DFTB3/3OB Hamiltonian for biochemical reactions; allowing for accurate modeling of ionic compound solvation properties while overcoming the discontinuous nature of conventional PCM models when chemical reaction coordinates. The VRSCOSMO model is shown to accurately model the solvation properties of over 200 chemical compounds while also providing smooth, continuous reaction surfaces for a series of biologically motivated phosphoryl transesterification reactions. Both of these methods incorporate charge-dependent behavior into the non-bonded interactions variationally, allowing the 'size' of atoms to change in meaningful ways with respect to changes in local charge state, as to provide an accurate, predictive and transferable models for the interactions between the quantum mechanical system and their solvated surroundings.

The Production of Biodiesel from Cottonseed Oil Using Rhizopus oryzae Whole Cell Biocatalysts

NASA Astrophysics Data System (ADS)

Athalye, Sneha Kishor

Biodiesel is an environmentally friendly alternative to fossil fuels which have become increasingly expensive in recent times. An alternate approach to alkaline biodiesel production is needed as catalyst miscibility with the glycerol by-product, generation of large amounts of waste water, and saponification of the feedstock are major disadvantages associated with the process. Lipases are water soluble enzymes which act as catalysts in many lipid based reactions. Reuse of lipases can significantly reduce cost of enzymatic biodiesel production; however retention of lipolytic activity still remains a challenge. Use of microbial cells immobilized on various surfaces like sponge, foam and plastics as biocatalysts instead of extracted enzyme could help overcome this problem. A novel, rigid biomass support with high surface area made from recyclable polyethylene (Bioblok(TM)) was used in this study. Several fungal and bacterial species have been reported to possess appreciable levels of lipase activity. The biomass production and immobilization as well as lipase activity of three different species; Candida rugosa (ATCC #38772), Aspergillus oryzae (ATCC #58299), and Rhizopus oryzae (ATTC #34612) were tested. C. rugosa did not attach well to the support particles while A.oryzae had lower biomass accumulation of 6.1 g (dry cell wt)/L compared to 11.8 g (dry cell wt)/L for R.oryzae. Hence Rhizopus oryzae, fungal specie with cell surface bound lipase was selected for the current study. The study investigated the influence of media composition and growth time of the R.oryzae whole cell biocatalysts, immobilized on the BSPs, for FAME production from cottonseed oil. R.oryzae BSPs grown in basal media supplemented with 1% (w/v) of glucose or oil or both for 48 h, 72 h or 90 h were used in a 36 h transesterification reaction with cottonseed oil and methanol. BSPs grown in both glucose and oil supplemented medium for 72 h had the highest conversion of 22.4% (wt/wt) and a biomass accumulation of 15.6 g (dry cell wt)/L. A reduction in dynamic viscosity of the reaction mixture from 47.3 centipoise to 30.6 centipoise was observed. The impact of moisture addition to the reaction mixture and use of ethanol as acylating agent on R.oryzae BSP fatty acid alkyl ester production was also tested. The presence of 10 wt % moisture in the reaction system had a significant effect (p ≤ 0.05) on the transesterification reaction with ethanol unlike methanol. Fatty acid ethyl ester concentration tripled from 39.3 to 129.1 g/L when moisture was added during transesterification .When oil to acyl acceptor ratio was increased from 1:3 and 1:6 to determine effect of excess alcohol on conversion, an ester conversion of 128.1 g/L for methanol and 129.1 g/L for ethanol were observed. Use of excess amount of acylating agent had a significant adverse effect (p ≤ 0.05) on the overall FAAE production due to deactivation of lipases on contact with large amounts of insoluble alcohol in the oil phase of the reaction. The effect of short chain alcohols on the enzymatic transesterification of cottonseed oil using freeze dried Rhizopus oryzae biomass was examined with and without water addition using methanol, ethanol, 1-Propanol and 1-Butanol at various molar ratios. 1- Butanol in the absence of water resulted in a significantly higher (p . 0.1) conversion of cottonseed oil to 12.5 % fatty acid butyl esters (FABEs). Addition of 10 % water to the reaction mixture significantly reduced (p ≤ 0.1) conversion. No significant difference (p > 0.1) between the conversions was observed for time points after 24 h for a 72 h reaction. 1- Butanol in ratios higher than 3:1 to cottonseed oil had a significant impact (p ≤ 0.1) on conversion. Increasing the amount of biomass used during the reaction lead to significantly higher conversion (p ≤ 0.1). The highest conversion of 27.9 % was observed for the transesterification reaction between cottonseed oil and 1-Butanol, in a 1:6 molar ratio, in the absence of water, when 100 mg of freeze dried R.oryzae biomass was used. The present study concluded that R.oryzae biomass attached better to the Bioblok. material and had highest lipase activity when grown in presence of oil and glucose for 72h. Addition of water to the reaction system gave higher fatty acid alkyl ester conversion when whole immobilized R.oryzae BSPs were used but absence of water promoted conversion with freeze dried biomass.

Biodiesel synthesis via transesterification of lipid Chlorophyta cultivated in walne rich carbon medium using KOH/Zeolite catalyst

NASA Astrophysics Data System (ADS)

Dianursanti, Hayati, Siti Zahrotul; Putri, Dwini Normayulisa

2017-11-01

Microalgae from the Chlorophyta division such as Nannochloropsis oculata and Chlorella vulgaris are highly potential to be developed as biodiesel feedstocks because they have a high oil content up to 58%. Biodiesel is produced by transesterification of triglycerides and alcohols with the aid of homogeneous catalysts such as KOH. However, the use of KOH catalysts produces soaps in the biodiesel synthesis. Heterogeneous catalysts are known to solve this problem. One of them is natural zeolite. Zeolite can be used as a catalyst and as a support catalyst. Loading KOH on the zeolite surface is expected to increase alkalinity in KOH/Zeolite catalysts so as to increase the activity of KOH/Zeolite catalyst in transesterification of triglyceride with methanol. In this experimental lipid of microalgae will be used for produced biodiesel via transesterification reaction with methanol and KOH/Zeolite as a catalyst heterogeneous at 60 °C for 3h and utilized catalyst modificated KOH/Zeolite with variation 0.5 M, 1 M and 1.5 M KOH. The modified zeolite was then analyzed by XRF, XRD and BET. The result showed that the yield of biodiesel from lipid N.oculata was 81,09% by 0.5KOH/Zeolite catalyst, 86,53% by 1KOH/Zeolite catalyst, 1,5KOH/Zeolite and 88,13% by 1.5KOH/Zeolit, while the biodiesel produced from lipid C.vulgaris was 59.29% by 0.5KOH/Zeolite, 82.27% by 1KOH/Zeolite and 83.72% by 1.5KOH/Zeolite.

In-Water and Neat Batch and Continuous-Flow Direct Esterification and Transesterification by a Porous Polymeric Acid Catalyst

NASA Astrophysics Data System (ADS)

Baek, Heeyoel; Minakawa, Maki; Yamada, Yoichi M. A.; Han, Jin Wook; Uozumi, Yasuhiro

2016-05-01

A porous phenolsulphonic acid—formaldehyde resin (PAFR) was developed. The heterogeneous catalyst PAFR was applied to the esterification of carboxylic acids and alcohols, affording the carboxylic acid esters in a yield of up to 95% where water was not removed from the reaction mixture. Surprisingly, the esterification in water as a solvent proceeded to afford the desired esters in high yield. PAFR provided the corresponding esters in higher yield than other homogeneous and heterogeneous catalysts. The transesterification of alcohols and esters was also investigated by using PAFR, giving the corresponding esters. PAFR was applied to the batch-wise and continuous-flow production of biodiesel fuel FAME. The PAFR-packed flow reactor that was developed for the synthesis of carboxylic acids and FAME worked for four days without loss of its catalytic activity.

Biodiesel production from heterotrophic microalgal oil.

PubMed

Miao, Xiaoling; Wu, Qingyu

2006-04-01

The present study introduced an integrated method for the production of biodiesel from microalgal oil. Heterotrophic growth of Chlorella protothecoides resulted in the accumulation of high lipid content (55%) in cells. Large amount of microalgal oil was efficiently extracted from these heterotrophic cells by using n-hexane. Biodiesel comparable to conventional diesel was obtained from heterotrophic microalgal oil by acidic transesterification. The best process combination was 100% catalyst quantity (based on oil weight) with 56:1 molar ratio of methanol to oil at temperature of 30 degrees C, which reduced product specific gravity from an initial value of 0.912 to a final value of 0.8637 in about 4h of reaction time. The results suggested that the new process, which combined bioengineering and transesterification, was a feasible and effective method for the production of high quality biodiesel from microalgal oil.

Study of KOH/Al2O3 as heterogeneous catalyst for biodiesel production via in situ transesterification from microalgae.

PubMed

Ma, Guixia; Hu, Wenrong; Pei, Haiyan; Jiang, Liqun; Ji, Yan; Mu, Ruimin

2015-01-01

Heterogeneous KOH/Al2O3 catalysts, synthesized by the wet impregnation method with different KOH loadings (20-40 wt%) and calcination temperatures from 400°C to 800°C, were used to produce biodiesel from Chlorella vulgaris biomass by in situ transesterification. The highest yield of biodiesel of 89.53±1.58% was achieved at calcination temperature of 700°C for 2 h and 35 wt% loading of KOH, and at the optimal reaction condition of 10 wt% of catalyst content, 8 mL/g of methanol to biomass ratio and at 60°C for 5 h. The characteristics of the catalysts were analysed by X-ray diffraction, scanning electron microscopy and Brunauer-Emmett-Teller.

Synthesis of DHA/EPA-rich phosphatidylcholine by immobilized phospholipase A1: effect of water addition and vacuum condition.

PubMed

Li, Daoming; Qin, Xiaoli; Wang, Weifei; Li, Zhigang; Yang, Bo; Wang, Yonghua

2016-08-01

DHA/EPA-rich phosphatidylcholine (PC) was successfully synthesized by immobilized phospholipase A1 (PLA1)-catalyzed transesterification of PC and DHA/EPA-rich ethyl esters in a solvent-free system. Effects of reaction temperature, water addition and substrate mass ratio on the incorporation of DHA/EPA were evaluated using response surface methods (RSM). Water addition had most significant effect on the incorporation. Reaction temperature and substrate mass ratio, however, had no significant effect on the incorporation. The maximal incorporation was 19.09 % (24 h) under the following conditions: temperature 55.7 °C, water addition 1.1 wt % and substrate mass ratio (ethyl esters/PC) 6.8:1. Furthermore, effects of water addition (from 0 to 1.25 wt %) on DHA/EPA incorporation and the composition of products were further investigated. The immobilized PLA1 was more active when water addition was above 0.5 wt %. By monitoring the reaction processes with different water addition, a possible reaction scheme was proposed for transesterification of PC with DHA/EPA-rich ethyl esters. In summary, PC and sn2-lysophosphatidylocholine (LPC) were predominant in the mixtures at early stages of reaction, whereas sn1-LPC and glycerophosphocholine (GPC) predominant at later stages. The vacuum employed after 24 h significantly increased the incorporation of DHA/EPA and the composition of PC, and the highest incorporation (30.31 %) of DHA/EPA was obtained at 72 h and the yield of PC was 47.2 %.

A study on production of biodiesel using a novel solid oxide catalyst derived from waste.

PubMed

Majhi, Samrat; Ray, Srimanta

2016-05-01

The issues of energy security, dwindling supply and inflating price of fossil fuel have shifted the global focus towards fuel of renewable origin. Biodiesel, having renewable origin, has exhibited great potential as substitute for fossil fuels. The most common route of biodiesel production is through transesterification of vegetable oil in presence of homogeneous acid or base or solid oxide catalyst. But, the economics of biodiesel is not competitive with respect to fossil fuel due to high cost of production. The vegetable oil waste is a potential alternative for biodiesel production, particularly when disposal of used vegetable oil has been restricted in several countries. The present study evaluates the efficacy of a low-cost solid oxide catalyst derived from eggshell (a food waste) in transesterification of vegetable oil and simulated waste vegetable oil (SWVO). The impact of thermal treatment of vegetable oil (to simulate frying operation) on transesterification using eggshell-derived solid oxide catalyst (ESSO catalyst) was also evaluated along with the effect of varying reaction parameters. The study reported that around 90 % biodiesel yield was obtained with vegetable oil at methanol/oil molar ratio of 18:1 in 3 h reaction time using 10 % ESSO catalyst. The biodiesel produced with ESSO catalyst from SWVO, thermally treated at 150 °C for 24 h, was found to conform with the biodiesel standard, but the yield was 5 % lower compared to that of the untreated oil. The utilization of waste vegetable oil along with waste eggshell as catalyst is significant for improving the overall economics of the biodiesel in the current market. The utilization of waste for societal benefit with the essence of sustainable development is the novelty of this work.

Highly efficient enzymatic acetylation of flavonoids: Development of solvent-free process and kinetic evaluation

DOE PAGES

Milivojevic, Ana; Corovic, Marija; Carevic, Milica; ...

2017-09-23

Solubility and stability of flavonoid glycosides, valuable natural constituents of cosmetics and pharmaceuticals, could be improved by lipase-catalyzed acylation. Focus of this study was on development of eco-friendly process for the production of flavonoid acetates. By using phloridzin as model compound and triacetin as acetyl donor and solvent, 100% conversion and high productivity (23.32 g l –1 day –1) were accomplished. Complete conversions of two other glycosylated flavonoids, naringin and esculin, in solvent-free system were achieved, as well. Comprehensive kinetic mechanism based on two consecutive mono-substrate reactions was established where first one represents formation of flavonoid monoacetate and within secondmore » reaction diacetate is being produced from monoacetate. Both steps were regarded as reversible Michaelis-Menten reactions without inhibition. Apparent kinetic parameters for two consecutive reactions (V m constants for substrates and products and K m constants for forward and reverse reactions) were estimated for three examined acetyl acceptors and excellent fitting of experimental data (R 2 > 0.97) was achieved. Obtained results showed that derived kinetic model could be applicable for solvent-free esterifications of different flavonoid glycosides. As a result, it was valid for entire transesterification course (72 h of reaction) which, combined with complete conversions and green character of synthesis, represents firm basis for further process development.« less

Highly efficient enzymatic acetylation of flavonoids: Development of solvent-free process and kinetic evaluation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Milivojevic, Ana; Corovic, Marija; Carevic, Milica

Solubility and stability of flavonoid glycosides, valuable natural constituents of cosmetics and pharmaceuticals, could be improved by lipase-catalyzed acylation. Focus of this study was on development of eco-friendly process for the production of flavonoid acetates. By using phloridzin as model compound and triacetin as acetyl donor and solvent, 100% conversion and high productivity (23.32 g l –1 day –1) were accomplished. Complete conversions of two other glycosylated flavonoids, naringin and esculin, in solvent-free system were achieved, as well. Comprehensive kinetic mechanism based on two consecutive mono-substrate reactions was established where first one represents formation of flavonoid monoacetate and within secondmore » reaction diacetate is being produced from monoacetate. Both steps were regarded as reversible Michaelis-Menten reactions without inhibition. Apparent kinetic parameters for two consecutive reactions (V m constants for substrates and products and K m constants for forward and reverse reactions) were estimated for three examined acetyl acceptors and excellent fitting of experimental data (R 2 > 0.97) was achieved. Obtained results showed that derived kinetic model could be applicable for solvent-free esterifications of different flavonoid glycosides. As a result, it was valid for entire transesterification course (72 h of reaction) which, combined with complete conversions and green character of synthesis, represents firm basis for further process development.« less

Production of Mahua Oil Ethyl Ester (MOEE) and its Performance test on four stroke single cylinder VCR engine

NASA Astrophysics Data System (ADS)

Soudagar, Manzoor Elahi M.; Kittur, Prasanna; Parmar, Fulchand; Batakatti, Sachin; Kulkarni, Prasad; Kallannavar, Vinayak

2017-08-01

Biodiesel is a substitute for gasoline that is produced from vegetable oils and animal fats. It has gained popularity due to depleting fossil fuel resources, its renewable character and comparable combustion properties to diesel fuel. Biodiesel is formed from non-edible oils, edible oils, tallow, animal fats and waste cooked oils. Biodiesels are monoalkyl esters of elongated chain fatty acids. Biodiesel can be a viable choice for satisfying long term energy requirements if they are managed proficiently. The method of the transesterification shows how the reaction occurs and advances. In this study, biodiesel is produced from Madhuca indica seeds commonly known as Mahua by using transesterification process using a low capacity pressure reactor and by-product of transesterification is glycerol, which is used in preparation of soaps. Mahua Oil Ethyl Ester (MOEE) was produced from the Mahua oil and is mixed with diesel to get different ratios of blends. MOEE was tested in a 4-stroke single cylinder VCR diesel engine. The study was extended to understand the effect of biodiesel blend magnitude on the performance of engine parameters like, brake thermal efficiency, brake power and fuel properties like flash point, cloud point, kinematic viscosity, calorific value, cetane number and density were studied.

Development of a millimetrically scaled biodiesel transesterification device that relies on droplet-based co-axial fluidics

PubMed Central

Yeh, S. I.; Huang, Y. C.; Cheng, C. H.; Cheng, C. M.; Yang, J. T.

2016-01-01

In this study, we investigated a fluidic system that adheres to new concepts of energy production. To improve efficiency, cost, and ease of manufacture, a millimetrically scaled device that employs a droplet-based co-axial fluidic system was devised to complete alkali-catalyzed transesterification for biodiesel production. The large surface-to-volume ratio of the droplet-based system, and the internal circulation induced inside the moving droplets, significantly enhanced the reaction rate of immiscible liquids used here – soybean oil and methanol. This device also decreased the molar ratio between methanol and oil to near the stoichiometric coefficients of a balanced chemical equation, which enhanced the total biodiesel volume produced, and decreased the costs of purification and recovery of excess methanol. In this work, the droplet-based co-axial fluidic system performed better than other methods of continuous-flow production. We achieved an efficiency that is much greater than that of reported systems. This study demonstrated the high potential of droplet-based fluidic chips for energy production. The small energy consumption and low cost of the highly purified biodiesel transesterification system described conforms to the requirements of distributed energy (inexpensive production on a moderate scale) in the world. PMID:27426677

Biodiesel production with continuous supercritical process: non-catalytic transesterification and esterification with or without carbon dioxide.

PubMed

Tsai, Yu-Ting; Lin, Ho-mu; Lee, Ming-Jer

2013-10-01

The non-catalytic transesterification of refined sunflower oil with supercritical methanol, in the presence of carbon dioxide, was conducted in a tubular reactor at temperatures from 553.2 to 593.2K and pressures up to 25.0 MPa. The FAME yield can be achieved up to about 0.70 at 593.2 K and 10.0 MPa in 23 min with methanol:oil of 25:1 in molar ratio. The effect of adding CO2 on the FAME yield is insignificant. The kinetic behavior of the non-catalytic esterification and transesterification of oleic acid or waste cooking oil (WCO) with supercritical methanol was also investigated. By using the supercritical process, the presence of free fatty acid (FFA) in WCO gives positive contribution to FAME production. The FAME yield of 0.90 from WCO can be achieved in 13 min at 573.2K. The kinetic data of supercritical transesterification and esterifaication were correlated well with a power-law model. Copyright © 2012 Elsevier Ltd. All rights reserved.

Spectroscopic Investigation of the Electrosynthesis of Diphenyl Carbonate from CO and Phenol on Gold Electrodes

PubMed Central

2018-01-01

In this work, we study the synthesis of diphenyl carbonate (DPC) from phenol and CO on gold electrodes studied by means of in situ Fourier transform infrared spectroscopy (FTIR). The results show that, on gold electrodes, the formation of DPC is observed at potentials as low as 0.4 V vs Ag/AgCl, together with the formation of dimethyl carbonate (DMC) from the carbonylation of methanol that was used as a solvent. The spectroelectrochemical results also suggest that the formation of DPC occurs via the replacement of the methoxy groups from DMC with phenoxy groups from phenol and not directly by the carbonylation of phenol. Although this transesterification process is known to occur with heterogeneous catalysts, it has not been reported under electrochemical conditions. These are interesting findings, since the direct DPC production by carbonylation of phenol to DPC is usually performed with Pd-based catalysts. With this reaction scheme of transesterification happening under electrochemical conditions, other non-Pd catalysts could be used as well for one-step DPC production from phenol and CO. These findings give important mechanistic insights into this reaction and open up possibilities to an alternative process for the production of DPC. PMID:29657886

Investigation of acyl migration in mono- and dicaffeoylquinic acids under aqueous basic, aqueous acidic, and dry roasting conditions.

PubMed

Deshpande, Sagar; Jaiswal, Rakesh; Matei, Marius Febi; Kuhnert, Nikolai

2014-09-17

Acyl migration in chlorogenic acids describes the process of migration of cinnamoyl moieties from one quinic acid alcohol group to another, thus interconverting chlorogenic acid regioisomers. It therefore constitutes a special case of transesterification reaction. Acyl migration constitutes an important reaction pathway in both coffee roasting and brewing, altering the structure of chlorogenic acid initially present in the green coffee bean. In this contribution we describe detailed and comprehensive mechanistic studies comparing inter- and intramolecular acyl migration involving the seven most common chlorogenic acids in coffee. We employe aqueous acidic and basic conditions mimicking the brewing of coffee along with dry roasting conditions. We show that under aqueous basic conditions intramolecular acyl migration is fully reversible with basic hydrolysis competing with acyl migration. 3-Caffeoylquinic acid was shown to be most labile to basic hydrolysis. We additionally show that the acyl migration process is strongly pH dependent with increased transesterification taking place at basic pH. Under dry roasting conditions acyl migration competes with dehydration to form lactones. We argue that acyl migration precedes lactonization, with 3-caffeoylquinic acid lactone being the predominant product.

Synthesis of structured lipids by transesterification of trilinolein catalyzed by Lipozyme IM60.

PubMed

Sellappan, S; Akoh, C C

2001-04-01

Structured lipids (SL) containing caprylic, stearic, and linoleic acids were synthesized by enzymatic transesterification using Lipozyme IM60. Pure trilinolein and free fatty acids were used as substrates. Incorporation of stearic acid was higher than that of caprylic acid in all parameters. Highest incorporations of both acids were achieved at 32 h, mole ratio of 1:4:4 (trilinolein/caprylic/stearic acids), water content of 1% (wt %), temperature of 55 degrees C, and 10% (wt %) enzyme load. The maximal incorporations of caprylic and stearic acids were 23.73 and 62.46 mol %, respectively. Reaction time, water content, and enzyme load had major influences on the reaction, whereas substrate mole ratio and temperature showed less influence. Lipozyme showed good stability over six reuses. Differential scanning calorimetric analysis of SL gave a melting profile with a very low melting peak of 0-3.3 degrees C and a solid fat content of 25.21% at 0 degrees C. The melting profile and solid fat content of SL were compared with those of fats extracted from commercially available solid and liquid margarine products. The data suggest that enzymatically produced SL could be used in liquid margarine products.

Alginate as immobilization matrix and stabilizing agent in a two-phase liquid system: application in lipase-catalysed reactions.

PubMed

Hertzberg, S; Kvittingen, L; Anthonsen, T; Skjåk-Braek, G

1992-01-01

Alginate was evaluated as an immobilization matrix for enzyme-catalyzed reactions in organic solvents. In contrast to most hydrogels, calcium alginate was found to be stable in a range of organic solvents and to retain the enzyme inside the gel matrix. In hydrophobic solvents, the alginate gel (greater than 95% water) thus provided a stable, two-phase liquid system. The lipase from Candida cylindracea, after immobilization in alginate beads, catalysed esterification and transesterification in n-hexane under both batch and continuous-flow conditions. The operational stability of the lipase was markedly enhanced by alginate entrapment. In the esterification of butanoic acid with n-butanol, better results were obtained in the typical hydrophilic calcium alginate beads than in less hydrophilic matrices. The effects of substrate concentration, matrix area, and polarity of the substrate alcohols and of the organic solvent on the esterification activity were examined. The transesterification of octyl 2-bromopropanoate with ethanol was less efficient than that of ethyl 2-bromopropanoate with octanol. By using the hydrophilic alginate gel as an immobilization matrix in combination with a mobile hydrophobic phase, a two-phase liquid system was achieved with definite advantages for a continuous, enzyme-catalysed process.

Methyl Ester Production via Heterogeneous Acid-Catalyzed Simultaneous Transesterification and Esterification Reactions

NASA Astrophysics Data System (ADS)

Indrayanah, S.; Erwin; Marsih, I. N.; Suprapto; Murwani, I. K.

2017-05-01

The heterogeneous acid catalysts (MgF2 and ZnF2) have been used to catalyze the simultaneous transesterification and esterification reactions of crude palm oil (CPO) with methanol. Catalysts were synthesized by sol-gel method (combination of fluorolysis and hydrolysis). The physicochemical, structural, textural, thermal stability of the prepared catalysts was investigated by N2 adsorption-desorption, XRD, FT-IR, SEM and TG/DTG. Both MgF2 and ZnF2 have rutile structures with a different phase. The surface area of ZnF2 is smaller than that of MgF2, but the pore size and volume of ZnF2 are larger than those of MgF2. However, these materials are thermally stable. The performance of the catalysts is determined from the yield of catalysts toward the formation of methyl ester determined based on the product of methyl ester obtained from the reaction. The catalytic activity of ZnF2 is higher than MgF2 amounted to 85.21% and 26.82% with the optimum condition. The high activity of ZnF2 could be attributed to its pore diameter and pore volume but was not correlated with its surface area. The yield of methyl ester decreased along with the increase in molar ratio of methanol/CPO from 85.21 to 80.99 for ZnF2, respectively.

Protease activation in glycerol-based deep eutectic solvents.

PubMed

Zhao, Hua; Baker, Gary A; Holmes, Shaletha

2011-11-01

Deep eutectic solvents (DESs) consisting of mixtures of a choline salt (chloride or acetate form) and glycerol are prepared as easily accessible, biodegradable, and inexpensive alternatives to conventional aprotic cation-anion paired ionic liquids. These DES systems display excellent fluidity coupled with thermal stability to nearly 200 °C. In this work, the transesterification activities of cross-linked proteases (subtilisin and α-chymotrypsin), immobilized on chitosan, were individually examined in these novel DESs. In the 1:2 molar ratio mixture of choline chloride/glycerol containing 3% (v/v) water, cross-linked subtilisin exhibited an excellent activity (2.9 μmo l min(-1) g(-1)) in conjunction with a selectivity of 98% in the transesterification reaction of N-acetyl-L-phenylalanine ethyl ester with 1-propanol. These highly encouraging results advocate more extensive exploration of DESs in protease-mediated biotransformations of additional polar substrates and use of DESs in biocatalysis more generally.

Synthesis of fatty acid methyl ester from palm oil (Elaeis guineensis) with Ky(MgCa)2xO3 as heterogeneous catalyst.

PubMed

Olutoye, M A; Lee, S C; Hameed, B H

2011-12-01

Fatty acid methyl esters (FAME) were produced from palm oil using eggshell modified with magnesium and potassium nitrates to form a composite, low-cost heterogeneous catalyst for transesterification. The catalyst, prepared by the combination of impregnation/co-precipitation was calcined at 830 °C for 4 h. Transesterification was conducted at a constant temperature of 65 °C in a batch reactor. Design of experiment (DOE) was used to optimize the reaction parameters, and the conditions that gave highest yield of FAME (85.8%) was 5.35 wt.% catalyst loading at 4.5 h with 16:1 methanol/oil molar ratio. The results revealed that eggshell, a solid waste, can be utilized as low-cost catalyst after modification with magnesium and potassium nitrates for biodiesel production. Copyright © 2011 Elsevier Ltd. All rights reserved.

In-Water and Neat Batch and Continuous-Flow Direct Esterification and Transesterification by a Porous Polymeric Acid Catalyst

PubMed Central

Baek, Heeyoel; Minakawa, Maki; Yamada, Yoichi M. A.; Han, Jin Wook; Uozumi, Yasuhiro

2016-01-01

A porous phenolsulphonic acid—formaldehyde resin (PAFR) was developed. The heterogeneous catalyst PAFR was applied to the esterification of carboxylic acids and alcohols, affording the carboxylic acid esters in a yield of up to 95% where water was not removed from the reaction mixture. Surprisingly, the esterification in water as a solvent proceeded to afford the desired esters in high yield. PAFR provided the corresponding esters in higher yield than other homogeneous and heterogeneous catalysts. The transesterification of alcohols and esters was also investigated by using PAFR, giving the corresponding esters. PAFR was applied to the batch-wise and continuous-flow production of biodiesel fuel FAME. The PAFR-packed flow reactor that was developed for the synthesis of carboxylic acids and FAME worked for four days without loss of its catalytic activity. PMID:27189631

Subcritical ethylic biodiesel production from wet animal fat and vegetable oils: A net energy ratio analysis

DOE PAGES

Sales, Emerson A.; Ghirardi, Maria L.; Jorquera, Orlando

2016-08-23

Ethylic transesterification process for biodiesel production without any chemical or biochemical catalysts at different subcritical thermodynamic conditions was performed using wet animal fat, soybean and palm oils as feedstock. The results indicate that 2 h of reaction at 240 °C with pressures varying from 20 to 45 bar was sufficient to transform almost all lipid fraction of the samples to biodiesel, depending on the reactor dead volume and proportions between reactants. Conversions of 100%, 84% and 98.5% were obtained for animal fat, soybean oil and palm oil, respectively, in the presence of water, with a net energy ration values ofmore » 2.6, 2.1 and 2.5 respectively. Finally, these results indicate that the process is energetically favorable, and thus represents a cleaner technology with environmental advantages when compared to traditional esterification or transesterification processes.« less

Subcritical ethylic biodiesel production from wet animal fat and vegetable oils: A net energy ratio analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sales, Emerson A.; Ghirardi, Maria L.; Jorquera, Orlando

Ethylic transesterification process for biodiesel production without any chemical or biochemical catalysts at different subcritical thermodynamic conditions was performed using wet animal fat, soybean and palm oils as feedstock. The results indicate that 2 h of reaction at 240 °C with pressures varying from 20 to 45 bar was sufficient to transform almost all lipid fraction of the samples to biodiesel, depending on the reactor dead volume and proportions between reactants. Conversions of 100%, 84% and 98.5% were obtained for animal fat, soybean oil and palm oil, respectively, in the presence of water, with a net energy ration values ofmore » 2.6, 2.1 and 2.5 respectively. Finally, these results indicate that the process is energetically favorable, and thus represents a cleaner technology with environmental advantages when compared to traditional esterification or transesterification processes.« less

Ultrasonic assisted biodiesel production of microalgae by direct transesterification

NASA Astrophysics Data System (ADS)

Kalsum, Ummu; Mahfud, Mahfud; Roesyadi, Achmad

2017-03-01

Microalgae are considered as the third generation source of biofuel and an excellent candidate for biofuel production to replace the fossil energy. The use of ultrasonic in producing biodiesel by direct transesterification of Nannochloropsis occulata using KOH as catalyst and methanol as a solvent was investigated. The following condition were determined as an optimum by experimental evaluates:: 1: 15 microalga to methanol (molar ratio); 3% catalyst concentration at temperature 40°C after 30 minute of ultrasonication. The highest yield of biodiesel produced was 30.3%. The main components of methyl ester from Nannochloropsis occulata were palmitic (C16 :0),, oleic (C18:1), stearic (C18;0), arahidic (C20:0) and myristic (C14:0). This stated that the application of ultrasounic for direct transesterificaiton of microalgae effectively reduced the reaction time compared to the reported values of conventional heating systems.

Biodiesel production from palm oil using calcined waste animal bone as catalyst.

PubMed

Obadiah, Asir; Swaroopa, Gnanadurai Ajji; Kumar, Samuel Vasanth; Jeganathan, Kenthorai Raman; Ramasubbu, Alagunambi

2012-07-01

Waste animal bones was employed as a cost effective catalyst for the transesterification of palm oil. The catalyst was calcined at different temperatures to transform the calcium phosphate in the bones to hydroxyapatite and 800 °C was found to give the best yield of biodiesel. The catalyst was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive spectrometry (EDS) and Fourier transform infrared spectrometry (FT-IR). Under the optimal reaction conditions of 20 wt.% of catalyst, 1:18 oil to methanol molar ratio, 200 rpm of stirring of reactants and at a temperature of 65 °C, the methyl ester conversion was 96.78% and it was achieved in 4h. The catalyst performed equally well as the laboratory-grade CaO. Animal bone is therefore a useful raw material for the production of a cheap catalyst for transesterification. Copyright © 2012 Elsevier Ltd. All rights reserved.

Assisted Sonication vs Conventional Transesterification Numerical Simulation and Sensitivity Study

NASA Astrophysics Data System (ADS)

Janajreh, Isam; Noorul Hussain, Mohammed; El Samad, Tala

2015-10-01

Transeterification is known as slow reaction that can take over several hours to complete as the two immiscible liquid reactants combine to form biodiesel and the less favorable glycerol. The quest of finding the perfect catalyst, optimal operational conditions, and reactor configuration to accelerate the reaction in mere few minutes that ensures high quality biodiesel, in economically viable way is coming along with sonication. This drastic reduction is a key enabler for the development of a continuous processing that otherwise is fairly costly and low throughput using conventional method. The reaction kinetics of sonication assisted as inferred by several authors is several time faster and this work implements these rates in a high fidelity numerical simulation model. This flow model is based on Navier-Stokes equations coupled with energy equation for non-isothermal flow and the transport equations of the multiple reactive species. The model is initially validated against experimental data from previous work of the authors using an annular reactor configuration. Following the validation, comparison of the reaction rate is shown to gain more insight to the distribution of the reaction and its attained rates. The two models (conventional and sonication) then compared on the basis of their sensitivity to the methane to oil molar ratio as the most pronounced process parameter. Both the exit reactor yield and the distribution of the species are evaluated with favorable yield under sonication process. These results pave the way to build a more robust process intensified reactor having an integrated selective heterogeneous catalyst to steer the reaction. This can avoid the downstream cleaning processes, cutting reaction time, and render economic benefit to the process.

Effect of Lanthanum-Natural Zeolite, La/NZA catalyst on biodiesel production from crude palm oil

NASA Astrophysics Data System (ADS)

Setianingsih, A.; Wisrayetti; Khairat; Bahri, S.

2018-04-01

Biodiesel can be produced from vegetable oils through the trans-esterification process. In this study, potential vegetable oil of Crude Palm Oil (CPO) was used as sample. The purposes of this research were to produce biodiesel from CPO as an alternative fuel, having study the ratio of impregnation of Lanthanum on NZA, and its catalyst weight to the biodiesel yield. The La/NZA catalyst is made as followed, first the natural zeolite size was reduced using grinding, then activated using HCl 6 N and NH4Cl 1 N, followed with the drying process. La is impregnated into NZA as solution having variations of 1 and 3% (w/w) of NZA, then it was followed with dried in an oven, calcination, oxidation and reduction. Production of biodiesel is carried out through two stages of esterification and transesterification processes. In the trans-esterification process conducted with the various variation of catalyst weight i.e. 1, 2 and 3% of La/NZA (w/w) for a total weight of 80 grams of CPO sample, having the ratio of oil : methanol 1 : 9. Reaction was lasted for 60 minutes at 60°C having 400 rpm stirring speed. From the result, the conversion of 85.37% is given by the run on using 3% La/NZA catalyst having catalyst weight 1%.

Conversion of polar and non-polar algae oil lipids to fatty acid methyl esters with solid acid catalysts--A model compound study.

PubMed

Asikainen, Martta; Munter, Tony; Linnekoski, Juha

2015-09-01

Bio-based fuels are becoming more and more important due to the depleting fossil resources. The production of biodiesel from algae oil is challenging compared to terrestrial vegetable oils, as algae oil consists of polar fatty acids, such as phospholipids and glycolipids, as well as non-polar triglycerides and free fatty acids common in vegetable oils. It is shown that a single sulphonated solid acid catalyst can perform the esterification and transesterification reactions of both polar and non-polar lipids. In mild reaction conditions (60-70 °C) Nafion NR50 catalyst produces methyl palmitate (FAME) from the palmitic acid derivatives of di-, and tri-glyceride, free fatty acid, and phospholipid with over 80% yields, with the glycolipid derivative giving nearly 40% yields of FAME. These results demonstrate how the polar and non-polar lipid derivatives of algal oil can be utilised as feedstocks for biodiesel production with a single catalyst in one reaction step. Copyright © 2015 Elsevier Ltd. All rights reserved.

Multiscale methods for computational RNA enzymology

PubMed Central

Panteva, Maria T.; Dissanayake, Thakshila; Chen, Haoyuan; Radak, Brian K.; Kuechler, Erich R.; Giambaşu, George M.; Lee, Tai-Sung; York, Darrin M.

2016-01-01

RNA catalysis is of fundamental importance to biology and yet remains ill-understood due to its complex nature. The multi-dimensional “problem space” of RNA catalysis includes both local and global conformational rearrangements, changes in the ion atmosphere around nucleic acids and metal ion binding, dependence on potentially correlated protonation states of key residues and bond breaking/forming in the chemical steps of the reaction. The goal of this article is to summarize and apply multiscale modeling methods in an effort to target the different parts of the RNA catalysis problem space while also addressing the limitations and pitfalls of these methods. Classical molecular dynamics (MD) simulations, reference interaction site model (RISM) calculations, constant pH molecular dynamics (CpHMD) simulations, Hamiltonian replica exchange molecular dynamics (HREMD) and quantum mechanical/molecular mechanical (QM/MM) simulations will be discussed in the context of the study of RNA backbone cleavage transesterification. This reaction is catalyzed by both RNA and protein enzymes, and here we examine the different mechanistic strategies taken by the hepatitis delta virus ribozyme (HDVr) and RNase A. PMID:25726472

Aquivion Perfluorosulfonic Superacid as an Efficient Pickering Interfacial Catalyst for the Hydrolysis of Triglycerides.

PubMed

Shi, Hui; Fan, Zhaoyu; Hong, Bing; Pera-Titus, Marc

2017-09-11

Rational design of the surface properties of heterogeneous catalysts can boost the interfacial activity in biphasic reactions through the generation of Pickering emulsions. This concept, termed Pickering interfacial catalysis (PIC), has shown promising credentials in acid-catalyzed transesterification, ester hydrolysis, acetalization, etherification, and alkylation reactions. PIC has now been applied to the efficient, solvent-free hydrolysis of the triglyceride glyceryl trilaurate to lauric acid, catalyzed by Aquivion perfluorosulfonic superacid at mild conditions (100 °C and ambient pressure). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Hydrothermal Treatment on Structural and Catalytic Properties of [CTA]-MCM-41 Silica.

PubMed

Zapelini, Iago W; Silva, Laura L; Cardoso, Dilson

2018-05-21

The [CTA]-MCM-41 hybrid silica is a useful and simply prepared heterogeneous basic catalyst for the transesterification reaction. Here, the effect of hydrothermal treatment during catalyst preparation was investigated, with the aim of improving the structural stability of this catalyst during the reaction. It was observed that the hydrothermal step led to the formation of a material with a higher degree of organization and a greater wall thickness, which improved its structural stability. However, the catalyst prepared using this treatment presented lower catalytic activity, due to the presence of fewer active sites.

Transesterification process to manufacture ethyl ester of rape oil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Korus, R.A.; Hoffman, D.S.; Bam, N.

1993-12-31

A process for the production of the ethyl ester of winter rape [EEWR] for use as a biodiesel fuel has been studied. The essential part of the process is the transesterification of rape oil with ethanol, in the presence of a catalyst, to yield the ethyl ester of rape oil as a product and glycerin as a by-product. Experiments have been performed to determine the optimum conditions for the preparation of EEWR. The process variables were: (1) temperature, (2) catalyst, (3) rate of agitation, (4) water content of the alcohol used, and (5) the amount of excess alcohol used. Themore » optimum conditions were: (1) room temperature, (2) 0.5% sodium methoxide or 1% potassium hydroxide catalyst by weight of rapeseed oil, (3) extremely vigorous agitation with some splashing during the initial phase of the reaction and agitation was not necessary after the reaction mixture became homogeneous, (4) absolute ethanol was necessary for high conversion, and (5) 50% excess ethanol with NaOCH{sub 3} or 100% excess with KOH gave a maximum conversion. Viscosity, cloud point and pour point of the EEWR were measured. A preliminary break-even cost for the commercial production of EEWR was found to be $0.55/liter [$2.08/US gallon].« less

New ether-functionalized ionic liquids for lipase-catalyzed synthesis of biodiesel.

PubMed

Zhao, Hua; Song, Zhiyan; Olubajo, Olarongbe; Cowins, Janet V

2010-09-01

Ionic liquids (ILs) are being explored as solvents for the enzymatic methanolysis of triglycerides. However, most available ILs (especially hydrophobic ones) have poor capability in dissolving lipids, while hydrophilic ILs tend to cause enzyme inactivation. Recently, we synthesized a new type of ether-functionalized ionic liquids (ILs) carrying anions of acetate or formate; they are capable of dissolving a variety of substrates and are also lipase-compatible (Green Chem., 2008, 10, 696-705). In the present study, we carried out the lipase-catalyzed transesterifications of Miglyol oil 812 and soybean oil in these novel ILs. These ILs are capable of dissolving oils at the reaction temperature (50 degrees C); meanwhile, lipases maintained high catalytic activities in these media even in high concentrations of methanol (up to 50% v/v). High conversions of Miglyol oil were observed in mixtures of IL and methanol (70/30, v/v) when the reaction was catalyzed by a variety of lipases and different enzyme preparations (free and immobilized), especially with the use of two alkylammonium ILs 2 and 3. The preliminary study on the transesterification of soybean oil in IL/methanol mixtures further confirms the potential of using oil-dissolving and lipase-stabilizing ILs in the efficient production of biodiesels.

Data on PKO biodiesel production using CaO catalyst from Turkey bones.

PubMed

Ayoola, A A; Fayomi, O S I; Usoro, I F

2018-08-01

In this research paper the production of biodiesel from palm kernel oil (PKO) using CaO obtained from waste turkey bones (WTB) and analytical grade calcium oxide was investigated. Treated WTB was reduced to fine particulate size of <150 µm and then calcinated at 800 °C for 3 h to increase its catalytic activity by its conversion from Calcium phosphate hydroxide (Ca 10 P 6 O 26 H 2 ) to CaO. X-ray diffraction (XRD) and X-ray fluorescent (XRF) analysis of the analytical grade CaO, uncalcined and calcined WTB were carried out to establish their elemental chemical composition. The transesterification reaction between the triglyceride of palm kernel oil (PKO) and methanol was carried out at a constant agitation speed of 600 rpm and temperature of 65 °C, with varied methanol to oil molar ratio (8-14), catalyst concentration (1-7 wt/wt%) and the reaction time (1-3 h). Minitab 17 software (using response surface method) was employed for the design of experiment and statistical analysis required in the transesterification process of biodiesel production. The qualities of the biodiesel produced were assessed and the results obtained showed conformity of the biodiesel produced to the ASTM standard for biodiesel.

Effect of one step KOH activation and CaO modified carbon in transesterification reaction

NASA Astrophysics Data System (ADS)

Yacob, Abd Rahim; Zaki, Muhammad Azam Muhammad

2017-11-01

In this work, one step activation was introduced using potassium hydroxide (KOH) and calcium oxide (CaO) modified palm kernel shells. Various concentration of calcium oxide was used as catalyst while maintaining the same concentration of potassium hydroxide to activate and impregnate the palm kernel shell before calcined at 500°C for 5 hours. All the prepared samples were characterized using Fourier Transform Infrared (FTIR) and Field Emission Scanning Electron Microscope (FESEM). FTIR analysis of raw palm kernel shell showed the presence of various functional groups. However, after activation, most of the functional groups were eliminated. The basic strength of the prepared samples were determined using back titration method. The samples were then used as base heterogeneous catalyst for the transesterification reaction of rice bran oil with methanol. Analysis of the products were performed using Gas Chromatography Flame Ionization Detector (GC-FID) to calculate the percentage conversion of the biodiesel products. This study shows, as the percentage of one step activation potassium and calcium oxide doped carbon increases thus, the basic strength also increases followed by the increase in biodiesel production. Optimization study shows that the optimum biodiesel production was at 8 wt% catalyst loading, 9:1 methanol: oil molar ratio at 65°C and 6 hours which gives a conversion up to 95%.

Formation of ethyl ferulate from feruloylated oligosaccharide by transesterification of rice koji enzyme under sake mash conditions.

PubMed

Suzuki, Nobukazu; Ito, Toshihiko; Hiroshima, Kai; Tokiwano, Tetsuo; Hashizume, Katsumi

2016-03-01

Formation of ethyl ferulate (EF) and ferulic acid (FA) under sake mash conditions was studied using feruloylated oligosaccharide (FO), prepared from rice grains, as the substrate for rice koji enzyme. EF and FA were produced from FO over six times faster than from alkyl ferulates however, under the same ethanol concentration, only small differences were observed between the EF/FA ratios when either FO or methyl ferulate were used as substrates. Esterification and hydrolysis of FO or methyl ferulate showed similar pH dependencies and similar EF/FA ratios for each substrate in all of the pH ranges tested. Ethanol concentration clearly affected the EF/FA ratio; the ratio increased as ethanol concentration increased. Formation of EF and FA in the sake mash simulated rice digest was accelerated by addition of exogenous FO. These results indicated that supply of FO to sake mash is a crucial step for EF and FA formation, and ethanol is an influencing factor in the EF/FA ratio. The rice koji enzyme reaction suggested that EF and FA are formed through a common feruloylated enzyme intermediate complex by transesterification or hydrolysis, and these reactions occur competitively. Copyright © 2015 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Construction of combustion models for rapeseed methyl ester bio-diesel fuel for internal combustion engine applications.

PubMed

Golovitchev, Valeri I; Yang, Junfeng

2009-01-01

Bio-diesel fuels are non-petroleum-based diesel fuels consisting of long chain alkyl esters produced by the transesterification of vegetable oils, that are intended for use (neat or blended with conventional fuels) in unmodified diesel engines. There have been few reports of studies proposing theoretical models for bio-diesel combustion simulations. In this study, we developed combustion models based on ones developed previously. We compiled the liquid fuel properties, and the existing detailed mechanism of methyl butanoate ester (MB, C(5)H(10)O(2)) oxidation was supplemented by sub-mechanisms for two proposed fuel constituent components, C(7)H(16) and C(7)H(8)O (and then, by mp2d, C(4)H(6)O(2) and propyne, C(3)H(4)) to represent the combustion model for rapeseed methyl ester described by the chemical formula, C(19)H(34)O(2) (or C(19)H(36)O(2)). The main fuel vapor thermal properties were taken as those of methyl palmitate C(19)H(36)O(2) in the NASA polynomial form of the Burcat database. The special global reaction was introduced to "crack" the main fuel into its constituent components. This general reaction included 309 species and 1472 reactions, including soot and NO(x) formation processes. The detailed combustion mechanism was validated using shock-tube ignition-delay data under diesel engine conditions. For constant volume and diesel engine (Volvo D12C) combustion modeling, this mechanism could be reduced to 88 species participating in 363 reactions.

Lipase-catalyzed simultaneous biosynthesis of biodiesel and glycerol carbonate from corn oil in dimethyl carbonate.

PubMed

Min, Ji Young; Lee, Eun Yeol

2011-09-01

Biodiesel [fatty acid methyl esters (FAMEs)] and glycerol carbonate were synthesized from corn oil and dimethyl carbonate (DMC) via transesterification using lipase (Novozyme 435) in solvent-free reaction in which excess DMC was used as the substrate and reaction medium. Glycerol carbonate was also simultaneously formed from DMC and glycerol. Conversions of FAMEs and glycerol carbonate were examined in batch reactions. The FAMEs and glycerol carbonate reached 94 and 62.5% from oil and DMC (molar ratio of 1:10) with 0.2% (v/v) water and 10% (w/w) Novozyme 435 (based on oil weight) at 60 °C. When Novozyme 435 was washed with acetone after each reaction, more than 80% activity still remained after seven recycling. © Springer Science+Business Media B.V. 2011

Two step esterification-transesterification process of wet greasy sewage sludge for biodiesel production.

PubMed

Urrutia, C; Sangaletti-Gerhard, N; Cea, M; Suazo, A; Aliberti, A; Navia, R

2016-01-01

Sewage sludge generated in municipal wastewater treatment plants was used as a feedstock for biodiesel production via esterification/transesterification in a two-step process. In the first esterification step, greasy and secondary sludge were tested using acid and enzymatic catalysts. The results indicate that both catalysts performed the esterification of free fatty acids (FFA) simultaneously with the transesterification of triacylglycerols (TAG). Acid catalyst demonstrated better performance in FFA esterification compared to TAG transesterification, while enzymatic catalyst showed the ability to first hydrolyze TAG in FFA, which were esterified to methyl esters. In addition, FAME concentration using greasy sludge were higher (63.9% and 58.7%), compared with those of secondary sludge (11% and 16%), using acid and enzymatic catalysts, respectively. Therefore, only greasy sludge was used in the second step of alkaline transesterification. The alkaline transesterification of the previously esterified greasy sludge reached a maximum FAME concentration of 65.4% when using acid catalyst. Copyright © 2015 Elsevier Ltd. All rights reserved.

Transesterification of Waste Activated Sludge for Biosolids Reduction and Biodiesel Production.

PubMed

Maeng, Min Ho; Cha, Daniel K

2018-02-01

  Transesterification of waste activated sludge (WAS) was evaluated as a cost-effective technique to reduce excess biosolids and recover biodiesel feedstock from activated sludge treatment processes. A laboratory-scale sequencing batch reactor (SBR) was operated with recycling transesterification-treated WAS back to the aeration basin. Seventy percent recycling of WAS resulted in a 48% reduction of excess biosolids in comparison with a conventional SBR, which was operated in parallel as the control SBR. Biodiesel recovery of 8.0% (dried weight basis) was achieved at an optimum transesterification condition using acidic methanol and xylene as cosolvent. Average effluent soluble chemical oxygen demand (COD) and total suspended solids (TSS) concentrations from the test SBR and control SBR were comparable, indicating that the recycling of transesterification-treated WAS did not have detrimental effect on the effluent quality. This study demonstrated that transesterification and recycling of WAS may be a feasible technique for reducing excess biosolids, while producing valuable biodiesel feedstock from the activated sludge process.

Egg shell waste as heterogeneous nanocatalyst for biodiesel production: Optimized by response surface methodology.

PubMed

Pandit, Priti R; Fulekar, M H

2017-08-01

Worldwide consumption of hen eggs results in availability of large amount of discarded egg waste particularly egg shells. In the present study, the waste shells were utilized for the synthesis of highly active heterogeneous calcium oxide (CaO) nanocatalyst to transesterify dry biomass into methyl esters (biodiesel). The CaO nanocatalyst was synthesied by calcination-hydration-dehydration technique and fully characterized by infrared spectroscopy, X-ray powder diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), brunauer-emmett-teller (BET) elemental and thermogravimetric analysis. TEM image showed that the nano catalyst had spherical shape with average particle size of 75 nm. BET analysis indicated that the catalyst specific surface area was 16.4 m 2  g -1 with average pore diameter of 5.07 nm. The effect of nano CaO catalyst was investigated by direct transesterification of dry biomass into biodiesel along with other reaction parameters such as catalyst ratio, reaction time and stirring rate. The impact of the transesterification reaction parameters and microalgal biodiesel yield were analyzed by response surface methodology based on a full factorial, central composite design. The significance of the predicted mode was verified and 86.41% microalgal biodiesel yield was reported at optimal parameter conditions 1.7% (w/w), catalyst ratio, 3.6 h reaction time and stirring rate of 140.6 rpm. The biodiesel conversion was determined by 1 H nuclear magnetic resonance spectroscopy (NMR). The fuel properties of prepared biodiesel were found to be highly comply with the biodiesel standard ASTMD6751 and EN14214. Copyright © 2017 Elsevier Ltd. All rights reserved.

Biodiesel synthesis using chicken manure biochar and waste cooking oil.

PubMed

Jung, Jong-Min; Lee, Sang-Ryong; Lee, Jechan; Lee, Taewoo; Tsang, Daniel C W; Kwon, Eilhann E

2017-11-01

This study laid an emphasis on the possible employment of biochar generated from pyrolysis of chicken manure to establish a green platform for producing biodiesel. To this end, the pseudo-catalytic transesterification reaction using chicken manure biochar and waste cooking oil was investigated. Compared with a commercial porous material (SiO 2 ), chicken manure biochar generated from 350°C showed better performance, resulting in 95.6% of the FAME yield at 350°C. The Ca species in chicken manure biochar imparted strong catalytic capability by providing the basicity for transesterification. The identified catalytic effect also led to the thermal cracking of unsaturated FAMEs, which decreased the overall FAME yield. For example, 40-60% of converted FAMEs were thermally degraded. To avoid undesirable thermal cracking arising from the high content of the Ca species in chicken manure biochar, the fabrication of chicken manure biochar at temperatures ≥350°C was highly recommended. Copyright © 2017 Elsevier Ltd. All rights reserved.

Rapid synthesis of propyl caffeate in ionic liquid using a packed bed enzyme microreactor under continuous-flow conditions.

PubMed

Wang, Jun; Gu, Shuang-Shuang; Cui, Hong-Sheng; Yang, Liu-Qing; Wu, Xiang-Yang

2013-12-01

Propyl caffeate has the highest antioxidant activity among caffeic acid alkyl esters, but its industrial production via enzymatic transesterification in batch reactors is hindered by a long reaction time (24h). To develop a rapid process for the production of propyl caffeate in high yield, a continuous-flow microreactor composed of a two-piece PDMS in a sandwich-like microchannel structure was designed for the transesterification of methyl caffeate and 1-propanol catalyzed by Novozym 435 in [B mim][CF3SO3]. The maximum yield (99.5%) in the microreactor was achieved in a short period of time (2.5h) with a flow rate of 2 μL/min, which kinetic constant Km was 16 times lower than that of a batch reactor. The results indicated that the use of a continuous-flow packed bed enzyme microreactor is an efficient method of producing propyl caffeate with an overall yield of 84.0%. Copyright © 2013 Elsevier Ltd. All rights reserved.

Hyperbaric hyperoxia reversibly inhibits erythrocyte phospholipid fatty acid turnover

NASA Technical Reports Server (NTRS)

Dise, Craig A.; Clark, James M.; Lambersten, Christian J.; Goodman, David B. P.

1987-01-01

The effect of hyperbaric hyperoxia on the acylation of membrane phospholipid was studied by measuring the rates of activation of exogenous tritiated oleic acid to acyl thioester and of transesterification of the thioester into membrane phospholipids in intact human erythrocytes obtained 1 h after an exposure of the subjects to a hyperbaric oxygen atmosphere (3.5 h, 100 pct O2, 3 ATA). Exposure to pure oxygen was found to inhibit both the acylation and transesterification reactions by more than 30 percent, with partial recovery detected 24 h later. On the other hand, no rate changes were observed when isolated membranes from the same batches of cells were used in similar experiments. It is suggested that the decrease in the incorporation of tritiated oleic acid after hyperbaric hyperoxia may reflect an early event in the pathogenesis of oxygen-induced cellular injury and that it may be a useful index for the assessment of the tolerance of tissues to hyperoxia.

Concurrent production of biodiesel and chemicals through wet in situ transesterification of microalgae.

PubMed

Im, Hanjin; Kim, Bora; Lee, Jae W

2015-10-01

This work addresses an unprecedented way of co-producing biodiesel (FAEE) and valuable chemicals of ethyl levulinate (EL), ethyl formate (EF) and diethyl ether (DEE) from wet in situ transesterification of microalgae. EL, EF, and DEE were significantly produced up to 23.1%, 10.3%, and 52.1% of the maximum FAEE mass with the FAEE yield higher than 90% at 125 °C. Experiments to elucidate a detailed route of EL and EF synthesis were fulfilled and it was found that its main route to the production of EL and EF was the acid hydrolysis of algal cells and esterification with ethanol. To investigate the effect of reaction variables on the products yields, comprehensive experiments were carried out with varying temperatures, solvent and alcohol volumes, moisture contents and catalyst amounts. Coproduction of DEE, EL, EF and FAEE can contribute to elevating the economic feasibility of microalgae-based biodiesel supply chain. Copyright © 2015 Elsevier Ltd. All rights reserved.

[Comparative assessment of Cladophora, Spirogyra and Oedogonium biomass for the production of fatty acid methyl esters].

PubMed

Haq, I; Muhammad, A; Hameed, U

2014-01-01

The use of alternative fuels for the mitigation of ecological impacts by use of diesel has been focus of intensive research. In the present work, algal oils extracted from cultivated biomass of Cladophora sp., Spirogyra sp. and Oedogonium sp. were evaluated for the lipase-mediated synthesis of fatty acid monoalkyl esters (FAME, biodiesel). To optimize the transesterification of these oils, different parameters such as the alkyl group donor, reaction temperature, stirring time and oil to alcohol ratio were investigated. Four different alcohols i.e. methanol, ethanol, n-propanol and n-butanol were tested as alkyl group donor for the biosynthesis FAME and methanol was found to be the best. Similarly, temperature 50 C and stirring time of 6 h were optimized for the transesterification of oils with methanol. The maximum biodiesel conversions from Cladophora (75.0%), Spirogyra (87.5%) and Oedogonium (92.0%) were obtained when oil to alcohol ratio was 1 : 8.

Osmium (VI) complexes of the 3', 5'-dinucleoside monophosphates, ApU and UpA.

PubMed

Daniel, F B; Behrman, E J

1976-02-10

The dinucleoside monophosphates, ApU and UpA, react with potassium osmate (VI) and 2,2'-bipyridyl to form the corresponding oxo-osmium (VI) bipyridyl sugar ester in which the osmate group is bonded to the terminal 2',3'-glycol. Osmium (VIII) tetroxide and 2,2'-bipyridyl react with the dinucleosides to form the corresponding oxo-osmium (VI) bipyridyl heterocyclic esters which result from addition of the tetroxide to the 5,6-double bond of the uracil residue. Although capable of transesterification reactions, these heterocyclic esters are exceptionally stable toward exchange reactions in solution. No apparent exchange was observed after 1 month. This reaction thus seems promising for single-site osmium labeling in polynucleotides.

Reactivity of a Carbon-Supported Single-Site Molybdenum Dioxo Catalyst for Biodiesel Synthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mouat, Aidan R.; Lohr, Tracy L.; Wegener, Evan C.

2016-08-23

A single-site molybdenum dioxo catalyst, (O c) 2Mo(=O) 2@C, was prepared via direct grafting of MoO 2Cl 2(dme) (dme = 1,2-dimethoxyethane) on high-surface- area activated carbon. The physicochemical and chemical properties of this catalyst were fully characterized by N 2 physisorption, ICP-AES/OES, PXRD, STEM, XPS, XAS, temperature-programmed reduction with H 2 (TPR-H 2), and temperature-programmed NH 3 desorption (TPD-NH 3). The single-site nature of the Mo species is corroborated by XPS and TPR-H 2 data, and it exhibits the lowest reported MoO x Tmax of reduction reported to date, suggesting a highly reactive MoVI center. (O c) 2Mo(=O) 2@C catalyzesmore » the transesterification of a variety of esters and triglycerides with ethanol, exhibiting high activity at moderate temperatures (60-90 °C) and with negligible deactivation. (O c) 2Mo(=O) 2@C is resistant to water and can be recycled at least three times with no loss of activity. The transesterification reaction is determined experimentally to be first order in [ethanol] and first order in [Mo] with ΔH = 10.5(8) kcal mol -1 and ΔS = -32(2) eu. The low energy of activation is consistent with the moderate conditions needed to achieve rapid turnover. This highly active carbon-supported single-site molybdenum dioxo species is thus an efficient, robust, and lowcost catalyst with significant potential for transesterification processes.« less

Metaloxide--ZrO2 catalysts for the esterification and transesterification of free fatty acids and triglycerides to obtain bio-diesel

DOEpatents

Kim, Manhoe; Salley, Steven O.; Ng, K. Y. Simon

2016-09-06

Mixed metal oxide catalysts (ZnO, CeO, La2O3, NiO, Al203, SiO2, TiO2, Nd2O3, Yb2O3, or any combination of these) supported on zirconia (ZrO2) or hydrous zirconia are provided. These mixed metal oxide catalysts can be prepared via coprecipitation, impregnation, or sol-gel methods from metal salt precursors with/without a Zirconium salt precursor. Metal oxides/ZrO2 catalyzes both esterification and transesterification of oil containing free fatty acids in one batch or in single stage. In particular, these mixed metal oxides supported or added on zirconium oxide exhibit good activity and selectivity for esterification and transesterification. The low acid strength of this catalyst can avoid undesirable side reaction such as alcohol dehydration or cracking of fatty acids. Metal oxides/ZrO2 catalysts are not sensitive to any water generated from esterification. Thus, esterification does not require a water free condition or the presence of excess methanol to occur when using the mixed metal oxide catalyst. The FAME yield obtained with metal oxides/ZrO2 is higher than that obtained with homogeneous sulfuric acid catalyst. Metal oxides/ZrO2 catalasts can be prepared as strong pellets and in various shapes for use directly in a flow reactor. Furthermore, the pellet has a strong resistance toward dissolution to aqueous or oil phases.

Glycerol triacetate as solvent and acyl donor in the production of isoamyl acetate with Candida antarctica lipase B.

PubMed

Wolfson, Adi; Atyya, Aviad; Dlugy, Christina; Tavor, Dorith

2010-03-01

Glycerol triacetate was successfully used as a green solvent and as the acyl donor in the transesterification of isoamyl alcohol to produce isoamyl acetate using free and immobilized Candida antarctica lipase B. Immobilized lipase was more catalytically active than free lipase and could be easily separated from the reaction mixture by filtration. In addition, it was found that increasing either the reaction temperature or the enzyme to substrate ratio increased the conversion of isoamyl alcohol. Using triacetin as the solvent also enabled the separation of product by simple extraction with petroleum ether and catalyst recycling.

Effect of Reaction Temperature on Biodiesel Production from Chlorella vulgaris using CuO/Zeolite as Heterogeneous Catalyst

NASA Astrophysics Data System (ADS)

Dianursanti; Delaamira, M.; Bismo, S.; Muharam, Y.

2017-02-01

Human needs for fossil energy increase every year. Biodiesel is the main way to resolve this world problem. Biodiesel produces from vegetable oil. But then, the alternative way came from the uses of microalgae in Chlorella vulgaris type causes by its simplicity of growing. In the other hand, this microalgae known for its high lipid content by considering several parameter such as light intensity, medium nutrition, pH and also salinity. Lipid content will be extracted by using Bligh-Dryer method which will be reacted with methanol along transesterification. Beside, there come another matter which is the utilization of homogeny catalyst. The difficulty of separation is the main matter so then biodiesel need to be washed in case normalizing the pH and this process will decrease the quality of biodiesel. To resolve this problem, we’ll be using a heterogeneous catalyst, zeolite, with ability to catalyst the process. Zeolite is easier to separate from the biodiesel so there will not be needed washing process. Heterogeneous catalyst work as well as homogeneous. Variation implemented on transesterification included reaction temperature of 40°C, 60°C, and 80°C. Reaction time, catalyst percentage and the solvent amount remain steady on 4 hours, 3% and 1:400. Complete best result obtained at 60°C with the yield of 36,78%. Through this, heterogeneous catalyst CuO/Zeolite proved to have a capability for replacing homogeneous catalyst and simplify the production of biodiesel particularly in separation step.

KF-loaded mesoporous Mg-Fe bi-metal oxides: high performance transesterification catalysts for biodiesel production.

PubMed

Tao, Guiju; Hua, Zile; Gao, Zhe; Zhu, Yan; Zhu, Yan; Chen, Yu; Shu, Zhu; Zhang, Lingxia; Shi, Jianlin

2013-09-21

Using newly developed mesoporous Mg-Fe bi-metal oxides as supports, a novel kind of high performance transesterification catalysts for biodiesel production has been synthesized. More importantly, the impregnation solvent was for the first time found to substantially affect the structures and catalytic performances of the resultant transesterification catalysts.

Mechanistic Insights into RNA Transphosphorylation from Kinetic Isotope Effects and Linear Free Energy Relationships of Model Reactions

PubMed Central

Chen, Haoyuan; Giese, Timothy J.; Huang, Ming; Wong, Kin-Yiu; Harris, Michael E.; York, Darrin M.

2015-01-01

Phosphoryl transfer reactions are ubiquitous in biology, and the understanding of the mechanisms whereby these reactions are catalyzed by protein and RNA enzymes is central to reveal design principles for new therapeutics. Two of the most powerful experimental probes of chemical mechanism involve the analysis of linear free energy relations (LFERs) and the measurement of kinetic isotope effects (KIEs). These experimental data report directly on differences in bonding between the ground state and the rate-controlling transition state, which is the most critical point along the reaction free energy pathway. However, interpretation of LFER and KIE data in terms of transition state structure and bonding optimally requires the use of theoretical models. In this work, we apply density-functional calculations to determine KIEs for a series of phosphoryl transfer reactions of direct relevance to the 2’-O-transphosphorylation that leads to cleavage of the phosphodiester backbone of RNA. We first examine a well-studied series of phosphate and phosphorothioate mono-, di- and triesters that are useful as mechanistic probes and for which KIEs have been measured. Close agreement is demonstrated between the calculated and measured KIEs, establishing the reliability of our quantum model calculations. Next, we examine a series of RNA transesterification model reactions with a wide range of leaving groups in order to provide a direct connection between observed Brønsted coefficients and KIEs with the structure and bonding in the transition state. These relations can be used for prediction or to aid in the interpretation of experimental data for similar non-enzymatic and enzymatic reactions. Finally, we apply these relations to RNA phosphoryl transfer catalyzed by ribonuclease A, and demonstrate the reaction coordinate-KIE correlation is reasonably preserved. A prediction of the secondary deuterium KIE in this reaction is also provided. These results demonstrate the utility of building up knowledge of mechanism through the systematic study of model systems to provide insight into more complex biological systems such as phosphoryl transfer enzymes and ribozymes. PMID:25223953

Mechanistic insights into RNA transphosphorylation from kinetic isotope effects and linear free energy relationships of model reactions.

PubMed

Chen, Haoyuan; Giese, Timothy J; Huang, Ming; Wong, Kin-Yiu; Harris, Michael E; York, Darrin M

2014-10-27

Phosphoryl transfer reactions are ubiquitous in biology and the understanding of the mechanisms whereby these reactions are catalyzed by protein and RNA enzymes is central to reveal design principles for new therapeutics. Two of the most powerful experimental probes of chemical mechanism involve the analysis of linear free energy relations (LFERs) and the measurement of kinetic isotope effects (KIEs). These experimental data report directly on differences in bonding between the ground state and the rate-controlling transition state, which is the most critical point along the reaction free energy pathway. However, interpretation of LFER and KIE data in terms of transition-state structure and bonding optimally requires the use of theoretical models. In this work, we apply density-functional calculations to determine KIEs for a series of phosphoryl transfer reactions of direct relevance to the 2'-O-transphosphorylation that leads to cleavage of the phosphodiester backbone of RNA. We first examine a well-studied series of phosphate and phosphorothioate mono-, di- and triesters that are useful as mechanistic probes and for which KIEs have been measured. Close agreement is demonstrated between the calculated and measured KIEs, establishing the reliability of our quantum model calculations. Next, we examine a series of RNA transesterification model reactions with a wide range of leaving groups in order to provide a direct connection between observed Brønsted coefficients and KIEs with the structure and bonding in the transition state. These relations can be used for prediction or to aid in the interpretation of experimental data for similar non-enzymatic and enzymatic reactions. Finally, we apply these relations to RNA phosphoryl transfer catalyzed by ribonuclease A, and demonstrate the reaction coordinate-KIE correlation is reasonably preserved. A prediction of the secondary deuterium KIE in this reaction is also provided. These results demonstrate the utility of building up knowledge of mechanism through the systematic study of model systems to provide insight into more complex biological systems such as phosphoryl transfer enzymes and ribozymes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Role of metal ions in catalysis by HIV integrase analyzed using a quantitative PCR disintegration assay.

PubMed

Diamond, Tracy L; Bushman, Frederic D

2006-01-01

Paired metal ions have been proposed to be central to the catalytic mechanisms of RNase H nucleases, bacterial transposases, Holliday junction resolvases, retroviral integrases and many other enzymes. Here we present a sensitive assay for DNA transesterification in which catalysis by human immunodeficiency virus-type 1 (HIV-1) integrase (IN) connects two DNA strands (disintegration reaction), allowing detection using quantitative PCR (qPCR). We present evidence suggesting that the three acidic residues of the IN active site function through metal binding using metal rescue. In this method, the catalytic acidic residues were each substituted with cysteines. Mn2+ binds tightly to the sulfur atoms of the cysteine residues, but Mg2+ does not. We found that Mn2+, but not Mg2+, could rescue catalysis of each cysteine-substituted enzyme, providing evidence for functionally important metal binding by all three residues. We also used the PCR-boosted assay to show that HIV-1 IN could carry out transesterification reactions involving DNA 5' hydroxyl groups as well as 3' hydroxyls as nucleophiles. Lastly, we show that Mn2+ by itself (i.e. without enzyme) can catalyze formation of a low level of PCR-amplifiable product under extreme conditions, allowing us to estimate the rate enhancement due to the IN-protein scaffold as at least 60 million-fold.

Adaptable liquid crystal elastomers with transesterification-based bond exchange reactions.

PubMed

Hanzon, Drew W; Traugutt, Nicholas A; McBride, Matthew K; Bowman, Christopher N; Yakacki, Christopher M; Yu, Kai

2018-02-14

Adaptable liquid crystal elastomers (LCEs) have recently emerged to provide a new and robust method to program monodomain LCE samples. When a constant stress is applied with active bond exchange reactions (BERs), polymer chains and mesogens gradually align in the strain direction. Mesogen alignment is maintained after removing the BER stimulus (e.g. by lowering the temperature) and the programmed LCE samples exhibit free-standing two-way shape switching behavior. Here, a new adaptable main-chain LCE system was developed with thermally induced transesterification BERs. The network combines the conventional properties of LCEs, such as an isotropic phase transition and soft elasticity, with the dynamic features of adaptable network polymers, which are malleable to stress relaxation due to the BERs. Polarized Fourier transform infrared measurements confirmed the alignment of polymer chains and mesogens after strain-induced programming. The influence of the creep stress, temperature, and time on the strain amplitude of two-way shape switching was examined. The LCE network demonstrates an innovative feature of reprogrammability, where the reversible shape-switching memory of programmed LCEs is readily deleted by free-standing heating as random BERs disrupt the mesogen alignment, so LCEs are reprogrammed after returning to the polydomain state. Due to the dynamic nature of the LCE network, it also exhibits a surface welding effect and can be fully dissolved in the organic solvent, which might be utilized for green and sustainable recycling of LCEs.

Role of metal ions in catalysis by HIV integrase analyzed using a quantitative PCR disintegration assay

PubMed Central

Diamond, Tracy L.; Bushman, Frederic D.

2006-01-01

Paired metal ions have been proposed to be central to the catalytic mechanisms of RNase H nucleases, bacterial transposases, Holliday junction resolvases, retroviral integrases and many other enzymes. Here we present a sensitive assay for DNA transesterification in which catalysis by human immunodeficiency virus-type 1 (HIV-1) integrase (IN) connects two DNA strands (disintegration reaction), allowing detection using quantitative PCR (qPCR). We present evidence suggesting that the three acidic residues of the IN active site function through metal binding using metal rescue. In this method, the catalytic acidic residues were each substituted with cysteines. Mn2+ binds tightly to the sulfur atoms of the cysteine residues, but Mg2+ does not. We found that Mn2+, but not Mg2+, could rescue catalysis of each cysteine-substituted enzyme, providing evidence for functionally important metal binding by all three residues. We also used the PCR-boosted assay to show that HIV-1 IN could carry out transesterification reactions involving DNA 5′ hydroxyl groups as well as 3′ hydroxyls as nucleophiles. Lastly, we show that Mn2+ by itself (i.e. without enzyme) can catalyze formation of a low level of PCR-amplifiable product under extreme conditions, allowing us to estimate the rate enhancement due to the IN-protein scaffold as at least 60 million-fold. PMID:17085478

Biodiesel production from wet microalgae feedstock using sequential wet extraction/transesterification and direct transesterification processes.

PubMed

Chen, Ching-Lung; Huang, Chien-Chang; Ho, Kao-Chia; Hsiao, Ping-Xuan; Wu, Meng-Shan; Chang, Jo-Shu

2015-10-01

Although producing biodiesel from microalgae seems promising, there is still a lack of technology for the quick and cost-effective conversion of biodiesel from wet microalgae. This study was aimed to develop a novel microalgal biodiesel producing method, consisting of an open system of microwave disruption, partial dewatering (via combination of methanol treatment and low-speed centrifugation), oil extraction, and transesterification without the pre-removal of the co-solvent, using Chlamydomonas sp. JSC4 with 68.7 wt% water content as the feedstock. Direct transesterification with the disrupted wet microalgae was also conducted. The biomass content of the wet microalgae increased to 56.6 and 60.5 wt%, respectively, after microwave disruption and partial dewatering. About 96.2% oil recovery was achieved under the conditions of: extraction temperature, 45°C; hexane/methanol ratio, 3:1; extraction time, 80 min. Transesterification of the extracted oil reached 97.2% conversion within 15 min at 45°C and 6:1 solvent/methanol ratio with simultaneous Chlorophyll removal during the process. Nearly 100% biodiesel conversion was also obtained while conducting direct transesterification of the disrupted oil-bearing microalgal biomass. Copyright © 2015 Elsevier Ltd. All rights reserved.

Radical scavenging activity of lipophilized products from lipase-catalyzed transesterification of triolein with cinnamic and ferulic acids.

PubMed

Choo, Wee-Sim; Birch, Edward John

2009-02-01

Lipase-catalyzed transesterification of triolein with cinnamic and ferulic acids using an immobilized lipase from Candida antarctica (E.C. 3.1.1.3) was conducted to evaluate the antioxidant activity of the lipophilized products as model systems for enhanced protection of unsaturated oil. The lipophilized products were identified using ESI-MS. Free radical scavenging activity was determined using the DPPH radical method. The polarity of the solvents proved important in determining the radical scavenging activity of the substrates. Ferulic acid showed much higher radical scavenging activity than cinnamic acid, which has limited activity. The esterification of cinnamic acid and ferulic acid with triolein resulted in significant increase and decrease in the radical scavenging activity, respectively. These opposite effects were due to the effect of addition of electron-donating alkyl groups on the predominant mechanism of reaction (hydrogen atom transfer or electron transfer) of a species with DPPH. The effect of esterification of cinnamic acid was confirmed using ethyl cinnamate which greatly enhances the radical scavenging activity. Although, compared to the lipophilized cinnamic acid product, the activity was lower. The radical scavenging activity of the main component isolated from lipophilized cinnamic acid product using solid phase extraction, monocinnamoyl dioleoyl glycerol, was as good as the unseparated mixture of lipophilized product. Based on the ratio of a substrate to DPPH concentration, lipophilized ferulic acid was a much more efficient radical scavenger than lipophilized cinnamic acid.

Ultrasonication Assisted Production of Biodiesel from Sunflower Oil by Using CuO: Mg Heterogeneous Nanocatalyst

NASA Astrophysics Data System (ADS)

Varghese, Rintu; Jose, Sony; Joyprabu, H.; Johnson, I.

2017-08-01

Biodiesel is a clean, renewable, biodegradable, eco-friendly and alternative fuel used in the diesel engine. The present work was carried out at constant operational conditions such as methanol to oil molar ratio 6:1, catalyst concentration 0.25%, 30 minute reaction time and the reaction temperature at 60°C. Biodiesel was synthesized by transesterification of sunflower oil (SFO) with methanol, using CuO: Mgas nanocatalyst. This nanocatalyst was prepared by quick precipitation method. The biodiesel yield of 71.78% was achieved under reaction condition. The presence of methyl ester groups at the produced biodiesel was confirmed using the Gas Chromatography-Mass Spectrometry (GC-MS). The FAME conversion yield up to 82.83 % could be obtained under the operating conditions.

Multiphysics numerical modeling of the continuous flow microwave-assisted transesterification process.

PubMed

Muley, Pranjali D; Boldor, Dorin

2012-01-01

Use of advanced microwave technology for biodiesel production from vegetable oil is a relatively new technology. Microwave dielectric heating increases the process efficiency and reduces reaction time. Microwave heating depends on various factors such as material properties (dielectric and thermo-physical), frequency of operation and system design. Although lab scale results are promising, it is important to study these parameters and optimize the process before scaling up. Numerical modeling approach can be applied for predicting heating and temperature profiles including at larger scale. The process can be studied for optimization without actually performing the experiments, reducing the amount of experimental work required. A basic numerical model of continuous electromagnetic heating of biodiesel precursors was developed. A finite element model was built using COMSOL Multiphysics 4.2 software by coupling the electromagnetic problem with the fluid flow and heat transfer problem. Chemical reaction was not taken into account. Material dielectric properties were obtained experimentally, while the thermal properties were obtained from the literature (all the properties were temperature dependent). The model was tested for the two different power levels 4000 W and 4700 W at a constant flow rate of 840ml/min. The electric field, electromagnetic power density flow and temperature profiles were studied. Resulting temperature profiles were validated by comparing to the temperatures obtained at specific locations from the experiment. The results obtained were in good agreement with the experimental data.

Preparation of biodiesel with the help of ultrasonic and hydrodynamic cavitation.

PubMed

Ji, Jianbing; Wang, Jianli; Li, Yongchao; Yu, Yunliang; Xu, Zhichao

2006-12-22

An alkali-catalyzed biodiesel production method with power ultrasonic (19.7 kHz) has been developed that allows a short reaction time and high yield because of emulsification and cavitation of the liquid-liquid immiscible system. Orthogonality experiments were employed to evaluate the effects of synthesis parameters. Furthermore, hydrodynamic cavitation was used for biodiesel production in comparison to ultrasonic method. Both methods were proved to be efficient, and time and energy saving for the preparation of biodiesel by transesterification of soybean oil.

A new hypercrosslinked supermicroporous polymer, with scope for sulfonation, and its catalytic potential for the efficient synthesis of biodiesel at room temperature.

PubMed

Bhunia, Subhajit; Banerjee, Biplab; Bhaumik, Asim

2015-03-25

We have designed a new hypercrosslinked supermicroporous polymer (HMP-1) with a BET surface area of 913 m(2) g(-1) by FeCl3 via a catalyzed Friedel-Crafts alkylation reaction between carbazole and α,α'-dibromo-p-xylene. Upon sulfonation HMP-1 yielded a very efficient solid acid catalyst for the production of biodiesels via esterification/transesterification of free fatty acids (FFA)/esters at room temperature.

Transesterification catalyzed by Lipozyme TLIM for biodiesel production from low cost feedstock

NASA Astrophysics Data System (ADS)

Halim, Siti Fatimah Abdul; Hassan, Hamizura; Amri, Nurulhuda; Bashah, Nur Alwani Ali

2015-05-01

The development of new strategies to efficiently synthesize biodiesel is of extreme important. This is because biodiesel has been accepted worldwide as an alternative fuel for diesel engines. Biodiesel as alkyl ester derived from vegetable oil has considerable advantages in terms of environmental protection. The diminishing petroleum reserves are the major driving force for researchers to look for better strategies in producing biodiesel. The main hurdle to commercialization of biodiesel is the cost of the raw material. Biodiesel is usually produced from food-grade vegetable oil that is more expensive than diesel fuel. Therefore, biodiesel produced from food-grade vegetable oil is currently not economically feasible. Use of an inexpensive raw material such as waste cooking palm oil and non edible oil sea mango are an attractive option to lower the cost of biodiesel. This study addresses an alternative method for biodiesel production which is to use an enzymatic approach in producing biodiesel fuel from low cost feedstock waste cooking palm oil and unrefined sea mango oil using immobilized lipase Lipozyme TL IM. tert-butanol was used as the reaction medium, which eliminated both negative effects caused by excessive methanol and glycerol as the byproduct. Two variables which is methanol to oil molar ratio and enzyme loading were examine in a batch system. Transesterification of waste cooking palm oil reach 65% FAME yield (methanol to oil molar ratio 6:1 and 10% Novozyme 435 based on oil weight), while transesterification of sea mango oil can reach 90% FAME yield (methanol to oil molar ratio 6:1 and 10% Lipozyme TLIM based on oil weight).

Atomistic Model for the Polyamide Formation from β-Lactam Catalyzed by Candida Antarctica Lipase B

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baum, Iris; Elsasser, Brigitta M.; Schwab, Leendert

2011-04-01

Candida antarctica lipase B (CALB) is an established biocatalyst for a variety of transesterification, amidation, and polymerization reactions. In contrast to polyesters, polyamides are not yet generally accessible via enzymatic polymerization. In this regard, an enzyme-catalyzed ring-opening polymerization of {beta}-lactam (2-azetidinone) using CALB is the first example of an enzymatic polyamide formation yielding unbranched poly({beta}-alanine), nylon 3. The performance of this polymerization, however, is poor, considering the maximum chain length of 18 monomer units with an average length of 8, and the molecular basis of the reaction so far is not understood. We have employed molecular modeling techniques using dockingmore » tools, molecular dynamics, and QM/MM procedures to gain insight into the mechanistic details of the various reaction steps involved. As a result, we propose a catalytic cycle for the oligomerization of {beta}-lactam that rationalizes the activation of the monomer, the chain elongation by additional {beta}-lactam molecules, and the termination of the polymer chain. In addition, the processes leading to a premature chain termination are studied. Particularly, the QM/MM calculation enables an atomistic description of all eight steps involved in the catalytic cycle, which features an in situ-generated {beta}-alanine as the elongating monomer and which is compatible with the experimental findings.« less

In-situ pyrogenic production of biodiesel from swine fat.

PubMed

Lee, Jechan; Tsang, Yiu Fai; Jung, Jong-Min; Oh, Jeong-Ik; Kim, Hyung-Wook; Kwon, Eilhann E

2016-11-01

In-situ production of fatty acid methyl esters from swine fat via thermally induced pseudo-catalytic transesterification on silica was investigated in this study. Instead of methanol, dimethyl carbonate (DMC) was used as acyl acceptor to achieve environmental benefits and economic viability. Thermo-gravimetric analysis of swine fat reveals that swine fat contains 19.57wt.% of water and impurities. Moreover, the fatty acid profiles obtained under various conditions (extracted swine oil+methanol+NaOH, extracted swine oil+DMC+pseudo-catalytic, and swine fat+DMC+pseudo-catalytic) were compared. These profiles were identical, showing that the introduced in-situ transesterification is technically feasible. This also suggests that in-situ pseudo-catalytic transesterification has a high tolerance against impurities. This study also shows that FAME yield via in-situ pseudo-catalytic transesterification of swine fat reached up to 97.2% at 380°C. Therefore, in-situ pseudo-catalytic transesterification can be applicable to biodiesel production of other oil-bearing biomass feedstocks. Copyright © 2016 Elsevier Ltd. All rights reserved.

Wet in situ transesterification of microalgae using ethyl acetate as a co-solvent and reactant.

PubMed

Park, Jeongseok; Kim, Bora; Chang, Yong Keun; Lee, Jae W

2017-04-01

This study addresses wet in situ transesterification of microalgae for the production of biodiesel by introducing ethyl acetate as both reactant and co-solvent. Ethyl acetate and acid catalyst are mixed with wet microalgae in one pot and the mixture is heated for simultaneous lipid extraction and transesterification. As a single reactant and co-solvent, ethyl acetate can provide higher FAEE yield and more saccharification of carbohydrates than the case of binary ethanol and chloroform as a reactant and a co-solvent. The optimal yield was 97.8wt% at 114°C and 4.06M catalyst with 6.67mlEtOAC/g dried algae based on experimental results and response surface methodology (RSM). This wet in situ transesterification of microalgae using ethyl acetate doesn't require an additional co-solvent and it also promises more economic benefit as combining extraction and transesterification in a single process. Copyright © 2017 Elsevier Ltd. All rights reserved.

Utilization of waste crab shell (Scylla serrata) as a catalyst in palm olein transesterification.

PubMed

Boey, Peng-Lim; Maniam, Gaanty Pragas; Hamid, Shafida Abd

2009-01-01

Aquaculture activity has increased the population of crab, hence increasing the generation of related wastes, particularly the shell. In addition, the number of molting process in crabs compounds further the amount of waste shell generated. As such, in the present work, the application of the waste crab shell as a source of CaO in transesterification of palm olein to biodiesel (methyl ester) was investigated. Preliminary XRD results revealed that thermally activated crab shell contains mainly CaO. Parametric study has been investigated and optimal conditions were found to be methanol/oil mass ratio, 0.5:1; catalyst amount, 4 wt. %; and reaction temperature, 338 K. As compared to laboratory CaO, the catalyst from waste crab shell performs well, thus creating another low-cost catalyst source for producing biodiesel as well as adding value to the waste crab shell. Reusability of crab shell CaO has also been studied and the outcome confirmed that the catalyst is capable to be reutilized up to 11 times, without any major deterioration.

Biodiesel fuel production from waste cooking oil by the inclusion complex of heteropoly acid with bridged bis-cyclodextrin.

PubMed

Zou, Changjun; Zhao, Pinwen; Shi, Lihong; Huang, Shaobing; Luo, Pingya

2013-10-01

The inclusion complex of Cs2.5H0.5PW12O40 with bridged bis-cyclodextrin (CsPW/B) is prepared as a highly efficient catalyst for the direct production of biodiesel via the transesterification of waste cooking oil. CsPW/B is characterized by X-ray diffraction, and the biodiesel is analyzed by Gas Chromatography-Mass Spectrometer. The conversion rate of waste cooking oil is up to 94.2% under the optimum experimental conditions that are methanol/oil molar ratio of 9:1, catalyst dosage of 3 wt%, temperature of 65 °C and reaction time of 180 min. The physical properties of biodiesel sample satisfy the requirement of ASTM D6751 standards. The novel CsPW/B catalyst used for the transesterification can lead to 96.9% fatty acid methyl esters and 86.5% of the biodiesel product can serve as the ideal substitute for diesel fuel, indicating its excellent potential application in biodiesel production. Copyright © 2013 Elsevier Ltd. All rights reserved.

Waste cooking oil as source for renewable fuel in Romania

NASA Astrophysics Data System (ADS)

Allah, F. Um Min; Alexandru, G.

2016-08-01

Biodiesel is non-toxic renewable fuel which has the potential to replace diesel fuel with little or no modifications in diesel engine. Waste cooking oil can be used as source to produce biodiesel. It has environmental and economic advantages over other alternative fuels. Biodiesel production from transesterification is affected by water content, type f alcohol, catalyst type and concentration, alcohol to oil ratio, temperature, reaction rate, pH, free fatty acid (FFA) and stirrer speed. These parameters and their effect on transesterification are discussed in this paper. Properties of biodiesel obtained from waste cooking oil are measured according to local standards by distributor and their comparison with European biodiesel standard is also given in this paper. Comparison has shown that these properties lie within the limits of the EN 14214 standard. Furthermore emission performance of diesel engine for biodiesel-diesel blends has resulted in reduction of greenhouse gas emissions. Romanian fuel market can ensure energy security by mixing fuel share with biodiesel produced from waste cooking oil. Life cycle assessment of biodiesel produced from waste cooking oil has shown its viability economically and environmentally.

Enhancing Biodiesel from Kemiri Sunan Oil Manufacturing using Ultrasonics

NASA Astrophysics Data System (ADS)

Supriyadi, Slamet; Purwanto; Anggoro, Didi Dwi; Hermawan

2018-02-01

Kemiri Sunan (Reutalis trisperma (Blanco) Airy Shaw) is a potential plant to be developed as biodiesel feedstock. The advantage of Kemiri Sunan seeds when compared to other biodiesel raw materials is their high oil content. This plant is also very good for land conservation. Due the increasingly demand for biodiesel, research and new methods to increase its biodiesel production continue to be undertaken. The weakness of conventional biodiesel manufacturing process is in the mixing process in which mechanical stirring and heating in the trans-esterification process require more energy and a longer time. A higher and stronger mixing process is required to increase the contact area between the two phases of the mixed substance to produce the emulsion. Ultrasonic is a tool that can be useful for a liquid mixing process that tends to be separated. Ultrasonic waves can cause mixing intensity at the micro level and increase mass transfer, so the reaction can be performed at a much faster rate. This study is to figure out the effect of ultrasonic irradiation on the transesterification process of biodiesel from Kemiri Sunan Oil.

Transesterification of sago starch and waste palm cooking oil in densified CO2

NASA Astrophysics Data System (ADS)

Muljana, H.; Sugih, A. K.; Christina, N.; Fangdinata, K.; Renaldo, J.; Rudy; Heeres, H. J.; Picchioni, F.

2017-07-01

In this work, the synthesis of biodegradable and yet renewable thermoplastics materials through a transesterification reaction of sago starch and waste palm cooking oil (WPO) in densified CO2 as the solvent is reported. The aim of this research is to investigate the potential used of sago starch and WPO as raw materials in the thermoplastics starch synthesis. The starch esters was successfully synthesized using sago starch and WPO as reagent in densified CO2 as shown from the presence of carbonyl group (C=O, 1743 cm-1) in the FT-IR spectra coupled with the presence of the proton (1H-NMR) of the fatty acid in the starch backbone (0.8 - 2 ppm). The product crystallinity decreases as shown in XRD results and resulting with a change in the thermal properties (melting and crystalline temperature) of the products. In addition, the products show a different granular morphology and a higher hydrophobicity compared with native sago starch. This research shows the potential used of sago starch and WPO in the thermoplastics starch synthesis and opens a new perspective on the product application.

Selective preparation of zeolite X and A from flyash and its use as catalyst for biodiesel production.

PubMed

Volli, Vikranth; Purkait, M K

2015-10-30

This work discusses the utilization of flyash for synthesis of heterogeneous catalyst for transesterification. Different types of zeolites were synthesized from alkali fusion followed by hydrothermal treatment of coal flyash as source material. The synthesis conditions were optimized to obtain highly crystalline zeolite based on degree of crystallinity and cation exchange capacity (CEC). The effect of CEC, acid treatment, Si/Al ratio and calcination temperature (800, 900 and 1000 °C) on zeolite formation was also studied. Pure, single phase and highly crystalline zeolite was obtained at flyash/NaOH ratio (1:1.2), fusion temperature (550 °C), fusion time (1 h), hydrothermal temperature (110 °C) and hydrothermal time (12h). The synthesized zeolite was ion-exchanged with potassium and was used as catalyst for transesterification of mustard oil to obtain a maximum conversion of 84.6% with 5 wt% catalyst concentration, 12:1 methanol to oil molar ratio, reaction time of 7 h at 65 °C. The catalyst was reused for 3 times with marginal reduction in activity. Copyright © 2015 Elsevier B.V. All rights reserved.

Biodiesel production from crude Jatropha oil catalyzed by non-commercial immobilized heterologous Rhizopus oryzae and Carica papaya lipases.

PubMed

Rodrigues, J; Canet, A; Rivera, I; Osório, N M; Sandoval, G; Valero, F; Ferreira-Dias, S

2016-08-01

The aim of this study was to evaluate the feasibility of biodiesel production by transesterification of Jatropha oil with methanol, catalyzed by non-commercial sn-1,3-regioselective lipases. Using these lipases, fatty acid methyl esters (FAME) and monoacylglycerols are produced, avoiding the formation of glycerol as byproduct. Heterologous Rhizopus oryzae lipase (rROL) immobilized on different synthetic resins and Carica papaya lipase (rCPL) immobilized on Lewatit VP OC 1600 were tested. Reactions were performed at 30°C, with seven stepwise methanol additions. For all biocatalysts, 51-65% FAME (theoretical maximum=67%, w/w) was obtained after 4h transesterification. Stability tests were performed in 8 or 10 successive 4h-batches, either with or without rehydration of the biocatalyst between each two consecutive batches. Activity loss was much faster when biocatalysts were rehydrated. For rROL, half-life times varied from 16 to 579h. rROL on Lewatit VPOC 1600 was more stable than for rCPL on the same support. Copyright © 2016 Elsevier Ltd. All rights reserved.

Enantiomeric separation of pharmaceutically important drug intermediates using a Metagenomic lipase and optimization of its large scale production.

PubMed

Kumar, Rakesh; Banoth, Linga; Banerjee, Uttam Chand; Kaur, Jagdeep

2017-02-01

In the present study, efficient enzymatic methods were developed using a recombinant metagenomic lipase (LipR1) for the synthesis of corresponding esters by the transesterification of five different pharmaceutically important secondary alcohols. The recombinant lipase (specific activity=87m6U/mg) showed maximum conversion in presence of ionic liquid with Naphthyl-ethanol (eeP=99%), Indanol and Methyl-4 pyridine methanol (eeS of 98% and 99%) respectively in 1h. Vinyl acetate was found as suitable acyl donor in transesterification reactions. It was interesting to observe that maximum eeP of 85% was observed in just 15min with 1-indanol. As this enzyme demonstrated pharmaceutical applications, attempts were made to scale up the enzyme production on a pilot scale in a 5litre bioreactor. Different physical parameters affecting enzyme production and biomass concentration such as agitation rate, aeration rate and inoculum concentration were evaluated. Maximum lipase activity of 8463U/ml was obtained at 7h of cultivation at 1 lpm, 300rpm and 1.5% inoculum. Copyright © 2016 Elsevier B.V. All rights reserved.

Prediction of normalized biodiesel properties by simulation of multiple feedstock blends.

PubMed

García, Manuel; Gonzalo, Alberto; Sánchez, José Luis; Arauzo, Jesús; Peña, José Angel

2010-06-01

A continuous process for biodiesel production has been simulated using Aspen HYSYS V7.0 software. As fresh feed, feedstocks with a mild acid content have been used. The process flowsheet follows a traditional alkaline transesterification scheme constituted by esterification, transesterification and purification stages. Kinetic models taking into account the concentration of the different species have been employed in order to simulate the behavior of the CSTR reactors and the product distribution within the process. The comparison between experimental data found in literature and the predicted normalized properties, has been discussed. Additionally, a comparison between different thermodynamic packages has been performed. NRTL activity model has been selected as the most reliable of them. The combination of these models allows the prediction of 13 out of 25 parameters included in standard EN-14214:2003, and confers simulators a great value as predictive as well as optimization tool. (c) 2010 Elsevier Ltd. All rights reserved.

Biodiesel production from ethanolysis of DPO using deep eutectic solvent (DES) based choline chloride - ethylene glycol as co-solvent

NASA Astrophysics Data System (ADS)

Taslim, Indra, Leonardo; Manurung, Renita; Winarta, Agus; Ramadhani, Debbie Aditia

2017-03-01

Biodiesel is usually produced from transesterification using methanol or ethanol as alcohol. However, biodiesel produced using methanol has several disadvantages because methanol is toxic and not entirely bio-based as it is generally produced from petroleum, natural gas and coal. On the other hand, ethanol also has several disadvantages such as lower reactivity in transesterification process and formation of stable emulsion between ester and glycerol. To improve ethanolysis process, deep eutectic solvent (DES) was prepared from choline chloride and ethylene glycol to be used as co-solvent in ethanolysis. Deep eutectic solvent was prepared by mixing choline chloride and ethylene glycol at molar ratio of 1:2, temperature of 80 °C, and stirring speed of 300 rpm for 1 hour. The DES was characterized by its density and viscosity. The ethanolysis of DPO / Degummed Palm Oil was performed at 70 °C, ethanol to oil molar ratio of 9:1, catalyst (potassium hydroxide) concentration of 0.75 wt.% concentration, co-solvent (DES) concentration of 1, 2, 3, 4, 5 and 6 wt.%, stirring speed of 600 rpm, and reaction time of 1 hour. The obtained biodiesel was then characterized by its density, viscosity and ester content. The oil - ethanol phase condition was observed in reaction tube. The oil - ethanol phase with DES tends to form meniscus compared to that without DES. Which implied that oil and ethanol become more slightly miscible, which favours the reaction. Using DES as co-solvent in ethanolysis resulted in an increase in yield and easier purification. The esters properties met the international standards ASTM D6751, with highest yield achieved at 81.72 % with 99.35 % ethyl ester contents at 4% DES concentration.

Effect of alcohol on skin permeation and metabolism of an ester-type prodrug in Yucatan micropig skin.

PubMed

Fujii, Makiko; Ohara, Rieko; Matsumi, Azusa; Ohura, Kayoko; Koizumi, Naoya; Imai, Teruko; Watanabe, Yoshiteru

2017-11-15

We studied the effect that three alcohols, ethanol (EA), propanol (PA), and isopropanol (IPA), have on the skin permeation of p-hydroxy benzoic acid methyl ester (HBM), a model ester-type prodrug. HBM was applied to Yucatan micropig skin in a saturated phosphate buffered solution with or without 10% alcohol, and HBM and related materials in receptor fluid and skin were determined with HPLC. In the absence of alcohol, p-hydroxy benzoic acid (HBA), a metabolite of HBM, permeated the skin the most. The three alcohols enhanced the penetration of HBM at almost the same extent. The addition of 10% EA or PA to the HBM solution led to trans-esterification into the ethyl ester or propyl ester of HBA, and these esters permeated skin as well as HBA and HBM did. In contrast, the addition of 10% IPA promoted very little trans-esterification. Both hydrolysis and trans-esterification in the skin S9 fraction were inhibited by BNPP, an inhibitor of carboxylesterase (CES). Western blot and native PAGE showed the abundant expression of CES in micropig skin. Both hydrolysis and trans-esterification was simultaneously catalyzed by CES during skin permeation. Our data indicate that the alcohol used in dermal drug preparations should be selected not only for its ability to enhance the solubility and permeation of the drug, but also for the effect on metabolism of the drug in the skin. Copyright © 2017 Elsevier B.V. All rights reserved.

Direct transesterification of fresh microalgal cells.

PubMed

Liu, Jiao; Liu, Yanan; Wang, Haitao; Xue, Song

2015-01-01

Transesterification of lipids is a vital step during the processes of both biodiesel production and fatty acid analysis. By comparing the yields and fatty acid profiles obtained from microalgal oil and dry microalgal cells, the reliability of method for the transesterification of micro-scale samples was tested. The minimum amount of microalgal cells needed for accurate analysis was found to be approximately 300μg dry cells. This direct transesterification method of fresh cells was applied to eight microalgal species, and the results indicate that the efficiency of the developed method is identical to that of conventional method, except for Spirulina whose lipid content is very low, which means the total lipid content should been considered. Copyright © 2014 Elsevier Ltd. All rights reserved.

Oil industry waste: a potential feedstock for biodiesel production.

PubMed

Abbas, Javeria; Hussain, Sabir; Iqbal, Muhammad Javid; Nadeem, Habibullah; Qasim, Muhammad; Hina, Saadia; Hafeez, Farhan

2016-08-01

The worldwide rising energy demands and the concerns about the sustainability of fossil fuels have led to the search for some low-cost renewable fuels. In this scenario, the production of biodiesel from various vegetable and animal sources has attracted worldwide attention. The present study was conducted to evaluate the production of biodiesel from the oil industry waste following base-catalysed transesterification. The transesterification reaction gave a yield of 83.7% by 6:1 methanol/oil molar ratio, at 60°C over 80 min of reaction time in the presence of NaOH. The gas chromatographic analysis of the product showed the presence of 16 fatty acid methyl esters with linoleic and oleic acid as principal components representing about 31% and 20.7% of the total methyl esters, respectively. The fourier transform infrared spectroscopy spectrum of oil industry waste and transesterified product further confirmed the formation of methyl esters. Furthermore, the fuel properties of oil industry waste methyl esters, such as kinematic viscosity, cetane number, cloud point, pour point, flash point, acid value, sulphur content, cold filter plugging point, copper strip corrosion, density, oxidative stability, higher heating values, ash content, water content, methanol content and total glycerol content, were determined and discussed in the light of ASTM D6751 and EN 14214 biodiesel standards. Overall, this study presents the production of biodiesel from the oil industry waste as an approach of recycling this waste into value-added products.

Effect of solvents and oil content on direct transesterification of wet oil-bearing microalgal biomass of Chlorella vulgaris ESP-31 for biodiesel synthesis using immobilized lipase as the biocatalyst.

PubMed

Tran, Dang-Thuan; Chen, Ching-Lung; Chang, Jo-Shu

2013-05-01

In this work, a one-step extraction/transesterification process was developed to directly convert wet oil-bearing microalgal biomass of Chlorella vulgaris ESP-31 into biodiesel using immobilized Burkholderia lipase as the catalyst. The microalgal biomass (water content of 86-91%; oil content 14-63%) was pre-treated by sonication to disrupt the cell walls and then directly mixed with methanol and solvent to carry out the enzymatic transesterification. Addition of a sufficient amount of solvent (hexane is most preferable) is required for the direct transesterification of wet microalgal biomass, as a hexane-to-methanol mass ratio of 1.65 was found optimal for the biodiesel conversion. The amount of methanol and hexane required for the direct transesterification process was also found to correlate with the lipid content of the microalga. The biodiesel synthesis process was more efficient and economic when the lipid content of the microalgal biomass was higher. Therefore, using high-lipid-content microalgae as feedstock appears to be desirable. Copyright © 2012 Elsevier Ltd. All rights reserved.

Chemically-modified cellulose paper as a microstructured catalytic reactor.

PubMed

Koga, Hirotaka; Kitaoka, Takuya; Isogai, Akira

2015-01-15

We discuss the successful use of chemically-modified cellulose paper as a microstructured catalytic reactor for the production of useful chemicals. The chemical modification of cellulose paper was achieved using a silane-coupling technique. Amine-modified paper was directly used as a base catalyst for the Knoevenagel condensation reaction. Methacrylate-modified paper was used for the immobilization of lipase and then in nonaqueous transesterification processes. These catalytic paper materials offer high reaction efficiencies and have excellent practical properties. We suggest that the paper-specific interconnected microstructure with pulp fiber networks provides fast mixing of the reactants and efficient transport of the reactants to the catalytically-active sites. This concept is expected to be a promising route to green and sustainable chemistry.

New eutectic ionic liquids for lipase activation and enzymatic preparation of biodiesel†

PubMed Central

Zhao, Hua; Baker, Gary A.; Holmes, Shaletha

2012-01-01

The enzymatic preparation of biodiesel has been hampered by the lack of suitable solvents with desirable properties such as high lipase compatibility, low cost, low viscosity, high biodegradability, and ease of product separation. Recent interest in using ionic liquids (ILs) as advanced reaction media has led to fast reaction rates and high yields in the enzymatic synthesis of biodiesel. However, conventional (i.e., cation–anion paired) ILs based on imidazolium and other quaternary ammonium salts remain too expensive for wide application at industrial scales. In this study, we report on newly-synthesized eutectic ILs derived from choline acetate or choline chloride coupled with biocompatible hydrogen-bond donors, such as glycerol. These eutectic solvents have favorable properties including low viscosity, high biodegradability, and excellent compatibility with Novozym® 435, a commercial immobilized Candida antarctica lipase B. Furthermore, in a model biodiesel synthesis system, we demonstrate high reaction rates for the enzymatic transesterification of Miglyol® oil 812 with methanol, catalyzed by Novozym® 435 in choline acetate/glycerol (1 : 1.5 molar ratio). The high conversion (97%) of the triglyceride obtained within 3 h, under optimal conditions, suggests that these novel eutectic solvents warrant further exploration as potential media in the enzymatic production of biodiesel. PMID:21283901

Homogeneous, heterogeneous and enzymatic catalysis for transesterification of high free fatty acid oil (waste cooking oil) to biodiesel: a review.

PubMed

Lam, Man Kee; Lee, Keat Teong; Mohamed, Abdul Rahman

2010-01-01

In the last few years, biodiesel has emerged as one of the most potential renewable energy to replace current petrol-derived diesel. It is a renewable, biodegradable and non-toxic fuel which can be easily produced through transesterification reaction. However, current commercial usage of refined vegetable oils for biodiesel production is impractical and uneconomical due to high feedstock cost and priority as food resources. Low-grade oil, typically waste cooking oil can be a better alternative; however, the high free fatty acids (FFA) content in waste cooking oil has become the main drawback for this potential feedstock. Therefore, this review paper is aimed to give an overview on the current status of biodiesel production and the potential of waste cooking oil as an alternative feedstock. Advantages and limitations of using homogeneous, heterogeneous and enzymatic transesterification on oil with high FFA (mostly waste cooking oil) are discussed in detail. It was found that using heterogeneous acid catalyst and enzyme are the best option to produce biodiesel from oil with high FFA as compared to the current commercial homogeneous base-catalyzed process. However, these heterogeneous acid and enzyme catalyze system still suffers from serious mass transfer limitation problems and therefore are not favorable for industrial application. Nevertheless, towards the end of this review paper, a few latest technological developments that have the potential to overcome the mass transfer limitation problem such as oscillatory flow reactor (OFR), ultrasonication, microwave reactor and co-solvent are reviewed. With proper research focus and development, waste cooking oil can indeed become the next ideal feedstock for biodiesel.

RNA catalysis and the origins of life

NASA Technical Reports Server (NTRS)

Orgel, Leslie E.

1986-01-01

The role of RNA catalysis in the origins of life is considered in connection with the discovery of riboszymes, which are RNA molecules that catalyze sequence-specific hydrolysis and transesterification reactions of RNA substrates. Due to this discovery, theories positing protein-free replication as preceding the appearance of the genetic code are more plausible. The scope of RNA catalysis in biology and chemistry is discussed, and it is noted that the development of methods to select (or predict) RNA sequences with preassigned catalytic functions would be a major contribution to the study of life's origins.

DOE Office of Scientific and Technical Information (OSTI.GOV)

S.I. Zherebtsov; A.I. Moiseev

Changes in the group and individual compositions of the wax fractions of bitumen in the course of brown coal methylation were studied. With the use of IR and NMR spectroscopy and chromatography-mass spectrometry, it was found that the esters of methylated coal waxes consisted of the native esters of fatty acids and the methyl esters of these acids formed as a result of an alkylation treatment. Esterification and transesterification were predominant among the reactions of aliphatic fraction components. A positive effect of methanol alkylation on an increase in the yield of the aliphatic fractions was found.

Comprehensive near infrared study of Jatropha oil esterification with ethanol for biodiesel production

NASA Astrophysics Data System (ADS)

Oliveira, Alianda Dantas de; Sá, Ananda Franco de; Pimentel, Maria Fernanda; Pacheco, José Geraldo A.; Pereira, Claudete Fernandes; Larrechi, Maria Soledad

2017-01-01

This work presents a comprehensive near infrared study for in-line monitoring of the esterification reaction of high acid oils, such as Jatropha curcas oil, using ethanol. Parallel reactions involved in the process were carried out to select a spectral region that characterizes the evolution of the esterification reaction. Using absorbance intensities at 5176 cm- 1, the conversion and kinetic behaviors of the esterification reaction were estimated. This method was applied to evaluate the influence of temperature and catalyst concentration on the estimates of initial reaction rate and ester conversion as responses to a 22 factorial experimental design. Employment of an alcohol/oil ratio of 16:1, catalyst concentration of 1.5% w/w, and temperatures at 65 °C or 75 °C, made it possible to reduce the initial acidity from 18% to 1.3% w/w, which is suitable for transesterification of high free fatty acid oils for biodiesel production. Using the proposed analytical method in the esterification reaction of raw materials with high free fatty acid content for biodiesel makes the monitoring process inexpensive, fast, simple, and practical.

Pressure modulates the self-cleavage step of the hairpin ribozyme

NASA Astrophysics Data System (ADS)

Schuabb, Caroline; Kumar, Narendra; Pataraia, Salome; Marx, Dominik; Winter, Roland

2017-03-01

The ability of certain RNAs, denoted as ribozymes, to not only store genetic information but also catalyse chemical reactions gave support to the RNA world hypothesis as a putative step in the development of early life on Earth. This, however, might have evolved under extreme environmental conditions, including the deep sea with pressures in the kbar regime. Here we study pressure-induced effects on the self-cleavage of hairpin ribozyme by following structural changes in real-time. Our results suggest that compression of the ribozyme leads to an accelerated transesterification reaction, being the self-cleavage step, although the overall process is retarded in the high-pressure regime. The results reveal that favourable interactions between the reaction site and neighbouring nucleobases are strengthened under pressure, resulting therefore in an accelerated self-cleavage step upon compression. These results suggest that properly engineered ribozymes may also act as piezophilic biocatalysts in addition to their hitherto known properties.

Photothermal triggering of self-healing processes applied to the reparation of bio-based polymer networks

NASA Astrophysics Data System (ADS)

Altuna, F. I.; Antonacci, J.; Arenas, G. F.; Pettarin, V.; Hoppe, C. E.; Williams, R. J. J.

2016-04-01

Green laser irradiation successfully activated self-healing processes in epoxy-acid networks modified with low amounts of gold nanoparticles (NPs). A bio-based polymer matrix, obtained by crosslinking epoxidized soybean oil (ESO) with an aqueous citric acid (CA) solution, was self-healed through molecular rearrangements produced by transesterification reactions of β-hydroxyester groups generated in the polymerization reaction. The temperature increase required for the triggering of these thermally activated reactions was attained by green light irradiation of the damaged area. Compression force needed to assure a good contact between crack faces was achieved by volume dilatation generated by the same temperature rise. Gold NPs dispersed in the polymer efficiently generated heat in the presence of electromagnetic radiation under plasmon resonance, acting as nanometric heating sources and allowing remote activation of the self-healing in the crosslinked polymer.

Activating catalysts with mechanical force.

PubMed

Piermattei, Alessio; Karthikeyan, S; Sijbesma, Rint P

2009-05-01

Homogeneously catalysed reactions can be 'switched on' by activating latent catalysts. Usually, activation is brought about by heat or an external chemical agent. However, activation of homogeneous catalysts with a mechanical trigger has not been demonstrated. Here, we introduce a general method to activate latent catalysts by mechanically breaking bonds between a metal and one of its ligands. We have found that silver(I) complexes of polymer-functionalized N-heterocyclic carbenes, which are latent organocatalysts, catalyse a transesterification reaction when exposed to ultrasound in solution. Furthermore, ultrasonic activation of a ruthenium biscarbene complex with appended polymer chains results in catalysis of olefin metathesis reactions. In each case, the catalytic activity results from ligand dissociation, brought about by transfer of mechanical forces from the polymeric substituents to the coordination bond. Mechanochemical catalyst activation has potential applications in transduction and amplification of mechanical signals, and mechanically initiated polymerizations hold promise as a novel repair mechanism in self-healing materials.

BBD Optimization of K-ZnO Catalyst Modification Process for Heterogeneous Transesterification of Rice Bran Oil to Biodiesel

NASA Astrophysics Data System (ADS)

Kabo, K. S.; Yacob, A. R.; Bakar, W. A. W. A.; Buang, N. A.; Bello, A. M.; Ruskam, A.

2016-07-01

Environmentally benign zinc oxide (ZnO) was modified with 0-15% (wt.) potassium through wet impregnation and used in transesterification of rice bran oil (RBO) to form biodiesel. The catalyst was characterized by X-Ray powder Diffraction (XRD), its basic sites determined by back titration and Response Surface Methodology (RSM) Box-Behnken Design (BBD) was used to optimize the modification process variables on the basic sites of the catalyst. The transesterification product, biodiesel was analyzed by Nuclear Magnetic Resonance (NMR) spectroscopy. The result reveals K-modified ZnO with highly increased basic sites. Quadratic model with high regression R2 = 0.9995 was obtained from the ANOVA of modification process, optimization at maximum basic sites criterion gave optimum modification conditions of K-loading = 8.5% (wt.), calcination temperature = 480 oC and time = 4 hours with response and basic sites = 8.14 mmol/g which is in close agreement with the experimental value of 7.64 mmol/g. The catalyst was used and a value of 95.53% biodiesel conversion was obtained and effect of potassium leaching was not significant in the process

Biodiesel Production: Utilization of Loofah Sponge to Immobilize Rhizopus chinensis CGMCC #3.0232 Cells as a Whole-Cell Biocatalyst.

PubMed

He, Qiyang; Xia, Qianjun; Wang, Yuejiao; Li, Xun; Zhang, Yu; Hu, Bo; Wang, Fei

2016-07-28

Rhizopus chinensis cells immobilized on loofah (Luffa cylindrica) sponges were used to produce biodiesel via the transesterification of soybean oil. In whole-cell immobilization, loofah sponge is considered to be a superior alternative to conventional biomass carriers because of its biodegradable and renewable properties. During cell cultivation, Rhizopus chinensis mycelia can spontaneously and firmly adhere to the surface of loofah sponge particles. The optimal conditions for processing 9.65 g soybean oil at 40°C and 180 rpm using a 3:1 methanol-to-oil molar ratio were found to be 8% cell addition and 3-10% water content (depending on the oil's weight). Under optimal conditions, an over 90% methyl ester yield was achieved after the first reaction batch. The operational stability of immobilized Rhizopus chinensis cells was assayed utilizing a 1:1 methanol-to-oil molar ratio, thus resulting in a 16.5-fold increase in half-life when compared with immobilized cells of the widely studied Rhizopus oryzae. These results suggest that transesterification of vegetable oil using Rhizopus chinensis whole cells immobilized onto loofah sponge is an effective approach for biodiesel production.

Effect on the use of ultrasonic cavitation for biodiesel production from crued Jatropha curcas L. seed oil with a high content of free fatty acid

NASA Astrophysics Data System (ADS)

Worapun, Ittipon; Pianthong, Kulachate; Thaiyasuit, Prachasanti; Thinvongpituk, Chawalit

2010-03-01

A typical way to produce biodiesel is the transesterification of plant oils. This is commonly carried out by treating the pre-extracted oil with an appropriate alcohol in the presence of an acidic or alkaline catalyst over one or two hours in a batch reactor.Because oils and methanol are not completely miscible. It has been widely demonstrated that low-frequency ultrasonic irradiation is an effective tool for emulsifying immiscible liquids. The objective of this research is to investigate the optimum conditions for biodiesel production from crude Jatropha curcas oil with short chain alcohols by ultrasonic cavitation (at 40 kHz frequency and 400 Watt) assisted, using two step catalyst method. Usually, the crude Jatropha curcas oil has very high free fatty acid which obstructs the transesterification reaction. As a result it provides low yield of biodiesel production. In the first step, the reaction was carried out in the presence of sulfuric acid as an acid catalyst. The product was then further transesterified with potassium hydroxide in the second step. The effects of different operating parameters such as molar ratio of reactants, catalyst quantity, and operating temperature, have been studied with the aim of process optimization. It has been observed that the mass transfer and kinetic rate enhancements were due to the increase in interfacial area and activity of the microscopic and macroscopic bubbles formed. For example, the product yield levels of more than 90% have been observed with the use of ultrasonic cavitation in about 60 minutes under room temperature operating conditions.

Lipase-catalyzed kinetic resolution of novel antitubercular benzoxazole derivatives.

PubMed

Łukowska-Chojnacka, Edyta; Kowalkowska, Anna; Napiórkowska, Agnieszka

2018-04-01

Novel benzoxazole derivatives were synthesized, and their antitubercular activity against sensitive and drug-resistant Mycobacterium tuberculosis strains (M. tuberculosis H 37 Rv, M. tuberculosis sp. 210, M. tuberculosis sp. 192, Mycobacterium scrofulaceum, Mycobacterium intracellulare, Mycobacterium fortuitum, Mycobacterium avium, and Mycobacterium kansasii) was evaluated. The chemical step included preparation of ketones, alcohols, and esters bearing benzoxazole moiety. All racemic mixtures of alcohols and esters were separated in Novozyme SP 435-catalyzed transesterification and hydrolysis, respectively. The transesterification reactions were carried out in various organic solvents (tert-butyl methyl ether, toluene, diethyl ether, and diisopropyl ether), and depending on the solvent, the enantioselectivity of the reactions ranged from 4 to >100. The enzymatic hydrolysis of esters was performed in 2 phase tert-butyl methyl ether/phosphate buffer (pH = 7.2) system and provided also enantiomerically enriched products (ee 88-99%). The antitubercular activity assay has shown that synthesized compounds exhibit an interesting antitubercular activity. Racemic mixtures of alcohols, (±)-4-(1,3-benzoxazol-2-ylsulfanyl)butan-2-ol ((±)-3a), (±)-4-[(5-bromo-1,3-benzoxazol-2-yl)sulfanyl]butan-2-ol ((±)-3b), and (±)-4-[(5,7-dibromo-1,3-benzoxazol-2-yl)sulfanyl]butan-2-ol ((±)-3c), displayed as high activity against M. scrofulaceum, M. intracellulare, M. fortuitum, and M. kansasii as commercially available antituberculosis drug-Isoniazid. Moreover, these compounds exhibited twice higher activity toward M. avium (MIC 12.5) compared with Isoniazid (MIC 50). © 2017 Wiley Periodicals, Inc.

The ligand effect on the hydrolytic reactivity of Zn(II) complexes toward phosphate diesters.

PubMed

Bonfá, Lodovico; Gatos, Maddalena; Mancin, Fabrizio; Tecilla, Paolo; Tonellato, Umberto

2003-06-16

The catalytic effects of the Zn(II) complexes of a series of poliaminic ligands in the hydrolysis of the activated phosphodiesters bis-p-nitrophenyl phosphate (BNP) and 2-hydroxypropyl-p-nitrophenyl phosphate (HPNP) have been investigated. The reactions show first-order rate dependency on both substrate and metal ion complex and a pH dependence which is diagnostic of the acid dissociation of the reactive species. The mechanism of the metal catalyzed transesterification of HPNP has been assessed by solvent isotopic kinetic effect studies and involves the intramolecular nucleophilic attack of the substrate alcoholic group, activated by metal ion coordination. The intrinsic reactivity of the different complexes is controlled by the nature and structure of the ligand: complexes of tridentate ligands, particularly if characterized by a facial coordination mode, are more reactive than those of tetradentate ligands which can hardly allow binding sites for the substrate. In the case of tridentate ligands that form complexes with a facial coordination mode, a linear Brønsted correlation between the reaction rate (log k) and the pK(a) of the active nucleophile is obtained. The beta(nuc) values are 0.75 for the HPNP transesterification and 0.20 for the BNP hydrolysis. These values are indicated as the result of the combination of two opposite Lewis acid effects of the Zn(II) ion: the activation of the substrate and the efficiency of the metal coordinated nucleophile. The latter factor apparently prevails in determining the intrinsic reactivity of the Zn(II) complexes.

About the activity and selectivity of less well-known metathesis catalysts during ADMET polymerizations

PubMed Central

Mutlu, Hatice; Montero de Espinosa, Lucas; Türünç, Oĝuz

2010-01-01

Summary We report on the catalytic activity of commercially available Ru-indenylidene and “boomerang” complexes C1, C2 and C3 in acyclic diene metathesis (ADMET) polymerization of a fully renewable α,ω-diene. A high activity of these catalysts was observed for the synthesis of the desired renewable polyesters with molecular weights of up to 17000 Da, which is considerably higher than molecular weights obtained using the same monomer with previously studied catalysts. Moreover, olefin isomerization side reactions that occur during the ADMET polymerizations were studied in detail. The isomerization reactions were investigated by degradation of the prepared polyesters via transesterification with methanol, yielding diesters. These diesters, representing the repeat units of the polyesters, were then quantified by GC-MS. PMID:21160555

Water-soluble resist for environmentally friendly lithography

NASA Astrophysics Data System (ADS)

Lin, Qinghuang; Simpson, Logan L.; Steinhaeusler, Thomas; Wilder, Michelle; Willson, C. Grant; Havard, Jennifer M.; Frechet, Jean M. J.

1996-05-01

This paper describes an 'environmentally friendly,' water castable, water developable photoresist system. The chemically amplified negative-tone resist system consists of three water-soluble components: a polymer, poly(methyl acrylamidoglycolate methyl ether), [poly(MAGME)]; a photoacid generator, dimethyl dihydroxyphenylsulfonium triflate and a crosslinker, butanediol. Poly(MAGME) was synthesized by solution free radical polymerization. In the three-component resist system, the acid generated by photolysis of the photoacid generator catalyzes the crosslinking of poly(MAGME) in the exposed regions during post-exposure baking, thus rendering the exposed regions insoluble in water. Negative tone relief images are obtained by developing with pure water. The resist is able to resolve 1 micrometer line/space features (1:1 aspect ratio) with an exposure dose of 100 mJ/cm2 at 248 nm. The resist can be used to generate etched copper relief images on printed circuit boards using aqueous sodium persulfate as the etchant. The crosslinking mechanism has been investigated by model compound studies using 13C NMR. These studies have revealed that the acid catalyzed reaction of the poly(MAGME) with butanediol proceeds via both transesterification and transacetalization (transaminalization) reactions at low temperatures, and also via transamidation at high temperatures.

Integrated Energy System with Beneficial Carbon Dioxide (CO2) Use - Final Scientific/Technical Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Xiaolei; Rink, Nancy T

2011-04-29

This report presents an integrated energy system that combines the production of substitute natural gas through coal hydrogasification with an algae process for beneficial carbon dioxide (CO2) use and biofuel production (funded under Department of Energy (DOE) contract DE-FE0001099). The project planned to develop, test, operate and evaluate a 2 ton-per-day coal hydrogasification plant and 25-acre algae farm at the Arizona Public Service (APS) 1000 Megawatt (MW) Cholla coal-fired power plant in Joseph City, Arizona. Conceptual design of the integrated system was undertaken with APS partners Air Liquide (AL) and Parsons. The process engineering was separated into five major areas:more » flue gas preparation and CO2 delivery, algae farming, water management, hydrogasification, and biofuel production. The process flow diagrams, energy and material balances, and preliminary major equipment needs for each major area were prepared to reflect integrated process considerations and site infrastructure design basis. The total project also included research and development on a bench-scale hydrogasifier, one-dimensional (1-D) kinetic-model simulation, extensive algae stressing, oil extraction, lipid analysis and a half-acre algae farm demonstration at APS?s Redhawk testing facility. During the project, a two-acre algae testing facility with a half-acre algae cultivation area was built at the APS Redhawk 1000 MW natural gas combined cycle power plant located 55 miles west of Phoenix. The test site integrated flue gas delivery, CO2 capture and distribution, algae cultivation, algae nursery, algae harvesting, dewatering and onsite storage as well as water treatment. The site environmental, engineering, and biological parameters for the cultivators were monitored remotely. Direct biodiesel production from biomass through an acid-catalyzed transesterification reaction and a supercritical methanol transesterification reaction were evaluated. The highest oil-to-biodiesel conversion of 79.9% was achieved with a stressed algae sample containing 40% algae oil. The effort concluded that producing biodiesel directly from the algae biomass could be an efficient, cost-effective and readily scalable way to produce biodiesel by eliminating the oil extraction process.« less

Synthesis of retinyl palmitate catalyzed by Candida sp.99-125 lipase immobilized on fiber-like SBA-15 mesoporous material.

PubMed

Kai, Zhu; Jianqiang, Wang; Yan-hua, Wang; Hui, Liu; Ping-fang, Han; Ping, Wei

2011-09-01

Candida sp.99-125 lipase was suitable for transesterification of fats and oils to produce fatty acid methyl ester. The adsorption of Candida sp.99-125 lipase onto the fiber-like SBA-15 mesoporous material has been studied. The unaltered structural order of the fiber-like SBA-15 before and after the adsorption has been confirmed by FT-IR, SEM and N2 adsorption. The amount of adsorbed Candida sp.99-125 lipase depends both on the solution pH and reaction time. Good adsorption capacity of Candida sp.99-125 lipase on fiber-like SBA-15 may be due to solution pH from 5.0 to 9.0 especially at 7.0 (93.99 mg enzyme per gram silica is obtained and the activity recovery is 281.05%). A high lipase loading (135.9 mg enzyme per gram silica) was obtained, but it did not produce a proportionate level of catalytic activity. The immobilized Candida sp.99-125 lipase showed increased adaptability in the hydrolysis of p-nitrophenyl acetate compared to free Candida sp.99-125 lipase at pH 5.0-9.0. Meanwhile, the immobilized Candida sp.99-125 lipase showed higher thermal stability than that of free Candida sp.99-125 lipase. And the synthesis of retinyl palmitate in organic solvent with the immobilized Candida sp.99-125 lipase was investigated. The influence factors, such as: the solvent used, the molar ratio and concentrations of substrates, the reaction time and the amount of lipase were studied and optimized. In the conditions of transesterificating 0.164 g retinyl acetate and 0.32 g palmitic acid, 10 mL of solvent hexane, 1:4 of mass ratio of lipase to retinyl acetate, and 6 hours of reaction time, 74.6% of retinyl acetate was converted into retinyl plamitate.

Production and Use of Lipases in Bioenergy: A Review from the Feedstocks to Biodiesel Production

PubMed Central

Ribeiro, Bernardo Dias; de Castro, Aline Machado; Coelho, Maria Alice Zarur; Freire, Denise Maria Guimarães

2011-01-01

Lipases represent one of the most reported groups of enzymes for the production of biofuels. They are used for the processing of glycerides and fatty acids for biodiesel (fatty acid alkyl esters) production. This paper presents the main topics of the enzyme-based production of biodiesel, from the feedstocks to the production of enzymes and their application in esterification and transesterification reactions. Growing technologies, such as the use of whole cells as catalysts, are addressed, and as concluding remarks, the advantages, concerns, and future prospects of enzymatic biodiesel are presented. PMID:21785707

Medium-chain alkyl esters of tyrosol and hydroxytyrosol antioxidants by cuphea oil transesterification

USDA-ARS?s Scientific Manuscript database

Effective lipophilic antioxidants were readily prepared by non-aqueous enzymatic transesterification of plant phenols with cuphea oil. Tyrosol (2-(4-hydroxyphenyl)ethanol) and hydroxytyrosol (2-(3,4-dihydroxyphenyl)ethanol), abundantly available phenols from olive oil processing byproduct, were foun...

Direct transesterification of spent coffee grounds for biodiesel production

USDA-ARS?s Scientific Manuscript database

Studies of spent coffee grounds (SCGs) as a potential biodiesel feedstock in recent years mostly started from solvent extraction to obtain coffee oil, and then converted it into coffee biodiesel in two steps, acid esterification followed by alkaline transesterification. This paper presents a direct ...

In-situ transesterification of wet spent coffee grounds for sustainable biodiesel production.

PubMed

Park, Jeongseok; Kim, Bora; Lee, Jae W

2016-12-01

This work addresses in-situ transesterification of wet spent coffee grounds (SCGs) for the production of biodiesel. For in-situ transesterification process, the methanol, organic solvent and acid catalyst were mixed with wet SCG in one pot and the mixture was heated for simultaneous lipid extraction and transesterification. Maximum yield of fatty acid methyl esters (FAME) was 16.75wt.% based on the weight of dry SCG at 95°C. Comprehensive experiments were conducted with varying temperatures and various amounts of moisture, methanol, co-solvent and acid catalyst. Moderate polar and alcohol-miscible organic solvent is suitable for the high FAME yield. Unsaturated FAMEs are subject to oxidative cleavage by nitric acid and shorter chain (C6 and C10) FAMEs were mainly produced while sulfuric acid yielded long chain unsaturated FAMEs (C16 and C18). Utilization of wet SCGs as a biodiesel feedstock gives economic and environmental benefits by recycling the municipal waste. Copyright © 2016 Elsevier Ltd. All rights reserved.

Process design of in situ esterification-transesterifica tion for biodiesel production from residual oil of spent bleaching earth (SBE)

NASA Astrophysics Data System (ADS)

Suryani, A.; Mubarok, Z.; Suprihatin; Romli, M.; Yunira, E. N.

2017-05-01

Indonesia is the largest producer of Crude Palm Oil (CPO) in the world. CPO refining process produces spent bleaching earth (SBE), which still contains 20-30% oil. This residual oil is very potential to be developed as a biodiesel feedstock. The purpose of this research was to develop an in situbiodiesel production process of residual oil of SBE, which covered stirring speed of esterification and transesterification and also transesterification time to produce biodiesel with the best characteristics. The production was conducted in a 100 L reactor. The stirring speeds applied were 650 rpm and 730 rpm, and the transesterification time varied at 60, 90 and 120 minutes. The combination of 730 rpm stirring speed for 90 minutes transesterification resulted in the best biodiesel characteristics with the yield of 85%, the specific energy of 6,738 kJ/kg and the heater efficiency of 48%. The physico-chemical properties of biodiesel was in conformity with the SNI of Biodiesel.

Enzymatic transesterification of microalgal oil from Chlorella vulgaris ESP-31 for biodiesel synthesis using immobilized Burkholderia lipase.

PubMed

Tran, Dang-Thuan; Yeh, Kuei-Ling; Chen, Ching-Lung; Chang, Jo-Shu

2012-03-01

An indigenous microalga Chlorella vulgaris ESP-31 grown in an outdoor tubular photobioreactor with CO(2) aeration obtained a high oil content of up to 63.2%. The microalgal oil was then converted to biodiesel by enzymatic transesterification using an immobilized lipase originating from Burkholderia sp. C20. The conversion of the microalgae oil to biodiesel was conducted by transesterification of the extracted microalgal oil (M-I) and by transesterification directly using disrupted microalgal biomass (M-II). The results show that M-II achieved higher biodiesel conversion (97.3 wt% oil) than M-I (72.1 wt% oil). The immobilized lipase worked well when using wet microalgal biomass (up to 71% water content) as the oil substrate. The immobilized lipase also tolerated a high methanol to oil molar ratio (>67.93) when using the M-II approach, and can be repeatedly used for six cycles (or 288 h) without significant loss of its original activity. Copyright © 2012 Elsevier Ltd. All rights reserved.

Evolution of the feruloyl esterase MtFae1a from Myceliophthora thermophila towards improved catalysts for antioxidants synthesis.

PubMed

Varriale, Simona; Cerullo, Gabriella; Antonopoulou, Io; Christakopoulos, Paul; Rova, Ulrika; Tron, Thierry; Fauré, Régis; Jütten, Peter; Piechot, Alexander; Brás, Joana L A; Fontes, Carlos M G A; Faraco, Vincenza

2018-06-01

The chemical syntheses currently employed for industrial purposes, including in the manufacture of cosmetics, present limitations such as unwanted side reactions and the need for harsh chemical reaction conditions. In order to overcome these drawbacks, novel enzymes are developed to catalyze the targeted bioconversions. In the present study, a methodology for the construction and the automated screening of evolved variants library of a Type B feruloyl esterase from Myceliophthora thermophila (MtFae1a) was developed and applied to generation of 30,000 mutants and their screening for selecting the variants with higher activity than the wild-type enzyme. The library was generated by error-prone PCR of mtfae1a cDNA and expressed in Saccharomyces cerevisiae. Screening for extracellular enzymatic activity towards 4-nitrocatechol-1-yl ferulate, a new substrate developed ad hoc for high-throughput assays of feruloyl esterases, led to the selection of 30 improved enzyme variants. The best four variants and the wild-type MtFae1a were investigated in docking experiments with hydroxycinnamic acid esters using a model of 3D structure of MtFae1a. These variants were also used as biocatalysts in transesterification reactions leading to different target products in detergentless microemulsions and showed enhanced synthetic activities, although the screening strategy had been based on improved hydrolytic activity.

Biodiesel production from castor oil using heterogeneous Ni doped ZnO nanocatalyst.

PubMed

Baskar, G; Aberna Ebenezer Selvakumari, I; Aiswarya, R

2018-02-01

In the present study, castor oil with high free fatty acid was used for biodiesel production using heterogeneous Ni doped ZnO nanocatalyst. Ni doped ZnO nanocomposite calcinated at 800 °C has shown better catalytic activity. Process parameters on heterogeneous catalysis of castor oil into biodiesel were optimized using conventional and Response Surface Methodology (RSM). RSM was found more accurate in estimating the optimum conditions with higher biodiesel yield (95.20%). The optimum conditions for transesterification was found to be oil to methanol molar ratio of 1:8, catalyst loading 11% (w/w), reaction temperature of 55 °C for 60 min of reaction time by response surface method. The reusability studies showed that the nanocatalyst can be reused efficiently for 3 cycles. Copyright © 2017 Elsevier Ltd. All rights reserved.

Lipase-Catalyzed Kinetic Resolution of Novel Antifungal N-Substituted Benzimidazole Derivatives.

PubMed

Łukowska-Chojnacka, Edyta; Staniszewska, Monika; Bondaryk, Małgorzata; Maurin, Jan K; Bretner, Maria

2016-04-01

A series of new N-substituted benzimidazole derivatives was synthesized and their antifungal activity against Candida albicans was evaluated. The chemical step included synthesis of appropriate ketones containing benzimidazole ring, reduction of ketones to the racemic alcohols, and acetylation of alcohols to the esters. All benzimidazole derivatives were obtained with satisfactory yields and in relatively short times. All synthesized compounds exhibit significant antifungal activity against Candida albicans 900028 ATCC (% cell inhibition at 0.25 μg concentration > 98%). Additionally, racemic mixtures of alcohols were separated by lipase-catalyzed kinetic resolution. In the enzymatic step a transesterification reaction was applied and the influence of a lipase type and solvent on the enantioselectivity of the reaction was studied. The most selective enzymes were Novozyme SP 435 and lipase Amano AK from Pseudomonas fluorescens (E > 100). © 2016 Wiley Periodicals, Inc.

Lipase-Catalyzed Synthesis of Sugar Esters in Honey and Agave Syrup.

PubMed

Siebenhaller, Sascha; Gentes, Julian; Infantes, Alba; Muhle-Goll, Claudia; Kirschhöfer, Frank; Brenner-Weiß, Gerald; Ochsenreither, Katrin; Syldatk, Christoph

2018-01-01

Honey and agave syrup are high quality natural products and consist of more than 80% sugars. They are used as sweeteners, and are ingredients of cosmetics or medical ointments. Furthermore, both have low water content, are often liquid at room temperature and resemble some known sugar-based deep eutectic solvents (DES). Since it has been shown that it is possible to synthesize sugar esters in these DESs, in the current work honey or, as vegan alternative, agave syrup are used simultaneously as solvent and substrate for the enzymatic sugar ester production. For this purpose, important characteristics of the herein used honey and agave syrup were determined and compared with other available types. Subsequently, an enzymatic transesterification of four fatty acid vinyl esters was accomplished in ordinary honey and agave syrup. Notwithstanding of the high water content for transesterification reactions of the solvent, the successful sugar ester formation was proved by thin-layer chromatography (TLC) and compared to a sugar ester which was synthesized in a conventional DES. For a clear verification of the sugar esters, mass determinations by ESI-Q-ToF experiments and a NMR analysis were done. These environmentally friendly produced sugar esters have the potential to be used in cosmetics or pharmaceuticals, or to enhance their effectiveness.

Lipase-Catalyzed Synthesis of Sugar Esters in Honey and Agave Syrup

PubMed Central

Siebenhaller, Sascha; Gentes, Julian; Infantes, Alba; Muhle-Goll, Claudia; Kirschhöfer, Frank; Brenner-Weiß, Gerald; Ochsenreither, Katrin; Syldatk, Christoph

2018-01-01

Honey and agave syrup are high quality natural products and consist of more than 80% sugars. They are used as sweeteners, and are ingredients of cosmetics or medical ointments. Furthermore, both have low water content, are often liquid at room temperature and resemble some known sugar-based deep eutectic solvents (DES). Since it has been shown that it is possible to synthesize sugar esters in these DESs, in the current work honey or, as vegan alternative, agave syrup are used simultaneously as solvent and substrate for the enzymatic sugar ester production. For this purpose, important characteristics of the herein used honey and agave syrup were determined and compared with other available types. Subsequently, an enzymatic transesterification of four fatty acid vinyl esters was accomplished in ordinary honey and agave syrup. Notwithstanding of the high water content for transesterification reactions of the solvent, the successful sugar ester formation was proved by thin-layer chromatography (TLC) and compared to a sugar ester which was synthesized in a conventional DES. For a clear verification of the sugar esters, mass determinations by ESI-Q-ToF experiments and a NMR analysis were done. These environmentally friendly produced sugar esters have the potential to be used in cosmetics or pharmaceuticals, or to enhance their effectiveness. PMID:29487847

Lipase-Catalyzed Synthesis of Sugar Esters in Honey and Agave Syrup

NASA Astrophysics Data System (ADS)

Siebenhaller, Sascha; Gentes, Julian; Infantes, Alba; Muhle-Goll, Claudia; Kirschhöfer, Frank; Brenner-Weiß, Gerald; Ochsenreither, Katrin; Syldatk, Christoph

2018-02-01

Honey and agave syrup are high quality natural products and consist of more than 80% sugars. They are used as sweeteners, and are ingredients of cosmetics or medical ointments. Furthermore, both have low water content, are often liquid at room temperature and resemble some known sugar-based deep eutectic solvents. Since it has been shown that it is possible to synthesize sugar esters in these deep eutectic solvents, in the current work honey or, as vegan alternative, agave syrup are used simultaneously as solvent and substrate for the enzymatic sugar ester production. For this purpose, important characteristics of the herein used honey and agave syrup were determined and compared with other available types. Subsequently, an enzymatic transesterification of four fatty acid vinyl esters was accomplished in ordinary honey and agave syrup. Notwithstanding of the high water content for transesterification reactions of the solvent, the successful sugar ester formation was proved by thin-layer chromatography and compared to a sugar ester which was synthesized in a conventional deep eutectic solvent. For a clear verification of the sugar esters, mass determinations by ESI-Q-ToF experiments and a NMR analysis were done. These environmentally friendly produced sugar esters have the potential to be used in cosmetics or pharmaceuticals, or to enhance their effectiveness.

Immobilized lipase from Candida sp. 99-125 on hydrophobic silicate: characterization and applications.

PubMed

Zhao, Bin; Liu, Xinlong; Jiang, Yanjun; Zhou, Liya; He, Ying; Gao, Jing

2014-08-01

Lipase Candida sp. 99-125 has been proved to be quite effective in catalyzing organic synthesis reactions and is much cheaper than commercial lipases. Mesoporous silicates are attractive materials for the immobilization of enzymes due to their unique structures. The present research designed a hydrophobic silicate with uniform pore size suitable for the comfort of lipase Candida sp. 99-125 for improving its activity and stability. The resulting immobilized lipase (LP@PMO) by adsorption was employed to catalyze hydrolysis, esterification, and transesterification reactions, and the performances were compared with the lipase immobilized on hydrophilic silicate (LP@PMS) and native lipase. The LP@PMO showed as high activity as that of native lipase in hydrolysis and much increased catalytic activity and reusability in the reactions for biodiesel production. Besides, LP@PMO also possessed better organic stability. Such results demonstrate that immobilization of lipase onto hydrophobic supports is a promising strategy to fabricate highly active and stable biocatalysts for applications.

An economically viable synthesis of biodiesel from a crude Millettia pinnata oil of Jharkhand, India as feedstock and crab shell derived catalyst.

PubMed

Madhu, Devarapaga; Chavan, Supriya B; Singh, Veena; Singh, Bhaskar; Sharma, Yogesh C

2016-08-01

Biodiesel has emerged as a prominent source to replace petroleum diesel. The cost incurred in the production of biodiesel is higher than that for refining of crude oil to obtain mineral diesel. The heterogeneous catalyst was prepared from crab shells by calcining the crushed mass at 800°C. The solid waste catalyst was characterized with XRD, XPS, BET, SEM-EDS, and FT-IR. Millettia pinnata (karanja) oil extracted from its seeds was used as a feedstock for the synthesis of biodiesel. Biodiesel was synthesized through esterification followed by transesterification in a two-step process. Characterization of biodiesel was done using proton NMR spectroscopy. Reaction parameters such as reaction time, reaction temperature, concentration of catalyst and stirrer speed were optimized. Reusability of catalyst was checked and found that there was no loss of catalytic activity up to five times. Copyright © 2016. Published by Elsevier Ltd.

Biodiesel production from Nannochloropsis gaditana lipids through transesterification catalyzed by Rhizopus oryzae lipase.

PubMed

Navarro López, Elvira; Robles Medina, Alfonso; González Moreno, Pedro Antonio; Esteban Cerdán, Luis; Martín Valverde, Lorena; Molina Grima, Emilio

2016-03-01

Biodiesel (fatty acid methyl esters, FAMEs) was produced from saponifiable lipids (SLs) extracted from wet Nannochloropsis gaditana biomass using methanolysis catalyzed by Rhizopus oryzae intracellular lipase. SLs were firstly extracted with ethanol to obtain 31 wt% pure SLs. But this low SL purity also gave a low biodiesel conversion (58%). This conversion increased up to 80% using SLs purified by crystallization in acetone (95 wt% purity). Polar lipids play an important role in decreasing the reaction velocity - using SLs extracted with hexane, which have lower polar lipid content (37.4% versus 49.0% using ethanol), we obtained higher reaction velocities and less FAME conversion decrease when the same lipase batch was reused. 83% of SLs were transformed to biodiesel using a 70 wt% lipase/SL ratio, 11:1 methanol/SL molar ratio, 10 mL t-butanol/g SLs after 72 h. The FAME conversion decreased to 71% after catalyzing three reactions with the same lipase batch. Copyright © 2015 Elsevier Ltd. All rights reserved.

Enzymatic production of biodiesel from Nannochloropsis gaditana lipids: Influence of operational variables and polar lipid content.

PubMed

Navarro López, Elvira; Robles Medina, Alfonso; González Moreno, Pedro A; Jiménez Callejón, María J; Esteban Cerdán, Luis; Martín Valverde, Lorena; Castillo López, Beatriz; Molina Grima, Emilio

2015-01-01

Fatty acid methyl esters (FAMEs, biodiesel) were produced from Nannochloropsis gaditana wet biomass (12% saponifiable lipids, SLs) by extraction of SLs and lipase catalyzed transesterification. Lipids were extracted by ethanol (96%)-hexane, and 31% pure SLs were obtained with 85% yield. When the lipids were degummed, SL purity increased to 95%. Novozym 435 was selected from four lipases tested. Both the lipidic composition and the use of t-butanol instead of hexane increased the reaction velocity and the conversion, since both decreased due to the adsorption of polar lipids on the lipase immobilization support. The best FAME yield (94.7%) was attained at a reaction time of 48h and using 10mL of t-butanol/g SL, 0.225gN435/g SL, 11:1 methanol/SL molar ratio and adding the methanol in three steps. In these conditions the FAME conversion decreased by 9.8% after three reaction cycles catalyzed by the same lipase batch. Copyright © 2015 Elsevier Ltd. All rights reserved.

Production of biodiesel from Jatropha curcas L. oil catalyzed by SO₄²⁻/ZrO₂ catalyst: effect of interaction between process variables.

PubMed

Yee, Kian Fei; Lee, Keat Teong; Ceccato, Riccardo; Abdullah, Ahmad Zuhairi

2011-03-01

This study reports the conversion of Jatrophacurcas L. oil to biodiesel catalyzed by sulfated zirconia loaded on alumina catalyst using response surface methodology (RSM), specifically to study the effect of interaction between process variables on the yield of biodiesel. The transesterification process variables studied were reaction temperature, reaction duration, molar ratio of methanol to oil and catalyst loading. Results from this study revealed that individual as well as interaction between variables significantly affect the yield of biodiesel. With this information, it was found that 4h of reaction at 150°C, methanol to oil molar ratio of 9.88 mol/mol and 7.61 wt.% for catalyst loading gave an optimum biodiesel yield of 90.32 wt.%. The fuel properties of Jatropha biodiesel were characterized and it indeed met the specification for biodiesel according to ASTM D6751. Copyright © 2010 Elsevier Ltd. All rights reserved.

Enzymatic Production of Biodiesel: Strategies to Overcome Methanol Inactivation.

PubMed

Lotti, Marina; Pleiss, Jürgen; Valero, Francisco; Ferrer, Pau

2018-05-01

Lipase-catalyzed transesterification of triglycerides and alcohols to obtain biodiesel is an environmentally friendly and sustainable route for fuels production since, besides proceeding in mild reaction conditions, it allows for the use of low-cost feedstocks that contain water and free fatty acids, for example non-edible oils and waste oils. This review article reports recent advances in the field and focus in particular on a major issue in the enzymatic process, the inactivation of most lipases caused by methanol, the preferred acyl acceptor used for alcoholysis. The recent results about immobilization of enzymes on nano-materials and the use of whole-cell biocatalysts, as well as the use of cell-surface display technologies and metabolic engineering strategies for microbial production of biodiesel are described. It is discussed also insight into the effects of methanol on lipases obtained by modeling approaches and report on studies aimed at mining novel alcohol stable enzymes or at improving robustness in existing ones by protein engineering. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Production of biodiesel by transesterification of corn and soybean oils with ethanol or butanol using resin-bound truncated Candida antarctica lipase B

USDA-ARS?s Scientific Manuscript database

Enzymatic catalysts, such as lipases, have advantages over chemical catalysts for transesterification of triglycerides to produce biodiesel. A gene encoding a synthetic truncated Candida antarctica lipase B (CALB) was generated via automated PCR and expressed in Saccharomyces cerevisiae. Western b...

Modeling the Crystallization Behavior of Biodiesel at Low Temperatures

USDA-ARS?s Scientific Manuscript database

The most common form of biodiesel is made by transesterification of vegetable oil or animal fat fatty acids with methanol (FAME). Biodiesel from feedstocks such as palm oil (PME), rapeseed oil (RME), soybean oil (SME) or used cooking oil (UCOME) is susceptible to performance issues during cold weat...

Oleochemical industry future through biotechnology.

PubMed

Abdelmoez, Wael; Mustafa, Ahmad

2014-01-01

Lipases are the most widely used class of enzymes in organic synthesis. Enzymatic processes have been implemented in a broad range of industries as they are specific, save raw materials, energy and chemicals, environmentally friendly and fast in action compared to conventional processes. The most notable benefit is the moderate process temperature and pressure with no unwanted side reactions. In the past two decades, intensive research was carried out towards enzymatic synthesis of oleochemicals. This review has a sharp focus on the current implemented enzymatic processes for producing different oleochemicals such as fatty acids, glycerin, biodiesel, biolubricant and different alkyl esters via different processes including hydrolysis, esterification, transesterification and intraesterification.

A review and assessment of hydrodynamic cavitation as a technology for the future.

PubMed

Gogate, Parag R; Pandit, Aniruddha B

2005-01-01

In the present work, the current status of the hydrodynamic cavitation reactors has been reviewed discussing the bubble dynamics analysis, optimum design considerations, design correlations for cavitational intensity (in terms of collapse pressure)/cavitational yield and different successful chemical synthesis applications clearly illustrating the utility of these types of reactors. The theoretical discussion based on the modeling of the bubble dynamics equations aims at understanding the design information related to the dependency of the cavitational intensity on the operating parameters and recommendations have been made for the choice of the optimized conditions of operating parameters. The design information based on the theoretical analysis has also been supported with some experimental illustrations concentrating on the chemical synthesis applications. Assessment of the hydrodynamic cavitation reactors and comparison with the sonochemical reactors has been done by citing the different industrially important reactions (oxidation of toluene, o-xylene, m-xylene, p-xylene, mesitylene, o-nitrotoluene, p-nitrotoluene, m-nitrotoluene, o-chlorotoluene and p-chlorotoulene, and trans-esterification reaction i.e., synthesis of bio-diesel). Some recommendations have also been made for the future work to be carried out as well as the choice of the operating conditions for realizing the dream of industrial scale applications of the cavitational reactors.

Production of Fatty Acid Methyl Esters via the In Situ Transesterification of Soybean Oil in Carbon Dioxide-Expanded Methanol

USDA-ARS?s Scientific Manuscript database

The production of fatty acid methyl esters (FAME) by direct alkali- and acid-catalyzed in situ transesterification of soybean flakes in CO2-expanded methanol was examined at various temperatures and pressures. Attempts to synthesize FAME from soy flakes via alkaline catalysis, using sodium methoxid...

Mixed alkyl esters from cottonseed oil: Improved biodiesel properties and blends with ultra-low sulfur diesel fuel

USDA-ARS?s Scientific Manuscript database

Transesterification of refined cottonseed oil was carried out with methanol, ethanol, 1-butanol, and various mixtures of these alcohols at constant volume ratio of alcohol to oil (1:2) using KOH (1 wt%) as catalyst to produce biodiesel. In the mixed alcohol transesterifications, the formation of met...

Simultaneous determination of main reaction components in the reaction mixture during biodiesel production.

PubMed

Sánek, Lubomír; Pecha, Jiří; Kolomazník, Karel

2013-03-01

The proposed analytical method allows for simultaneous determination by GC using a programed temperature vaporization injector and a flame ionization detector of the main reaction components (i.e. glycerol, methyl esters, mono-, di-, and triacylglycerols) in the reaction mixture during biodiesel production. The suggested method is convenient for the rapid and simple evaluation of the kinetic data gained during the transesterification reaction and, also partially serves as an indicator of the quality of biodiesel and mainly, as the indicator of the efficiency of the whole production process (i.e. the conversion of triacylglycerols to biodiesel and its time progress). The optimization of chromatographic conditions (e.g. the oven temperature program, injector setting, amount of derivatization reagent, and the derivatization reaction time) was performed. The method has been validated with crude samples of biodiesel made from waste-cooking oils in terms of linearity, precision, accuracy, sensitivity, and limits of detection and quantification. The results confirmed a satisfactory degree of accuracy and repeatability (the mean RSDs were usually below 2%) necessary for the reliable quantitative determination of all components in the considerable concentration range (e.g. 10-1100 μg/mL in case of methyl esters). Compound recoveries ranging from 96 to 104% were obtained. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Palm-Based Neopentyl Glycol Diester: A Potential Green Insulating Oil.

PubMed

Raof, Nurliyana A; Yunus, Robiah; Rashid, Umer; Azis, Norhafiz; Yaakub, Zaini

2018-01-01

The transesterification of high oleic palm oil methyl ester (HOPME) with neopentyl glycol (NPG) has been investigated. The present study revealed the application of low-pressure technology as a new synthesis method to produce NPG diesters. Single variable optimization and response surface methodology (RSM) were implemented to optimize the experimental conditions to achieve the maximum composition (wt%) of NPG diesters. The main objective of this study was to optimize the production of NPG diesters and to characterize the optimized esters with typical chemical, physical and electrical properties to study its potential as insulating oil. The transesterification reaction between HOPME and NPG was conducted in a 1L three-neck flask reactor at specified temperature, pressure, molar ratio and catalyst concentration. For the optimization, four factors have been studied and the diester product was characterized by using gas chromatography (GC) analysis. The synthesized esters were then characterized with typical properties of transformer oil such as flash point, pour point, viscosity and breakdown voltage and were compared with mineral insulating oil and commercial NPG dioleate. For formulation, different samples of NPG diesters with different concentration of pour point depressant were prepared and each sample was tested for its pour point measurement. The optimum conditions inferred from the analyses were: molar ratio of HOPME to NPG of 2:1.3, temperature = 182°C, pressure = 0.6 mbar and catalyst concentration of 1.2%. The synthesized NPG diesters showed very important improvement in fire safety compared to mineral oil with flash point of 300°C and 155°C, respectively. NPG diesters also exhibit a relatively good viscosity of 21 cSt. The most striking observation to emerge from the data comparison with NPG diester was the breakdown voltage, which was higher than mineral oil and definitely in conformance to the IEC 61099 limit at 67.5 kV. The formulation of synthesized NPD diesters with VISCOPLEX® pour point depressant has successfully increased the pour point of NPG diester from -14°C to -48°C. The reaction time for the transesterification of HOPME with NPG to produce NPG diester was successfully reduced to 1 hour from the 14 hours required in the earlier synthesis method. The main highlight of this study was the excess reactant which is no longer methyl ester but the alcohol (NPG). The optimum reaction conditions for the synthesis were molar ratio of 2:1.13 for NPG:HOPME, 182°C, 0.6 mbar and catalyst concentration of 1.2 wt%. The maximum NPG diester yield of 87 wt% was consistent with the predicted yield of 87.7 wt% obtained from RSM. The synthesized diester exhibited better insulating properties than the commercial products especially with regards to the breakdown voltage, flash point and moisture content. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Determination of Total Lipids as Fatty Acid Methyl Esters (FAME) by in situ Transesterification: Laboratory Analytical Procedure (LAP)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Wychen, Stefanie; Ramirez, Kelsey; Laurens, Lieve M. L.

2016-01-13

This procedure is based on a whole biomass transesterification of lipids to fatty acid methyl esters to represent an accurate reflection of the potential of microalgal biofuels. Lipids are present in many forms and play various roles within an algal cell, from cell membrane phospholipids to energy stored as triacylglycerols.

Base catalytic transesterification of vegetable oil.

PubMed

Mainali, Kalidas

2012-01-01

Sustainable economic and industrial growth requires safe, sustainable resources of energy. Biofuel is becoming increasingly important as an alternative fuel for the diesel engine. The use of non-edible vegetable oils for biofuel production is significant because of the increasing demand for edible oils as food. With the recent debate of food versus fuel, some non-edible oils like soapnut and Jatropha (Jatropha curcus. L) are being investigated as possible sources of biofuel. Recent research has focused on the application of heterogeneous catalysis. This review considers catalytic transesterification and the possibility of heterogeneous base catalysts. The process of transesterification, and the effect of parameters, mechanism and kinetics are reviewed. Although chromatography (GC and HPLC) are the analytical methods most often used for biofuel characterization, other techniques and some improvements to analytical methods are discussed.

Single-step transesterification with simultaneous concentration and stable isotope analysis of fatty acid methyl esters by gas chromatography-combustion-isotope ratio mass spectrometry.

PubMed

Panetta, Robert J; Jahren, A Hope

2011-05-30

Gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) is increasingly applied to food and metabolic studies for stable isotope analysis (δ(13) C), with the quantification of analyte concentration often obtained via a second alternative method. We describe a rapid direct transesterification of triacylglycerides (TAGs) for fatty acid methyl ester (FAME) analysis by GC-C-IRMS demonstrating robust simultaneous quantification of amount of analyte (mean r(2) =0.99, accuracy ±2% for 37 FAMEs) and δ(13) C (±0.13‰) in a single analytical run. The maximum FAME yield and optimal δ(13) C values are obtained by derivatizing with 10% (v/v) acetyl chloride in methanol for 1 h, while lower levels of acetyl chloride and shorter reaction times skewed the δ(13) C values by as much as 0.80‰. A Bland-Altman evaluation of the GC-C-IRMS measurements resulted in excellent agreement for pure oils (±0.08‰) and oils extracted from French fries (±0.49‰), demonstrating reliable simultaneous quantification of FAME concentration and δ(13) C values. Thus, we conclude that for studies requiring both the quantification of analyte and δ(13) C data, such as authentication or metabolic flux studies, GC-C-IRMS can be used as the sole analytical method. Copyright © 2011 John Wiley & Sons, Ltd.

A study on the performance and emission characteristics of esterified pinnai oil tested in VCR engine.

PubMed

Ashok Kumar, T; Chandramouli, R; Mohanraj, T

2015-11-01

Biodiesel is a clean renewable fuel derived from vegetable oils and animal fats. It is biodegradable, oxygenated, non toxic and free from sulfur and aromatics. The biodiesel prepared from pinnai oil undergoes acid esterification followed by alkaline transesterification process. The fatty acid methyl esters components were identified using gas chromatography and compared with the standard properties. The properties of biodiesel are comparable with diesel. The yield of the biodiesel production depends upon the process parameters such as reaction temperature, pH, time duration and amount of catalyst. The yield of biodiesel by transesterification process was 73% at 55°C. This fuel was tested in a variable compression ratio engine with blend ratios of B10 and B20. During the test runs the compression ratio of the engine was varied from 15:1 to 18:1 and the torque is adjusted from zero to maximum value of 22Nm. The performance characteristics such as the brake thermal efficiency, brake specific energy consumption and exhaust gas temperature of the engine are analyzed. The combustion characteristics of biodiesel like ignition delay, combustion duration and maximum gas temperature and the emission characteristics are also analyzed. The performance characteristics, combustion characteristics and engine emission are effective in the variable compression ratio engine with biodiesel and it is compared with diesel. Copyright © 2015 Elsevier Inc. All rights reserved.

Biodegradable products by lipase biocatalysis.

PubMed

Linko, Y Y; Lämsä, M; Wu, X; Uosukainen, E; Seppälä, J; Linko, P

1998-11-18

The interest in the applications of biocatalysis in organic syntheses has rapidly increased. In this context, lipases have recently become one of the most studied groups of enzymes. We have demonstrated that lipases can be used as biocatalyst in the production of useful biodegradable compounds. A number of examples are given. 1-Butyl oleate was produced by direct esterification of butanol and oleic acid to decrease the viscosity of biodiesel in winter use. Enzymic alcoholysis of vegetable oils without additional organic solvent has been little investigated. We have shown that a mixture of 2-ethyl-1-hexyl esters can be obtained in a good yield by enzymic transesterification from rapeseed oil fatty acids for use as a solvent. Trimethylolpropane esters were also similarly synthesized as lubricants. Finally, the discovery that lipases can also catalyze ester syntheses and transesterification reactions in organic solvent systems has opened up the possibility of enzyme catalyzed production of biodegradable polyesters. In direct polyesterification of 1,4-butanediol and sebacic acid, polyesters with a mass average molar mass of the order of 56,000 g mol-1 or higher, and a maximum molar mass of about 130,000 g mol-1 were also obtained by using lipase as biocatalyst. Finally, we have demonstrated that also aromatic polyesters can be synthesized by lipase biocatalysis, a higher than 50,000 g mol-1 mass average molar mass of poly(1,6-hexanediyl isophthalate) as an example.

An investigation of biodiesel production from wastes of seafood restaurants.

PubMed

El-Gendy, Nour Sh; Hamdy, A; Abu Amr, Salem S

2014-01-01

This work illustrates a comparative study on the applicability of the basic heterogeneous calcium oxide catalyst prepared from waste mollusks and crabs shells (MS and CS, resp.) in the transesterification of waste cooking oil collected from seafood restaurants with methanol for production of biodiesel. Response surface methodology RSM based on D-optimal deign of experiments was employed to study the significance and interactive effect of methanol to oil M : O molar ratio, catalyst concentration, reaction time, and mixing rate on biodiesel yield. Second-order quadratic model equations were obtained describing the interrelationships between dependent and independent variables to maximize the response variable (biodiesel yield) and the validity of the predicted models were confirmed. The activity of the produced green catalysts was better than that of chemical CaO and immobilized enzyme Novozym 435. Fuel properties of the produced biodiesel were measured and compared with those of Egyptian petro-diesel and international biodiesel standards. The biodiesel produced using MS-CaO recorded higher quality than that produced using CS-CaO. The overall biodiesel characteristics were acceptable, encouraging application of CaO prepared from waste MS and CS for production of biodiesel as an efficient, environmentally friendly, sustainable, and low cost heterogeneous catalyst.

Synthesis of methyl esters from relevant palm products in near-critical methanol with modified-zirconia catalysts.

PubMed

Laosiripojana, N; Kiatkittipong, W; Sutthisripok, W; Assabumrungrat, S

2010-11-01

The transesterification and esterification of palm products i.e. crude palm oil (CPO), refined palm oil (RPO) and palm fatty acid distillate (PFAD) under near-critical methanol in the presence of synthesized SO(4)-ZrO(2), WO(3)-ZrO(2) and TiO(2)-ZrO(2) (with various sulfur- and tungsten loadings, Ti/Zr ratios, and calcination temperatures) were studied. Among them, the reaction of RPO with 20%WO(3)-ZrO(2) (calcined at 800 degrees C) enhanced the highest fatty acid methyl ester (FAME) yield with greatest stability after several reaction cycles; furthermore, it required shorter time, lower temperature and less amount of methanol compared to the reactions without catalyst. These benefits were related to the high acid-site density and tetragonal phase formation of synthesized WO(3)-ZrO(2). For further improvement, the addition of toluene as co-solvent considerably reduced the requirement of methanol to maximize FAME yield, while the addition of molecular sieve along with catalyst significantly increased FAME yield from PFAD and CPO due to the inhibition of hydrolysis reaction. Copyright 2010 Elsevier Ltd. All rights reserved.

Biodiesel production from various oils under supercritical fluid conditions by Candida antartica lipase B using a stepwise reaction method.

PubMed

Lee, Jong Ho; Kwon, Cheong Hoon; Kang, Jeong Won; Park, Chulhwan; Tae, Bumseok; Kim, Seung Wook

2009-05-01

In this study, we evaluate the effects of various reaction factors, including pressure, temperature, agitation speed, enzyme concentration, and water content to increase biodiesel production. In addition, biodiesel was produced from various oils to establish the optimal enzymatic process of biodiesel production. Optimal conditions were determined to be as follows: pressure 130 bar, temperature 45 degrees C, agitation speed 200 rpm, enzyme concentration 20%, and water contents 10%. Among the various oils used for production, olive oil showed the highest yield (65.18%) upon transesterification. However, when biodiesel was produced using a batch system, biodiesel conversion yield was not increased over 65%; therefore, a stepwise reaction was conducted to increase biodiesel production. When a reaction medium with an initial concentration of methanol of 60 mmol was used and adjusted to maintain this concentration of methanol every 1.5 h during biodiesel production, the conversion yield of biodiesel was 98.92% at 6 h. Finally, reusability was evaluated using immobilized lipase to determine if this method was applicable for industrial biodiesel production. When biodiesel was produced repeatedly, the conversion rate was maintained at over 85% after eight reuses.

Lipase catalyzed epoxidation of fatty acid methyl esters derived from unsaturated vegetable oils in absence of carboxylic acid.

PubMed

Sustaita-Rodríguez, Alejandro; Ramos-Sánchez, Víctor H; Camacho-Dávila, Alejandro A; Zaragoza-Galán, Gerardo; Espinoza-Hicks, José C; Chávez-Flores, David

2018-04-11

Nowadays the industrial chemistry reactions rely on green technologies. Enzymes as lipases are increasing its use in diverse chemical processes. Epoxidized fatty acid methyl esters obtained from transesterification of vegetable oils have recently found applications as polymer plasticizer, agrochemical, cosmetics, pharmaceuticals and food additives. In this research article, grapeseed, avocado and olive oils naturally containing high percents of mono and poly unsaturations were used as starting materials for the production of unsaturated fatty acid methyl esters. The effect of lauric acid as an active oxygen carrier was studied on epoxidation reactions where unsaturated fatty acid methyl esters were converted to epoxy fatty acid methyl esters using immobilized Candida antarctica Lipase type B as catalyst and hydrogen peroxide as oxygen donor at mild temperature and pressure conditions. After this study it was confirmed by 1 H NMR, 13 C NMR and GC-MS that the addition of lauric acid to the enzymatic reaction is unnecessary to transform the alkenes in to epoxides. It was found that quantitative conversions were possible in despite of a carboxylic acid absence.

A monolithic lipase reactor for biodiesel production by transesterification of triacylglycerides into fatty acid methyl esters

PubMed Central

Urban, Jiri; Svec, Frantisek; Fréchet, Jean M.J.

2011-01-01

An enzymatic reactor with lipase immobilized on a monolithic polymer support has been prepared and used to catalyze the transesterification of triacylglycerides into the fatty acid methyl esters commonly used for biodiesel. A design of experiments procedure was used to optimize the monolithic reactor with variables including control of the surface polarity of the monolith via variations in the length of the hydrocarbon chain in alkyl methacrylate monomer, time of grafting of 1-vinyl-4,4-dimethylazlactone used to activate the monolith, and time used for the immobilization of porcine lipase. Optimal conditions involved the use of a poly(stearyl methacrylate-co-ethylene dimethacrylate) monolith, grafted first with vinylazlactone, then treated with lipase for 2 h to carry out the immobilization of the enzyme. Best conditions for the transesterification of glyceryl tributyrate included a temperature of 37°C and a 10 min residence time of the substrate in the bioreactor. The reactor did not lose its activity even after pumping through it a solution of substrate equaling 1,000 reactor volumes. This enzymatic reactor was also used for the transesterification of triacylglycerides from soybean oil to fatty acid methyl esters thus demonstrating the ability of the reactor to produce biodiesel. PMID:21915852

A monolithic lipase reactor for biodiesel production by transesterification of triacylglycerides into fatty acid methyl esters.

PubMed

Urban, Jiri; Svec, Frantisek; Fréchet, Jean M J

2012-02-01

An enzymatic reactor with lipase immobilized on a monolithic polymer support has been prepared and used to catalyze the transesterification of triacylglycerides into the fatty acid methyl esters commonly used for biodiesel. A design of experiments procedure was used to optimize the monolithic reactor with variables including control of the surface polarity of the monolith via variations in the length of the hydrocarbon chain in alkyl methacrylate monomer, time of grafting of 1-vinyl-4,4-dimethylazlactone used to activate the monolith, and time used for the immobilization of porcine lipase. Optimal conditions involved the use of a poly(stearyl methacrylate-co-ethylene dimethacrylate) monolith, grafted first with vinylazlactone, then treated with lipase for 2 h to carry out the immobilization of the enzyme. Best conditions for the transesterification of glyceryl tributyrate included a temperature of 37°C and a 10 min residence time of the substrate in the bioreactor. The reactor did not lose its activity even after pumping through it a solution of substrate equaling 1,000 reactor volumes. This enzymatic reactor was also used for the transesterification of triacylglycerides from soybean oil to fatty acid methyl esters thus demonstrating the ability of the reactor to produce biodiesel. Copyright © 2011 Wiley Periodicals, Inc.

Production of Biodiesel from Acid Oil via a Two-Step Enzymatic Transesterification.

PubMed

Choi, Nakyung; Lee, Jeom-Sig; Kwak, Jieun; Lee, Junsoo; Kim, In-Hwan

2016-11-01

A two-step enzymatic transesterification process in a solvent-free system has been developed as a novel approach to the production of biodiesel using acid oil from rice bran oil soapstock. The acid oil consisted of 53.7 wt% fatty acids, 2.4 wt% monoacylglycerols, 9.1 wt% diacylglycerols, 28.8 wt% triacylglycerols, and 6.0 wt% others. Three immobilized lipases were evaluated as potential biocatalysts, including Novozym 435 from Candida antarctica, Lipozyme RM IM from Rhizomucor miehei, and Lipozyme TL IM from Thermomyces lanuginosus. The effects of molar ratio of acid oil to ethanol, temperature, and enzyme loading were investigated to determine the optimum conditions for the transesterification with the three immobilized lipases. The optimum conditions of the three immobilized lipases were a molar ratio of 1:5 (acid oil to ethanol), the temperature range of 30-40°C, and the enzyme loading range of 5-10%. The two-step transesterification was then conducted under the optimum conditions of each lipase. The stepwise use of Novozym 435 and Lipozyme TL IM or Lipozyme RM IM and Lipozyme TL IM resulted in similar or higher levels of yield to the individual lipases. The maximum yields obtained in both stepwise uses were ca. 92%.

A "Warm Formamide" Scenario for the Origins of Life Might not be so Hot: Comment on "Formamide and the Origin of Life"

NASA Technical Reports Server (NTRS)

Burton, Aaron S.

2012-01-01

In this review, Saladino et al. present an intriguing hypothesis surrounding the role of formamide in the origins of life on Earth, backed by experimental results supporting each step from formamide to RNA polymers. The overall premise is that, from formamide and inorganic phosphate, RNA molecules over 100 nucleotides in length can be produced. In addition, many carboxylic acids likely relevant to prebiotic metabolism, are formed along the way. Thus, from a rather simple organic molecule that has been observed in outer space (formamide), you can generate many of the compounds necessary for the origins of life. However, because high temperatures (160 C) are required for the formamide reactions, it remains unclear where the "warm formamide" scenario could have occurred. Low-temperature, aqueous hydrogen cyanide-based prebiotic chemistry that we know actually happened has been shown to produce many of the molecules invoked in the formamide hypothesis: amino acids, carboxylic acids, sugar acids, and nucleobases have all been found in meteorites recovered on Earth, providing a plausible route for their synthesis and delivery. In contrast, a large portion of the formamide hypothesis is based on relatively hightemperature reactions, A plausible milieu for high-temperature reactions with concentrated formamide is yet to be described, and is critical for this hypothesis to be validated. Hydrothermal vents are attractive heat sources, and the higher boiling point of formamide has been invoked as a mechanism to concentrate it from an aqueous solution, Unless the water can actually evaporate, however, there would be no net enrichment. For example, in the context of a deep-sea vent, any water "removed" by heating would be quickly replaced. Some of the individual reactions underpinning the present hypothesis have been met with skepticism because they go against conventional wisdom, To name a few of the surprising results: the observation that nucleosides can be converted to cyclic phosphates when heated in the presence of minerals and inorganie phosphate; that 3'-5' cGMP and cAMP nucleotides polymerize rapidly into RNA oligomers, even in the absence of monovalent counterions and that end-to-end ligation reactions between RNA oligomers occur in essentially pure water, without requiring any activating groups or counterions. Because the polymerization reactions are simply transesterification reactions, that they readily occur in the absence of cations makes one wonder why nearly all ribozyme-catalyzed transesterification reactions are metal-ion dependent; similarly, that the end-to-end ligation reactions do not require activation runs counter to the observation that all protein-catalyzed ligation and polymerization reactions of RNA and DNA require activated substrates. Detailed mechanistic studies of the reported reactions are warranted and could provide important insights for understanding the chemistry behind the origins of life. Because the authors have produced many of the experimental results supporting their hypothesis, they could demonstrate the validity of their hypothesis by converting formamide into approx 100 nucleotide RNA oligomers, using the products of one reaction as the reactants for the next reaction, under specific conditions plausible on the pre-biotic Earth. Such a demonstration would represent a milestone for our understanding of the origins of life.

Biodiesel forming reactions using heterogeneous catalysis

NASA Astrophysics Data System (ADS)

Liu, Yijun

Biodiesel synthesis from biomass provides a means for utilizing effectively renewable resources, a way to convert waste vegetable oils and animal fats to a useful product, a way to recycle carbon dioxide for a combustion fuel, and production of a fuel that is biodegradable, non-toxic, and has a lower emission profile than petroleum-diesel. Free fatty acid (FFA) esterification and triglyceride (TG) transesterification with low molecular weight alcohols constitute the synthetic routes to prepare biodiesel from lipid feedstocks. This project was aimed at developing a better understanding of important fundamental issues involved in heterogeneous catalyzed biodiesel forming reactions using mainly model compounds, representing part of on-going efforts to build up a rational base for assay, design, and performance optimization of solid acids/bases in biodiesel synthesis. As FFA esterification proceeds, water is continuously formed as a byproduct and affects reaction rates in a negative manner. Using sulfuric acid (as a catalyst) and acetic acid (as a model compound for FFA), the impact of increasing concentrations of water on acid catalysis was investigated. The order of the water effect on reaction rate was determined to be -0.83. Sulfuric acid lost up to 90% activity as the amount of water present increased. The nature of the negative effect of water on esterification was found to go beyond the scope of reverse hydrolysis and was associated with the diminished acid strength of sulfuric acid as a result of the preferential solvation by water molecules of its catalytic protons. The results indicate that as esterification progresses and byproduct water is produced, deactivation of a Bronsted acid catalyst like H2SO4 occurs. Using a solid composite acid (SAC-13) as an example of heterogeneous catalysts and sulfuric acid as a homogeneous reference, similar reaction inhibition by water was demonstrated for homogeneous and heterogeneous catalysis. This similarity together with other comparisons between the catalytic behaviors of liquid and solid acids suggests a common mode of operation of their Bronsted acid sites in carrying out esterification of a carboxylic acid with alcohol. The hypothesized Eley-Rideal type heterogeneous reaction mechanism involving a nucleophilic attack between adsorbed carboxylic acid and unadsorbed alcohol as the rate-limiting step was found to fit well the experimental observations and successfully predict the esterification rate obtained with SAC-13 as reaction progresses. The SAC-13 catalysis assay was also extended to carboxylic acids of higher molecular weights. A set of carboxylic acids with various alkyl chain lengths was used to investigate the structural effect of reacting carboxylic acids on heterogeneous catalyzed esterification. It was found that the reactivity of carboxylic acids was controlled by steric factors as the alkyl chain linearly lengthened. Despite their increased hydrophobicity, large carboxylic acids hardly impacted the deactivating effect of water on Bronsted acid sites. However, catalyst reusability and regeneration showed significant dependency on the size of the carboxylic acid used. With the use of larger reacting carboxylic acids, SAC-13 underwent more significant activity loss in consecutive reaction cycles due to stronger adsorption of the larger organics in the polymeric domains of the Nafion resin. In parallel to the research activity on acid catalyzed esterification, the use of strong solid bases with organic functionality (quarternary ammonium, QN+) was investigated from a fundamental perspective. Using triacetin as a model compound for TG molecules, the effectiveness of this Bronsted base functionality in transesterification was demonstrated even at mild reaction conditions. But its catalytic behavior including catalyst selectivity and deactivation was significantly affected by the nature of the adopted support. A purposive design of the immobilizing matrix is expected to optimize the activity, selectivity, and stability of the QN+ groups, thus enhancing their applicability in practical biodiesel synthesis from lipid feedstocks. As the solid organic base-matrix composite catalyst remains to be better designed to fit the need of TG methanolysis, inorganic solid bases composed of metal oxides appear to be a more feasible choice given that their thermal robustness generally allows the achievement of sufficient activity by increasing reaction temperature and potentially permits a convenient regeneration by recalcination. A study dealing with the methanolysis of real lipid feedstock (poultry fat) was carried out using Mg-Al hydrotalcite derived catalysts. From a practical standpoint, the impact of a variety of operational variables on reaction, such as catalyst pretreatments, temperature, reactants molar ratio, and usage of co-solvent were addressed. As a result, biodiesel synthesis from poultry fat was successfully conducted by appropriately adjusting these variables. However, many underlying aspects associated with catalyst performance remain unexamined and unexplained.

Magnetic amphiphilic hybrid carbon nanotubes containing N-doped and undoped sections: powerful tensioactive nanostructures

NASA Astrophysics Data System (ADS)

Purceno, Aluir D.; Machado, Bruno F.; Teixeira, Ana Paula C.; Medeiros, Tayline V.; Benyounes, Anas; Beausoleil, Julien; Menezes, Helvecio C.; Cardeal, Zenilda L.; Lago, Rochel M.; Serp, Philippe

2014-11-01

In this work, unique amphiphilic magnetic hybrid carbon nanotubes (CNTs) are synthesized and used as tensioactive nanostructures in different applications. These CNTs interact very well with aqueous media due to the hydrophilic N-doped section, whereas the undoped hydrophobic one has strong affinity for organic molecules. The amphiphilic character combined with the magnetic properties of these CNTs opens the door to completely new and exciting applications in adsorption science and catalysis. These amphiphilic N-doped CNTs can also be used as powerful tensioactive emulsification structures. They can emulsify water/organic mixtures and by a simple magnetic separation the emulsion can be easily broken. We demonstrate the application of these CNTs in the efficient adsorption of various molecules, in addition to promoting biphasic processes in three different reactions, i.e. transesterification of soybean oil, quinoline extractive oxidation with H2O2 and a metal-catalyzed aqueous oxidation of heptanol with molecular oxygen.In this work, unique amphiphilic magnetic hybrid carbon nanotubes (CNTs) are synthesized and used as tensioactive nanostructures in different applications. These CNTs interact very well with aqueous media due to the hydrophilic N-doped section, whereas the undoped hydrophobic one has strong affinity for organic molecules. The amphiphilic character combined with the magnetic properties of these CNTs opens the door to completely new and exciting applications in adsorption science and catalysis. These amphiphilic N-doped CNTs can also be used as powerful tensioactive emulsification structures. They can emulsify water/organic mixtures and by a simple magnetic separation the emulsion can be easily broken. We demonstrate the application of these CNTs in the efficient adsorption of various molecules, in addition to promoting biphasic processes in three different reactions, i.e. transesterification of soybean oil, quinoline extractive oxidation with H2O2 and a metal-catalyzed aqueous oxidation of heptanol with molecular oxygen. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr04005h

Effect of sludge features and extraction-esterification technology on the synthesis of biodiesel from secondary wastewater treatment sludges.

PubMed

Patiño, Yolanda; Mantecón, Laura G; Polo, Sara; Faba, Laura; Díaz, Eva; Ordóñez, Salvador

2018-01-01

Secondary sludge from municipal wastewater treatment plant is proposed as a promising alternative lipid feedstock for biodiesel production. A deep study combining different type of raw materials (sludge coming from the oxic, anoxic and anaerobic steps of the biological treatment) with different technologies (liquid-liquid and solid-liquid extractions followed by acid catalysed transesterification and in situ extraction-transesterification procedure) allows a complete comparison of available technologies. Different parameters - contact time, catalyst concentration, pretreatments - were considered, obtaining more than 17% FAMEs yield after 50min of sonication with the in situ procedure and 5% of H 2 SO 4 . This result corresponds to an increment of more than 65% respect to the best results reported at typical conditions. Experimental data were used to propose a mathematical model for this process, demonstrating that the mass transfer of lipids from the sludge to the liquid is the limiting step. Copyright © 2017 Elsevier Ltd. All rights reserved.

Biodiesel production from Spirulina microalgae feedstock using direct transesterification near supercritical methanol condition.

PubMed

Mohamadzadeh Shirazi, Hamed; Karimi-Sabet, Javad; Ghotbi, Cyrus

2017-09-01

Microalgae as a candidate for production of biodiesel, possesses a hard cell wall that prevents intracellular lipids leaving out from the cells. Direct or in situ supercritical transesterification has the potential for destruction of microalgae hard cell wall and conversion of extracted lipids to biodiesel that consequently reduces the total energy consumption. Response surface methodology combined with central composite design was applied to investigate process parameters including: Temperature, Time, Methanol-to-dry algae, Hexane-to-dry algae, and Moisture content. Thirty-two experiments were designed and performed in a batch reactor, and biodiesel efficiency between 0.44% and 99.32% was obtained. According to fatty acid methyl ester yields, a quadratic experimental model was adjusted and the significance of parameters was evaluated using analysis of variance (ANOVA). Effects of single and interaction parameters were also interpreted. In addition, the effect of supercritical process on the ultrastructure of microalgae cell wall using scanning electron spectrometry (SEM) was surveyed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Microwave Assisted Enzymatic Kinetic Resolution of (±)-1-Phenyl-2-propyn-1-ol in Nonaqueous Media

PubMed Central

Devendran, Saravanan; Yadav, Ganapati D.

2014-01-01

Kinetic resolution of 1-phenyl-2-propyn-1-ol, an important chiral synthon, was studied through trans-esterification with acyl acetate to investigate synergism between microwave irradiation and enzyme catalysis. Lipases from different microbial origins were employed for the kinetic resolution of (R/S)-1-phenyl-2-propyn-1-ol, among which Candida antarctica lipase B, immobilized on acrylic resin (Novozym 435), was found to be the best catalyst in n-hexane as solvent. Vinyl acetate was the most effective among different acyl esters studied. The effect of various parameters was studied in a systematic manner. Definite synergism between microwave and enzyme was observed. The initial rate was improved around 1.28 times under microwave irradiation than conventional heating. Under optimum conditions, maximum conversion (48.78%) and high enantiomeric excess (93.25%) were obtained in 2 h. From modeling studies, it is concluded that the reaction follows the Ping-Pong bi-bi mechanism with dead end alcohol inhibition. Kinetic parameters were obtained by using nonlinear regression. This process is green, clean, and easily scalable as compared to the chemical process. PMID:24707487

Transesterification of rapeseed oil for biodiesel production in trickle-bed reactors packed with heterogeneous Ca/Al composite oxide-based alkaline catalyst.

PubMed

Meng, Yong-Lu; Tian, Song-Jiang; Li, Shu-Fen; Wang, Bo-Yang; Zhang, Min-Hua

2013-05-01

A conventional trickle bed reactor and its modified type both packed with Ca/Al composite oxide-based alkaline catalysts were studied for biodiesel production by transesterification of rapeseed oil and methanol. The effects of the methanol usage and oil flow rate on the FAME yield were investigated under the normal pressure and methanol boiling state. The oil flow rate had a significant effect on the FAME yield for the both reactors. The modified trickle bed reactor kept over 94.5% FAME yield under 0.6 mL/min oil flow rate and 91 mL catalyst bed volume, showing a much higher conversion and operational stability than the conventional type. With the modified trickle bed reactor, both transesterification and methanol separation could be performed simultaneously, and glycerin and methyl esters were separated additionally by gravity separation. Copyright © 2013 Elsevier Ltd. All rights reserved.

Methods and catalysts for making biodiesel from the transesterification and esterification of unrefined oils

DOEpatents

Yan, Shuli [Detroit, MI; Salley, Steven O [Grosse Pointe Park, MI; Ng, K Y. Simon [West Bloomfield, MI

2012-04-24

A method of forming a biodiesel product and a heterogeneous catalyst system used to form said product that has a high tolerance for the presence of water and free fatty acids (FFA) in the oil feedstock is disclosed. This catalyst system may simultaneously catalyze both the esterification of FAA and the transesterification of triglycerides present in the oil feedstock. The catalyst system according to one aspect of the present disclosure represents a class of zinc and lanthanum oxide heterogeneous catalysts that include different ratios of zinc oxide to lanthanum oxides (Zn:La ratio) ranging from about 10:0 to 0:10. The Zn:La ratio in the catalyst is believed to have an effect on the number and reactivity of Lewis acid and base sites, as well as the transesterification of glycerides, the esterification of fatty acids, and the hydrolysis of glycerides and biodiesel.

High Glass Transition Temperature Renewable Polymers via Biginelli Multicomponent Polymerization.

PubMed

Boukis, Andreas C; Llevot, Audrey; Meier, Michael A R

2016-04-01

A novel and straightforward one-pot multicomponent polycondensation method was established in this work. The Biginelli reaction is a versatile multicomponent reaction of an aldehyde, a β-ketoester (acetoacetate) and urea, which can all be obtained from renewable resources, yielding diversely substituted 3,4-dihydropyrimidin-2(1H)-ones (DHMPs). In this study, renewable diacetoacetate monomers with different spacer chain lengths (C3, C6, C10, C20) were prepared via simple transesterification of renewable diols and commercial acetoacetates. The diacetoacetate monomers were then reacted with renewable dialdehydes, i.e., terephthalaldehyde and divanillin in a Biginelli type step-growth polymerization. The obtained DHMP polymers (polyDHMPs) displayed high molar masses, high glass transition temperatures (Tg) up to 203 °C and good thermal stability (Td5%) of 280 °C. The Tg of the polyDHMPs could be tuned by variation of the structure of the dialdehyde or the diacetoacetate component. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Process integration possibilities for biodiesel production from palm oil using ethanol obtained from lignocellulosic residues of oil palm industry.

PubMed

Gutiérrez, Luis F; Sánchez, Oscar J; Cardona, Carlos A

2009-02-01

In this paper, integration possibilities for production of biodiesel and bioethanol using a single source of biomass as a feedstock (oil palm) were explored through process simulation. The oil extracted from Fresh Fruit Bunches was considered as the feedstock for biodiesel production. An extractive reaction process is proposed for transesterification reaction using in situ produced ethanol, which is obtained from two types of lignocellulosic residues of palm industry (Empty Fruit Bunches and Palm Press Fiber). Several ways of integration were analyzed. The integration of material flows between ethanol and biodiesel production lines allowed a reduction in unit energy costs down to 3.4%, whereas the material and energy integration leaded to 39.8% decrease of those costs. The proposed integrated configuration is an important option when the technology for ethanol production from biomass reaches such a degree of maturity that its production costs be comparable with those of grain or cane ethanol.

Extraction of microalgal lipids and the influence of polar lipids on biodiesel production by lipase-catalyzed transesterification.

PubMed

Navarro López, Elvira; Robles Medina, Alfonso; González Moreno, Pedro Antonio; Esteban Cerdán, Luis; Molina Grima, Emilio

2016-09-01

In order to obtain microalgal saponifiable lipids (SLs) fractions containing different polar lipid (glycolipids and phospholipids) contents, SLs were extracted from wet Nannochloropsis gaditana microalgal biomass using seven extraction systems, and the polar lipid contents of some fractions were reduced by low temperature acetone crystallization. We observed that the polar lipid content in the extracted lipids depended on the polarity of the first solvent used in the extraction system. Lipid fractions with polar lipid contents between 75.1% and 15.3% were obtained. Some of these fractions were transformed into fatty acid methyl esters (FAMEs, biodiesel) by methanolysis, catalyzed by the lipases Novozym 435 and Rhizopus oryzae in tert-butanol medium. We observed that the reaction velocity was higher the lower the polar lipid content, and that the final FAME conversions achieved after using the same lipase batch to catalyze consecutive reactions decreased in relation to an increase in the polar lipid content. Copyright © 2016 Elsevier Ltd. All rights reserved.

Rapid alkali catalyzed transesterification of microalgae lipids to biodiesel using simultaneous cooling and microwave heating and its optimization.

PubMed

Chee Loong, Teo; Idris, Ani

2014-12-01

Biodiesel with improved yield was produced from microalgae biomass under simultaneous cooling and microwave heating (SCMH). Nannochloropsis sp. and Tetraselmis sp. which were known to contain higher lipid species were used. The yield obtained using this novel technique was compared with the conventional heating (CH) and microwave heating (MWH) as the control method. The results revealed that the yields obtained using the novel SCMH were higher; Nannochloropsis sp. (83.33%) and Tetraselmis sp. (77.14%) than the control methods. Maximum yields were obtained using SCMH when the microwave was set at 50°C, 800W, 16h of reaction with simultaneous cooling at 15°C; and water content and lipid to methanol ratio in reaction mixture was kept to 0 and 1:12 respectively. GC analysis depicted that the biodiesel produced from this technique has lower carbon components (<19 C) and has both reasonable CN and IV reflecting good ignition and lubricating properties. Copyright © 2014 Elsevier Ltd. All rights reserved.

Intrinsic sequence specificity of the Cas1 integrase directs new spacer acquisition

PubMed Central

Rollie, Clare; Schneider, Stefanie; Brinkmann, Anna Sophie; Bolt, Edward L; White, Malcolm F

2015-01-01

The adaptive prokaryotic immune system CRISPR-Cas provides RNA-mediated protection from invading genetic elements. The fundamental basis of the system is the ability to capture small pieces of foreign DNA for incorporation into the genome at the CRISPR locus, a process known as Adaptation, which is dependent on the Cas1 and Cas2 proteins. We demonstrate that Cas1 catalyses an efficient trans-esterification reaction on branched DNA substrates, which represents the reverse- or disintegration reaction. Cas1 from both Escherichia coli and Sulfolobus solfataricus display sequence specific activity, with a clear preference for the nucleotides flanking the integration site at the leader-repeat 1 boundary of the CRISPR locus. Cas2 is not required for this activity and does not influence the specificity. This suggests that the inherent sequence specificity of Cas1 is a major determinant of the adaptation process. DOI: http://dx.doi.org/10.7554/eLife.08716.001 PMID:26284603

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, XS; Michaelis, VK; Ong, TC

The controllable synthesis of well-ordered layered materials with specific nanoarchitecture poses a grand challenge in materials chemistry. Here the solvothermal synthesis of two structurally analogous 5-coordinate organosilicate complexes through a novel transesterification mechanism is reported. Since the polycrystalline nature of the intrinsic hypervalent Si complex thwarts the endeavor in determining its structure, a novel strategy concerning the elegant addition of a small fraction of B species as an effective crystal growth mediator and a sacrificial agent is proposed to directly prepare diffraction-quality single crystals without disrupting the intrinsic elemental type. In the determined crystal structure, two monomeric primary building unitsmore » (PBUs) self-assemble into a dimeric asymmetric secondary BU via strong Na+O2- ionic bonds. The designed one-pot synthesis is straightforward, robust, and efficient, leading to a well-ordered (10)-parallel layered Si complex with its principal interlayers intercalated with extensive van der Waals gaps in spite of the presence of substantial Na+ counter-ions as a result of unique atomic arrangement in its structure. However, upon fast pyrolysis, followed by acid leaching, both complexes are converted into two SiO2 composites bearing BET surface areas of 163.3 and 254.7m(2)g(-1) for the pyrolyzed intrinsic and B-assisted Si complexes, respectively. The transesterification methodology merely involving alcoholysis but without any hydrolysis side reaction is designed to have generalized applicability for use in synthesizing new layered metal-organic compounds with tailored PBUs and corresponding metal oxide particles with hierarchical porosity.« less

Fast transmethylation of serum lipids using microwave irradiation.

PubMed

Lin, Yu Hong; Loewke, James D; Hyun, Duk Y; Leazer, Jay; Hibbeln, Joseph R

2012-11-01

Microwave irradiation as the energy source for one-step direct transesterification of fatty acids in human serum lipids was examined in a solvent system of methanol: hexane: acetyl chloride based on a Lepage & Roy assay. Innovative and explosion proof single-mode or multimode microwave accelerated reaction system was employed. Recoveries were calculated as the percentage of fatty acid concentrations measured by microwave assay to those by the reference method of the Lepage & Roy assay that utilized conductive heating at 100 °C for 60 min. Under conditions of 100 °C for 1 min in Single-mode (S4-100 × 1), or 125 °C for 5 min in Multimode (M5-125 × 5), the recoveries were 100-103 % for the total fatty acids and 96-106 % for each categorized fatty acid, including saturates, monounsaturates, n-6 PUFA, and n-3 PUFA. For individual PUFA, the mean recoveries were 102-105 % for 18:2n-6 and 18:3n-3; 99, 109, and 95 % for 20:4n-6, 20:5n-3, and 22:6n-3, respectively. Thus, fatty acid concentrations determined by microwave fatty acid assay were accurate to those results by the reference method, when the microwave conditions were optimal. In summary, the microwave irradiation could replace conductive heating in one-step direct transesterification, and reduce the duration from 60 min to 5 min or less. This methodology may be applied in both the absolute and relative quantification of serum total fatty acids.

Fast Transmethylation of Serum Lipids using Microwave Irradiation

PubMed Central

Lin, Yu Hong; Loewke, James D.; Hyun, Duk Y.; Leazer, Jay; Hibbeln, Joseph R.

2012-01-01

Microwave irradiation as the energy source for one–step direct transesterification of fatty acids in human serum lipids was examined in solvent system of methanol: hexane: acetyl chloride based on Lepage & Roy assay. Innovative and explosion proof single–mode or multimode microwave accelerate reaction system was employed. Recoveries were calculated as the percentage of fatty acid concentrations measured by microwave assay to those by reference method Lepage & Roy assay that utilized conductive heating at 100 °C for 60 min. At conditions of 100 °C for 1 min in Single–mode (S4–100×1), or 125 °C for 5 min in Multimode (M5–125×5), the recoveries were 100–103% for the total fatty acids and 96–106% for each categorized fatty acid, including saturates, monounsaturates, n-6 PUFA, and n-3 PUFA. For individual PUFA, the mean recoveries were 102–105% for 18:2n-6 and 18:3n-3; 99, 109, and 95% for 20:4n-6, 20:5n-3, and 22:6n-3, respectively. Thus, fatty acid concentrations determined by microwave fatty acid assay were accurate to those results by the reference method, when the microwave conditions were optimal. In summary, the microwave irradiation could replace conductive heating in one–step direct transesterification, and reduce duration from 60 min to 5 min or less. This methodology may be applied in both the absolute and relative quantification of serum total fatty acids. PMID:23015312

Biodiesel production from waste cooking oil using copper doped zinc oxide nanocomposite as heterogeneous catalyst.

PubMed

Gurunathan, Baskar; Ravi, Aiswarya

2015-01-01

A novel CZO nanocomposite was synthesized and used as heterogeneous catalyst for transesterification of waste cooking oil into biodiesel using methanol as acyl acceptor. The synthesized CZO nanocomposite was characterized in FESEM with an average size of 80 nm as nanorods. The XRD patterns indicated the substitution of ZnO in the hexagonal lattice of Cu nanoparticles. The 12% (w/w) nanocatalyst concentration, 1:8 (v:v) O:M ratio, 55 °C temperature and 50 min of reaction time were found as optimum for maximum biodiesel yield of 97.71% (w/w). Hence, the use of CZO nanocomposite can be used as heterogeneous catalyst for biodiesel production from waste cooking oil. Copyright © 2015 Elsevier Ltd. All rights reserved.

Supported catalyst systems and method of making biodiesel products using such catalysts

DOEpatents

Kim, Manhoe; Yan, Shuli; Salley, Steven O.; Ng, K. Y. Simon

2015-10-20

A heterogeneous catalyst system, a method of preparing the catalyst system and a method of forming a biodiesel product via transesterification reactions using the catalyst system is disclosed. The catalyst system according to one aspect of the present disclosure represents a class of supported mixed metal oxides that include at least calcium oxide and another metal oxide deposited on a lanthanum oxide or cerium oxide support. Preferably, the catalysts include CaO--CeO.sub.2ZLa.sub.2O.sub.3 or CaO--La.sub.2O.sub.3/CeO.sub.2. Optionally, the catalyst may further include additional metal oxides, such as CaO--La.sub.2O.sub.3--GdOxZLa.sub.2O.sub.3.

Selective ethanolysis of sunflower oil with Lipozyme RM IM, an immobilized Rhizomucor miehei lipase, to obtain a biodiesel-like biofuel, which avoids glycerol production through the monoglyceride formation.

PubMed

Calero, Juan; Verdugo, Cristóbal; Luna, Diego; Sancho, Enrique D; Luna, Carlos; Posadillo, Alejandro; Bautista, Felipa M; Romero, Antonio A

2014-12-25

The obtaining of Ecodiesel, a biofuel applicable to diesel engines which keeps the glycerin as monoglyceride (MG), was achieved through a selective ethanolysis process of sunflower oil, by application of Lipozyme RM IM, a Rhizomucor miehei lipase immobilized on macroporous anion exchange resins. This biocatalyst that was already described in the synthesis of conventional biodiesel has also shown its efficiency in the present selective enzymatic process, after optimization of the influence of various reaction parameters. Thus, an adequate activity is obtained that is maintained throughout five successive reuses. Quantitative conversions of triglycerides (TG) with high yields to fatty acid ethyl esters (FAEE) were obtained under mild reaction conditions that correspond to the transformation of TG in a mixture of two moles of FAEE and a mole of MG, thus avoiding the glycerol production. Thus, the selective transesterification reaction of sunflower oil with absolute ethanol can be carried out under standard conditions with oil/ethanol volume ratio 12/3.5 (mL), at constant pH obtained by the addition of 50 μl of aqueous solution of 10 N NaOH, reaction temperature of 40 °C and 40 mg of Lipozyme RM IM. Under these experimental conditions six successive reactions can be efficiently carried out. Copyright © 2014 Elsevier B.V. All rights reserved.

Corrosion-Related Consequences of Biodiesel in Contact with Natural Seawater

DTIC Science & Technology

2010-03-01

petroleum diesel, biodiesel contains no sulfur. In the U.S. the term “biodiesel” is standardized as fatty acid methyl ester ( FAME ). Biodiesel content is...Form 298 (Rev. 8-98) Prescribed by ANSI Std Z39-18 to methyl (or ethyl) esters with a process known as transesterification.4 The transesterification...biodegradation of the vegetable methyl esters in agitated San Francisco Bay water was less than 4 days at 17 °C.4,22 The highest corrosion rates

Heterogeneous catalysis for sustainable biodiesel production via esterification and transesterification.

PubMed

Lee, Adam F; Bennett, James A; Manayil, Jinesh C; Wilson, Karen

2014-11-21

Concern over the economics of accessing fossil fuel reserves, and widespread acceptance of the anthropogenic origin of rising CO2 emissions and associated climate change from combusting such carbon sources, is driving academic and commercial research into new routes to sustainable fuels to meet the demands of a rapidly rising global population. Here we discuss catalytic esterification and transesterification solutions to the clean synthesis of biodiesel, the most readily implemented and low cost, alternative source of transportation fuels to meet future societal demands.

Optimized synthesis of lipase-catalyzed hexyl acetate in n-hexane by response surface methodology.

PubMed

Shieh, C J; Chang, S W

2001-03-01

Hexyl acetate, a short-chain ester with fruity odor, is a significant green note flavor compound and widely used in the food industry. The ability for immobilized lipase from Mucor miehei (Lipozyme IM-77) to catalyze the transesterification of hexanol with triacetin was investigated in this study. Response surface methodology and five-level-five-factor central composite rotatable design were adopted to evaluate the effects of synthesis variables, such as reaction time (2-10 h), temperature (25-65 degrees C), enzyme amount (10-50%; 0.024-0.118 BAUN), substrate molar ratio of triacetin to hexanol (1:1 to 3:1), and added water content (0-20%) on percentage molar conversion of hexyl acetate. The results showed that reaction temperature and substrate molar ratio were the most important parameters and that added water content had less of an effect on percent molar conversion. On the basis of canonical analysis, optimum synthesis conditions were as follows: reaction time, 7.7 h; temperature, 52.6 degrees C; enzyme amount, 37.1% (0.089 BAUN); substrate molar ratio, 2.7:1; and added water, 12.5%. The predicted value was 88.9% molar conversion, and the actual experimental value was 86.6% molar conversion.

Extraction of caustic potash from spent tea for biodiesel Production

NASA Astrophysics Data System (ADS)

Sulaiman, Sarina; Faiz Che Fisol, Ahmad; Sharikh, Atikah Mohamed; Noraini Jimat, Dzun; Jamal, Parveen

2018-01-01

Biodiesel is an alternative to non-renewable fossil fuels due to its low gas emission and economical value. This study aims to extract caustic potash (KOH) from spent tea and to optimize the transesterfication process based on parameters such as amount of catalyst, reaction temperature and methanol to oil ratio. The spent tea was first dried at 60°C prior to calcination at 600°C for two hours. Caustic Potash were extracted from the calcined spent tea. The transesterification process was done based on Design of Experiments (DOE) to study the effects of amount of catalyst ranging from 0.5 wt % to 2.5 wt %, reaction temperature from 55°C to 65°C and methanol to oil ratio from 6:1 to 12:1 at a constant agitation rate of 300 rpm for three hours. The calcined spent tea produced was recorded the highest at 54.3 wt % and the extracted catalyst was 2.4 wt %. The optimized biodiesel yield recorded was 56.95% at the optimal conditions of 2.5 wt % amount of catalyst, 65°C reaction temperature and 9:1 methanol to oil ratio.

A Review of Enzymatic Transesterification of Microalgal Oil-Based Biodiesel Using Supercritical Technology

PubMed Central

Taher, Hanifa; Al-Zuhair, Sulaiman; Al-Marzouqi, Ali H.; Haik, Yousef; Farid, Mohammed M.

2011-01-01

Biodiesel is considered a promising replacement to petroleum-derived diesel. Using oils extracted from agricultural crops competes with their use as food and cannot realistically satisfy the global demand of diesel-fuel requirements. On the other hand, microalgae, which have a much higher oil yield per hectare, compared to oil crops, appear to be a source that has the potential to completely replace fossil diesel. Microalgae oil extraction is a major step in the overall biodiesel production process. Recently, supercritical carbon dioxide (SC-CO2) has been proposed to replace conventional solvent extraction techniques because it is nontoxic, nonhazardous, chemically stable, and inexpensive. It uses environmentally acceptable solvent, which can easily be separated from the products. In addition, the use of SC-CO2 as a reaction media has also been proposed to eliminate the inhibition limitations that encounter biodiesel production reaction using immobilized enzyme as a catalyst. Furthermore, using SC-CO2 allows easy separation of the product. In this paper, conventional biodiesel production with first generation feedstock, using chemical catalysts and solvent-extraction, is compared to new technologies with an emphasis on using microalgae, immobilized lipase, and SC-CO2 as an extraction solvent and reaction media. PMID:21915372

Theoretical aspects of methyl acetate and methanol activation on MgO(100) and (501) catalyst surfaces with application in FAME production

NASA Astrophysics Data System (ADS)

Man, Isabela-Costinela; Soriga, Stefan Gabriel; Parvulescu, Vasile

2017-01-01

Density functional theory (DFT) calculations were carried out to study the activation of methyl acetate and methanol on MgO(100) and MgO(501) surfaces and integrated in the context of transesterification, interesterification and glycerolysis reactions used in biodiesel industry. First results indicate the importance of including of dispersion forces in the calculations. On MgO(100) the reverse reactions steps of Csbnd O and Csbnd H dissociations and on MgO(501) the same reverse reaction step of Csbnd H dissociations of methyl acetate are energetically favorable, while the dissociation of Csbnd O bond into methoxide and acetate fragments on the edge of MgO(501) was found to be exothermic with a low activation energy. For methanol, the dissociation of Osbnd H bond on MgO(100) surface in the presence of the second coadsorbed methanol molecule becomes more energetically favoured compared to the isolated molecule, due to the fact that the methoxide fragment is stabilized by intermolecular hydrogen bonding. This is reflected by the decrease of the activation energy of the forward reaction step and the increase of the activation energy of the backward reaction step, increasing the probability to have dissociated molecules among the undissociated ones. These results represent a step forward for better understanding from atomistic point of view the paths of these reactions on these surfaces for the corresponding catalytic processes.

ZnO nanorods as catalyts for biodiesel production from olive oil

NASA Astrophysics Data System (ADS)

Molina, Carmen Maria Miralda

The motivation to determine a viable alternative to petroleum based energy has risen in recent years due to increased greenhouse gas emissions, environmental pollution, and the fear of exhausting oil and natural gas reserves. Biodiesel derived from the transesterification of vegetable oils or animal fats has emerged as a viable alternative to petroleum diesel. However, for this to become an option available to the average consumer it is vital to find an effective catalyst. Metal oxides have emerged as potential heterogeneous catalysts. ZnO in particular is attractive because it is abundant. The use of nanostructures has been shown to improve the catalytic performance of ZnO. ZnO nanorods were synthesized using a solution approach. The crystalline structure, morphology, and surface area were confirmed using XRD, SEM, and BET surface area respectively. The characterized nanorods were used as catalysts for the production of biodiesel. The nanorods achieved conversions of 94.8% at 150°C for reaction times of eight hours. They also demonstrated better catalytic performance, attributed to their increased degree of crystallinity, than conventional ZnO. A kinetic study at 150°C to determine the reaction rate parameters was also conducted. Due to the presence of three distinct phases in the reaction, initially the reaction rate is dominated by mass transfer limitations. However, these are eventually overcome and the reaction proceeds with a pseudo-first order with respect to the oil and a reaction rate constant of 0.5136 h-1.

Ultrasound-assisted in-situ transesterification of wet Aurantiochytrium sp. KRS 101 using potassium carbonate.

PubMed

Sung, Mina; Han, Jong-In

2018-08-01

A new in-situ transesterification method was developed for wet biomass: K 2 CO 3 was used as an alkaline catalyst and, Aurantiochytrium sp. KRS 101 as oleaginous DHA-producing microalgae. It was found that the presence of water greatly impaired the overall efficiency even with the powerful catalyst that had worked surpassingly well with dry biomass, and thus a mechanical aid like ultrasonication was needed to make advantage of full potential of the alkaline catalyst. The total fatty acid ethyl ester (FAEE) recovery yield of 94.6% was achieved with sonication at 100 g/L of biomass (40% moisture), 3% of K 2 CO 3 , 70 °C and 30 min. All these suggest that the ultrasound assisted in-situ transesterification can offer a feasible means for FAEE recovery and it was so by way of overcoming the physical limitation of mass transfer caused the presence of water and providing effective contacts between reactants. Copyright © 2018. Published by Elsevier Ltd.

Noncatalytic transformation of the crude lipid of ChlorellaI vulgaris into fatty acid methyl ester (FAME) with charcoal via a thermo-chemical process.

PubMed

Kwon, Eilhann E; Jeon, Young Jae; Yi, Haakrho

2013-02-01

The noncatalytic transformation of the crude lipid of Chlorella vulgaris (C. vulgaris) into fatty acid methyl ester (FAME) via a thermo-chemical process was mainly investigated in this work. The crude lipid of C. vulgaris was recovered by means of solvent extraction from C. vulgaris cultivated in a raceway pond. The conventional catalyzed transesterification of crude lipid of C. vulgaris is notably inhibited by the impurities contained in the crude lipid of C. vulgaris. These impurities are inevitably derived from the solvent extraction process for C. vulgaris. However, this work presents the noncatalytic transesterification of microalgal lipid into FAME, which could be an alternative option. For example, the noncatalytic transformation of microalgal lipid into FAME provides evidence that the esterification of free fatty acids (FFAs) and the transesterification of triglycerides can be combined into a single step less susceptible to the impurities and with a high conversion efficiency (∼97%). Copyright © 2012 Elsevier Ltd. All rights reserved.

Efficient production of biodiesel from waste grease: one-pot esterification and transesterification with tandem lipases.

PubMed

Yan, Jinyong; Li, Aitao; Xu, Yi; Ngo, Thao P N; Phua, Szechao; Li, Zhi

2012-11-01

A novel concept and efficient method for producing biodiesel (FAME) from grease (15-40wt% free fatty acid, FFA) were developed by using tandem lipases for one-pot esterification of FFA and transesterification of triglyceride with methanol in a solvent-free system. Combining immobilized Candida antarctica lipase B (CALB) (Novozyme 435) favoring the esterification and immobilized Thermomyces lanuginosus lipase (TLL) (Lipozyme TLIM) preferring the transesterification at 2:8 (wt/wt) gave FAME in 80% yield, being better than that with Novozyme 435 or Lipozyme TLIM. Recombinant Escherichia coli (Calb/Tll) co-expressing CALB and TLL was engineered as a more efficient tandem-lipases system. Using wet or dry cells (4wt%) gave FAME in 87% or 95% yield, which is much better than that with E. coli cells expressing either CALB or TLL alone. Cells of E. coli (Calb/Tll) were recycled for five times and retained 75% productivity, thus being practical for producing biodiesel from grease. Copyright © 2012 Elsevier Ltd. All rights reserved.

A whole biodiesel conversion process combining isolation, cultivation and in situ supercritical methanol transesterification of native microalgae.

PubMed

Jazzar, Souhir; Quesada-Medina, Joaquín; Olivares-Carrillo, Pilar; Marzouki, Mohamed Néjib; Acién-Fernández, Francisco Gabriel; Fernández-Sevilla, José María; Molina-Grima, Emilio; Smaali, Issam

2015-08-01

A coupled process combining microalgae production with direct supercritical biodiesel conversion using a reduced number of operating steps is proposed in this work. Two newly isolated native microalgae strains, identified as Chlorella sp. and Nannochloris sp., were cultivated in both batch and continuous modes. Maximum productivities were achieved during continuous cultures with 318mg/lday and 256mg/lday for Chlorella sp. and Nannochloris sp., respectively. Microalgae were further characterized by determining their photosynthetic performance and nutrient removal efficiency. Biodiesel was produced by catalyst-free in situ supercritical methanol transesterification of wet unwashed algal biomass (75wt.% of moisture). Maximum biodiesel yields of 45.62wt.% and 21.79wt.% were reached for Chlorella sp. and Nannochloris sp., respectively. The analysis of polyunsaturated fatty acids of Chlorella sp. showed a decrease in their proportion when comparing conventional and supercritical transesterification processes (from 37.4% to 13.9%, respectively), thus improving the quality of the biodiesel. Copyright © 2015 Elsevier Ltd. All rights reserved.

One-pot process combining transesterification and selective hydrogenation for biodiesel production from starting material of high degree of unsaturation.

PubMed

Yang, Ru; Su, Mengxing; Li, Min; Zhang, Jianchun; Hao, Xinmin; Zhang, Hua

2010-08-01

A one-pot process combining transesterification and selective hydrogenation was established to produce biodiesel from hemp (Cannabis sativa L.) seed oil which is eliminated as a potential feedstock by a specification of iodine value (IV; 120 g I(2)/100g maximum) contained in EN 14214. A series of alkaline earth metal oxides and alkaline earth metal supported copper oxide were prepared and tested as catalysts. SrO supported 10 wt.% CuO showed the superior catalytic activity for transesterification with a biodiesel yield of 96% and hydrogenation with a reduced iodine value of 113 and also exhibited a promising selectivity for eliminating methyl linolenate and increasing methyl oleate without rising methyl stearate in the selective hydrogenation. The fuel properties of the selective hydrogenated methyl esters are within biodiesel specifications. Furthermore, cetane numbers and iodine values were well correlated with the compositions of the hydrogenated methyl esters according to degrees of unsaturation. (c) 2010 Elsevier Ltd. All rights reserved.

Industrial wastes as a promising renewable source for production of microbial lipid and direct transesterification of the lipid into biodiesel.

PubMed

Cheirsilp, Benjamas; Louhasakul, Yasmi

2013-08-01

Two strategies of converting industrial wastes to microbial lipid and direct transesterification of obtained lipid into biodiesel were attempted. Several oleaginous yeasts were cultivated on industrial wastes. The yeasts grew well on the wastes with low C/N ratio (i.e. serum latex) but accumulated high lipid content only when the wastes had a high C/N ratio (i.e. palm oil mill effluent and crude glycerol). The yeast lipids have similar fatty acid composition to that of plant oil indicating their potential use as biodiesel feedstocks. The combination of these wastes and two-phase cultivation for cell growth and lipid accumulation improved lipid productivity of the selected yeast. The direct transesterification process that eliminates cell drying and lipid extraction steps, gave comparable yield of biodiesel (fatty acid methyl ester >70% within 1h) to that of conventional method. These two successful strategies may contribute greatly to industrializing oil production from microbes and industrial wastes. Copyright © 2013 Elsevier Ltd. All rights reserved.

Spatially resolved observation of crystal-face-dependent catalysis by single turnover counting

NASA Astrophysics Data System (ADS)

Roeffaers, Maarten B. J.; Sels, Bert F.; Uji-I, Hiroshi; de Schryver, Frans C.; Jacobs, Pierre A.; de Vos, Dirk E.; Hofkens, Johan

2006-02-01

Catalytic processes on surfaces have long been studied by probing model reactions on single-crystal metal surfaces under high vacuum conditions. Yet the vast majority of industrial heterogeneous catalysis occurs at ambient or elevated pressures using complex materials with crystal faces, edges and defects differing in their catalytic activity. Clearly, if new or improved catalysts are to be rationally designed, we require quantitative correlations between surface features and catalytic activity-ideally obtained under realistic reaction conditions. Transmission electron microscopy and scanning tunnelling microscopy have allowed in situ characterization of catalyst surfaces with atomic resolution, but are limited by the need for low-pressure conditions and conductive surfaces, respectively. Sum frequency generation spectroscopy can identify vibrations of adsorbed reactants and products in both gaseous and condensed phases, but so far lacks sensitivity down to the single molecule level. Here we adapt real-time monitoring of the chemical transformation of individual organic molecules by fluorescence microscopy to monitor reactions catalysed by crystals of a layered double hydroxide immersed in reagent solution. By using a wide field microscope, we are able to map the spatial distribution of catalytic activity over the entire crystal by counting single turnover events. We find that ester hydrolysis proceeds on the lateral {1010} crystal faces, while transesterification occurs on the entire outer crystal surface. Because the method operates at ambient temperature and pressure and in a condensed phase, it can be applied to the growing number of liquid-phase industrial organic transformations to localize catalytic activity on and in inorganic solids. An exciting opportunity is the use of probe molecules with different size and functionality, which should provide insight into shape-selective or structure-sensitive catalysis and thus help with the rational design of new or more productive heterogeneous catalysts.

Diesel Fuel from Used Frying Oil

PubMed Central

Buczek, Bronislaw

2014-01-01

New conversion technologies of used edible oils and waste animal fats into a biofuel appropriate for use in standard diesel engines have been developed, taking into consideration environmental requirements and improvement in the economics of current trans-esterification technologies. The variation in the properties of substrates made from used rape oil after treatment with mixed adsorbents (active carbon, magnesium silicate) was studied in this work. The obtained results are compared with the quality requirements for the substrates used in Vogel & Noot GmbH technology for transesterification of oils and fats. PMID:24574908

Application of a 1,1,3,3-tetramethylguanidine (TMG)/MeOH-CO2 in situ derivatization procedure for the gas chromatographic characterization of the fatty acid profile in olive oil.

PubMed

Saliu, F; Anzano, M; Franzetti, A

2015-03-01

1,1,3,3-Tetramethylguanidine (TMG), methanol and carbon dioxide were investigated as switchable polarity solvents (SPS) in the simultaneous derivatization and extraction of triacylglycerols for the gas chromatographic (GC) characterization of olive oil. Three commercial olive oils were used as test samples. Results of the developed method did not differ statistically from those provided by reference derivatization procedures. The transesterification reaction was carried out under a very mild condition, one step and in situ, and no particular matrix interferences were evidenced. The method represented the first example of the use of a switchable polarity mixture for the preparation of methyl ester derivatives of fatty acids (FAME).

Biodiesel production from waste frying oil using waste animal bone and solar heat.

PubMed

Corro, Grisel; Sánchez, Nallely; Pal, Umapada; Bañuelos, Fortino

2016-01-01

A two-step catalytic process for the production of biodiesel from waste frying oil (WFO) at low cost, utilizing waste animal-bone as catalyst and solar radiation as heat source is reported in this work. In the first step, the free fatty acids (FFA) in WFO were esterified with methanol by a catalytic process using calcined waste animal-bone as catalyst, which remains active even after 10 esterification runs. The trans-esterification step was catalyzed by NaOH through thermal activation process. Produced biodiesel fulfills all the international requirements for its utilization as a fuel. A probable reaction mechanism for the esterification process is proposed considering the presence of hydroxyapatite at the surface of calcined animal bones. Copyright © 2015 Elsevier Ltd. All rights reserved.

Green polymer chemistry: The role of Candida antarctica lipase B in polymer functionalization

NASA Astrophysics Data System (ADS)

Castano Gil, Yenni Marcela

The synthesis of functional polymers with well-defined structure, end-group fidelity and physico-chemical properties useful for biomedical applications has proven challenging. Chemo-enzymatic methods are an alternative strategy to increase the diversity of functional groups in polymeric materials. Specifically, enzyme-catalyzed polymer functionalization carried out under solventless conditions is a great advancement in the design of green processes for biomedical applications, where the toxicity of solvents and catalyst residues need to be considered. Enzymes offer several distinct advantages, including high efficiency, catalyst recyclability, and mild reaction conditions. This reseach aimed to precisely functionalized polymers using two methods: enzyme-catalyzed functionalization via polymerization and chemo-enzymatic functionalization of pre-made polymers for drug delivery. In the first method, well-defined poly(caprolactone)s were generated using alkyne-based initiating systems catalyzed by CALB. Propargyl alcohol and 4-dibenzocyclooctynol (DIBO) were shown to efficiently initiate the ring opening polymerization of epsilon-caprolactone under metal free conditions and yielded polymers with Mn ~4 to 24 KDa and relatively narrow molecular mass distribution. In the second methodology, we present quantitative enzyme-catalyzed transesterification of vinyl esters and ethyl esters with poly(ethylene glycol)s (PEG)s that will serve as building blocks for dendrimer synthesis, followed by introducing a new process for the exclusive gamma-conjugation of folic acid. Specifically, fluorescein-acrylate was enzymatically conjugated with PEG. Additionally, halo-ester functionalized PEGs were successfully prepared by the transesterification of alkyl halo-esters with PEGs. 1H and 13C NMR spectroscopy, SEC and MALDI-ToF mass spectrometry confirmed the structure and purity of the products.

Designed Single-Step Synthesis, Structure, and Derivative Textural Properties of Well-Ordered Layered Penta-Coordinate Silicon Alcoholate Complexes

PubMed Central

Li, Xiansen; Michaelis, Vladimir K.; Ong, Ta-Chung; Smith, Stacey J.; Griffin, Robert G.; Wang, Evelyn N.

2014-01-01

The controllable synthesis of well-ordered layered materials with specific nanoarchitecture poses a grand challenge in materials chemistry. We report the solvothermal synthesis of two structurally analogous 5-coordinate organosilicate complexes via a novel transesterification mechanism. Since the polycrystalline nature of the intrinsic hypervalent Si complex thwarts the endeavor in determining its structure, a novel strategy concerning the elegant addition of a small fraction of B species as an effective crystal growth mediator and a sacrificial agent is proposed to directly prepare diffraction-quality single crystals without disrupting the intrinsic elemental type. In the determined crystal structure, two monomeric primary building units (PBUs) self-assemble into a dimeric asymmetric secondary BU via strong Na+-O2− ionic bonds. The designed one-pot synthesis is straightforward, robust, and efficient, leading to a well-ordered (10ī)-parallel layered Si complex with its principal interlayers intercalated with extensive van der Waals gaps in spite of the presence of substantial Na+ counterions as a result of unique atomic arrangement in its structure. On the other hand, upon fast pyrolysis, followed by acid leaching, both complexes are converted into two SiO2 composites bearing BET surface areas of 163.3 and 254.7 m2 g−1 for the pyrolyzed intrinsic and B-assisted Si complexes, respectively. The transesterification methodology merely involving alcoholysis but without any hydrolysis side reaction is designed to have generalized applicability for use in synthesizing new layered metal-organic compounds with tailored PBUs and corresponding metal oxide particles with hierarchical porosity. PMID:24737615

Bioremediation of cooking oil waste using lipases from wastes

PubMed Central

do Prado, Débora Zanoni; Facanali, Roselaine; Marques, Márcia Mayo Ortiz; Nascimento, Augusto Santana; Fernandes, Célio Junior da Costa; Zambuzzi, William Fernando

2017-01-01

Cooking oil waste leads to well-known environmental impacts and its bioremediation by lipase-based enzymatic activity can minimize the high cytotoxic potential. In addition, they are among the biocatalysts most commercialized worldwide due to the versatility of reactions and substrates. However, although lipases are able to process cooking oil wastes, the products generated from this process do not necessarily become less toxic. Thus, the aim of the current study is to analyze the bioremediation of lipase-catalyzed cooking oil wastes, as well as their effect on the cytotoxicity of both the oil and its waste before and after enzymatic treatment. Thus, assessed the post-frying modification in soybean oil and in its waste, which was caused by hydrolysis reaction catalyzed by commercial and home-made lipases. The presence of lipases in the extracts obtained from orange wastes was identified by zymography. The profile of the fatty acid esters formed after these reactions was detected and quantified through gas chromatography and fatty acids profile compared through multivariate statistical analyses. Finally, the soybean oil and its waste, with and without enzymatic treatment, were assessed for toxicity in cytotoxicity assays conducted in vitro using fibroblast cell culture. The soybean oil wastes treated with core and frit lipases through transesterification reaction were less toxic than the untreated oils, thus confirming that cooking oil wastes can be bioremediated using orange lipases. PMID:29073166

Kinetic Evaluation of Lipid Oils Conversion to Biofuel Using Layered Double Hydroxide Doped with Triazabicyclodece Catalyst

NASA Astrophysics Data System (ADS)

Nato Lopez, Frank D.

Worldwide, there is an ever increasing need for sustainable, renewable fuels that will accommodate the rapidly increasing energy demand and provide independence from fossil fuels. The search for a sustainable alternative to petroleum based fuels has been a great challenge to the scientific community; therefore, great efforts are being made to overcome the fossil fuels dependence by exploring the prominent field of biofuels (bioethanol and biodiesel). Traditional biodiesel is produced from feedstocks such as vegetable oils and animal fats by converting the triglycerides with methanol in the presence of a homogeneous catalyst to produce fatty acid methyl esters (FAMEs). However, drawbacks of this process are the undesired glycerol byproduct and post reaction processing, including separation from reaction mixture, that results in high costs factors. In the present work, the reaction kinetics of a glycerol-free biodiesel method is studied. This method consists of the transesterification of a vegetable oil (i.e. canola oil) using dimethyl carbonate (DMC) as an alternative methylating agent in presence of layered double hydroxides doped with triazabicyclodecene catalyst (a basic organocatalyst). Furthermore, is theorized that this heterogeneous catalyst (TBD/LDH) simultaneously converts both FFAs and triglycerides due to acid sites formed by Al3+ active sites of the LDH structure. Additionally, the versatility of the Raman in situ technique was used as quantitative analysis tool to monitor the reaction kinetics and collect real time data.

"New" Compounds from Old Plastics: Recycling PET Plastics via Depolymerization. An Activity for the Undergraduate Organic Lab

NASA Astrophysics Data System (ADS)

Kaufman, Don; Wright, Geoff; Kroemer, Ryan; Engel, Josh

1999-11-01

This paper describes work done to develop a meaningful undergraduate organic lab activity that illustrates chemistry of the real world while utilizing reactions typically included in the organic lecture and lab. We show how a common plastic can be converted into several compounds using ester hydrolysis and SN2 reactions. Contributing to the critical shortage of landfill space faced by many communities is the large quantity of plastic refuse. Thus, there is a real need to recycle plastic products. One way to recycle plastics such as polyethyleneterephthalate (PET), the polyester from which numerous consumer products such as 2-liter soda bottles are made, is to depolymerize them and then to use the resulting monomers to produce new products. PET is industrially depolymerized via an acid-catalyzed transesterification reaction conducted under conditions of high temperature and pressure that are not feasible in the undergraduate lab. Despite literature reports that PET is remarkably resistant to hydrolysis, we found that PET can be readily hydrolyzed by refluxing with potassium hydroxide or potassium tert-butoxide in amyl alcohol to give terephthalic acid in high yield. It is then possible to readily synthesize terephthalate diesters via SN2 reactions of ammonium terephthalate salts with alkyl halides. Fischer esterification can also be used to prepare the diesters, but yields are significantly lower.

Bioremediation of cooking oil waste using lipases from wastes.

PubMed

Okino-Delgado, Clarissa Hamaio; Prado, Débora Zanoni do; Facanali, Roselaine; Marques, Márcia Mayo Ortiz; Nascimento, Augusto Santana; Fernandes, Célio Junior da Costa; Zambuzzi, William Fernando; Fleuri, Luciana Francisco

2017-01-01

Cooking oil waste leads to well-known environmental impacts and its bioremediation by lipase-based enzymatic activity can minimize the high cytotoxic potential. In addition, they are among the biocatalysts most commercialized worldwide due to the versatility of reactions and substrates. However, although lipases are able to process cooking oil wastes, the products generated from this process do not necessarily become less toxic. Thus, the aim of the current study is to analyze the bioremediation of lipase-catalyzed cooking oil wastes, as well as their effect on the cytotoxicity of both the oil and its waste before and after enzymatic treatment. Thus, assessed the post-frying modification in soybean oil and in its waste, which was caused by hydrolysis reaction catalyzed by commercial and home-made lipases. The presence of lipases in the extracts obtained from orange wastes was identified by zymography. The profile of the fatty acid esters formed after these reactions was detected and quantified through gas chromatography and fatty acids profile compared through multivariate statistical analyses. Finally, the soybean oil and its waste, with and without enzymatic treatment, were assessed for toxicity in cytotoxicity assays conducted in vitro using fibroblast cell culture. The soybean oil wastes treated with core and frit lipases through transesterification reaction were less toxic than the untreated oils, thus confirming that cooking oil wastes can be bioremediated using orange lipases.

Application of a chitosan-immobilized Talaromyces thermophilus lipase to a batch biodiesel production from waste frying oils.

PubMed

Romdhane, Ines Belhaj-Ben; Romdhane, Zamen Ben; Bouzid, Maha; Gargouri, Ali; Belghith, Hafedh

2013-12-01

Waste frying oil, which not only harms people's health but also causes environmental pollution, can be a good alternative to partially substitute petroleum diesel through transesterification reaction. This oil contained 8.8 % of free fatty acids, which cause a problem in a base-catalyzed process. In this study, synthesis of biodiesel was efficiently catalyzed by the covalently immobilized Talaromyces thermophilus lipase and allowed bioconversion yield up to 92 % after 24 h of reaction time. The optimal molar ratio was four to six parts of methanol to one part of oil with a biocatalyst loaded of 25 wt.% of oil. Further, experiments revealed that T. thermophilus lipase, immobilized by a multipoint covalent liaison onto activated chitosan via a short spacer (glutaraldehyde), was sufficiently tolerant to methanol. In fact, using the stepwise addition of methanol, no significant difference was observed from the one-step whole addition at the start of reaction. The batch biodiesel synthesis was performed in a fixed bed reactor with a lipase loaded of 10 g. The bioconversion yield of 98 % was attained after a 5-h reaction time. The bioreactor was operated successfully for almost 150 h without any changes in the initial conversion yield. Most of the chemical and physical properties of the produced biodiesel meet the European and USA standard specifications of biodiesel fuels.

A new generation of zirconia supported metal oxide catalysts for converting low grade renewable feedstocks to biodiesel.

PubMed

Kim, Manhoe; DiMaggio, Craig; Salley, Steven O; Simon Ng, K Y

2012-08-01

A new class of zirconia supported mixed metal oxides (ZnO-TiO(2)-Nd(2)O(3)/ZrO(2) and ZnO-SiO(2)-Yb(2)O(3)/ZrO(2)) has demonstrated the ability to convert low quality, high free fatty acid (FFA) bio-oils into biodiesel. Pelletized catalysts of ZrO(2) supported metal oxides were prepared via a sol-gel process and tested in continuous flow packed bed reactors for up to 6 months. In a single pass, while operating at mild to moderate reaction conditions, 195 °C and 300 psi, these catalysts can perform simultaneous esterification and transesterification reactions on feedstock of 33% FFA and 67% soybean oil to achieve FAME yields higher than 90%. Catalytic activity of the ZrO(2) supported metal oxide catalysts was highly dependent on the metal oxide composition. These heterogeneous catalysts will enable biodiesel manufacturers to avoid problems inherent in homogeneous processes, such as separation and washing, corrosive conditions, and excessive methanol usage. Copyright © 2012 Elsevier Ltd. All rights reserved.

Biodiesel production from microbial granules in sequencing batch reactor.

PubMed

Liu, Lin; Hong, Yuling; Ye, Xin; Wei, Lili; Liao, Jie; Huang, Xu; Liu, Chaoxiang

2018-02-01

Effect of reaction variables of in situ transesterification on the biodiesel production, and the characteristic differences of biodiesel obtained from aerobic granular sludge (AG) and algae-bacteria granular consortia (AAG) were investigated. The results indicated that the effect of variables on the biodiesel yield decreased in the order of methanol quantity > catalyst concentration > reaction time, yet the parameters change will not significantly affect biodiesel properties. The maximum biodiesel yield of AAG was 66.21 ± 1.08 mg/g SS, what is significant higher than that of AG (35.44 ± 0.92 mg/g SS). Although methyl palmitate was the dominated composition of biodiesel obtained from both granules, poly-unsaturated fatty acid in the AAG showed a higher percentage (21.86%) than AG (1.2%) due to Scenedesmus addition. Further, microbial analysis confirmed that the composition of biodiesel obtained from microbial granules was also determined by bacterial community, and Xanthomonadaceae and Rhodobacteraceae were the dominant bacteria of AG and AAG, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

Catalysts of Cu(II) and Co(II) ions adsorbed in chitosan used in transesterification of soy bean and babassu oils - a new route for biodiesel syntheses.

PubMed

da Silva, Rondinelly Brandão; Lima Neto, Alcides Fernandes; Soares Dos Santos, Lucas Samuel; de Oliveira Lima, José Renato; Chaves, Mariana Helena; Dos Santos, José Ribeiro; de Lima, Geraldo Magela; de Moura, Edmilson Miranda; de Moura, Carla Verônica Rodarte

2008-10-01

Catalysts of Cu(II) and Co(II) adsorbed in chitosan was used in transesterification of soy bean and babassu oils. The catalysts were characterized by infrared, atomic absorption and TG, and biodiesels was characterized by infrared, NMR, CG, TG, physic chemistry analysis. The maximum adsorption values found for copper and cobalt cations were 1.584 and 1.260mgg(-1), respectively, in 180min. However, conversion of oils in biodiesel was better when used Co(II) adsorbed in chitosan.

New Biofuel Integrating Glycerol into Its Composition Through the Use of Covalent Immobilized Pig Pancreatic Lipase

PubMed Central

Luna, Diego; Posadillo, Alejandro; Caballero, Verónica; Verdugo, Cristóbal; Bautista, Felipa M.; Romero, Antonio A.; Sancho, Enrique D.; Luna, Carlos; Calero, Juan

2012-01-01

By using 1,3-specific Pig Pancreatic lipase (EC 3.1.1.3 or PPL), covalently immobilized on AlPO4/Sepiolite support as biocatalyst, a new second-generation biodiesel was obtained in the transesterification reaction of sunflower oil with ethanol and other alcohols of low molecular weight. The resulting biofuel is composed of fatty acid ethyl esters and monoglycerides (FAEE/MG) blended in a molar relation 2/1. This novel product, which integrates glycerol as monoacylglycerols (MG) into the biofuel composition, has similar physicochemical properties compared to those of conventional biodiesel and also avoids the removal step of this by-product. The biocatalyst was found to be strongly fixed to the inorganic support (75%). Nevertheless, the efficiency of the immobilized enzyme was reduced to half (49.1%) compared to that of the free PPL. The immobilized enzyme showed a remarkable stability as well as a great reusability (more than 40 successive reuses) without a significant loss of its initial catalytic activity. Immobilized and free enzymes exhibited different reaction mechanisms, according to the different results in the Arrhenius parameters (Ln A and Ea). However, the use of supported PPL was found to be very suitable for the repetitive production of biofuel due to its facile recyclability from the reaction mixture. PMID:22949849

Production and Characterization of Biodiesel from Tung Oil

NASA Astrophysics Data System (ADS)

Park, Ji-Yeon; Kim, Deog-Keun; Wang, Zhong-Ming; Lu, Pengmei; Park, Soon-Chul; Lee, Jin-Suk

The feasibility of biodiesel production from tung oil was investigated. The esterification reaction of the free fatty acids of rung oil was performed using Amberlyst-15. Optimal molar ratio of methanol to oil was determined to be 7.5:1, and Amberlyst-15 was 20.8wt% of oil by response surface methodology. Under these reaction conditions, the acid value of rung oil was reduced to 0.72mg KOH/g. In the range of the molar equivalents of methanol to oil under 5, the esterification was strongly affected by the amount of methanol but not the catalyst. When the molar ratio of methanol to oil was 4.1:1 and Amberlyst-15 was 29.8wt% of the oil, the acid value decreased to 0.85mg KOH/g. After the transesterification reaction of pretreated rung oil, the purity of rung biodiesel was 90.2wt%. The high viscosity of crude rung oil decreased to 9.8mm2/s at 40 °C. Because of the presence of eleostearic acid, which is a main component of tung oil, the oxidation stability as determined by the Rancimat method was very low, 0.5h, but the cold filter plugging point, -11 °C, was good. The distillation process did not improve the fatty acid methyl ester content and the viscosity.

Production and characterization of biodiesel from tung oil.

PubMed

Park, Ji-Yeon; Kim, Deog-Keun; Wang, Zhong-Ming; Lu, Pengmei; Park, Soon-Chul; Lee, Jin-Suk

2008-03-01

The feasibility of biodiesel production from tung oil was investigated. The esterification reaction of the free fatty acids of tung oil was performed using Amberlyst-15. Optimal molar ratio of methanol to oil was determined to be 7.5:1, and Amberlyst-15 was 20.8 wt% of oil by response surface methodology. Under these reaction conditions, the acid value of tung oil was reduced to 0.72 mg KOH/g. In the range of the molar equivalents of methanol to oil under 5, the esterification was strongly affected by the amount of methanol but not the catalyst. When the molar ratio of methanol to oil was 4.1:1 and Amberlyst-15 was 29.8 wt% of the oil, the acid value decreased to 0.85 mg KOH/g. After the transesterification reaction of pretreated tung oil, the purity of tung biodiesel was 90.2 wt%. The high viscosity of crude tung oil decreased to 9.8mm(2)/s at 40 degrees C. Because of the presence of eleostearic acid, which is a main component of tung oil, the oxidation stability as determined by the Rancimat method was very low, 0.5h, but the cold filter plugging point, -11 degrees C, was good. The distillation process did not improve the fatty acid methyl ester content and the viscosity.

Fluorescent fingerprints of edible oils and biodiesel by means total synchronous fluorescence and Tucker3 modeling

NASA Astrophysics Data System (ADS)

Insausti, Matías; de Araújo Gomes, Adriano; Camiña, José Manuel; de Araújo, Mario Cesar Ugulino; Band, Beatriz Susana Fernández

2017-03-01

The present work proposes the use of total synchronous fluorescence spectroscopy (TSFS) as a discrimination methodology for fluorescent compounds in edible oils, which are preserved after the transesterification processes in the biodiesel production. In the same way, a similar study is presented to identify fluorophores that do not change in expired vegetal oils, to associate physicochemical parameters to fluorescent measures, as contribution to a fingerprint for increasing the chemical knowledge of these products. The fluorescent fingerprints were obtained by Tucker3 decomposition of a three-way array of the total synchronous fluorescence matrices. This chemometric method presents the ability for modeling non-bilinear data, as Total Synchronous Fluorescence Spectra data, and consists in the decomposition of the three way data arrays (samples × Δλ × λ excitation), into four new data matrices: A (scores), B (profile in Δλ mode), C (profile in spectra mode) and G (relationships between A, B and C). In this study, 50 samples of oil from soybean, corn and sunflower seeds before and after its expiration time, as well as 50 biodiesel samples obtained by transesterification of the same oils were measured by TSFS. This study represents an immediate application of chemical fingerprint for the discrimination of non-expired and expired edible oils and biodiesel. This method does not require the use of reagents or laborious procedures for the chemical characterization of samples.

Synthesis of Biodiesel from Crude Palm Oil by Using Contact Glow Discharge Electrolysis

NASA Astrophysics Data System (ADS)

Saksono, Nelson; Aditya Siswosoebrotho, Danar; Pranata, Jeremia J. C.; Bismo, Setijo

2018-03-01

This research has evaluated the use of Contact Glow Discharge Electrolysis method in the synthesis of biodiesel. The purpose of this research is to get the synthesis process and biodiesel product. The solution used is the mix of Crude Palm Oil and methanol with molar ratio of 1:24, and catalyst of NaOH and KOH with variation of concentration 0.5% - 1.5%-wt. The result shows that the biodiesel can be made from transesterification reaction that may be initiated by radical methoxide. The use of electrolyte KOH is better than NaOH based on the yield of biodiesel and the energy consumption. The optimum yield reaches 97%, at the synthesis for 30 minutes with the use of KOH 1%-wt with the energy consumption of 1.32 kJ/mL.

High performance catalytic distillation using CNTs-based holistic catalyst for production of high quality biodiesel

PubMed Central

Zhang, Dongdong; Wei, Dali; Li, Qi; Ge, Xin; Guo, Xuefeng; Xie, Zaiku; Ding, Weiping

2014-01-01

For production of biodiesel from bio oils by heterogeneous catalysis, high performance catalysts of transesterification and the further utilization of glycerol have been the two points of research. The process seemed easy, however, has never been well established. Here we report a novel design of catalytic distillation using hierachically integrated CNTs-based holistic catalyst to figure out the two points in one process, which shows high performance both for the conversion of bio oils to biodiesel and, unexpectedly, for the conversion of glycerol to more valuable chemicals at the same time. The method, with integration of nano, meso to macro reactor, has overwhelming advantages over common technologies using liquid acids or bases to catalyze the reactions, which suffer from the high cost of separation and unsolved utilization of glycerol. PMID:24503897

High performance catalytic distillation using CNTs-based holistic catalyst for production of high quality biodiesel

NASA Astrophysics Data System (ADS)

Zhang, Dongdong; Wei, Dali; Li, Qi; Ge, Xin; Guo, Xuefeng; Xie, Zaiku; Ding, Weiping

2014-02-01

For production of biodiesel from bio oils by heterogeneous catalysis, high performance catalysts of transesterification and the further utilization of glycerol have been the two points of research. The process seemed easy, however, has never been well established. Here we report a novel design of catalytic distillation using hierachically integrated CNTs-based holistic catalyst to figure out the two points in one process, which shows high performance both for the conversion of bio oils to biodiesel and, unexpectedly, for the conversion of glycerol to more valuable chemicals at the same time. The method, with integration of nano, meso to macro reactor, has overwhelming advantages over common technologies using liquid acids or bases to catalyze the reactions, which suffer from the high cost of separation and unsolved utilization of glycerol.

Data on kinetic, energy and emission performance of biodiesel from waste frying oil.

PubMed

Silva Filho, Silverio Catureba da; Miranda, Amanda Carvalho; Silva, Thadeu Alfredo Farias; Calarge, Felipe Araújo; Souza, Roberto Rodrigo de; Santana, José Carlos Curvelo; Tambourgi, Elias Basile

2018-06-01

The data presented in this article are related to the research article "Environmental and techno-economic considerations on biodiesel production from waste frying oil in São Paulo city" (Silva Filho et al., 2018) [1]. This article presents the variation of the concentration of waste frying oil (WFO) with the reaction time and temperature during the transesterification of WTOs collected in the residences and restaurants of the city of São Paulo. Then, the biodiesel samples were mixed with the S-10 diesel oil in order to obtain the B10, B20, B30, B40, B50, B75 and B100 blends, which were tested in a diesel engine and their power, fuel consumption and gas emissions (CO, CO 2 and SO 2 ) have been measured to verify their greenhouse effect and energy efficiency.

Lipase Immobilization on Silica Xerogel Treated with Protic Ionic Liquid and its Application in Biodiesel Production from Different Oils.

PubMed

Carvalho, Nayára B; Vidal, Bruna T; Barbosa, Anderson S; Pereira, Matheus M; Mattedi, Silvana; Freitas, Lisiane Dos S; Lima, Álvaro S; Soares, Cleide M F

2018-06-21

Treated silica xerogel with protic ionic liquid (PIL) and bifunctional agents (glutaraldehyde and epichlorohydrin) is a novel support strategy used in the effective immobilization of lipase from Burkholderia cepacia (LBC) by covalent binding. As biocatalysts with the highest activity recovery yields, LBC immobilized by covalent binding with epichlorohydrin without (203%) and with PIL (250%), was assessed by the following the hydrolysis reaction of olive oil and characterized biochemically (Michaelis⁻Menten constant, optimum pH and temperature, and operational stability). Further, the potential transesterification activity for three substrates: sunflower, soybean, and colza oils, was also determined, achieving a conversion of ethyl esters between 70 and 98%. The supports and the immobilized lipase systems were characterized using Fourier transform infrared spectra (FTIR), scanning electron microscopy (SEM), elemental analysis, and thermogravimetric (TG) analysis.

Escherichia coli as a fatty acid and biodiesel factory: current challenges and future directions.

PubMed

Rahman, Ziaur; Rashid, Naim; Nawab, Javed; Ilyas, Muhammad; Sung, Bong Hyun; Kim, Sun Chang

2016-06-01

Biodiesel has received widespread attention as a sustainable, environment-friendly, and alternative source of energy. It can be derived from plant, animal, and microbial organisms in the form of vegetable oil, fats, and lipids, respectively. However, biodiesel production from such sources is not economically feasible due to extensive downstream processes, such as trans-esterification and purification. To obtain cost-effective biodiesel, these bottlenecks need to be overcome. Escherichia coli, a model microorganism, has the potential to produce biodiesel directly from ligno-cellulosic sugars, bypassing trans-esterification. In this process, E. coli is engineered to produce biodiesel using metabolic engineering technology. The entire process of biodiesel production is carried out in a single microbial cell, bypassing the expensive downstream processing steps. This review focuses mainly on production of fatty acid and biodiesel in E. coli using metabolic engineering approaches. In the first part, we describe fatty acid biosynthesis in E. coli. In the second half, we discuss bottlenecks and strategies to enhance the production yield. A complete understanding of current developments in E. coli-based biodiesel production and pathway optimization strategies would reduce production costs for biofuels and plant-derived chemicals.

Production and application of biodiesel from waste cooking oil

NASA Astrophysics Data System (ADS)

Tuly, S. S.; Saha, M.; Mustafi, N. N.; Sarker, M. R. I.

2017-06-01

Biodiesel has been identified as an alternative and promising fuel source to reduce the dependency on conventional fossil fuel in particular diesel. In this work, waste cooking oil (WCO) of restaurants is considered to produce biodiesel. A well-established transesterification reaction by sodium hydroxide (NaOH) catalytic and supercritical methanol (CH3OH) methods are applied to obtain biodiesel. In the catalytic transesterification process, biodiesel and glycerine are simultaneously produced. The impact of temperature, methanol/WCO molar ratio and sodium hydroxide concentration on the biodiesel formation were analysed and presented. It was found that the optimum 95% of biodiesel was obtained when methanol/WCO molar ratio was 1:6 under 873 K temperature with the presence of 0.2% NaOH as a catalyst. The waste cooking oil blend proportions were 10%, 15%, 20% and 25% and named as bio-diesel blends B-10, B-15, B-20, and B-25, respectively. Quality of biodiesel was examined according to ASTM 6751: biodiesel standards and testing methods. Important fuel properties of biodiesel, such as heating value, cetane index, viscosity, and others were also investigated. A four-stroke single cylinder naturally aspirated DI diesel engine was operated using in both pure form and as a diesel blend to evaluate the combustion and emission characteristics of biodiesel. Engine performance is examined by measuring brake specific fuel consumption and fuel conversion efficiency. The emission of carbon monoxide (CO), carbon dioxide (CO2), nitrogen oxides (NOx), and others were measured. It was measured that the amount of CO2 increases and CO decreases both for pure diesel and biodiesel blends with increasing engine load. However, for same load, a higher emission of CO2 from biodiesel blends was recorded than pure diesel.

Low cost heterogenous catalyst from (Achatina Fulica) snail shell and its application for biodiesel conversion via microwave irradiation

NASA Astrophysics Data System (ADS)

Fatimah, Is; Kurniastuti, E. A.; Basthiani, I. A.; Fakhri, A.

2017-11-01

Research on preparation of heterogenous catalyst from Achatina Fulica snail shell and its application biodiesel conversion has been investigation. Research aimed to obtain low cost and reusable catalyst for biodiesel production. The catalyst was prepared by grinding and calcining the snail shell at 900°C for 2 hours. The obtained solid was analysed by using XRD, SEM-EDX. FTIR, and also basicity measurement. Catalyst was used in the cenvertion of rice bran oil transesterification at varied volume of oil methanol ratio of 20-80 under microwave and reflux methode. The transesterification result were analyzed by using GCMS.

Discovery and characterizaton of a novel lipase with transesterification activity from hot spring metagenomic library.

PubMed

Yan, Wei; Li, Furong; Wang, Li; Zhu, Yaxin; Dong, Zhiyang; Bai, Linhan

2017-03-01

A new gene encoding a lipase (designated as Lip-1 ) was identified from a metagenomic bacterial artificial chromosome(BAC) library prepared from a concentrated water sample collected from a hot spring field in Niujie, Eryuan of Yunnan province in China. The open reading frame of this gene encoded 622 amino acid residues. It was cloned, fused with the oleosin gene and over expressed in Escherichia coli to prepare immobilized lipase artificial oil body AOB-sole-lip-1. The monomeric Sole-lip-1 fusion protein presented a molecular mass of 102.4 kDa. Enzyme assays using olive oil and methanol as the substrates in petroleum ether confirmed its transesterification activity. Hexadecanoic acid methyl ester, 8,11-Octadecadienoic acid methyl ester, 8-Octadecenoic acid methyl ester, and Octadecanoic acid methyl ester were detected. It showed favorable transesterification activity with optimal temperature 45 °C. Besides, the maximal biodiesel yield was obtained when the petroleum ether system as the organic solvent and the substrate methanol in 350 mmol/L (at a molar ratio of methanol of 10.5:1) and the water content was 1%. In light of these advantages, this lipase presents a promising resource for biodiesel production.

Kinetic Study on the CsXH3−X PW12O40/Fe-SiO2 Nanocatalyst for Biodiesel Production

PubMed Central

Feyzi, Mostafa; Norouzi, Leila; Rafiee, Hamid Reza

2013-01-01

The kinetic of the transesterification reaction over the CsXH3−XPW12O40/Fe-SiO2 catalyst prepared using sol-gel and impregnation procedures was investigated in different operational conditions. Experimental conditions were varied as follows: reaction temperature 323–333 K, methanol/oil molar ratio = 12/1, and the reaction time 0–240 min. The H3PW12O40 heteropolyacid has recently attracted significant attention due to its potential for application in the production of biodiesel, in either homogeneous or heterogeneous catalytic conditions. Although fatty acids esterification reaction has been known for some time, data is still scarce regarding kinetic and thermodynamic parameters, especially when catalyzed by nonconventional compounds such as H3PW12O40. Herein, a kinetic study utilizing Gc-Mas in situ allows for evaluating the effects of operation conditions on reaction rate and determining the activation energy along with thermodynamic constants including ΔG, ΔS, and ΔH. It indicated that the CsXH3−XPW12O40/Fe-SiO2 magnetic nanocatalyst can be easily recycled with a little loss by magnetic field and can maintain higher catalytic activity and higher recovery even after being used 5 times. Characterization of catalyst was carried out by using scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform-infrared spectroscopy (FT-IR), N2 adsorption-desorption measurements methods, thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). PMID:24391465

Microwave irradiation biodiesel processing of waste cooking oil

NASA Astrophysics Data System (ADS)

Motasemi, Farough; Ani, Farid Nasir

2012-06-01

Major part of the world's total energy output is generated from fossil fuels, consequently its consumption has been continuously increased which accelerates the depletion of fossil fuel reserves and also increases the price of these valuable limited resources. Biodiesel is a renewable, non-toxic and biodegradable diesel fuel which it can be the best environmentally friendly and easily attainable alternative for fossil fuels. The costs of feedstock and production process are two important factors which are particularly against large-scale biodiesel production. This study is intended to optimize three critical reaction parameters including intensity of mixing, microwave exit power and reaction time from the transesterification of waste cooking oil by using microwave irradiation in an attempt to reduce the production cost of biodiesel. To arrest the reaction, similar quantities of methanol/oil molar ratio (6:1) and potassium hydroxide (2% wt) as the catalyst were used. The results showed that the best yield percentage (95%) was obtained using 300W microwave exit power, 300 rpm stirrer speed (intensity of mixing) and 78°C for 5 min. It was observed that increasing the intensity of mixing greatly ameliorates the yield percentage of biodiesel (up to 17%). Moreover, the results demonstrate that increasing the reaction time in the low microwave exit power (100W) improves the yield percentage of biodiesel, while it has a negative effect on the conversion yield in the higher microwave exit power (300W). From the obtained results it was clear that FAME was within the standards of biodiesel fuel.

Role of the His-Cys finger of Moloney murine leukemia virus integrase protein in integration and disintegration.

PubMed Central

Jonsson, C B; Roth, M J

1993-01-01

Retroviral integrases mediate site-specific endonuclease and transesterification reactions in the absence of exogenous energy. The basis for the sequence specificity in these integrase-viral DNA recognition processes is unknown. Structural analogs of the disintegration substrate were made to analyze the disintegration reaction mechanism for the Moloney murine leukemia virus (M-MuLV) integrase (IN). Modifications in the target DNA portion of the disintegration substrate decreased enzymatic activity, while substitution of the highly conserved CA in the viral long terminal repeat portion had no effect on activity. The role of the His-Cys finger region in catalysis was addressed by N-ethylmaleimide (NEM) modification of the cysteine residues of M-MuLV IN as well as by mutations. Both integration activities, 3' processing, and strand transfer, were completely inhibited by NEM modification of M-MuLV IN, while disintegration activity was only partially sensitive. However, structural analogs of the disintegration substrates that were modified in the target DNA and had the conserved CA removed were not active with NEM-treated M-MuLV IN. In addition, mutants made in the His-Cys region of M-MuLV IN were examined and found to also be completely blocked in integration but not disintegration activity. These data suggest that the domains of M-MuLV IN that are required for the forward integration reaction substrate differ from those required for the reverse disintegration reaction substrate. Images PMID:8350412

Hierarchical ZIF-8 toward Immobilizing Burkholderia cepacia Lipase for Application in Biodiesel Preparation.

PubMed

Adnan, Miaad; Li, Kai; Wang, Jianhua; Xu, Li; Yan, Yunjun

2018-05-10

A hierarchical mesoporous zeolitic imidazolate framework (ZIF-8) was processed based on cetyltrimethylammonium bromide (CTAB) as a morphological regulating agent and amino acid (l-histidine) as assisting template agent. Burkholderia cepacia lipase (BCL) was successfully immobilized by ZIF-8 as the carrier via an adsorption method (BCL-ZIF-8). The immobilized lipase (BCL) showed utmost activity recovery up to 1279%, a 12-fold boost in its free counterpart. BCL-ZIF-8 was used as a biocatalyst in the transesterification reaction for the production of biodiesel with 93.4% yield. There was no significant lowering of conversion yield relative to original activity for BCL-ZIF-8 when continuously reused for eight cycles. This work provides a new outlook for biotechnological importance by immobilizing lipase on the hybrid catalyst (ZIF-8) and opens the door for its uses in the industrial field.

Waste cockle shell as natural catalyst for biodiesel production from jatropha oil

NASA Astrophysics Data System (ADS)

Hadi, Norulakmal Nor; Idrus, Nur Afini; Ghafar, Faridah; Salleh, Marmy Roshaidah Mohd

2017-12-01

Due to the increasing of industrialization and modernization of the world, the demand of petroleum has risen rapidly. The increasing demand for energy and environmental awareness has prompted many researches to embark on alternative fuel platforms that are environmentally acceptable. In this study, jatropha oil was used to produce biodiesel by a new transesterification routine in which cockle shell was used as source of heterogeneous catalyst. The investigation showed the catalyst that was calcined at temperature of 800 °C has the optimum capability to produce high yield. The highest yield of biodiesel production of 93.20 % were obtained by using 1.5 wt% of catalyst. The reaction was conducted at a temperature of 65 °C with the optimum methanol to oil ratio of 6:1. It was found that the physical properties of the biodiesel produced were significant to ASTM standard of fatty acid methyl ester (FAME).

Recent advances in the production of value added chemicals and lipids utilizing biodiesel industry generated crude glycerol as a substrate - Metabolic aspects, challenges and possibilities: An overview.

PubMed

Vivek, Narisetty; Sindhu, Raveendran; Madhavan, Aravind; Anju, Alphonsa Jose; Castro, Eulogio; Faraco, Vincenza; Pandey, Ashok; Binod, Parameswaran

2017-09-01

One of the major ecological concerns associated with biodiesel production is the generation of waste/crude glycerol during the trans-esterification process. Purification of this crude glycerol is not economically viable. In this context, the development of an efficient and economically viable strategy would be biotransformation reactions converting the biodiesel derived crude glycerol into value added chemicals. Hence the process ensures the sustainability and waste management in biodiesel industry, paving a path to integrated biorefineries. This review addresses a waste to wealth approach for utilization of crude glycerol in the production of value added chemicals, current trends, challenges, future perspectives, metabolic approaches and the genetic tools developed for the improved synthesis over wild type microorganisms were described. Copyright © 2017 Elsevier Ltd. All rights reserved.

Physical and structural characterisation of starch/polyester blends with tartaric acid.

PubMed

Olivato, J B; Müller, C M O; Carvalho, G M; Yamashita, F; Grossmann, M V E

2014-06-01

Starch/PBAT blends were produced by reactive extrusion with tartaric acid (TA) as an additive. The effects of TA, glycerol and starch+PBAT on the mechanical, optical and structural properties of the films were evaluated, with formulations based in a constrained mixture design. Tartaric acid acts as a compatibiliser and promotes the acid hydrolysis of starch chains. These two functions explain the observed film resistance and opacity. TA reduced the weight loss in water. Scanning electron microscopy (SEM) images showed that TA reduces the interfacial tension between the polymeric phases, resulting in more homogeneous films. Nuclear magnetic resonance ((13)C CPMAS) and Fourier transform infrared spectroscopy (FT-IR) suggest that tartaric acid is able to react with the hydroxyl groups of the starch by esterification/transesterification reactions, confirming its role as a compatibiliser. The addition of TA results in materials with better properties that are suitable for use in food packaging. Published by Elsevier B.V.

Characterization of a tannase from Emericella nidulans immobilized on ionic and covalent supports for propyl gallate synthesis.

PubMed

Gonçalves, Heloísa Bressan; Jorge, João Atílio; Pessela, Benevides Costa; Lorente, Glória Fernandez; Guisán, José Manuel; Guimarães, Luis Henrique Souza

2013-04-01

The extracellular tannase from Emericela nidulans was immobilized on different ionic and covalent supports. The derivatives obtained using DEAE-Sepharose and Q-Sepharose were thermally stable from 60 to 75 °C, with a half life (t50) >24 h at 80 °C at pH 5.0. The glyoxyl-agarose and amino-glyoxyl derivatives showed a thermal stability which was lower than that observed for ionic supports. However, when the stability to pH was considered, the derivatives obtained from covalent supports were more stable than those obtained from ionic supports. DEAE-Sepharose and Q-Sepharose derivatives as well as the free enzyme were stable in 30 and 50 % (v/v) 1-propanol. The CNBr-agarose derivative catalyzed complete tannic acid hydrolysis, whereas the Q-Sepharose derivative catalyzed the transesterification reaction to produce propyl gallate (88 % recovery), which is an important antioxidant.

Productions of sunflower oil biodiesel and used cooking oil through heterogeneous catalysts compared to conventional homogeneous catalysts

NASA Astrophysics Data System (ADS)

Gutiérrez-Zapata, C. A.; Blanco Martínez, D.; Collazos, C. A.; Castellanos Acuña, H. E.; Cuervo, J. A.; Fernandez, C. P.

2017-01-01

This document compares homogeneous and heterogeneous catalysts used by production of biodiesel of sunflower oil and cooking oil used in frying. For this, NaOH was used as a catalyst homogeneous, and K2CO3 and Na2CO3 supported in gamma-alumina (K2CO3/γ Al2O3 y Na2CO3 /γ-Al2O3) were synthesized as heterogeneous catalysts, which were characterized by X-ray diffraction. The transesterification tests were carried out for the sunflower oil and used cooking oil, in a reflux system, to different molar relations methanol/oil, depending on the type of oil and characterization of the same. The reflux system is performed at a temperature of 55-60°C for one hour. Finally, biofuel was characterized and the yield of the reaction was calculated.

Ultrasonic enhancement of lipase-catalysed transesterification for biodiesel synthesis.

PubMed

Bhangu, Sukhvir Kaur; Gupta, Shweta; Ashokkumar, Muthupandian

2017-01-01

The production of biodiesel was carried out from canola oil and methanol catalysed by lipase from Candida rugosa under different ultrasonic experimental conditions using horn (20kHz) and plate (22, 44, 98 and 300kHz) transducers. The effects of experimental conditions such as horn tip diameter, ultrasonic power, ultrasonic frequency and enzyme concentrations on biodiesel yield were investigated. The results showed that the application of ultrasound decreased the reaction time from 22-24h to 1.5h with the use of 3.5cm ultrasonic horn, an applied power of 40W, methanol to oil molar ratio of 5:1 and enzyme concentration of 0.23wt/wt% of oil. Low intensity ultrasound is efficient and a promising tool for the enzyme catalysed biodiesel synthesis as higher intensities tend to inactivate the enzyme and reduce its efficiency. Copyright © 2016 Elsevier B.V. All rights reserved.

Radiation grafted adsorbents for newly emerging environmental applications

NASA Astrophysics Data System (ADS)

Mahmoud Nasef, Mohamed; Ting, T. M.; Abbasi, Ali; Layeghi-moghaddam, Alireza; Sara Alinezhad, S.; Hashim, Kamaruddin

2016-01-01

Radiation induced grafting (RIG) is acquired to prepare a number of adsorbents for newly emerging environmental applications using a single route involving RIG of glycidymethacrylate (GMA) onto polyethylene-polypropylene (PE-PP) non-woven fabric. The grafted fabric was subjected to one of three functionalization reactions to impart desired ionic characters. This included treatment with (1) N-dimethyl-D-glucamine, (2) triethylamine and (3) triethylamine and alkalisation with KOH. Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM) were used to study the changes in chemical and physical structures of the obtained fibrous adsorbents. The potential applications of the three adsorbents for removal of boron from solutions, capturing CO2 from CO2/N2 mixtures and catalysing transesterification of triacetin/methanol to methyl acetate (biodiesel) were explored. The obtained fibrous adsorbents provide potential alternatives to granular resins for the investigated applications and require further development.

From Classical to High Throughput Screening Methods for Feruloyl Esterases: A Review.

PubMed

Ramírez-Velasco, Lorena; Armendáriz-Ruiz, Mariana; Rodríguez-González, Jorge Alberto; Müller-Santos, Marcelo; Asaff-Torres, Ali; Mateos-Díaz, Juan Carlos

2016-01-01

Feruloyl esterases (FAEs) are a diverse group of hydrolases widely distributed in plants and microorganisms which catalyzes the cleavage and formation of ester bonds between plant cell wall polysaccharides and phenolic acids. FAEs have gained importance in biofuel, medicine and food industries due to their capability of acting on a large range of substrates for cleaving ester bonds and synthesizing highadded value molecules through esterification and transesterification reactions. During the past two decades extensive studies have been carried out on the production, characterization and classification of FAEs, however only a few reports of suitable High Throughput Screening assays for this kind of enzymes have been reported. This review is focused on a concise but complete revision of classical to High Throughput Screening methods for FAEs, highlighting its advantages and disadvantages, and finally suggesting future perspectives for this important research field.

Enhancement of biodiesel synthesis from soybean oil by potassium fluoride modification of a calcium magnesium oxides catalyst.

PubMed

Fan, Mingming; Zhang, Pingbo; Ma, Qinke

2012-01-01

Transesterification of soybean oil with methanol was carried out in the presence of CaO-MgO and KF-modified CaO-MgO catalysts at atmospheric pressure. While the methyl ester yield for the CaO-MgO catalyst with a ratio of 8:2 (CaO:MgO) was 63.6%, it was 97.9% for the KF-modified catalyst at a 2% catalyst to the reactants (methanol/oil mixture) weight ratio, a temperature of 65 °C, a methanol-soybean oil ratio of 9:1 and a reaction time of 2.5 h. The KF/CaO-MgO catalyst still yielded 86.7% after four successive uses. The catalytic performance of the KF/CaO-MgO catalyst was attributed to the formation of active KCaF(3) and K(2)MgF(4) centers. Copyright © 2011 Elsevier Ltd. All rights reserved.

The synthesis of amphipathic prodrugs of 1,2-diol drugs with saccharide conjugates by high regioselective enzymatic protocol.

PubMed

Quan, Jing; Chen, Zhichun; Han, Chengyou; Lin, Xianfu

2007-02-15

A facile, high regioselective enzymatic synthesis approach for the preparation of amphipathic prodrugs with saccharides of mephenesin and chlorphenesin was developed. Firstly, transesterification of two drugs with divinyl dicarboxylates with different carbon chain length was performed under the catalysis of Candida antarctica lipase acrylic resin and Lipozyme in anhydrous acetone at 50 degrees C, respectively. A series of lipophilic derivatives with vinyl groups of mephenesin and chlorphenesin were prepared. The influences of different organic solvents, enzyme sources, reaction time, and the acylation reagents on the synthesis of vinyl esters were investigated. And then, protease-catalyzed high regioselective acylation of D-glucose and D-mannose with vinyl esters of mephenesin and chlorphenesin gave drug-saccharide derivatives in good yields. The studies of lipophilicity and hydrolysis in vitro of prodrugs verified that drug-saccharide derivatives had amphipathic properties, and both lipophilic and amphipathic drug derivatives had obvious controlled release characteristics.

Efficient synthetic protocols in glycerol under heterogeneous catalysis.

PubMed

Cravotto, Giancarlo; Orio, Laura; Gaudino, Emanuela Calcio; Martina, Katia; Tavor, Dorith; Wolfson, Adi

2011-08-22

The massive increase in glycerol production from the transesterification of vegetable oils has stimulated a large effort to find novel uses for this compound. Hence, the use of glycerol as a solvent for organic synthesis has drawn particular interest. Drawbacks of this green and renewable solvent are a low solubility of highly hydrophobic molecules and a high viscosity, which often requires the use of a fluidifying co-solvent. These limitations can be easily overcome by performing reactions under high-intensity ultrasound and microwaves in a stand-alone or combined manner. These non-conventional techniques facilitate and widen the use of glycerol as a solvent in organic synthesis. Glycerol allows excellent acoustic cavitation even at high temperatures (70-100 °C), which is otherwise negligible in water. Herein, we describe three different types of applications: 1) the catalytic transfer hydrogenation of benzaldehyde to benzyl alcohol in which glycerol plays the dual role of the solvent and hydrogen donor; 2) the palladium-catalyzed Suzuki cross-coupling; and (3) the Barbier reaction. In all cases glycerol proved to be a greener, less expensive, and safer alternative to the classic volatile organic solvents. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure-property studies of thermoplastic and thermosetting polyurethanes using palm and soya oils-based polyols.

PubMed

Mohammed, Issam Ahmed; Al-Mulla, Emad Abbas Jaffar; Kadar, Nurul Khizien Abdul; Ibrahim, Mazlan

2013-01-01

Palm and soya oils were converted to monoglycerides via transesterification of triglycerides with glycerol by one step process to produce renewable polyols. Thermoplastic polyurethanes (TPPUs) were prepared from the reaction of the monoglycerides which act as polyol with 4,4'-methylenediphenyldiisocyanate (MDI) whereas, thermosetting polyurethanes (TSPUs) were prepared from the reaction of glycerol, MDI and monoglycerides in one pot. Characterization of the polyurethanes was carried out by FT-IR, (1)H NMR, and iodine value and sol-gel fraction. The TSPUs showed good thermal properties compared to TPPUs as well as TSPUs exhibits good properties in pencil hardness and adhesion, however poorer in flexural and impact strength compared to TPPUs. The higher percentage of cross linked fraction, the higher degree of cross linking occurred, which is due to the higher number of double bond presents in the TSPUs. These were reflected in iodine value test as the highest iodine value of the soya-based thermosetting polyurethanes confirmed the highest degree of cross linking. Polyurethanes based on soya oil showed better properties compared to palm oil. This study is a breakthrough development of polyurethane resins using palm and soya oils as one of the raw materials.

Two-Stage Conversion of High Free Fatty Acid Jatropha curcas Oil to Biodiesel Using Brønsted Acidic Ionic Liquid and KOH as Catalysts

PubMed Central

Das, Subrata; Thakur, Ashim Jyoti; Deka, Dhanapati

2014-01-01

Biodiesel was produced from high free fatty acid (FFA) Jatropha curcas oil (JCO) by two-stage process in which esterification was performed by Brønsted acidic ionic liquid 1-(1-butylsulfonic)-3-methylimidazolium chloride ([BSMIM]Cl) followed by KOH catalyzed transesterification. Maximum FFA conversion of 93.9% was achieved and it reduced from 8.15 wt% to 0.49 wt% under the optimum reaction conditions of methanol oil molar ratio 12 : 1 and 10 wt% of ionic liquid catalyst at 70°C in 6 h. The ionic liquid catalyst was reusable up to four times of consecutive runs under the optimum reaction conditions. At the second stage, the esterified JCO was transesterified by using 1.3 wt% KOH and methanol oil molar ratio of 6 : 1 in 20 min at 64°C. The yield of the final biodiesel was found to be 98.6% as analyzed by NMR spectroscopy. Chemical composition of the final biodiesel was also determined by GC-MS analysis. PMID:24987726

Utilization of deep-sea microbial esterase PHE21 to generate chiral sec-butyl acetate through kinetic resolutions.

PubMed

Wang, Yilong; Xu, Yongkai; Zhang, Yun; Sun, Aijun; Hu, Yunfeng

2018-06-08

We previously identified and characterized 1 novel deep-sea microbial esterase PHE21 and used PHE21 as a green biocatalyst to generate chiral ethyl (S)-3-hydroxybutyrate, 1 key chiral chemical, with high enantiomeric excess and yield through kinetic resolution. Herein, we further explored the potential of esterase PHE21 in the enantioselective preparation of secondary butanol, which was hard to be resolved by lipases/esterases. Despite the fact that chiral secondary butanols and their ester derivatives were hard to prepare, esterase PHE21 was used as a green biocatalyst in the generation of (S)-sec-butyl acetate through hydrolytic reactions and the enantiomeric excess, and the conversion of (S)-sec-butyl acetate reached 98% and 52%, respectively, after process optimization. Esterase PHE21 was also used to generate (R)-sec-butyl acetate through asymmetric transesterification reactions, and the enantiomeric excess and conversion of (R)-sec-butyl acetate reached 64% and 43%, respectively, after process optimization. Deep-sea microbial esterase PHE21 was characterized to be a useful biocatalyst in the kinetic resolution of secondary butanol and other valuable chiral secondary alcohols. © 2018 Wiley Periodicals, Inc.

A review on lipase-catalyzed reactions in ultrasound-assisted systems.

PubMed

Lerin, Lindomar A; Loss, Raquel A; Remonatto, Daniela; Zenevicz, Mara Cristina; Balen, Manuela; Netto, Vendelino Oenning; Ninow, Jorge L; Trentin, Cláudia M; Oliveira, J Vladimir; de Oliveira, Débora

2014-12-01

The named "green chemistry" has been receiving increasing prominence due to its environmentally friendly characteristics. The use of enzymes as catalysts in processes of synthesis to replace the traditional use of chemical catalysts present as main advantage the fact of following the principles of the green chemistry. However, processes of enzymatic nature generally provide lower yields when compared to the conventional chemical processes. Therefore, in the last years, the ultrasound has been extensively used in enzymatic processes, such as the production of esters with desirable characteristics for the pharmaceutical, cosmetics, and food industry, for the hydrolysis and glycerolysis of vegetable oils, production of biodiesel, etc. Several works found in the open literature suggest that the energy released by the ultrasound during the cavitation phenomena can be used to enhance mass transfer (substrate/enzyme), hence increasing the rate of products formation, and also contributing to enhance the enzyme catalytic activity. Furthermore, the ultrasound is considered a "green" technology due to its high efficiency, low instrumental requirement and significant reduction of the processing time in comparison to other techniques. The main goal of this review was to summarize studies available to date regarding the application of ultrasound in enzyme-catalyzed esterification, hydrolysis, glycerolysis and transesterification reactions.

Pilot-scale production of biodiesel from waste fats and oils using tetramethylammonium hydroxide.

PubMed

Šánek, Lubomír; Pecha, Jiří; Kolomazník, Karel; Bařinová, Michaela

2016-02-01

Annually, a great amount of waste fats and oils not suitable for human consumption or which cannot be further treated are produced around the world. A potential way of utilizing this low-cost feedstock is its conversion into biodiesel. The majority of biodiesel production processes today are based on the utilization of inorganic alkali catalysts. However, it has been proved that an organic base - tetramethylammonium hydroxide - can be used as a very efficient transesterification catalyst. Furthermore, it can be employed for the esterification of free fatty acids - reducing even high free fatty acid contents to the required level in just one step. The work presented herein, is focused on biodiesel production from waste frying oils and animal fats using tetramethylammonium hydroxide at the pilot-plant level. The results showed that the process performance in the pilot unit - using methanol and TMAH as a catalyst, is comparable to the laboratory procedure, even when the biodiesel is produced from waste vegetable oils or animal fats with high free fatty acid content. The reaction conditions were set at: 1.5% w/w of TMAH, reaction temperature 65°C, the feedstock to methanol molar ratio to 1:6, and the reaction time to 120min. The conversion of triglycerides to FAME was approximately 98%. The cloud point of the biodiesel obtained from waste animal fat was also determined. Copyright © 2015 Elsevier Ltd. All rights reserved.

Synthesis of zinc aluminate with high surface area by microwave hydrothermal method applied in the transesterification of soybean oil (biodiesel)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Quirino, M.R.; Oliveira, M.J.C.; Keyson, D.

Highlights: • ZnAl{sub 2}O{sub 4} spinel was synthesized by the microwave hydrothermal method in only 15 or 30 min. • The powders show high specific surface area. • ZAT{sub b}15 showed activity of 52.22% for the conversion of soybean oil into biodiesel. - Abstract: Zinc aluminate is a material with high thermal stability and high mechanical strength that, owing to these properties, is used as a catalyst or support. In this work, zinc aluminate spinel was synthesized by the microwave hydrothermal method in only 15 or 30 min at a low temperature (150 °C) without templates, using only Al(NO{sub 3}){submore » 3}·9H{sub 2}O, Zn(NO{sub 3}){sub 2}·6H{sub 2}O, and urea as precursors and applied in the transesterification of soybean oil. X-ray diffraction analysis showed that ZnAl{sub 2}O{sub 4} had a cubic structure without secondary phases. The nitrogen adsorption measurements (BET) revealed a high surface area (266.57 m{sup 2} g{sup −1}) for the nanopowder synthesized in 15 min. This powder showed activity of 52.22% for the catalytic conversion of soybean oil into biodiesel by transesterification.« less

Characterization of bioimprinted tannase and its kinetic and thermodynamics properties in synthesis of propyl gallate by transesterification in anhydrous medium.

PubMed

Nie, Guangjun; Zheng, Zhiming; Gong, Guohong; Zhao, Genhai; Liu, Yan; Song, Junying; Dai, Jun

2012-08-01

Tannase has been extensively applied to synthesize gallic acid esters. Bioimprinting technique can evidently enhance transesterification-catalyzing performance of tannase. In order to promote the practical utilization of the modified tannase, a few enzymatic characteristics of the enzyme and its kinetic and thermodynamics properties in synthesis of propyl gallate by transesterification in anhydrous medium have been studied. The investigations of pH and temperature found that the imprinted tannase holds an optimum activity at pH 5.0 and 40 °C. On the other hand, the bioimprinting technique has a profound enhancing effect on the adapted tannase in substrate affinity and thermostability. The kinetic and thermodynamic analyses showed that the modified tannase has a longer half-time of 1,710 h at 40 °C; the kinetic constants, the activation energy of reversible thermal inactivation, and the activation energy of irreversible thermal inactivation, respectively, are 0.054 mM, 17.35 kJ mol(-1), and 85.54 kJ mol(-1) with tannic acid as a substrate at 40 °C; the free energy of Gibbs (ΔG) and enthalpy (ΔH) were found to be 97.1 and 82.9 kJ mol(-1) separately under the same conditions.

Facile fabrication of a stable and recyclable lipase@amine-functionalized ZIF-8 nanoparticles for esters hydrolysis and transesterification

NASA Astrophysics Data System (ADS)

Cheong, Ling-Zhi; Wei, Yayu; Wang, Hongbin; Wang, Zhiying; Su, Xiurong; Shen, Cai

2017-08-01

Zeolitic imidazolate frameworks (ZIF) represent one of the metal organic frameworks (MOF) with high potential for enzyme immobilization due to their exceptional chemical and thermal stability, negligible cytotoxicity, and easy synthesis under mild biocompatible conditions. Amine-functionalized ZIF-8 (An-ZIF-8) are capable of forming multipoint attachment via hydrogen bonding with lipase which will immobilize and further enhance stabilization of lipase. In addition, increased hydrophilicity of An-ZIF-8 will increase partitioning of An-ZIF-8 immobilized lipase at the aqueous/organic interface which enable lipase to expose its active site and retain its catalytic activity at its highest. Present study reports the use of ZIF-8 and An-ZIF-8 nanoparticles as carrier for Burkholderia cepacia lipase (BCL), compares the ester hydrolysis and transesterification activities of immobilized lipase with those of free lipase, and evaluates the reusability and recovery rate of the immobilized lipase. An-ZIF-8 nanoparticles (average 130.42 ± 0.55 nm) were facilely synthesized via mixing ZIF-8 nanoparticles with ammonia hydroxide solution. Despite having similar characteristics of high crystallinity and forming cuboid-like particles, An-ZIF-8 demonstrated significantly ( P < 0.05) lower Brunauer-Emmett-Teller (BET) surface area and higher thermal stability than ZIF-8. BCL were successfully immobilized on ZIF-8 (BCL@ZIF-8) and An-ZIF-8 (BCL@An-ZIF-8) nanoparticles with an average lipase loading rate of 8 mg/g MOF. The immobilized BCL demonstrated no significant differences in terms of esters hydrolysis and transesterification activities with those of free BCL. BCL@An-ZIF-8 demonstrated superior catalytic stability in comparison to BCL@ZIF-8 with retainment of more than 80% of its initial hydrolysis and transesterification activity for at least 10 repeated runs. In addition, more than 80% of the BCL@An-ZIF-8 can be easily recovered during each cycle of the reusability test through simple centrifugation.

A new macrocyclic terbium(III) complex for use in RNA footprinting experiments

PubMed Central

Belousoff, Matthew J.; Ung, Phuc; Forsyth, Craig M.; Tor, Yitzhak; Spiccia, Leone; Graham, Bim

2009-01-01

Reaction of terbium triflate with a heptadentate ligand derivative of cyclen, L1 = 2-[7-ethyl-4,10-bis(isopropylcarbamoylmethyl)-1,4,7,10-tetraazacyclododec-1-yl]-N-isopropylacetamide, produced a new synthetic ribonuclease, [Tb(L1)(OTf)(OH2)](OTf)2·MeCN (C1). X-ray crystal structure analysis indicates that the terbium(III) centre in C1 is 9-coordinate, with a capped square-antiprism geometry. Whilst the terbium(III) center is tightly bound by the L1 ligand, two of the coordination sites are occupied by labile water and triflate ligands. In water, the triflate ligand is likely to be displaced, forming [Tb(L1)(OH2)2]3+, which is able to effectively promote RNA cleavage. This complex greatly accelerates the rate of intramolecular transesterification of an activated model RNA phosphodiester, uridine-3′-p-nitrophenylphosphate (UpNP), with kobs = 5.5(1) × 10-2 s-1 at 21°C and pH 7.5, corresponding to an apparent second-order rate constant of 277(5) M-1s-1. By contrast, the analogous complex of an octadentate derivative of cyclen featuring only a single labile coordination site, [Tb(L2)(OH2)](OTf)3 (C2), where L2 = 2-[4,7,10-tris(isopropylcarbamoylmethyl)-1,4,7,10-tetraazacyclododec-1-yl]-N-isopropyl-acetamide, is inactive. [Tb(L1)(OH2)2]3+ is also capable of hydrolyzing short transcripts of the HIV-1 transactivation response (TAR) element, HIV-1 dimerization initiation site (DIS) and ribosomal A-site, as well as formyl methionine transfer RNA (tRNAfMet), albeit at a considerably slower rate than UpNP transesterification (kobs = 2.78(8) × 10-5 M-1s-1 for TAR cleavage at 37°C, pH 6.5, corresponding to an apparent second-order rate constant of 0.56(2) M-1s-1). Cleavage is concentrated at the single-stranded “bulge” regions of these RNA motifs. Exploiting this selectivity, [Tb(L1)(OH2)23+ was successfully employed in footprinting experiments, in which binding of the Tat peptide and neomycin B to the bulge region of the TAR stem-loop was confirmed. PMID:19119812

Solvent-Free Lipase-Catalyzed Synthesis of Diacylgycerols as Low-Calorie Food Ingredients.

PubMed

Vázquez, Luis; González, Noemí; Reglero, Guillermo; Torres, Carlos

2016-01-01

Problems derived from obesity and overweight have recently promoted the development of fat substitutes and other low-calorie foods. On the one hand, fats with short- and medium-chain fatty acids are a source of quick energy, easily hydrolyzable and hardly stored as fat. Furthermore, 1,3-diacylglycerols are not hydrolyzed to 2-monoacylglycerols in the gastrointestinal tract, reducing the formation of chylomicron and lowers the serum level of triacylglycerols by decreasing its resynthesis in the enterocyte. In this work, these two effects were combined to synthesize short- and medium-chain 1,3-diacylglycerols, leading to a product with great potential as for their low-calorie properties. Lipase-catalyzed transesterification reactions were performed between short- and medium-chain fatty acid ethyl esters and glycerol. Different variables were investigated, such as the type of biocatalyst, the molar ratio FAEE:glycerol, the adsorption of glycerol on silica gel, or the addition of lecithin. Best reaction conditions were evaluated considering the percentage of 1,3-DAG produced and the reaction rate. Except Novozym 435 (Candida antarctica), other lipases required the adsorption of glycerol on silica gel to form acylglycerols. Lipases that gave the best results with adsorption were Novozym 435 and Lipozyme RM IM (Rhizomucor miehei) with 52 and 60.7% DAG at 32 h, respectively. Because of its specificity for sn-1 and sn-3 positions, lipases leading to a higher proportion of 1,3-DAG vs. 1,2-DAG were Lipozyme RM IM (39.8 and 20.9%, respectively) and Lipase PLG (Alcaligenes sp.) (35.9 and 19.3%, respectively). By adding 1% (w/w) of lecithin to the reaction with Novozym 435 and raw glycerol, the reaction rate was considerably increased from 41.7 to 52.8% DAG at 24 h.

Solvent-Free Lipase-Catalyzed Synthesis of Diacylgycerols as Low-Calorie Food Ingredients

PubMed Central

Vázquez, Luis; González, Noemí; Reglero, Guillermo; Torres, Carlos

2016-01-01

Problems derived from obesity and overweight have recently promoted the development of fat substitutes and other low-calorie foods. On the one hand, fats with short- and medium-chain fatty acids are a source of quick energy, easily hydrolyzable and hardly stored as fat. Furthermore, 1,3-diacylglycerols are not hydrolyzed to 2-monoacylglycerols in the gastrointestinal tract, reducing the formation of chylomicron and lowers the serum level of triacylglycerols by decreasing its resynthesis in the enterocyte. In this work, these two effects were combined to synthesize short- and medium-chain 1,3-diacylglycerols, leading to a product with great potential as for their low-calorie properties. Lipase-catalyzed transesterification reactions were performed between short- and medium-chain fatty acid ethyl esters and glycerol. Different variables were investigated, such as the type of biocatalyst, the molar ratio FAEE:glycerol, the adsorption of glycerol on silica gel, or the addition of lecithin. Best reaction conditions were evaluated considering the percentage of 1,3-DAG produced and the reaction rate. Except Novozym 435 (Candida antarctica), other lipases required the adsorption of glycerol on silica gel to form acylglycerols. Lipases that gave the best results with adsorption were Novozym 435 and Lipozyme RM IM (Rhizomucor miehei) with 52 and 60.7% DAG at 32 h, respectively. Because of its specificity for sn-1 and sn-3 positions, lipases leading to a higher proportion of 1,3-DAG vs. 1,2-DAG were Lipozyme RM IM (39.8 and 20.9%, respectively) and Lipase PLG (Alcaligenes sp.) (35.9 and 19.3%, respectively). By adding 1% (w/w) of lecithin to the reaction with Novozym 435 and raw glycerol, the reaction rate was considerably increased from 41.7 to 52.8% DAG at 24 h. PMID:26904539

Scale-up of industrial biodiesel production to 40 m(3) using a liquid lipase formulation.

PubMed

Price, Jason; Nordblad, Mathias; Martel, Hannah H; Chrabas, Brent; Wang, Huali; Nielsen, Per Munk; Woodley, John M

2016-08-01

In this work, we demonstrate the scale-up from an 80 L fed-batch scale to 40 m(3) along with the design of a 4 m(3) continuous process for enzymatic biodiesel production catalyzed by NS-40116 (a liquid formulation of a modified Thermomyces lanuginosus lipase). Based on the analysis of actual pilot plant data for the transesterification of used cooking oil and brown grease, we propose a method applying first order integral analysis to fed-batch data based on either the bound glycerol or free fatty acid content in the oil. This method greatly simplifies the modeling process and gives an indication of the effect of mixing at the various scales (80 L to 40 m(3) ) along with the prediction of the residence time needed to reach a desired conversion in a CSTR. Suitable process metrics reflecting commercial performance such as the reaction time, enzyme efficiency, and reactor productivity were evaluated for both the fed-batch and CSTR cases. Given similar operating conditions, the CSTR operation on average, has a reaction time which is 1.3 times greater than the fed-batch operation. We also showed how the process metrics can be used to quickly estimate the selling price of the enzyme. Assuming a biodiesel selling price of 0.6 USD/kg and a one-time use of the enzyme (0.1% (w/woil ) enzyme dosage); the enzyme can then be sold for 30 USD/kg which ensures that that the enzyme cost is not more than 5% of the biodiesel revenue. Biotechnol. Bioeng. 2016;113: 1719-1728. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Neural and hybrid modeling: an alternative route to efficiently predict the behavior of biotechnological processes aimed at biofuels obtainment.

PubMed

Curcio, Stefano; Saraceno, Alessandra; Calabrò, Vincenza; Iorio, Gabriele

2014-01-01

The present paper was aimed at showing that advanced modeling techniques, based either on artificial neural networks or on hybrid systems, might efficiently predict the behavior of two biotechnological processes designed for the obtainment of second-generation biofuels from waste biomasses. In particular, the enzymatic transesterification of waste-oil glycerides, the key step for the obtainment of biodiesel, and the anaerobic digestion of agroindustry wastes to produce biogas were modeled. It was proved that the proposed modeling approaches provided very accurate predictions of systems behavior. Both neural network and hybrid modeling definitely represented a valid alternative to traditional theoretical models, especially when comprehensive knowledge of the metabolic pathways, of the true kinetic mechanisms, and of the transport phenomena involved in biotechnological processes was difficult to be achieved.

Neural and Hybrid Modeling: An Alternative Route to Efficiently Predict the Behavior of Biotechnological Processes Aimed at Biofuels Obtainment

PubMed Central

Saraceno, Alessandra; Calabrò, Vincenza; Iorio, Gabriele

2014-01-01

The present paper was aimed at showing that advanced modeling techniques, based either on artificial neural networks or on hybrid systems, might efficiently predict the behavior of two biotechnological processes designed for the obtainment of second-generation biofuels from waste biomasses. In particular, the enzymatic transesterification of waste-oil glycerides, the key step for the obtainment of biodiesel, and the anaerobic digestion of agroindustry wastes to produce biogas were modeled. It was proved that the proposed modeling approaches provided very accurate predictions of systems behavior. Both neural network and hybrid modeling definitely represented a valid alternative to traditional theoretical models, especially when comprehensive knowledge of the metabolic pathways, of the true kinetic mechanisms, and of the transport phenomena involved in biotechnological processes was difficult to be achieved. PMID:24516363

The development of the super-biodiesel production continuously from Sunan pecan oil through the process of reactive distillation

NASA Astrophysics Data System (ADS)

Yohana, Eflita; Yulianto, Moh. Endy; Ikhsan, Diyono; Nanta, Aditya Marga; Puspitasari, Ristiyanti

2016-06-01

In general, a vegetable oil-based biodiesel production commercially operates a batch process with high investments and operational costs. Thus, it is necessary to develop super-biodiesel production from sunan pecan oil continuously through the process of reactive distillation. There are four advantages of the reactive distillation process for the biodiesel production, as follows: (i) it incorporates the process of transesterification reaction, and product separation of residual reactants become one stage of the process, so it saves the investment and operation costs, (ii) it reduces the need for raw materials because the methanol needed corresponds to the stoichiometry, so it also reduces the operation costs, (iii) the holdup time in the column is relatively short (5±0,5 minutes) compared to the batch process (1-2 hours), so it will reduce the operational production costs, and (iv) it is able to shift the reaction equilibrium, because the products and reactants that do not react are instantly separated (based on Le Chatelier's principles) so the conversion will be increased. However, the very crucial problem is determining the design tools and process conditions in order to maximize the conversion of the transesterification reaction in both phases. Thus, the purpose of this research was to design a continuous reactive distillation process by using a recycled condensate to increase the productivity of the super-biodiesel from sunan pecan oil. The research was carried out in three stages including (i) designing and fabricating the reactive distillation equipment, (ii) testing the tool performance and the optimization of the biodiesel production, and (iii) biodiesel testing on the diesel engine. These three stages were needed in designing and scaling-up the process tools and the process operation commercially. The reactive distillation process tools were designed and manufactured with reference to the design system tower by Kitzer, et.al. (2008). The manufactured reactive distillation consisted of packing distillation columns equipped with a reboiler and condenser, with the prototype made of stainless steel material equipped with sigh glass. The filling column expands the contact of liquid-vapor phase so that the two reactants between methanol and oil would be converted into methyl ester and glycerol. The initial results of the study indicated that the relatively good condition is reached at the peak temperature and the base of the column of 62°C and 71°C with NaOH 2% of methanol weight as the catalyst at the feed ratio of methanol and the sunan pecan oil 4:1. The result of the performance test of the diesel engine indicated that the efficiency of the biodiesel fuel was achieved relatively good at 1.7% with 2500 rpm engine speed.

Presidential Green Chemistry Challenge: 2003 Academic Award

EPA Pesticide Factsheets

Presidential Green Chemistry Challenge 2003 award winner, Professor Richard A. Gross, developed a transesterification to make polyol-containing polyesters using lipase, replacing heavy metal catalysts and hazardous solvents.

Potential use of chicken egg shells and cacao pod husk as catalyst for biodiesel production

NASA Astrophysics Data System (ADS)

Andherson, T.; Rachmat, D.; Risanti, Doty D.

2018-04-01

Chicken eggshells and cacao pod husk are known as waste materials that can be used to produce catalyst of CaO and K2CO3, respectively. Waste cooking oil (WCO) is an alternative raw material to produce economical and cheaper biodiesel. WCO first undergoes a pre-treatment process that aims to remove free fatty acid (FFA). Biodiesel was produced by transesterification between triglyceride and alcohol with the presence of a catalyst. To obtain the catalyst, eggshell was calcined in a furnace at temperatures of 600 °C, 700 °C, 800 °C, and 900 °C for 6 hours. On the other hand, K2CO3 catalyst synthesis was carried out by carbonization cacao pod husk at temperature of 650°C and subsequently extracted using aquadest solvent. Catalysts were then characterized by XRD and FTIR. The biodiesel synthesis in this research was conducted at 65°C with molar ratio of 1: 6 WCO to methanol, reaction time for 1 and 2 hours, for K2CO3 and CaO, respectively. The optimum condition for the reaction using CaO was obtained for CaO that carbonized at 900°C. It produced 81.43% conversion of biodiesel. On the other hand, reaction using K2CO3 could reach a higher conversion of 85%. From the results it was clear that the biodiesel fuel production was within the recommended SNI 7182: 2015 standard.

Synthesis of High-Quality Biodiesel Using Feedstock and Catalyst Derived from Fish Wastes.

PubMed

Madhu, Devarapaga; Arora, Rajan; Sahani, Shalini; Singh, Veena; Sharma, Yogesh Chandra

2017-03-15

A low-cost and high-purity calcium oxide (CaO) was prepared from waste crab shells, which were extracted from the dead crabs, was used as an efficient solid base catalyst in the synthesis of biodiesel. Raw fish oil was extracted from waste parts of fish through mechanical expeller followed by solvent extraction. Physical as well as chemical properties of raw fish oil were studied, and its free fatty acid composition was analyzed with GC-MS. Stable and high-purity CaO was obtained when the material was calcined at 800 °C for 4 h. Prepared catalyst was characterized by XRD, FT-IR, and TGA/DTA. The surface structure of the catalyst was analyzed with SEM, and elemental composition was determined by EDX spectra. Esterification followed by transesterification reactions were conducted for the synthesis of biodiesel. The effect of cosolvent on biodiesel yield was studied in each experiment using different solvents such as toluene, diethyl ether, hexane, tetrahydrofuran, and acetone. High-quality and pure biodiesel was synthesized and characterized by 1 H NMR and FT-IR. Biodiesel yield was affected by parameters such as reaction temperature, reaction time, molar ratio (methanol:oil), and catalyst loading. Properties of synthesized biodiesel such as density, kinematic viscosity, and cloud point were determined according to ASTM standards. Reusability of prepared CaO catalyst was checked, and the catalyst was found to be stable up to five runs without significant loss of catalytic activity.

Molecular dynamics simulation of bovine pancreatic ribonuclease A-CpA and transition state-like complexes.

PubMed

Formoso, Elena; Matxain, Jon M; Lopez, Xabier; York, Darrin M

2010-06-03

The mechanisms of enzymes are intimately connected with their overall structure and dynamics in solution. Experimentally, it is considerably challenging to provide detailed atomic level information about the conformational events that occur at different stages along the chemical reaction path. Here, theoretical tools may offer new potential insights that complement those obtained from experiments that may not yield an unambiguous mechanistic interpretation. In this study, we apply molecular dynamics simulations of bovine pancreatic ribonuclease A, an archetype ribonuclease, to study the conformational dynamics, structural relaxation, and differential solvation that occur at discrete stages of the transesterification and cleavage reaction. Simulations were performed with explicit solvation with rigorous electrostatics and utilize recently developed molecular mechanical force field parameters for transphosphorylation and hydrolysis transition state analogues. Herein, we present results for the enzyme complexed with the dinucleotide substrate cytidilyl-3',5'-adenosine (CpA) in the reactant, and transphosphorylation and hydrolysis transition states. A detailed analysis of active site structures and hydrogen-bond patterns is presented and compared. The integrity of the overall backbone structure is preserved in the simulations and supports a mechanism whereby His12 stabilizes accumulating negative charge at the transition states through hydrogen-bond donation to the nonbridge oxygens. Lys41 is shown to be highly versatile along the reaction coordinate and can aid in the stabilization of the dianionic transition state, while being poised to act as a general acid catalyst in the hydrolysis step.

Molecular Dynamics Simulation of Bovine Pancreatic Ribonuclease A - CpA and Transition State-like Complexes

PubMed Central

Formoso, Elena; Matxain, Jon M.; Lopez, Xabier; York, Darrin M.

2010-01-01

The mechanisms of enzymes are intimately connected with their overall structure and dynamics in solution. Experimentally it is considerably challenging to provide detailed atomic level information about the conformational events that occur at different stages along the chemical reaction path. Here, theoretical tools may offer new potential insights that complement those obtained from experiments that may not yield an unambiguous mechanistic interpretation. In this study we apply molecular dynamics simulations of bovine pancreatic ribonuclease A, an archetype ribonuclease, in order to study the conformational dynamics, structural relaxation, and differential solvation that occurs at discreet stages of the transesterification and cleavage reaction. Simulations were performed with explicit solvation with rigorous electrostatics, and utilize recently developed molecular mechanical force field parameters for transphosphorylation and hydrolysis transition state analogs. Herein, we present results for the enzyme complexed with the dinucleotide substrate cytidilyl-3′,5′-adenosine (CpA) in the reactant, and transphosphorylation and hydrolysis transition states. A detailed analysis of active site structures and hydrogen bond patterns are presented and compared. The integrity of the overall backbone structure is preserved in the simulations, and support a mechanism whereby His12 stabilizes accumulating negative charge at the transition states through hydrogen bond donation to the non-bridge oxygens. Lys41 is shown to be highly versatile along the reaction coordinate, and can aid in the stabilization of the dianionic transition state, while being poised to act as a general acid catalyst in the hydrolysis step. PMID:20455590

Enzymatic monoesterification of symmetric diols: restriction of molecular conformations influences selectivity.

PubMed

Tomer, Sanjiv O; Soni, Hemant P

2017-10-31

We have experimentally demonstrated that by 'locking' the molecular conformation through the introduction of a double or triple bond in the center of a symmetric diol, enzymatic monoesterification can be achieved selectively. The enzyme Candida antarctica lipase B, generally used for the transesterification of diols, can be effectively used for the monoesterification of symmetrical diols in an unbuffered system also. By varying the chain length of a carboxylic acid moiety, we have established that optimum selectivity and efficiency can be achieved in the range of 4.8 to 5.0 pK a values. Selectivity can be improved up to 98.75% for a monoester in an overall 73% yield (mixture of a monoester and a diester) when but-2-yne-1,4-diol reacted with hexanoic acid. Water, a by-product, provides an interfacial environment for the enzyme to work in the organic reaction medium. The uniqueness of the reported monoesterification protocol is that it involves only the mechanical stirring of the reaction mixture at room temperature in the presence of the enzyme for 24 h. High percentage yield with selectivity for a monoester, easier product isolation and overall, environmental sustainability are added advantages. The synthesized monoesters are characterized by using HNMR and high resolution mass spectrometry (HRMS).

Production and optimization of biodiesel using mixed immobilized biocatalysts in packed bed reactor.

PubMed

Bakkiyaraj, S; Syed, Mahin Basha; Devanesan, M G; Thangavelu, Viruthagiri

2016-05-01

Vegetable oils are used as raw materials for biodiesel production using transesterification reaction. Several methods for the production of biodiesel were developed using chemical (alkali and acidic compounds) and biological catalysts (lipases). Biodiesel production catalyzed by lipases is energy and cost-saving processes and is carried out at normal temperature and pressure. The need for an efficient method for screening larger number of variables has led to the adoption of statistical experimental design. In the present study, packed bed reactor was designed to study with mixed immobilized biocatalysts to have higher productivity under optimum conditions. Contrary to the single-step acyl migration mechanism, a two-step stepwise reaction mechanism involving immobilized Candida rugosa lipase and immobilized Rhizopus oryzae cells was employed for the present work. This method was chosen because enzymatic hydrolysis followed by esterification can tolerate high free fatty acid containing oils. The effects of flow rate and bed height on biodiesel yield were studied using two factors five-level central composite design (CCD) and response surface methodology (RSM). Maximum biodiesel yield of 85 and 81 % was obtained for jatropha oil and karanja oil with the optimum bed height and optimum flow rate of 32.6 cm and 1.35 L/h, and 32.6 cm and 1.36 L/h, respectively.

Highly Productive and Enantioselective Enzyme Catalysis under Continuous Supported Liquid-Liquid Conditions Using a Hybrid Monolithic Bioreactor.

PubMed

Sandig, Bernhard; Buchmeiser, Michael R

2016-10-20

Enzyme-containing ionic liquids (ILs) were immobilized in cellulose-2.5-acetate microbeads particles embedded in a porous monolithic polyurethane matrix. This bioreactor was used under continuous liquid-liquid conditions by dissolving the substrates in a nonpolar organic phase immiscible with the ILs, thereby creating a biphasic system. Lipases (candida antarctica lipase B, CALB, candida rugosa lipase, CRL) were used to catalyze the enantioselective transesterification of racemic (R,S)-1-phenylethanol with vinyl butyrate and vinyl acetate, the esterification of (+/-)-2-isopropyl-5-methylcyclohexanol with propionic anhydride and the amidation of (R,S)-1-phenylethylamine with ethyl methoxyacetate. With this unique setup, very high productivities, that is, turnover numbers (TONs) up to 5.1×10 6 and space-time yields (STYs) up to 28 g product L -1  h -1 , exceeding the corresponding values for batch-type reactions by a factor of 3100 and 40, respectively, were achieved while maintaining or even enhancing enantioselectivity compared to batch reactions via kinetic resolution. To our best knowledge, this is the first continuously operated bioreactor using supported liquid-liquid conditions that shows these features in the synthesis of chiral esters and amides. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The surface chemistry of nanocrystalline MgO catalysts for FAME production: An in situ XPS study of H2O, CH3OH and CH3OAc adsorption

NASA Astrophysics Data System (ADS)

Montero, J. M.; Isaacs, M. A.; Lee, A. F.; Lynam, J. M.; Wilson, K.

2016-04-01

An in situ XPS study of water, methanol and methyl acetate adsorption over as-synthesised and calcined MgO nanocatalysts is reported with a view to gaining insight into the surface adsorption of key components relevant to fatty acid methyl esters (biodiesel) production during the transesterification of triglycerides with methanol. High temperature calcined NanoMgO-700 adsorbed all three species more readily than the parent material due to the higher density of electron-rich (111) and (110) facets exposed over the larger crystallites. Water and methanol chemisorb over the NanoMgO-700 through the conversion of surface O2 - sites to OH- and coincident creation of Mg-OH or Mg-OCH3 moieties respectively. A model is proposed in which the dissociative chemisorption of methanol occurs preferentially over defect and edge sites of NanoMgO-700, with higher methanol coverages resulting in physisorption over weakly basic (100) facets. Methyl acetate undergoes more complex surface chemistry over NanoMgO-700, with C-H dissociation and ester cleavage forming surface hydroxyl and acetate species even at extremely low coverages, indicative of preferential adsorption at defects. Comparison of C 1s spectra with spent catalysts from tributyrin transesterification suggest that ester hydrolysis plays a key factor in the deactivation of MgO catalysts for biodiesel production.

Catalysis and Sonocatalysis for the Synthesis of Biofuels

NASA Astrophysics Data System (ADS)

Deshmane, Vishwanath Ganpat

The goal of this study was to investigate the synthesis of biofuels from edible and non-edible sources using commercially available and laboratory synthesized heterogeneous catalysts with and without the aid of ultrasound. The transesterification of soybean oil using calcium methoxide as solid base catalyst and the process parameters affecting the yield of biodiesel such as the catalyst concentration, methanol/oil molar ratio and the reaction temperature were investigated in detail. The kinetics of this process with and without ultrasound was also evaluated using a previously reported kinetic and mass transfer model for heterogeneous systems. Nanocrystalline mesoporous ZrO 2 with high surface area and thermal stability was synthesized using ethylene diamine as precipitating agent. Sulfonation of obtained Zr(OH) 2 at different digestion times was carried out using sulfuric acid and chlorosulfonic acid as the sulfonating agents and the effects of process parameters including digestion time, pH, precursor concentration and calcination temperature on structural, textural and catalytic properties were studied. Parametric and optimization (Taguchi statistical methodology) studies were carried out to evaluate the effects of cellulase, cellobiase, cellulose concentration and ultrasonic power on the intensification of cellulose hydrolysis to glucose. The catalysts and cellulose were characterized by using BET, NH3-TPD, XRD, SEM, TGA-DSC, EDX and FTIR. The results of these studies suggest that synthesis of biofuels can be improved by heterogeneous catalysts and ultrasound with potential reduction in production costs compared with conventional methods.

Function and application of a non-ester-hydrolyzing carboxylesterase discovered in tulip.

PubMed

Nomura, Taiji

2017-01-01

Plants have evolved secondary metabolite biosynthetic pathways of immense rich diversity. The genes encoding enzymes for secondary metabolite biosynthesis have evolved through gene duplication followed by neofunctionalization, thereby generating functional diversity. Emerging evidence demonstrates that some of those enzymes catalyze reactions entirely different from those usually catalyzed by other members of the same family; e.g. transacylation catalyzed by an enzyme similar to a hydrolytic enzyme. Tuliposide-converting enzyme (TCE), which we recently discovered from tulip, catalyzes the conversion of major defensive secondary metabolites, tuliposides, to antimicrobial tulipalins. The TCEs belong to the carboxylesterase family in the α/β-hydrolase fold superfamily, and specifically catalyze intramolecular transesterification, but not hydrolysis. This non-ester-hydrolyzing carboxylesterase is an example of an enzyme showing catalytic properties that are unpredictable from its primary structure. This review describes the biochemical and physiological aspects of tulipalin biogenesis, and the diverse functions of plant carboxylesterases in the α/β-hydrolase fold superfamily.

Synthesis and emulsifying properties of carbohydrate fatty acid esters produced from Agave tequilana fructans by enzymatic acylation.

PubMed

Casas-Godoy, Leticia; Arrizon, Javier; Arrieta-Baez, Daniel; Plou, Francisco J; Sandoval, Georgina

2016-08-01

Carbohydrate fatty acid esters are non-ionic surfactants with a broad spectrum of applications. These molecules are generally synthesized using short carbohydrates or linear fructans; however in this research carbohydrate fatty acid esters were produced for the first time with branched fructans from Agave tequilana. Using immobilized lipases we successfully acylated A. tequilana fructans with vinyl laurate, obtaining products with different degrees of polymerization (DP). Lipozyme 435 was the most efficient lipase to catalyze the transesterification reaction. HPLC and ESI-MS analysis proved the presence of a mixture of acylated products as a result of the chemical complexity of fructans in the A. tequilana. The ESI-MS spectra showed a molecular mass shift between 183 and 366g/mol for fructooligosaccharides with a DP lower than 6, which indicated the presence of Agave fructans that had been mono- and diacylated with lauric acid. The carbohydrate fatty acid esters (CFAE) obtained showed good emulsifying properties in W/O emulsions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Production of biodiesel from Coelastrella sp. microalgae

NASA Astrophysics Data System (ADS)

Mansur, Dieni; Fitriady, Muhammad Arifuddin; Susilaningsih, Dwi; Simanungkalit, Sabar Pangihutan

2017-11-01

Microalgae have a wide area of usage and one of them it can be used for biodiesel production. In biodiesel production, lipids containing triglyceride or free fatty acid are converted into methyl ester through trans/esterification reactions. Lipids from microalgae can be extracted by acetone and dimethyl carbonate using homogenizer. Esterification of the lipids was investigated using various catalysts and source of methyl group. Activity of homogeneous catalyst such as HCl and H2SO4 and heterogeneous catalysts such as montmorillonit K-10 and ledgestone was investigated. Moreover, methanol and dimethyl carbonate as source of methyl group were also studied. Among of catalysts with methanol as source of methyl group, it was found that yield of crude biodiesel derived from Choelestrella Sp. microalgae was high over H2SO4 catalyst. On the other hand, over H2SO4 catalyst using dimethyl carbonate as source of methyl group, yield of crude biodiesel significant increase. However, FAME composition of crude biodiesel was high over HCl catalyst.

Synthesis of fatty acid methyl ester from crude jatropha (Jatropha curcas Linnaeus) oil using aluminium oxide modified Mg-Zn heterogeneous catalyst.

PubMed

Olutoye, M A; Hameed, B H

2011-06-01

The synthesis of fatty acid methyl esters (FAME) as a substitute to petroleum diesel was investigated in this study from crude jatropha oil (CJO), a non-edible, low-cost alternative feedstock, using aluminium modified heterogeneous basic oxide (Mg-Zn) catalyst. The transesterification reaction with methanol to methyl esters yielded 94% in 6h with methanol-oil ratio of 11:1, catalyst loading of 8.68 wt.% at 182°C and the properties of CJO fuel produced were determine and found to be comparable to the standards according to ASTM. In the range of experimental parameters investigated, it showed that the catalyst is selective to production of methyl esters from oil with high free fatty acid (FFA) and water content of 7.23% and 3.28%, respectively in a single stage process. Thus, jatropha oil is a promising feedstock for methyl ester production and large scale cultivation will help to reduce the product cost. Copyright © 2011 Elsevier Ltd. All rights reserved.

Synthesis of fatty acid methyl ester from used vegetable cooking oil by solid reusable Mg 1-x Zn 1+x O2 catalyst.

PubMed

Olutoye, M A; Hameed, B H

2011-02-01

Fatty acid methyl ester was produced from used vegetable cooking oil using Mg(1-)(x) Zn(1+)(x)O(2) solid catalyst and the performance monitored in terms of ester content obtained. Used vegetable cooking oil was employed to reduce operation cost of biodiesel. The significant operating parameters which affect the overall yield of the process were studied. The highest ester content, 80%, was achieved with the catalyst during 4h 15 min reaction at 188°C with methanol to oil ratio of 9:1 and catalyst loading of 2.55 wt% oil. Also, transesterification of virgin oil gave higher yield with the heterogeneous catalyst and showed high selectivity towards ester production. The used vegetable cooking oil did not require any rigorous pretreatment. Catalyst stability was examined and there was no leaching of the active components, and its performance was as good at the fourth as at the first cycle. Copyright © 2010 Elsevier Ltd. All rights reserved.

Conversion of crude Jatropha curcas seed oil into biodiesel using liquid recombinant Candida rugosa lipase isozymes.

PubMed

Kuo, Ting-Chun; Shaw, Jei-Fu; Lee, Guan-Chiun

2015-09-01

The versatile Candida rugosa lipase (CRL) has been widely used in biotechnological applications. However, there have not been feasibility reports on the transesterification of non-edible oils to produce biodiesel using the commercial CRL preparations, mixtures of isozymes. In the present study, four liquid recombinant CRL isozymes (CRL1-CRL4) were investigated to convert various non-edible oils into biodiesel. The results showed that recombinant CRL2 and CRL4 exhibited superior catalytic efficiencies for producing fatty acid methyl ester (FAME) from Jatropha curcas seed oil. A maximum 95.3% FAME yield was achieved using CRL2 under the optimal conditions (50 wt% water, an initial 1 equivalent of methanol feeding, and an additional 0.5 equivalents of methanol feeding at 24h for a total reaction time of 48 h at 37 °C). We concluded that specific recombinant CRL isozymes could be excellent biocatalysts for the biodiesel production from low-cost crude Jatropha oil. Copyright © 2015 Elsevier Ltd. All rights reserved.

Covalently Cross-linked Elastomers with Self-Healing and Malleable Abilities Enabled by Boronic Ester Bonds.

PubMed

Chen, Yi; Tang, Zhenghai; Zhang, Xuhui; Liu, Yingjun; Wu, Siwu; Guo, Baochun

2018-06-26

Covalently cross-linked rubbers are renowned for their high elasticity that play an indispensable role in various applications including tires, seals, medical implants. Development of self-healing and malleable rubbers is highly desirable as it allows for damage repair and reprocessibility to extend the lifetime and alleviate environmental pollution. Herein, we propose a facile approach to prepare permanently cross-linked yet self-healing and recyclable diene-rubber by programming dynamic boronic ester linkages into the network. The network is synthesized through one-pot thermally initiated thiol-ene "click" reaction between a novel dithiol-containing boronic ester cross-linker and commonly used styrene-butadiene rubber (SBR) without modifying the macromolecular structure. The resulted samples are covalently cross-linked and possess relatively high mechanical strength which can be readily tailored by varying boronic ester content. Owning to the transesterification of boronic ester bonds, the samples can alter network topologies, endowing the materials with self-healing ability and malleability.

Utilization of Biodiesel By-Products for Biogas Production

PubMed Central

Kolesárová, Nina; Hutňan, Miroslav; Bodík, Igor; Špalková, Viera

2011-01-01

This contribution reviews the possibility of using the by-products from biodiesel production as substrates for anaerobic digestion and production of biogas. The process of biodiesel production is predominantly carried out by catalyzed transesterification. Besides desired methylesters, this reaction provides also few other products, including crude glycerol, oil-pressed cakes, and washing water. Crude glycerol or g-phase is heavier separate liquid phase, composed mainly by glycerol. A couple of studies have demonstrated the possibility of biogas production, using g-phase as a single substrate, and it has also shown a great potential as a cosubstrate by anaerobic treatment of different types of organic waste or energy crops. Oil cakes or oil meals are solid residues obtained after oil extraction from the seeds. Another possible by-product is the washing water from raw biodiesel purification, which is an oily and soapy liquid. All of these materials have been suggested as feasible substrates for anaerobic degradation, although some issues and inhibitory factors have to be considered. PMID:21403868

Whole-cell based solvent-free system for one-pot production of biodiesel from waste grease.

PubMed

Li, Aitao; Ngo, Thao P N; Yan, Jinyong; Tian, Kaiyuan; Li, Zhi

2012-06-01

A whole-cell based solvent-free system was developed for efficient conversion of waste grease to biodiesel via one-pot esterification and transesterification. By isolation and screening of lipase-producing strains from soil, Serratia marcescens YXJ-1002 was discovered for the biotransformation of grease to biodiesel. The lipase (SML) from this strain was cloned and expressed in Escherichia coli as an intracellular enzyme, showing 6 times higher whole-cell based hydrolysis activity than that of wild type strain. The recombinant cells were used for biodiesel production from waste grease in one-pot reactions containing no solvent with the addition of methanol in several small portions, and 97% yield of biodiesel (FAME) was achieved under optimized conditions. In addition, the whole-cell biocatalysts showed excellent reusability, retaining 74% productivity after 4 cycles. The developed system, biocatalyst, and process enable the efficient, low-cost, and green production of biodiesel from waste grease, providing with a potential industrial application. Copyright © 2012 Elsevier Ltd. All rights reserved.

Poly(ortho esters)--from concept to reality.

PubMed

Heller, Jorge; Barr, John

2004-01-01

The development of poly(ortho esters) dates back to the early 1970s, and during that time, four distinct families were developed. These polymers can be prepared by a transesterification reaction or by the addition of polyols to diketene acetals, and it is the latter method that has proven to be preferred one. The latest polymer, now under intense development, incorporates a latent acid segment in the polymer backbone that takes advantage of the acid-labile nature of the ortho ester linkages and allows control over erosion rates. By use of diols having selected chain flexibility, polymers that range from hard, brittle materials to materials that have a gel-like consistency at room temperature can be obtained. Drug release from solid materials will be illustrated with 5-fluorouacil and bovine serum albumin, and drug release from gel-like materials will be illustrated with mepivacaine, now in Phase II clinical trials as a delivery system to treat post-operative pain. A brief summary of preclinical toxicology studies is also presented.

Hierarchical Na-doped cubic ZrO2 synthesis by a simple hydrothermal route and its application in biodiesel production

NASA Astrophysics Data System (ADS)

Lara-García, Hugo A.; Romero-Ibarra, Issis C.; Pfeiffer, Heriberto

2014-10-01

Hierarchical growth of cubic ZrO2 phase was successfully synthesized via a simple hydrothermal process in the presence of different surfactants (cationic, non-ionic and anionic) and sodium hydroxide. The structural and microstructural characterizations of different ZrO2 powders were performed using various techniques, such as X-ray diffraction, transmission electron microscopy, N2 adsorption-desorption, scanning electron microscopy and infrared. Results indicated that sodium addition stabilized the cubic ZrO2 phase by a Na-doping process, independently of the surfactant used. In contrast, microstructural characteristics varied as a function of the surfactant and sodium presence. In addition, water vapor (H2O) and carbon dioxide (CO2) sorption properties were evaluated on ZrO2 samples. Results evidenced that sample surface reactivity changed as a function of the sodium content. Finally, this surface reactivity was evaluated on the biodiesel transesterification reaction using the different synthesized samples, obtaining yields of 93%.

Superparamagnetic poly(methyl methacrylate) beads for nattokinase purification from fermentation broth.

PubMed

Yang, Chengli; Xing, Jianmin; Guan, Yueping; Liu, Huizhou

2006-09-01

An effective method for purification of nattokinase from fermentation broth using magnetic poly(methyl methacrylate) (PMMA) beads immobilized with p-aminobenzamidine was proposed in this study. Firstly, magnetic PMMA beads with a narrow size distribution were prepared by spraying suspension polymerization. Then, they were highly functionalized via transesterification reaction with polyethylene glycol. The surface hydroxyl-modified magnetic beads obtained were further modified with chloroethylamine to transfer the surface amino-modified magnetic functional beads. The morphology and surface functionality of the magnetic beads were examined by scanning electron microscopy and Fourier transform infrared. An affinity ligand, p-aminobenzamidine was covalently immobilized to the amino-modified magnetic beads by the glutaraldehyde method for nattokinase purification directly from the fermentation broth. The purification factor and the recovery of the enzyme activity were found to be 8.7 and 85%, respectively. The purification of nattokinase from fermentation broth by magnetic beads only took 40 min, which shows a very fast purification of nattokinase compared to traditional purification methods.

In Situ Biodiesel Production from Fast-Growing and High Oil Content Chlorella pyrenoidosa in Rice Straw Hydrolysate

PubMed Central

Li, Penglin; Miao, Xiaoling; Li, Rongxiu; Zhong, Jianjiang

2011-01-01

Rice straw hydrolysate was used as lignocellulose-based carbon source for Chlorella pyrenoidosa cultivation and the feasibility of in situ biodiesel production was investigated. 13.7 g/L sugar was obtained by enzymatic hydrolyzation of rice straw. Chlorella pyrenoidosa showed a rapid growth in the rice straw hydrolysate medium, the maximum biomass concentration of 2.83 g/L was obtained in only 48 hours. The lipid content of the cells reached as high as 56.3%. In situ transesterification was performed for biodiesel production. The optimized condition was 1 g algal powder, 6 mL n-hexane, and 4 mL methanol with 0.5 M sulfuric acid at the temperature of 90°C in 2-hour reaction time, under which over 99% methyl ester content and about 95% biodiesel yield were obtained. The results suggested that the method has great potential in the production of biofuels with lignocellulose as an alternative carbon source for microalgae cultivation. PMID:21318171

De novo Biosynthesis of Biodiesel by Escherichia coli in Optimized Fed-Batch Cultivation

PubMed Central

Cai, Ke; Tan, Xiaoming; Lu, Xuefeng

2011-01-01

Biodiesel is a renewable alternative to petroleum diesel fuel that can contribute to carbon dioxide emission reduction and energy supply. Biodiesel is composed of fatty acid alkyl esters, including fatty acid methyl esters (FAMEs) and fatty acid ethyl esters (FAEEs), and is currently produced through the transesterification reaction of methanol (or ethanol) and triacylglycerols (TAGs). TAGs are mainly obtained from oilseed plants and microalgae. A sustainable supply of TAGs is a major bottleneck for current biodiesel production. Here we report the de novo biosynthesis of FAEEs from glucose, which can be derived from lignocellulosic biomass, in genetically engineered Escherichia coli by introduction of the ethanol-producing pathway from Zymomonas mobilis, genetic manipulation to increase the pool of fatty acyl-CoA, and heterologous expression of acyl-coenzyme A: diacylglycerol acyltransferase from Acinetobacter baylyi. An optimized fed-batch microbial fermentation of the modified E. coli strain yielded a titer of 922 mg L−1 FAEEs that consisted primarily of ethyl palmitate, -oleate, -myristate and -palmitoleate. PMID:21629774

Production of Biodiesel from Lipid of Phytoplankton Chaetoceros calcitrans through Ultrasonic Method

PubMed Central

Kwangdinata, Raymond; Raya, Indah; Zakir, Muhammad

2014-01-01

A research on production of biodiesel from lipid of phytoplankton Chaetoceros calcitrans through ultrasonic method has been done. In this research, we carried out a series of phytoplankton cultures to determine the optimum time of growth and biodiesel synthesis process from phytoplankton lipids. Process of biodiesel synthesis consists of two steps, that is, isolation of phytoplankton lipids and biodiesel synthesis from those lipids. Oil isolation process was carried out by ultrasonic extraction method using ethanol 96%, while biodiesel synthesis was carried out by transesterification reaction using methanol and KOH catalyst under sonication. Weight of biodiesel yield per biomass Chaetoceros calcitrans is 35.35%. Characterization of biodiesel was well carried out in terms of physical properties which are density and viscosity and chemical properties which are FFA content, saponification value, and iodine value. These values meet the American Society for Testing and Materials (ASTM D6751) standard levels, except for the viscosity value which was 1.14 g·cm−3. PMID:24688372

Magnetic Cross-Linked Enzyme Aggregates (mCLEAs) of Candida antarctica lipase: an efficient and stable biocatalyst for biodiesel synthesis.

PubMed

Cruz-Izquierdo, Álvaro; Picó, Enrique A; López, Carmen; Serra, Juan L; Llama, María J

2014-01-01

Enzyme-catalyzed production of biodiesel is the object of extensive research due to the global shortage of fossil fuels and increased environmental concerns. Herein we report the preparation and main characteristics of a novel biocatalyst consisting of Cross-Linked Enzyme Aggregates (CLEAs) of Candida antarctica lipase B (CALB) which are covalently bound to magnetic nanoparticles, and tackle its use for the synthesis of biodiesel from non-edible vegetable and waste frying oils. For this purpose, insolubilized CALB was covalently cross-linked to magnetic nanoparticles of magnetite which the surface was functionalized with -NH2 groups. The resulting biocatalyst combines the relevant catalytic properties of CLEAs (as great stability and feasibility for their reutilization) and the magnetic character, and thus the final product (mCLEAs) are superparamagnetic particles of a robust catalyst which is more stable than the free enzyme, easily recoverable from the reaction medium and reusable for new catalytic cycles. We have studied the main properties of this biocatalyst and we have assessed its utility to catalyze transesterification reactions to obtain biodiesel from non-edible vegetable oils including unrefined soybean, jatropha and cameline, as well as waste frying oil. Using 1% mCLEAs (w/w of oil) conversions near 80% were routinely obtained at 30°C after 24 h of reaction, this value rising to 92% after 72 h. Moreover, the magnetic biocatalyst can be easily recovered from the reaction mixture and reused for at least ten consecutive cycles of 24 h without apparent loss of activity. The obtained results suggest that mCLEAs prepared from CALB can become a powerful biocatalyst for application at industrial scale with better performance than those currently available.

Magnetic Cross-Linked Enzyme Aggregates (mCLEAs) of Candida antarctica Lipase: An Efficient and Stable Biocatalyst for Biodiesel Synthesis

PubMed Central

Cruz-Izquierdo, Álvaro; Picó, Enrique A.; López, Carmen; Serra, Juan L.; Llama, María J.

2014-01-01

Enzyme-catalyzed production of biodiesel is the object of extensive research due to the global shortage of fossil fuels and increased environmental concerns. Herein we report the preparation and main characteristics of a novel biocatalyst consisting of Cross-Linked Enzyme Aggregates (CLEAs) of Candida antarctica lipase B (CALB) which are covalently bound to magnetic nanoparticles, and tackle its use for the synthesis of biodiesel from non-edible vegetable and waste frying oils. For this purpose, insolubilized CALB was covalently cross-linked to magnetic nanoparticles of magnetite which the surface was functionalized with –NH2 groups. The resulting biocatalyst combines the relevant catalytic properties of CLEAs (as great stability and feasibility for their reutilization) and the magnetic character, and thus the final product (mCLEAs) are superparamagnetic particles of a robust catalyst which is more stable than the free enzyme, easily recoverable from the reaction medium and reusable for new catalytic cycles. We have studied the main properties of this biocatalyst and we have assessed its utility to catalyze transesterification reactions to obtain biodiesel from non-edible vegetable oils including unrefined soybean, jatropha and cameline, as well as waste frying oil. Using 1% mCLEAs (w/w of oil) conversions near 80% were routinely obtained at 30°C after 24 h of reaction, this value rising to 92% after 72 h. Moreover, the magnetic biocatalyst can be easily recovered from the reaction mixture and reused for at least ten consecutive cycles of 24 h without apparent loss of activity. The obtained results suggest that mCLEAs prepared from CALB can become a powerful biocatalyst for application at industrial scale with better performance than those currently available. PMID:25551445

Comparative analysis for the production of fatty acid alkyl esterase using whole cell biocatalyst and purified enzyme from Rhizopus oryzae on waste cooking oil (sunflower oil).

PubMed

Balasubramaniam, Bharathiraja; Sudalaiyadum Perumal, Ayyappasamy; Jayaraman, Jayamuthunagai; Mani, Jayakumar; Ramanujam, Praveenkumar

2012-08-01

The petroleum fuel is nearing the line of extinction. Recent research and technology have provided promising outcomes to rely on biodiesel as the alternative and conventional source of fuel. The use of renewable source - vegetable oil constitutes the main stream of research. In this preliminary study, Waste Cooking Oil (WCO) was used as the substrate for biodiesel production. Lipase enzyme producing fungi Rhizopus oryzae 262 and commercially available pure lipase enzyme were used for comparative study in the production of Fatty Acid Alkyl Esters (FAAE). The whole cell (RO 262) and pure lipase enzyme (PE) were immobilized using calcium alginate beads. Calcium alginate was prepared by optimizing with different molar ratios of calcium chloride and different per cent sodium alginate. Entrapment immobilization was done for whole cell biocatalyst (WCB). PE was also immobilized by entrapment for the transesterification reaction. Seven different solvents - methanol, ethanol, n-propanol, n-butanol, iso-propanol, iso-butanol and iso-amyl alcohol were used as the acyl acceptors. The reaction parameters like temperature (30°C), molar ratio (1:3 - oil:solvent), reaction time (24 h), and amount of enzyme (10% mass ratio to oil) were also optimized for methanol alone. The same parameters were adopted for the other acyl acceptors too. Among the different acyl acceptors - methanol, whose reaction parameters were optimized showed maximum conversion of triglycerides to FAAE-94% with PE and 84% with WCB. On the whole, PE showed better catalytic converting ability with all the acyl acceptor compared to WCB. Gas chromatography analysis (GC) was done to determine the fatty acid composition of WCO (sunflower oil) and FAAE production with different acyl acceptors. Copyright © 2012 Elsevier Ltd. All rights reserved.

Accelerating research into bio-based FDCA-polyesters by using small scale parallel film reactors.

PubMed

Gruter, Gert-Jan M; Sipos, Laszlo; Adrianus Dam, Matheus

2012-02-01

High Throughput experimentation has been well established as a tool in early stage catalyst development and catalyst and process scale-up today. One of the more challenging areas of catalytic research is polymer catalysis. The main difference with most non-polymer catalytic conversions is the fact that the product is not a well defined molecule and the catalytic performance cannot be easily expressed only in terms of catalyst activity and selectivity. In polymerization reactions, polymer chains are formed that can have various lengths (resulting in a molecular weight distribution rather than a defined molecular weight), that can have different compositions (when random or block co-polymers are produced), that can have cross-linking (often significantly affecting physical properties), that can have different endgroups (often affecting subsequent processing steps) and several other variations. In addition, for polyolefins, mass and heat transfer, oxygen and moisture sensitivity, stereoregularity and many other intrinsic features make relevant high throughput screening in this field an incredible challenge. For polycondensation reactions performed in the melt often the viscosity becomes already high at modest molecular weights, which greatly influences mass transfer of the condensation product (often water or methanol). When reactions become mass transfer limited, catalyst performance comparison is often no longer relevant. This however does not mean that relevant experiments for these application areas cannot be performed on small scale. Relevant catalyst screening experiments for polycondensation reactions can be performed in very efficient small scale parallel equipment. Both transesterification and polycondensation as well as post condensation through solid-stating in parallel equipment have been developed. Next to polymer synthesis, polymer characterization also needs to be accelerated without making concessions to quality in order to draw relevant conclusions.

Optimization of technological conditions for one-pot synthesis of (S)-alpha-cyano-3-phenoxybenzyl acetate in organic media.

PubMed

Zhang, Ting-Zhou; Yang, Li-Rong; Zhu, Zi-Qiang

2005-03-01

Optically active form of alpha-cyano-3-phenoxybenzyl (CPB) alcohol, building block of pyrethroid insecticides, was synthesized as its acetate by the combination of anion-exchange resin (D301)-catalyzed transcyanation between m-phenoxybenzaldehyde (m-PBA) and acetone cyanohydrin (AC), and lipase (from Alcaligenes sp.)-catalyzed enantioselective transesterification of the resulting cyanohydrin with vinyl acetate. Through optimizing technological conditions, the catalyzing efficiency was improved considerably compared to methods previously reported. Concentrations of CPB acetate were determined by gas chromatograph. The enantio excess (e.e.) values of CPB acetate were measured by NMR (nuclear magnetic resonance) method. Effects of solvents and temperatures on this reaction were studied. Cyclohexane was shown to be the best solvent among the three tested solvents. 55 degrees C was the optimal temperature for higher degree of conversion. External diffusion limitation was excluded by raising the rotational speed to 220 r/min. However, internal diffusion could not be ignored, since the catalyst (lipase) was an immobilized enzyme and its particle dimension was not made small enough. The reaction rate was substantially accelerated when the reactant (m-PBA) concentration was as high as 249 mmol/L, but decreased when the initial concentration of m-PBA reached to 277 mmol/L. It was also found that the catalyzing capability of recovered lipase was high enough to use several batches. Study of the mole ratio of AC to m-PBA showed that 2:1 was the best choice. The strategy of adding base catalyst D301 was found to be an important factor in improving the degree of conversion of the reaction from 20% to 80%. The highest degree of conversion of the reaction has reached up to 80%.

Synthesis and evaluation of odour-active methionyl esters of fatty acids via esterification and transesterification of butter oil.

PubMed

Li, Cheng; Sun, Jingcan; Fu, Caili; Yu, Bin; Liu, Shao Quan; Li, Tianhu; Huang, Dejian

2014-02-15

Methionol-derived fatty acid esters were synthesised by both chemical and lipase catalysed esterification between fatty acids and methionol. Beneficial effects of both methods were compared qualitatively and quantitatively by GC-MS/GC-FID results. And the high acid and heat stability of our designed methionyl esters meet the requirement of the food industry. Most importantly, the sensory test showed that fatty acid carbon-chain length had an important effect on the flavour attributes of methionyl esters. Moreover, through Lipozyme TL IM-mediated transesterification, valuable methionol-derived esters were synthesised from the readily available natural material butter oil as the fatty acid source. The conversion of methionol and yield of each methionyl ester were also elucidated by GC-MS-FID. Copyright © 2013 Elsevier Ltd. All rights reserved.

The interplay of descriptor-based computational analysis with pharmacophore modeling builds the basis for a novel classification scheme for feruloyl esterases.

PubMed

Udatha, D B R K Gupta; Kouskoumvekaki, Irene; Olsson, Lisbeth; Panagiotou, Gianni

2011-01-01

One of the most intriguing groups of enzymes, the feruloyl esterases (FAEs), is ubiquitous in both simple and complex organisms. FAEs have gained importance in biofuel, medicine and food industries due to their capability of acting on a large range of substrates for cleaving ester bonds and synthesizing high-added value molecules through esterification and transesterification reactions. During the past two decades extensive studies have been carried out on the production and partial characterization of FAEs from fungi, while much less is known about FAEs of bacterial or plant origin. Initial classification studies on FAEs were restricted on sequence similarity and substrate specificity on just four model substrates and considered only a handful of FAEs belonging to the fungal kingdom. This study centers on the descriptor-based classification and structural analysis of experimentally verified and putative FAEs; nevertheless, the framework presented here is applicable to every poorly characterized enzyme family. 365 FAE-related sequences of fungal, bacterial and plantae origin were collected and they were clustered using Self Organizing Maps followed by k-means clustering into distinct groups based on amino acid composition and physico-chemical composition descriptors derived from the respective amino acid sequence. A Support Vector Machine model was subsequently constructed for the classification of new FAEs into the pre-assigned clusters. The model successfully recognized 98.2% of the training sequences and all the sequences of the blind test. The underlying functionality of the 12 proposed FAE families was validated against a combination of prediction tools and published experimental data. Another important aspect of the present work involves the development of pharmacophore models for the new FAE families, for which sufficient information on known substrates existed. Knowing the pharmacophoric features of a small molecule that are essential for binding to the members of a certain family opens a window of opportunities for tailored applications of FAEs. Copyright © 2010 Elsevier Inc. All rights reserved.

Production of Renewable Diesel Fuel

DOT National Transportation Integrated Search

2012-06-01

Vegetable oils have been investigated as a way to provide a renewable source for diesel fuel. A successful approach to using : vegetable oils in diesel engines has been transesterification of the oils with simple alcohols to produce mono-alkyl esters...

Performance of structured lipids incorporating selected phenolic and ascorbic acids.

PubMed

Gruczynska, Eliza; Przybylski, Roman; Aladedunye, Felix

2015-04-15

Conditions applied during frying require antioxidant which is stable at these conditions and provides protection for frying oil and fried food. Novel structured lipids containing nutraceuticals and antioxidants were formed by enzymatic transesterification, exploring canola oil and naturally occurring antioxidants such as ascorbic and selected phenolic acids as substrates. Lipozyme RM IM lipase from Rhizomucor miehei was used as biocatalyst. Frying performance and oxidative stability of the final transesterification products were evaluated. The novel lipids showed significantly improved frying performance compared to canola oil. Oxidative stability assessment of the structured lipids showed significant improvement in resistance to oxidative deterioration compared to original canola oil. Interestingly, the presence of ascorbic acid in an acylglycerol structure protected α-tocopherol against thermal degradation, which was not observed for the phenolic acids. Developed structured lipids containing nutraceuticals and antioxidants may directly affect nutritional properties of lipids also offering nutraceutical ingredients for food formulation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Evaluation of hydrolysis-esterification biodiesel production from wet microalgae.

PubMed

Song, Chunfeng; Liu, Qingling; Ji, Na; Deng, Shuai; Zhao, Jun; Li, Shuhong; Kitamura, Yutaka

2016-08-01

Wet microalgae hydrolysis-esterification route has the advantage to avoid the energy-intensive units (e.g. drying and lipid extraction) in the biodiesel production process. In this study, techno-economic evaluation of hydrolysis-esterification biodiesel production process was carried out and compared with conventional (usually including drying, lipid extraction, esterification and transesterification) biodiesel production process. Energy and material balance of the conventional and hydrolysis-esterification processes was evaluated by Aspen Plus. The simulation results indicated that drying (2.36MJ/L biodiesel) and triolein transesterification (1.89MJ/L biodiesel) are the dominant energy-intensive stages in the conventional route (5.42MJ/L biodiesel). By contrast, the total energy consumption of hydrolysis-esterification route can be reduced to 1.81MJ/L biodiesel, and approximately 3.61MJ can be saved to produce per liter biodiesel. Copyright © 2016 Elsevier Ltd. All rights reserved.

Cellulose acetate fibers prepared from different raw materials with rapid synthesis method.

PubMed

Chen, Jinghuan; Xu, Jikun; Wang, Kun; Cao, Xuefei; Sun, Runcang

2016-02-10

Transesterification is a mild process to prepare cellulose acetate (CA) as compared with the traditional method. In this study, CA fibers were produced from six cellulose raw materials based on a simple and rapid transesterification method. The properties of the CA solutions and the obtained CA fibers were investigated in detail. Results showed that all of the cellulose raw materials were esterified within 15 min, and spinning dopes could be obtained by concentrating the CA solutions via vacuum distillation. The XRD, FT-IR, (1)H, (13)C and HSQC NMR analysis confirmed the successful synthesis of CA. The degree of substitution (DS) of the obtained CA was significantly affected by the degree of polymerization (DP) of cellulose raw materials, which further influenced the viscosity of CA solutions as well as the structural, thermal and mechanical properties of the CA fibers. Copyright © 2015 Elsevier Ltd. All rights reserved.

Biodiesel production from microbial oil derived from wood isolate Trichoderma reesei.

PubMed

Bharathiraja, B; Sowmya, V; Sridharan, Sridevi; Yuvaraj, D; Jayamuthunagai, J; Praveenkumar, R

2017-09-01

In the present study Trichoderma reesei, a wood isolate can yield high biomass quantities up to 30g/L, yielding 32.4% of lipids of dry cell weight (DCW). Biodiesel production from Trichoderma reesei involved simple unit operations like filtration and ultrasonication, yet giving good lipid yield with desirable bio-diesel properties. Optimization of ultrasonication conditions was done to ensure maximum lipid extraction. SEM analysis of ultrasonicated samples showed distinct breakage of fungal hyphae. The lipids were found to contain 49.7% saturated fatty acids. Transesterification using chemical and biological catalysts were compared and 96.09% efficiency was observed for lipase-catalyzed transesterification. The bio-diesel properties satisfied ASTM and EN specifications with cetane number: 53.1, iodine value: 63.34g, saponification value: 235.07mg KOH/g, cold flow plugging point: 9.13°C. Copyright © 2017 Elsevier Ltd. All rights reserved.

Bio-diesel production directly from the microalgae biomass of Nannochloropsis by microwave and ultrasound radiation.

PubMed

Koberg, Miri; Cohen, Moshe; Ben-Amotz, Ami; Gedanken, Aharon

2011-03-01

This work offers an optimized method for the direct conversion of harvested Nannochloropsis algae into bio-diesel using two novel techniques. The first is a unique bio-technology-based environmental system utilizing flue gas from coal burning power stations for microalgae cultivation. This method reduces considerably the cost of algae production. The second technique is the direct transesterification (a one-stage method) of the Nannochloropsis biomass to bio-diesel production using microwave and ultrasound radiation with the aid of a SrO catalyst. These two techniques were tested and compared to identify the most effective bio-diesel production method. Based on our results, it is concluded that the microwave oven method appears to be the most simple and efficient method for the one-stage direct transesterification of the as-harvested Nannochloropsis algae. Copyright © 2010 Elsevier Ltd. All rights reserved.

Enzymatic transesterification of waste vegetable oil to produce biodiesel.

PubMed

Lopresto, C G; Naccarato, S; Albo, L; De Paola, M G; Chakraborty, S; Curcio, S; Calabrò, V

2015-11-01

An experimental study on enzymatic transesterification was performed to produce biodiesel from waste vegetable oils. Lipase from Pseudomonas cepacia was covalently immobilized on a epoxy-acrylic resin support. The immobilized enzyme exhibited high catalytic specific surface and allowed an easy recovery, regeneration and reutilisation of biocatalyst. Waste vegetable oils - such as frying oils, considered not competitive with food applications and wastes to be treated - were used as a source of glycerides. Ethanol was used as a short chain alcohol and was added in three steps with the aim to reduce its inhibitory effect on lipase activity. The effect of biocatalyst/substrate feed mass ratios and the waste oil quality have been investigated in order to estimate the process performances. Biocatalyst recovery and reuse have been also studied with the aim to verify the stability of the biocatalyst for its application in industrial scale. Copyright © 2015 Elsevier Inc. All rights reserved.

Evaluation of Method-Specific Extraction Variability for the Measurement of Fatty Acids in a Candidate Infant/Adult Nutritional Formula Reference Material.

PubMed

Place, Benjamin J

2017-05-01

To address community needs, the National Institute of Standards and Technology has developed a candidate Standard Reference Material (SRM) for infant/adult nutritional formula based on milk and whey protein concentrates with isolated soy protein called SRM 1869 Infant/Adult Nutritional Formula. One major component of this candidate SRM is the fatty acid content. In this study, multiple extraction techniques were evaluated to quantify the fatty acids in this new material. Extraction methods that were based on lipid extraction followed by transesterification resulted in lower mass fraction values for all fatty acids than the values measured by methods utilizing in situ transesterification followed by fatty acid methyl ester extraction (ISTE). An ISTE method, based on the identified optimal parameters, was used to determine the fatty acid content of the new infant/adult nutritional formula reference material.

Methylphenidate and its ethanol transesterification metabolite ethylphenidate: brain disposition, monoamine transporters and motor activity.

PubMed

Williard, Robin L; Middaugh, Lawrence D; Zhu, Hao-Jie B; Patrick, Kennerly S

2007-02-01

Ethylphenidate is formed by metabolic transesterification of methylphenidate and ethanol. Study objectives were to (a) establish that ethylphenidate is formed in C57BL/6 (B6) mice; (b) compare the stimulatory effects of ethylphenidate and methylphenidate enantiomers; (c) determine methylphenidate and ethylphenidate plasma and brain distribution and (d) establish in-vitro effects of methylphenidate and ethylphenidate on monoamine transporter systems. Experimental results were that: (a) coadministration of ethanol with the separate methylphenidate isomers enantioselectively produced l-ethylphenidate; (b) d and dl-forms of methylphenidate and ethylphenidate produced dose-responsive increases in motor activity with stimulation being less for ethylphenidate; (c) plasma and whole-brain concentrations were greater for ethylphenidate than methylphenidate and (d) d and DL-methylphenidate and ethylphenidate exhibited comparably potent low inhibition of the dopamine transporter, whereas ethylphenidate was a less potent norepinephrine transporter inhibitor. These experiments establish the feasibility of the B6 mouse model for examining the interactive effects of ethanol and methylphenidate. As reported for humans, concurrent exposure of B6 mice to methylphenidate and ethanol more readily formed l-ethylphenidate than d-ethylphenidate, and the l-isomers of both methylphenidate and ethylphenidate were biologically inactive. The observed reduced stimulatory effect of d-ethylphenidate relative to d-methylphenidate appears not to be the result of brain dispositional factors, but rather may be related to its reduced inhibition of the norepinephrine transporter, perhaps altering the interaction of dopaminergic and noradrenergic neural systems.

Solvent Free Transesterification of Glycerol Into Glycerol Carbonate Over Nanostructured CaAl Hydrotalcite Catalyst.

PubMed

Devarajan, Arulselvan; Thiripuranthagan, Sivakumar; Radhakrishnan, Ramakrishnan; Kumaravel, Sakthivel

2018-07-01

Drastic increase in green house gases due to fossil fuels usage urges the mankind to look for alternative fuel resources. Biodiesel is one of the alternative fuels which attracted the attention of many researchers. In recent years, bio-diesel drags much attention as an alternative clean fuel. Glycerol is an unavoidable byproduct in the transesterification process of vegetable oils into bio diesel and therefore market is flooded with glycerol. So it is high time to find ways of utilizing the abundant glycerol into value added products. Herein we report the catalytic transesterification of glycerol using dimethyl carbonate over MgAl-hydrotalcite (MgAl-HT), CaAl-hydrotalcite (CaAl-HT) and nano structured CaAl-HT catalysts. All the catalysts were characterized by XRD, FT-IR, TPD-CO2, BET, SEM and HR-TEM techniques. Among them Ca4Al-HT was found to be best in terms of conversion of glycerol (82.4%) and selectivity (95.9%) towards glycerol carbonate. The effect of CTAB template concentration in the nano synthesis of Ca4Al-HT on conversion and selectivity was studied and Ca4Al-HT synthesized with 0.4 moles of CTAB showed the best conversion of glycerol (98.7%) and the highest selectivity towards glycerol carbonate (97.9%). The recyclability test performed with the best catalyst showed that the catalyst was recyclable even after 5 cycles. Valorization of glycerol yields glycerol carbonate (GC) which is a very good polar solvent with high boiling point, building block in several organic syntheses and used in the production of surfactants, poly urethanes etc.

Supercritical water reformation of crude glycerol solution for hydrogen production.

DOT National Transportation Integrated Search

2009-12-01

Glycerol, also known as glycerin, is a less desirable byproduct formed in the production of biodiesel via the transesterification otriglycerides and presents a nontrivial issue in terms of developing other beneficial end uses. With an inflated glycer...

Biodiesel

USDA-ARS?s Scientific Manuscript database

Biodiesel is a renewable alternative to petrodiesel that is prepared from plant oils or animal fats. Biodiesel is prepared via transesterification and the resulting fuel properties must be compliant with international fuel standards such as ASTM D6751 and EN 14214. Numerous catalysts, methods, and l...

Metal ion-dependent DNAzymes and their applications as biosensors.

PubMed

Lan, Tian; Lu, Yi

2012-01-01

Long considered to serve solely as the genetic information carrier, DNA has been shown in 1994 to be able to act as DNA catalysts capable of catalyzing a trans-esterification reaction similar to the action of ribozymes and protein enzymes. Although not yet found in nature, numerous DNAzymes have been isolated through in vitro selection for catalyzing many different types of reactions in the presence of different metal ions and thus become a new class of metalloenzymes. What remains unclear is how DNA can carry out catalysis with simpler building blocks and fewer functional groups than ribozymes and protein enzymes and how DNA can bind metal ions specifically to perform these functions. In the past two decades, many biochemical and biophysical studies have been carried out on DNAzymes, especially RNA-cleaving DNAzymes. Important insights have been gained regarding their metal-dependent activity, global folding, metal binding sites, and catalytic mechanisms for these DNAzymes. Because of their high metal ion selectivity, one of the most important practical applications for DNAzymes is metal ion detection, resulting in highly sensitive and selective fluorescent, colorimetric, and electrochemical sensors for a wide range of metal ions such as Pb(2+), UO2 2 +,[Formula: see text] including paramagnetic metal ions such as Cu(2+). This chapter summarizes recent progresses in in vitro selection of metal ion-selective DNAzymes, their biochemical and biophysical studies and sensing applications.

Synthesis of decacationic [60]fullerene decaiodides giving photoinduced production of superoxide radicals and effective PDT-mediation on antimicrobial photoinactivation

PubMed Central

Wang, Min; Maragani, Satyanarayana; Huang, Liyi; Jeon, Seaho; Canteenwala, Taizoon; Hamblin, Michael R.; Chiang, Long Y.

2013-01-01

We report a novel class of highly water-soluble decacationic methano[60]fullerene decaiodides C60[>M(C3N6+C3)2]-(I−)10[1-(I−)10] capable of co-producing singlet oxygen (Type-II) and highly reactive hydroxyl radicals, formed from superoxide radicals in Type-I photosensitizing reactions, upon illumination at both UVA and white light wavelengths. The O2-·-production efficiency of 1-(I−)10 was confirmed by using an O2-·-reactive bis(2,4-dinitrobenzenesulfonyl)tetrafluorofluorescein probe and correlated to the photoinduced electron-transfer event going from iodide anions to C360∗[>M(C3N6+C3)2] leading to C60-·[>M(C3N6+C3)2]. Incorporation of a defined number (ten) of quaternary ammonium cationic charges per C60 in 1 was aimed to enhance its ability to target pathogenic Gram-positive and Gram-negative bacterial cells. We used the well-characterized malonato[60]fullerene diester mono-adduct C60[>M(t-Bu)2] as the starting fullerene derivative to provide a better synthetic route to C60[>M(C3N6+C3)2] via transesterification reaction under trifluoroacetic acid catalyzed conditions. These compounds may be used as effective photosensitizers and nano-PDT drugs for photoinactivation of pathogens. PMID:23474903

Utilization of discard bovine bone as a support for immobilization of recombinant Rhizopus oryzae lipase expressed in Pichia pastoris.

PubMed

Clementz, Adriana L; Del Peso, Gonzalo; Canet, Albert; Yori, Juan C; Valero, Francisco

2016-09-01

In this study the possibility of using discard bovine bone as support for immobilization of Rhizopus oryzae lipase expressed in Pichia pastoris was analyzed. Discard bovine bone were milled and then subjected to a chemical treatment with acetone in order to remove lipids and blood traces. Two types of supports were evaluated: bovine bone and calcined bovine bone for 2 h at 600°C. Supports were characterized by: ICP, SEM, XRD, FTIR, XPS, and N 2 adsorption isotherms. Calcined bovine bone presented appropriate characteristics for the lipase immobilization due to the removal of collagen: high porosity, large surface area and suitable porous structure. Biocatalysts were prepared with different initial enzyme load. For the equilibrium adsorption studies, the Langmuir isotherm was used to fit the data results. The immobilization occurs in monolayer to a value of 35 UA mg -1 . The activities of biocatalysts were tested in transesterification reaction of olive oil. For the enzyme load used in the test, a final yield percentage of 49.6 was achieved after six methanol additions and 180 min of reaction, similar values were obtained using Relizyme as support. Therefore, the bovine bone discard is an economical and appropriate choice for use support immobilization of enzymes. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:1246-1253, 2016. © 2016 American Institute of Chemical Engineers.

Fire and explosion hazards related to the industrial use of potassium and sodium methoxides.

PubMed

Kwok, Q; Acheson, B; Turcotte, R; Janès, A; Marlair, G

2013-04-15

Sodium and potassium methoxides are used as an intermediary for a variety of products in several industrial applications. For example, current production of so called "1G-biodiesel" relies on processing a catalytic reaction called "transesterification". This reaction transforms lipid resources from biomass materials into fatty acid methyl and ethyl esters. 1-G biodiesel processes imply the use of methanol, caustic potash (KOH), and caustic soda (NaOH) for which the hazards are well characterized. The more recent introduction of the direct catalysts CH3OK and CH3ONa may potentially introduce new process hazards. From an examination of existing MSDSs concerning these products, it appears that no consensus currently exists on their intrinsic hazardous properties. Recently, l'Institut National de l'Environnement Industriel et des Risques (France) and the Canadian Explosives Research Laboratory (Canada) have embarked upon a joint effort to better characterize the thermal hazards associated with these catalysts. This work employs the more conventional tests for water reactivity as an ignition source, fire and dust explosion hazards, using isothermal nano-calorimetry, isothermal basket tests, the Fire Propagation Apparatus and a standard 20 L sphere, respectively. It was found that these chemicals can become self-reactive close to room temperature under specific conditions and can generate explosible dusts. Copyright © 2013 Crown. Published by Elsevier B.V. All rights reserved.

Comparative toxicity and mutagenicity of biodiesel exhaust

EPA Science Inventory

Biodiesel (BD) is commercially made from the transesterification of plant and animal derived oils. The composition of biodiesel exhaust (BE) depends on the type of fuel, the blend ratio and the engine and operating conditions. While numerous studies have characterized the health ...

In situ Transesterification of Microalgal Oil to Produce Algal Biodiesel

DOT National Transportation Integrated Search

2012-06-01

This research was to process whole microalgae cells for biodiesel production without first extracting lipids. The ultimate : goal is develop a novel process for algal biodiesel production directly from microalgae cells in a single step, i.e., in situ...

Natural wax organogels for cookies

USDA-ARS?s Scientific Manuscript database

Organogels formed from vegetable oil and an organogelator have drawn great interest as alternatives to trans fats. Unlike the current alternatives to trans fats such as tropical oils, fully hydrogenated oils and their transesterifed oils containing high contents of saturated fats, organogels can be ...