Piezoelectric Polymer/Ceramic Composite

DTIC Science & Technology

1989-05-02

allowed the production of films with a good surface structure. Samples were then thoroughly cleaned with isopropyl alcohol in an ultrasonic bath to...TrFe (Solef 11010) were kindly supplied by Laporte Industries of Lutcn, U.K. Electroactive properties of four composite films, together with those of...Piezel (see Appendix for specification), a commercially available composite of PZT/VDF-TrFE, manufactured by the Daikin Industry Limited of Japan have

Liquid phase methanol reactor staging process for the production of methanol

DOEpatents

Bonnell, Leo W.; Perka, Alan T.; Roberts, George W.

1988-01-01

The present invention is a process for the production of methanol from a syngas feed containing carbon monoxide, carbon dioxide and hydrogen. Basically, the process is the combination of two liquid phase methanol reactors into a staging process, such that each reactor is operated to favor a particular reaction mechanism. In the first reactor, the operation is controlled to favor the hydrogenation of carbon monoxide, and in the second reactor, the operation is controlled so as to favor the hydrogenation of carbon dioxide. This staging process results in substantial increases in methanol yield.

Hynol: An economic process for methanol production from biomass and natural gas with reduced CO2 emission

NASA Astrophysics Data System (ADS)

Steinberg, M.; Dong, Yuanji

1993-10-01

The Hynol process is proposed to meet the demand for an economical process for methanol production with reduced CO2 emission. This new process consists of three reaction steps: (1) hydrogasification of biomass, (2) steam reforming of the produced gas with additional natural gas feedstock, and (3) methanol synthesis of the hydrogen and carbon monoxide produced during the previous two steps. The H2-rich gas remaining after methanol synthesis is recycled to gasify the biomass in an energy neutral reactor so that there is no need for an expensive oxygen plant as required by commercial steam gasifiers. Recycling gas allows the methanol synthesis reactor to perform at a relatively lower pressure than conventional while the plant still maintains high methanol yield. Energy recovery designed into the process minimizes heat loss and increases the process thermal efficiency. If the Hynol methanol is used as an alternative and more efficient automotive fuel, an overall 41% reduction in CO2 emission can be achieved compared to the use of conventional gasoline fuel. A preliminary economic estimate shows that the total capital investment for a Hynol plant is 40% lower than that for a conventional biomass gasification plant. The methanol production cost is $0.43/gal for a 1085 million gal/yr Hynol plant which is competitive with current U.S. methanol and equivalent gasoline prices. Process flowsheet and simulation data using biomass and natural gas as cofeedstocks are presented. The Hynol process can convert any condensed carbonaceous material, especially municipal solid waste (MSW), to produce methanol.

DNA barcoding and morphological analysis for rapid identification of most economically important crop-infesting Sunn pests belonging to Eurygaster Laporte, 1833 (Hemiptera, Scutelleridae).

PubMed

Syromyatnikov, Mikhail Y; Golub, Victor B; Kokina, Anastasia V; Victoria A Soboleva; Popov, Vasily N

2017-01-01

The genus Eurygaster Laporte, 1833 includes ten species five of which inhabit the European part of Russia. The harmful species of the genus is E. integriceps . Eurygaster species identification based on the morphological traits is very difficult, while that of the species at the egg or larval stages is extremely difficult or impossible. Eurygaster integriceps , E. maura , and E. testudinaria differ only slightly between each other morphologically, E. maura and E. testudinaria being almost indiscernible. DNA barcoding based on COI sequences have shown that E. integriceps differs significantly from these closely related species, which enables its rapid and accurate identification. Based on COI nucleotide sequences, three species of Sunn pests, E. maura , E. testudinarius , E. dilaticollis , could not be differentiated from each other through DNA barcoding. The difference in the DNA sequences between the COI gene of E. integriceps and COI genes of E. maura and E. testudinarius was more than 4%. In the present study DNA barcoding of two Eurygaster species was performed for the first time on E. integriceps , the most dangerous pest in the genus, and E. dilaticollis that only inhabits natural ecosystems. The PCR-RFLP method was developed in this work for the rapid identification of E. integriceps .

DNA barcoding and morphological analysis for rapid identification of most economically important crop-infesting Sunn pests belonging to Eurygaster Laporte, 1833 (Hemiptera, Scutelleridae)

PubMed Central

Syromyatnikov, Mikhail Y.; Golub, Victor B.; Kokina, Anastasia V.; Victoria A. Soboleva; Popov, Vasily N.

2017-01-01

Abstract The genus Eurygaster Laporte, 1833 includes ten species five of which inhabit the European part of Russia. The harmful species of the genus is E. integriceps. Eurygaster species identification based on the morphological traits is very difficult, while that of the species at the egg or larval stages is extremely difficult or impossible. Eurygaster integriceps, E. maura, and E. testudinaria differ only slightly between each other morphologically, E. maura and E. testudinaria being almost indiscernible. DNA barcoding based on COI sequences have shown that E. integriceps differs significantly from these closely related species, which enables its rapid and accurate identification. Based on COI nucleotide sequences, three species of Sunn pests, E. maura, E. testudinarius, E. dilaticollis, could not be differentiated from each other through DNA barcoding. The difference in the DNA sequences between the COI gene of E. integriceps and COI genes of E. maura and E. testudinarius was more than 4%. In the present study DNA barcoding of two Eurygaster species was performed for the first time on E. integriceps, the most dangerous pest in the genus, and E. dilaticollis that only inhabits natural ecosystems. The PCR-RFLP method was developed in this work for the rapid identification of E. integriceps. PMID:29118620

Hynol Process Engineering: Process Configuration, Site Plan, and Equipment Design

DTIC Science & Technology

1996-02-01

feed stock. Compared with other methanol production processes, direct emissions of carbon dioxide can be substantially reduced by using the Hynol...A bench scale methanol production facility is being constructed to demonstrate the technical feasibility of producing methanol from biomass using the ...Hynol process. The plant is being designed to convert 50 lb./hr of biomass to methanol. The biomass consists of wood, and natural gas is used as a co

Hydrogen and methanol exchange processes for (TMP)Rh-OCH3(CH3OH) in binary solutions of methanol and benzene.

PubMed

Sarkar, Sounak; Li, Shan; Wayland, Bradford B

2011-04-18

Tetramesityl porphinato rhodium(III) methoxide ((TMP)Rh-OCH(3)) binds with methanol in benzene to form a 1:1 methanol complex ((TMP)Rh-OCH(3)(CH(3)OH)) (1). Dynamic processes are observed to occur for the rhodium(III) methoxide methanol complex (1) that involve both hydrogen and methanol exchange. Hydrogen exchange between coordinated methanol and methoxide through methanol in solution results in an interchange of the environments for the non-equivalent porphyrin faces that contain methoxide and methanol ligands. Interchange of the environments of the coordinated methanol and methoxide sites in 1 produces interchange of the inequivalent mesityl o-CH(3) groups, but methanol ligand exchange occurs on one face of the porphyrin and the mesityl o-CH(3) groups remain inequivalent. Rate constants for dynamic processes are evaluated by full line shape analysis for the (1)H NMR of the mesityl o-CH(3) and high field methyl resonances of coordinated methanol and methoxide groups in 1. The rate constant for interchange of the inequivalent porphyrin faces is associated with hydrogen exchange between 1 and methanol in solution and is observed to increase regularly with the increase in the mole fraction of methanol. The rate constant for methanol ligand exchange between 1 and the solution varies with the solution composition and fluctuates in a manner that parallels the change in the activation energy for methanol diffusion which is a consequence of solution non-ideality from hydrogen bonded clusters.

Achievable Imperative - Baseline Health of the Reserve Component

DTIC Science & Technology

2001-03-22

Sekikawa, Akira, Ronald E . Laporte , Toshihiko Satoh and Genero Ochi. "Health Workers Need Information From Countries With Better Health Indicators Than...Statistic Quarterly, 48 (1995): 48. 21Thomas E . McKone, Beverly M. Huey, Edward Downing, and Laura M. Duffy, eds., Strategies to Protect the Health of...lmsmr/MSMRTOC.htm>. Internet. Accessed 10 October 2001. McKone, Thomas E ., Beverly M. Huey, Edward Downing, and Laura M. Duffy, eds. Strategies to

Fuel and power coproduction: The Liquid Phase Methanol (LPMEOH{trademark}) process demonstration at Kingsport

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

Drown, D.P.; Brown, W.R.; Heydorn, E.C.

1997-12-31

The Liquid Phase Methanol (LPMEOH{trademark}) process uses a slurry bubble column reactor to convert syngas (primarily a mixture of carbon monoxide and hydrogen) to methanol. Because of its superior heat management, the process is able to be designed to directly handle the carbon monoxide (CO)-rich syngas characteristic of the gasification of coal, petroleum coke, residual oil, wastes, or of other hydrocarbon feedstocks. When added to an integrated gasification combined cycle (IGCC) power plant, the LPMEOH{trademark} process converts a portion of the CO-rich syngas produced by the gasifier to methanol, and the remainder of the unconverted gas is used to fuelmore » the gas turbine combined-cycle power plant. The LPMEOH{trademark} process has the flexibility to operate in a daily electricity demand load-following manner. Coproduction of power and methanol via IGCC and the LPMEOH{trademark} process provides opportunities for energy storage for electrical demand peak shaving, clean fuel for export, and/or chemical methanol sales.« less

Waste-to-methanol: Process and economics assessment.

PubMed

Iaquaniello, Gaetano; Centi, Gabriele; Salladini, Annarita; Palo, Emma; Perathoner, Siglinda; Spadaccini, Luca

2017-11-01

The waste-to-methanol (WtM) process and related economics are assessed to evidence that WtM is a valuable solution both from economic, strategic and environmental perspectives. Bio-methanol from Refuse-derived-fuels (RdF) has an estimated cost of production of about 110€/t for a new WtM 300t/d plant. With respect to waste-to-energy (WtE) approach, this solution allows various advantages. In considering the average market cost of methanol and the premium as biofuel, the WtM approach results in a ROI (Return of Investment) of about 29%, e.g. a payback time of about 4years. In a hybrid scheme of integration with an existing methanol plant from natural gas, the cost of production becomes a profit even without considering the cap for bio-methanol production. The WtM process allows to produce methanol with about 40% and 30-35% reduction in greenhouse gas emissions with respect to methanol production from fossil fuels and bio-resources, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

Dusty galaxies in the Epoch of Reionization: simulations

NASA Astrophysics Data System (ADS)

Behrens, C.; Pallottini, A.; Ferrara, A.; Gallerani, S.; Vallini, L.

2018-06-01

The recent discovery of dusty galaxies well into the Epoch of Reionization (redshift z > 6) poses challenging questions about the properties of the interstellar medium in these pristine systems. By combining state-of-the-art hydrodynamic and dust radiative transfer simulations, we address these questions focusing on the recently discovered dusty galaxy A2744_YD4 (z = 8.38, Laporte et al.). We show that we can reproduce the observed spectral energy distribution (SED) only using different physical values with respect to the inferred ones by Laporte et al., i.e. a star formation rate of SFR = 78 M_{⊙} yr^{-1}, a factor ≈4 higher than deduced from simple SED fitting. In this case, we find: (i) dust attenuation (corresponding to τV = 1.4) is consistent with a Milky Way (MW) extinction curve; (ii) the dust-to-metal ratio is low, fd ˜ 0.08, implying that early dust formation is rather inefficient; (iii) the luminosity-weighted dust temperature is high, T_d=91± 23 K, as a result of the intense (≈100 × MW) interstellar radiation field; and (iv) due to the high Td, the Atacama Large Millimeter/submillimeter Array Band 7 detection can be explained by a limited dust mass, Md = 1.6 × 106 M⊙. Finally, the high dust temperatures might solve the puzzling low infrared excess (IRX) recently deduced for high-z galaxies from the IRX-β relation.

A revision of Meladema diving beetles (Coleoptera, Dytiscidae), with the description of a new species from the central Mediterranean based on molecules and morphology.

PubMed

Bilton, David T; Ribera, Ignacio

2017-01-01

Meladema Laporte, 1835 are relatively large, stream-dwelling diving beetles, distributed widely in the Western Palaearctic, from the Atlantic Islands to Turkey, and from southern France and the Balkans to the central Sahara. In addition to the three previously recognised taxa ( M. coriacea Laporte, 1835, M. imbricata (Wollaston, 1871) and M. lanio (Fabricius, 1775)) we describe a new, cryptic, species from the central Mediterranean area, which can be distinguished from M. coriacea on both DNA sequence data and morphology, and provide a key to known species of the genus. Based on the study of genotyped material, both recent and archival, as well as the examination of a large number of museum specimens, we show that M. lepidoptera sp. n. occurs to the apparent exclusion of M. coriacea on Corsica, Sardinia and islands of the Tuscan Archipelago, but that both taxa are found in peninsular Italy, where they may occasionally hybridize. In the absence of the original type series, we designate a neotype for M. coriacea , and take the opportunity to designate a lectotype for M. lanio . Morphological variation in Meladema species is discussed, including that seen in known and presumed hybrids. Our study highlights the incomplete state of knowledge of Mediterranean biodiversity, even in relatively large, supposedly well-studied taxa.

The genera in the second catalogue (1833–1836) of Dejean’s Coleoptera collection

PubMed Central

Bousquet, Yves; Bouchard, Patrice

2013-01-01

Abstract All genus-group names listed in the second edition of the catalogue (1833-1836) of Dejean’s beetle collection are recorded. For each new genus-group name the originally included available species are listed and for generic names with at least one available species, the type species and the current status are given. Names available prior to the publication of Dejean’s second catalogue (1833-1836) are listed in an appendix. The following new synonymies are proposed: Cyclonotum Dejean, 1833 (= Dactylosternum Wollaston, 1854) [Hydrophilidae], Hyporhiza Dejean, 1833 (= Rhinaspis Perty, 1830) [Scarabaeidae], Aethales Dejean, 1834 (= Epitragus Latreille, 1802) [Tenebrionidae], Arctylus Dejean, 1834 (= Praocis Eschscholtz, 1829) [Tenebrionidae], Euphron Dejean, 1834 (= Derosphaerus Thomson, 1858) [Tenebrionidae], Hipomelus Dejean, 1834 (= Trachynotus Latreille, 1828) [Tenebrionidae], Pezodontus Dejean, 1834 (= Odontopezus Alluaud, 1889) [Tenebrionidae], Zygocera Dejean, 1835 (= Disternopsis Breuning, 1939) [Cerambycidae], and Physonota Chevrolat, 1836 (= Anacassis Spaeth, 1913) [Chrysomelidae]. Heterogaster pilicornis Dejean, 1835 [Cerambycidae] and Labidomera trimaculata Chevrolat, 1836 [Chrysomelidae] are placed for the first time in synonymy with Anisogaster flavicans Deyrolle, 1862 and Chrysomela clivicollis Kirby, 1837 respectively. Type species of the following genus-group taxa are proposed: Sphaeromorphus Dejean, 1833 (Sphaeromorphus humeralis Erichson, 1843) [Scarabaeidae], Adelphus Dejean, 1834 (Helops marginatus Fabricius, 1792) [Tenebrionidae], Cyrtoderes Dejean, 1834 (Tenebrio cristatus DeGeer, 1778) [Tenebrionidae], Selenepistoma Dejean, 1834 (Opatrum acutum Wiedemann, 1823) [Tenebrionidae], Charactus Dejean, 1833 (Lycus limbatus Fabricius, 1801) [Lycidae], Corynomalus Chevrolat, 1836 (Eumorphus limbatus Olivier, 1808) [Endomychidae], Hebecerus Dejean, 1835 (Acanthocinus marginicollis Boisduval, 1835) [Cerambycidae], Pterostenus Dejean, 1835 (Cerambyx abbreviatus Fabricius, 1801) [Cerambycidae], Psalicerus Dejean, 1833 (Lucanus femoratus Fabricius, 1775) [Lucanidae], and Pygolampis Dejean, 1833 (Lampyris glauca Olivier, 1790) [Lampyridae]. A new name, Neoeutrapela Bousquet and Bouchard [Tenebrionidae], is proposed for Eutrapela Dejean, 1834 (junior homonym of Eutrapela Hübner, 1809). The following generic names, made available in Dejean’s catalogue, were found to be older than currently accepted valid names: Catoxantha Dejean, 1833 over Catoxantha Solier, 1833 [Buprestidae], Pristiptera Dejean, 1833 over Pelecopselaphus Solier, 1833 [Buprestidae], Charactus Dejean, 1833 over Calopteron Laporte, 1836 [Lycidae], Cyclonotum Dejean, 1833 over Dactylosternum Wollaston, 1854 [Hydrophilidae], Ancylonycha Dejean, 1833 over Holotrichia Hope, 1837 [Scarabaeidae], Aulacium Dejean, 1833 over Mentophilus Laporte, 1840 [Scarabaeidae], Sciuropus Dejean, 1833 over Ancistrosoma Curtis, 1835 [Scarabaeidae], Sphaeromorphus Dejean, 1833 over Ceratocanthus White, 1842 [Scarabaeidae], Psalicerus Dejean, 1833 over Leptinopterus Hope, 1838 [Lucanidae], Adelphus Dejean, 1834 over Praeugena Laporte, 1840 [Tenebrionidae], Amatodes Dejean, 1834 over Oncosoma Westwood, 1843 [Tenebrionidae], Cyrtoderes Dejean, 1834 over Phligra Laporte, 1840 [Tenebrionidae], Euphron Dejean, 1834 over Derosphaerus Thomson, 1858 [Tenebrionidae], Pezodontus Dejean, 1834 over Odontopezus Alluaud, 1889 [Tenebrionidae], Anoplosthaeta Dejean, 1835 over Prosopocera Blanchard, 1845 [Cerambycidae], Closteromerus Dejean, 1835 over Hylomela Gahan, 1904 [Cerambycidae], Hebecerus Dejean, 1835 over Ancita Thomson, 1864 [Cerambycidae], Mastigocera Dejean, 1835over Mallonia Thomson, 1857 [Cerambycidae], Zygocera Dejean, 1835 over Disternopsis Breuning, 1939 [Cerambycidae], Australica Chevrolat, 1836 over Calomela Hope, 1840 [Chrysomelidae], Edusa Chevrolat, 1836 over Edusella Chapuis, 1874 [Chrysomelidae], Litosonycha Chevrolat, 1836 over Asphaera Duponchel and Chevrolat, 1842 [Chrysomelidae], and Pleuraulaca Chevrolat, 1836 over Iphimeis Baly, 1864 [Chrysomelidae]. In each of these cases, Reversal of Precedence (ICZN 1999: 23.9) or an applicationto the International Commission on Zoological Nomenclature will be necessary to retain usage of the younger synonyms. PMID:23794836

Reactions of C1 Building Blocks

NASA Astrophysics Data System (ADS)

Stöcker, Michael

The chapter “Reactions of C1 Building Blocks” covers the direct conversion of methane to aromatics, the methanol-to-hydrocarbons (MTHC) conversion with respect to gasoline (methanol to gasoline) and olefins (methanol to olefins, methanol-to-propene) as well as some combinations like the TIGAS and Mobil's olefin-to-gasoline and distillate processes. The main focus within this chapter will be on the industrial processes, especially concerning the MTHC reactions - including catalytic systems, reaction conditions, process - and to a minor extent related to the mechanistic aspects and kinetic considerations.

The Potential Organ Involved in Cantharidin Biosynthesis in Epicauta chinensis Laporte (Coleoptera: Meloidae)

PubMed Central

Jiang, Ming; Lü, Shumin

2017-01-01

Cantharidin, a terpenoid defensive toxin mainly produced by blister beetles, is among the most widely known insect natural products in the world. However, little is known about the site of cantharidin biosynthesis in vivo. Our previous research showed that 3-hydroxy-3-methylglutary-CoA reductase (HMGR) is an essential enzyme in cantharidin biosynthesis. In this report, we further investigated cantharidin titer and HMGR mRNA expression levels in different tissues of male and female Epicauta chinensis, and performed a comparative analysis of HMGR transcript levels in male Tenebrio molitor, a Tenebrionidae beetle that cannot produce cantharidin. HMGR transcripts had a positive correlation with cantharidin production. Furthermore, the specifically high amounts of HMGR transcript and abundant cantharidin production in fat body of male E. chinensis indicated the process of cantharidin synthesis may occur in the fat body. PMID:28423415

Metabolic Engineering of Corynebacterium glutamicum for Methanol Metabolism

PubMed Central

Witthoff, Sabrina; Schmitz, Katja; Niedenführ, Sebastian; Nöh, Katharina; Noack, Stephan

2015-01-01

Methanol is already an important carbon feedstock in the chemical industry, but it has found only limited application in biotechnological production processes. This can be mostly attributed to the inability of most microbial platform organisms to utilize methanol as a carbon and energy source. With the aim to turn methanol into a suitable feedstock for microbial production processes, we engineered the industrially important but nonmethylotrophic bacterium Corynebacterium glutamicum toward the utilization of methanol as an auxiliary carbon source in a sugar-based medium. Initial oxidation of methanol to formaldehyde was achieved by heterologous expression of a methanol dehydrogenase from Bacillus methanolicus, whereas assimilation of formaldehyde was realized by implementing the two key enzymes of the ribulose monophosphate pathway of Bacillus subtilis: 3-hexulose-6-phosphate synthase and 6-phospho-3-hexuloisomerase. The recombinant C. glutamicum strain showed an average methanol consumption rate of 1.7 ± 0.3 mM/h (mean ± standard deviation) in a glucose-methanol medium, and the culture grew to a higher cell density than in medium without methanol. In addition, [13C]methanol-labeling experiments revealed labeling fractions of 3 to 10% in the m + 1 mass isotopomers of various intracellular metabolites. In the background of a C. glutamicum Δald ΔadhE mutant being strongly impaired in its ability to oxidize formaldehyde to CO2, the m + 1 labeling of these intermediates was increased (8 to 25%), pointing toward higher formaldehyde assimilation capabilities of this strain. The engineered C. glutamicum strains represent a promising starting point for the development of sugar-based biotechnological production processes using methanol as an auxiliary substrate. PMID:25595770

Transesterification of waste vegetable oil under pulse sonication using ethanol, methanol and ethanol-methanol mixtures.

PubMed

Martinez-Guerra, Edith; Gude, Veera Gnaneswar

2014-12-01

This study reports on the effects of direct pulse sonication and the type of alcohol (methanol and ethanol) on the transesterification reaction of waste vegetable oil without any external heating or mechanical mixing. Biodiesel yields and optimum process conditions for the transesterification reaction involving ethanol, methanol, and ethanol-methanol mixtures were evaluated. The effects of ultrasonic power densities (by varying sample volumes), power output rates (in W), and ultrasonic intensities (by varying the reactor size) were studied for transesterification reaction with ethanol, methanol and ethanol-methanol (50%-50%) mixtures. The optimum process conditions for ethanol or methanol based transesterification reaction of waste vegetable oil were determined as: 9:1 alcohol to oil ratio, 1% wt. catalyst amount, 1-2 min reaction time at a power output rate between 75 and 150 W. It was shown that the transesterification reactions using ethanol-methanol mixtures resulted in biodiesel yields as high as >99% at lower power density and ultrasound intensity when compared to ethanol or methanol based transesterification reactions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Biological Methanol Production by a Type II Methanotroph Methylocystis bryophila.

PubMed

Patel, Sanjay K S; Mardina, Primata; Kim, Sang-Yong; Lee, Jung-Kul; Kim, In-Won

2016-04-28

Methane (CH₄) is the most abundant component in natural gas. To reduce its harmful environmental effect as a greenhouse gas, CH₄ can be utilized as a low-cost feed for the synthesis of methanol by methanotrophs. In this study, several methanotrophs were examined for their ability to produce methanol from CH₄; including Methylocella silvestris, Methylocystis bryophila, Methyloferula stellata, and Methylomonas methanica. Among these methanotrophs, M. bryophila exhibited the highest methanol production. The optimum process parameters aided in significant enhancement of methanol production up to 4.63 mM. Maximum methanol production was observed at pH 6.8, 30°C, 175 rpm, 100 mM phosphate buffer, 50 mM MgCl₂ as a methanol dehydrogenase inhibitor, 50% CH₄ concentration, 24 h of incubation, and 9 mg of dry cell mass ml(-1) inoculum load, respectively. Optimization of the process parameters, screening of methanol dehydrogenase inhibitors, and supplementation with formate resulted in significant improvements in methanol production using M. bryophila. This report suggests, for the first time, the potential of using M. bryophila for industrial methanol production from CH₄.

Process assessment of small scale low temperature methanol synthesis

NASA Astrophysics Data System (ADS)

Hendriyana, Susanto, Herri; Subagjo

2015-12-01

Biomass is a renewable energy resource and has the potential to make a significant impact on domestic fuel supplies. Biomass can be converted to fuel like methanol via several step process. The process can be split into following main steps: biomass preparation, gasification, gas cooling and cleaning, gas shift and methanol synthesis. Untill now these configuration still has a problem like high production cost, catalyst deactivation, economy of scale and a huge energy requirements. These problems become the leading inhibition for biomass conversion to methanol, which should be resolved to move towards the economical. To address these issues, we developed various process and new configurations for methanol synthesis via methyl formate. This configuration combining two reactors: the one reactor for the carbonylation of methanol and CO to form methyl formate, and the second for the hydrogenolysis of methyl formate and H2 to form two molecule of methanol. Four plant process configurations were compared with the biomass basis is 300 ton/day. The first configuration (A) is equipped with a steam reforming process for converting methane to CO and H2 for increasing H2/CO ratio. CO2 removal is necessary to avoid poisoning the catalyst. COSORB process used for the purpose of increasing the partial pressure of CO in the feed gas. The steam reforming process in B configuration is not used with the aim of reducing the number of process equipment, so expect lower investment costs. For C configuration, the steam reforming process and COSORB are not used with the aim of reducing the number of process equipment, so expect lower investment costs. D configuration is almost similar to the configuration A. This configuration difference is in the synthesis of methanol which was held in a single reactor. Carbonylation and hydrogenolysis reactions carried out in the same reactor one. These processes were analyzed in term of technical process, material and energy balance and economic analysis. The presented study is an attempt to compile most of these efforts in order to guide future work to get cheaper low cost investment. From our study the interesting configuration to the next development is D configuration with methanol yield 112 ton/day and capital cost with 526.4 106 IDR. The configuration of D with non-discounted and discounted rate had the break-even point approximately six and eight years.

Use of aluminum phosphate as the dehydration catalyst in single step dimethyl ether process

DOEpatents

Peng, Xiang-Dong; Parris, Gene E.; Toseland, Bernard A.; Battavio, Paula J.

1998-01-01

The present invention pertains to a process for the coproduction of methanol and dimethyl ether (DME) directly from a synthesis gas in a single step (hereafter, the "single step DME process"). In this process, the synthesis gas comprising hydrogen and carbon oxides is contacted with a dual catalyst system comprising a physical mixture of a methanol synthesis catalyst and a methanol dehydration catalyst. The present invention is an improvement to this process for providing an active and stable catalyst system. The improvement comprises the use of an aluminum phosphate based catalyst as the methanol dehydration catalyst. Due to its moderate acidity, such a catalyst avoids the coke formation and catalyst interaction problems associated with the conventional dual catalyst systems taught for the single step DME process.

Technical and economical evaluation of carbon dioxide capture and conversion to methanol process

NASA Astrophysics Data System (ADS)

Putra, Aditya Anugerah; Juwari, Handogo, Renanto

2017-05-01

Phenomenon of global warming, which is indicated by increasing of earth's surface temperature, is caused by high level of greenhouse gases level in the atmosphere. Carbon dioxide, which increases year by year because of high demand of energy, gives the largest contribution in greenhouse gases. One of the most applied solution to mitigate carbon dioxide level is post-combustion carbon capture technology. Although the technology can absorb up to 90% of carbon dioxide produced, some worries occur that captured carbon dioxide that is stored underground will be released over time. Utilizing captured carbon dioxide could be a promising solution. Captured carbon dioxide can be converted into more valuable material, such as methanol. This research will evaluate the conversion process of captured carbon dioxide to methanol, technically and economically. From the research, it is found that technically methanol can be made from captured carbon dioxide. Product gives 25.6905 kg/s flow with 99.69% purity of methanol. Economical evaluation of the whole conversion process shows that the process is economically feasible. The capture and conversion process needs 176,101,157.69 per year for total annual cost and can be overcome by revenue gained from methanol product sales.

Evidence for Conversion of Methanol to Formaldehyde in Nonhuman Primate Brain

PubMed Central

Zhai, Rongwei; Zheng, Na; Rizak, Joshua; Hu, Xintian

2016-01-01

Many studies have reported that methanol toxicity to primates is mainly associated with its metabolites, formaldehyde (FA) and formic acid. While methanol metabolism and toxicology have been best studied in peripheral organs, little study has focused on the brain and no study has reported experimental evidence that demonstrates transformation of methanol into FA in the primate brain. In this study, three rhesus macaques were given a single intracerebroventricular injection of methanol to investigate whether a metabolic process of methanol to FA occurs in nonhuman primate brain. Levels of FA in cerebrospinal fluid (CSF) were then assessed at different time points. A significant increase of FA levels was found at the 18th hour following a methanol injection. Moreover, the FA level returned to a normal physiological level at the 30th hour after the injection. These findings provide direct evidence that methanol is oxidized to FA in nonhuman primate brain and that a portion of the FA generated is released out of the brain cells. This study suggests that FA is produced from methanol metabolic processes in the nonhuman primate brain and that FA may play a significant role in methanol neurotoxicology. PMID:27066393

Supercritical methanol for polyethylene terephthalate depolymerization: Observation using simulator

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

Genta, Minoru; Iwaya, Tomoko; Sasaki, Mitsuru

2007-07-01

To apply PET depolymerization in supercritical methanol to commercial recycling, the benefits of supercritical methanol usage in PET depolymerization was investigated from the viewpoint of the reaction rate and energy demands. PET was depolymerized in a batch reactor at 573 K in supercritical methanol under 14.7 MPa and in vapor methanol under 0.98 MPa in our previous work. The main products of both reactions were the PET monomers of dimethyl terephthalate (DMT) and ethylene glycol (EG). The rate of PET depolymerization in supercritical methanol was faster than that of PET depolymerization in vapor methanol. This indicates supercritical fluid is beneficialmore » in reducing reaction time without the use of a catalyst. We depicted the simple process flow of PET depolymerization in supercritical methanol and in vapor methanol, and by simulation evaluated the total heat demand of each process. In this simulation, bis-hydroxyethyl terephthalate (BHET) was used as a model component of PET. The total heat demand of PET depolymerization in supercritical methanol was 2.35 x 10{sup 6} kJ/kmol Produced-DMT. That of PET depolymerization in vapor methanol was 2.84 x 10{sup 6} kJ/kmol Produced-DMT. The smaller total heat demand of PET depolymerization in supercritical methanol clearly reveals the advantage of using supercritical fluid in terms of energy savings.« less

Endogenous Methanol Regulates Mammalian Gene Activity

PubMed Central

Komarova, Tatiana V.; Petrunia, Igor V.; Shindyapina, Anastasia V.; Silachev, Denis N.; Sheshukova, Ekaterina V.; Kiryanov, Gleb I.; Dorokhov, Yuri L.

2014-01-01

We recently showed that methanol emitted by wounded plants might function as a signaling molecule for plant-to-plant and plant-to-animal communications. In mammals, methanol is considered a poison because the enzyme alcohol dehydrogenase (ADH) converts methanol into toxic formaldehyde. However, the detection of methanol in the blood and exhaled air of healthy volunteers suggests that methanol may be a chemical with specific functions rather than a metabolic waste product. Using a genome-wide analysis of the mouse brain, we demonstrated that an increase in blood methanol concentration led to a change in the accumulation of mRNAs from genes primarily involved in detoxification processes and regulation of the alcohol/aldehyde dehydrogenases gene cluster. To test the role of ADH in the maintenance of low methanol concentration in the plasma, we used the specific ADH inhibitor 4-methylpyrazole (4-MP) and showed that intraperitoneal administration of 4-MP resulted in a significant increase in the plasma methanol, ethanol and formaldehyde concentrations. Removal of the intestine significantly decreased the rate of methanol addition to the plasma and suggested that the gut flora may be involved in the endogenous production of methanol. ADH in the liver was identified as the main enzyme for metabolizing methanol because an increase in the methanol and ethanol contents in the liver homogenate was observed after 4-MP administration into the portal vein. Liver mRNA quantification showed changes in the accumulation of mRNAs from genes involved in cell signalling and detoxification processes. We hypothesized that endogenous methanol acts as a regulator of homeostasis by controlling the mRNA synthesis. PMID:24587296

Process for the conversion of carbonaceous feedstocks to particulate carbon and methanol

DOEpatents

Steinberg, Meyer; Grohse, Edward W.

1995-01-01

A process for the production of a pollutant-free particulate carbon (i.e., a substantially ash-, sulfur- and nitrogen-free carbon) from carbonaceous feedstocks. The basic process involves de-oxygenating one of the gas streams formed in a cyclic hydropyrolysis-methane pyrolysis process in order to improve conversion of the initial carbonaceous feedstock. De-oxygenation is effected by catalytically converting carbon monoxide, carbon dioxide, and hydrogen contained in one of the pyrolysis gas streams, preferably the latter, to a methanol co-product. There are thus produced two products whose use is known per se, viz., a substantially pollutant-free particulate carbon black and methanol. These products may be admixed in the form of a liquid slurry of carbon black in methanol.

Process assessment of small scale low temperature methanol synthesis

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

Hendriyana; Chemical Engineering Department, Faculty of Industrial Technology, InstitutTeknologi Bandung; Susanto, Herri, E-mail: herri@che.itb.ac.id

2015-12-29

Biomass is a renewable energy resource and has the potential to make a significant impact on domestic fuel supplies. Biomass can be converted to fuel like methanol via several step process. The process can be split into following main steps: biomass preparation, gasification, gas cooling and cleaning, gas shift and methanol synthesis. Untill now these configuration still has a problem like high production cost, catalyst deactivation, economy of scale and a huge energy requirements. These problems become the leading inhibition for biomass conversion to methanol, which should be resolved to move towards the economical. To address these issues, we developedmore » various process and new configurations for methanol synthesis via methyl formate. This configuration combining two reactors: the one reactor for the carbonylation of methanol and CO to form methyl formate, and the second for the hydrogenolysis of methyl formate and H{sub 2} to form two molecule of methanol. Four plant process configurations were compared with the biomass basis is 300 ton/day. The first configuration (A) is equipped with a steam reforming process for converting methane to CO and H{sub 2} for increasing H{sub 2}/CO ratio. CO{sub 2} removal is necessary to avoid poisoning the catalyst. COSORB process used for the purpose of increasing the partial pressure of CO in the feed gas. The steam reforming process in B configuration is not used with the aim of reducing the number of process equipment, so expect lower investment costs. For C configuration, the steam reforming process and COSORB are not used with the aim of reducing the number of process equipment, so expect lower investment costs. D configuration is almost similar to the configuration A. This configuration difference is in the synthesis of methanol which was held in a single reactor. Carbonylation and hydrogenolysis reactions carried out in the same reactor one. These processes were analyzed in term of technical process, material and energy balance and economic analysis. The presented study is an attempt to compile most of these efforts in order to guide future work to get cheaper low cost investment. From our study the interesting configuration to the next development is D configuration with methanol yield 112 ton/day and capital cost with 526.4 10{sup 6} IDR. The configuration of D with non-discounted and discounted rate had the break-even point approximately six and eight years.« less

Romania program targets methanol and Fischer-Tropsch research

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

Not Available

1987-03-01

Currently, the chemical organic industry, the petrochemical and engine fuels industry in Romania are entirely based on hydrocarbons from oil. To reduce the oil dependence of this sector and to ensure the stipulated growth rate of 8-9%, research and development programs have been set up with a view to the diversification of raw materials. In research on hydrocarbons from alcohol conversion, three process variants are known, i.e. olefins from methanol, gasolines from methanol and a combined gasolines and aromatic hydrocarbons from methanol. The Romanian process of methanol conversion to hydrocarbons is very flexible, with all the variants mentioned being carriedmore » out in the same plant by modifying the catalysts. In research on hydrocarbons from synthesis gas a modern process is being developed for gasification of brown coal in a fluidized bed, under pressure, in the presence of oxygen and water vapors. In the field of carbon oxide hydrogenation, studies have been carried out on selective Fischer-Tropsch processes in which the reaction products are high value hydrocarbon fractions.« less

Process for the conversion of carbonaceous feedstocks to particulate carbon and methanol

DOEpatents

Steinberg, M.; Grohse, E.W.

1995-06-27

A process is described for the production of a pollutant-free particulate carbon (i.e., a substantially ash-, sulfur- and nitrogen-free carbon) from carbonaceous feedstocks. The basic process involves de-oxygenating one of the gas streams formed in a cyclic hydropyrolysis-methane pyrolysis process in order to improve conversion of the initial carbonaceous feedstock. De-oxygenation is effected by catalytically converting carbon monoxide, carbon dioxide, and hydrogen contained in one of the pyrolysis gas streams, preferably the latter, to a methanol co-product. There are thus produced two products whose use is known per se, viz., a substantially pollutant-free particulate carbon black and methanol. These products may be admixed in the form of a liquid slurry of carbon black in methanol. 3 figs.

HYNOL PROCESS ENGINEERING: PROCESS CONFIGURATION, SITE PLAN, AND EQUIPMENT DESIGN

EPA Science Inventory

The report describes the design of the hydropyrolysis reactor system of the Hynol process. (NOTE: A bench scale methanol production facility is being constructed to demonstrate the technical feasibility of producing methanol from biomass using the Hynol process. The plant is bein...

Methanol from CO2 by organo-cocatalysis: CO2 capture and hydrogenation in one process step.

PubMed

Reller, Christian; Pöge, Matthias; Lißner, Andreas; Mertens, Florian O R L

2014-12-16

Carbon dioxide chemically bound to alcohol-amines was hydrogenated to methanol under retrieval of these industrially used CO2 capturing reagents. The energetics of the process can be seen as a partial cancellation of the exothermic heat of reaction of the hydrogenation with the endothermic one of the CO2 release from the capturing reagent. The process provides a means to significantly improve the energy efficiency of CO2 to methanol conversions.

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

Martinez-Guerra, Edith; Gude, Veera Gnaneswar, E-mail: gude@cee.msstate.edu

Highlights: • Pulse sonication effect on transesterification of waste vegetable oil was studied. • Effects of ethanol, methanol, and alcohol mixtures on FAMEs yield were evaluated. • Effect of ultrasonic intensity, power density, and its output rates were evaluated. • Alcohol mixtures resulted in higher biodiesel yields due to better solubility. - Abstract: This study reports on the effects of direct pulse sonication and the type of alcohol (methanol and ethanol) on the transesterification reaction of waste vegetable oil without any external heating or mechanical mixing. Biodiesel yields and optimum process conditions for the transesterification reaction involving ethanol, methanol, andmore » ethanol–methanol mixtures were evaluated. The effects of ultrasonic power densities (by varying sample volumes), power output rates (in W), and ultrasonic intensities (by varying the reactor size) were studied for transesterification reaction with ethanol, methanol and ethanol–methanol (50%-50%) mixtures. The optimum process conditions for ethanol or methanol based transesterification reaction of waste vegetable oil were determined as: 9:1 alcohol to oil ratio, 1% wt. catalyst amount, 1–2 min reaction time at a power output rate between 75 and 150 W. It was shown that the transesterification reactions using ethanol–methanol mixtures resulted in biodiesel yields as high as >99% at lower power density and ultrasound intensity when compared to ethanol or methanol based transesterification reactions.« less

Gasoline from coal in the state of Illinois: feasibility study. Volume I. Design. [KBW gasification process, ICI low-pressure methanol process and Mobil M-gasoline process

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

Not Available

1980-01-01

Volume 1 describes the proposed plant: KBW gasification process, ICI low-pressure methanol process and Mobil M-gasoline process, and also with ancillary processes, such as oxygen plant, shift process, RECTISOL purification process, sulfur recovery equipment and pollution control equipment. Numerous engineering diagrams are included. (LTN)

Compact Fuel-Cell System Would Consume Neat Methanol

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram; Kindler, Andrew; Valdez, Thomas

2007-01-01

In a proposed direct methanol fuel-cell electric-power-generating system, the fuel cells would consume neat methanol, in contradistinction to the dilute aqueous methanol solutions consumed in prior direct methanol fuel-cell systems. The design concept of the proposed fuel-cell system takes advantage of (1) electro-osmotic drag and diffusion processes to manage the flows of hydrogen and water between the anode and the cathode and (2) evaporative cooling for regulating temperature. The design concept provides for supplying enough water to the anodes to enable the use of neat methanol while ensuring conservation of water for the whole fuel-cell system.

Rapid detection of methanol in artisanal alcoholic beverages

NASA Astrophysics Data System (ADS)

de Goes, R. E.; Muller, M.; Fabris, J. L.

2015-09-01

In the industry of artisanal beverages, uncontrolled production processes may result in contaminated products with methanol, leading to risks for consumers. Owing to the similar odor of methanol and ethanol, as well as their common transparency, the distinction between them is a difficult task. Contamination may also occur deliberately due to the lower price of methanol when compared to ethanol. This paper describes a spectroscopic method for methanol detection in beverages based on Raman scattering and Principal Component Analysis. Associated with a refractometric assessment of the alcohol content, the method may be applied in field for a rapid detection of methanol presence.

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

Fishkind, H.H.

The overall environmental impact of the eucalyptus to methanol energy system in Florida is assessed. The environmental impacts associated with the following steps of the process are considered: (1) the greenhouse and laboratory; (2) the eucalyptus plantation; (3) transporting the mature logs; (4) the hammermill; and (5) the methanol synthesis plant. Next, the environmental effects of methanol as an undiluted motor fuel, methanol as a gasoline blend, and gasoline as motor fuels are compared. Finally, the environmental effects of the eucalypt gasification/methanol synthesis system are compared to the coal liquefaction and conversion system.

Indonesia to build methanol plant

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

Alperowicz, N.

1992-08-05

P.T. Kaltim Methanol Industri (Jakarta), a company set up to build a new methanol plant in Indonesia, expects to award contracts for the construction of a new plant, Indonesia's second methanol unit, by the end of this year. P.T. Kaltim Methanol is a private company owned by P.T. Humpuss, an industrial group active in transport, airlines, and shipping of LNG and methanol. The 2,000-m.t./day plant will be built at Bontang, Kalimantan Island, close to the fertilizer producer P.T. Pupuk Kaltim and near the country's largest natural gas reserves. The site is also a deepsea port, handy for transportation of readymore » product. Three groups are in discussions with the investor on plant supply as well as methanol offtake deals. They are H G/Kockner; John Brown/Davy/Lucky Goldstar, offering the ICI process independently; and Lurgi/Metallgesellschaft (MG), proposing the Lurgi process. At least 60% of the output is expected to be exported, and both ICI and MG are understood to be interested in selling product from the future plant. Japan, Southeast Asia, and the US are targeted.« less

Potential of Immobilized Whole-Cell Methylocella tundrae as a Biocatalyst for Methanol Production from Methane.

PubMed

Mardina, Primata; Li, Jinglin; Patel, Sanjay K S; Kim, In-Won; Lee, Jung-Kul; Selvaraj, Chandrabose

2016-07-28

Methanol is a versatile compound that can be biologically synthesized from methane (CH4) by methanotrophs using a low energy-consuming and environment-friendly process. Methylocella tundrae is a type II methanotroph that can utilize CH4 as a carbon and energy source. Methanol is produced in the first step of the metabolic pathway of methanotrophs and is further oxidized into formaldehyde. Several parameters must be optimized to achieve high methanol production. In this study, we optimized the production conditions and process parameters for methanol production. The optimum incubation time, substrate, pH, agitation rate, temperature, phosphate buffer and sodium formate concentration, and cell concentration were determined to be 24 h, 50% CH4, pH 7, 150 rpm, 30°C, 100 mM and 50 mM, and 18 mg/ml, respectively. The optimization of these parameters significantly improved methanol production from 0.66 to 5.18 mM. The use of alginate-encapsulated cells resulted in enhanced methanol production stability and reusability of cells after five cycles of reuse under batch culture conditions.

Selection of Sustainable Processes using Sustainability Footprint Method: A Case Study of Methanol Production from Carbon Dioxide

EPA Science Inventory

Chemical products can be obtained by process pathways involving varying amounts and types of resources, utilities, and byproduct formation. When such competing process options such as six processes for making methanol as are considered in this study, it is necessary to identify t...

CARNOL PROCESS FOR CO2 MITIGATION FROM POWER PLANTS AND THE TRANSFORMATION SECTOR

EPA Science Inventory

The report describes an alternative mitigation process that would convert waste carbon dioxide (CO2) to carbon an methanol using natural gas as process feedstock. The process yields 1 mole of methanol from each mole of CO2 recovered, resulting in a net zero CO2 emission when the ...

Comparison of fluoride intercalation/de-intercalation processes on graphite electrodes in aqueous and aqueous methanolic HF media

NASA Astrophysics Data System (ADS)

Noel, M.; Santhanam, R.; Francisca Flora, M.

The solvent can play a major role in the intercalation/de-intercalation process and the stability of graphite substrates towards this process. This fact is established in the present work that involves fluoride intercalation/de-intercatlation on graphite electrodes in aqueous and aqueous methanolic HF solutions where the HF concentration is varied between 1.0 and 18.0 M. In addition to cyclic voltammetry and potentiostatic polarization, open-circuit potential decay measurements, scanning electron microscopy and X-ray diffraction measurements have been employed. In general, addition of methanol and increasing concentration of HF raise the overall intercalation/de-intercalation efficiency. Methanol is adsorbed preferentially on the graphite lattice and, hence, suppresses both oxygen evolution and the formation of passive graphite oxides. In 15.0 M HF, the optimum methanol concentration is 5 vol.%. This suggests that, in addition to the adsorption effect, there is some weakening of the structured water molecules that facilitates the solvated fluoride ions for efficient intercalation.

Effects of Biofuel and Variant Ambient Pressure on FlameDevelopment and Emissions of Gasoline Engine.

NASA Astrophysics Data System (ADS)

Hashim, Akasha; Khalid, Amir; Sapit, Azwan; Samsudin, Dahrum

2016-11-01

There are many technologies about exhaust emissions reduction for wide variety of spark ignition (SI) engine have been considered as the improvement throughout the combustion process. The stricter on legislation of emission and demands of lower fuel consumption needs to be priority in order to satisfy the demand of emission quality. Besides, alternative fuel such as methanol-gasoline blends is used as working fluid in this study due to its higher octane number and self-sustain concept which capable to contribute positive effect to the combustion process. The purpose of this study is to investigate the effects of methanol-gasoline fuel with different blending ratio and variant ambient pressures on flame development and emission for gasoline engine. An experimental study is carried towards to the flame development of methanol-gasoline fuel in a constant volume chamber. Schlieren optical visualization technique is a visual process that used when high sensitivity is required to photograph the flow of fluids of varying density used for captured the combustion images in the constant volume chamber and analysed through image processing technique. Apart from that, the result showed combustion burn rate increased when the percentage of methanol content in gasoline increased. Thus, high percentage of methanol-gasoline blends gave greater flame development area. Moreover, the emissions of CO, NOX and HC are performed a reduction when the percentage of methanol content in gasoline is increased. Contrarily, the emission of Carbon dioxide, CO2 is increased due to the combustion process is enhanced.

Heterogeneous Chemistry Involving Methanol in Tropospheric Clouds

NASA Technical Reports Server (NTRS)

Tabazadeh, A.; Yokelson, R. J.; Singh, H. B.; Hobbs, P. V.; Crawford, J. H.; Iraci, L. T.

2004-01-01

In this report we analyze airborne measurements to suggest that methanol in biomass burning smoke is lost heterogeneously in clouds. When a smoke plume intersected a cumulus cloud during the SAFARI 2000 field project, the observed methanol gas phase concentration rapidly declined. Current understanding of gas and aqueous phase chemistry cannot explain the loss of methanol documented by these measurements. Two plausible heterogeneous reactions are proposed to explain the observed simultaneous loss and production of methanol and formaldehyde, respectively. If the rapid heterogeneous processing of methanol, seen in a cloud impacted by smoke, occurs in more pristine clouds, it could affect the oxidizing capacity of the troposphere on a global scale.

Fuel Processing System for a 5kW Methanol Fuel Cell Power Unit.

DTIC Science & Technology

1985-11-27

report documents the development and design of a 5kW neat methanol reformer for phosphoric acid fuel cell power plants . The reformer design was based...VAPORIZATION OF METHANOL ........... 4.3 REFORMING/SHIFT CATALYST BED ......... 2 5.0 COMPONENT TESTING............... 5.1 COMBUSTION TUBE...69 36 Catalyst Bed Temperature Profile Before and After Transient ................. 70 37 Assembly -5kw Neat Methanol Reformer. ......... 72 Page No

Biofiltration of methanol vapor

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

Shareefdeen, Z.; Baltzis, B.C.; Oh, Youngsook

1993-03-05

Biofiltration of solvent and fuel vapors may offer a cost-effective way to comply with increasingly strict air emission standards. An important step in the development of this technology is to derive and validate mathematical models of the biofiltration process for predictive and scaleup calculations. For the study of methanol vapor biofiltration, an 8-membered bacterial consortium was obtained from methanol-exposed soil. The bacteria were immobilized on solid support and packed into a 5-cm diameter, 60-cm-high column provided with appropriate flowmeters and sampling ports. The solid support was prepared by mixing two volumes of peat with three volumes of perlite particles. Twomore » series of experiments were performed. In the first, the inlet methanol concentration was kept constant while the superficial air velocity was varied from run to run. In the second series, the air flow rate (velocity) was kept constant while the inlet methanol concentration was varied. The unit proved effective in removing methanol at rates up to 112.8 g h[sup [minus]1] m[sup [minus]3] packing. A mathematical model has been derived and validated. The model described and predicted experimental results closely. Both experimental data and model predictions suggest that the methanol biofiltration process was limited by oxygen diffusion and methanol degradation kinetics.« less

Physiological response of Pichia pastoris GS115 to methanol-induced high level production of the Hepatitis B surface antigen: catabolic adaptation, stress responses, and autophagic processes

PubMed Central

2012-01-01

Background Pichia pastoris is an established eukaryotic host for the production of recombinant proteins. Most often, protein production is under the control of the strong methanol-inducible aox1 promoter. However, detailed information about the physiological alterations in P. pastoris accompanying the shift from growth on glycerol to methanol-induced protein production under industrial relevant conditions is missing. Here, we provide an analysis of the physiological response of P. pastoris GS115 to methanol-induced high-level production of the Hepatitis B virus surface antigen (HBsAg). High product titers and the retention of the protein in the endoplasmic reticulum (ER) are supposedly of major impact on the host physiology. For a more detailed understanding of the cellular response to methanol-induced HBsAg production, the time-dependent changes in the yeast proteome and ultrastructural cell morphology were analyzed during the production process. Results The shift from growth on glycerol to growth and HBsAg production on methanol was accompanied by a drastic change in the yeast proteome. In particular, enzymes from the methanol dissimilation pathway started to dominate the proteome while enzymes from the methanol assimilation pathway, e.g. the transketolase DAS1, increased only moderately. The majority of methanol was metabolized via the energy generating dissimilatory pathway leading to a corresponding increase in mitochondrial size and numbers. The methanol-metabolism related generation of reactive oxygen species induced a pronounced oxidative stress response (e.g. strong increase of the peroxiredoxin PMP20). Moreover, the accumulation of HBsAg in the ER resulted in the induction of the unfolded protein response (e.g. strong increase of the ER-resident disulfide isomerase, PDI) and the ER associated degradation (ERAD) pathway (e.g. increase of two cytosolic chaperones and members of the AAA ATPase superfamily) indicating that potential degradation of HBsAg could proceed via the ERAD pathway and through the proteasome. However, the amount of HBsAg did not show any significant decline during the cultivation revealing its general protection from proteolytic degradation. During the methanol fed-batch phase, induction of vacuolar proteases (e.g. strong increase of APR1) and constitutive autophagic processes were observed. Vacuolar enclosures were mainly found around peroxisomes and not close to HBsAg deposits and, thus, were most likely provoked by peroxisomal components damaged by reactive oxygen species generated by methanol oxidation. Conclusions In the methanol fed-batch phase P. pastoris is exposed to dual stress; stress resulting from methanol degradation and stress resulting from the production of the recombinant protein leading to the induction of oxidative stress and unfolded protein response pathways, respectively. Finally, the modest increase of methanol assimilatory enzymes compared to the strong increase of methanol dissimilatory enzymes suggests here a potential to increase methanol incorporation into biomass/product through metabolic enhancement of the methanol assimilatory pathway. PMID:22873405

Mobil process converts methanol to high-quality synthetic gasoline

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

Wood, A.

1978-12-11

If production of gasoline from coal becomes commercially attractive in the United States, a process under development at the Mobil Research and Development Corp. may compete with better known coal liquefaction processes. Mobil process converts methanol to high-octane, unleaded gasoline; methanol can be produced commercially from coal. If gasoline is the desired product, the Mobil process offers strong technical and cost advantages over H-coal, Exxon donor solvent, solvent-refined coal, and Fischer--Tropsch processes. The cost analysis, contained in a report to the Dept. of Energy, concludes that the Mobil process produces more-expensive liquid products than any other liquefaction process except Fischer--Tropsch.more » But Mobil's process produces ready-to-use gasoline, while the others produce oils which require further expensive refining to yield gasoline. Disadvantages and advantages are discussed.« less

Methanol induces cytosolic calcium variations, membrane depolarization and ethylene production in arabidopsis and tobacco.

PubMed

Tran, Daniel; Dauphin, Aurélien; Meimoun, Patrice; Kadono, Takashi; Nguyen, Hieu T H; Arbelet-Bonnin, Delphine; Zhao, Tingting; Errakhi, Rafik; Lehner, Arnaud; Kawano, Tomonori; Bouteau, François

2018-03-20

Methanol is a volatile organic compound released from plants through the action of pectin methylesterases (PMEs), which demethylesterify cell wall pectins. Plant PMEs play a role in developmental processes but also in responses to herbivory and infection by fungal or bacterial pathogens. However, molecular mechanisms that explain how methanol could affect plant defences remain poorly understood. Using cultured cells and seedlings from Arabidopsis thaliana and tobacco BY2 expressing the apoaequorin gene, allowing quantification of cytosolic Ca2+, a reactive oxygen species (ROS) probe (CLA, Cypridina luciferin analogue) and electrophysiological techniques, we followed early plant cell responses to exogenously supplied methanol applied as a liquid or as volatile. Methanol induces cytosolic Ca2+ variations that involve Ca2+ influx through the plasma membrane and Ca2+ release from internal stores. Our data further suggest that these Ca2+ variations could interact with different ROS and support a signalling pathway leading to well known plant responses to pathogens such as plasma membrane depolarization through anion channel regulation and ethylene synthesis. Methanol is not only a by-product of PME activities, and our data suggest that [Ca2+]cyt variations could participate in signalling processes induced by methanol upstream of plant defence responses.

On the classification of diseases.

PubMed

Smart, Benjamin

2014-08-01

Identifying the necessary and sufficient conditions for individuating and classifying diseases is a matter of great importance in the fields of law, ethics, epidemiology, and of course, medicine. In this paper, I first propose a means of achieving this goal, ensuring that no two distinct disease-types could correctly be ascribed to the same disease-token. I then posit a metaphysical ontology of diseases-that is, I give an account of what a disease is. This is essential to providing the most effective means of interfering with disease processes. Following existing work in the philosophy of medicine and epidemiology (primarily Christopher Boorse; Caroline Whitbeck; Alexander Broadbent), philosophy of biology (Joseph LaPorte; D.L. Hull), conditional analyses of causation (J.L. Mackie; David Lewis), and recent literature on dispositional essentialism (Stephen Mumford and Rani Anjum; Alexander Bird), I endorse a dispositional conception of disease. Following discussion of various conceptions of disease-identity, their relations to the clinical and pathological effects of the diseases in question, and how diseases are treated, I conclude (i) that diseases should be individuated by their causes, and (ii) that diseases are causal processes best seen as simultaneously acting sequences of mutually manifesting dispositions.

Crystal morphology optimization of thiamine hydrochloride in solvent system: Experimental and molecular dynamics simulation studies

NASA Astrophysics Data System (ADS)

Yang, Yang; Han, Dandan; Du, Shichao; Wu, Songgu; Gong, Junbo

2018-01-01

Thiamine hydrochloride (THCL) was produced in methanol accompanied with agglomeration in industry, the plate like morphology of THCL in methanol was not deserve to have a good quality. Selecting a suitable solvent should be considered because solvent could be one of the essential factors to impact morphology. Methanol and methanol/ethyl acetate solvent (0.2 vol fraction of methanol) was selected as the solvent system in reactive crystallization of THCL. The experiment results show the THCL crystal morphology in methanol/ethyl acetate solvent system was granular and more regular than that in methanol. In order to explicate the different crystal morphology in different solvents, molecular dynamics (MD) simulation was introduced to simulate crystal morphology in different solvents. The attachment energy (AE) model was employed to investigate the morphology of THCL under vacuum conditions, methanol and methanol/ethyl acetate solvent conditions, respectively. The simulation crystal morphology was in a good agreement with that of experimented. The particle of THCL in methanol/ethyl acetate solvent has less tendency to agglomeration, and then it is favorable to the downstream process, such as filtration, storage and transportation.

UV Photodesorption of Methanol in Pure and CO-rich Ices: Desorption Rates of the Intact Molecule and of the Photofragments

NASA Astrophysics Data System (ADS)

Bertin, Mathieu; Romanzin, Claire; Doronin, Mikhail; Philippe, Laurent; Jeseck, Pascal; Ligterink, Niels; Linnartz, Harold; Michaut, Xavier; Fillion, Jean-Hugues

2016-02-01

Wavelength-dependent photodesorption rates have been determined using synchrotron radiation for condensed pure and mixed methanol ice in the 7-14 eV range. The VUV photodesorption of intact methanol molecules from pure methanol ices is found to be of the order of 10-5 molecules/photon, that is two orders of magnitude below what is generally used in astrochemical models. This rate gets even lower (<10-6 molecules/photon) when the methanol is mixed with CO molecules in the ices. This is consistent with a picture in which photodissociation and recombination processes are at the origin of intact methanol desorption from pure CH3OH ices. Such low rates are explained by the fact that the overall photodesorption process is dominated by the desorption of the photofragments CO, CH3, OH, H2CO, and CH3O/CH2OH, whose photodesorption rates are given in this study. Our results suggest that the role of the photodesorption as a mechanism to explain the observed gas phase abundances of methanol in cold media is probably overestimated. Nevertheless, the photodesorption of radicals from methanol-rich ices may stand at the origin of the gas phase presence of radicals such as CH3O, therefore, opening new gas phase chemical routes for the formation of complex molecules.

Hydrogenation of silyl formates: sustainable production of silanol and methanol from hydrosilane and carbon dioxide.

PubMed

Koo, Jangwoo; Kim, Seung Hyo; Hong, Soon Hyeok

2018-05-10

A new process for simultaneously obtaining two chemical building blocks, methanol and silanol, was realized starting from silyl formates which can be derived from silane and carbon dioxide. Understanding the reaction mechanism enabled us to improve the reaction efficiency by the addition of a small amount of methanol.

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, J.W.; Wender, I.; Palekar, V.M.

1995-01-31

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Molecular mechanism of the adsorption process of an iodide anion into liquid-vapor interfaces of water-methanol mixtures

NASA Astrophysics Data System (ADS)

Annapureddy, Harsha V. R.; Dang, Liem X.

2012-12-01

To enhance our understanding of the molecular mechanism of ion adsorption to the interface of mixtures, we systematically carried out a free energy calculations study involving the transport of an iodide anion across the interface of a water-methanol mixture. Many body affects are taken into account to describe the interactions among the species. The surface propensities of I- at interfaces of pure water and methanol are well understood. In contrast, detailed knowledge of the molecular level adsorption process of I- at aqueous mixture interfaces has not been reported. In this paper, we explore how this phenomenon will be affected for mixed solvents with varying compositions of water and methanol. Our potential of mean force study as function of varying compositions indicated that I- adsorption free energies decrease from pure water to pure methanol but not linearly with the concentration of methanol. We analyze the computed density profiles and hydration numbers as a function of concentrations and ion positions with respect to the interface to further explain the observed phenomenon.

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1995-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Gas processing developments. Why not use methanol for hydrate control

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

Nielsen, R.B.; Bucklin, R.W.

1983-04-01

Hydrate formation in turboexpander plants can be avoided more economically by using methanol than by using solid bed dehydration. Although the first turboexpander plant used methanol, most expander installations now have used solid bed dehydration. The reasons are obscure, since methanol often grants greater ease of operation as well as lower capital and operating costs, especially when the water in the feed gas is low or when recompression is required. Natural gas generally contains water before processing. High pressure, low temperature, or both favor the combination of water with light gases to form hydrates. Free water always must be presentmore » for hydrates to form. Hydrates cause problems by plugging pipelines, valves, and other process equipment. Therefore, proper equipment design requires accurate prediction of the limiting conditions at which hydrates are formed anytime a gas stream containing hydrate formers and free water is cooled below 80 F. (16 refs.)« less

Efficient green methanol synthesis from glycerol

NASA Astrophysics Data System (ADS)

Haider, Muhammad H.; Dummer, Nicholas F.; Knight, David W.; Jenkins, Robert L.; Howard, Mark; Moulijn, Jacob; Taylor, Stuart H.; Hutchings, Graham J.

2015-12-01

The production of biodiesel from the transesterification of plant-derived triglycerides with methanol has been commercialized extensively. Impure glycerol is obtained as a by-product at roughly one-tenth the mass of the biodiesel. Utilization of this crude glycerol is important in improving the viability of the overall process. Here we show that crude glycerol can be reacted with water over very simple basic or redox oxide catalysts to produce methanol in high yields, together with other useful chemicals, in a one-step low-pressure process. Our discovery opens up the possibility of recycling the crude glycerol produced during biodiesel manufacture. Furthermore, we show that molecules containing at least two hydroxyl groups can be converted into methanol, which demonstrates some aspects of the generality of this new chemistry.

Metabolic construction strategies for direct methanol utilization in Saccharomyces cerevisiae.

PubMed

Dai, Zhongxue; Gu, Honglian; Zhang, Shangjie; Xin, Fengxue; Zhang, Wenming; Dong, Weiliang; Ma, Jiangfeng; Jia, Honghua; Jiang, Min

2017-12-01

The aim of this study was to metabolically construct Saccharomyces cerevisiae for achievement of direct methanol utilization and value added product (mainly pyruvate) production. After successful integration of methanol oxidation pathway originated from Pichia pastoris into the chromosome of S. cerevisiae, the recombinant showed 1.04g/L consumption of methanol and 3.13% increase of cell growth (OD 600 ) when using methanol as the sole carbon source. Moreover, 0.26g/L of pyruvate was detected in the fermentation broth. The supplementation of 1g/L yeast extract could further improve cell growth with increase of 11.70% and methanol consumption to 2.35g/L. This represents the first genetically modified non-methylotrophic eukaryotic microbe for direct methanol utilization and would be of great value concerning the development of biotechnological processes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Method and system for producing lower alcohols. [Heteropolyatomic lead salt coated with alkali metal formate

DOEpatents

Rathke, J.W.; Klingler, R.J.; Heiberger, J.J.

1983-09-26

It is an object of the present invention to provide an improved catalyst for the reaction of carbon monoxide with water to produce methanol and other lower alcohols. It is a further object to provide a process for the production of methanol from carbon monoxide and water in which a relatively inexpensive catalyst permits the reaction at low pressures. It is also an object to provide a process for the production of methanol from carbon monoxide and water in which a relatively inexpensive catalyst permits the reaction at low pressures. It is also an object to provide a process for the production of methanol in which ethanol is also directly produced. It is another object to provide a process for the production of mixtures of methanol with ethanol and propanol from the reaction of carbon monoxide and water at moderate pressure with inexpensive catalysts. It is likewise an object to provide a system for the catalytic production of lower alcohols from the reaction of carbon monoxide and water at moderate pressure with inexpensive catalysts. In accordance with the present invention, a catalyst is provided for the reaction of carbon monoxide and water to produce lower alcohols. The catalyst includes a lead heteropolyatomic salt in mixture with a metal formate or a precursor to a metal formate.

Investigation of the In-Situ Oxidation of Methanol in Fuel Cells.

DTIC Science & Technology

1981-09-01

ability of the catalyst to tolerate carbon monoxide. Finally, a performance curve was obtained for the anodic oxidation of methanol : CH3OH ... CH3OH + H20 •» C02 + 3H2 In present methanol -air fuel cell power plants , the steam reforming process is usually carried out in a unit which is...KCY YIO"(CS (Continue on reverse ride it neeessnry and identity ay block number) Fuel Cell Platinum Catalysts Methanol Direct Oxidation Internal

Methanol from Wood Waste: A Technical and Economic Study.

DTIC Science & Technology

1977-06-01

percent of the gas is converted to methanol , the balance passing as inerts to the boiler. The reaction is as follows: catalyst 2H + CO ’ CH3OH 2 *-3...the boiler. Catalyst life is expected to be 6 years for methanol synthesis and 2 to 3 years for the shift reactor . PLANT SIZE In a chemical processing...percent of methyl alcohol ( methanol ) in gasoline for automotive use. / At a current consumption rate of 110 billion gallons per year (gpy), 11 billion

SYSTEM AND PROCESS FOR PRODUCTION OF METHANOL FROM COMBINED WIND TURBINE AND FUEL CELL POWER

EPA Science Inventory

The paper examines an integrated use of ultra-clean wind turbines and high temperature fuel cells to produce methanol, especially for transportation purposes. The principal utility and application of the process is the production of transportation fuel from domestic resources to ...

EVALUATION OF A PROCESS TO CONVERT BIOMASS TO METHANOL FUEL

EPA Science Inventory

The report gives results of a review of the design of a reactor capable of gasifying approximately 50 lb/hr of biomass for a pilot-scale facility to develop, demonstrate, and evaluate the Hynol Process, a high-temperature, high-pressure method for converting biomass into methanol...

EVALUATION OF A PROCESS TO CONVERT BIOMASS TO METHANOL FUEL - PROJECT SUMMARY

EPA Science Inventory

The report gives results of a review of the design of a reactor capable of gasifying approximately 50 lb/hr of biomass for a pilot-scale facility to develop, demonstrate, and evaluate the Hynol Process, a high-temperature, high-pressure method for converting biomass into methanol...

Atmospheric deposition of methanol over the Atlantic Ocean

PubMed Central

Yang, Mingxi; Nightingale, Philip D.; Beale, Rachael; Liss, Peter S.; Blomquist, Byron; Fairall, Christopher

2013-01-01

In the troposphere, methanol (CH3OH) is present ubiquitously and second in abundance among organic gases after methane. In the surface ocean, methanol represents a supply of energy and carbon for marine microbes. Here we report direct measurements of air–sea methanol transfer along a ∼10,000-km north–south transect of the Atlantic. The flux of methanol was consistently from the atmosphere to the ocean. Constrained by the aerodynamic limit and measured rate of air–sea sensible heat exchange, methanol transfer resembles a one-way depositional process, which suggests dissolved methanol concentrations near the water surface that are lower than what were measured at ∼5 m depth, for reasons currently unknown. We estimate the global oceanic uptake of methanol and examine the lifetimes of this compound in the lower atmosphere and upper ocean with respect to gas exchange. We also constrain the molecular diffusional resistance above the ocean surface—an important term for improving air–sea gas exchange models. PMID:24277830

Methanol-enhanced removal and metabolic conversion of formaldehyde by a black soybean from formaldehyde solutions.

PubMed

Tan, Hao; Xiong, Yun; Li, Kun-Zhi; Chen, Li-Mei

2017-02-01

Methanol regulation of some biochemical and physiological characteristics in plants has been documented in several references. This study showed that the pretreatment of methanol with an appropriate concentration could stimulate the HCHO uptake by black soybean (BS) plants. The process of methanol-stimulated HCHO uptake by BS plants was optimized using the Central Composite Design and response surface methodology for the three variables, methanol concentration, HCHO concentration, and treatment time. Under optimized conditions, the best stimulation effect of methanol on HCHO uptake was obtained. 13 C-NMR analysis indicated that the H 13 CHO metabolism produced H 13 COOH, [2- 13 C]Gly, and [3- 13 C]Ser in BS plant roots. Methanol pretreatment enhanced the metabolic conversion of H 13 CHO in BS plant roots, which consequently increased HCHO uptake by BS plants. Therefore, methanol pretreatment might be used to increase HCHO uptake by plants in the phytoremediation of HCHO-polluted solutions.

Atmospheric deposition of methanol over the Atlantic Ocean.

PubMed

Yang, Mingxi; Nightingale, Philip D; Beale, Rachael; Liss, Peter S; Blomquist, Byron; Fairall, Christopher

2013-12-10

In the troposphere, methanol (CH3OH) is present ubiquitously and second in abundance among organic gases after methane. In the surface ocean, methanol represents a supply of energy and carbon for marine microbes. Here we report direct measurements of air-sea methanol transfer along a ∼10,000-km north-south transect of the Atlantic. The flux of methanol was consistently from the atmosphere to the ocean. Constrained by the aerodynamic limit and measured rate of air-sea sensible heat exchange, methanol transfer resembles a one-way depositional process, which suggests dissolved methanol concentrations near the water surface that are lower than what were measured at ∼5 m depth, for reasons currently unknown. We estimate the global oceanic uptake of methanol and examine the lifetimes of this compound in the lower atmosphere and upper ocean with respect to gas exchange. We also constrain the molecular diffusional resistance above the ocean surface-an important term for improving air-sea gas exchange models.

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

Roy, Santanu; Dang, Liem X.

In this paper, we present the first computer simulation of methanol exchange dynamics between the first and second solvation shells around different cations and anions. After water, methanol is the most frequently used solvent for ions. Methanol has different structural and dynamical properties than water, so its ion solvation process is different. To this end, we performed molecular dynamics simulations using polarizable potential models to describe methanol-methanol and ion-methanol interactions. In particular, we computed methanol exchange rates by employing the transition state theory, the Impey-Madden-McDonald method, the reactive flux approach, and the Grote-Hynes theory. We observed that methanol exchange occursmore » at a nanosecond time scale for Na+ and at a picosecond time scale for other ions. We also observed a trend in which, for like charges, the exchange rate is slower for smaller ions because they are more strongly bound to methanol. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. The calculations were carried out using computer resources provided by the Office of Basic Energy Sciences.« less

UV PHOTODESORPTION OF METHANOL IN PURE AND CO-RICH ICES: DESORPTION RATES OF THE INTACT MOLECULE AND OF THE PHOTOFRAGMENTS

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

Bertin, Mathieu; Doronin, Mikhail; Philippe, Laurent

2016-02-01

Wavelength-dependent photodesorption rates have been determined using synchrotron radiation for condensed pure and mixed methanol ice in the 7–14 eV range. The VUV photodesorption of intact methanol molecules from pure methanol ices is found to be of the order of 10{sup −5} molecules/photon, that is two orders of magnitude below what is generally used in astrochemical models. This rate gets even lower (<10{sup −6} molecules/photon) when the methanol is mixed with CO molecules in the ices. This is consistent with a picture in which photodissociation and recombination processes are at the origin of intact methanol desorption from pure CH{sub 3}OHmore » ices. Such low rates are explained by the fact that the overall photodesorption process is dominated by the desorption of the photofragments CO, CH{sub 3}, OH, H{sub 2}CO, and CH{sub 3}O/CH{sub 2}OH, whose photodesorption rates are given in this study. Our results suggest that the role of the photodesorption as a mechanism to explain the observed gas phase abundances of methanol in cold media is probably overestimated. Nevertheless, the photodesorption of radicals from methanol-rich ices may stand at the origin of the gas phase presence of radicals such as CH{sub 3}O, therefore, opening new gas phase chemical routes for the formation of complex molecules.« less

Surface-induced dissociation of methanol cations: A non-ergodic process

DOE PAGES

Shukla, Anil K.

2017-09-01

Here, dissociation of methanol molecular cations, CH 3OH +, to CH 2OH + on collision with a self-assembled monolayer surface of fluorinated alkyl thiol on gold 111 crystal has been studied at 12.5 eV collision energy. Two energetically and spatially distinct processes contribute to the dissociation process: one involving loss of very large amount of energy approaching the initial kinetic energy of the primary ions with scattering of fragment ions over a broad angular range between surface normal and surface parallel while the second process results from small amount of energy loss with fragment ions scattered over a narrow angularmore » range close to the surface parallel. There is a third process with relatively small contribution to total dissociation whose characteristics are very similar to the low energy loss process. Finally, these results demonstrate that surface-induced dissociation of methanol cations via hydrogen loss is non-ergodic.« less

Surface-induced dissociation of methanol cations: A non-ergodic process

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

Shukla, Anil K.

Here, dissociation of methanol molecular cations, CH 3OH +, to CH 2OH + on collision with a self-assembled monolayer surface of fluorinated alkyl thiol on gold 111 crystal has been studied at 12.5 eV collision energy. Two energetically and spatially distinct processes contribute to the dissociation process: one involving loss of very large amount of energy approaching the initial kinetic energy of the primary ions with scattering of fragment ions over a broad angular range between surface normal and surface parallel while the second process results from small amount of energy loss with fragment ions scattered over a narrow angularmore » range close to the surface parallel. There is a third process with relatively small contribution to total dissociation whose characteristics are very similar to the low energy loss process. Finally, these results demonstrate that surface-induced dissociation of methanol cations via hydrogen loss is non-ergodic.« less

A quantitative study of methanol/sorbitol co-feeding process of a Pichia pastoris Mut+/pAOX1-lacZ strain

PubMed Central

2013-01-01

Background One of the main challenges for heterologous protein production by the methylotrophic yeast Pichia pastoris at large-scale is related to its high oxygen demand. A promising solution is a co-feeding strategy based on a methanol/sorbitol mixture during the induction phase. Nonetheless, a deep understanding of the cellular physiology and the regulation of the AOX1 promoter, used to govern heterologous protein production, during this co-feeding strategy is still scarce. Results Transient continuous cultures with a dilution rate of 0.023 h-1 at 25°C were performed to quantitatively assess the benefits of a methanol/sorbitol co-feeding process with a Mut+ strain in which the pAOX1-lacZ construct served as a reporter gene. Cell growth and metabolism, including O2 consumption together with CO2 and heat production were analyzed with regard to a linear change of methanol fraction in the mixed feeding media. In addition, the regulation of the promoter AOX1 was investigated by means of β-galactosidase measurements. Our results demonstrated that the cell-specific oxygen consumption (qO2) could be reduced by decreasing the methanol fraction in the feeding media. More interestingly, maximal β-galactosidase cell-specific activity (>7500 Miller unit) and thus, optimal pAOX1 induction, was achieved and maintained in the range of 0.45 ~ 0.75 C-mol/C-mol of methanol fraction. In addition, the qO2 was reduced by 30% at most in those conditions. Based on a simplified metabolic network, metabolic flux analysis (MFA) was performed to quantify intracellular metabolic flux distributions during the transient continuous cultures, which further shed light on the advantages of methanol/sorbitol co-feeding process. Finally, our observations were further validated in fed-batch cultures. Conclusion This study brings quantitative insight into the co-feeding process, which provides valuable data for the control of methanol/sorbitol co-feeding, aiming at enhancing biomass and heterologous protein productivities under given oxygen supply. According to our results, β-galactosidase productivity could be improved about 40% using the optimally mixed feed. PMID:23565774

A quantitative study of methanol/sorbitol co-feeding process of a Pichia pastoris Mut⁺/pAOX1-lacZ strain.

PubMed

Niu, Hongxing; Jost, Laurent; Pirlot, Nathalie; Sassi, Hosni; Daukandt, Marc; Rodriguez, Christian; Fickers, Patrick

2013-04-08

One of the main challenges for heterologous protein production by the methylotrophic yeast Pichia pastoris at large-scale is related to its high oxygen demand. A promising solution is a co-feeding strategy based on a methanol/sorbitol mixture during the induction phase. Nonetheless, a deep understanding of the cellular physiology and the regulation of the AOX1 promoter, used to govern heterologous protein production, during this co-feeding strategy is still scarce. Transient continuous cultures with a dilution rate of 0.023 h(-1) at 25°C were performed to quantitatively assess the benefits of a methanol/sorbitol co-feeding process with a Mut+ strain in which the pAOX1-lacZ construct served as a reporter gene. Cell growth and metabolism, including O2 consumption together with CO2 and heat production were analyzed with regard to a linear change of methanol fraction in the mixed feeding media. In addition, the regulation of the promoter AOX1 was investigated by means of β-galactosidase measurements. Our results demonstrated that the cell-specific oxygen consumption (qO2) could be reduced by decreasing the methanol fraction in the feeding media. More interestingly, maximal β-galactosidase cell-specific activity (>7500 Miller unit) and thus, optimal pAOX1 induction, was achieved and maintained in the range of 0.45 ~ 0.75 C-mol/C-mol of methanol fraction. In addition, the qO2 was reduced by 30% at most in those conditions. Based on a simplified metabolic network, metabolic flux analysis (MFA) was performed to quantify intracellular metabolic flux distributions during the transient continuous cultures, which further shed light on the advantages of methanol/sorbitol co-feeding process. Finally, our observations were further validated in fed-batch cultures. This study brings quantitative insight into the co-feeding process, which provides valuable data for the control of methanol/sorbitol co-feeding, aiming at enhancing biomass and heterologous protein productivities under given oxygen supply. According to our results, β-galactosidase productivity could be improved about 40% using the optimally mixed feed.

Methanol ice co-desorption as a mechanism to explain cold methanol in the gas-phase

NASA Astrophysics Data System (ADS)

Ligterink, N. F. W.; Walsh, C.; Bhuin, R. G.; Vissapragada, S.; van Scheltinga, J. Terwisscha; Linnartz, H.

2018-05-01

Context. Methanol is formed via surface reactions on icy dust grains. Methanol is also detected in the gas-phase at temperatures below its thermal desorption temperature and at levels higher than can be explained by pure gas-phase chemistry. The process that controls the transition from solid state to gas-phase methanol in cold environments is not understood. Aims: The goal of this work is to investigate whether thermal CO desorption provides an indirect pathway for methanol to co-desorb at low temperatures. Methods: Mixed CH3OH:CO/CH4 ices were heated under ultra-high vacuum conditions and ice contents are traced using RAIRS (reflection absorption IR spectroscopy), while desorbing species were detected mass spectrometrically. An updated gas-grain chemical network was used to test the impact of the results of these experiments. The physical model used is applicable for TW Hya, a protoplanetary disk in which cold gas-phase methanol has recently been detected. Results: Methanol release together with thermal CO desorption is found to be an ineffective process in the experiments, resulting in an upper limit of ≤ 7.3 × 10-7 CH3OH molecules per CO molecule over all ice mixtures considered. Chemical modelling based on the upper limits shows that co-desorption rates as low as 10-6 CH3OH molecules per CO molecule are high enough to release substantial amounts of methanol to the gas-phase at and around the location of the CO thermal desorption front in a protoplanetary disk. The impact of thermal co-desorption of CH3OH with CO as a grain-gas bridge mechanism is compared with that of UV induced photodesorption and chemisorption.

Synthesis of Magnetite Nanoparticles and Its Application As Electrode Material for the Electrochemical Oxidation of Methanol

NASA Astrophysics Data System (ADS)

Shah, Muhammad Tariq; Balouch, Aamna; Panah, Pirah; Rajar, Kausar; Mahar, Ali Muhammad; Khan, Abdullah; Jagirani, Muhammad Saqaf; Khan, Humaira

2018-06-01

In this study, magnetite (Fe3O4) nanoparticles were synthesized by a simple and facile chemical co-precipitation method at ambient laboratory conditions. The synthesized Fe3O4 nanostructures were characterized for their morphology, size, crystalline structure and component analysis using field emission scanning electron microscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, x-ray diffraction and electron dispersive x-ray spectroscopy. The Fe3O4 nanoparticles showed semi-spherical geometry with an average particle diameter up to 14 nm. The catalytic properties of Fe3O4 nanoparticles were evaluated for electrochemical oxidation of methanol. For this purpose, the magnetite NPs were coated on the surface of an indium tin oxide (ITO) electrode and used as a working electrode in the electrochemical oxidation of methanol. The effect of potential scan rate, the concentration of methanol, the volume of electrolyte and catalyst (Fe3O4 NPs) deposition volume was studied to get high peak current densities for methanol oxidation. The stability and selectivity of the fabricated electrode (Fe3O4/ITO) were also assessed during the electrochemical process. This study revealed that the Fe3O4/ITO electrode was highly stable and selective towards methanol electrochemical oxidation in basic (KOH) media. Bare ITO and Fe3O4 NPs modified glassy (Fe3O4/GCE) electrodes were also tested in the electro-oxidation study of methanol, but their peak current density responses were very low as compared to the Fe3O4/ITO electrode, which showed high electrocatalytic activity towards methanol oxidation under similar conditions. We hope that Fe3O4 nanoparticles (NPs) will be an alternative for methanol oxidation as compared to the expensive noble metals (Pt, Au, and Pd) for energy generation processes.

Biocatalytic conversion of methane to methanol as a key step for development of methane-based biorefineries.

PubMed

Hwang, In Yeub; Lee, Seung Hwan; Choi, Yoo Seong; Park, Si Jae; Na, Jeong Geol; Chang, In Seop; Kim, Choongik; Kim, Hyun Cheol; Kim, Yong Hwan; Lee, Jin Won; Lee, Eun Yeol

2014-12-28

Methane is considered as a next-generation carbon feedstock owing to the vast reserves of natural and shale gas. Methane can be converted to methanol by various methods, which in turn can be used as a starting chemical for the production of value-added chemicals using existing chemical conversion processes. Methane monooxygenase is the key enzyme that catalyzes the addition of oxygen to methane. Methanotrophic bacteria can transform methane to methanol by inhibiting methanol dehydrogenase. In this paper, we review the recent progress made on the biocatalytic conversion of methane to methanol as a key step for methane-based refinery systems and discuss future prospects for this technology.

Enhanced Ultraviolet Photon Capture in Ligand-Sensitized Nanocrystals

DOE PAGES

Agbo, Peter; Xu, Tao; Sturzbecher-Hoehne, Manuel; ...

2016-04-06

The small absorption cross sections (ϵ < 10 M -1 cm -1 ) characteristic of Laporte-forbidden transitions in the f-elements have limited the practical implementation of lanthanide nanoparticles in solar capture devices. And while various strategies designed to circumvent the problems of low f-f oscillator strengths have been investigated, comparatively little work has explored the utility of organic ligands with high absorption coefficients (ϵ ≈ 10 3 -10 5 M -1 cm -1 ) in sensitizing excited states in lanthanide nanocrystals. Here, we detail the photophysics of NaGd 1-x Eu x F 4 nanoparticles featuring surface display of the ligandmore » 3,4,3-LI(1,2-HOPO), an aromatic antenna functioning as the terminal light absorber in this system. The result is a ligand-nanocrystal hybrid that converts UV (250-360 nm) light into red Eu(III) luminescence with an external quantum yield of 3.3%. Here, we analyze this sensitization process, responsible for a 10 4 -fold increase in luminescence relative to metal-centered excitation, through a quantitative treatment of energy transfer between ligand and metal states.« less

Methanol: A Versatile Fuel for Immediate Use

ERIC Educational Resources Information Center

Reed, T. B.; Lerner, R. M.

1973-01-01

Advocates the large-scale production and use of methanol as a substitute for the diminishing reserves of low-cost petroleum resources. Describes the manufacturing process and advantages of the versatile fuel. (JR)

Transport properties of proton-exchange membranes: Effect of supercritical-fluid processing and chemical functionality

NASA Astrophysics Data System (ADS)

Pulido Ayazo

NafionRTM membranes commonly used in direct methanol fuel cells (DMFC), are tipically limited by high methanol permeability (also known as the cross-over limitation). These membranes have phase segregated sulfonated ionic domains in a perfluorinated backbone, which makes processing challenging and limited by phase equilibria considerations. This study used supercritical fluids (SCFs) as a processing alternative, since the gas-like mass transport properties of SCFs allow a better penetration into the membranes and the use of polar co-solvents influenced their morphology, fine-tuning the physical and transport properties in the membrane. Measurements of methanol permeability and proton conductivity were performed to the NafionRTM membranes processed with SCFs at 40ºC and 200 bar and the co-solvents as: acetone, tetrahydrofuran (THF), isopropyl alcohol, HPLC-grade water, acetic acid, cyclohexanone. The results obtained for the permeability data were of the order of 10 -8-10-9 cm2/s, two orders of magnitude lower than unprocessed Nafion. Proton conductivity results obtained using AC impedance electrochemical spectroscopy was between 0.02 and 0.09 S/cm, very similar to the unprocessed Nafion. SCF processing with ethanol as co-solvent reduced the methanol permeability by two orders of magnitude, while the proton conductivity was only reduced by 4%. XRD analysis made to the treated samples exhibited a decreasing pattern in the crystallinity, which affects the transport properties of the membrane. Also, SAXS profiles of the Nafion membranes processed were obtained with the goal of determining changes produced by the SCF processing in the hydrophilic domains of the polymer. With the goal of searching for new alternatives in proton exchange membranes (PEMs) triblock copolymer of poly(styrene-isobutylene-styrene) (SIBS) and poly(styrene-isobutylene-styrene) SEBS were studied. These sulfonated tri-block copolymers had lower methanol permeabilities, but also lower proton conductivity, even with blends of these and blends with Nafion membranes. Other alternative studied was the functionalization of the membranes SIBS with metallic cations, which decreased the methanol permeability in the membranes containing the cations Mg2+, Zn2+ and Al 3+, while the proton conductivity was maintained more or less constant. The permeation of methanol vapor was investigated and the behavior through the membranes studied followed a pattern of Fick's Law, while the pattern shown by the permeation in liquid phase was non-Fickian.

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.

Extraction of glutathione from EFB fermentation waste using methanol with sonication process

NASA Astrophysics Data System (ADS)

Muryanto, Muryanto; Alvin, Nurdin, Muhammad; Hanifah, Ummu; Sudiyani, Yanni

2017-11-01

Glutathione is important compound on the human body. Glutathione have a widely use at pharmacy and cosmetics as detoxification, skin whitening agent, antioxidant and many other. This study aims to obtain glutathione from Saccharomyces cerevisiae in fermentation waste of second generation bioethanol. The remaining yeast in the empty fruit bunch (EFB) fermentation was separated from the fermentation solution use centrifugation process and then extracted using a methanol-water solution. The extraction process was done by maceration which was assisted by sonication process. Solvent concentration and time of sonication were varied to see its effect on glutathione concentration. The concentration of glutathione from the extraction process was analyzed using alloxan method with UV-Vis spectrophotometer. The results show that the highest glutathione concentration was approximately 1.32 g/L obtained with methanol solvent at 90 minutes of maceration following with 15 minutes sonication.

Investigation to biodiesel production by the two-step homogeneous base-catalyzed transesterification.

PubMed

Ye, Jianchu; Tu, Song; Sha, Yong

2010-10-01

For the two-step transesterification biodiesel production made from the sunflower oil, based on the kinetics model of the homogeneous base-catalyzed transesterification and the liquid-liquid phase equilibrium of the transesterification product, the total methanol/oil mole ratio, the total reaction time, and the split ratios of methanol and reaction time between the two reactors in the stage of the two-step reaction are determined quantitatively. In consideration of the transesterification intermediate product, both the traditional distillation separation process and the improved separation process of the two-step reaction product are investigated in detail by means of the rigorous process simulation. In comparison with the traditional distillation process, the improved separation process of the two-step reaction product has distinct advantage in the energy duty and equipment requirement due to replacement of the costly methanol-biodiesel distillation column. Copyright 2010 Elsevier Ltd. All rights reserved.

Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1993-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Modeling methanol transfer in the mesoporous catalyst for the methanol-to-olefins reaction by the time-fractional diffusion equation

NASA Astrophysics Data System (ADS)

Zhokh, Alexey A.; Strizhak, Peter E.

2018-04-01

The solutions of the time-fractional diffusion equation for the short and long times are obtained via an application of the asymptotic Green's functions. The derived solutions are applied to analysis of the methanol mass transfer through H-ZSM-5/alumina catalyst grain. It is demonstrated that the methanol transport in the catalysts pores may be described by the obtained solutions in a fairly good manner. The measured fractional exponent is equal to 1.20 ± 0.02 and reveals the super-diffusive regime of the methanol mass transfer. The presence of the anomalous transport may be caused by geometrical restrictions and the adsorption process on the internal surface of the catalyst grain's pores.

Methanol from wood waste : a technical and economic study

Treesearch

A. E. Hokanson; R. M. Rowell

1977-01-01

A methanol-from-wood waste facility having a capacity of 50 million gallons per year requires 1,500 ovendry tons (ODT) of wood waste per day. The yield of methanol from wood is about 38 percent, or about 100 gallons per ODT of wood. This yield is based on all process energy required coming from the wood waste. At a wood waste cost of $15/ODT, the selling price of...

Coke formation and carbon atom economy of methanol-to-olefins reaction.

PubMed

Wei, Yingxu; Yuan, Cuiyu; Li, Jinzhe; Xu, Shutao; Zhou, You; Chen, Jingrun; Wang, Quanyi; Xu, Lei; Qi, Yue; Zhang, Qing; Liu, Zhongmin

2012-05-01

The methanol-to-olefins (MTO) process is becoming the most important non-petrochemical route for the production of light olefins from coal or natural gas. Maximizing the generation of the target products, ethene and propene, and minimizing the production of byproducts and coke, are major considerations in the efficient utilization of the carbon resource of methanol. In the present work, the heterogeneous catalytic conversion of methanol was evaluated by performing simultaneous measurements of the volatile products generated in the gas phase and the confined coke deposition in the catalyst phase. Real-time and complete reaction profiles were plotted to allow the comparison of carbon atom economy of methanol conversion over the catalyst SAPO-34 at varied reaction temperatures. The difference in carbon atom economy was closely related with the coke formation in the SAPO-34 catalyst. The confined coke compounds were determined. A new type of confined organics was found, and these accounted for the quick deactivation and low carbon atom economy under low-reaction-temperature conditions. Based on the carbon atom economy evaluation and coke species determination, optimized operating conditions for the MTO process are suggested; these conditions guarantee high conversion efficiency of methanol. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Process for producing ethanol from syngas

DOEpatents

Krause, Theodore R; Rathke, Jerome W; Chen, Michael J

2013-05-14

The invention provides a method for producing ethanol, the method comprising establishing an atmosphere containing methanol forming catalyst and ethanol forming catalyst; injecting syngas into the atmosphere at a temperature and for a time sufficient to produce methanol; and contacting the produced methanol with additional syngas at a temperature and for a time sufficient to produce ethanol. The invention also provides an integrated system for producing methanol and ethanol from syngas, the system comprising an atmosphere isolated from the ambient environment; a first catalyst to produce methanol from syngas wherein the first catalyst resides in the atmosphere; a second catalyst to product ethanol from methanol and syngas, wherein the second catalyst resides in the atmosphere; a conduit for introducing syngas to the atmosphere; and a device for removing ethanol from the atmosphere. The exothermicity of the method and system obviates the need for input of additional heat from outside the atmosphere.

Predicted exhaust emissions from a methanol and jet fueled gas turbine combustor

NASA Technical Reports Server (NTRS)

Adelman, H. G.; Browning, L. H.; Pefley, R. K.

1975-01-01

A computer model of a gas turbine combustor has been used to predict the kinetic combustion and pollutant formation processes for methanol and simulated jet fuel. Use of the kinetic reaction mechanisms has also allowed a study of ignition delay and flammability limit of these two fuels. The NOX emissions for methanol were predicted to be from 69 to 92% lower than those for jet fuel at the same equivalence ratio which is in agreement with experimentally observed results. The high heat of vaporization of methanol lowers both the combustor inlet mixture temperatures and the final combustion temperatures. The lower combustion temperatures lead to low NOX emissions while the lower inlet mixture temperatures increase methanol's ignition delay. This increase in ignition delay dictates the lean flammability limit of methanol to be 0.8, while jet fuel is shown to combust at 0.4.

Research Progress on the Indirect Hydrogenation of Carbon Dioxide to Methanol.

PubMed

Du, Xian-Long; Jiang, Zheng; Su, Dang Sheng; Wang, Jian-Qiang

2016-02-19

Methanol is a sustainable source of liquid fuels and one of the most useful organic chemicals. To date, most of the work in this area has focused on the direct hydrogenation of CO2 to methanol. However, this process requires high operating temperatures (200-250 °C), which limits the theoretical yield of methanol. Thus, it is desirable to find a new strategy for the efficient conversion of CO2 to methanol at relatively low reaction temperatures. This Minireview seeks to outline the recent advances on the indirect hydrogenation of CO2 to methanol. Much emphasis is placed on discussing specific systems, including hydrogenation of CO2 derivatives (organic carbonates, carbamates, formates, cyclic carbonates, etc.) and cascade reactions, with the aim of critically highlighting both the achievements and remaining challenges associated with this field. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Technoeconomic Comparison of Biofuels: Ethanol, Methanol, and Gasoline from Gasification of Woody Residues (Presentation)

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

Tarud, J.; Phillips, S.

This presentation provides a technoeconomic comparison of three biofuels - ethanol, methanol, and gasoline - produced by gasification of woody biomass residues. The presentation includes a brief discussion of the three fuels evaluated; discussion of equivalent feedstock and front end processes; discussion of back end processes for each fuel; process comparisons of efficiencies, yields, and water usage; and economic assumptions and results, including a plant gate price (PGP) for each fuel.

Well-dispersed NiO nanoparticles supported on nitrogen-doped carbon nanotube for methanol electrocatalytic oxidation in alkaline media

NASA Astrophysics Data System (ADS)

Wang, Pengcheng; Zhou, Yingke; Hu, Min; Chen, Jian

2017-01-01

Nitrogen-doped carbon nanotube supporting NiO nanoparticles were synthesized by a chemical precipitation process coupled with subsequent calcination. The morphology and structure of the composites were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), and the electrochemical performance was evaluated using cyclic voltammetry and chronoamperometric technique. The effects of nitrogen doping, calcination temperature and content of NiO nanoparticles on the electrocatalytic activity toward methanol oxidation were systematically studied. The results show that the uniformly dispersed ultrafine NiO nanoparticles supported on nitrogen-doped carbon nanotube are obtained after calcination at 400 °C. The optimized composite catalysts present high electrocatalytic activity, fast charge-transfer process, excellent accessibility and stability for methanol oxidation reaction, which are promising for application in the alkaline direct methanol fuel cells.

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.

Dimethyl ether production from methanol and/or syngas

DOEpatents

Dagle, Robert A; Wang, Yong; Baker, Eddie G; Hu, Jianli

2015-02-17

Disclosed are methods for producing dimethyl ether (DME) from methanol and for producing DME directly from syngas, such as syngas from biomass. Also disclosed are apparatus for DME production. The disclosed processes generally function at higher temperatures with lower contact times and at lower pressures than conventional processes so as to produce higher DME yields than do conventional processes. Certain embodiments of the processes are carried out in reactors providing greater surface to volume ratios than the presently used DME reactors. Certain embodiments of the processes are carried out in systems comprising multiple microchannel reactors.

Otto Laporte Award Talk - In light of Fluid Mechanics

NASA Astrophysics Data System (ADS)

Gharib, Morteza

2015-11-01

Fluid mechanics, in its inherent non-linear beauty, has been its own laboratory, testing our perseverance and dedication to a branch of science that, despite its perceived maturity, still has many surprises to offer. For many of us, the study of fluid flow has been our path to understanding the complexity of nature. My journey has taken me through many interesting projects including the development of new visualization tools, scrutinizing the rhythms of the human heart, observing flow vortices and studying the dynamics of soap films. But this lecture is mainly devoted to a new example of my research activities where light and flow physics interweave to display another intriguing multi-physics beauty of nature.

Performance of biofuel processes utilising separate lignin and carbohydrate processing.

PubMed

Melin, Kristian; Kohl, Thomas; Koskinen, Jukka; Hurme, Markku

2015-09-01

Novel biofuel pathways with increased product yields are evaluated against conventional lignocellulosic biofuel production processes: methanol or methane production via gasification and ethanol production via steam-explosion pre-treatment. The novel processes studied are ethanol production combined with methanol production by gasification, hydrocarbon fuel production with additional hydrogen produced from lignin residue gasification, methanol or methane synthesis using synthesis gas from lignin residue gasification and additional hydrogen obtained by aqueous phase reforming in synthesis gas production. The material and energy balances of the processes were calculated by Aspen flow sheet models and add on excel calculations applicable at the conceptual design stage to evaluate the pre-feasibility of the alternatives. The processes were compared using the following criteria: energy efficiency from biomass to products, primary energy efficiency, GHG reduction potential and economy (expressed as net present value: NPV). Several novel biorefinery concepts gave higher energy yields, GHG reduction potential and NPV. Copyright © 2015 Elsevier Ltd. All rights reserved.

THE EFFECT OF METHANOL USED AS VEHICULUM ON SERUM PHENACETIN CONCENTRATION IN THE RAT.

PubMed

Lukasik, Marcin; Malkowska, Anna; Bamburowicz-Klimkowska, Magdalena; Polak, Piotr; Szutowski, Miroslaw M

2016-09-01

The xenobiotic absorption process is dependent on many factors, related both to the substance and form of its administration. During administration of small amounts of drugs, the effect of vehiculum on drug fate in the body becomes also evident. The intensity of absorption depends on numerous factors not necessarily related to the substance and its formulation, and also on biotransformation and active transport processes. Additional problem is the fact that many medicines are lipophilic compounds and insoluble in the water (e.g. phenacetin). Methanol and its aqueous solutions facilitate administration to the experimental animals, in the dissolved form of a number of medicines practically insoluble in water. Taking into consideration that methanol is particularly for rats, of low toxicity, it is quite frequently applied as vehiculum. The aim of this study was to investigate the potential interactions that may occur during the use of methanol as vehiculum and compare changes when were used solution 1% of carboxymethylcellulose. The study was performed on male Wistar rats. The tests were performed using phenacetin, which is recognized as biomarker of CYP 2E 1 isoform activity. Phenacetin was given per os in a single dose of 100 mg/kg b. w. Various procedures of phenacetin administration were tested, including solubilization in methanol or suspension in 1% water solution of carboxymethylcellulose. The results of this study show that methanol influences the phenacetin bioavailability and kinetics. Comparing the administration of this drug in methanol solutions against 1% of carboxymethylcellulose, it is in the case of phenacetin triple increase in AUC0-4 h. The presence of methanol affects the shape of kinetic curves of phenacetin causing higher their course until 4 hours after administration.

Commercial-scale demonstration of the Liquid Phase Methanol (LPMEOH{trademark}) process. Technical progress report number 9, July 1--September 30, 1996

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

NONE

The Liquid Phase Methanol (LPMEOH{trademark}) Demonstration Project at Kingsport, Tennessee, is a $213.7 million cooperative agreement between the US Department of Energy (DOE) and Air Products Liquid Phase Conversion Company, L.P. (the Partnership). The LPMEOH{trademark} Process Demonstration Unit is being built at a site located at the Eastman Chemical Company (Eastman) complex in Kingsport. The project involves the construction of an 80,000 gallons per day (260 tons per day (TPD)) methanol unit utilizing coal-derived synthesis gas from Eastman`s integrated coal gasification facility. The new equipment consists of synthesis gas feed preparation and compression facilities, the liquid phase reactor and auxiliaries,more » product distillation facilities, and utilities. This liquid phase process suspends fine catalyst particles in an inert liquid, forming a slurry. The slurry dissipates the heat of the chemical reaction away from the catalyst surface, protecting the catalyst and allowing the methanol synthesis reaction to proceed at higher rates. At the Eastman complex, the technology is being integrated with existing coal-gasifiers.« less

Improving the Isotretinoin Photostability by Incorporating in Microemulsion Matrix

PubMed Central

Patel, Mrunali R.; Patel, Rashmin B.; Parikh, Jolly R.; Patel, Bharat G.

2011-01-01

The present paper demonstrates the increased photostability of isotretinoin when loaded in microemulsion. The photodegradation of isotretinoin, in methanol and microemulsion formulation was studied under direct sun light. The photodegradation process was monitored by UV spectrophotometry. In methanol solution, isotretinoin undergoes complete photodegradation just within a few minutes of light exposure. Isotretinoin incorporated in microemulsion formulation showed an increased stability in comparison to the methanol solutions. In particular for isotretinoin, a residual concentration of 75% was still present after a light irradiance versus a residual value of just 16% measured at the same time in methanol solution. Further, degradation kinetic parameters of isotretinoin-loaded microemulsion formulation were demonstrated increase isotretinoin half-life about five-times in comparison with a methanol solution under a direct sun light. PMID:22389863

Electrochemical characterization of Pt-Ru-Pd catalysts for methanol oxidation reaction in direct methanol fuel cells.

PubMed

Choi, M; Han, C; Kim, I T; An, J C; Lee, J J; Lee, H K; Shim, J

2011-01-01

PtRuPd nanoparticles on carbon black were prepared and characterized as electrocatalysts for methanol oxidation reaction in direct methanol fuel cells. Nano-sized Pd (2-4 nm) particles were deposited on Pt/C and PtRu/C (commercial products) by a simple chemical reduction process. The structural and physical information of the PtRuPd/C were confirmed by TEM and XRD, and their electrocatalytic activities were measured by cyclic voltammetry and linear sweep voltammetry. The catalysts containing Pd showed higher electrocatalytic activity for methanol oxidation reaction than the other catalysts. This might be attributed to an increase in the electrochemical surface area of Pt, which is caused by the addition of Pd; this results in increased catalyst utilization.

ICI and Penspen in Nigerian and Qatari methanol deals

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

Alperowicz, N.

The U.K. consulting and engineering company Penspen Ltd. (London) has signed a second joint venture agreement in Qatar and has selected the ICI (London) methanol process. The technology will also be used in a world-scale methanol plant in Nigeria that Penspen is helping to set up. Under the first agreement, signed on January 1 with Qatar General Petroleum Corp. (QGPC), a 50/50 venture is being formed to build a $370-million, 2,000-m.t./day methanol plant at Umm Said. ICI will provide its low-pressure technology and help market 75% of the output. Completion is due late 1994.

Electro-oxidation of methanol and ethanol using PtRu/C, PtSn/C and PtSnRu/C electrocatalysts prepared by an alcohol-reduction process

NASA Astrophysics Data System (ADS)

Neto, Almir Oliveira; Dias, Ricardo R.; Tusi, Marcelo M.; Linardi, Marcelo; Spinacé, Estevam V.

PtRu/C, PtSn/C and PtSnRu/C electrocatalysts were prepared by the alcohol reduction process using ethylene glycol as the solvent and reduction agent and Vulcan Carbon XC72 as the support. The electrocatalysts were characterized by EDX, XRD and cyclic voltammetry. The electrochemical oxidation of methanol and ethanol were studied by chronoamperometry using a thin porous coating technique. The PtSn/C electrocatalyst prepared by this methodology showed superior performance compared to the PtRu/C and PtSnRu/C electrocatalysts for methanol and ethanol oxidation at room temperature.

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

Underwood, R.P.

As part of the DOE-sponsored contract Synthesis of Dimethyl Ether and Alternative Fuels in the Liquid Phase from Coal-Derived Syngas'' experimental evaluations of the one-step synthesis of alternative fuels were carried out. The objective of this work was to develop novel processes for converting coal-derived syngas to fuels or fuel additives. Building on a technology base acquired during the development of the Liquid Phase Methanol (LPMEOH) process, this work focused on the development of slurry reactor based processes. The experimental investigations, which involved bench-scale reactor studies, focused primarily on three areas: (1) One-step, slurry-phase syngas conversion to hydrocarbons or methanol/hydrocarbonmore » mixtures using a mixture of methanol synthesis catalyst and methanol conversion catalyst in the same slurry reactor. (2) Slurry-phase conversion of syngas to mixed alcohols using various catalysts. (3) One-step, slurry-phase syngas conversion to mixed ethers using a mixture of mixed alcohols synthesis catalyst and dehydration catalyst in the same slurry reactor. The experimental results indicate that, of the three types of processes investigated, slurry phase conversion of syngas to mixed alcohols shows the most promise for further process development. Evaluations of various mixed alcohols catalysts show that a cesium-promoted Cu/ZnO/Al[sub 2]O[sub 3] methanol synthesis catalyst, developed in Air Products' laboratories, has the highest performance in terms of rate and selectivity for C[sub 2+]-alcohols. In fact, once-through conversion at industrially practical reaction conditions yielded a mixed alcohols product potentially suitable for direct gasoline blending. Moreover, an additional attractive aspect of this catalyst is its high selectivity for branched alcohols, potential precursors to iso-olefins for use in etherification.« less

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

Underwood, R.P.

As part of the DOE-sponsored contract ``Synthesis of Dimethyl Ether and Alternative Fuels in the Liquid Phase from Coal-Derived Syngas`` experimental evaluations of the one-step synthesis of alternative fuels were carried out. The objective of this work was to develop novel processes for converting coal-derived syngas to fuels or fuel additives. Building on a technology base acquired during the development of the Liquid Phase Methanol (LPMEOH) process, this work focused on the development of slurry reactor based processes. The experimental investigations, which involved bench-scale reactor studies, focused primarily on three areas: (1) One-step, slurry-phase syngas conversion to hydrocarbons or methanol/hydrocarbonmore » mixtures using a mixture of methanol synthesis catalyst and methanol conversion catalyst in the same slurry reactor. (2) Slurry-phase conversion of syngas to mixed alcohols using various catalysts. (3) One-step, slurry-phase syngas conversion to mixed ethers using a mixture of mixed alcohols synthesis catalyst and dehydration catalyst in the same slurry reactor. The experimental results indicate that, of the three types of processes investigated, slurry phase conversion of syngas to mixed alcohols shows the most promise for further process development. Evaluations of various mixed alcohols catalysts show that a cesium-promoted Cu/ZnO/Al{sub 2}O{sub 3} methanol synthesis catalyst, developed in Air Products` laboratories, has the highest performance in terms of rate and selectivity for C{sub 2+}-alcohols. In fact, once-through conversion at industrially practical reaction conditions yielded a mixed alcohols product potentially suitable for direct gasoline blending. Moreover, an additional attractive aspect of this catalyst is its high selectivity for branched alcohols, potential precursors to iso-olefins for use in etherification.« less

Commercial-scale demonstration of the Liquid Phase Methanol (LPMEOH{trademark}) process. Technical progress report number 6, October 1--December 31, 1995

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

NONE

1996-12-31

The project involves the construction of an 80,000 gallons per day (260 TPD) methanol unit utilizing coal-derived synthesis gas from Eastman`s integrated coal gasification facility. The new equipment consists of synthesis gas feed preparation and compression facilities, the liquid phase reactor and auxiliaries, product distillation facilities, and utilities. The technology to be demonstrated is the product of a cooperative development effort by Air Products and DOE in a program that started in 1981. Developed to enhance electric power generation using integrated gasification combined cycle (IGCC) technology, the LPMEOH{trademark} process is ideally suited for directly processing gases produced by modern-day coalmore » gasifiers. This liquid phase process suspends fine catalyst particles in an inert liquid, forming a slurry. The slurry dissipates the heat of the chemical reaction away from the catalyst surface protecting the catalyst and allowing the methanol synthesis reaction to proceed at higher rates. At the Eastman complex, the technology will be integrated with existing coal-gasifiers. A carefully developed test plan will allow operations at Eastman to simulate electricity demand load-following in coal-based IGCC facilities. The operations will also demonstrate the enhanced stability and heat dissipation of the conversion process, its reliable on/off operation, and its ability to produce methanol as a clean liquid fuel without additional upgrading. An off-site product testing program will be conducted to demonstrate the suitability of the methanol product as a transportation fuel and as a fuel for stationary applications for small modular electric power generators for distributed power.« less

Purification process for .sup.153Gd produced in natural europium targets

DOEpatents

Johnsen, Amanda M; Soderquist, Chuck Z; McNamara, Bruce K; Risher, Darrell R

2013-04-23

An alteration of the traditional zinc/zinc-amalgam reduction procedure which eliminates both the hazardous mercury and dangerous hydrogen gas generation. In order to avoid the presence of water and hydrated protons in the working solution, which can oxidize Eu.sup.2+ and cause hydrogen gas production, a process utilizing methanol as the process solvent is described. While methanol presents some flammability hazard in a radiological hot cell, it can be better managed and is less of a flammability hazard than hydrogen gas generation.

Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO2 Hydrogenation Processes

PubMed Central

2017-01-01

The recent advances in the development of heterogeneous catalysts and processes for the direct hydrogenation of CO2 to formate/formic acid, methanol, and dimethyl ether are thoroughly reviewed, with special emphasis on thermodynamics and catalyst design considerations. After introducing the main motivation for the development of such processes, we first summarize the most important aspects of CO2 capture and green routes to produce H2. Once the scene in terms of feedstocks is introduced, we carefully summarize the state of the art in the development of heterogeneous catalysts for these important hydrogenation reactions. Finally, in an attempt to give an order of magnitude regarding CO2 valorization, we critically assess economical aspects of the production of methanol and DME and outline future research and development directions. PMID:28656757

Challenge of representing entropy at different levels of resolution in molecular simulation.

PubMed

Huang, Wei; van Gunsteren, Wilfred F

2015-01-22

The role of entropic contributions in processes involving biomolecules is illustrated using the process of vaporization or condensation of the solvents water and methanol and the process of polypeptide folding in solution using molecular models at different levels of resolution: subatomic, atomic, supra-atomic, and supramolecular. For the folding process, a β-hexapeptide that adopts, as inferred from NMR experiments, both a right-handed 2.710/12-helical fold and a left-handed 314-helical fold in methanol, is used to illustrate the challenge of modeling thermodynamically driven processes at different levels of resolution.

Optimization of the quenching method for metabolomics analysis of Lactobacillus bulgaricus.

PubMed

Chen, Ming-ming; Li, Ai-li; Sun, Mao-cheng; Feng, Zhen; Meng, Xiang-chen; Wang, Ying

2014-04-01

This study proposed a quenching protocol for metabolite analysis of Lactobacillus delbrueckii subsp. bulgaricus. Microbial cells were quenched with 60% methanol/water, 80% methanol/glycerol, or 80% methanol/water. The effect of the quenching process was assessed by the optical density (OD)-based method, flow cytometry, and gas chromatography-mass spectrometry (GC-MS). The principal component analysis (PCA) and orthogonal partial least squares-discriminant analysis (OPLS-DA) were employed for metabolite identification. The results indicated that quenching with 80% methanol/water solution led to less damage to the L. bulgaricus cells, characterized by the lower relative fraction of prodium iodide (PI)-labeled cells and the higher OD recovery ratio. Through GC-MS analysis, higher levels of intracellular metabolites (including focal glutamic acid, aspartic acid, alanine, and AMP) and a lower leakage rate were detected in the sample quenched with 80% methanol/water compared with the others. In conclusion, we suggested a higher concentration of cold methanol quenching for L. bulgaricus metabolomics due to its decreasing metabolite leakage.

Optimization of the quenching method for metabolomics analysis of Lactobacillus bulgaricus *

PubMed Central

Chen, Ming-ming; Li, Ai-li; Sun, Mao-cheng; Feng, Zhen; Meng, Xiang-chen; Wang, Ying

2014-01-01

This study proposed a quenching protocol for metabolite analysis of Lactobacillus delbrueckii subsp. bulgaricus. Microbial cells were quenched with 60% methanol/water, 80% methanol/glycerol, or 80% methanol/water. The effect of the quenching process was assessed by the optical density (OD)-based method, flow cytometry, and gas chromatography-mass spectrometry (GC-MS). The principal component analysis (PCA) and orthogonal partial least squares-discriminant analysis (OPLS-DA) were employed for metabolite identification. The results indicated that quenching with 80% methanol/water solution led to less damage to the L. bulgaricus cells, characterized by the lower relative fraction of prodium iodide (PI)-labeled cells and the higher OD recovery ratio. Through GC-MS analysis, higher levels of intracellular metabolites (including focal glutamic acid, aspartic acid, alanine, and AMP) and a lower leakage rate were detected in the sample quenched with 80% methanol/water compared with the others. In conclusion, we suggested a higher concentration of cold methanol quenching for L. bulgaricus metabolomics due to its decreasing metabolite leakage. PMID:24711354

Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

DOEpatents

Tierney, J.W.; Wender, I.; Palekar, V.M.

1995-01-24

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1995-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Proceedings: Fourteenth annual EPRI conference on fuel science

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

Not Available

1990-05-01

EPRI's Fourteenth Annual Contractors' Conference on Fuel Science was held on May 18--19, 1989 in Palo Alto, CA. The conference featured results of work on coal science, coal liquefaction, methanol production, and coal oil coprocessing and coal upgrading. The following topics were discussed: recent development in coal liquefaction at the Wilsonville Clean Coal Research Center; British coal's liquid solvent extraction (LSE) process; feedstock reactivity in coal/oil co-processing; utility applications for coal-oil coprocessed fuels; effect of coal rank and quality on two-stage liquefaction; organic sulfur compounds in coals; the perchloroethylene refining process of high-sulfur coals; extraction of sulfur coals; extraction ofmore » sulfur from coal; agglomeration of bituminous and subbituminous coals; solubilization of coals by cell-free extracts derived from polyporus versicolor; remediation technologies and services; preliminary results from proof-of-concept testing of heavy liquid cyclone cleaning technology; clean-up of soil contaminated with tarry/oily organics; midwest ore processing company's coal benefication technology: recent prep plant, scale and laboratory activities; combustion characterization of coal-oil agglomerate fuels; status report on the liquid phase methanol project; biomimetic catalysis; hydroxylation of C{sub 2} {minus} C{sub 3} and cycloc{sub 6} hydrocarbons with Fe cluster catalysts as models for methane monooxygenase enzyme; methanol production scenarios; and modeling studies of the BNL low temperature methanol catalyst. Individual projects are processed separately for the data bases.« less

Modeling and Simulation of the Direct Methanol Fuel Cell

NASA Technical Reports Server (NTRS)

Wohr, M.; Narayanan, S. R.; Halpert, G.

1996-01-01

From intro.: The direct methanol liquid feed fuel cell uses aqueous solutions of methanol as fuel and oxygen or air as the oxidant and uses an ionically conducting polymer membrane such as Nafion(sup r)117 and the electrolyte. This type of direct oxidation cell is fuel versatile and offers significant advantages in terms of simplicity of design and operation...The present study focuses on the results of a phenomenological model based on current understanding of the various processed operating in these cells.

Environmental information volume: Liquid Phase Methanol (LPMEOH{trademark}) project

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

NONE

1996-05-01

The purpose of this project is to demonstrate the commercial viability of the Liquid Phase Methanol Process using coal-derived synthesis gas, a mixture of hydrogen and carbon monoxide. This report describes the proposed actions, alternative to the proposed action, the existing environment at the coal gasification plant at Kingsport, Tennessee, environmental impacts, regulatory requirements, offsite fuel testing, and DME addition to methanol production. Appendices include the air permit application, solid waste permits, water permit, existing air permits, agency correspondence, and Eastman and Air Products literature.

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.

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.

CO2 to methanol conversion using hydride terminated porous silicon nanoparticles.

PubMed

Dasog, M; Kraus, S; Sinelnikov, R; Veinot, J G C; Rieger, B

2017-03-09

Porous silicon nanoparticles (Si-NPs) prepared via magnesiothermic reduction were used to convert carbon dioxide (CO 2 ) into methanol. The hydride surface of the silicon nanoparticles acted as a CO 2 reducing reagent without any catalyst at temperatures above 100 °C. The Si nanoparticles were reused up to four times without significant loss in methanol yields. The reduction process was monitored using in situ FT-IR and the materials were characterized using SEM, TEM, NMR, XPS, and powder XRD techniques. The influence of reaction temperature, pressure, and Si-NP concentration on CO 2 reduction were also investigated. Finally, Si particles produced directly from sand were used to convert CO 2 to methanol.

Gas-to-gasoline plant half complete

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

Williams, B.

New Zealand has reached the midpoint in construction of the world's first commercial natural gas-to-gasoline (GTG) plant. Plans call for mid-1985 mechanical completion of the $1.475 billion GTG project in Motunui; limited production would begin by year-end 1985 with the plant fully on-stream by 1986, yielding about 628,000 tons (570,000 metric tons)/yr or about 14,450 bbl/stream-day of high-octane, low-sulfur gasoline. The process configuration combines for the first time on a commercial scale the ICI low-pressure gas-to-methanol scheme with Mobil's fixed bed zeolite catalyst process for converting methanol to gasoline. The GTG plant will be the world's biggest methanol plant andmore » New Zealand's largest grassroots industrial facility.« less

C1 Metabolism in Corynebacterium glutamicum: an Endogenous Pathway for Oxidation of Methanol to Carbon Dioxide

PubMed Central

Witthoff, Sabrina; Mühlroth, Alice

2013-01-01

Methanol is considered an interesting carbon source in “bio-based” microbial production processes. Since Corynebacterium glutamicum is an important host in industrial biotechnology, in particular for amino acid production, we performed studies of the response of this organism to methanol. The C. glutamicum wild type was able to convert 13C-labeled methanol to 13CO2. Analysis of global gene expression in the presence of methanol revealed several genes of ethanol catabolism to be upregulated, indicating that some of the corresponding enzymes are involved in methanol oxidation. Indeed, a mutant lacking the alcohol dehydrogenase gene adhA showed a 62% reduced methanol consumption rate, indicating that AdhA is mainly responsible for methanol oxidation to formaldehyde. Further studies revealed that oxidation of formaldehyde to formate is catalyzed predominantly by two enzymes, the acetaldehyde dehydrogenase Ald and the mycothiol-dependent formaldehyde dehydrogenase AdhE. The Δald ΔadhE and Δald ΔmshC deletion mutants were severely impaired in their ability to oxidize formaldehyde, but residual methanol oxidation to CO2 was still possible. The oxidation of formate to CO2 is catalyzed by the formate dehydrogenase FdhF, recently identified by us. Similar to the case with ethanol, methanol catabolism is subject to carbon catabolite repression in the presence of glucose and is dependent on the transcriptional regulator RamA, which was previously shown to be essential for expression of adhA and ald. In conclusion, we were able to show that C. glutamicum possesses an endogenous pathway for methanol oxidation to CO2 and to identify the enzymes and a transcriptional regulator involved in this pathway. PMID:24014532

Microbial methanol uptake in northeast Atlantic waters

PubMed Central

Dixon, Joanna L; Beale, Rachael; Nightingale, Philip D

2011-01-01

Methanol is the predominant oxygenated volatile organic compound in the troposphere, where it can significantly influence the oxidising capacity of the atmosphere. However, we do not understand which processes control oceanic concentrations, and hence, whether the oceans are a source or a sink to the atmosphere. We report the first methanol loss rates in seawater by demonstrating that 14C-labelled methanol can be used to determine microbial uptake into particulate biomass, and oxidation to 14CO2. We have found that methanol is used predominantly as a microbial energy source, but also demonstrated its use as a carbon source. We report biological methanol oxidation rates between 2.1 and 8.4 nmol l−1 day−1 in surface seawater of the northeast Atlantic. Kinetic experiments predict a Vmax of up to 29 nmol l−1 day−1, with a high affinity Km constant of 9.3 n in more productive coastal waters. We report surface concentrations of methanol in the western English channel of 97±8 n (n=4) between May and June 2010, and for the wider temperate North Atlantic waters of 70±13 n (n=6). The biological turnover time of methanol has been estimated between 7 and 33 days, although kinetic experiments suggest a 7-day turnover in more productive shelf waters. Methanol uptake rates into microbial particles significantly correlated with bacterial and phytoplankton parameters, suggesting that it could be used as a carbon source by some bacteria and possibly some mixotrophic eukaryotes. Our results provide the first methanol loss rates from seawater, which will improve the understanding of the global methanol budget. PMID:21068775

Metagenomic Analyses Reveal the Involvement of Syntrophic Consortia in Methanol/Electricity Conversion in Microbial Fuel Cells

PubMed Central

Yamamuro, Ayaka; Kouzuma, Atsushi; Abe, Takashi; Watanabe, Kazuya

2014-01-01

Methanol is widely used in industrial processes, and as such, is discharged in large quantities in wastewater. Microbial fuel cells (MFCs) have the potential to recover electric energy from organic pollutants in wastewater; however, the use of MFCs to generate electricity from methanol has not been reported. In the present study, we developed single-chamber MFCs that generated electricity from methanol at the maximum power density of 220 mW m−2 (based on the projected area of the anode). In order to reveal how microbes generate electricity from methanol, pyrosequencing of 16S rRNA-gene amplicons and Illumina shotgun sequencing of metagenome were conducted. The pyrosequencing detected in abundance Dysgonomonas, Sporomusa, and Desulfovibrio in the electrolyte and anode and cathode biofilms, while Geobacter was detected only in the anode biofilm. Based on known physiological properties of these bacteria, it is considered that Sporomusa converts methanol into acetate, which is then utilized by Geobacter to generate electricity. This speculation is supported by results of shotgun metagenomics of the anode-biofilm microbes, which reconstructed relevant catabolic pathways in these bacteria. These results suggest that methanol is anaerobically catabolized by syntrophic bacterial consortia with electrodes as electron acceptors. PMID:24852573

Metagenomic analyses reveal the involvement of syntrophic consortia in methanol/electricity conversion in microbial fuel cells.

PubMed

Yamamuro, Ayaka; Kouzuma, Atsushi; Abe, Takashi; Watanabe, Kazuya

2014-01-01

Methanol is widely used in industrial processes, and as such, is discharged in large quantities in wastewater. Microbial fuel cells (MFCs) have the potential to recover electric energy from organic pollutants in wastewater; however, the use of MFCs to generate electricity from methanol has not been reported. In the present study, we developed single-chamber MFCs that generated electricity from methanol at the maximum power density of 220 mW m(-2) (based on the projected area of the anode). In order to reveal how microbes generate electricity from methanol, pyrosequencing of 16S rRNA-gene amplicons and Illumina shotgun sequencing of metagenome were conducted. The pyrosequencing detected in abundance Dysgonomonas, Sporomusa, and Desulfovibrio in the electrolyte and anode and cathode biofilms, while Geobacter was detected only in the anode biofilm. Based on known physiological properties of these bacteria, it is considered that Sporomusa converts methanol into acetate, which is then utilized by Geobacter to generate electricity. This speculation is supported by results of shotgun metagenomics of the anode-biofilm microbes, which reconstructed relevant catabolic pathways in these bacteria. These results suggest that methanol is anaerobically catabolized by syntrophic bacterial consortia with electrodes as electron acceptors.

Microfluidic distillation chip for methanol concentration detection.

PubMed

Wang, Yao-Nan; Liu, Chan-Chiung; Yang, Ruey-Jen; Ju, Wei-Jhong; Fu, Lung-Ming

2016-03-17

An integrated microfluidic distillation system is proposed for separating a mixed ethanol-methanol-water solution into its constituent components. The microfluidic chip is fabricated using a CO2 laser system and comprises a serpentine channel, a boiling zone, a heating zone, and a cooled collection chamber filled with de-ionized (DI) water. In the proposed device, the ethanol-methanol-water solution is injected into the microfluidic chip and driven through the serpentine channel and into the collection chamber by means of a nitrogen carrier gas. Following the distillation process, the ethanol-methanol vapor flows into the collection chamber and condenses into the DI water. The resulting solution is removed from the collection tank and reacted with a mixed indicator. Finally, the methanol concentration is inversely derived from the absorbance measurements obtained using a spectrophotometer. The experimental results show the proposed microfluidic system achieves an average methanol distillation efficiency of 97%. The practicality of the proposed device is demonstrated by detecting the methanol concentrations of two commercial fruit wines. It is shown that the measured concentration values deviate by no more than 3% from those obtained using a conventional bench top system. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Fabrication and Characterization of a Micro Methanol Sensor Using the CMOS-MEMS Technique.

PubMed

Fong, Chien-Fu; Dai, Ching-Liang; Wu, Chyan-Chyi

2015-10-23

A methanol microsensor integrated with a micro heater manufactured using the complementary metal oxide semiconductor (CMOS)-microelectromechanical system (MEMS) technique was presented. The sensor has a capability of detecting low concentration methanol gas. Structure of the sensor is composed of interdigitated electrodes, a sensitive film and a heater. The heater located under the interdigitated electrodes is utilized to provide a working temperature to the sensitive film. The sensitive film prepared by the sol-gel method is tin dioxide doped cadmium sulfide, which is deposited on the interdigitated electrodes. To obtain the suspended structure and deposit the sensitive film, the sensor needs a post-CMOS process to etch the sacrificial silicon dioxide layer and silicon substrate. The methanol senor is a resistive type. A readout circuit converts the resistance variation of the sensor into the output voltage. The experimental results show that the methanol sensor has a sensitivity of 0.18 V/ppm.

Fabrication and Characterization of a Micro Methanol Sensor Using the CMOS-MEMS Technique

PubMed Central

Fong, Chien-Fu; Dai, Ching-Liang; Wu, Chyan-Chyi

2015-01-01

A methanol microsensor integrated with a micro heater manufactured using the complementary metal oxide semiconductor (CMOS)-microelectromechanical system (MEMS) technique was presented. The sensor has a capability of detecting low concentration methanol gas. Structure of the sensor is composed of interdigitated electrodes, a sensitive film and a heater. The heater located under the interdigitated electrodes is utilized to provide a working temperature to the sensitive film. The sensitive film prepared by the sol-gel method is tin dioxide doped cadmium sulfide, which is deposited on the interdigitated electrodes. To obtain the suspended structure and deposit the sensitive film, the sensor needs a post-CMOS process to etch the sacrificial silicon dioxide layer and silicon substrate. The methanol senor is a resistive type. A readout circuit converts the resistance variation of the sensor into the output voltage. The experimental results show that the methanol sensor has a sensitivity of 0.18 V/ppm. PMID:26512671

Carbon Dioxide to Methanol: The Aqueous Catalytic Way at Room Temperature.

PubMed

Sordakis, Katerina; Tsurusaki, Akihiro; Iguchi, Masayuki; Kawanami, Hajime; Himeda, Yuichiro; Laurenczy, Gábor

2016-10-24

Carbon dioxide may constitute a source of chemicals and fuels if efficient and renewable processes are developed that directly utilize it as feedstock. Two of its reduction products are formic acid and methanol, which have also been proposed as liquid organic chemical carriers in sustainable hydrogen storage. Here we report that both the hydrogenation of carbon dioxide to formic acid and the disproportionation of formic acid into methanol can be realized at ambient temperature and in aqueous, acidic solution, with an iridium catalyst. The formic acid yield is maximized in water without additives, while acidification results in complete (98 %) and selective (96 %) formic acid disproportionation into methanol. These promising features in combination with the low reaction temperatures and the absence of organic solvents and additives are relevant for a sustainable hydrogen/methanol economy. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts

NASA Astrophysics Data System (ADS)

Shan, Junjun; Li, Mengwei; Allard, Lawrence F.; Lee, Sungsik; Flytzani-Stephanopoulos, Maria

2017-11-01

An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in catalysis, as typically it involves expensive or corrosive oxidants or reaction media that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid, which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. We find that the two products form through independent pathways, which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolite-supported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60-100 per cent. We anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol, acetic acid and other useful chemicals.

Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts

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

Shan, Junjun; Li, Mengwei; Allard, Lawrence F.

An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in catalysis, as typically it involves expensive or corrosive oxidants or reaction media(5-8) that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid,more » which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. Here, we find that the two products form through independent pathways, which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolitesupported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60-100 per cent. Finally, we anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol, acetic acid and other useful chemicals.« less

Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts

DOE PAGES

Shan, Junjun; Li, Mengwei; Allard, Lawrence F.; ...

2017-11-30

An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in catalysis, as typically it involves expensive or corrosive oxidants or reaction media(5-8) that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid,more » which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. Here, we find that the two products form through independent pathways, which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolitesupported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60-100 per cent. Finally, we anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol, acetic acid and other useful chemicals.« less

Methanol and ethanol modulate responses to danger- and microbe-associated molecular patterns

USDA-ARS?s Scientific Manuscript database

Methanol is a byproduct of cell wall modification, released through the action of pectin methylesterases (PMEs), which demethylesterify cell wall pectins. Plant PMEs play not only a role in developmental processes but also in responses to herbivory and infection by fungal or bacterial pathogens. Mol...

N-formylation of amines via the aerobic oxidation of methanol over supported gold nanoparticles.

PubMed

Ishida, Tamao; Haruta, Masatake

2009-01-01

Dress code: formyl. Gold nanoparticles supported on NiO catalyze the one-pot N-formylation of amines with methanol and molecular oxygen to produce formamide at a selectivity of 90 %. This process generates methyl formate in situ, followed by reaction with amines.

METHANOL PRODUCTION FROM BIOMASS AND NATURAL GAS AS TRANSPORTATION FUEL

EPA Science Inventory

Two processes are examined for production of methanol. They are assessed against the essential requirements of a future alternative fuel for road transport: that it (i) is producible in amounts comparable to the 19 EJ of motor fuel annually consumed in the U.S., (ii) minimizes em...

COPROCESSING OF FOSSIL FUELS AND BIOMASS FOR CO2 EMISSION REDUCTION IN THE TRANSPORTATION SECTOR

EPA Science Inventory

The paper discusses an evaluation of the Hydrocarb process for conversion of carbonaceous raw material to clean carbon and methanol products. hese products are valuable in the market either as fuel or as chemical commodities. s fuel, methanol and carbon can be used economically, ...

COPROCESSING OF FOSSIL FUELS AND BIOMASS FOR CO2 EMISSION REDUCTION IN THE TRANSPORTATION SECTOR

EPA Science Inventory

The paper discusses an evaluation of the Hydrocarb process for conversion of carbonaceous raw material to clean carbon and methanol products. As fuel, methanol and carbon can be used economically, either independently or in slurry form, in efficient heat engines (turbines and int...

Catalysis of the Carbonylation of Alcohols to Carboxylic Acids Including Acetic Acid Synthesis from Methanol.

ERIC Educational Resources Information Center

Forster, Denis; DeKleva, Thomas W.

1986-01-01

Monsanto's highly successful synthesis of acetic acid from methanol and carbon monoxide illustrates use of new starting materials to replace pretroleum-derived ethylene. Outlines the fundamental aspects of the acetic acid process and suggests ways of extending the synthesis to higher carboxylic acids. (JN)

VANADIA CATALYZED VAPOR PHASE OXIDATION OF METHANOL IN THE PRESENCE OF OZONE

EPA Science Inventory

Catalytic oxidation of methanol was carried out in the presence of ozone using vanadia based catalysts. The process can be used to selectively convert alcohols to aldehydes or ketones. It can also be used to control emissions of volatile organic compounds from Kraft mill and ot...

Catalyst activity maintenance study for the liquid phase dimethyl ether process

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

Peng, X.D.; Toseland, B.A.; Underwood, R.P.

1995-12-31

The co-production of dimethyl ether (DME) and methanol from syngas is a process of considerable commercial attractiveness. DME coproduction can double the productivity of a LPMEOH process when using coal-derived syngas. This in itself may offer chemical producers and power companies increased flexibility and more profitable operation. DME is also known as a clean burning liquid fuel; Amoco and Haldor-Topsoe have recently announced the use of DME as an alternative diesel fuel. Moreover, DME can be an interesting intermediate in the production of chemicals such as olefins and vinyl acetate. The current APCl liquid phase dimethyl ether (LPDME) process utilizesmore » a physical mixture of a commercial methanol synthesis catalyst and a dehydration catalyst (e.g., {gamma}-alumina). While this arrangement provides a synergy that results in much higher syngas conversion per pass compared to the methanol-only process, the stability of the catalyst system suffers. The present project is aimed at reducing catalyst deactivation both by understanding the cause(s) of catalyst deactivation and by developing modified catalyst systems. This paper describes the current understanding of the deactivation mechanism.« less

Microscopic solvent structure of subcritical and supercritical methanol from ultraviolet/visible absorption and fluorescence spectroscopies

NASA Astrophysics Data System (ADS)

Bulgarevich, Dmitry S.; Sako, Takeshi; Sugeta, Tsutomu; Otake, Katsuto; Takebayashi, Yoshihiro; Kamizawa, Chiyoshi; Uesugi, Masayuki; Kato, Masahiro

1999-09-01

Ultraviolet/visible absorption and fluorescence spectroscopies at different temperatures and pressures were applied to investigate the microscopic solvent structures of subcritical and supercritical methanol using 4-nitroanisole, ethyl-(4-dimethylamino)benzoate, Reichardt's dye, and anthracene as the probe molecules. It was found that at temperatures higher than 150 °C the long winding chains of sequentially hydrogen-bonded methanol molecules were probably broken, but the small hydrogen-bonded aggregates possibly existed in methanol even at higher temperature. It was also found that the solvation process of the anthracene molecule in the S0-ground state obeyed the Langmuir adsorption model. However, in the case of fluorescence measurements in supercritical methanol, we detected deviations from the simple Langmuir adsorption model. These deviations were explained in terms of preferential solvation of the solvent molecules around photoexcited anthracene. Judging from the experimental results, it was concluded that the local density augmentation of the supercritical methanol around the nonpolar solute was a short-ranged effect, which did not correspond directly to the large isothermal compressibility of fluid near the critical point.

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

Tan, Eric; Talmadge, M.; Dutta, Abhijit

The U.S. Department of Energy (DOE) promotes research for enabling cost-competitive liquid fuels production from lignocellulosic biomass feedstocks. The research is geared to advance the state of technology (SOT) of biomass feedstock supply and logistics, conversion, and overall system sustainability. As part of their involvement in this program, the National Renewable Energy Laboratory (NREL) and the Pacific Northwest National Laboratory (PNNL) investigate the economics of conversion pathways through the development of conceptual biorefinery process models. This report describes in detail one potential conversion process for the production of high octane gasoline blendstock via indirect liquefaction (IDL). The steps involve themore » conversion of biomass to syngas via indirect gasification followed by gas cleanup and catalytic syngas conversion to a methanol intermediate; methanol is then further catalytically converted to high octane hydrocarbons. The conversion process model leverages technologies previously advanced by research funded by the Bioenergy Technologies Office (BETO) and demonstrated in 2012 with the production of mixed alcohols from biomass. Biomass-derived syngas cleanup via tar and hydrocarbons reforming was one of the key technology advancements as part of that research. The process described in this report evaluates a new technology area with downstream utilization of clean biomass-syngas for the production of high octane hydrocarbon products through a methanol intermediate, i.e., dehydration of methanol to dimethyl ether (DME) which subsequently undergoes homologation to high octane hydrocarbon products.« less

Enzymatic conversion of waste cooking oils into alternative fuel--biodiesel.

PubMed

Chen, Guanyi; Ying, Ming; Li, Weizhun

2006-01-01

Production of biodiesel from pure oils through chemical conversion may not be applicable to waste oils/fats. Therefore, enzymatic conversion using immobilized lipase based on Rhizopus orzyae is considered in this article. This article studies this technological process, focusing on optimization of several process parameters, including the molar ratio of methanol to waste oils, biocatalyst load, and adding method, reaction temperature, and water content. The results indicate that methanol/oils ratio of 4, immobilized lipase/oils of 30 wt% and 40 degrees C are suitable for waste oils under 1 atm. The irreversible inactivation of the lipase is presumed and a stepwise addition of methanol to reduce inactivation of immobilized lipases is proposed. Under the optimum conditions the yield of methyl esters is around 88-90%.

Structural insights into methanol-stable variants of lipase T6 from Geobacillus stearothermophilus.

PubMed

Dror, Adi; Kanteev, Margarita; Kagan, Irit; Gihaz, Shalev; Shahar, Anat; Fishman, Ayelet

2015-11-01

Enzymatic production of biodiesel by transesterification of triglycerides and alcohol, catalyzed by lipases, offers an environmentally friendly and efficient alternative to the chemically catalyzed process while using low-grade feedstocks. Methanol is utilized frequently as the alcohol in the reaction due to its reactivity and low cost. However, one of the major drawbacks of the enzymatic system is the presence of high methanol concentrations which leads to methanol-induced unfolding and inactivation of the biocatalyst. Therefore, a methanol-stable lipase is of great interest for the biodiesel industry. In this study, protein engineering was applied to substitute charged surface residues with hydrophobic ones to enhance the stability in methanol of a lipase from Geobacillus stearothermophilus T6. We identified a methanol-stable variant, R374W, and combined it with a variant found previously, H86Y/A269T. The triple mutant, H86Y/A269T/R374W, had a half-life value at 70 % methanol of 324 min which reflects an 87-fold enhanced stability compared to the wild type together with elevated thermostability in buffer and in 50 % methanol. This variant also exhibited an improved biodiesel yield from waste chicken oil compared to commercial Lipolase 100L® and Novozyme® CALB. Crystal structures of the wild type and the methanol-stable variants provided insights regarding structure-stability correlations. The most prominent features were the extensive formation of new hydrogen bonds between surface residues directly or mediated by structural water molecules and the stabilization of Zn and Ca binding sites. Mutation sites were also characterized by lower B-factor values calculated from the X-ray structures indicating improved rigidity.

40 CFR Appendix A to Part 414 - Non-Complexed Metal-Bearing Waste Streams and Cyanide-Bearing Waste Streams

Code of Federal Regulations, 2010 CFR

2010-07-01

... Mercaptan/Ethanol + Hydrogen sulfide Methanol/H.P. Synthesis from natural gas via synthetic gas Oxo Alcohols... + Ammonia n-Propyl alcohol/Hydrogenation of propionaldehyde, Oxo process SAN resin/Suspension polymerization... methanol Acetaldehyde/Oxidation of ethylene with cupric chloride catalyst Acetic acid/Catalytic oxidation...

Using Photocatalytic Oxidation and Analytic Techniques to Remediate Lab Wastewater Containing Methanol

ERIC Educational Resources Information Center

Xiong, Qing; Luo, Mingliang; Bao, Xiaoming; Deng, Yurong; Qin, Song; Pu, Xuemei

2018-01-01

This experiment is dedicated to second-year and above undergraduates who are in their experimental session of the analytical chemistry course. Grouped students are required to use a TiO[subscript 2] photocatalytic oxidation process to treat the methanol-containing wastewater that resulted from their previous HPLC experiments. Students learn to…

Coal-to-methanol: an engineering evaluation of Texaco gasification and ICI methanol-synthesis route. Final report

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

Buckingham, P.A.; Cobb, D.D.; Leavitt, A.A.

1981-08-01

This report presents the results of a technical and economic evaluation of producing methanol from bituminous coal using Texaco coal gasification and ICI methanol synthesis. The scope of work included the development of an overall configuration for a large plant comprising coal preparation, air separation, coal gasification, shift conversion, COS hydrolysis, acid gas removal, methanol synthesis, methanol refining, and all required utility systems and off-site facilities. Design data were received from both Texaco and ICI while a design and cost estimate were received from Lotepro covering the Rectisol acid gas removal unit. The plant processes 14,448 tons per day (drymore » basis) of Illinois No. 6 bituminous coal and produces 10,927 tons per day of fuel-grade methanol. An overall thermal efficiency of 57.86 percent was calculated on an HHV basis and 52.64 percent based on LHV. Total plant investment at an Illinois plant site was estimated to be $1159 million dollars in terms of 1979 investment. Using EPRI's economic premises, the first-year product costs were calculated to $4.74 per million Btu (HHV) which is equivalent to $30.3 cents per gallon and $5.37 per million Btu (LHV).« less

Theoretical insights into the selective oxidation of methane to methanol in copper-exchanged mordenite

DOE PAGES

Zhao, Zhi -Jian; Kulkarni, Ambarish; Vilella, Laia; ...

2016-05-02

Selective oxidation of methane to methanol is one of the most difficult chemical processes to perform. A potential group of catalysts to achieve CH 4 partial oxidation are Cu-exchanged zeolites mimicking the active structure of the enzyme methane monooxygenase. However, the details of this conversion, including the structure of the active site, are still under debate. In this contribution, periodic density functional theory (DFT) methods were employed to explore the molecular features of the selective oxidation of methane to methanol catalyzed by Cu-exchanged mordenite (Cu-MOR). We focused on two types of previously suggested active species, CuOCu and CuOOCu. Our calculationsmore » indicate that the formation of CuOCu is more feasible than that of CuOOCu. In addition, a much lower C–H dissociation barrier is located on the former active site, indicating that C–H bond activation is easily achieved with CuOCu. We calculated the energy barriers of all elementary steps for the entire process, including catalyst activation, CH 4 activation, and CH 3OH desorption. Finally, our calculations are in agreement with experimental observations and present the first theoretical study examining the entire process of selective oxidation of methane to methanol.« less

Ecosystem-scale VOC fluxes during an extreme drought in a ...

EPA Pesticide Factsheets

Considerable amounts and varieties of biogenic volatile organic compounds (BVOCs) are exchanged between vegetation and the surrounding air. These BVOCs play key ecological and atmospheric roles that must be adequately represented for accurately modeling the coupled biosphere-atmosphere-climate Earth system. One key uncertainty in existing models is the response of BVOC fluxes to an important global change process: drought. We describe the diurnal and seasonal variation in isoprene, monoterpene and methanol fluxes from a temperate forest ecosystem before, during, and after an extreme 2012 drought event in the Ozark region of the central USA. BVOC fluxes were dominated by isoprene, which attained high emission rates of up to 35.4 mg m-2 h-1 at midday. Methanol fluxes were characterized by net deposition in the morning, changing to a net emission flux through the rest of the daylight hours. Net flux of CO2 reached its seasonal maximum approximately a month earlier than isoprenoid fluxes, which highlights the differential response of photosynthesis and isoprenoid emissions to progressing drought conditions. Nevertheless, both processes were strongly suppressed under extreme drought, although isoprene fluxes remained relatively high compared to reported fluxes from other ecosystems. Methanol exchange was less affected by drought throughout the season, confirming the complex processes driving biogenic methanol fluxes. The fraction of daytime (7-17 h) assimilated carbo

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%.

Lysine production from methanol at 50 degrees C using Bacillus methanolicus: Modeling volume control, lysine concentration, and productivity using a three-phase continuous simulation.

PubMed

Lee, G H; Hur, W; Bremmon, C E; Flickinger, M C

1996-03-20

A simulation was developed based on experimental data obtained in a 14-L reactor to predict the growth and L-lysine accumulation kinetics, and change in volume of a large-scale (250-m(3)) Bacillus methanolicus methanol-based process. Homoserine auxotrophs of B. methanolicus MGA3 are unique methylotrophs because of the ability to secrete lysine during aerobic growth and threonine starvation at 50 degrees C. Dissolved methanol (100 mM), pH, dissolved oxygen tension (0.063 atm), and threonine levels were controlled to obtain threonine-limited conditions and high-cell density (25 g dry cell weight/L) in a 14-L reactor. As a fed-batch process, the additions of neat methanol (fed on demand), threonine, and other nutrients cause the volume of the fermentation to increase and the final lysine concentration to decrease. In addition, water produced as a result of methanol metabolism contributes to the increase in the volume of the reactor. A three-phase approach was used to predict the rate of change of culture volume based on carbon dioxide production and methanol consumption. This model was used for the evaluation of volume control strategies to optimize lysine productivity. A constant volume reactor process with variable feeding and continuous removal of broth and cells (VF(cstr)) resulted in higher lysine productivity than a fed-batch process without volume control. This model predicts the variation in productivity of lysine with changes in growth and in specific lysine productivity. Simple modifications of the model allows one to investigate other high-lysine-secreting strains with different growth and lysine productivity characteristics. Strain NOA2#13A5-2 which secretes lysine and other end-products were modeled using both growth and non-growth-associated lysine productivity. A modified version of this model was used to simulate the change in culture volume of another L-lysine producing mutant (NOA2#13A52-8A66) with reduced secretion of end-products. The modified simulation indicated that growth-associated production dominates in strain NOA2#13A52-8A66. (c) 1996 John Wiley & Sons, Inc.

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.

Formation of nanoscale networks: selectively swelling amphiphilic block copolymers with CO2-expanded liquids

NASA Astrophysics Data System (ADS)

Gong, Jianliang; Zhang, Aijuan; Bai, Hua; Zhang, Qingkun; Du, Can; Li, Lei; Hong, Yanzhen; Li, Jun

2013-01-01

Polymeric films with nanoscale networks were prepared by selectively swelling an amphiphilic diblock copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP), with the CO2-expanded liquid (CXL), CO2-methanol. The phase behavior of the CO2-methanol system was investigated by both theoretical calculation and experiments, revealing that methanol can be expanded by CO2, forming homogeneous CXL under the experimental conditions. When treated with the CO2-methanol system, the spin cast compact PS-b-P4VP film was transformed into a network with interconnected pores, in a pressure range of 12-20 MPa and a temperature range of 45-60 °C. The formation mechanism of the network, involving plasticization of PS and selective swelling of P4VP, was proposed. Because the diblock copolymer diffusion process is controlled by the activated hopping of individual block copolymer chains with the thermodynamic barrier for moving PVP segments from one to another, the formation of the network structures is achieved in a short time scale and shows ``thermodynamically restricted'' character. Furthermore, the resulting polymer networks were employed as templates, for the preparation of polypyrrole networks, by an electrochemical polymerization process. The prepared porous polypyrrole film was used to fabricate a chemoresistor-type gas sensor which showed high sensitivity towards ammonia.Polymeric films with nanoscale networks were prepared by selectively swelling an amphiphilic diblock copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP), with the CO2-expanded liquid (CXL), CO2-methanol. The phase behavior of the CO2-methanol system was investigated by both theoretical calculation and experiments, revealing that methanol can be expanded by CO2, forming homogeneous CXL under the experimental conditions. When treated with the CO2-methanol system, the spin cast compact PS-b-P4VP film was transformed into a network with interconnected pores, in a pressure range of 12-20 MPa and a temperature range of 45-60 °C. The formation mechanism of the network, involving plasticization of PS and selective swelling of P4VP, was proposed. Because the diblock copolymer diffusion process is controlled by the activated hopping of individual block copolymer chains with the thermodynamic barrier for moving PVP segments from one to another, the formation of the network structures is achieved in a short time scale and shows ``thermodynamically restricted'' character. Furthermore, the resulting polymer networks were employed as templates, for the preparation of polypyrrole networks, by an electrochemical polymerization process. The prepared porous polypyrrole film was used to fabricate a chemoresistor-type gas sensor which showed high sensitivity towards ammonia. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr33188h

Utilization of methanol for polymer electrolyte fuel cells in mobile systems

NASA Astrophysics Data System (ADS)

Schmidt, V. M.; Brockerhoff, P.; Hohlein, B.; Menzer, R.; Stimming, U.

1994-04-01

The constantly growing volume of road traffic requires the introduction of new vehicle propulsion systems with higher efficiency and drastically reduced emission rates. As part of the fuel cell programme of the Research Centre Julich a vehicle propulsion system with methanol as secondary energy carrier and a polymer electrolyte membrane fuel cell (PEMFC) as the main component for energy conversion is developed. The fuel gas is produced by a heterogeneously catalyzed steam reforming reaction in which methanol is converted to H2, CO and CO2. The required energy is provided by the catalytic conversion of methanol for both heating up the system and reforming methanol. The high CO content of the fuel gas requires further processing of the gas or the development of new electrocatalysts for the anode. Various Pt-Ru alloys show promising behaviour as CO-tolerant anodes. The entire fuel cell system is discussed in terms of energy and emission balances. The development of important components is described and experimental results are discussed.

Properties of nanostructures obtained by anodization of aluminum in phosphoric acid at moderate potentials

NASA Astrophysics Data System (ADS)

Zaraska, L.; Sulka, G. D.; Jaskuła, M.

2009-01-01

The influence of the process duration, anodizing potential and methanol addition on the structural features of porous anodic alumina formed in a 0.3 M H3PO4 solutions by twostep self-organized anodizing was investigated for potentials ranging from 100 to 170 V. The structural features of porous structures including pore diameter and interpore distance were evaluated from FE-SEM top-view images for samples anodized in the presence and absence of methanol. For the highest studied anodizing time and methanol volume fraction, an excellent agreement between experimental values of the interpore distance and theoretical predictions was observed. The pore arrangement regularity was analyzed for various electrolyte compositions and anodizing potentials. It was found that the regularity ratio of porous alumina increases linearly with increasing anodizing potential and time. The addition of methanol improves the quality of nanostructures and especially better uniformity of pore sizes is observed in the presence of the highest studied methanol content.

[Optimizing carbon/energy metabolism to enhance monellin production by Pichia pastoris].

PubMed

Huai, Qiangqiang; Jia, Luqiang; Ding, Jian; Chen, Shanshan; Sun, Jiaowen; Shi, Zhongping

2018-02-25

In heterologous protein productions by Pichia pastoris, methanol induction is generally initiated when cell density reaches very high level. However, this traditional strategy suffers with the problems of difficulty in DO control, toxic by-metabolites accumulation and low targeted protein titer. Therefore, initiating methanol induction at lower cell concentration is considered as an alternative strategy to overcome those problems. However, the methanol/energy regulation mechanisms of initiating induction at lower concentration are not clear and seldom reported. In this article, with monellin production as a prototype, we analyzed the methanol/energy metabolism in protein expression process using the strategies of initiating induction at both higher/lower cells concentrations. We attempted to interpret the advantages of the "alternative" strategy, via online measurements of methanol consumption, CO₂ production and O₂ uptake rates. When adopting this "alternative" strategy and maintaining temperature at 30 °C, carbon flux ratio directing into monellin precursors synthesis reached the highest level of 65%. In addition, monellin synthesis was completely associated with cell growth.

Methanol-Independent Protein Expression by AOX1 Promoter with trans-Acting Elements Engineering and Glucose-Glycerol-Shift Induction in Pichia pastoris

PubMed Central

Wang, Jinjia; Wang, Xiaolong; Shi, Lei; Qi, Fei; Zhang, Ping; Zhang, Yuanxing; Zhou, Xiangshan; Song, Zhiwei; Cai, Menghao

2017-01-01

The alcohol oxidase 1 promoter (PAOX1) of Pichia pastoris is commonly used for high level expression of recombinant proteins. While the safety risk of methanol and tough process control for methanol induction usually cause problems especially in large-scale fermentation. By testing the functions of trans-acting elements of PAOX1 and combinatorially engineering of them, we successfully constructed a methanol-free PAOX1 start-up strain, in which, three transcription repressors were identified and deleted and, one transcription activator were overexpressed. The strain expressed 77% GFP levels in glycerol compared to the wide-type in methanol. Then, insulin precursor (IP) was expressed, taking which as a model, we developed a novel glucose-glycerol-shift induced PAOX1 start-up for this methanol-free strain. A batch phase with glucose of 40 g/L followed by controlling residual glucose not lower than 20 g/L was compatible for supporting cell growth and suppressing PAOX1. Then, glycerol induction was started after glucose used up. Accordingly, an optimal bioprocess was further determined, generating a high IP production of 2.46 g/L in a 5-L bioreactor with dramatical decrease of oxygen consumption and heat evolution comparing with the wild-type in methanol. This mutant and bioprocess represent a safe and efficient alternative to the traditional glycerol-repressed/methanol-induced PAOX1 system. PMID:28150747

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

Size-restricted proton transfer within toluene-methanol cluster ions.

PubMed

Chiang, Chi-Tung; Shores, Kevin S; Freindorf, Marek; Furlani, Thomas; DeLeon, Robert L; Garvey, James F

2008-11-20

To understand the interaction between toluene and methanol, the chemical reactivity of [(C6H5CH3)(CH3OH) n=1-7](+) cluster ions has been investigated via tandem quadrupole mass spectrometry and through calculations. Collision Induced Dissociation (CID) experiments show that the dissociated intracluster proton transfer reaction from the toluene cation to methanol clusters, forming protonated methanol clusters, only occurs for n = 2-4. For n = 5-7, CID spectra reveal that these larger clusters have to sequentially lose methanol monomers until they reach n = 4 to initiate the deprotonation of the toluene cation. Metastable decay data indicate that for n = 3 and n = 4 (CH3OH)3H(+) is the preferred fragment ion. The calculational results reveal that both the gross proton affinity of the methanol subcluster and the structure of the cluster itself play an important role in driving this proton transfer reaction. When n = 3, the cooperative effect of the methanols in the subcluster provides the most important contribution to allow the intracluster proton transfer reaction to occur with little or no energy barrier. As n >or= 4, the methanol subcluster is able to form ring structures to stabilize the cluster structures so that direct proton transfer is not a favored process. The preferred reaction product, the (CH3OH)3H(+) cluster ion, indicates that this size-restricted reaction is driven by both the proton affinity and the enhanced stability of the resulting product.

Methanol-Water Aqueous-Phase Reforming with the Assistance of Dehydrogenases at Near-Room Temperature.

PubMed

Shen, Yangbin; Zhan, Yulu; Li, Shuping; Ning, Fandi; Du, Ying; Huang, Yunjie; He, Ting; Zhou, Xiaochun

2018-03-09

As an excellent hydrogen-storage medium, methanol has many advantages, such as high hydrogen content (12.6 wt %), low cost, and availability from biomass or photocatalysis. However, conventional methanol-water reforming usually proceeds at high temperatures. In this research, we successfully designed a new effective strategy to generate hydrogen from methanol at near-room temperature. The strategy involved two main processes: CH 3 OH→HCOOH→H 2 and NADH→HCOOH→H 2 . The first process (CH 3 OH→HCOOH→H 2 ) was performed by an alcohol dehydrogenase (ADH), an aldehyde dehydrogenase (ALDH), and an Ir catalyst. The second procedure (NADH→HCOOH→H 2 ) was performed by formate dehydrogenase (FDH) and the Ir catalyst. The Ir catalyst used was a previously reported polymer complex catalyst [Cp*IrCl 2 (ppy); Cp*=pentamethylcyclopentadienyl, ppy=polypyrrole] with high catalytic activity for the decomposition of formic acid at room temperature and is compatible with enzymes, coenzymes, and poisoning chemicals. Our results revealed that the optimum hydrogen generation rate could reach up to 17.8 μmol h -1  g cat -1 under weak basic conditions at 30 °C. This will have high impact on hydrogen storage, production, and applications and should also provide new inspiration for hydrogen generation from methanol. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalog of the entomologic collections of the Faculty of Public Health of the University of Sao Paulo - (2nd series ii): Triatominae (Hemiptera, Reduviidae)

PubMed Central

Vendrami, Daniel Pagotto; Marrelli, Mauro Toledo; Obara, Marcos Takashi; Barata, José Maria Soares; Ceretti-Junior, Walter

2018-01-01

ABSTRACT This article reports a list with 912 specimens of the subfamily Triatominae deposited in the Entomological Collection of the Faculty of Public Health of the University of Sao Paulo. The collection is composed of 1 holotype, 3 alotypes, 15 paralectotypes, 77 paratypes, distributed in 5 tribes and 12 genera: Tribus Alberprosenini: genus Alberprosenia Martinez & Carcavallo, 1977; Tribus Bolboderini: genus Microtriatoma Prosen & Martinez, 1952; Tribus Cavernicolini: genus Cavernicola Barber, 1937; Tribus Rhodnini: genus Psammolestes Bergroth, 1941; genus Rhodnius Stal, 1859; Tribus Triatomini: genus Dipetalogaster Usinger 1939; genus Eratyrus Stal 1859; genus Hermanlentia Jurberg & Galvão, 1997; genus Linshcosteus Distant, 1904; 1944; genus Panstrongylus Berg 1879; genus Paratriatoma Barber 1938; genus Triatoma Laporte 1833. PMID:29846474

Employing Tip-Edge brackets on canines to simplify straight-wire mechanics.

PubMed

Rocke, R T

1994-10-01

The straight-wire appliance was developed in part to reduce wire bending and therefore make treatment results more predictable. Because tip prescription is built into the bracket slots, teeth are held at their final crown angulations throughout treatment. Straight-wire brackets are used in an attempt to produce bodily tooth movement. However, teeth tend to tip when a force is applied. This tipping, especially when canines are retracted, can deflect the arch wire causing supereruption of the incisors with a resultant increase in anterior overbite and an open bite in the canine/premolar area. Placing Tip-Edge brackets (TP Orthodontics, Inc., LaPorte, Ind.) on canines and employing tipping and uprighting mechanics on these teeth can overcome these problems. Two cases are presented to illustrate this approach to treatment.

Understanding Methanol Coupling on SrTiO 3 from First Principles

DOE PAGES

Huang, Runhong; Fung, Victor; Zhang, Yafen; ...

2018-03-19

Perovskites are interesting materials for catalysis due to their great tunability. However, the correlation of many reaction processes to the termination of a perovskite surface is still unclear. In this paper, we use the methanol coupling reaction on the SrTiO 3(100) surface as a probe reaction to investigate direct C–C coupling from a computational perspective. We use density functional theory to assess methanol adsorption, C–H activation, and direct C–C coupling reactions on the SrTiO 3(100) surface of different terminations. We find that, although methanol molecules dissociatively adsorb on both A and B terminations with similar strength, the dehydrogenation and C–Cmore » coupling reactions have significantly lower activation energies on the B termination than on the A termination. The predicted formation of methoxy and acetate on the SrTiO 3(100) B termination can well explain the ambient-pressure XPS data of methanol on the single-crystal SrTiO 3(100) surface at 250 °C. Finally, this work suggests that a choice of B termination of perovskites would be beneficial for the C–C coupling reaction of methanol.« less

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

Tan, Eric C. D.; Talmadge, Michael; Dutta, Abhijit

This report was developed as part of the U.S. Department of Energy’s Bioenergy Technologies Office’s (BETO’s) efforts to enable the development of technologies for the production of infrastructure-compatible, cost-competitive liquid hydrocarbon fuels from lignocellulosic biomass feedstocks. The research funded by BETO is designed to advance the state of technology of biomass feedstock supply and logistics, conversion, and overall system sustainability. It is expected that these research improvements will be made within the 2022 timeframe. As part of their involvement in this research and development effort, the National Renewable Energy Laboratory and the Pacific Northwest National Laboratory investigate the economics ofmore » conversion pathways through the development of conceptual biorefinery process models and techno-economic analysis models. This report describes in detail one potential conversion process for the production of high-octane gasoline blendstock via indirect liquefaction of biomass. The processing steps of this pathway include the conversion of biomass to synthesis gas or syngas via indirect gasification, gas cleanup, catalytic conversion of syngas to methanol intermediate, methanol dehydration to dimethyl ether (DME), and catalytic conversion of DME to high-octane, gasoline-range hydrocarbon blendstock product. The conversion process configuration leverages technologies previously advanced by research funded by BETO and demonstrated in 2012 with the production of mixed alcohols from biomass. Biomass-derived syngas cleanup via reforming of tars and other hydrocarbons is one of the key technology advancements realized as part of this prior research and 2012 demonstrations. The process described in this report evaluates a new technology area for the downstream utilization of clean biomass-derived syngas for the production of high-octane hydrocarbon products through methanol and DME intermediates. In this process, methanol undergoes dehydration to DME, which is subsequently converted via homologation reactions to high-octane, gasoline-range hydrocarbon products.« less

Submicron patterned metal hole etching

DOEpatents

McCarthy, Anthony M.; Contolini, Robert J.; Liberman, Vladimir; Morse, Jeffrey

2000-01-01

A wet chemical process for etching submicron patterned holes in thin metal layers using electrochemical etching with the aid of a wetting agent. In this process, the processed wafer to be etched is immersed in a wetting agent, such as methanol, for a few seconds prior to inserting the processed wafer into an electrochemical etching setup, with the wafer maintained horizontal during transfer to maintain a film of methanol covering the patterned areas. The electrochemical etching setup includes a tube which seals the edges of the wafer preventing loss of the methanol. An electrolyte composed of 4:1 water: sulfuric is poured into the tube and the electrolyte replaces the wetting agent in the patterned holes. A working electrode is attached to a metal layer of the wafer, with reference and counter electrodes inserted in the electrolyte with all electrodes connected to a potentiostat. A single pulse on the counter electrode, such as a 100 ms pulse at +10.2 volts, is used to excite the electrochemical circuit and perform the etch. The process produces uniform etching of the patterned holes in the metal layers, such as chromium and molybdenum of the wafer without adversely effecting the patterned mask.

Elimination of the azeotropic point of acetone and methanol by 1,3-dimethylimidazolium dimethylphosphate: an ab initio calculation study.

PubMed

Yu, Guangren; Liu, Xiaomin; Zhang, Xiaochun; Chen, Xiaochun; Liu, Zhiping; Abdeltawab, Ahmed A

2017-03-01

1,3-Dimethylimidazolium dimethylphosphate ([C 1 mim][DMP]) was observed experimentally to be able to eliminate the atmospheric azeotropic point of acetone and methanol, which is an important azeotrope generally encountered in furfural production and the Fischer-Tropsch process. Here, we employed ab initio calculation to understand the underlying mechanism of [C 1 mim][DMP] in eliminating the azeotropic point of acetone and methanol. Structure, energy and interaction in binary-, ternary- and quaternary-clusters composed of methanol, acetone, [C 1 mim] + or/and [DMP]‾ were calculated. The σ-hole, AIM and NBO analyses were performed to understand intermolecular interaction with electron density, electron occupancy, charge transfer and molecular orbital interaction. Hydrogen bond interaction plays a key role in azeotropic point elimination; due to the much stronger hydrogen bond interaction between methanol and [C 1 mim][DMP] than that between acetone and [C 1 mim][DMP], [C 1 mim][DMP] prefers to interact with methanol rather than acetone, and the original interaction between methanol and acetone is separated by [C 1 mim][DMP]. The hydrogen bond is from the orbital interaction between O lone-pair-electron orbitals of the hydrogen bond acceptor and σ * (C-H) or σ * (O-H) anti-bonding orbitals of the hydrogen bond donor, where remarkable electron or charge transfer occurs. These theoretical calculation results are in agreement with the experimental observation that [C 1 mim][DMP] eliminates the azeotropic point of methanol and acetone. This work shows that ab initio calculation may be employed to rationalize the design or synthesis of ionic liquids for separating azeotropes. Graphical Abstract Elimination of azeotropic point of acetone and methanol by [C 1 mim][DMP].

Adsorptive Separation of Methanol-Acetone on Isostructural Series of Metal-Organic Frameworks M-BTC (M = Ti, Fe, Cu, Co, Ru, Mo): A Computational Study of Adsorption Mechanisms and Metal-Substitution Impacts.

PubMed

Wu, Ying; Chen, Huiyong; Xiao, Jing; Liu, Defei; Liu, Zewei; Qian, Yu; Xi, Hongxia

2015-12-09

The adsorptive separation properties of M-BTC isostructural series (M = Ti, Fe, Cu, Co, Ru, Mo) for methanol-acetone mixtures were investigated by using various computational procedures of grand canonical Monte Carlo simulations (GCMC), density functional theory (DFT), and ideal adsorbed solution theory (IAST), following with comprehensive understanding of adsorbate-metal interactions on the adsorptive separation behaviors. The obtained results showed that the single component adsorptions were driven by adsorbate-framework interactions at low pressures and by framework structures at high pressures, among which the mass effects, electrostatics, and geometric accessibility of the metal sites also played roles. In the case of methanol-acetone separation, the selectivity of methanol on M-BTCs decreased with rising pressures due to the pressure-dependent separation mechanisms: the cooperative effects between methanol and acetone hindered the separation at low pressures, whereas the competitive effects of acetone further resulted in the lower selectivity at high pressures. Among these M-BTCs, Ti and Fe analogues exhibited the highest thermodynamic methanol/acetone selectivity, making them promising for adsorptive methanol/acetone separation processes. The investigation provides mechanistic insights on how the nature of metal centers affects the adsorption properties of MOFs, and will further promote the rational design of new MOF materials for effective gas mixture separation.

An Integrated Proteomics/Transcriptomics Approach Points to Oxygen as the Main Electron Sink for Methanol Metabolism in Methylotenera mobilis▿†

PubMed Central

Beck, David A. C.; Hendrickson, Erik L.; Vorobev, Alexey; Wang, Tiansong; Lim, Sujung; Kalyuzhnaya, Marina G.; Lidstrom, Mary E.; Hackett, Murray; Chistoserdova, Ludmila

2011-01-01

Methylotenera species, unlike their close relatives in the genera Methylophilus, Methylobacillus, and Methylovorus, neither exhibit the activity of methanol dehydrogenase nor possess mxaFI genes encoding this enzyme, yet they are able to grow on methanol. In this work, we integrated a genome-wide proteomics approach, shotgun proteomics, and a genome-wide transcriptomics approach, shotgun transcriptome sequencing (RNA-seq), of Methylotenera mobilis JLW8 to identify genes and enzymes potentially involved in methanol oxidation, with special attention to alternative nitrogen sources, to address the question of whether nitrate could play a role as an electron acceptor in place of oxygen. Both proteomics and transcriptomics identified a limited number of genes and enzymes specifically responding to methanol. This set includes genes involved in oxidative stress response systems, a number of oxidoreductases, including XoxF-type alcohol dehydrogenases, a type II secretion system, and proteins without a predicted function. Nitrate stimulated expression of some genes in assimilatory nitrate reduction and denitrification pathways, while ammonium downregulated some of the nitrogen metabolism genes. However, none of these genes appeared to respond to methanol, which suggests that oxygen may be the main electron sink during growth on methanol. This study identifies initial targets for future focused physiological studies, including mutant analysis, which will provide further details into this novel process. PMID:21764938

Design, fabrication and testing of an air-breathing micro direct methanol fuel cell with compound anode flow field

NASA Astrophysics Data System (ADS)

Wang, Luwen; Zhang, Yufeng; Zhao, Youran; An, Zijiang; Zhou, Zhiping; Liu, Xiaowei

2011-10-01

An air-breathing micro direct methanol fuel cell (μDMFC) with a compound anode flow field structure (composed of the parallel flow field and the perforated flow field) is designed, fabricated and tested. To better analyze the effect of the compound anode flow field on the mass transfer of methanol, the compound flow field with different open ratios (ratio of exposure area to total area) and thicknesses of current collectors is modeled and simulated. Micro process technologies are employed to fabricate the end plates and current collectors. The performances of the μDMFC with a compound anode flow field are measured under various operating parameters. Both the modeled and the experimental results show that, comparing the conventional parallel flow field, the compound one can enhance the mass transfer resistance of methanol from the flow field to the anode diffusion layer. The results also indicate that the μDMFC with an anode open ratio of 40% and a thickness of 300 µm has the optimal performance under the 7 M methanol which is three to four times higher than conventional flow fields. Finally, a 2 h stability test of the μDMFC is performed with a methanol concentration of 7 M and a flow velocity of 0.1 ml min-1. The results indicate that the μDMFC can work steadily with high methanol concentration.

Protein Engineering by Random Mutagenesis and Structure-Guided Consensus of Geobacillus stearothermophilus Lipase T6 for Enhanced Stability in Methanol

PubMed Central

Dror, Adi; Shemesh, Einav; Dayan, Natali

2014-01-01

The abilities of enzymes to catalyze reactions in nonnatural environments of organic solvents have opened new opportunities for enzyme-based industrial processes. However, the main drawback of such processes is that most enzymes have a limited stability in polar organic solvents. In this study, we employed protein engineering methods to generate a lipase for enhanced stability in methanol, which is important for biodiesel production. Two protein engineering approaches, random mutagenesis (error-prone PCR) and structure-guided consensus, were applied in parallel on an unexplored lipase gene from Geobacillus stearothermophilus T6. A high-throughput colorimetric screening assay was used to evaluate lipase activity after an incubation period in high methanol concentrations. Both protein engineering approaches were successful in producing variants with elevated half-life values in 70% methanol. The best variant of the random mutagenesis library, Q185L, exhibited 23-fold-improved stability, yet its methanolysis activity was decreased by one-half compared to the wild type. The best variant from the consensus library, H86Y/A269T, exhibited 66-fold-improved stability in methanol along with elevated thermostability (+4.3°C) and a 2-fold-higher fatty acid methyl ester yield from soybean oil. Based on in silico modeling, we suggest that the Q185L substitution facilitates a closed lid conformation that limits access for both the methanol and substrate excess into the active site. The enhanced stability of H86Y/A269T was a result of formation of new hydrogen bonds. These improved characteristics make this variant a potential biocatalyst for biodiesel production. PMID:24362426

Low-energy (<20 eV) and high-energy (1000 eV) electron-induced methanol radiolysis of astrochemical interest

NASA Astrophysics Data System (ADS)

Sullivan, Kristal K.; Boamah, Mavis D.; Shulenberger, Katie E.; Chapman, Sitara; Atkinson, Karen E.; Boyer, Michael C.; Arumainayagam, Christopher R.

2016-07-01

We report the first infrared study of the low-energy (<20 eV) electron-induced reactions of condensed methanol. Our goal is to simulate processes which occur when high-energy cosmic rays interact with interstellar and cometary ices, where methanol, a precursor of several prebiotic species, is relatively abundant. The interactions of high-energy radiation, such as cosmic rays (Emax ˜ 1020 eV), with matter produce large numbers of low-energy secondary electrons, which are known to initiate radiolysis reactions in the condensed phase. Using temperature programmed desorption (TPD) and infrared reflection absorption spectroscopy (IRAS), we have investigated low-energy (5-20 eV) and high-energy (˜1000 eV) electron-induced reactions in condensed methanol (CH3OH). IRAS has the benefit that it does not require thermal processing prior to product detection. Using IRAS, we have found evidence for the formation of ethylene glycol (HOCH2CH2OH), formaldehyde (CH2O), dimethyl ether (CH3OCH3), methane (CH4), carbon dioxide (CO2), carbon monoxide (CO), and the hydroxyl methyl radical (·CH2OH) upon both low-energy and high-energy electron irradiation of condensed methanol at ˜85 K. Additionally, TPD results, presented herein, are similar for methanol films irradiated with both 1000 eV and 20 eV electrons. These IRAS and TPD findings are qualitatively consistent with the hypothesis that high-energy condensed phase radiolysis is mediated by low-energy electron-induced reactions. Moreover, methoxymethanol (CH3OCH2OH) could serve as a tracer molecule for electron-induced reactions in the interstellar medium. The results of experiments such as ours may provide a fundamental understanding of how complex organic molecules are synthesized in cosmic ices.

Effects of specific inhibitors on anammox and denitrification in marine sediments.

PubMed

Jensen, Marlene Mark; Thamdrup, Bo; Dalsgaard, Tage

2007-05-01

The effects of three metabolic inhibitors (acetylene, methanol, and allylthiourea [ATU]) on the pathways of N2 production were investigated by using short anoxic incubations of marine sediment with a 15N isotope technique. Acetylene inhibited ammonium oxidation through the anammox pathway as the oxidation rate decreased exponentially with increasing acetylene concentration; the rate decay constant was 0.10+/-0.02 microM-1, and there was 95% inhibition at approximately 30 microM. Nitrous oxide reduction, the final step of denitrification, was not sensitive to acetylene concentrations below 10 microM. However, nitrous oxide reduction was inhibited by higher concentrations, and the sensitivity was approximately one-half the sensitivity of anammox (decay constant, 0.049+/-0.004 microM-1; 95% inhibition at approximately 70 microM). Methanol specifically inhibited anammox with a decay constant of 0.79+/-0.12 mM-1, and thus 3 to 4 mM methanol was required for nearly complete inhibition. This level of methanol stimulated denitrification by approximately 50%. ATU did not have marked effects on the rates of anammox and denitrification. The profile of inhibitor effects on anammox agreed with the results of studies of the process in wastewater bioreactors, which confirmed the similarity between the anammox bacteria in bioreactors and natural environments. Acetylene and methanol can be used to separate anammox and denitrification, but the effects of these compounds on nitrification limits their use in studies of these processes in systems where nitrification is an important source of nitrate. The observed differential effects of acetylene and methanol on anammox and denitrification support our current understanding of the two main pathways of N2 production in marine sediments and the use of 15N isotope methods for their quantification.

Improved carbon control in the sintering of structural PM parts

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

Nowotarski, M.; Gaines, G.

1981-12-01

The use of a nitrogen-methanol atmosphere and a system of control of the atmosphere in furnace zones to provide improved control of carbon in sintering of sprockets are described.A new process has been developed by the Linde Div. of Union Carbide for the sintering of structural PM parts. The process is based on a nitrogen/methanol sintering atmosphere and features superior carbon control (/plus or minus/.03%), elimination of sooting due to lubricant decomposition, and significantly reduced furnace atmosphere gas flows as compared to typical endothermic atmosphere gas consumption.

Correlating ultrasonic impulse and addition of ZnO promoter with CO2 conversion and methanol selectivity of CuO/ZrO2 catalysts.

PubMed

Ezeh, Collins I; Yang, Xiaogang; He, Jun; Snape, Colin; Cheng, Xiao Min

2018-04-01

The thermal characteristics of Cu-based catalysts for CO 2 utilization towards the synthesis of methanol were analysed and discussed in this study. The preparation process were varied by adopting ultrasonic irradiation at various impulses for the co-precipitation route and also, by introducing ZnO promoters using the solid-state reaction route. Prepared catalysts were characterised using XRD, TPR, TPD, SEM, BET and TG-DTA-DSC. In addition, the CO 2 conversion and CH 3 OH selectivity of these samples were assessed. Calcination of the catalysts facilitated the interaction of the Cu catalyst with the respective support bolstering the thermal stability of the catalysts. The characterisation analysis clearly reveals that the thermal performance of the catalysts was directly related to the sonication impulse and heating rate. Surface morphology and chemistry was enhanced with the aid of sonication and introduction of promoters. However, the impact of the promoter outweighs that of the sonication process. CO 2 conversion and methanol selectivity showed a significant improvement with a 270% increase in methanol yield. Copyright © 2017 Elsevier B.V. All rights reserved.

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

Phillips, S. D.; Tarud, J. K.; Biddy, M. J.

This report documents the National Renewable Energy Laboratory's (NREL's) assessment of the feasibility of making gasoline via the methanol-to-gasoline route using syngas from a 2,000 dry metric tonne/day (2,205 U.S. ton/day) biomass-fed facility. A new technoeconomic model was developed in Aspen Plus for this study, based on the model developed for NREL's thermochemical ethanol design report (Phillips et al. 2007). The necessary process changes were incorporated into a biomass-to-gasoline model using a methanol synthesis operation followed by conversion, upgrading, and finishing to gasoline. Using a methodology similar to that used in previous NREL design reports and a feedstock cost ofmore » $50.70/dry ton ($55.89/dry metric tonne), the estimated plant gate price is $16.60/MMBtu ($15.73/GJ) (U.S. $2007) for gasoline and liquefied petroleum gas (LPG) produced from biomass via gasification of wood, methanol synthesis, and the methanol-to-gasoline process. The corresponding unit prices for gasoline and LPG are $1.95/gallon ($0.52/liter) and $1.53/gallon ($0.40/liter) with yields of 55.1 and 9.3 gallons per U.S. ton of dry biomass (229.9 and 38.8 liters per metric tonne of dry biomass), respectively.« less

Thermally assisted sensor for conformity assessment of biodiesel production

NASA Astrophysics Data System (ADS)

Kawano, M. S.; Kamikawachi, R. C.; Fabris, J. L.; Muller, M.

2015-02-01

Although biodiesel can be intentionally tampered with, impairing its quality, ineffective production processes may also result in a nonconforming final fuel. For an incomplete transesterification reaction, traces of alcohol (ethanol or methanol) or remaining raw material (vegetable oil or animal fats) may be harmful to consumers, the environment or to engines. Traditional methods for biodiesel assessment are complex, time consuming and expensive, leading to the need for the development of new and more versatile processes for quality control. This work describes a refractometric fibre optic based sensor that is thermally assisted, developed to quantify the remaining methanol or vegetable oil in biodiesel blends. The sensing relies on a long period grating to configure an in-fibre interferometer. A complete analytical routine is demonstrated for the sensor allowing the evaluation of the biodiesel blends without segregation of the components. The results show the sensor can determine the presence of oil or methanol in biodiesel with a concentration ranging from 0% to 10% v/v. The sensor presented a resolution and standard combined uncertainty of 0.013% v/v and 0.62% v/v for biodiesel-oil samples, and 0.007% v/v and 0.22% v/v for biodiesel-methanol samples, respectively.

Oxo-exchange of gas-phase uranyl, neptunyl, and plutonyl with water and methanol.

PubMed

Lucena, Ana F; Odoh, Samuel O; Zhao, Jing; Marçalo, Joaquim; Schreckenbach, Georg; Gibson, John K

2014-02-17

A challenge in actinide chemistry is activation of the strong bonds in the actinyl ions, AnO2(+) and AnO2(2+), where An = U, Np, or Pu. Actinyl activation in oxo-exchange with water in solution is well established, but the exchange mechanisms are unknown. Gas-phase actinyl oxo-exchange is a means to probe these processes in detail for simple systems, which are amenable to computational modeling. Gas-phase exchange reactions of UO2(+), NpO2(+), PuO2(+), and UO2(2+) with water and methanol were studied by experiment and density functional theory (DFT); reported for the first time are experimental results for UO2(2+) and for methanol exchange, as well as exchange rate constants. Key findings are faster exchange of UO2(2+) versus UO2(+) and faster exchange with methanol versus water; faster exchange of UO2(+) versus PuO2(+) was quantified. Computed potential energy profiles (PEPs) are in accord with the observed kinetics, validating the utility of DFT to model these exchange processes. The seemingly enigmatic result of faster exchange for uranyl, which has the strongest oxo-bonds, may reflect reduced covalency in uranyl as compared with plutonyl.

Ultrasonication aided in-situ transesterification of microbial lipids to biodiesel.

PubMed

Zhang, Xiaolei; Yan, Song; Tyagi, Rajeshwar Dayal; Surampalli, Rao Y; Valéro, Jose R

2014-10-01

In-situ transesterification of microbial lipid to biodiesel has been paid substantial attention due to the fact that the lipid extraction and transesterification can be conducted in one-stage process. To improve the feasibility of in-situ transesterification, ultrasonication was employed to reduce methanol requirement and reaction time. The results showed that the use of ultrasonication could achieve high conversion of lipid to FAMEs (92.1% w lipid conversion/w total lipids) with methanol to lipid molar ratio 60:1 and NaOH addition 1% w/w lipid in 20 min, while methanol to lipid molar ratio 360:1, NaOH addition 1% w/w lipid, and reaction time 12h was required to obtain similar yield in in-situ transesterification without ultrasonication. The compositions of FAMEs obtained in case of ultrasonication aided in-situ transesterification were similar as that of two-stage extraction followed by transesterification processes. Copyright © 2014. Published by Elsevier Ltd.

Metabolic flux analysis of recombinant Pichia pastoris growing on different glycerol/methanol mixtures by iterative fitting of NMR-derived (13)C-labelling data from proteinogenic amino acids.

PubMed

Jordà, Joel; de Jesus, Sérgio S; Peltier, Solenne; Ferrer, Pau; Albiol, Joan

2014-01-25

The yeast Pichia pastoris has emerged as one of the most promising yeast cell factories for the production of heterologous proteins. The readily available genetic tools and the ease of high-cell density cultivations using methanol or glycerol/methanol mixtures are among the key factors for this development. Previous studies have shown that the use of mixed feeds of glycerol and methanol seem to alleviate the metabolic burden derived from protein production, allowing for higher specific and volumetric process productivities. However, initial studies of glycerol/methanol co-metabolism in P. pastoris by classical metabolic flux analyses using (13)C-derived Metabolic Flux Ratio (METAFoR) constraints were hampered by the reduced labelling information obtained when using C3:C1 substrate mixtures in relation to the conventional C6 substrate, that is, glucose. In this study, carbon flux distributions through the central metabolic pathways in glycerol/methanol co-assimilation conditions have been further characterised using biosynthetically directed fractional (13)C labelling. In particular, metabolic flux distributions were obtained under 3 different glycerol/methanol ratios and growth rates by iterative fitting of NMR-derived (13)C-labelling data from proteinogenic amino acids using the software tool (13)CFlux2. Specifically, cells were grown aerobically in chemostat cultures fed with 80:20, 60:40 and 40:60 (w:w) glycerol/methanol mixtures at two dilutions rates (0.05 hour(-1) and 0.16 hour(-1)), allowing to obtain additional data (biomass composition and extracellular fluxes) to complement pre-existing datasets. The performed (13)C-MFA reveals a significant redistribution of carbon fluxes in the central carbon metabolism as a result of the shift in the dilution rate, while the ratio of carbon sources has a lower impact on carbon flux distribution in cells growing at the same dilution rate. At low growth rate, the percentage of methanol directly dissimilated to CO2 ranges between 50% and 70%. At high growth rate the methanol is completely dissimilated to CO2 by the direct pathway, in the two conditions of highest methanol content. Copyright © 2013 Elsevier B.V. All rights reserved.

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

Huang, Runhong; Fung, Victor; Zhang, Yafen

Perovskites are interesting materials for catalysis due to their great tunability. However, the correlation of many reaction processes to the termination of a perovskite surface is still unclear. In this paper, we use the methanol coupling reaction on the SrTiO 3(100) surface as a probe reaction to investigate direct C–C coupling from a computational perspective. We use density functional theory to assess methanol adsorption, C–H activation, and direct C–C coupling reactions on the SrTiO 3(100) surface of different terminations. We find that, although methanol molecules dissociatively adsorb on both A and B terminations with similar strength, the dehydrogenation and C–Cmore » coupling reactions have significantly lower activation energies on the B termination than on the A termination. The predicted formation of methoxy and acetate on the SrTiO 3(100) B termination can well explain the ambient-pressure XPS data of methanol on the single-crystal SrTiO 3(100) surface at 250 °C. Finally, this work suggests that a choice of B termination of perovskites would be beneficial for the C–C coupling reaction of methanol.« less

Ethanol and other oxygenateds from low grade carbonaceous resources

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

Joo, O.S.; Jung, K.D.; Han, S.H.

1995-12-31

Anhydrous ethanol and other oxygenates of C2 up can be produced quite competitively from low grade carbonaceous resources in high yield via gasification, methanol synthesis, carbonylation of methanol an hydrogenation consecutively. Gas phase carbonylation of methanol to form methyl acetate is the key step for the whole process. Methyl acetate can be produced very selectively in one step gas phase reaction on a fixed bed column reactor with GHSV over 5,000. The consecutive hydrogenation of methyl or ethyl acetate produce anhydrous ethanol in high purity. It is also attempted to co-produce methanol and DME in IGCC, in which low grademore » carbonaceous resources are used as energy sources, and the surplus power and pre-power gas can be stored in liquid form of methanol and DME during base load time. Further integration of C2 up oxygenate production with IGCC can improve its economics. The attempt of above extensive technology integration can generate significant industrial profitability as well as reduce the environmental complication related with massive energy consumption.« less

Experimental and theoretical study of the microsolvation of sodium atoms in methanol clusters: differences and similarities to sodium-water and sodium-ammonia.

PubMed

Dauster, Ingo; Suhm, Martin A; Buck, Udo; Zeuch, Thomas

2008-01-07

Methanol clusters are generated in a continuous He-seeded supersonic expansion and doped with sodium atoms in a pick-up cell. By this method, clusters of the type Na(CH(3)OH)(n) are formed and subsequently photoionized by applying a tunable dye-laser system. The microsolvation process of the Na 3s electron is studied by determining the ionization potentials (IPs) of these clusters size-selectively for n = 2-40. A decrease is found from n = 2 to 6 and a constant value of 3.19 +/- 0.07 eV for n = 6-40. The experimentally-determined ionization potentials are compared with ionization potentials derived from quantum-chemical calculations, assuming limiting vertical and adiabatic processes. In the first case, energy differences are calculated between the neutral and the ionized cationic clusters of the same geometry. In the second case, the ionized clusters are used in their optimized relaxed geometry. These energy differences and relative stabilities of isomeric clusters vary significantly with the applied quantum-chemical method (B3LYP or MP2). The comparison with the experiment for n = 2-7 reveals strong variations of the ionization potential with the cluster structure indicating that structural diversity and non-vertical pathways give significant signal contributions at the threshold. Based on these findings, a possible explanation for the remarkable difference in IP evolutions of methanol or water and ammonia is presented: for methanol and water a rather localized surface or semi-internal Na 3s electron is excited to either high Rydberg or more localized states below the vertical ionization threshold. This excitation is followed by a local structural relaxation that couples to an autoionization process. For small clusters with n < 6 for methanol and n < 4 for water the addition of solvent molecules leads to larger solvent-metal-ion interaction energies, which consequently lead to lower ionization thresholds. For n = 6 (methanol) and n = 4 (water) this effect comes to a halt, which may be connected with the completion of the first cationic solvation shell limiting the release of local relaxation energy. For Na(NH(3))(n), a largely delocalized and internal electron is excited to autoionizing electronic states, a process that is no longer local and consequently may depend on cluster size up to very large n.

O-H anharmonic vibrational motions in Cl(-)···(CH3OH)(1-2) ionic clusters. Combined IRPD experiments and AIMD simulations.

PubMed

Beck, Jordan P; Cimas, Alvaro; Lisy, James M; Gaigeot, Marie-Pierre

2014-02-05

The structures of Cl(-)-(Methanol)1,2 clusters have been unraveled combining Infrared Predissociation (IR-PD) experiments and DFT-based molecular dynamics simulations (DFT-MD) at 100 K. The dynamical IR spectra extracted from DFT-MD provide the initial 600 cm(-1) large anharmonic red-shift of the O-H stretch from uncomplexed methanol (3682 cm(-1)) to Cl(-)-(Methanol)1 complex (3085 cm(-1)) as observed in the IR-PD experiment, as well as the subtle supplementary blue- and red-shifts of the O-H stretch in Cl(-)-(Methanol)2 depending on the structure. The anharmonic vibrational calculations remarkably provide the 100 cm(-1) O-H blue-shift when the two methanol molecules are simultaneously organized in the anion first hydration shell (conformer 2A), while they provide the 240 cm(-1) O-H red-shift when the second methanol is in the second hydration shell of Cl(-) (conformer 2B). RRKM calculations have also shown that 2A/2B conformers interconvert on a nanosecond time-scale at the estimated 100 K temperature of the clusters formed by evaporative cooling of argon prior to the IR-PD process. Copyright © 2013 Elsevier B.V. All rights reserved.

Direct synthesis of ethanol from dimethyl ether and syngas over combined H-Mordenite and Cu/ZnO catalysts.

PubMed

Li, Xingang; San, Xiaoguang; Zhang, Yi; Ichii, Takashi; Meng, Ming; Tan, Yisheng; Tsubaki, Noritatsu

2010-10-25

Ethanol was directly synthesized from dimethyl ether (DME) and syngas with the combined H-Mordenite and Cu/ZnO catalysts that were separately loaded in a dual-catalyst bed reactor. Methyl acetate (MA) was formed by DME carbonylation over the H-Mordenite catalyst. Thereafter, ethanol and methanol were produced by MA hydrogenation over the Cu/ZnO catalyst. With the reactant gas containing 1.0% DME, the optimized temperature for the reaction was at 493 K to reach 100% conversion. In the products, the yield of methanol and ethanol could reach 46.3% and 42.2%, respectively, with a small amount of MA, ethyl acetate, and CO(2). This process is environmentally friendly as the main byproduct methanol can be recycled to DME by a dehydration reaction. In contrast, for the physically mixed catalysts, the low conversion of DME and high selectivity of methanol were observed.

Liquid methanol under a static electric field

NASA Astrophysics Data System (ADS)

Cassone, Giuseppe; Giaquinta, Paolo V.; Saija, Franz; Saitta, A. Marco

2015-02-01

We report on an ab initio molecular dynamics study of liquid methanol under the effect of a static electric field. We found that the hydrogen-bond structure of methanol is more robust and persistent for field intensities below the molecular dissociation threshold whose value (≈0.31 V/Å) turns out to be moderately larger than the corresponding estimate obtained for liquid water. A sustained ionic current, with ohmic current-voltage behavior, flows in this material for field intensities above 0.36 V/Å, as is also the case of water, but the resulting ionic conductivity (≈0.40 S cm-1) is at least one order of magnitude lower than that of water, a circumstance that evidences a lower efficiency of proton transfer processes. We surmise that this study may be relevant for the understanding of the properties and functioning of technological materials which exploit ionic conduction, such as direct-methanol fuel cells and Nafion membranes.

Sensing mechanism of SnO2/ZnO nanofibers for CH3OH sensors: heterojunction effects

NASA Astrophysics Data System (ADS)

Tang, Wei

2017-11-01

SnO2/ZnO composite nanofibers were synthesized by a simple electrospinning method. The prepared SnO2/ZnO gas sensors exhibited good linear and high response to methanol. The enhanced sensing behavior of SnO2/ZnO might be associated with the homotypic heterojunction effects formed in n-SnO2/n-ZnO nanograins boundaries. In addition, the possible sensing mechanisms of methanol on SnO2/ZnO surface were investigated by density functional theory in order to make the methanol adsorption and desorption process clear. Zn doped SnO2 model was adopted to approximate the SnO2/ZnO structure because of the calculation power limitations. Calculation results showed that when exposed to methanol, the methanol would react with bridge oxygen O2c , planar O3c and pre adsorbed oxygen vacancy on the lattice surface. The -CH3 and -OH of methanol molecule would both lose one H atom. The lost H atoms bonded with oxygen at the adsorption sites. The final products were HCHO and H2O. Electrons were transferred from methanol to the lattice surface to reduce the resistance of semiconductor gas sensitive materials, which is in agreement with the experimental phenomena. More adsorption models of other interfering gases, such as ethanol, formaldehyde and acetone will be built and calculated to explain the selectivity issue from the perspective of adsorption energy, transferred charge and density of states in the future work.

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.

Monodispersed bimetallic PdAg nanoparticles with twinned structures: Formation and enhancement for the methanol oxidation

PubMed Central

Yin, Zhen; Zhang, Yining; Chen, Kai; Li, Jing; Li, Wenjing; Tang, Pei; Zhao, Huabo; Zhu, Qingjun; Bao, Xinhe; Ma, Ding

2014-01-01

Monodispersed bimetallic PdAg nanoparticles can be fabricated through the emulsion-assisted ethylene glycol (EG) ternary system. Different compositions of bimetallic PdAg nanoparticles, Pd80Ag20, Pd65Ag35 and Pd46Ag54 can be obtained via adjusting the reaction parameters. For the formation process of the bimetallic PdAg nanoparticles, there have two-stage growth processes: firstly, nucleation and growth of the primary nanoclusters; secondly, formation of the secondary nanoparticles with the size-selection and relax process via the coalescence or aggregation of the primary nanoclusters. The as-prepared PdAg can be supported on the carbon black without any post-treatment, which exhibited high electro-oxidation activity towards methanol oxidation under alkaline media. More importantly, carbon-supported Pd80Ag20 nanoparticles reveal distinctly superior activities for the methanol oxidation, even if compared with commercial Pt/C electro-catalyst. It is concluded that the enhanced activity is dependant on the unique twinning structure with heterogeneous phase due to the dominating coalescence growth in EG ternary system. PMID:24608736

Conceptual process design and economics for the production of high-octane gasoline blendstock via indirect liquefaction of biomass through methanol/dimethyl ether intermediates

DOE PAGES

Tan, Eric C. D.; Talmadge, Michael; Dutta, Abhijit; ...

2015-10-28

This paper describes in detail one potential conversion process for the production of high-octane gasoline blendstock via indirect liquefaction of biomass. The processing steps of this pathway include the conversion of biomass to synthesis gas via indirect gasification, gas clean-up via reforming of tars and other hydrocarbons, catalytic conversion of syngas to methanol, methanol dehydration to dimethyl ether (DME), and the homologation of DME over a zeolite catalyst to high-octane gasoline-range hydrocarbon products. The current process configuration has similarities to conventional methanol-to-gasoline (MTG) technologies, but there are key distinctions, specifically regarding the product slate, catalysts, and reactor conditions. A techno-economicmore » analysis is performed to investigate the production of high-octane gasoline blendstock. The design features a processing daily capacity of 2000 tonnes (2205 short tons) of dry biomass. The process yields 271 liters of liquid fuel per dry tonne of biomass (65 gal/dry ton), for an annual fuel production rate of 178 million liters (47 MM gal) at 90% on-stream time. The estimated total capital investment for an nth-plant is $438 million. The resulting minimum fuel selling price (MFSP) is $0.86 per liter or $3.25 per gallon in 2011 US dollars. A rigorous sensitivity analysis captures uncertainties in costs and plant performance. Sustainability metrics for the conversion process are quantified and assessed. The potential premium value of the high-octane gasoline blendstock is examined and found to be at least as competitive as fossil-derived blendstocks. A simple blending strategy is proposed to demonstrate the potential for blending the biomass-derived blendstock with petroleum-derived intermediates. Published 2015. This article is a U.S. Government work and is in the public domain in the USA. Biofuels, Bioproducts and Biorefining published by Society of Industrial Chemistry and John Wiley & Sons Ltd.« less

Study of a combined heterotrophic and sulfur autotrophic denitrification technology for removal of nitrate in water.

PubMed

Liu, Huijuan; Jiang, Wei; Wan, Dongjin; Qu, Jiuhui

2009-09-30

A combined two-step process of heterotrophic denitrification in a fluidized reactor and sulfur autotrophic denitrification processes (CHSAD) was developed for the removal of nitrate in drinking water. In this process, the advantage of high efficiency of heterotrophic denitrification with non-excessive methanol and the advantage of non-pollution of sulfur autotriphic denitrification were integrated in this CHSAD process. And, this CHSAD process had the capacity of pH balance and could control the concentration of SO(4)(2-) in effluent by adjusting the operation condition. When the influent nitrate was 30 mg NO(3)(-)-N/L, the reactor could be operated efficiently at the hydraulic retention time (HRT) ranging from 20 to 40 min with C:N ratio (mg CH(3)OH:mg NO(3)(-)-N) of 2.0 (methanol as carbon source). The nitrate removal was nearly 100% and there was no accumulated nitrite or residual methanol in the effluent. The effluent pH was about 7.5 and the sulfate concentration was lower than 130 mg/L. The maximum volume-loading rate of the reactor was 2.16 kg NO(3)(-)-N/(m(3)d). The biomass and scanning electron microscopy graphs of biofilm were also analyzed.

Integrating metabolic modeling and population heterogeneity analysis into optimizing recombinant protein production by Komagataella (Pichia) pastoris.

PubMed

Theron, Chrispian W; Berrios, Julio; Delvigne, Frank; Fickers, Patrick

2018-01-01

The methylotrophic yeast Komagataella (Pichia) pastoris has become one of the most utilized cell factories for the production of recombinant proteins over the last three decades. This success story is linked to its specific physiological traits, i.e., the ability to grow at high cell density in inexpensive culture medium and to secrete proteins at high yield. Exploiting methanol metabolism is at the core of most P. pastoris-based processes but comes with its own challenges. Co-feeding cultures with glycerol/sorbitol and methanol is a promising approach, which can benefit from improved understanding and prediction of metabolic response. The development of profitable processes relies on the construction and selection of efficient producing strains from less efficient ones but also depends on the ability to master the bioreactor process itself. More specifically, how a bioreactor processes could be monitored and controlled to obtain high yield of production. In this review, new perspectives are detailed regarding a multi-faceted approach to recombinant protein production processes by P. pastoris; including gaining improved understanding of the metabolic pathways involved, accounting for variations in transcriptional and translational efficiency at the single cell level and efficient monitoring and control of methanol levels at the bioreactor level.

A new species of Clidicus with asymmetrical parameres (Coleoptera, Staphylinidae, Scydmaeninae).

PubMed

JaŁoszyŃski, PaweŁ

2018-03-20

Clidicus Laporte, 1832 currently comprises 27 species distributed in India (Karnataka, Tamil Nadu), Sri Lanka, Indonesia (Java, Kalimantan, Sumatra), Malaysia (Sabah, Sarawak), Laos, Vietnam, the Philippines (Mindanao), China (Hainan) and Australia (Queensland). Some species have conspicuously large adults reaching 8.5 mm, and they represent the largest known Scydmaeninae. Species of Clidicus were relatively poorly known until recently, when Orousset (2014) revised a large portion of this genus and described several new species. Other major studies include Besuchet (1971), who described Sri Lankan species, Jałoszyński et al. (2003) who recorded four new species from Vietnam and Laos, Jałoszyński (2009) with the first description of a Philippine species, and Zhou Li (2015), who discovered the first species in China. Another new species, representing the second Clidicus occurring in the Philippines, is described below.

Studies on brain biogenic amines in methanolic extract of Cuscuta reflexa Roxb. and Corchorus olitorius Linn. seed treated mice.

PubMed

Gupta, Malaya; Mazumder, Upal Kanti; Pal, Dilipkumar; Bhattacharya, Shiladitya; Chakrabarty, Sumit

2003-01-01

The methanolic extract of both Cuscuta reflexa stem and Corchorus olitorius seed showed marked protection against convulsion induced by chemoconvulsive agents in mice. The catecholamines contained were significantly increased in the processed extract treated mice. The amount of GABA, which is most likely to be involved in seizure activity, was increased significantly in mice brain after a six week treatment. Results of the present study revealed that both the processed extracts showed a significant anticonvulsive property by altering the level of catecholamines and brain amino acids in mice.

Environmental life cycle assessment of methanol and electricity co-production system based on coal gasification technology.

PubMed

Śliwińska, Anna; Burchart-Korol, Dorota; Smoliński, Adam

2017-01-01

This paper presents a life cycle assessment (LCA) of greenhouse gas emissions generated through methanol and electricity co-production system based on coal gasification technology. The analysis focuses on polygeneration technologies from which two products are produced, and thus, issues related to an allocation procedure for LCA are addressed in this paper. In the LCA, two methods were used: a 'system expansion' method based on two approaches, the 'avoided burdens approach' and 'direct system enlargement' methods and an 'allocation' method involving proportional partitioning based on physical relationships in a technological process. Cause-effect relationships in the analysed production process were identified, allowing for the identification of allocation factors. The 'system expansion' method involved expanding the analysis to include five additional variants of electricity production technologies in Poland (alternative technologies). This method revealed environmental consequences of implementation for the analysed technologies. It was found that the LCA of polygeneration technologies based on the 'system expansion' method generated a more complete source of information on environmental consequences than the 'allocation' method. The analysis shows that alternative technologies chosen for generating LCA results are crucial. Life cycle assessment was performed for the analysed, reference and variant alternative technologies. Comparative analysis was performed between the analysed technologies of methanol and electricity co-production from coal gasification as well as a reference technology of methanol production from the natural gas reforming process. Copyright © 2016 Elsevier B.V. All rights reserved.

Early Mars may have had a methanol ocean

NASA Astrophysics Data System (ADS)

Tang, Yan; Chen, Qianwang; Huang, Yujie

2006-01-01

The detection of gray crystalline hematite deposits on Mars by Thermal Emission Spectrometer (TES) has been used to argue for the presence of liquid water on Mars in the distant past. By methanol-thermal treatment of anhydrous FeCl 3 at low temperatures (70-160 °C), crystalline gray hematite with layered structure was synthesized, based on this result an alternative explanation for the origin of martian hematite deposits is suggested. Methane could be abundant in the early martian atmosphere; process such as photochemical oxidation of methane could result in the formation of ocean or pool of organic compounds such as methanol, which provides an environment for the formation of large-scale hematite deposits on Mars.

Investigation of grafted ETFE-based polymer membranes as alternative electrolyte for direct methanol fuel cells

NASA Astrophysics Data System (ADS)

Aricò, A. S.; Baglio, V.; Cretı̀, P.; Di Blasi, A.; Antonucci, V.; Brunea, J.; Chapotot, A.; Bozzi, A.; Schoemans, J.

Low cost ethylene-tetrafluoroethylene (ETFE)-based grafted membranes have been prepared by a process based on electron beam irradiation, subsequent grafting, cross-linking and sulfonation procedure. Two different grafted membranes varying by their grafting and cross-linking levels have been investigated for applications in direct methanol fuel cells (DMFCs) operating between 90 and 130 °C. DMFC assemblies based on these membranes showed cell resistance and performance values comparable to Nafion 117. Stable electrochemical performance was recorded during 1 month of cycled operation. Tailoring of grafting and cross-linking properties allows a significant reduction of methanol cross-over while maintaining suitable conductivity and performance levels.

Role of catechol in the radical reduction of B-alkylcatecholboranes in presence of methanol.

PubMed

Povie, Guillaume; Villa, Giorgio; Ford, Leigh; Pozzi, Davide; Schiesser, Carl H; Renaud, Philippe

2010-02-07

Mechanistic investigations on the previously reported reduction of B-alkylcatecholboranes in the presence of methanol led to the disclosure of a new mechanism involving catechol as a reducing agent. More than just revising the mechanism of this reaction, we disclose here the surprising role of catechol, a chain breaking antioxidant, which becomes a source of hydrogen atoms in an efficient radical chain process.

Synthesis of nanoporous CuO/TiO2/Pd-NiO composite catalysts by chemical dealloying and their performance for methanol and ethanol electro-oxidation

NASA Astrophysics Data System (ADS)

Niu, Mengying; Xu, Wence; Zhu, Shengli; Liang, Yanqin; Cui, Zhenduo; Yang, Xianjin; Inoue, Akihisa

2017-09-01

Nanoporous CuO/TiO2/Pd-NiO-x (x = 0, 1, 3, 5, 7 at%) catalysts have been synthesized by dealloying Cu-Ti-Pd-Ni alloy ribbons in acid solution. The nanoporous structure and chemical composition of the catalysts distribute uniformly. Based on the electrochemical active area (EASA), electrocatalytic activity and stability, the np-CuO/TiO2/Pd-NiO-3 catalyst possesses the best performance for methanol and ethanol electro-oxidation. For methanol and ethanol electro-oxidation, the anodic current densities in forward scan of the np-CuO/TiO2/Pd-NiO-3 catalyst are about 5.6 times and 2.1 times larger than that of the np-CuO/TiO2/Pd catalyst, respectively. The introduction of NiO provides more electrochemical active sites due to the improved geometrical and bifunctional mechanism. NiO promotes the adsorption of oxygen-containing species (OHads) on the catalyst surface, and electron effect between Pd and Ni is favorable for charge transfer. This accelerates the removal of intermediate products during the oxidation process. The electrocatalytic processes of methanol and ethanol oxidation in alkaline solution are controlled by both charge transfer and diffusion.

Bioenergetic Strategy for the Biodegradation of p-Cresol by the Unicellular Green Alga Scenedesmus obliquus

PubMed Central

Papazi, Aikaterini; Assimakopoulos, Konstantinos; Kotzabasis, Kiriakos

2012-01-01

Cultures from the unicellular green alga Scenedesmus obliquus biodegrade the toxic p-cresol (4-methylphenol) and use it as alternative carbon/energy source. The biodegradation procedure of p-cresol seems to be a two-step process. HPLC analyses indicate that the split of the methyl group (first step) that is possibly converted to methanol (increased methanol concentration in the growth medium), leading, according to our previous work, to changes in the molecular structure and function of the photosynthetic apparatus and therefore to microalgal biomass increase. The second step is the fission of the intermediately produced phenol. A higher p-cresol concentration results in a higher p-cresol biodegradation rate and a lower total p-cresol biodegradability. The first biodegradation step seems to be the most decisive for the effectiveness of the process, because methanol offers energy for the further biodegradation reactions. The absence of LHCII from the Scenedesmus mutant wt-lhc stopped the methanol effect and significantly reduced the p-cresol biodegradation (only 9%). The present contribution deals with an energy distribution between microalgal growth and p-cresol biodegradation, activated by p-cresol concentration. The simultaneous biomass increase with the detoxification of a toxic phenolic compound (p-cresol) could be a significant biotechnological aspect for further applications. PMID:23251641

Bronchodilatory and B-adrenergic effects of methanolic and aqueous extracts of Althaea root on isolated tracheobronchial smooth rat muscle.

PubMed

Alani, Behrang; Zare, Mohammad; Noureddini, Mahdi

2015-01-01

The smooth muscle contractions of the tracheobronchial airways are mediated through the balance of adrenergic, cholinergic and peptidergic nervous mechanisms. This research was designed to determine the bronchodilatory and B-adrenergic effects of methanolic and aqueous extracts of root Althaea on the isolated tracheobronchial smooth muscle of the rat. In this experimental study, 116 tracheobronchial sections (5 mm) from 58 healthy male Sprague-Dawley rats were dissected and divided into 23 groups. The effect of methanolic and aqueous extracts of the root Althaea was assayed at different concentrations (0.2, 0.6, 2.6, 6.6, 14.6 μg/ml) and epinephrine (5 μm) in the presence and absence of propranolol (1 μM) under one g tension based on the isometric method. This assay was recorded in an organ bath containing Krebs-Henseleit solution for tracheobronchial smooth muscle contractions using potassium chloride (KCl) (60 mM) induction. Epinephrine (5 μm) alone and root methanolic and aqueous extract concentrations (0.6-14.6 μg/ml) reduced tracheobronchial smooth muscle contractions induced using KCl (60 mM) in a dose dependent manner. Propranolol inhibited the antispasmodic effect of epinephrine on tracheobronchial smooth muscle contractions, but could not reduce the antispasmodic effect of the root extract concentrations. The methanolic and aqueous extracts of Althaea root inhibited the tracheobronchial smooth muscle contractions of rats in a dose dependent manner, but B-adrenergic receptors do not appear to engage in this process. Understanding the mechanism of this process can be useful in the treatment of pulmonary obstructive diseases like asthma.

Recombinant protein expression in Pichia pastoris strains with an engineered methanol utilization pathway

PubMed Central

2012-01-01

Βackground The methylotrophic yeast Pichia pastoris has become an important host organism for recombinant protein production and is able to use methanol as a sole carbon source. The methanol utilization pathway describes all the catalytic reactions, which happen during methanol metabolism. Despite the importance of certain key enzymes in this pathway, so far very little is known about possible effects of overexpressing either of these key enzymes on the overall energetic behavior, the productivity and the substrate uptake rate in P. pastoris strains. Results A fast and easy-to-do approach based on batch cultivations with methanol pulses was used to characterize different P. pastoris strains. A strain with MutS phenotype was found to be superior over a strain with Mut+ phenotype in both the volumetric productivity and the efficiency in expressing recombinant horseradish peroxidase C1A. Consequently, either of the enzymes dihydroxyacetone synthase, transketolase or formaldehyde dehydrogenase, which play key roles in the methanol utilization pathway, was co-overexpressed in MutS strains harboring either of the reporter enzymes horseradish peroxidase or Candida antarctica lipase B. Although the co-overexpression of these enzymes did not change the stoichiometric yields of the recombinant MutS strains, significant changes in the specific growth rate, the specific substrate uptake rate and the specific productivity were observed. Co-overexpression of dihydroxyacetone synthase yielded a 2- to 3-fold more efficient conversion of the substrate methanol into product, but also resulted in a reduced volumetric productivity. Co-overexpression of formaldehyde dehydrogenase resulted in a 2-fold more efficient conversion of the substrate into product and at least similar volumetric productivities compared to strains without an engineered methanol utilization pathway, and thus turned out to be a valuable strategy to improve recombinant protein production. Conclusions Co-overexpressing enzymes of the methanol utilization pathway significantly affected the specific growth rate, the methanol uptake and the specific productivity of recombinant P. pastoris MutS strains. A recently developed methodology to determine strain specific parameters based on dynamic batch cultivations proved to be a valuable tool for fast strain characterization and thus early process development. PMID:22330134

Electron microscopic analysis and structural characterization of novel NADP(H)-containing methanol: N,N'-dimethyl-4-nitrosoaniline oxidoreductases from the gram-positive methylotrophic bacteria Amycolatopsis methanolica and Mycobacterium gastri MB19.

PubMed Central

Bystrykh, L V; Vonck, J; van Bruggen, E F; van Beeumen, J; Samyn, B; Govorukhina, N I; Arfman, N; Duine, J A; Dijkhuizen, L

1993-01-01

The quaternary protein structure of two methanol:N,N'-dimethyl-4-nitrosoaniline (NDMA) oxidoreductases purified from Amycolatopsis methanolica and Mycobacterium gastri MB19 was analyzed by electron microscopy and image processing. The enzymes are decameric proteins (displaying fivefold symmetry) with estimated molecular masses of 490 to 500 kDa based on their subunit molecular masses of 49 to 50 kDa. Both methanol:NDMA oxidoreductases possess a tightly but noncovalently bound NADP(H) cofactor at an NADPH-to-subunit molar ratio of 0.7. These cofactors are redox active toward alcohol and aldehyde substrates. Both enzymes contain significant amounts of Zn2+ and Mg2+ ions. The primary amino acid sequences of the A. methanolica and M. gastri MB19 methanol:NDMA oxidoreductases share a high degree of identity, as indicated by N-terminal sequence analysis (63% identity among the first 27 N-terminal amino acids), internal peptide sequence analysis, and overall amino acid composition. The amino acid sequence analysis also revealed significant similarity to a decameric methanol dehydrogenase of Bacillus methanolicus C1. Images PMID:8449887

Production of polyhydroxyalkanoates from methanol by a new methylotrophic bacterium Methylobacterium sp. GW2.

PubMed

Yezza, A; Fournier, D; Halasz, A; Hawari, J

2006-11-01

A new bacterial strain, isolated from groundwater contaminated with explosives, was characterized as a pink-pigmented facultative methylotroph, affiliated to the genus Methylobacterium. The bacterial isolate designated as strain GW2 was found capable of producing the homopolymer poly-3-hydroxybutyrate (PHB) from various carbon sources such as methanol, ethanol, and succinate. Methanol acted as the best substrate for the production of PHB reaching 40 % w/w dry biomass. PHB accumulation was observed to be a growth-associated process, so that there was no need for two-step fermentation. Optimal growth occurred at 0.5 % (v/v) methanol concentration, and growth was strongly inhibited at alpha concentration above 2 % (v/v). Methylobacterium sp. strain GW2 was also able to accumulate the copolyester poly-3-hydroxybutyrate-poly-3-hydroxyvalerate (PHB/HV) when valeric acid was supplied as an auxiliary carbon source to methanol. After 66 h, a copolymer content of 30 % (w/w) was achieved with a PHB to PHV ratio of 1:2. Biopolymers produced by strain GW2 had an average molecular weight ranging from 229,350 to 233,050 Da for homopolymer PHB and from 362,430 to 411,300 Da for the copolymer PHB/HV.

Flash-point prediction for binary partially miscible mixtures of flammable solvents.

PubMed

Liaw, Horng-Jang; Lu, Wen-Hung; Gerbaud, Vincent; Chen, Chan-Cheng

2008-05-30

Flash point is the most important variable used to characterize fire and explosion hazard of liquids. Herein, partially miscible mixtures are presented within the context of liquid-liquid extraction processes. This paper describes development of a model for predicting the flash point of binary partially miscible mixtures of flammable solvents. To confirm the predictive efficacy of the derived flash points, the model was verified by comparing the predicted values with the experimental data for the studied mixtures: methanol+octane; methanol+decane; acetone+decane; methanol+2,2,4-trimethylpentane; and, ethanol+tetradecane. Our results reveal that immiscibility in the two liquid phases should not be ignored in the prediction of flash point. Overall, the predictive results of this proposed model describe the experimental data well. Based on this evidence, therefore, it appears reasonable to suggest potential application for our model in assessment of fire and explosion hazards, and development of inherently safer designs for chemical processes containing binary partially miscible mixtures of flammable solvents.

Can Supported Reduced Vanadium Oxides form H2 from CH3OH? A Computational Gas-Phase Mechanistic Study.

PubMed

González-Navarrete, Patricio; Andrés, Juan; Calatayud, Monica

2018-02-01

A detailed density functional theory study is presented to clarify the mechanistic aspects of the methanol (CH 3 OH) dehydrogenation process to yield hydrogen (H 2 ) and formaldehyde (CH 2 O). A gas-phase vanadium oxide cluster is used as a model system to represent reduced V(III) oxides supported on TiO 2 catalyst. The theoretical results provide a complete scenario, involving several reaction pathways in which different methanol adsorption sites are considered, with presence of hydride and methoxide intermediates. Methanol dissociative adsorption process is both kinetically and thermodynamically feasible on V-O-Ti and V═O sites, and it might lead to form hydride species with interesting catalytic reactivity. The formation of H 2 and CH 2 O on reduced vanadium sites, V(III), is found to be more favorable than for oxidized vanadium species, V(V), taking place along energy barriers of 29.9 and 41.0 kcal/mol, respectively.

Methanol synthesis on ZnO(0001{sup ¯}). IV. Reaction mechanisms and electronic structure

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

Frenzel, Johannes, E-mail: johannes.frenzel@theochem.rub.de; Marx, Dominik

2014-09-28

Methanol synthesis from CO and H{sub 2} over ZnO, which requires high temperatures and high pressures giving rise to a complex interplay of physical and chemical processes over this heterogeneous catalyst surface, is investigated using ab initio simulations. The redox properties of the surrounding gas phase are known to directly impact on the catalyst properties and thus, set the overall catalytic reactivity of this easily reducible oxide material. In Paper III of our series [J. Kiss, J. Frenzel, N. N. Nair, B. Meyer, and D. Marx, J. Chem. Phys. 134, 064710 (2011)] we have qualitatively shown that for the partiallymore » hydroxylated and defective ZnO(0001{sup ¯}) surface there exists an intricate network of surface chemical reactions. In the present study, we employ advanced molecular dynamics techniques to resolve in detail this reaction network in terms of elementary steps on the defective surface, which is in stepwise equilibrium with the gas phase. The two individual reduction steps were investigated by ab initio metadynamics sampling of free energy landscapes in three-dimensional reaction subspaces. By also sampling adsorption and desorption processes and thus molecular species that are in the gas phase but close to the surface, our approach successfully generated several alternative pathways of methanol synthesis. The obtained results suggest an Eley-Rideal mechanism for both reduction steps, thus involving “near-surface” molecules from the gas phase, to give methanol preferentially over a strongly reduced catalyst surface, while important side reactions are of Langmuir-Hinshelwood type. Catalyst re-reduction by H{sub 2} stemming from the gas phase is a crucial process after each reduction step in order to maintain the catalyst's activity toward methanol formation and to close the catalytic cycle in some reaction channels. Furthermore, the role of oxygen vacancies, side reactions, and spectator species is investigated and mechanistic details are discussed based on extensive electronic structure analysis.« less

Process for purification of waste water produced by a Kraft process pulp and paper mill

NASA Technical Reports Server (NTRS)

Humphrey, M. F. (Inventor)

1979-01-01

The water from paper and pulp wastes obtained from a mill using the Kraft process is purified by precipitating lignins and lignin derivatives from the waste stream with quaternary ammonium compounds, removing other impurities by activated carbon produced from the cellulosic components of the water, and then separating the water from the precipitate and solids. The activated carbon also acts as an aid to the separation of the water and solids. If recovery of lignins is also desired, then the precipitate containing the lignins and quaternary ammonium compounds is dissolved in methanol. Upon acidification, the lignin is precipitated from the solution. The methanol and quaternary ammonium compound are recovered for reuse from the remainder.

Preparation of Grinding Aid Using Waste Acid Residue from Plasticizer Plant

NASA Astrophysics Data System (ADS)

Li, Lingxiao; Feng, Yanchao; Liu, Manchao; Zhao, Fengqing

2017-09-01

The grinding aid for granulated blast-furnace slag were prepared from waste acid residue from plasticizer plant through neutralization, de-methanol and granulation process. In this process, sulfuric acid was transformed into gypsum which has much contribution for grinding effect by combined use with the glycerol and poly glycerin in the waste. Fly ash was used for granulation for the composite grinding aid. Methanol can be recycled in the process. The result showed that the suitable addition of grinding aid is 0.03 % of granulated blast-furnace slag (mass). In this case, the specific surface area is 14% higher than that of the blank. Compared with the common grinding aids, it has excellent performance and low cost.

Multiple hydrogen bonding in excited states of aminopyrazine in methanol solution: time-dependent density functional theory study.

PubMed

Chai, Shuo; Yu, Jie; Han, Yong-Chang; Cong, Shu-Lin

2013-11-01

Aminopyrazine (AP) and AP-methanol complexes have been theoretically studied by using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The excited-state hydrogen bonds are discussed in detail. In the ground state the intermolecular multiple hydrogen bonds can be formed between AP molecule and protic solvents. The AP monomer and hydrogen-bonded complex of AP with one methanol are photoexcited initially to the S2 state, and then transferred to the S1 state via internal conversion. However the complex of AP with two methanol molecules is directly excited to the S1 state. From the calculated electronic excited energies and simulated absorption spectra, we find that the intermolecular hydrogen bonds are strengthened in the electronic excited states. The strengthening is confirmed by the optimized excited-state geometries. The photochemical processes in the electronic excited states are significantly influenced by the excited-state hydrogen bond strengthening. Copyright © 2013 Elsevier B.V. All rights reserved.

Separation and conversion dynamics of nuclear-spin isomers of gaseous methanol

PubMed Central

Sun, Zhen-Dong; Ge, Meihua; Zheng, Yujun

2015-01-01

All symmetrical molecules with non-zero nuclear spin exist in nature as nuclear-spin isomers (NSIs). However, owing to the lack of experimental information, knowledge is rare about interconversions of NSIs of gaseous molecules with torsional symmetry. Here we report our separation and conversion observations on NSI-torsion-specific transition systems of gaseous methanol from a light-induced drift experiment involving partially spatial separation of the ortho and para isomers. We find that vibrationally excited molecules of the methanol spin isomer have a smaller collision cross-section than their ground-state counterparts. Interconversion of the enriched ortho isomer with the para isomer, which is generally considered improbable, has been quantitatively studied by sensitive detections of the spectral intensities. Rather counterintuitively, this reveals that the interconversion is inhibited with increasing pressure. Our results suggest that the spin conversion mechanism in methanol is via a quantum relaxation process with the quantum Zeno effect induced by molecular collisions. PMID:25880882

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

Morris, G.D.L.

One of the many joint venture alliances recently announced in the petrochemical sector is ending in divorce. Hoechst Celanese Chemical (Dallas) and Methanex Corp. (Vancouver) are in the process of dissolving the partnership they had formed to restart Hoechst Celanese's methanol plant at Clear Lake, TX. Hoechst Celanese says it is actively seeking replacement partners and has several likely prospects, while Methanex is concentrating on its other ventures. Those include its just-completed acquisition of Fletcher Challenge's (Auckland, NZ) methanol business and a joint venture with American Cyanamid to convert an ammonia plant at Fortier, LA to methanol. Methanex will stillmore » be the world's largest producer of methanol. Officially, the negotiations between Methanex and Hoechst Celanese just broke down over the last month or so,' says Steve Yurich, operations manager for the Clear Lake plant. Market sources, however, say that Methanex found itself with too many irons in the fire' and pulled out before it ran into financial or perhaps even antitrust difficulties.« less

Bioavailability of butachlor and myclobutanil residues in soil to earthworms.

PubMed

Yu, Y L; Wu, X M; Li, S N; Fang, H; Tan, Y J; Yu, J Q

2005-05-01

To establish chemical extraction procedures for predicting bioavailability of butachlor and myclobutanil in soil, several solvent systems, including methanol, methanol-water (9:1), methanol-water (1:1), acetone-water (5:3), petroleum ether and water, were assessed for their feasibility in determining extractability of the target compounds from soil samples. Experimental data showed that the extractability of butachlor and myclobutanil by the solvents was well linearly correlated with their bioavailability to Eisenia foetida and Allolobophora caliginosa, indicating that these extraction procedures may be efficient for predicting bioavailability of the two pesticides. The concentrations of the pesticides accumulated in E. foetida and A. caliginosa varied with species, suggesting that the availability of the soil-sequestered pesticide is a species-dependent process.

Design of a Facility to Implement a Low Cost Process for Production of NHC

DTIC Science & Technology

1979-05-15

CO4PANY V. i In brief, crude NHC is produced by sequential batch- wise solution processing, initially converting BIO to the sulfide ligand with subsequent...L 1.03 50 214 R-3 (Dibutyl Sulfide ) L 0.84 -112 360 R-4 (Pyridine) L 0.98 - 44 240 1-Octyne L 0.75 -110 260 Acetone L 0.79 -138 134 Methanol L 0.79...R3 -- 25-Octyne- 300 C5 30 TOL 4 NHC -AREA 40 LEGEND: 82 - Diborane R2 - Dioxane B10 - Decaborane R3 - Butyl Sulfide C5 - Pentane MEOH - Methanol C6

Intensification of esterification of acids for synthesis of biodiesel using acoustic and hydrodynamic cavitation.

PubMed

Kelkar, Mandar A; Gogate, Parag R; Pandit, Aniruddha B

2008-03-01

Cavitation results in conditions of turbulence and liquid circulation in the reactor which can aid in eliminating mass transfer resistances. The present work illustrates the use of cavitation for intensification of biodiesel synthesis (esterification) reaction, which is mass transfer limited reaction considering the immiscible nature of the reactants, i.e., fatty acids and alcohol. Esterification of fatty acid (FA) odour cut (C(8)-C(10)) with methanol in the presence of concentrated H(2)SO(4) as a catalyst has been studied in hydrodynamic cavitation reactor as well as in the sonochemical reactor. The different reaction operating parameters such as molar ratio of acid to alcohol, catalyst quantity have been optimized under acoustic as well as hydrodynamic cavitating conditions in addition to the optimization of the geometry of the orifice plate in the case of hydrodynamic cavitation reactors. Few experiments have also been carried out with other acid (lower and higher)/methanol combination viz. caprylic acid and capric acids with methanol with an aim of investigating the efficacy of cavitation for giving the desired yields and also to quantify the degree of process intensification that can be achieved using the same. It has been observed that ambient operating conditions of temperature and pressure and reaction times of <3h, for all the different combinations of acid (lower and higher)/methanol studied in the present work, was sufficient for giving >90% conversion (mol%). This clearly establishes the efficacy of cavitation as an excellent way to achieve process intensification of the biodiesel synthesis process.

Bioprocess and downstream optimization of recombinant human growth hormone in Pichia pastoris

PubMed Central

Azadi, Saeed; Sadjady, Seyed Kazem; Mortazavi, Seyed Alireza; Naghdi, Nasser; Mahboubi, Arash; Solaimanian, Roya

2018-01-01

The methylotrophic yeast Pichia pastoris is a well-established expression host, which is often used in the production of protein pharmaceuticals. This work aimed to evaluate the effect of various concentrations of ascorbic acid in mixed feeding strategy with sorbitol/methanol on productivity of recombinant human growth hormone (r-hGH). The relevant concentration of ascorbic acid (5, 10, or 20 mmol) and 50 g/L sorbitol were added in batch-wise mode to the medium at the beginning of induction phase. The rate of methanol addition was increased stepwise during the first 12 h of production and then kept constant. Total protein and r-hGH concentrations were analyzed and the results compared with sorbitol/methanol feeding using one-way analysis of variance. Moreover, an effective clarification process using activated carbon was developed to remove process contaminants like pigments and endotoxins. Finally, a three-step chromatographic process was applied to purify the product. According to the obtained results, addition of 10 mmol ascorbic acid to sorbitol/methanol co-feeding could significantly increase cell biomass (1.7 fold), total protein (1.14 fold), and r-hGH concentration (1.43 fold). One percent activated carbon could significantly decrease pigments and endotoxins without any significant changes in r-hGH assay. The result of the study concluded that ascorbic acid in combination with sorbitol could effectively enhance the productivity of r-hGH. This study also demonstrated that activated carbon clarification is a simple method for efficient removal of endotoxin and pigment in production of recombinant protein in the yeast expression system. PMID:29853932

Facility Layout Problems Using Bays: A Survey

NASA Astrophysics Data System (ADS)

Davoudpour, Hamid; Jaafari, Amir Ardestani; Farahani, Leila Najafabadi

2010-06-01

Layout design is one of the most important activities done by industrial Engineers. Most of these problems have NP hard Complexity. In a basic layout design, each cell is represented by a rectilinear, but not necessarily convex polygon. The set of fully packed adjacent polygons is known as a block layout (Asef-Vaziri and Laporte 2007). Block layout is divided by slicing tree and bay layout. In bay layout, departments are located in vertical columns or horizontal rows, bays. Bay layout is used in real worlds especially in concepts such as semiconductor and aisles. There are several reviews in facility layout; however none of them focus on bay layout. The literature analysis given here is not limited to specific considerations about bay layout design. We present a state of art review for bay layout considering some issues such as the used objectives, the techniques of solving and the integration methods in bay.

An annotated catalogue of the type material of Elateroidea Leach, 1815 (Coleoptera) deposited in the Coleoptera collection of the Museum of Zoology of the University of São Paulo, Brazil.

PubMed

Ferreira, Vinicius De Souza

2015-03-25

The Museum of Zoology of the University of São Paulo (MZSP) houses one of the most important Coleoptera collections of Brazil and Neotropical Region with nearly 900,000 adult mounted material and about 1,500,000 specimens to be mounted. The superfamily Elateroidea Leach, 1815 (including Cantharoidea) comprises about 24,077 described species in 17 families. The MZSP owns type material of Brachypsectridae LeConte & Horn, 1883, Cantharidae, 1856 (1815), Cerophytidae Latreille, 1834, Elateridae Leach 1815, Eucnemidae Eschscholtz, 1829, Lampyridae Rafinesque, 1815, Lycidae Laporte, 1836, Phengodidae LeConte, 1861 and Rhinorhipidae Lawrence, 1988. This catalogue includes type material of 166 species distributed in 69 genera. Among 1,223 type specimens, are 86 holotypes, 1,133 paratypes, 2 allotypes, 1 lectotype and 1 paralectotype.

Fluid Dynamics Prize Otto Laporte Lecture:Turbulence and Aeroacoustics

NASA Astrophysics Data System (ADS)

Comte-Bellot, Genevieve

2014-11-01

Some significant advances obtained over the years for two closely related fields, Turbulence and Aeroacoustics, are presented. Particular focus is placed on experimental results and on physical mechanisms. For example, for a 2D channel flow, skewness factors of velocity fluctuations are discussed. The study of isotropic turbulence generated by grids in the «Velvet wind tunnel» of Stanley Corrsin, constitutes a masterpiece. Of particular note are the Eulerian memory times, analysed for all wavenumbers. Concerning hot-wire anemometry, the potential of the new constant voltage technique is presented. Some results obtained with Particule Image Velocimetry are also reported. Two flow control examples are illustrated: lift generation for a circular cylinder, and noise reduction for a high speed jet. Finally, the propagation of acoustic waves through turbulence is considered. Experimental data are here completed by numerical simulations showing the possible occurrence of caustics.

Photochemical behavior of fenpropathrin and λ-cyhalothrin in solution.

PubMed

Liu, P Y; Li, B; Liu, H D; Tian, L

2014-02-01

The photodegradation processes of fenpropathrin and λ-cyhalothrin were studied in hexane, methanol/water (1:1, v/v), and acetone in both ultraviolet light and simulated sunlight. Intermediates in the photodegradation process were identified using gas chromatography/mass spectrometry (GC/MS), and the analysis of intermediates was used to speculate on possible photodegradation pathways. The photodegradation processes of fenpropathrin and λ-cyhalothrin followed pseudo first-order kinetics. The photodegradation rates varied according to the solvent in decreasing order: hexane>methanol/water (1:1, v/v)>acetone. The effects of substances coexisting in the environment on the photodegradation of pyrethroids were also investigated in the research. Acetone, humic acid, and riboflavin increased photodegradation rates while L-ascorbic acid slowed the process. This study provides a theoretical basis for the removal of pyrethroid pollution from the natural environment.

Catalyst and process development for the H/sub 2/ preparation from future fuel cell feedstocks. Quarterly progress report, October 1, 1978-December 31, 1978

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

Yarrington, R M; Feins, I R; Hwang, H S

1979-01-01

The work done under this contract in the last quarter of 1978 was concerned with Phase I, which involved preliminary catalyst and process evaluation. The processes under study are hydrogen assisted steam reforming (HASR), catalytic partial oxidation (CPO), and autothermal steam reforming (ATR). Existing Engelhard test units were modified to carry out preliminary runs using the first two processes. Technical analysis to support work in this area consisted of heat and material balances constrained by equilibrium considerations. In a third task, the steam reforming of methanol to produce hydrogen was studied over two commercial low-temperature shift catalysts. Aging runs indicatedmore » good initial performance on both catalysts, but methanol conversion started to decline after a few hundred hours on stream.« less

On-line monitoring of methanol and methyl formate in the exhaust gas of an industrial formaldehyde production plant by a mid-IR gas sensor based on tunable Fabry-Pérot filter technology.

PubMed

Genner, Andreas; Gasser, Christoph; Moser, Harald; Ofner, Johannes; Schreiber, Josef; Lendl, Bernhard

2017-01-01

On-line monitoring of key chemicals in an industrial production plant ensures economic operation, guarantees the desired product quality, and provides additional in-depth information on the involved chemical processes. For that purpose, rapid, rugged, and flexible measurement systems at reasonable cost are required. Here, we present the application of a flexible mid-IR filtometer for industrial gas sensing. The developed prototype consists of a modulated thermal infrared source, a temperature-controlled gas cell for absorption measurement and an integrated device consisting of a Fabry-Pérot interferometer and a pyroelectric mid-IR detector. The prototype was calibrated in the research laboratory at TU Wien for measuring methanol and methyl formate in the concentration ranges from 660 to 4390 and 747 to 4610 ppmV. Subsequently, the prototype was transferred and installed at the project partner Metadynea Austria GmbH and linked to their Process Control System via a dedicated micro-controller and used for on-line monitoring of the process off-gas. Up to five process streams were sequentially monitored in a fully automated manner. The obtained readings for methanol and methyl formate concentrations provided useful information on the efficiency and correct functioning of the process plant. Of special interest for industry is the now added capability to monitor the start-up phase and process irregularities with high time resolution (5 s).

Assessing metabolic heterogeneity in genetically homogeneous populations of bacteria using SIMS

NASA Astrophysics Data System (ADS)

McClelland, H. L. O.; Fike, D. A.; Jones, C.; Bradley, A. S.

2016-12-01

Biogeochemical cycles of elements are catalyzed by microbes, and can be assessed using a wide array of geochemical techniques. As the spatial resolution of these analytical techniques improves over time, it has become apparent that spatial heterogeneity of geochemical processes may impose noise on a range of geochemical signals. This spatial heterogeneity may reflect population structure, as well as metabolic heterogeneity among cells. New analytical approaches are required to understand, at the cellular level, differences in biogeochemical cycling of elements. We are developing such approaches by applying secondary-ion mass spectrometry (SIMS) techniques to populations of model organisms. In this work we report initial results from the analysis of genetically homogeneous cultures of Methylobacterium extorquens PA1, a facultative methylotrophic Alphaproteobacterium that has been extensively studied growing on both single carbon (e.g., methanol) and multi-carbon (e.g., succinate) substrates. PA1 cultures acclimated to succinate exhibited a more pronounced lag when grown on methanol compared with populations acclimated to methanol. However neither acclimation condition results in a pronounced lag during growth on succinate. When grown on a mixture of methanol and succinate, Methylobacterium co-utilize these substrates on a population level. We investigated the degree to which this apparent coutilisation is representative of individual cells, or whether it is a superposition of distinct metabolically specialized subpopulations. To explore this metabolic heterogeneity, we have grown populations of PA1 in liquid media containing a mixture of both methanol and succinate with one or the other substrate labelled with 13C. SIMS analysis of the isotopic composition of each cell allows us to infer the substrate, or mix of substrates, used for anabolic processes in each cell, along with cell-specfic growth rates via the exponential dilution of a 15N label.

Surface studies of low molecular weight photolysis products from UV-ozone oxidised polystyrene

NASA Astrophysics Data System (ADS)

Davidson, M. R.; Mitchell, S. A.; Bradley, R. H.

2005-05-01

The production of low molecular weight oxidised material during UV-ozone treatment of polystyrene has been studied by XPS, GC-MS, FTIR and UV/visible spectroscopy. XPS analysis of the oxidised polystyrene surfaces before and after washing with water or methanol indicates that the removal of oxidation products and the surface that remains after washing is strongly dependent on the choice of solvent. Methanol washing removes a greater proportion of the more highly oxidised carbonyl and carboxyl groups resulting in a surface with a lower oxygen content than that remaining after water washing. Extended exposure to UV-ozone treatment reveals a two-stage oxidation process with mono-substituted benzene rings such as benzaldehyde, acetophenone and benzoic acid being produced at exposure times less than 15 min. Compounds, more typical of those formed via dehydration reactions of existing oxidised species, are produced at longer exposure times. UV-visible spectroscopy and Fourier transform infrared spectroscopy also confirm the presence of carboxylic acid, aromatic ketones and esters. Measurements of water contact angle on a 10 min treated surface reveals that methanol washing produces a more hydrophilic surface than water washing, the resulting water contact angles being 47° and 62° respectively. Ageing of methanol washed surfaces for 24 h leads to a recovery of the water contact angle back to 62° which suggests some form of post-washing surface relaxation process. Since XPS analyses show no increase in the oxygen concentration of the methanol washed surfaces after a 24 h ageing period, the increase in contact angle found with ageing is attributed to the reorientation of very near-surface functional groups i.e. within the XPS sampling depth.

Infrared Spectra and Thermodynamic Properties of Co2/Methanol Ices

NASA Astrophysics Data System (ADS)

Maté, Belén; Gálvez, Óscar; Herrero, Víctor J.; Escribano, Rafael

2009-01-01

Ices of mixtures of carbon dioxide and methanol have been studied in a range of temperatures relevant for star-forming regions, comets, polar caps of planets and satellites, and other solar system bodies. We have performed temperature-programmed desorption measurements and recorded IR spectra of various types of samples. The presence of two slightly different structures of CO2 is manifest. A distorted CO2 structure is characterized by bandshifts between 5 cm-1 (ν3) and 10 cm-1 (ν2) with respect to normal CO2. If the samples are heated above 130 K, the distorted CO2 sublimates and only the normal structure remains. The latter can stay trapped until the sublimation of crystalline methanol (150 K). The desorption energy (E d ~ 20 kJ mol-1) of CO2 from methanol ice, and the specific adsorption surface area (6 m2 g-1) of amorphous CH3OH ice, have been determined. CO2 does not penetrate into crystalline ice. Whereas the desorption energy is similar to that of CO2/H2O samples, the specific surface of methanol is much smaller than that of amorphous solid water (ASW). The interaction of CO2 molecules with water and methanol is similar but ices of CH3OH are much less porous than ASW. The inclusion of CO2 into previously formed ices containing these two species would take place preferentially into ASW. However, in processes of simultaneous deposition, methanol ice can admit a larger amount of CO2 than water ice. CO2/CH3OH ices formed by simultaneous deposition admit two orders of magnitude more CO2 than sequentially deposited ices. These findings can have direct relevance to the interpretation of observations from protostellar environments (e.g., RAFGL7009S) and comet nuclei.

Promoting the Synthesis of Methanol: Understanding the Requirements for an Industrial Catalyst for the Conversion of CO2.

PubMed

Behrens, Malte

2016-11-21

The hydrogenation of CO 2 to methanol is a potential process for the sustainable production of synthetic liquid fuels. The Cu/ZnO catalyst employed for this reaction has been studied extensively for many years, and recent progress now has the potential to turn it into a prototype for complex promotional interactions in heterogeneous catalysis. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of sludge age on methanogenic and glycogen accumulating organisms in an aerobic granular sludge process fed with methanol and acetate

PubMed Central

Pronk, M; Abbas, B; Kleerebezem, R; van Loosdrecht, M C M

2015-01-01

The influence of sludge age on granular sludge formation and microbial population dynamics in a methanol- and acetate-fed aerobic granular sludge system operated at 35°C was investigated. During anaerobic feeding of the reactor, methanol was initially converted to methane by methylotrophic methanogens. These methanogens were able to withstand the relatively long aeration periods. Lowering the anaerobic solid retention time (SRT) from 17 to 8 days enabled selective removal of the methanogens and prevented unwanted methane formation. In absence of methanogens, methanol was converted aerobically, while granule formation remained stable. At high SRT values (51 days), γ-Proteobacteria were responsible for acetate removal through anaerobic uptake and subsequent aerobic growth on storage polymers formed [so called metabolism of glycogen-accumulating organisms (GAO)]. When lowering the SRT (24 days), Defluviicoccus-related organisms (cluster II) belonging to the α-Proteobacteria outcompeted acetate consuming γ-Proteobacteria at 35°C. DNA from the Defluviicoccus-related organisms in cluster II was not extracted by the standard DNA extraction method but with liquid nitrogen, which showed to be more effective. Remarkably, the two GAO types of organisms grew separately in two clearly different types of granules. This work further highlights the potential of aerobic granular sludge systems to effectively influence the microbial communities through sludge age control in order to optimize the wastewater treatment processes. PMID:26059251

Characterization and methanol electrooxidation studies of Pt(111)/Os surfaces prepared by spontaneous deposition.

PubMed

Johnston, Christina M; Strbac, Svetlana; Lewera, Adam; Sibert, Eric; Wieckowski, Andrzej

2006-09-12

Catalytic activity of the Pt(111)/Os surface toward methanol electrooxidation was optimized by exploring a wide range of Os coverage. Various methods of surface analyses were used, including electroanalytical, STM, and XPS methods. The Pt(111) surface was decorated with nanosized Os islands by spontaneous deposition, and the Os coverage was controlled by changing the exposure time to the Os-containing electrolyte. The structure of Os deposits on Pt(111) was characterized and quantified by in situ STM and stripping voltammetry. We found that the optimal Os surface coverage of Pt(111) for methanol electrooxidation was 0.7 +/- 0.1 ML, close to 1.0 +/- 0.1 Os packing density. Apparently, the high osmium coverage Pt(111)/Os surface provides more of the necessary oxygen-containing species (e.g., Os-OH) for effective methanol electrooxidation than the Pt(111)/Os surfaces with lower Os coverage (vs e.g., Ru-OH). Supporting evidence for this conjecture comes from the CO electrooxidation data, which show that the onset potential for CO stripping is lowered from 0.53 to 0.45 V when the Os coverage is increased from 0.2 to 0.7 ML. However, the activity of Pt(111)/Os for methanol electrooxidation decreases when the Os coverage is higher than 0.7 +/- 0.1 ML, indicating that Pt sites uncovered by Os are necessary for sustaining significant methanol oxidation rates. Furthermore, osmium is inactive for methanol electrooxidation when the platinum substrate is absent: Os deposits on Au(111), a bulk Os ingot, and thick films of electrodeposited Os on Pt(111), all compare poorly to Pt(111)/Os. We conclude that a bifunctional mechanism applies to the methanol electrooxidation similarly to Pt(111)/Ru, although with fewer available Pt sites. Finally, the potential window for methanol electrooxidation on Pt(111)/Os was observed to shift positively versus Pt(111)/Ru. Because of the difference in the Os and Ru oxophilicity under electrochemical conditions, the Os deposit provides fewer oxygen-containing species, at least below 0.5 V vs RHE. Both higher coverage of Os than Ru and the higher potentials are required to provide a sufficient number of active oxygen-containing species for the effective removal of the site-blocking CO from the catalyst surface when the methanol electrooxidation process occurs.

A Review of Study on Thermal Energy Transport System by Synthesis and Decomposition Reactions of Methanol

NASA Astrophysics Data System (ADS)

Liu, Qiusheng; Yabe, Akira; Kajiyama, Shiro; Fukuda, Katsuya

The study on thermal energy transport system by synthesis and decomposition reactions of methanol was reviewed. To promote energy conservation and global environment protection, a two-step liquid-phase methanol synthesis process, which starts with carbonylation of methanol to methyl formate, then followed by the hydrogenolysis of the formate, was studied to recover wasted or unused discharged heat from industrial sources for the thermal energy demands of residential and commercial areas by chemical reactions. The research and development of the system were focused on the following three points. (1) Development of low-temperature decomposition and synthetic catalysts, (2) Development of liquid phase reactor (heat exchanger accompanying chemical reaction), (3) Simulation of the energy transport efficiency of entire system which contains heat recovery and supply sections. As the result of the development of catalyst, promising catalysts which agree with the development purposes for the methyl formate decomposition reaction and the synthetic reaction are being developed though some studies remain for the methanol decomposition and synthetic reactions. In the fundamental development of liquid phase reactor, the solubilities of CO and H2 gases in methanol and methyl formate were measured by the method of total pressure decrease due to absorption under pressures up to 1500kPa and temperatures up to 140°C. The diffusivity of CO gas in methanol was determined by measuring the diameter and solution time of single CO bubbles in methanol. The chemical reaction rate of methanol synthesis by hydrogenolysis of methyl formate was measured using a plate-type of Raney copper catalyst in a reactor with rectangular channel and in an autoclave reactor. The reaction characteristics were investigated by carrying out the experiments at various temperatures, flow rates and at various catalyst development conditions. We focused on the effect of Raney copper catalyst thickness on the liquid-phase chemical reaction by varying the development time of the catalyst. Investigation results of the catalyst such as surface area, pore radius, lattice size, and photographs of scanning electron microscope (SEM) were also given. In the simulation of energy transport efficiency of this system, by simulating the energy transfer system using two-step liquid phase methanol decomposition and synthetic reactions, and comparing with the technology so far, it can be expected that an innovative energy transfer system is possible to realize.

Effects of the Methanolic Extract of Vitellaria paradoxa Stem Bark Against Scopolamine-Induced Cognitive Dysfunction and Oxidative Stress in the Rat Hippocampus.

PubMed

Foyet, Harquin Simplice; Asongalem, Acha Emmanuel; Oben, Eyong Kenneth; Cioanca, Oana; Hancianu, Monica; Hritcu, Lucian

2016-10-01

Vitellaria paradoxa C.F. Gaertn (Sapotaceae) is a perennial three which naturally grows in the northern part of Cameroon. It has been traditionally used in the Cameroonian folk medicine for treating inflammation and pain. In the present study, we evaluate the possible anti-amnesic and antioxidative effects of the methanolic extract of V. paradoxa stem bark in an Alzheimer's disease (AD) rat model of scopolamine. Rats received a single injection of scopolamine (1.5 mg/kg) before behavioral testing and were treated with the methanolic extract (25 and 50 mg/kg), daily, for eight continuous days. Also, the antioxidant activity in the hippocampus was assessed using the total content of reduced glutathione and malondialdehyde levels. The scopolamine-treated rats exhibited the following: decrease of exploratory time and discrimination index within the novel object recognition test, decrease of spontaneous alternations percentage within Y-maze task, and increase of working memory errors, reference memory errors, and time taken to consume all five baits within radial arm-maze task. Administration of the methanolic extract significantly improved these parameters, suggesting positive effects on memory formation processes and antioxidant potential. Our results suggest that the methanolic extract ameliorates scopolamine-induced memory impairment by attenuation of the oxidative stress in the rat hippocampus.

Methylotrophy in the thermophilic Bacillus methanolicus, basic insights and application for commodity production from methanol.

PubMed

Müller, Jonas E N; Heggeset, Tonje M B; Wendisch, Volker F; Vorholt, Julia A; Brautaset, Trygve

2015-01-01

Using methanol as an alternative non-food feedstock for biotechnological production offers several advantages in line with a methanol-based bioeconomy. The Gram-positive, facultative methylotrophic and thermophilic bacterium Bacillus methanolicus is one of the few described microbial candidates with a potential for the conversion of methanol to value-added products. Its capabilities of producing and secreting the commercially important amino acids L-glutamate and L-lysine to high concentrations at 50 °C have been demonstrated and make B. methanolicus a promising target to develop cell factories for industrial-scale production processes. B. methanolicus uses the ribulose monophosphate cycle for methanol assimilation and represents the first example of plasmid-dependent methylotrophy. Recent genome sequencing of two physiologically different wild-type B. methanolicus strains, MGA3 and PB1, accompanied with transcriptome and proteome analyses has generated fundamental new insight into the metabolism of the species. In addition, multiple key enzymes representing methylotrophic and biosynthetic pathways have been biochemically characterized. All this, together with establishment of improved tools for gene expression, has opened opportunities for systems-level metabolic engineering of B. methanolicus. Here, we summarize the current status of its metabolism and biochemistry, available genetic tools, and its potential use in respect to overproduction of amino acids.

Facile Synthesis of Core/Shell-like NiCo2O4-Decorated MWCNTs and its Excellent Electrocatalytic Activity for Methanol Oxidation

PubMed Central

Ko, Tae-Hoon; Devarayan, Kesavan; Seo, Min-Kang; Kim, Hak-Yong; Kim, Byoung-Suhk

2016-01-01

The design and development of an economic and highly active non-precious electrocatalyst for methanol electrooxidation is challenging due to expensiveness of the precursors as well as processes and non-ecofriendliness. In this study, a facile preparation of core-shell-like NiCo2O4 decorated MWCNTs based on a dry synthesis technique was proposed. The synthesized NiCo2O4/MWCNTs were characterized by infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and selected area energy dispersive spectrum. The bimetal oxide nanoparticles with an average size of 6 ± 2 nm were homogeneously distributed onto the surface of the MWCNTs to form a core-shell-like nanostructure. The NiCo2O4/MWCNTs exhibited excellent electrocatalytic activity for the oxidation of methanol in an alkaline solution. The NiCo2O4/MWCNTs exhibited remarkably higher current density of 327 mA/cm2 and a lower onset potential of 0.128 V in 1.0 M KOH with as high as 5.0 M methanol. The impressive electrocatalytic activity of the NiCo2O4/MWCNTs is promising for development of direct methanol fuel cell based on non-Pt catalysts. PMID:26828633

Effect of Lagerstroemia tomentosa and Diospyros virginiana methanolic extracts on different drug-resistant strains of Mycobacterium tuberculosis

PubMed Central

Esfahani, B. Nasr; Hozoorbakhsh, F.; Rashed, Kh.; Havaei, S.A.; Heidari, K.; Moghim, Sh.

2014-01-01

Mycobacterium tuberculosis (MTB) is the causative agent of tuberculosis. The increasing incidence of multi drug resistance tuberculosis (MDR-TB) and extensively drug resistance tuberculosis (XDR-TB) worldwide highlighted the urgent need to search for alternative antimycobacterial agents. More and more people in developing countries utilize traditional medicine for their major primary health care needs. It has been determined that pharmaceutical plant, Lagerstroemia tomentosa and Diospyros virginiana, possesses some antibacterial effect. In this study, the antimycobacterial effects of L. tomentosa and D. virginiana methanolic extracts on sensitive and resistant isolates of MTB were examined. Leaf methanolic extract was prepared using methanol 70%. Sensitivity and resistance of isolates was determined by proportion method. The effects of two different methonolic extract concentrations (20 and 40 μg/ml) of the plants were examined against 6 sensitive and resistant strains of MTB with different patterns of drug resistance. MTB H37Rv (ATCC 27294) was set as control in all culturing and sensitivity testing processes. The results showed that L. tomentosa and D. virginiana methanolic extracts had weak inhibitory effect on different strains of MTB. The highest percentage of inhibition for L. tomentosa and D. virginiana was observed 38% and 33.3%, respectively. PMID:25657789

Mobil plans methanol plant in Nigeria

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

Alperowicz, N.

1992-08-12

Mobil Chemical (Houston) is in discussions with Nigerian National Petroleum Corp. (NNPC; Lagos) on a joint venture methanol plant at Port Harcourt, Nigeria. The U.S. firm has invited process owners to submit proposals for a 1-million m.t./year unit and hopes to select the technology by the end of this year. Three proposals have been submitted: Lurgi, offering its own low-pressure process; John Brown/Davy, with the ICI process; and M.W. Kellogg, proposing its own technology. Shareholding in the joint venture is yet to be decided, but it is likely to be a 50/50 tie-up. Marketing of Mobil's share or of themore » entire tonnage would be handled by Mobil Petrochemical International (Brussels). The plant could be onstream in late 1996.« less

Different routes to methanol: Inelastic neutron scattering spectroscopy of adsorbates on supported copper catalysts

DOE PAGES

Kandemir, Timur; Friedrich, Matthias; Parker, Stewart F.; ...

2016-04-14

We have investigated methanol synthesis with model supported copper catalysts, Cu/ZnO and Cu/MgO, using CO/H 2 and CO 2/H 2 as feedstocks. Under CO/H 2 both catalysts show chemisorbed methoxy as a stable intermediate, the Cu/MgO catalyst also shows hydroxyls on the support. Under CO 2/H 2 the catalysts behave differently, in that formate is also seen on the catalyst. For the Cu/ZnO catalyst hydroxyls are present on the metal whereas for the Cu/MgO hydroxyls are found on the support. Furthermore, these results are consistent with a recently published model for methanol synthesis and highlight the key role of ZnOmore » in the process.« less

Method for the photocatalytic conversion of gas hydrates

DOEpatents

Taylor, Charles E.; Noceti, Richard P.; Bockrath, Bradley C.

2001-01-01

A method for converting methane hydrates to methanol, as well as hydrogen, through exposure to light. The process includes conversion of methane hydrates by light where a radical initiator has been added, and may be modified to include the conversion of methane hydrates with light where a photocatalyst doped by a suitable metal and an electron transfer agent to produce methanol and hydrogen. The present invention operates at temperatures below 0.degree. C., and allows for the direct conversion of methane contained within the hydrate in situ.

Synergistic effect of graphene oxide on the methanol oxidation for fuel cell application

NASA Astrophysics Data System (ADS)

Siwal, Samarjeet; Ghosh, Sarit; Nandi, Debkumar; Devi, Nishu; Perla, Venkata K.; Barik, Rasmita; Mallick, Kaushik

2017-09-01

Aromatic polypyrene was synthesized by the oxidative polymerization of pyrene with potassium tetrachloropalladate (II), as oxidant. During the polymerization process the palladium salt was reduced to metallic palladium and forms the metal-polymer composite material. Polypyrene stabilized palladium nanoparticles showed electrocatalytic activity toward the oxidation of methanol. The performance of the electrocatalytic activity was substantially improved with the incorporation of graphene oxide to the palladium-polypyrene composite and the synergistic performance was attributed to the electronic and structural properties of the system.

High Contrast Organic Crystal Optical Modulator for Phased Array Antenna and Optical Signal Processing

DTIC Science & Technology

1994-10-27

Thus, we investigated several other secondary amines for use in the condensation of the picoline salt with various substituted benza!dehydes. C I I...a 10 gallon glass lined reactor was charged with 12 L of methanol, 3.120 kg of picoline , and 6.046 kg of methyl toluene sulfonate. The I reaction...dimethylamino benzaldehyde was added to the newly formed picoline salt, I together with an additional 6 L of methanol. Finally, 500 mL of pyrrolidine were slowly

Ag(I)-Promoted Dehydroxylation and Site-Selective 1,7-Disulfonylation of Diaryl(1 H-indol-2-yl)methanols.

PubMed

Zhou, Yu; Cao, Wen-Bin; Zhang, Ling-Ling; Xu, Xiao-Ping; Ji, Shun-Jun

2018-06-01

A novel dehydroxylation and site-selective 1,7-disulfonylation reaction of diaryl(1 H-indol-2-yl)methanols with sodium sulfinates was described. The protocol provided an efficient strategy for the synthesis of disulfonylated 2-(diarylmethyl)indoles by exploring a range of substrates. The mechanistic studies revealed that silver nitrate served as both a Lewis acid and an oxidant for the sequential 1,7-disulfonylation process leading to the formation of final products.

Simultaneous heterotrophic and sulfur-oxidizing autotrophic denitrification process for drinking water treatment: control of sulfate production.

PubMed

Sahinkaya, Erkan; Dursun, Nesrin; Kilic, Adem; Demirel, Sevgi; Uyanik, Sinan; Cinar, Ozer

2011-12-15

A long-term performance of a packed-bed bioreactor containing sulfur and limestone was evaluated for the denitrification of drinking water. Autotrophic denitrification rate was limited by the slow dissolution rate of sulfur and limestone. Dissolution of limestone for alkalinity supplementation increased hardness due to release of Ca(2+). Sulfate production is the main disadvantage of the sulfur autotrophic denitrification process. The effluent sulfate concentration was reduced to values below drinking water guidelines by stimulating the simultaneous heterotrophic and autotrophic denitrification with methanol supplementation. Complete removal of 75 mg/L NO(3)-N with effluent sulfate concentration of around 225 mg/L was achieved when methanol was supplemented at methanol/NO(3)-N ratio of 1.67 (mg/mg), which was much lower than the theoretical value of 2.47 for heterotrophic denitrification. Batch studies showed that sulfur-based autotrophic NO(2)-N reduction rate was around three times lower than the reduction rate of NO(3)-N, which led to NO(2)-N accumulation at high loadings. Copyright © 2011 Elsevier Ltd. All rights reserved.

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.

Final Report

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

David W. Mazyck; Angela Lindner; CY Wu, Rick Sheahan, Ashok Jain

2007-06-30

Forest products provide essential resources for human civilization, including energy and materials. In processing forest products, however, unwanted byproducts, such as volatile organic compounds (VOCs) and hazardous air pollutants (HAPs) are generated. The goal of this study was to develop a cost effective and reliable air pollution control system to reduce VOC and HAP emissions from pulp, paper and paperboard mills and solid wood product facilities. Specifically, this work focused on the removal of VOCs and HAPs from high volume low concentration (HVLC) gases, particularly methanol since it is the largest HAP constituent in these gases. Three technologies were developedmore » and tested at the bench-scale: (1) A novel composite material of activated carbon coated with a photocatalyst titanium dioxide (TiO{sub 2}) (referred to as TiO{sub 2}-coated activated carbon or TiO{sub 2}/AC), (2) a novel silica gel impregnated with nanosized TiO{sub 2} (referred to as silica-titania composites or STC), and (3) biofiltration. A pilot-scale reactor was also fabricated and tested for methanol removal using the TiO{sub 2}/AC and STC. The technical feasibility of removing methanol with TiO{sub 2}/AC was studied using a composite synthesized via a spay desiccation method. The removal of methanol consists of two consecutive operation steps: removal of methanol using fixed-bed activated carbon adsorption and regeneration of spent activated carbon using in-situ photocatalytic oxidation. Regeneration using photocatalytic oxidation employed irradiation of the TiO{sub 2} catalyst with low-energy ultraviolet (UV) light. Results of this technical feasibility study showed that photocatalytic oxidation can be used to regenerate a spent TiO{sub 2}/AC adsorbent. A TiO{sub 2}/AC adsorbent was then developed using a dry impregnation method, which performed better than the TiO{sub 2}/AC synthesized using the spray desiccation method. The enhanced performance was likely a result of the better distribution of TiO2 particles on the activated carbon surface. A method for pore volume impregnation using microwave irradiation was also developed. A commercial microwave oven (800 W) was used as the microwave source. Under 2450 MHz microwave irradiation, TTIP was quickly hydrolyzed and anatase TiO2 was formed in a short time (< 20 minutes). Due to the volumetric heating and selective heating of microwave, the solvent and by-products were quickly removed which reduced energy consumption and processing time. Activated carbon and TiO{sub 2}/AC were also tested for the removal of hydrogen sulfide, which was chosen as the representative total reduced sulfur (TRS) species. The BioNuchar AC support itself was a good H{sub 2}S remover. After coating TiO{sub 2} by dry impregnation, H{sub 2}S removal efficiency of TiO{sub 2}/AC decreased compared with the virgin AC due to the change of surface pH. Under UV light irradiation, H{sub 2}S removal efficiency of TiO{sub 2}/AC composite doubled, and its sulfate conversion efficiency was higher than that of AC. The formation of sulfate is preferred since the sulfate can be removed from the composite by rising with water. A pilot-scale fluidized bed reactor was designed to test the efficiency of methanol oxidation with TiO{sub 2}/AC in the presence of UV light. TiO{sub 2}/AC was prepared using the spray desiccation method. The TiO{sub 2}/AC was pre-loaded with (1) methanol (equivalent to about 2%wt) and (2) methanol and water. When the TiO{sub 2}/AC loaded with methanol only was exposed to UV light for one hour in the reactor, most of the methanol remained in the carbon pores and, thus, was not oxidized. The TiO{sub 2}/AC loaded with methanol and water desorbed about 2/3 of the methanol from its pores during fluidization, however, only a small portion of this desorbed methanol was oxidized. A biofilter system employing biological activated carbon was developed for methanol removal. The biofilter contained a mixed packing with Westvaco BioNuchar granular activated carbon, perlite, Osmocote slow release ammonium nitrate pellets, and Agrasoke water crystals in a 4:2:1:1 ratio by volume. The biofilter was inoculated with a bacterial culture collected from a Florida pulp and paperboard plant. A non-inoculated biofilter column was also tested. Use of a biological inoculum enriched from biofilm in the pulp and paper process has the potential to enhance the performance of a GAC biofilter. During testing, packing material was removed from the inlet and oulet of the biofilters and analyzed for genetic diversity using molecular techniques. The biofilter inoculated with specifically-enhanced inoculum showed higher bacterial diversity for methylotrophs and all bacteria, as compared to a non-inoculated biofilter. Mixed methylotrophic cultures, selected as potential biofilter inocula, showed increased methanol removal with highest concentrations of nitrogen provided as nitrate.« less

High-resolution direct 3D printed PLGA scaffolds: print and shrink.

PubMed

Chia, Helena N; Wu, Benjamin M

2014-12-17

Direct three-dimensional printing (3DP) produces the final part composed of the powder and binder used in fabrication. An advantage of direct 3DP is control over both the microarchitecture and macroarchitecture. Prints which use porogen incorporated in the powder result in high pore interconnectivity, uniform porosity, and defined pore size after leaching. The main limitations of direct 3DP for synthetic polymers are the use of organic solvents which can dissolve polymers used in most printheads and limited resolution due to unavoidable spreading of the binder droplet after contact with the powder. This study describes a materials processing strategy to eliminate the use of organic solvent during the printing process and to improve 3DP resolution by shrinking with a non-solvent plasticizer. Briefly, poly(lactic-co-glycolic acid) (PLGA) powder was prepared by emulsion solvent evaporation to form polymer microparticles. The printing powder was composed of polymer microparticles dry mixed with sucrose particles. After printing with a water-based liquid binder, the polymer microparticles were fused together to form a network by solvent vapor in an enclosed vessel. The sucrose is removed by leaching and the resulting scaffold is placed in a solution of methanol. The methanol acts as a non-solvent plasticizer and allows for polymer chain rearrangement and efficient packing of polymer chains. The resulting volumetric shrinkage is ∼80% at 90% methanol. A complex shape (honey-comb) was designed, printed, and shrunken to demonstrate isotropic shrinking with the ability to reach a final resolution of ∼400 μm. The effect of type of alcohol (i.e. methanol or ethanol), concentration of alcohol, and temperature on volumetric shrinking was studied. This study presents a novel materials processing strategy to overcome the main limitations of direct 3DP to produce high resolution PLGA scaffolds.

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

Seco, Roger; Karl, Thomas; Guenther, Alex B.

Considerable amounts and varieties of biogenic volatile organic compounds (BVOCs) are exchanged between vegeta-tion and the surrounding air. These BVOCs play key ecological and atmospheric roles that must be adequately repre-sented for accurately modeling the coupled biosphere–atmosphere–climate earth system. One key uncertainty in existing models is the response of BVOC fluxes to an important global change process: drought. We describe the diur-nal and seasonal variation in isoprene, monoterpene, and methanol fluxes from a temperate forest ecosystem before, during, and after an extreme 2012 drought event in the Ozark region of the central USA. BVOC fluxes were domi-nated by isoprene, whichmore » attained high emission rates of up to 35.4 mg m -2h -1 at midday. Methanol fluxes were characterized by net deposition in the morning, changing to a net emission flux through the rest of the daylight hours. Net flux of CO 2 reached its seasonal maximum approximately a month earlier than isoprenoid fluxes, which high-lights the differential response of photosynthesis and isoprenoid emissions to progressing drought conditions. Never-theless, both processes were strongly suppressed under extreme drought, although isoprene fluxes remained relatively high compared to reported fluxes from other ecosystems. Methanol exchange was less affected by drought throughout the season, conflrming the complex processes driving biogenic methanol fluxes. The fraction of daytime (7–17 h) assimilated carbon released back to the atmosphere combining the three BVOCs measured was 2% of gross primary productivity (GPP) and 4.9% of net ecosystem exchange (NEE) on average for our whole measurement cam-paign, while exceeding 5% of GPP and 10% of NEE just before the strongest drought phase. The MEGANv2.1 model correctly predicted diurnal variations in fluxes driven mainly by light and temperature, although further research is needed to address model BVOC fluxes during drought events.« less

Real-time observation of the dehydrogenation processes of methanol on clean Ru(001) and Ru(001)-p(2×2) O surfaces by a temperature-programmed electron-stimulated desorption ion angular distribution/time-of-flight system

NASA Astrophysics Data System (ADS)

Sasaki, Takehiko; Itai, Yuichiro; Iwasawa, Yasuhiro

1999-12-01

Decomposition processes of methanol on clean and oxygen-precovered Ru(001) surfaces have been visualized in real time with a temperature-programmed (TP) electron-stimulated desorption ion angular distribution (ESDIAD)/time-of-flight (TOF) system. The mass of desorbed ions during temperature-programmed surface processes was identified by TOF measurements. In the case of methanol (CH 3OD) adsorption on Ru(001)-p(2×2)-O, a halo pattern of H + from the methyl group of methoxy species was observed at 100-200 K, followed by a broad pattern from the methyl group at 230-250 K and by a near-center pattern from O + ions originating from adsorbed CO above 300 K. The halo pattern is attributed to a perpendicular conformation of the CO bond axis of the methoxy species, leading to off-normal CH bond scission. On the other hand, methanol adsorbed on clean Ru(001) did not give any halo pattern but a broad pattern was observed along the surface normal, indicating that the conformation of the methoxy species is not ordered on the clean surface. Comparison between the ESDIAD images of the oxygen-precovered surface and the clean surface suggests that the precovered oxygen adatoms induce ordering of the methoxy species. Real-time ESDIAD measurements revealed that the oxygen atoms at the Ru(001)-p(2×2)-O surface have a positive effect on selective dehydrogenation of the methoxy species to CO+H 2 and a blocking effect on CO bond breaking of the methoxy species.

Theoretical Insights into Direct Methane to Methanol Conversion over Supported Dicopper Oxo Nanoclusters

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

Doan, Hieu A.; Li, Zhanyong; Farha, Omar K.

In this study, the prospect of using copper oxide nanoclusters grown by atomic layer deposition on a porphyrin support for selective oxidation of methane to methanol was examined by means of density functional theory (DFT) calculations. Ab initio thermodynamic analysis indicates that an active site in the form of Cu(μ-O)Cu can be stabilized by activation in O2 at 465K. Furthermore, a moderate methane activation energy barrier (Ea=54kJ/mol) is predicted, and the hydrogen abstraction activity of the active site could be attributed to the radical character of the bridging oxygen. Methanol extraction in this system is limited by a thermodynamic barriermore » to desorption of ΔG=57kJ/mol at 473K; however, desorption can be facilitated by the addition of water in a “stepped conversion” process. Overall, our results indicate similar activity between porphyrin-supported copper oxide nanoclusters and existing Cu-exchanged zeolites and provide a computational proof-of-concept for utilizing functionalized organic linkers in metal-organic frameworks (MOFs) for selective oxidation of methane to methanol.« less

Theoretical Insights into Direct Methane to Methanol Conversion over Supported Dicopper Oxo Nanoclusters

DOE PAGES

Doan, Hieu A.; Li, Zhanyong; Farha, Omar K.; ...

2018-04-08

In this study, the prospect of using copper oxide nanoclusters grown by atomic layer deposition on a porphyrin support for selective oxidation of methane to methanol was examined by means of density functional theory (DFT) calculations. Ab initio thermodynamic analysis indicates that an active site in the form of Cu(μ-O)Cu can be stabilized by activation in O2 at 465K. Furthermore, a moderate methane activation energy barrier (Ea=54kJ/mol) is predicted, and the hydrogen abstraction activity of the active site could be attributed to the radical character of the bridging oxygen. Methanol extraction in this system is limited by a thermodynamic barriermore » to desorption of ΔG=57kJ/mol at 473K; however, desorption can be facilitated by the addition of water in a “stepped conversion” process. Overall, our results indicate similar activity between porphyrin-supported copper oxide nanoclusters and existing Cu-exchanged zeolites and provide a computational proof-of-concept for utilizing functionalized organic linkers in metal-organic frameworks (MOFs) for selective oxidation of methane to methanol.« less

Comparison of large scale purification processes of naproxen enantiomers by chromatography using methanol-water and methanol-supercritical carbon dioxide mobile phases.

PubMed

Kamarei, Fahimeh; Vajda, Péter; Guiochon, Georges

2013-09-20

This paper compares two methods used for the preparative purification of a mixture of (S)-, and (R)-naproxen on a Whelk-O1 column, using either high performance liquid chromatography or supercritical fluid chromatography. The adsorption properties of both enantiomers were measured by frontal analysis, using methanol-water and methanol-supercritical carbon dioxide mixtures as the mobile phases. The measured adsorption data were modeled, providing the adsorption isotherms and their parameters, which were derived from the nonlinear fit of the isotherm models to the experimental data points. The model used was a Bi-Langmuir isotherm, similar to the model used in many enantiomeric separations. These isotherms were used to calculate the elution profiles of overloaded elution bands, assuming competitive Bi-Langmuir behavior of the two enantiomers. The analysis of these profiles provides the basis for a comparison between supercritical fluid chromatographic and high performance liquid chromatographic preparative scale separations. It permits an illustration of the advantages and disadvantages of these methods and a discussion of their potential performance. Copyright © 2013 Elsevier B.V. All rights reserved.

Dramatic improvement in water retention and proton conductivity in electrically aligned functionalized CNT/SPEEK nanohybrid PEM.

PubMed

Gahlot, Swati; Kulshrestha, Vaibhav

2015-01-14

Nanohybrid membranes of electrically aligned functionalized carbon nanotube f CNT with sulfonated poly ether ether ketone (SPEEK) have been successfully prepared by solution casting. Functionalization of CNTs was done through a carboxylation and sulfonation route. Further, a constant electric field (500 V·cm(-2)) has been applied to align CNTs in the same direction during the membrane drying process. All the membranes are characterized chemically, thermally, and mechanically by the means of FTIR, DSC, DMA, UTM, SEM, TEM, and AFM techniques. Intermolecular interactions between the components in hybrid membranes are established by FTIR. Physicochemical measurements were done to analyze membrane stability. Membranes are evaluated for proton conductivity (30-90 °C) and methanol crossover resistance to reveal their potential for direct methanol fuel cell application. Incorporation of f CNT reasonably increases the ion-exchange capacity, water retention, and proton conductivity while it reduces the methanol permeability. The maximum proton conductivity has been found in the S-sCNT-5 nanohybrid PEM with higher methanol crossover resistance. The prepared membranes can be also used for electrode material for fuel cells and batteries.

California methanol assessment. Volume 2: Technical report

NASA Technical Reports Server (NTRS)

Otoole, R.; Dutzi, E.; Gershman, R.; Heft, R.; Kalema, W.; Maynard, D.

1983-01-01

Energy feedstock sources for methanol; methanol and other synfuels; transport, storage, and distribution; air quality impact of methanol use in vehicles, chemical methanol production and use; methanol utilization in vehicles; methanol utilization in stationary applications; and environmental and regulatory constraints are discussed.

Effects of large volume injection of aliphatic alcohols as sample diluents on the retention of low hydrophobic solutes in reversed-phase liquid chromatography.

PubMed

David, Victor; Galaon, Toma; Aboul-Enein, Hassan Y

2014-01-03

Recent studies showed that injection of large volume of hydrophobic solvents used as sample diluents could be applied in reversed-phase liquid chromatography (RP-LC). This study reports a systematic research focused on the influence of a series of aliphatic alcohols (from methanol to 1-octanol) on the retention process in RP-LC, when large volumes of sample are injected on the column. Several model analytes with low hydrophobic character were studied by RP-LC process, for mobile phases containing methanol or acetonitrile as organic modifiers in different proportions with aqueous component. It was found that starting with 1-butanol, the aliphatic alcohols can be used as sample solvents and they can be injected in high volumes, but they may influence the retention factor and peak shape of the dissolved solutes. The dependence of the retention factor of the studied analytes on the injection volume of these alcohols is linear, with a decrease of its value as the sample volume is increased. The retention process in case of injecting up to 200μL of upper alcohols is dependent also on the content of the organic modifier (methanol or acetonitrile) in mobile phase. Copyright © 2013 Elsevier B.V. All rights reserved.

Mechanistical Studies on the Irradiation of Methanol in Extraterrestrial Ices

NASA Astrophysics Data System (ADS)

Bennett, Chris J.; Chen, Shih-Hua; Sun, Bing-Jian; Chang, Agnes H. H.; Kaiser, Ralf I.

2007-05-01

Pure ices of amorphous methanol, CH3OH(X1A'), were irradiated at 11 K by 5 keV electrons at 100 nA for 1 hr. These energetic electrons simulate electronic energy transfer processes that occur as interstellar ices, comets, and icy solar system bodies are subjected to irradiation from MeV ions and secondary electrons produced in this process. The results were analyzed quantitatively via absorption-reflection-absorption Fourier transform infrared (FTIR) spectroscopy, with the identification of new species aided by high-level electronic structure calculations. The unimolecular decomposition of methanol was found to proceed via the formation of (1) the hydroxymethyl radical, CH2OH(X2A''), and atomic hydrogen, H(2S1/2), (2) the methoxy radical, CH3O(X2A'), plus atomic hydrogen, (3) formaldehyde, H2CO(X1A1) plus molecular hydrogen, H2(X1Σ+g), and (4) the formation of methane, CH4(X1A1), together with atomic oxygen, O(1D). The accessibility of the last channel indicates that the reverse process, oxygen addition into methane to form methanol, should also be feasible. A kinetic model is presented for the decomposition of methanol into these species, as well as the formyl radical, HCO(X2A'), and carbon monoxide, CO(X1Σ+). During the subsequent warming up of the sample, radicals previously generated within the matrix were mobilized and found to recombine to form methyl formate, CH3OCHO(X1A'), glycolaldehyde, CH2OHCHO(X1A'), and ethylene glycol, HOCH 2CH2OH(X1A). Upper limits for the production of these species by the recombination of neighboring radicals produced during irradiation as well as during the warm-up procedure are presented. The generation of these molecules by irradiation of ices in the solid state and their subsequent sublimation into the gas phase can help explain their high abundances as observed toward hot molecular cores and underlines their importance in astrobiology.

In-situ biodiesel and sugar production from rice bran under subcritical condition

NASA Astrophysics Data System (ADS)

Zullaikah, Siti; Rahkadima, Yulia Tri

2015-12-01

An integrated method of producing biodiesel and sugar using subcritical water and methanol has been employed as a potential way to reduce the high cost of single biofuel production from rice bran. The effects of temperature, methanol to water ratio and reaction time on the biodiesel yield and purity, and the concentration of sugar in hydrolysate were investigated systematically. Biodiesel with yield and purity of 65.21%and 73.53%, respectively, was obtained from rice bran with initial free fatty acid (FFA) content of 37.64% under the following conditions: T= 200 oC, P= 4.0 MPa (using CO2 as pressurizing gas), ratio of rice bran/water/methanol of 1/2/6 (g/mL/mL), and 3 h of reaction time. FFAs level was reduced to 10.00% with crude biodiesel recovery of 88.69%. However, the highest biodiesel yield (67.39%) and crude biodiesel recovery (100.00%) were obtained by decreasing the amount of methanol so that the ratio of rice bran/water/methanol became 1/4/4, g/mL/mL. In addition, the highest sugar concentration of 0.98 g/L was obtained at 180 oC and 4.0 MPa with ratio of rice bran/water/methanol of 1/4/4 (g/mL/mL) and reaction time of 3 h. Since no catalyst was employed and the biodiesel and reducing sugar were produced directly from rice bran with high water and FFA contents, the process was simple and environmentally friendly, which would make the production of biofuel more economical and sustainable.

Effect of cryopreservant combinations on the motility and morphology of curimba (Prochilodus lineatus) sperm.

PubMed

Felizardo, V O; Mello, R A; Murgas, L D S; Andrade, E S; Drumond, M M; Rosa, P V

2010-12-01

This study investigated the application of intra- and extra-cellular cryoprotectant combinations on the quality of curimba Prochilodus lineatus semen subjected to cryopreservation. Semen treatments were tested with 8% DMSO or methanol as intracellular cryoprotectant, 5% egg yolk or lactose as extracellular cryoprotectant and 5% BTS. These cryoprotectant combinations are suitable for curimba but have not been tested at the lesser concentrations proposed or in combination with BTS. Semen samples collected from 19 curimbas were diluted into one of four cryoprotectant combinations: DMSO+yolk; DMSO+lactose; methanol+yolk; and methanol+lactose. After dilution, semen samples were cryopreserved in 0.5 mL straws for 10 days in a liquid nitrogen tank. Semen was thawed in a water bath at 60°C for 8s. We evaluated the quality of fresh, diluted (pre-freezing) and post-freezing semen according to sperm motility rate (%) and duration (s). Sperm morphology was also analyzed in thawed semen. Sperm motility rate decreased progressively after dilution and thawing. The motility rate in post-freezing semen was higher in the treatments using DMSO+lactose and methanol+yolk. Sperm motility duration in post-freezing sperm was greater in the treatments using methanol rather than DMSO as intracellular cryoprotectant, irrespective of the extracellular cryoprotectant used. Abnormality frequency in thawed sperm was less in semen treated with egg yolk than with lactose. Thus the use of methanol intracellular cryoprotectant is recommended along with yolk extracellular cryoprotectant in the cryopreservation process for curimba semen. Copyright © 2010 Elsevier B.V. All rights reserved.

Anti-ulcerogenic effect of the methanol extract of Chasmanthera dependens (Hochst) stem on male Wistar rats.

PubMed

Tijani, Stephanie Abiola; Olaleye, Samuel B; Farombi, Ebenezer O

2018-04-19

Oxidative stress and free radical-mediated processes have been implicated in the pathogenesis of indomethacin-induced gastric ulcer. This study investigated the ability of the methanol extract of Chasmanthera dependens to protect the gastric mucosal from oxidative damage induced by oral administration of indomethacin in rats. The C. dependens stems were chopped into pieces, air-dried, and pulverized into powder. One kilogram of the powder was macerated in 1 L of methanol for 72 h. The mixture was filtered and evaporated using rotatory evaporator to obtain the extract of C. dependens. Adult male rats were divided into eight groups of six animals per group and were pretreated orally with the methanol extract of C. dependens (200, 400, and 800 mg/kg) or cimetidine (CIM), a standard drug (50 mg/kg), for 7 days. Gastric ulcer was induced orally with indomethacin. Ulcerogenic parameters, oxidative stress indices, and histopathological examination of the stomach were assessed to monitor the gastroprotective potential of C. dependens stem. Indomethacin caused severe gastric mucosa damage and significant reduction in the gastric mucosa antioxidant system with concomitant increase in the level of lipid peroxidation. Pretreatment with the methanol extract of C. dependens or CIM significantly reduced the formation of ulcer at the different doses administered. Similarly, pretreatments with the extract or CIM improved the antioxidant system, decreased acid output, lipid peroxidation, and improved the architecture of the gastric mucosa in ulcerated rats. The results show the gastroprotective effect of the methanolic extract of C. dependens, which may be attributed to its antioxidant properties.

METHANE STEAM REACTION OVER NICKEL CATALYSTS IN THE HYNOL PROCESS

EPA Science Inventory

The report discusses the reaction of methane-steam over nickel catalysts in the Hynol process, a process that uses biomass and natural gas as feedstocks to maximize methanol yields and minimize greenhouse gas emissions. EPA's APPCD has established a laboratory in which to conduct...

Enhanced Crystallization by Methanol Additive in Anti-solvent for Achieving High-quality MAPbI3 Perovskite Films in Humid Atmosphere.

PubMed

Yang, Fu; Kamarudin, Muhammad Akmal; Zhang, PuTao; Kapil, Gaurav; Ma, Tingli; Hayase, Shuzi

2018-05-04

Perovskite solar cells have attracted considerable attention owing to easy and low-cost solution manufacturing process with high power conversion efficiency. However, the fabrication process is usually performed inside glovebox to avoid the moisture, as organometallic halide perovskite is easily dissolved in water. In this study, we propose one-step fabrication of high-quality MAPbI3 perovskite films in 50 % RH humid ambient air by using diethyl ether as an anti-solvent and methanol as an additive into this anti-solvent. Because of the existence of methanol, the water molecules can be efficiently removed from the gaps of perovskite precursors and the perovskite film formation can be slightly controlled leading to pinhole-free and low roughness film. Concurrently, methanol can modify a proper DMSO ratio in the intermediate perovskite phase to regulate perovskite formation. Planar solar cells fabricated by using this method exhibited the best efficiency of 16.4 % with a reduced current density-voltage hysteresis. This efficiency value is approximately 160 % higher than the devices fabrication by using only diethyl ether treatment. From the impedance measurement, it is also found that the recombination reaction has been suppressed when the device prepared with additive anti-solvent way. This method presents a new path for controlling the growth and morphology of perovskite films in the humid climates and uncontrolled laboratories. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen in the Methanol Production Process

ERIC Educational Resources Information Center

Kralj, Anita Kovac; Glavic, Peter

2006-01-01

Hydrogen is a very important industrial gas in chemical processes. It is very volatile; therefore, it can escape from the process units and its mass balance is not always correct. In many industrial processes where hydrogen is reacted, kinetics are often related to hydrogen pressure. The right thermodynamic properties of hydrogen can be found for…

One-Pot and Facile Fabrication of Hierarchical Branched Pt-Cu Nanoparticles as Excellent Electrocatalysts for Direct Methanol Fuel Cells.

PubMed

Cao, Yanqin; Yang, Yong; Shan, Yufeng; Huang, Zhengren

2016-03-09

Hierarchical branched nanoparticles are one promising nanostructure with three-dimensional open porous structure composed of integrated branches for superior catalysis. We have successfully synthesized Pt-Cu hierarchical branched nanoparticles (HBNDs) with small size of about 30 nm and composed of integrated ultrathin branches by using a modified polyol process with introduction of poly(vinylpyrrolidone) and HCl. This strategy is expected to be a general strategy to prepare various metallic nanostructures for catalysis. Because of the special open porous structure, the as-prepared Pt-Cu HBNDs exhibit greatly enhanced specific activity toward the methanol oxidation reaction as much as 2.5 and 1.7 times compared with that of the commercial Pt-Ru and Pt-Ru/C catalysts, respectively. Therefore, they are potentially applicable as electrocatalysts for direct methanol fuel cells.

Disposable cartridge extraction of retinol and alpha-tocopherol from fatty samples.

PubMed

Bourgeois, C F; Ciba, N

1988-01-01

A new approach is proposed for liquid/solid extraction of retinol and alpha-tocopherol from samples, using a disposable kieselguhr cartridge. The substitution of the mixture methanol-ethanol-n-butanol (4 + 3 + 1) for methanol in the alkaline hydrolysis solution makes it now possible to process fatty samples. Methanol is necessary to solubilize the antioxidant ascorbic acid, and a linear chain alcohol such as n-butanol is necessary to reduce the size of soap micelles so that they can penetrate into the kieselguhr pores. In comparisons of the proposed method with conventional methods on mineral premixes and fatty feedstuffs, recovery and accuracy are at least as good by the proposed method. Advantages are increased rate of determinations and the ability to hydrolyze and extract retinol and alpha-tocopherol together from the same sample.

75 FR 53867 - Additions to Listing of Exempt Chemical Mixtures

Federal Register 2010, 2011, 2012, 2013, 2014

2010-09-02

...% acetonitrile), dimethylformamide, ethylene glycol, isopropanol, methanol, methanol/water (50:50), methanol..., acetonitrile, acetonitrile: water (>= 50% acetonitrile), dimethylformamide, ethylene glycol, isopropanol...% acetonitrile), dimethylformamide, ethylene glycol, isopropanol, methanol, methanol/water (50:50), methanol...

Development and Evaluation of a Spectral Analysis Method to Eliminate Organic Interference with Cavity Ring-Down Measurements of Water Isotope Ratios.

NASA Astrophysics Data System (ADS)

Lin, Z.; Kim-Hak, D.; Popp, B. N.; Wallsgrove, N.; Kagawa-Viviani, A.; Johnson, J.

2017-12-01

Cavity ring-down spectroscopy (CRDS) is a technology based on the spectral absorption of gas molecules of interest at specific spectral regions. The CRDS technique enables the analysis of hydrogen and oxygen stable isotope ratios of water by directly measuring individual isotopologue absorption peaks such as H16OH, H18OH, and D16OH. Early work demonstrated that the accuracy of isotope analysis by CRDS and other laser-based absorption techniques could be compromised by spectral interference from organic compounds, in particular methanol and ethanol, which can be prevalent in ecologically-derived waters. There have been several methods developed by various research groups including Picarro to address the organic interference challenge. Here, we describe an organic fitter and a post-processing algorithm designed to improve the accuracy of the isotopic analysis of the "organic contaminated" water specifically for Picarro models L2130-i and L2140-i. To create the organic fitter, the absorption features of methanol around 7200 cm-1 were characterized and incorporated into spectral analysis. Since there was residual interference remaining after applying the organic fitter, a statistical model was also developed for post-processing correction. To evaluate the performance of the organic fitter and the postprocessing correction, we conducted controlled experiments on the L2130-i for two water samples with different isotope ratios blended with varying amounts of methanol (0-0.5%) and ethanol (0-5%). When the original fitter was not used for spectral analysis, the addition of 0.5% methanol changed the apparent isotopic composition of the water samples by +62‰ for δ18O values and +97‰ for δ2H values, and the addition of 5% ethanol changed the apparent isotopic composition by -0.5‰ for δ18O values and -3‰ for δ2H values. When the organic fitter was used for spectral analysis, the maximum methanol-induced errors were reduced to +4‰ for δ18O values and +5‰ for δ2H values, and the maximum ethanol-induced errors were unchanged. When the organic fitter was combined with the post-processing correction, up to 99.8% of the total methanol-induced errors and 96% of the total ethanol-induced errors could be corrected. The applicability of the algorithm to natural samples such as plant and soil waters will be investigated.

A novel process for methanol synthesis. Final report

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

Tierney, J.W.; Wender, I.

1994-01-25

The use of methanol (MeOH) as a fuel additive and in MTBE production has renewed interest in the search for improved MeOH processes. Commercial processes are characterized by high pressures and temperatures with low per pass conversion (10--12%). Efforts are underway to find improved MeOH synthesis processes. A slurry phase ``concurrent`` synthesis of MeOH/methyl formate (MeF) which operates under relatively mild conditions (100{degrees}C lower than present commercial processes) was the subject of investigation in this work. Evidence for a reaction scheme involving the carbonylation of MeOH to MeF followed by the hydrogenolysis of MeF to two molecules of MeOH --more » the net result being the reaction of H{sub 2} with CO to give MeOH via MeF, is presented. Up to 90% per pass conversion and 98% selectivity to methanol at rates comparable to commercial processes have been obtained in spite of the presence of as much as 10,000 ppM CO{sub 2} and 3000 ppM H{sub 2}O in the gas and liquid respectively. The effect of process parameters such as temperature, pressure, H{sub 2}/CO ratio in the reactor, flow rate and catalyst loading were also investigated. The use of temperatures above 170{degrees}C at a pressure of 50 atm results in MeF being the limiting reactant. Small amounts of CH{sub 4} are also formed. Significant MeOH synthesis rates at a pressure in the range of 40--50 atm makes possible the elimination of an upstream shift reactor and the use of an air-blown syngas generator. The nature of the catalysts was studied and correlated with the behavior of the various species in the concurrent synthesis.« less

Biogeochemical Cycle of Methanol in Anoxic Deep-Sea Sediments

PubMed Central

Yanagawa, Katsunori; Tani, Atsushi; Yamamoto, Naoya; Hachikubo, Akihiro; Kano, Akihiro; Matsumoto, Ryo; Suzuki, Yohey

2016-01-01

The biological flux and lifetime of methanol in anoxic marine sediments are largely unknown. We herein reported, for the first time, quantitative methanol removal rates in subsurface sediments. Anaerobic incubation experiments with radiotracers showed high rates of microbial methanol consumption. Notably, methanol oxidation to CO2 surpassed methanol assimilation and methanogenesis from CO2/H2 and methanol. Nevertheless, a significant decrease in methanol was not observed after the incubation, and this was attributed to the microbial production of methanol in parallel with its consumption. These results suggest that microbial reactions play an important role in the sources and sinks of methanol in subseafloor sediments. PMID:27301420

Modelling bidirectional fluxes of methanol and acetaldehyde with the FORCAsT canopy exchange model

DOE PAGES

Ashworth, Kirsti; Chung, Serena H.; McKinney, Karena A.; ...

2016-12-15

Here, the FORCAsT canopy exchange model was used to investigate the underlying mechanisms governing foliage emissions of methanol and acetaldehyde, two short chain oxygenated volatile organic compounds ubiquitous in the troposphere and known to have strong biogenic sources, at a northern mid-latitude forest site. The explicit representation of the vegetation canopy within the model allowed us to test the hypothesis that stomatal conductance regulates emissions of these compounds to an extent that its influence is observable at the ecosystem scale, a process not currently considered in regional- or global-scale atmospheric chemistry models. Here, we found that FORCAsT could only reproducemore » the magnitude and diurnal profiles of methanol and acetaldehyde fluxes measured at the top of the forest canopy at Harvard Forest if light-dependent emissions were introduced to the model. With the inclusion of such emissions, FORCAsT was able to successfully simulate the observed bidirectional exchange of methanol and acetaldehyde. Although we found evidence that stomatal conductance influences methanol fluxes and concentrations at scales beyond the leaf level, particularly at dawn and dusk, we were able to adequately capture ecosystem exchange without the addition of stomatal control to the standard parameterisations of foliage emissions, suggesting that ecosystem fluxes can be well enough represented by the emissions models currently used.« less

Below-Room-Temperature C–H Bond Breaking on an Inexpensive Metal Oxide: Methanol to Formaldehyde on CeO 2(111)

DOE PAGES

Sutton, Jonathan E.; Danielson, Thomas; Beste, Ariana; ...

2017-11-14

C-H bond breaking is important for industrial commodity and specialty chemical transformations, including the upgrading of alcohols. Small primary alcohols – methanol and ethanol – are used industrially as precursors for the corresponding aldehydes at industrial scales. However, upgrading these primary alcohols involves C-H bond breaking and the processes are run at elevated temperatures (> 200 °C). In this work, new understanding from temperature programmed reaction (TPR) studies with methanol over a CeO 2(111) surface show the C-H bond breaking and the subsequent desorption of formaldehyde, even below room temperature. This is of particular interests because CeO 2 is amore » naturally abundant, inexpensive metal oxide. We combine density functional theory (DFT) and kinetic Monte Carlo (KMC) to simulate the TPR of methanol on CeO2. Our simulations show that the low temperature C H bond breaking occurs via disproportionation of adjacent methoxy species to form methanol and formaldehyde which each then desorb. We further show from DFT calculations that the same transition state with comparably low activation energies should be possible for other sustainable primary alcohols, with ethanol, 1-propanol, and 1-butanol having been explicitly calculated. In conclusion, these findings point out a new class of transition states to search for in seeking low temperature C-H bond breaking over inexpensive metal oxides.« less

Below-Room-Temperature C–H Bond Breaking on an Inexpensive Metal Oxide: Methanol to Formaldehyde on CeO 2(111)

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

Sutton, Jonathan E.; Danielson, Thomas; Beste, Ariana

C-H bond breaking is important for industrial commodity and specialty chemical transformations, including the upgrading of alcohols. Small primary alcohols – methanol and ethanol – are used industrially as precursors for the corresponding aldehydes at industrial scales. However, upgrading these primary alcohols involves C-H bond breaking and the processes are run at elevated temperatures (> 200 °C). In this work, new understanding from temperature programmed reaction (TPR) studies with methanol over a CeO 2(111) surface show the C-H bond breaking and the subsequent desorption of formaldehyde, even below room temperature. This is of particular interests because CeO 2 is amore » naturally abundant, inexpensive metal oxide. We combine density functional theory (DFT) and kinetic Monte Carlo (KMC) to simulate the TPR of methanol on CeO2. Our simulations show that the low temperature C H bond breaking occurs via disproportionation of adjacent methoxy species to form methanol and formaldehyde which each then desorb. We further show from DFT calculations that the same transition state with comparably low activation energies should be possible for other sustainable primary alcohols, with ethanol, 1-propanol, and 1-butanol having been explicitly calculated. In conclusion, these findings point out a new class of transition states to search for in seeking low temperature C-H bond breaking over inexpensive metal oxides.« less

A FEASIBILITY STUDY FOR THE COPROCESSING OF FOSSIL FUELS WITH BIOMASS BY THE HYDROCARB PROCESS

EPA Science Inventory

The report describes and gives results of an assessment of a new process concept for the production of carbon and methanol from fossil fuels. The Hydrocarb Process consists of the hydrogasification of carbonaceous material to produce methane, which is subsequently thermally decom...

Acute toxicity of methanol in the folate-deficient acatalasemic mouse.

PubMed

Smith, E N; Taylor, R T

1982-01-01

Formate acidosis is the chief measurable biochemical characteristic of acute methanol toxicity in man. Its marked elevation in the blood stream of primates has been proposed to account for their much greater susceptibility versus rodents to methanol poisoning. Therefore, a study was undertaken to assess whether folic acid deficient (FAD) mice which accumulate formate are much more sensitive to the lethal effects of this alcohol than folic acid sufficient (FAS) mice. Moreover, because some formate is oxidized by catalase-H2O2 in rodents, but not in primates, we also compared the urinary excretion and blood plasma accumulation of formate and the methanol sensitivity of acatalasemic mice. Methanol-dosed C57BL/6Csb (acatalasemic) mice exhibit slightly lower LD50S than CSa (normal catalase) mice, irrespective of their folate state. CSb-FAD mice excreted much more formate and developed higher plasma formate concentrations (11-17 mM) than identically dosed CSa-FAD animals (6 mM). However, in no instance did a folate deficiency produce a large reciprocal decrease in the oral or i.p. LD50 that would be expected from a huge increase (greater than 10-fold) in the 24-h blood plasma formate level. A low methionine (0.2%) intake did not decrease the oral methanol LD50 of CSb-FAD mice, although excess dietary methionine (1.8%) did lower it from 7.1 to 6.4 g/kg. Methanol treated (4 g/kg) Csb-FAD mice excreted 30.8-48.2% of the oral dose as urinary formate, depending on the level of dietary methionine. Csb-FAS and -FAD mice which were given 2 g/kg sodium formate orally (LD50 = 4.7 and 3.7 g/kg) cleared this dose from the blood within 24 h and excreted 58% and 76% of it, respectively, in the urine. Our results indicate that the plasma formate concentration does not correlate well with methanol lethality in Csb-FAS vs. -FAD mice. In addition, urinary excretion, not oxidation, is the primary means by which mice, and probably rats, eliminate high levels of blood formate. Since the Csb-FAD mouse attains high plasma formate levels and low blood pH-values similar to those which have been reported for methanol poisoned monkeys, it appears to be of value as an inexpensive small animal model for further studies of lethal methanol toxicity and the contribution of formate to this process.

Maser hunting in the galactic plane

NASA Astrophysics Data System (ADS)

Quinn, Lyshia Jane

The process of massive star formation greatly influences its surroundings through their outflows, vast UV output and shocks from their supernova death. They form at great distances from the Earth, enshrouded by dust and gas and have relatively short lifetimes. Astrophysical masers which form in these environments may act as locators of the star forming regions. The aim of this thesis is to study massive star formation using masers to probe these regions. The three main masers used in this thesis are the Class I and Class II methanol masers and the 6035 MHz ex-OH maser. The methanol masers are divided into two groups, Class I and Class II, based on their distance from a central source. The Class I masers are separated 1-2 pc from a central source, the central source is the star forming region. The Class II masers are associated close to a star forming source. They are often associated with a 6035 MHz ex-OH maser. The 6035 MHz ex-OH masers are less common than the 6668 MHz Class I methanol masers. They are often found at sites of the 6668 MHz Class I masers and 1665/7 MHz OH masers. This thesis presents two maser surveys, the Methanol Multibeam (MMB) survey and the Class I survey. The MMB survey is currently surveying the entire Galactic Plane for the 6668 MHz Class II methanol maser and the 6035 MHz ex-OH maser. Over 60% of the survey in the Southern hemisphere is now complete using the Parkes telescope. Over 900 6668 MHz Class I methanol masers and 110 6035 MHz ex-OH masers have been detected, with all of these masers pinpoint the location of newly forming high mass stars. Follow up observations to determine the precise locations of the 6668 MHz methanol and 6035 MHz ex-OH masers are currently underway. The first ever unbiased Class I survey has observed 1 sq degree of the Galactic Plane for the 44 GHz Class I methanol masers using the Mopra telescope in Australia. The 44 GHz Class II methanol masers are hypothesised to be associated with ! the outflows of high mass stellar objects. The Class I survey has detected 25 44 GHz methanol masers, with 23 being new detections. A smaller survey for 36 GHz Class I masers was also conducted using the Mopra telescope centered on the region with the highest population of 44 GHz Class I masers.

Lipid extraction of wet BLT0404 microalgae for biofuel application

NASA Astrophysics Data System (ADS)

Mansur, Dieni; Fitriady, Muhammad Arifuddin; Susilaningsih, Dwi; Simanungkalit, Sabar Pangihutan; Agustian, Egi

2017-01-01

Recently, research and development of microalgae for biodiesel production were conducted by researchers in the world. This research becomes popular because of an exponential growth of the microalgae under nutrient limitation. Lipid of microalgae grows faster than oil producing land crops. Therefore, microalgae lipid content could improve the economics of biodiesel production. The aim of this study was to investigate yield of lipid extract and chemicals compounds containing in non-acylglycerol neutral lipid from BLT 0404 microalga. The study was conducted because lipid extraction was an important step for biodiesel as well as biofuel production. The extraction was carried out using polar and non-polar mixture solvents. The polar solvent was methanol and non-polar one was chloroform. Process extraction was conducted under various stirring time between the microalgae and methanol and volume ratio between the methanol and chloroform. Methanol as a polar solvent was able to extract polar lipid (phospholipid and glycolipid) because it removed polar membrane lipid and lipid-associated to polar molecule. Moreover, the non-polar solvent was used for extraction non-acylglycerol neutral lipid (hydrocarbons, sterols, ketones, free fatty acids, carotenes, and chlorophylls) for biofuel production. Under ratio of microalgae: methanol: chloroform of 0.8: 4: 2 that stirring time of the microalgae with methanol was 30 min yielded 58% of total lipid extract. The yield value consisted of 14.5% of non-acylglycerol neutral lipid and 43.5% of polar lipid. The non-acylglycerol neutral lipid will be converted into biofuel. Therefore, analysis of its chemical compounds was required. The non-acylglycerol neutral lipid was analyzed by GCMS and found that the extract contained long chains of hydrocarbon compounds. The hydrocarbons consisted of C18-C30 that high peaks with larger percentage area were C20-C26. The results suggested that stirring between microalgae and methanol for 30 min was needed before additional of chloroform. Moreover, the ratio of methanol must be higher than chloroform due to the higher portion of polar lipid content in the microalgae.

Examining ruthenium chromophores for the photochemical reduction of CO2 to methanol

NASA Astrophysics Data System (ADS)

Boston, David J.

Our consumption of energy for transportation and electricity has been growing as quickly as our population. As this demand for energy increases we increase our production of carbon dioxide by the burning of fossil fuels to try and meet this increasing demand. A sustainable method to convert carbon dioxide (CO2) to a viable liquid fuel is one potential way in which both the increasing energy demand and increasing CO2 concentration issues can both be helped. Currently such methods being investigated include thermal, electrochemical, and photochemical processes. Because thermal conversion is not an ideal situation because of the requirement of strong reducing agents or extreme conditions such as steam reformation reactions, we need to find better alternatives such as electrochemical and photochemical methods. Both electrochemical and photochemical methods have the ability to be sustainable, however, the vast majority of these systems are limited to producing CO and/or formic acid, with only a few performing deeper reduction to products such formaldehyde, methanol and methane. All of the systems capable of reducing CO2 past two electrons involve either a heterogeneous catalyst (e.g. TiO2) or an electrode. In recent times Bocarsly and coworkers have shown that pyridine was capable of reducing CO2 to methanol through a sequential process of proton and electron transfers. This process seems to start with the formation of a CO2-pyridine adduct in solution that is reduced one more time to form formate/formic acid. The next reduction is a slow process and allows for a buildup of formate in solution leading to a higher formate concentration in solution. The subsequent reductions seem to occur very rapidly and form methanol at good efficiencies. Theoretical work done recently has argued for the necessity of the Pt, Pd, or GaP surface in the electrochemistry. Carter and coworkers have claimed that the surface of the electrode is a necessary part of the catalysis with the pyridinium being only a cocatalyst for the reduction of CO2. However, Musgrave and coworkers predict that the homogeneous reductions can take place with the aid of water molecules in solution. They allow for a PCET process to take place between the CO 2 and the pyridinium radical. This would allow for a second pathway for the catalytic reduction of CO2 to methanol. Work done during this dissertation has shown that the photochemical reduction of carbon dioxide to methanol is possible using pyridine in a similar manner to Bocarsly and coworkers in their electrochemical system. By replacing the electrode with Ru(phen)3Cl2 it is still possible to drive the reaction using excited states of the chromophore to provide the electrons with enough energy to reduce the pyridinium to the radical species. This system has been shown to produce up to 66 BM methanol after 6 hours of irradiation of 470 nm light. Production of formate is also observed, with ~27 mM being observed within the first hour of irradiation. This system was further investigated with the incorporation of the pyridine catalyst into a chromophore system using the complex [Ru(phen)2dppz](PF 6)2, [Ru(phen)2pbtpalpha](PF6) 2, and [Ru(phen)2pbtpbeta](PF6)2. Cyclic voltammetry experiments for these complexes show similar reduction potentials for with ~100 mV difference between them with [Ru(phen)2dppz](PF 6)2 being the most negative and [Ru(phen)2pbtpbeta](PF 6)2 being the most positive. When the electrolyte solution was saturated with CO2 only [Ru(phen)2pbtpalpha](PF 6)2 and [Ru(phen)2pbtpbeta](PF6) 2 showed a response signifying catalysis was taking place. Initial photochemical tests with these complexes showed that [Ru(phen)2pbtpalpha](PF 6)2 seemed to undergo dimer formation in the absence of CO 2 with [Ru(phen)2pbtpbeta](PF6)2 forming a singly reduced species that is oxidized upon introduction of additional CO2. Electrolysis of [Ru(phen)2pbtpbeta](PF6 )2 produces ~900 BM methanol with both CO and formate being produced as well. Photolysis of [Ru(phen)2pbtpbeta](PF6 )2 in DMF with 1 M H2O and 0.1M TEA, no CO formation observed, however, both methanol and formic acid were observed after 1 hours of irradiation with methanol reaching 45 BM, 285 microM formaldehyde and 650 microM formate.

New Zealand GTG plant more than halfway home

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

Pine, M.

The 76 preassembled modules making up the New Zealand Synthetic Fuels Corporation natural gas-to-gasoline (GTG) plant will be an operating plant by 1986. The plant will produce 14,400 barrels per day, about a third of the country's gasoline needs. The project is a good example of cooperation between a government and a multinational corporation in which Mobil is a 25% partner with the New Zealand government. With a commitment for about 16% of the gas reserves in the Maui field, the facility will first convert the gas to methanol using a standard commercial process, then convert the methanol to gasolinemore » by a unique Mobil process that uses a zeolite catalyst. 1 figure.« less

Atmospheric vs. anaerobic processing of metabolome samples for the metabolite profiling of a strict anaerobic bacterium, Clostridium acetobutylicum.

PubMed

Lee, Sang-Hyun; Kim, Sooah; Kwon, Min-A; Jung, Young Hoon; Shin, Yong-An; Kim, Kyoung Heon

2014-12-01

Well-established metabolome sample preparation is a prerequisite for reliable metabolomic data. For metabolome sampling of a Gram-positive strict anaerobe, Clostridium acetobutylicum, fast filtration and metabolite extraction with acetonitrile/methanol/water (2:2:1, v/v) at -20°C under anaerobic conditions has been commonly used. This anaerobic metabolite processing method is laborious and time-consuming since it is conducted in an anaerobic chamber. Also, there have not been any systematic method evaluation and development of metabolome sample preparation for strict anaerobes and Gram-positive bacteria. In this study, metabolome sampling and extraction methods were rigorously evaluated and optimized for C. acetobutylicum by using gas chromatography/time-of-flight mass spectrometry-based metabolomics, in which a total of 116 metabolites were identified. When comparing the atmospheric (i.e., in air) and anaerobic (i.e., in an anaerobic chamber) processing of metabolome sample preparation, there was no significant difference in the quality and quantity of the metabolomic data. For metabolite extraction, pure methanol at -20°C was a better solvent than acetonitrile/methanol/water (2:2:1, v/v/v) at -20°C that is frequently used for C. acetobutylicum, and metabolite profiles were significantly different depending on extraction solvents. This is the first evaluation of metabolite sample preparation under aerobic processing conditions for an anaerobe. This method could be applied conveniently, efficiently, and reliably to metabolome analysis for strict anaerobes in air. © 2014 Wiley Periodicals, Inc.

Application of a Burkholderia cepacia lipase-immobilized silica monolith to batch and continuous biodiesel production with a stoichiometric mixture of methanol and crude Jatropha oil

PubMed Central

2011-01-01

Background The enzymatic production of biodiesel through alcoholysis of triglycerides has become more attractive because it shows potential in overcoming the drawbacks of chemical processes. In this study, we investigate the production of biodiesel from crude, non-edible Jatropha oil and methanol to characterize Burkholderia cepacia lipase immobilized in an n-butyl-substituted hydrophobic silica monolith. We also evaluate the performance of a lipase-immobilized silica monolith bioreactor in the continuous production of biodiesel. Results The Jatropha oil used contained 18% free fatty acids, which is problematic in a base-catalyzed process. In the lipase-catalyzed reaction, the presence of free fatty acids made the reaction mixture homogeneous and allowed bioconversion to proceed to 90% biodiesel yield after a 12 hour reaction time. The optimal molar ratio of methanol to oil was 3.3 to 3.5 parts methanol to one part oil, with water content of 0.6% (w/w). Further experiments revealed that B. cepacia lipase immobilized in hydrophobic silicates was sufficiently tolerant to methanol, and glycerol adsorbed on the support disturbed the reaction to some extent in the present reaction system. The continuous production of biodiesel was performed at steady state using a lipase-immobilized silica monolith bioreactor loaded with 1.67 g of lipase. The yield of 95% was reached at a flow rate of 0.6 mL/h, although the performance of the continuous bioreactor was somewhat below that predicted from the batch reactor. The bioreactor was operated successfully for almost 50 days with 80% retention of the initial yield. Conclusions The presence of free fatty acids originally contained in Jatropha oil improved the reaction efficiency of the biodiesel production. A combination of B. cepacia lipase and its immobilization support, n-butyl-substituted silica monolith, was effective in the production of biodiesel. This procedure is easily applicable to the design of a continuous flow-through bioreactor system. PMID:22013896

Excessive S-Adenosyl-L-Methionine-Dependent Methylation Increases Levels of Methanol, Formaldehyde and Formic Acid in Rat Brain Striatal Homogenates: Possible role in S-adenosyl-L-methionine-induced Parkinson’s disease-like disorders

PubMed Central

Lee, Eun-Sook; Chen, Hongtao; Hardman, Chadwick; Simm, Anthony; Charlton, Clivel

2009-01-01

Aims Excessive methylation may be a precipitating factor for Parkinson’s disease (PD) since S-adenosylmethionine (SAM), the endogenous methyl donor, induces PD-like changes when injected into the rat brain. The hydrolysis of the methyl ester bond of the methylated proteins produces methanol. Since methanol is oxidized into formaldehyde, and formaldehyde into formic acid in the body, we investigated the effects of SAM on the production of methanol, formaldehyde and formic acid in rat brain striatal homogenates and the toxicity of these products in PC12 cells. Main methods radio-enzymatic and colorimetric assays, cell viability, Western blot. Key findings SAM increased the formation of methanol, formaldehyde and formic acid in a concentration and time-dependent manner. Concentrations of [3H-methyl]-SAM at 0.17, 0.33, 0.67 and 1.34 nM produced 3.8, 8.0, 18.3 and 34.4 fmol/mg protein/h of [3H] methanol in rat striatal homogenates, respectively. SAM also significantly generated formaldehyde and formic acid in striatal homogenates. Formaldehyde was the most toxic metabolite to differentiated PC12 pheochromocytoma cells in cell culture studies, indicating that formaldehyde formed endogenously may contribute to neuronal damage in excessive methylation conditions. Subtoxic concentration of formaldehyde decreased the expression of tyrosine hydroxylase, the limiting factor in dopamine synthesis. Formaldehyde was more toxic to catecholaminergic PC12 cells than C6 glioma cells, indicating that neurons are more vulnerable to formaldehyde than glia cells. Significance We suggest that excessive carboxylmethylation of proteins might be involved in the SAM-induced PD-like changes and in the aging process via the toxic effects of formaldehyde. PMID:18930743

First Detection of Methanol in a Class O Protostellar Disk

NASA Technical Reports Server (NTRS)

Velusamy, T.; Langer, William D.; Goldsmith, Paul F.

2000-01-01

We report the detection of emission from methanol in a compact source coincident with the position of the L1157 infrared source, which we attribute to molecules in the disk surrounding this young, Class O protostellar object. In addition, we identify a spectral feature in the outflow corresponding to an ethanol transition. Using the Caltech Owens Valley Millimeter Array with a synthesized beam size of 2", we detect spatially unresolved methanol in the 2(sub k) - 1(sub k) transitions at 3mm, which is coincident in position with the peak of the continuum emission. The gas phase methanol could be located in the central region (< 100 AU radius) of a flat disk, or in an extended heated surface layer (approx. 200 AU radius) of a flared disk. The fractional abundance of methanol X(CH3OH) is approx. 2 x l0(exp -8) in the flat disk model, and 3 x l0(exp -7) for the flared disk. The fractional abundance is small in the disk as a whole, but considerably larger in the warm portions. This difference indicates that substantial chemical processing probably takes place in the disk via depletion and desorption. The methanol desorbed from the grains in the warm surface layers returns to the icy grain mantles in the cooler interior of the disk, where it is available to become part of the composition of solar system-like bodies, such as comets, formed in the outer circumstellar region. This first millimeter-wavelength detection of a complex organic molecule in a young protostellar disk has implications for disk structure and chemical evolution and for potential use as a temperature probe. The research of TV and WL was conducted at the Jet Propulsion Laboratory, California Institute of Technology with support from the National Aeronautics and Space Administration.

Fuel processing in integrated micro-structured heat-exchanger reactors

NASA Astrophysics Data System (ADS)

Kolb, G.; Schürer, J.; Tiemann, D.; Wichert, M.; Zapf, R.; Hessel, V.; Löwe, H.

Micro-structured fuel processors are under development at IMM for different fuels such as methanol, ethanol, propane/butane (LPG), gasoline and diesel. The target application are mobile, portable and small scale stationary auxiliary power units (APU) based upon fuel cell technology. The key feature of the systems is an integrated plate heat-exchanger technology which allows for the thermal integration of several functions in a single device. Steam reforming may be coupled with catalytic combustion in separate flow paths of a heat-exchanger. Reactors and complete fuel processors are tested up to the size range of 5 kW power output of a corresponding fuel cell. On top of reactor and system prototyping and testing, catalyst coatings are under development at IMM for numerous reactions such as steam reforming of LPG, ethanol and methanol, catalytic combustion of LPG and methanol, and for CO clean-up reactions, namely water-gas shift, methanation and the preferential oxidation of carbon monoxide. These catalysts are investigated in specially developed testing reactors. In selected cases 1000 h stability testing is performed on catalyst coatings at weight hourly space velocities, which are sufficiently high to meet the demands of future fuel processing reactors.

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.

Wild Roman chamomile extracts and phenolic compounds: enzymatic assays and molecular modelling studies with VEGFR-2 tyrosine kinase.

PubMed

Guimarães, Rafaela; Calhelha, Ricardo C; Froufe, Hugo J C; Abreu, Rui M V; Carvalho, Ana Maria; Queiroz, Maria João R P; Ferreira, Isabel C F R

2016-01-01

Angiogenesis is a process by which new blood vessels are formed from the pre-existing vasculature, and it is a key process that leads to tumour development. Some studies have recognized phenolic compounds as chemopreventive agents; flavonoids, in particular, seem to suppress the growth of tumor cells modifying the cell cycle. Herein, the antiangiogenic activity of Roman chamomile (Chamaemelum nobile L.) extracts (methanolic extract and infusion) and the main phenolic compounds present (apigenin, apigenin-7-O-glucoside, caffeic acid, chlorogenic acid, luteolin, and luteolin-7-O-glucoside) was evaluated through enzymatic assays using the tyrosine kinase intracellular domain of the Vascular Endothelium Growth Factor Receptor-2 (VEGFR-2), which is a transmembrane receptor expressed fundamentally in endothelial cells involved in angiogenesis, and molecular modelling studies. The methanolic extract showed a lower IC50 value (concentration that provided 50% of VEGFR-2 inhibition) than the infusion, 269 and 301 μg mL(-1), respectively. Regarding phenolic compounds, luteolin and apigenin showed the highest capacity to inhibit the phosphorylation of VEGFR-2, leading us to believe that these compounds are involved in the activity revealed by the methanolic extract.

Measurement of Soret coefficients in a ternary mixture of toluene-methanol-cyclohexane in convection-free environment

NASA Astrophysics Data System (ADS)

Mialdun, A.; Ryzhkov, I.; Khlybov, O.; Lyubimova, T.; Shevtsova, V.

2018-01-01

We report on the measurement of Soret (ST) coefficients in the ternary system toluene (T)-methanol (M)-cyclohexane (Ch) onboard the International Space Station in the experiment selectable optical diagnostic instrument/DCMIX2 (Diffusion Coefficients Measurement in ternary mIXtures). Nine experiments were conducted in the range of mean temperatures between 298.15 K and 306.15 K in the mixture with composition 0.62 (T)-0.31 (M)-0.07 (Ch) in mass fractions. A linear dependence of the Soret coefficients on temperature was established for the ternary mixture. It has also been found that, over considered range of mean temperatures, the Soret coefficients of toluene are small and positive, while the Soret coefficients for methanol are negative and, at least, two times larger. The present work also presents a comprehensive study of possible methodologies to process raw data from the Soret experiment in ternary mixtures. All the experiments were processed by seven different schemes and two of them were identified as the most reliable. We also investigate the error propagation and explain the reasons for the discrepancy of the results obtained by different schemes.

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.

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

Tan, Eric C. D.; Talmadge, Michael; Dutta, Abhijit

This paper describes in detail one potential conversion process for the production of high-octane gasoline blendstock via indirect liquefaction of biomass. The processing steps of this pathway include the conversion of biomass to synthesis gas via indirect gasification, gas clean-up via reforming of tars and other hydrocarbons, catalytic conversion of syngas to methanol, methanol dehydration to dimethyl ether (DME), and the homologation of DME over a zeolite catalyst to high-octane gasoline-range hydrocarbon products. The current process configuration has similarities to conventional methanol-to-gasoline (MTG) technologies, but there are key distinctions, specifically regarding the product slate, catalysts, and reactor conditions. A techno-economicmore » analysis is performed to investigate the production of high-octane gasoline blendstock. The design features a processing daily capacity of 2000 tonnes (2205 short tons) of dry biomass. The process yields 271 liters of liquid fuel per dry tonne of biomass (65 gal/dry ton), for an annual fuel production rate of 178 million liters (47 MM gal) at 90% on-stream time. The estimated total capital investment for an nth-plant is $438 million. The resulting minimum fuel selling price (MFSP) is $0.86 per liter or $3.25 per gallon in 2011 US dollars. A rigorous sensitivity analysis captures uncertainties in costs and plant performance. Sustainability metrics for the conversion process are quantified and assessed. The potential premium value of the high-octane gasoline blendstock is examined and found to be at least as competitive as fossil-derived blendstocks. A simple blending strategy is proposed to demonstrate the potential for blending the biomass-derived blendstock with petroleum-derived intermediates. Published 2015. This article is a U.S. Government work and is in the public domain in the USA. Biofuels, Bioproducts and Biorefining published by Society of Industrial Chemistry and John Wiley & Sons Ltd.« less

Analysis of Wastewater Treatment Efficiency in a Soft Drinks Industry

NASA Astrophysics Data System (ADS)

Boguniewicz-Zabłocka, Joanna; Capodaglio, Andrea G.; Vogel, Daniel

2017-10-01

During manufacturing processes, most industrial plants generate wastewater which could become harmful to the environment. Discharge of untreated or improperly treated industrial wastewaters into surface water could, in fact, lead to deterioration of the receiving water body's quality. This paper concerns wastewater treatment solutions used in the soft drink production industry: wastewater treatment plant effectiveness analysis was determined in terms of basic pollution indicators, such as BOD, COD, TSS and variable pH. Initially, the performance of mechanic-biological systems for the treatment of wastewater from a specific beverages production process was studied in different periods, due to wastewater flow fluctuation. The study then showed the positive effects on treatment of wastewater augmentation by methanol, nitrogen and phosphorus salts dosed into it during the treatment process. Results confirm that after implemented modification (methanol, nitrogen and phosphorus additions) pollution removal occurs mostly with higher efficiency.

Nanoscopic length scale dependence of hydrogen bonded molecular associates’ dynamics in methanol

PubMed Central

Bertrand, C. E.; Self, J. L.; Copley, J. R. D.; Faraone, A.

2017-01-01

In a recent paper [C. E. Bertrand et al., J. Chem. Phys. 145, 014502 (2016)], we have shown that the collective dynamics of methanol shows a fast relaxation process related to the standard density-fluctuation heat mode and a slow non-Fickian mode originating from the hydrogen bonded molecular associates. Here we report on the length scale dependence of this slow relaxation process. Using quasielastic neutron scattering and molecular dynamics simulations, we show that the dynamics of the slow process is affected by the structuring of the associates, which is accessible through polarized neutron diffraction experiments. Using a series of partially deuterated samples, the dynamics of the associates is investigated and is found to have a similar time scale to the lifetime of hydrogen bonding in the system. Both the structural relaxation and the dynamics of the associates are thermally activated by the breaking of hydrogen bonding. PMID:28527447

Fuel processing requirements and techniques for fuel cell propulsion power

NASA Astrophysics Data System (ADS)

Kumar, R.; Ahmed, S.; Yu, M.

Fuels for fuel cells in transportation systems are likely to be methanol, natural gas, hydrogen, propane, or ethanol. Fuels other than hydrogen will need to be reformed to hydrogen on-board the vehicle. The fuel reformer must meet stringent requirements for weight and volume, product quality, and transient operation. It must be compact and lightweight, must produce low levels of CO and other byproducts, and must have rapid start-up and good dynamic response. Catalytic steam reforming, catalytic or noncatalytic partial oxidation reforming, or some combination of these processes may be used. This paper discusses salient features of the different kinds of reformers and describes the catalysts and processes being examined for the oxidation reforming of methanol and the steam reforming of ethanol. Effective catalysts and reaction conditions for the former have been identified; promising catalysts and reaction conditions for the latter are being investigated.

Experimental Identification of Ultrafast Reverse Hole Transfer at the Interface of the Photoexcited Methanol/Graphitic Carbon Nitride System.

PubMed

Chen, Zongwei; Zhang, Qun; Luo, Yi

2018-05-04

An experimental scrutiny of the photoexcited hole dynamics in a prototypical system is presented in which hole-scavenging methanol molecules are chemisorbed on a graphitic carbon nitride (g-C 3 N 4 ) substrate. A set of comparison and control experiments by means of femtosecond time-resolved transient absorption (fs-TA) spectroscopy were conducted. The elusive reverse hole transfer (RHT) process was identified, which occurs on a timescale of a few hundred picoseconds. The critical role of interfacially chemisorbed methoxy (instead of methanol) as the dominant species responsible for hole scavenging was confirmed by a control experiment using protonated g-C 3 N 4 as the substrate. A hot-hole transfer effect was revealed by implementing different interband photoexcitation scenarios. The RHT rate is the key factor governing the hole-scavenging ability of different hole scavengers. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Printable enzyme-embedded materials for methane to methanol conversion

DOE PAGES

Blanchette, Craig D.; Knipe, Jennifer M.; Stolaroff, Joshuah K.; ...

2016-06-15

An industrial process for the selective activation of methane under mild conditions would be highly valuable for controlling emissions to the environment and for utilizing vast new sources of natural gas. The only selective catalysts for methane activation and conversion to methanol under mild conditions are methane monooxygenases (MMOs) found in methanotrophic bacteria; however, these enzymes are not amenable to standard enzyme immobilization approaches. Using particulate methane monooxygenase (pMMO), we create a biocatalytic polymer material that converts methane to methanol. We demonstrate embedding the material within a silicone lattice to create mechanically robust, gas-permeable membranes, and direct printing of micron-scalemore » structures with controlled geometry. Remarkably, the enzymes retain up to 100% activity in the polymer construct. The printed enzyme-embedded polymer motif is highly flexible for future development and should be useful in a wide range of applications, especially those involving gas–liquid reactions.« less

Printable enzyme-embedded materials for methane to methanol conversion

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

Blanchette, Craig D.; Knipe, Jennifer M.; Stolaroff, Joshuah K.

An industrial process for the selective activation of methane under mild conditions would be highly valuable for controlling emissions to the environment and for utilizing vast new sources of natural gas. The only selective catalysts for methane activation and conversion to methanol under mild conditions are methane monooxygenases (MMOs) found in methanotrophic bacteria; however, these enzymes are not amenable to standard enzyme immobilization approaches. Using particulate methane monooxygenase (pMMO), we create a biocatalytic polymer material that converts methane to methanol. We demonstrate embedding the material within a silicone lattice to create mechanically robust, gas-permeable membranes, and direct printing of micron-scalemore » structures with controlled geometry. Remarkably, the enzymes retain up to 100% activity in the polymer construct. The printed enzyme-embedded polymer motif is highly flexible for future development and should be useful in a wide range of applications, especially those involving gas–liquid reactions.« less

Dynamic Modification of Pore Opening of SAPO-34 by Adsorbed Surface Methoxy Species during Induction of Catalytic Methanol-to-Olefins Reactions

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

Lo, Benedict T W.; Ye, Lin; Change, G.G. Z.

Here, we report that the pore opening of SAPO-34 can be significantly modified by an adsorbed surface methoxy species during induction of the catalytic methanol-to-olefins process, which offers molecular sieving properties due to physical obstacle of the methoxy group and its adsorption modification to other hydrocarbons. X-ray powder diffraction and Rietveld refinement clearly reveal that the adsorbed single carbon atom as the methoxy group is dynamically created from methanol dehydration on a Brønsted acid site in close proximity to the pore windows. As a result, industrial desirable smaller olefins such as ethylene and propylene can be favourably made at themore » expenses of higher olefins. The structures and fundamental understanding in alteration in the olefins selectivity during induction may allow rational optimisation in catalytic performance under the complex fluidisation conditions.« less

Catalytic distillation process

DOEpatents

Smith, Jr., Lawrence A.

1982-01-01

A method for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C.sub.4 feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

Printable enzyme-embedded materials for methane to methanol conversion

PubMed Central

Blanchette, Craig D.; Knipe, Jennifer M.; Stolaroff, Joshuah K.; DeOtte, Joshua R.; Oakdale, James S.; Maiti, Amitesh; Lenhardt, Jeremy M.; Sirajuddin, Sarah; Rosenzweig, Amy C.; Baker, Sarah E.

2016-01-01

An industrial process for the selective activation of methane under mild conditions would be highly valuable for controlling emissions to the environment and for utilizing vast new sources of natural gas. The only selective catalysts for methane activation and conversion to methanol under mild conditions are methane monooxygenases (MMOs) found in methanotrophic bacteria; however, these enzymes are not amenable to standard enzyme immobilization approaches. Using particulate methane monooxygenase (pMMO), we create a biocatalytic polymer material that converts methane to methanol. We demonstrate embedding the material within a silicone lattice to create mechanically robust, gas-permeable membranes, and direct printing of micron-scale structures with controlled geometry. Remarkably, the enzymes retain up to 100% activity in the polymer construct. The printed enzyme-embedded polymer motif is highly flexible for future development and should be useful in a wide range of applications, especially those involving gas–liquid reactions. PMID:27301270

Catalytic distillation process

DOEpatents

Smith, L.A. Jr.

1982-06-22

A method is described for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C[sub 4] feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

Conversion of Methanol, Ethanol and Propanol over Zeolites

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

Ramasamy, Karthikeyan K.; Wang, Yong

2013-06-04

Renewable fuel from lignocellulosic biomass has recently attracted more attention due to its environmental and the potential economic benefits over the crude oil [1]. In particular the production of fuel range hydrocarbon (HC) from alcohol generated lots of interest since the alcohol can be produced from biomass via thermochemical [2] (mixed alcohol from gasification derived synthesis gas) as well as the biochemical routes [3] (alcohol fermentation). Along with the development of ZSM5 synthesis and the discovery of methanol-to-gasoline (MTG) process by Mobil in 1970’s triggered lots of interest in research and development arena to understand the reaction mechanisms of alcoholsmore » over zeolites in particular ZSM5 [4]. More detailed research on methanol conversion was extensively reported [5] and in recent times the research work can be found on ethanol [6] and other alcohols as well but comprehensive comparison of catalyst activity and the deactivation mechanism of the conversion of various alcohols over zeolites has not been reported. The experiments were conducted on smaller alcohols such as methanol, ethanol and 1-propanol over HZSM5. The experimental results on the catalyst activity and the catalyst deactivation mechanism will be discussed.« less

Synthesis of Pt/rGO catalysts with two different reducing agents and their methanol electrooxidation activity

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

Vu, Thu Ha Thi, E-mail: ptntd2004@yahoo.fr; Tran, Thanh Thuy Thi, E-mail: tranthithanhthuygl@gmail.com; Le, Hong Ngan Thi

2016-01-15

Highlights: • Pt/rGO catalysts were successfully synthesized using either NaBH{sub 4} or ethylene glycol. • Synthesis using NaBH{sub 4} could improve electrocatalytic towards methanol oxidation of Pt/rGO catalyst. • 40%Pt/rGO synthesized using NaBH{sub 4} showed the best electrocatalytic performance. - Abstract: The synthesis processes of Platinum (Pt) on reduced graphene oxide (rGO) catalysts from graphene oxide (GO) using two reducing agents including sodium borohydride and ethylene glycol is reported. Structure and morphology of Pt/rGO catalysts are characterized by X-ray powder diffraction, transmission electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. Electrocatalytic methanol oxidation properties of these catalysts are evaluated bymore » cyclic voltammetry and chronoamperometry. The results show that catalyst synthesized using sodium borohydride has a higher metallic Pt content and an improved catalytic performance in comparison to catalyst synthesized using ethylene glycol. Moreover, effect of Pt loading amount on electrocatalytic methanol oxidation performance of catalysts synthesized using sodium borohydride is systematically investigated. The optimal Pt loading amount on graphene is determined to be 40%.« less

Remediating pesticide contaminated soils using solvent extraction

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

Sahle-Demessie, E.; Meckes, M.C.; Richardson, T.L.

Bench-scale solvent extraction studies were performed on soil samples obtained from a Superfund site contaminated with high levels of p,p{prime}-DDT, p,p{prime}-DDE and toxaphene. The effectiveness of the solvent extraction process was assessed using methanol and 2-propanol as solvents over a wide range of operating conditions. It was demonstrated that a six-stage methanol extraction using a solvent-to-soil ratio of 1.6 can decrease pesticide levels in the soil by more than 99% and reduce the volume of material requiring further treatment by 25 times or more. The high solubility of the pesticides in methanol resulted in rapid extraction rates, with the systemmore » reaching quasi-equilibrium state in 30 minutes. The extraction efficiency was influenced by the number of extraction stages, the solvent-to-soil ratio, and the soil moisture content. Various methods were investigated to regenerate and recycle the solvent. Evaporation and solvent stripping are low cost and reliable methods for removing high pesticide concentrations from the solvent. For low concentrations, GAC adsorption may be used. Precipitating and filtering pesticides by adding water to the methanol/pesticide solution was not successful when tested with soil extracts. 26 refs., 10 figs., 6 tabs.« less

Electrical enhancement of direct methanol fuel cells by metal-plasma ion implantation Pt-Ru/C multilayer catalysts.

PubMed

Weng, Ko-Wei; Chen, Yung-Lin; Chen, Ya-Chi; Lin, Tai-Nan

2009-02-01

Direct methanol fuel cells (DMFC) have been widely studied owing to their simple cell configuration, high volume energy density, short start-up time, high operational reliability and other favorable characteristics. However, major limitations include high production cost, poisoning of the catalyst and methanol crossover. This study adopts a simple technique for preparing Pt-Ru/C multilayer catalysts, including magnetron sputtering (MS) and metal-plasma ion implantation (MPII). The Pt catalysts were sputtered onto the gas diffusion layer (GDL), followed by the implantation of Ru catalysts using MPII (at an accelerating voltage of 20 kV and an implantation dose of 1 x 10(16) ions/cm2). Pt-Ru is repeatedly processed to prepare Pt-Ru/C multilayer catalysts. The catalyst film structure and microstructure were analyzed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electronic microscopy (SEM), respectively. The cell performance was tested using a potential stat/galvano-stat. The results reveal that the membrane electrode assembly (MEA) of four multilayer structures enhances the cell performance of DMFC. The measured power density is 2.2 mW/cm2 at a methanol concentration of 2 M, with an OCV of 0.493 V.

Diamond nanoparticles as a support for Pt and PtRu catalysts for direct methanol fuel cells.

PubMed

La-Torre-Riveros, Lyda; Guzman-Blas, Rolando; Méndez-Torres, Adrián E; Prelas, Mark; Tryk, Donald A; Cabrera, Carlos R

2012-02-01

Diamond in nanoparticle form is a promising material that can be used as a robust and chemically stable catalyst support in fuel cells. It has been studied and characterized physically and electrochemically, in its thin film and powder forms, as reported in the literature. In the present work, the electrochemical properties of undoped and boron-doped diamond nanoparticle electrodes, fabricated using the ink-paste method, were investigated. Methanol oxidation experiments were carried out in both half-cell and full fuel cell modes. Platinum and ruthenium nanoparticles were chemically deposited on undoped and boron doped diamond nanoparticles through the use of NaBH(4) as reducing agent and sodium dodecyl benzene sulfonate (SDBS) as a surfactant. Before and after the reduction process, samples were characterized by electron microscopy and spectroscopic techniques. The ink-paste method was also used to prepare the membrane electrode assembly with Pt and Pt-Ru modified undoped and boron-doped diamond nanoparticle catalytic systems, to perform the electrochemical experiments in a direct methanol fuel cell system. The results obtained demonstrate that diamond supported catalyst nanomaterials are promising for methanol fuel cells.

Bimetallo-radical carbon-hydrogen bond activation of methanol and methane.

PubMed

Cui, Weihong; Zhang, X Peter; Wayland, Bradford B

2003-04-30

Carbon-hydrogen bond cleavage reactions of CH3OH and CH4 by a dirhodium(II) diporphyrin complex with a m-xylyl tether (.Rh(m-xylyl)Rh.(1)) are reported. Kinetic-mechanistic studies show that the substrate reactions are bimolecular and occur through the use of two Rh(II) centers in the molecular unit of 1. Second-order rate constants (T = 296 K) for the reactions of 1 with methanol (k(CH3OH) = 1.45 x 10-2 M-1 s-1) and methane (k(CH4) = 0.105 M-1 s-1) show a clear kinetic preference for the methane activation process. The methanol and methane reactions with 1 have large kinetic isotope effects (k(CH3OH)/k(CD3OD) = 9.7 +/- 0.8, k(CH4)/k(CD4) = 10.8 +/- 1.0, T = 296 K), consistent with a rate-limiting step of C-H bond homolysis through a linear transition state. Activation parameters for reaction of 1 with methanol (DeltaH = 15.6 +/- 1.0 kcal mol-1; DeltaS = -14 +/- 5 cal K-1 mol-1) and methane (DeltaH = 9.8 +/- 0.5 kcal mol-1; DeltaS = -30 +/- 3 cal K-1 mol-1) are reported.

Effects of moisture content in cigar tobacco on nicotine extraction. Similarity between soxhlet and focused open-vessel microwave-assisted techniques.

PubMed

Ng, Lay-Keow; Hupé, Michel

2003-09-05

The effects of tobacco moisture on nicotine yield were investigated in this study. Soxhlet and microwave-assisted techniques were used to extract nicotine from cigar fillers of varying moisture contents (5-20%), using a polar (methanol) and a non-polar (isooctane) solvent. The extracts were analyzed by a gas chromatograph equipped with a flame-ionization detector. For both extraction techniques, higher nicotine yields were consistently obtained with methanol than with isooctane from the same samples. Solubility of nicotine salts in methanol but not in isooctane is the major cause of this observation. Moreover, pronounced effects of the tobacco moisture content on extraction efficiency were observed with isooctane but not with methanol. For microwave assisted extraction (MAE) with isooctane, nicotine yield increased from 3 to 70% as the moisture level in tobacco was raised from 3 to 13%, and leveled off thereafter. Similar observations were made with Soxhlet extraction. While MAE results were rationalized by the known cell-rupture process, a mechanism based on the interaction between the solvents and the structural components of the plant cells has been proposed to account for the observations made with Soxhlet extraction.

Non-carbon titanium cobalt nitride nanotubes supported platinum catalyst with high activity and durability for methanol oxidation reaction

NASA Astrophysics Data System (ADS)

Chen, Xiaoxiang; Li, Wuyi; Pan, Zhanchang; Xu, Yanbin; Liu, Gen; Hu, Guanghui; Wu, Shoukun; Li, Jinghong; Chen, Chun; Lin, Yingsheng

2018-05-01

Titanium cobalt nitride nanotubes (Ti0.95Co0.05N NTs) hybrid support, a novel robust non-carbon support material prepared by solvothermal and post-nitriding processes, is further decorated with Pt nanoparticles for the electrooxidation of methanol. The catalyst is characterized by X-ray diffraction (XRD), nitrogen adsorption/desorption, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and electrochemical measurements. The morphology, structure and composition of the synthesized Ti0.95Co0.05N NTs suggest that the nanotube wall is porous and consists of homogeneous cohesively attached nitrides nanocube particles. Notable, Ti0.95Co0.05N NTs supported Pt catalyst exhibits significantly improved catalytic activity and durability for methanol electrooxidation compared with the conventional JM Pt/C catalyst. The experimental data indicate that enhanced catalytic activity and stability of Pt/Ti0.95Co0.05N NTs towards methanol electrooxidation might be mainly attributed to the tubular nanostructures and synergistic effect introduced by the Co doping. Both of them are playing an important role in improving the activity and durability of the Ti0.95Co0.05N NTs catalyst.

Impact of quality parameters on the recovery of putrescine and cadaverine in fish using methanol-hydrochloric acid solvent extraction.

PubMed

Richard, Nicole L; Pivarnik, Lori F; Ellis, P Christopher; Lee, Chong M

2011-01-01

Methanol (MeOH) extraction by AOAC Official Method 996.07 has resulted in low amine recoveries in fresh fish tissue. Addition of 25% 0.4 M HCl to the 75% methanol-water extraction solvent resulted in higher recoveries of putrescine and cadaverine. Average putrescine recovery increased from 55 to 92% in flounder, scup, bluefish, and salmon; from 92 to 98% in mackerel; and from 83 to 107% in processed mackerel. Average cadaverine recovery increased from 57 to 95% in flounder, scup, bluefish, and salmon; from 91 to 97% in mackerel; and from 92 to 108% in processed mackerel. Fish stored on ice for 12 days also showed differences between background concentrations determined with the two solvents. However, the values decreased with storage time, indicating that degradation of the protein matrix may cause more comparable measurements between the two solvents. However, consistently higher putrescine and cadaverine measurements were determined using MeOH-HCl. Although significant differences in the extraction of amines from the high-fat fish tissue were not seen between MeOH and MeOH-HCl, it would be ideal to have one solvent for biogenic amine extraction. This study confirms that MeOH-HCl is a better solvent for complete extraction and recovery of putrescine and cadaverine in fresh and processed fish tissues.

The use of advanced steam reforming technology for hydrogen production

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

Abbishaw, J.B.; Cromarty, B.J.

1996-12-01

The demand for supplementary hydrogen production in refineries is growing significantly world-wide as environmental legislation concerning cleaner gasoline and diesel fuels is introduced. The main manufacturing method is by steam reforming. The process has been developed both to reduce the capital cost and increase efficiency, reliability and ease of operation. ICI Katalco`s Leading Concept Hydrogen or LCH process continues this process of improvement by replacing the conventional fired steam reformer with a type of heat exchange reformer known as the Gas Heated Reformer or GHR. The GHR was first used in the Leading Concept Ammonia process, LCA at ICI`s manufacturingmore » site at Severnside, England and commissioned in 1988 and later in the Leading Concept Methanol (LCM) process for methanol at Melbourne, Australia and commissioned in 1994. The development of the LCH process follows on from both LCA and LCM processes. This paper describes the development and use of the GHR in steam reforming, and shows how the GHR can be used in LCH. A comparison between the LCH process and a conventional hydrogen plant is given, showing the benefits of the LCH process in certain circumstances.« less

Mechanism of CO 2 hydrogenation over Cu/ZrO 2(2̅12) interface from first-principles kinetics Monte Carlo simulations

NASA Astrophysics Data System (ADS)

Hong, Qi-Jun; Liu, Zhi-Pan

2010-10-01

It has been a goal consistently pursued by chemists to understand and control the catalytic process over composite materials. In order to provide deeper insight on complex interfacial catalysis at the experimental conditions, we performed an extensive analysis on CO 2 hydrogenation over a Cu/ZrO 2 model catalyst by employing density functional theory (DFT) calculations and kinetic Monte Carlo (kMC) simulations based on the continuous stirred tank model. The free energy profiles are determined for the reaction at the oxygen-rich Cu/m-ZrO 2 (2̅12) interface, where all interfacial Zr are six-coordinated since the interface accumulates oxidative species at the reaction conditions. We show that not only methanol but also CO are produced through the formate pathway dominantly, whilst the reverse-water-gas-shift (RWGS) channel has only a minor contribution. H 2CO is a key intermediate species in the reaction pathway, the hydrogenation of which dictates the high temperature of CO 2 hydrogenation. The kinetics simulation shows that the CO 2 conversion is 1.20%, the selectivity towards methanol is 68% at 500 K and the activation energies for methanol and CO formation are 0.79 and 1.79 eV, respectively. The secondary reactions due to the product readsorption lower the overall turnover frequency (TOF) but increase the selectivity towards methanol by 16%. We also show that kMC is a more reliable tool for simulating heterogeneous catalytic processes compared to the microkinetics approach.

Expression of recombinant green fluorescent protein in Bacillus methanolicus.

PubMed

Nilasari, Dewi; Dover, Nir; Rech, Sabine; Komives, Claire

2012-01-01

Microbial biocatalysts are used in a wide range of industries to produce large scale quantities of proteins, amino acids, and commodity chemicals. While the majority of these processes use glucose or other low-cost sugars as the substrate, Bacillus methanolicus is one example of a biocatalyst that has shown sustained growth on methanol as a carbon source at elevated temperature (50-53°C optimum) resulting in reduced feed and utility costs. Specifically, the complete chemical process enabled by this approach takes methane from natural gas, and following a low-cost conversion to methanol, can be used for the production of high value products. In this study, production of recombinant green fluorescent protein (GFPuv) by B. methanolicus is explored. A plasmid was constructed that incorporates the methanol dehydrogenase (mdh) promoter of B. methanolicus MGA3 together with the GFPuv gene. The plasmid, pNW33N, was shown to be effective for expression in other Bacillus strains, although not previously in B. methanolicus. A published electroporation protocol for transformation of B. methanolicus was modified to result in expression of GFP using plasmid pNW33N-mdh-GFPuv (pNmG). Transformation was confirmed by both agarose gel electrophoresis and by observation of green fluorescence under UV light exposure. The mass yield of cells and protein were measured in shake flask experiments. The optimum concentration of methanol for protein production was found to be at 200 mM. Higher concentrations than 200 mM resulted in slightly higher biomass production but lower amounts of recombinant protein. Copyright © 2012 American Institute of Chemical Engineers (AIChE).

Enhanced photo-catalytic activity of ordered mesoporous indium oxide nanocrystals in the conversion of CO2 into methanol.

PubMed

Gondal, M A; Dastageer, M A; Oloore, L E; Baig, U; Rashid, S G

2017-07-03

Ordered mesoporous indium oxide nanocrystal (m-In 2 O 3 ) was synthesized by nanocasting technique, in which highly ordered mesoporous silca (SBA-15) was used as structural matrix. X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM) Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halanda (BJH) studies were carried out on m-In 2 O 3 and the results revealed that this material has a highly ordered mesoporous surface with reduced grain size, increased surface area and surface volume compared to the non porous indium oxide. The diffuse reluctance spectrum exhibited substantially improved light absorption efficiency in m-In 2 O 3 compared to normal indium oxide, however, no considerable change in the band gap energies of these materials was observed. When m-In 2 O 3 was used as a photo-catalyst in the photo-catalytic process of converting carbon dioxide (CO 2 ) into methanol under the pulsed laser radiation of 266-nm wavelengths, an enhanced photo-catalytic activity with the quantum efficiency of 4.5% and conversion efficiency of 46.3% were observed. It was found that the methanol production yield in this chemical process is as high as 485 µlg -1 h -1 after 150 min of irradiation, which is substantially higher than the yields reported in the literature. It is quite clear from the results that the introduction of mesoporosity in indium oxide, and the consequent enhancement of positive attributes required for a photo-catalyst, transformed photo-catalytically weak indium oxide into an effective photo-catalyst for the conversion of CO 2 into methanol.

[Numerical simulation and operation optimization of biological filter].

PubMed

Zou, Zong-Sen; Shi, Han-Chang; Chen, Xiang-Qiang; Xie, Xiao-Qing

2014-12-01

BioWin software and two sensitivity analysis methods were used to simulate the Denitrification Biological Filter (DNBF) + Biological Aerated Filter (BAF) process in Yuandang Wastewater Treatment Plant. Based on the BioWin model of DNBF + BAF process, the operation data of September 2013 were used for sensitivity analysis and model calibration, and the operation data of October 2013 were used for model validation. The results indicated that the calibrated model could accurately simulate practical DNBF + BAF processes, and the most sensitive parameters were the parameters related to biofilm, OHOs and aeration. After the validation and calibration of model, it was used for process optimization with simulating operation results under different conditions. The results showed that, the best operation condition for discharge standard B was: reflux ratio = 50%, ceasing methanol addition, influent C/N = 4.43; while the best operation condition for discharge standard A was: reflux ratio = 50%, influent COD = 155 mg x L(-1) after methanol addition, influent C/N = 5.10.

Structure and energetics of hydrogen-bonded networks of methanol on close packed transition metal surfaces

NASA Astrophysics Data System (ADS)

Murphy, Colin J.; Carrasco, Javier; Lawton, Timothy J.; Liriano, Melissa L.; Baber, Ashleigh E.; Lewis, Emily A.; Michaelides, Angelos; Sykes, E. Charles H.

2014-07-01

Methanol is a versatile chemical feedstock, fuel source, and energy storage material. Many reactions involving methanol are catalyzed by transition metal surfaces, on which hydrogen-bonded methanol overlayers form. As with water, the structure of these overlayers is expected to depend on a delicate balance of hydrogen bonding and adsorbate-substrate bonding. In contrast to water, however, relatively little is known about the structures methanol overlayers form and how these vary from one substrate to another. To address this issue, herein we analyze the hydrogen bonded networks that methanol forms as a function of coverage on three catalytically important surfaces, Au(111), Cu(111), and Pt(111), using a combination of scanning tunneling microscopy and density functional theory. We investigate the effect of intermolecular interactions, surface coverage, and adsorption energies on molecular assembly and compare the results to more widely studied water networks on the same surfaces. Two main factors are shown to direct the structure of methanol on the surfaces studied: the surface coverage and the competition between the methanol-methanol and methanol-surface interactions. Additionally, we report a new chiral form of buckled hexamer formed by surface bound methanol that maximizes the interactions between methanol monomers by sacrificing interactions with the surface. These results serve as a direct comparison of interaction strength, assembly, and chirality of methanol networks on Au(111), Cu(111), and Pt(111) which are catalytically relevant for methanol oxidation, steam reforming, and direct methanol fuel cells.

Methanol May Function as a Cross-Kingdom Signal

PubMed Central

Dorokhov, Yuri L.; Komarova, Tatiana V.; Petrunia, Igor V.; Kosorukov, Vyacheslav S.; Zinovkin, Roman A.; Shindyapina, Anastasia V.; Frolova, Olga Y.; Gleba, Yuri Y.

2012-01-01

Recently, we demonstrated that leaf wounding results in the synthesis of pectin methylesterase (PME), which causes the plant to release methanol into the air. Methanol emitted by a wounded plant increases the accumulation of methanol-inducible gene mRNA and enhances antibacterial resistance as well as cell-to-cell communication, which facilitates virus spreading in neighboring plants. We concluded that methanol is a signaling molecule involved in within-plant and plant-to-plant communication. Methanol is considered to be a poison in humans because of the alcohol dehydrogenase (ADH)-mediated conversion of methanol into toxic formaldehyde. However, recent data showed that methanol is a natural compound in normal, healthy humans. These data call into question whether human methanol is a metabolic waste product or whether methanol has specific function in humans. Here, to reveal human methanol-responsive genes (MRGs), we used suppression subtractive hybridization cDNA libraries of HeLa cells lacking ADH and exposed to methanol. This design allowed us to exclude genes involved in formaldehyde and formic acid detoxification from our analysis. We identified MRGs and revealed a correlation between increases in methanol content in the plasma and changes in human leukocyte MRG mRNA levels after fresh salad consumption by volunteers. Subsequently, we showed that the methanol generated by the pectin/PME complex in the gastrointestinal tract of mice induces the up- and downregulation of brain MRG mRNA. We used an adapted Y-maze to measure the locomotor behavior of the mice while breathing wounded plant vapors in two-choice assays. We showed that mice prefer the odor of methanol to other plant volatiles and that methanol changed MRG mRNA accumulation in the mouse brain. We hypothesize that the methanol emitted by wounded plants may have a role in plant-animal signaling. The known positive effect of plant food intake on human health suggests a role for physiological methanol in human gene regulation. PMID:22563443

Side draw control design for a high purity multi-component distillation column.

PubMed

A Udugama, Isuru; Munir, M T; Kirkpatrick, Rob; Young, Brent R; Yu, Wei

2018-05-01

Industrial methanol production involves a multi component feed containing methanol, water and trace levels of ethanol being refined to produce AA grade methanol at high product recovery. Due to practical constraints, the bottoms discharge of the column is primarily water with only trace of methanol impurities. As a result of these constraints, ethanol, which is a non-key middle boiling component gets "trapped" near the side draw of the column forming an ethanol bulge, which in turn results in non-linear, inverse, time and state varying behaviour of the side draw ethanol composition. In this work, we established that the existence of the ethanol bulge creates the complex process behaviour of the side draw ethanol composition and that this bulge needs to be explicitly controlled. This type of explicit composition bulge analysis and subsequent control has not been attempted on methanol distillation columns before. For this purpose a novel, robust and practical side draw control scheme to detect and remedy the excess ethanol bulge movement using override control is presented. The side draw controller, together with other regulatory controllers is shown to maintain on-specification operations of the column. Disturbance rejection tests carried out illustrate that the side draw control scheme will keep the column operating within commercial specification. It is also shown that a traditional DV control structure is unable to achieve this objective. Copyright © 2018 ISA. Published by Elsevier Ltd. All rights reserved.

Enzyme-like specificity in zeolites: a unique site position in mordenite for selective carbonylation of methanol and dimethyl ether with CO.

PubMed

Boronat, Mercedes; Martínez-Sánchez, Cristina; Law, David; Corma, Avelino

2008-12-03

The mechanism of methanol carbonylation at different positions of zeolite MOR is investigated by quantum-chemical methods in order to discover which are the active sites that can selectively catalyze the desired reaction. It is shown that when methanol carbonylation competes with hydrocarbon formation, the first reaction occurs preferentially within 8MR channels. However, the unique selectivity for the carbonylation of methanol and dimethyl ether in mordenite is not only due to the size of the 8MR channel: neither process occurs equally at the two T3-O31 and T3-O33 positions. We show that only the T3-O33 positions are selective and that this selectivity is due to the unusual orientation of the methoxy group in relation to the 8MR channel (parallel to the cylinder axis). Only in this situation does the transition state for the attack of CO fit perfectly in the 8MR channel, while the reaction with methanol or DME is sterically impeded. This result explains why T3-O31, while also located in the 8MR channel of mordenite, is not as selective as the T3-O33 position and why ferrierite, although it contains 8MR channels, is less selective than mordenite. The competing effect of water is explained at the molecular level, and the molecular microkinetic reaction model has been established.

Enhanced electrocatalytic activity and stability of monodisperse Pt nanocomposites for direct methanol fuel cells.

PubMed

Eris, Sinan; Daşdelen, Zeynep; Sen, Fatih

2018-03-01

Direct methanol fuel cells (DMFCs) are one of the most important fuel cells operating at low temperature using methanol as fuel and they need very efficient catalysts to activate the methanol. Generally, the most efficient fuel cell catalysts are platinum-based nanoparticles that can be used by different supporting materials such as different as prepared and functionalized carbon derivatives. For this purpose, herein, the carbon black has been mainly functionalized with an acidification process in order to increase the electrical conductivity and heterogeneous electron transfer rate of supporting materials. After functionalization of carbon black (f-CB), platinum salt (PtCl 4 ) was stabilized with propylamine (PA) in the presence of ethylene glycol (EG) and f-CB by microwave synthesis method. XPS, XRD, TEM and Raman Spectroscopy techniques were used to determine the morphology of the prepared catalyst. The results showed that the prepared nanocatalyst has face-centered cubic (fcc) structure and uniformly distribution on supporting material. Besides, chronoamperometry (CA) and cyclic voltammetry (CV) techniques were used to determine the electrochemical activity of functionalized carbon black supported Pt NPs (Pt/f-CB) towards methanol. From the results obtained from the CV and CA, it was found that the activity of the Pt/f-CB NPs (50 mA/cm 2 ) was almost 4-5 times higher than that of the Pt/CB NPs and commercial available Pt/C catalyst (ETEK). Copyright © 2017 Elsevier Inc. All rights reserved.

Hemin-utilizing G-quadruplex DNAzymes are strongly active in organic co-solvents.

PubMed

Canale, Thomas D; Sen, Dipankar

2017-05-01

The widespread use of organic solvents in industrial processes has focused in recent years on the utility of "green" solvents - those with less harmful environmental, health, and safety properties - such as methanol and formamide. However, protein enzymes, regarded as green catalysts, are often incompatible with organic solvents. Herein, we have explored the oxidative properties of a Fe(III)-heme, or hemin, utilizing catalytic DNA (heme·DNAzyme) in different green solvent-water mixtures. We find that the peroxidase and peroxygenase activities of the heme·DNAzyme are strongly enhanced in 20-30% v/v methanol or formamide, relative to water alone. Protic solvent content of >30% v/v gradually diminishes heme·DNAzyme catalytic activity; however, the heme·DNAzyme is still active in as high as 80% v/v methanol. In contrast to protic solvents, aqueous dimethylformamide solutions largely inhibit heme·DNAzyme activity. In view of the strong catalytic activity of heme·DNAzyme in aqueous methanol, we were able to determine that a 60% v/v methanol-water mixture gives the most optimal yield of the dibenzothiophene sulfoxide (DBTO) oxidation product of petroleum-derived dibenzothiophene (DBT). The high product yield reflects both DNAzyme catalysis and a high substrate availability. Overall, these results emphasize the excellent promise of G-quadruplex forming DNA catalysts in application to "greener" industrial chemistry. This article is part of a Special Issue entitled "G-quadruplex" Guest Editor: Dr. Concetta Giancola and Dr. Daniela Montesarchio. Copyright © 2016 Elsevier B.V. All rights reserved.

Enhancing monellin production by Pichia pastoris at low cell induction concentration via effectively regulating methanol metabolism patterns and energy utilization efficiency

PubMed Central

Jia, Luqiang; Tu, Tingyong; Huai, Qiangqiang; Sun, Jiaowen; Chen, Shanshan; Li, Xin; Ding, Jian

2017-01-01

In heterologous protein productions by P. pastoris, methanol induction is generally initiated when cell concentration reaches very high density. The alternative strategy by initiating methanol induction at lower cells concentration was also reported to be effective in easing DO control, reducing toxic by-metabolites accumulation and increasing targeted proteins titers. However, the methanol/energy regulation mechanisms are seldom reported. We theoretically analyzed the methanol/energy metabolisms in protein expression process with the strategies of initiating induction at higher or lower cells concentrations, using monellin production as a prototype. When initiating induction at lower cells concentration and controlling induction temperature at 30°C, monellin concentration reached the highest levels of 2.62~2.71 g/L, which was 2.5~4.9 fold of those obtained with the strategy of initiating induction at higher cells concentration. With the desired induction strategy, 1) carbon metabolism ratio directing into the precursors synthesis route for monellin production reached the highest level of 65%, carbon metabolism ratios towards to precursors synthesis and ATP regeneration routes were regulated at relatively balanced levels; 2) monellin synthesis was completely cell growth associated, with the largest associated coefficient and higher specific growth rate; 3) theoretical NADH (energy) utilization efficiency η was the highest, and η stayed high levels (≥0.8) during most period (89%) within induction phase to supply sufficient energy in supporting monellin synthesis. PMID:28981536

Experimental and Theoretical Studies on Gas-Phase Fragmentation Reactions of Protonated Methyl Benzoate: Concomitant Neutral Eliminations of Benzene, Carbon Dioxide, and Methanol

NASA Astrophysics Data System (ADS)

Xia, Hanxue; Zhang, Yong; Attygalle, Athula B.

2018-06-01

Protonated methyl benzoate, upon activation, fragments by three distinct pathways. The m/z 137 ion for the protonated species generated by helium-plasma ionization (HePI) was mass-selected and subjected to collisional activation. In one fragmentation pathway, the protonated molecule generated a product ion of m/z 59 by eliminating a molecule of benzene (Pathway I). The m/z 59 ion (generally recognized as the methoxycarbonyl cation) produced in this way, then formed a methyl carbenium ion in situ by decarboxylation, which in turn evoked an electrophilic aromatic addition reaction on the benzene ring by a termolecular process to generate the toluenium cation (Pathway II). Moreover, protonated methyl benzoate undergoes also a methanol loss (Pathway III). However, it is not a simple removal of a methanol molecule after a protonation on the methoxy group. The incipient proton migrates to the ring and randomizes to a certain degree before a subsequent transfer of one of the ring protons to the alkoxy group for the concomitant methanol elimination. The spectrum recorded from deuteronated methyl benzoate showed two peaks at m/z 105 and 106 for the benzoyl cation at a ratio of 2:1, confirming the charge-imparting proton is mobile. However, the proton transfer from the benzenium intermediate to the methoxy group for the methanol loss occurs before achieving a complete state of scrambling. [Figure not available: see fulltext.

Enhancing monellin production by Pichia pastoris at low cell induction concentration via effectively regulating methanol metabolism patterns and energy utilization efficiency.

PubMed

Jia, Luqiang; Tu, Tingyong; Huai, Qiangqiang; Sun, Jiaowen; Chen, Shanshan; Li, Xin; Shi, Zhongping; Ding, Jian

2017-01-01

In heterologous protein productions by P. pastoris, methanol induction is generally initiated when cell concentration reaches very high density. The alternative strategy by initiating methanol induction at lower cells concentration was also reported to be effective in easing DO control, reducing toxic by-metabolites accumulation and increasing targeted proteins titers. However, the methanol/energy regulation mechanisms are seldom reported. We theoretically analyzed the methanol/energy metabolisms in protein expression process with the strategies of initiating induction at higher or lower cells concentrations, using monellin production as a prototype. When initiating induction at lower cells concentration and controlling induction temperature at 30°C, monellin concentration reached the highest levels of 2.62~2.71 g/L, which was 2.5~4.9 fold of those obtained with the strategy of initiating induction at higher cells concentration. With the desired induction strategy, 1) carbon metabolism ratio directing into the precursors synthesis route for monellin production reached the highest level of 65%, carbon metabolism ratios towards to precursors synthesis and ATP regeneration routes were regulated at relatively balanced levels; 2) monellin synthesis was completely cell growth associated, with the largest associated coefficient and higher specific growth rate; 3) theoretical NADH (energy) utilization efficiency η was the highest, and η stayed high levels (≥0.8) during most period (89%) within induction phase to supply sufficient energy in supporting monellin synthesis.

The deep-subsurface sulfate reducer Desulfotomaculum kuznetsovii employs two methanol-degrading pathways.

PubMed

Sousa, Diana Z; Visser, Michael; van Gelder, Antonie H; Boeren, Sjef; Pieterse, Mervin M; Pinkse, Martijn W H; Verhaert, Peter D E M; Vogt, Carsten; Franke, Steffi; Kümmel, Steffen; Stams, Alfons J M

2018-01-16

Methanol is generally metabolized through a pathway initiated by a cobalamine-containing methanol methyltransferase by anaerobic methylotrophs (such as methanogens and acetogens), or through oxidation to formaldehyde using a methanol dehydrogenase by aerobes. Methanol is an important substrate in deep-subsurface environments, where thermophilic sulfate-reducing bacteria of the genus Desulfotomaculum have key roles. Here, we study the methanol metabolism of Desulfotomaculum kuznetsovii strain 17 T , isolated from a 3000-m deep geothermal water reservoir. We use proteomics to analyze cells grown with methanol and sulfate in the presence and absence of cobalt and vitamin B12. The results indicate the presence of two methanol-degrading pathways in D. kuznetsovii, a cobalt-dependent methanol methyltransferase and a cobalt-independent methanol dehydrogenase, which is further confirmed by stable isotope fractionation. This is the first report of a microorganism utilizing two distinct methanol conversion pathways. We hypothesize that this gives D. kuznetsovii a competitive advantage in its natural environment.

A comparative study of Averrhoabilimbi extraction method

NASA Astrophysics Data System (ADS)

Zulhaimi, H. I.; Rosli, I. R.; Kasim, K. F.; Akmal, H. Muhammad; Nuradibah, M. A.; Sam, S. T.

2017-09-01

In recent year, bioactive compound in plant has become a limelight in the food and pharmaceutical market, leading to research interest to implement effective technologies for extracting bioactive substance. Therefore, this study is focusing on extraction of Averrhoabilimbi by different extraction technique namely, maceration and ultrasound-assisted extraction. Fewplant partsof Averrhoabilimbiweretaken as extraction samples which are fruits, leaves and twig. Different solvents such as methanol, ethanol and distilled water were utilized in the process. Fruit extractsresult in highest extraction yield compared to other plant parts. Ethanol and distilled water have significant role compared to methanol in all parts and both extraction technique. The result also shows that ultrasound-assisted extraction gave comparable result with maceration. Besides, the shorter period on extraction process gives useful in term of implementation to industries.

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.

Vatellini Sharp (Coleoptera, Dytiscidae) from Brazil: two new species, new records, and a checklist.

PubMed

Braga, Rafael Benzi; Ferreira, Nelson

2016-05-12

The tribe Vatellini Sharp, 1882 is composed of 55 species divided in two genera. Even though a recent revision of the tribe was made, Vatellini of the new world are weakly explored with great gaps in the distributions of species. In Brazil the knowledge is based only on a few localities. In this work two new species are described and illustrated, Vatellus caissara sp. nov. and Vatellus yanomami sp. nov.; new records are given for Brazil: Vatellus maculosus Miller, 2005 in the state of Mato Grosso, Derovatellus lentus (Wehncke, 1876) in Amazonas, Pará and Rio de Janeiro, Vatellus lateralis (Sharp, 1882) in Alagoas, Ceará, Espírito Santo, Pará, Pernambuco and Rio Grande do Sul, Vatellus sahlbergi (Sharp, 1882) in Rio de Janeiro, and Vatellus tarsatus (Laporte, 1835) in Pará. A checklist with all species of Vatellini occurring in Brazil is provided and steps for identification of the new species are added in the key of Miller (2005).

Annotated catalogue of the click-beetle tribe Dimini (Coleoptera: Elateridae: Dendrometrinae).

PubMed

Kundrata, Robin; Musalkova, Marketa; Kubaczkova, Magdalena

2018-04-19

An annotated catalogue of the tribe Dimini (Coleoptera: Elateridae: Dendrometrinae) is presented. Altogether, 273 extant species are classified in 11 genera: Brancuccia Schimmel Platia, 1991 (eight species), Csikia Szombathy, 1910 (eight spp.), Dima Charpentier, 1825 (77 spp.), Neocsikia Ôhira Becker, 1972 (two spp.), Neodima Schimmel Platia, 1992a (two spp.), Paracsikia Schimmel Platia, 1991 (seven spp.), Parapenia Suzuki, 1982b (14 spp.), Penia Laporte, 1838 (108 spp.), Platiana Schimmel, 1993 (34 spp.), Pseudocsikia Schimmel Platia, 1991 (10 spp.), and Sabahdima Schimmel Platia, 1993 (three spp.). The only fossil genus included in this tribe is monotypic Alaodima Dolin, 1980. Dimini are distributed in the Palaearctic and Oriental Regions. For each taxon we provide synonyms, information on types, type localities, distribution, and bibliography. The lectotype of Penia apicalis Fleutiaux, 1936 is here designated in order to fix the identity of the species for future studies. Penia impressifrons Schimmel, 1993 from Vietnam is synonymized with Ceroleptus sulcatus (Fleutiaux, 1903), a representative of Elateridae: Oxynopterinae.

[Triatoma vandae sp.n. of the oliveirai complex from the State of Mato Grosso, Brazil (Hemiptera: Reduviidae: Triatominae)].

PubMed

Carcavallo, Rodolfo U; Jurberg, José; Rocha, Dayse da Silva; Galvao, Cleber; Noireau, François; Lent, Herman

2002-07-01

There are several specific complexes belonging to the genus Triatoma Laporte, 1832, which are generally associated to specific geographic areas. Recent publications have linked the oliveirai complex to ecosystems of Mato Grosso, which are also present in other Brazilian states and even in other bordering countries as eastern Paraguay. The study of the abundant material collected during the last years allowed the description of several new species of the oliveirai complex: T. jurbergi Carcavallo, Galvão Lent, 1998; T. baratai Carcavallo Jurberg, 2000 and T. klugi Carcavallo, Jurberg, Lent Galvão, 2001. Another new species belonging to the same complex is described here as T. vandae sp.n. It originates from the state of Mato Grosso, and has been reared in the insectary of the Laboratório Nacional e Internacional de Referência em Taxonomia de Triatomíneos, Departamento de Entomologia, Instituto Oswaldo Cruz-Fiocruz, Rio de Janeiro.

Installation and certification of continuous VOC emissions monitoring systems for a steel mill sinter plant

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

Taylor, K.L.; Macak, J.J. III; Cioffi, J.

1999-07-01

The counties of Lake, Porter, and LaPorte in Northwest Indiana are classified as severe non-attainment for the ozone National Ambient Air Quality Standard (NAAQS). In response to the non-attainment problem, the Indiana Department of Environmental Management (IDEM) promulgated a number of regulations over the last several years. One of these rules requires steel mills with sinter plants to control and continuously monitor volatile organic compound (VOC) emissions from the facilities. One of the accepted compliance methods is to install and certify Continuous Emission Monitoring Systems (CEMS) to monitor VOC emissions and volumetric flow rate in order to generate a VOCmore » emission number in units of pounds per hour. Compliance with the regulation also requires that the sinter plants accurately monitor sinter production in order to determine compliance during the winter months, when the limits are based on pounds of VOC emissions per ton of sinter produced.« less

Towards neat methanol operation of direct methanol fuel cells: a novel self-assembled proton exchange membrane.

PubMed

Li, Jing; Cai, Weiwei; Ma, Liying; Zhang, Yunfeng; Chen, Zhangxian; Cheng, Hansong

2015-04-18

We report here a novel proton exchange membrane with remarkably high methanol-permeation resistivity and excellent proton conductivity enabled by carefully designed self-assembled ionic conductive channels. A direct methanol fuel cell utilizing the membrane performs well with a 20 M methanol solution, very close to the concentration of neat methanol.

Temporal variations in rainwater methanol

NASA Astrophysics Data System (ADS)

Felix, J. D.; Jones, S. B.; Avery, G. B.; Willey, J. D.; Mead, R. N.; Kieber, R. J.

2014-10-01

This work reports the first comprehensive analysis of methanol concentrations in rainwater. Methanol concentrations measured in 49 rain events collected between 28 August 2007 and 10 July 2008 in Wilmington, NC, USA, ranged from below the detection limit of 6 nM to 9.3 μM with a volume-weighted average concentration of 1 ± 0.2 μM. Methanol concentrations in rainwater were up to ~200 times greater than concentrations reported previously in marine waters, indicating wet deposition as a potentially significant source of methanol to marine waters. Assuming that these methanol concentrations are an appropriate proxy for global methanol rainwater concentrations, the global methanol wet deposition sink is estimated as 20 Tg yr-1, which implies that previous methanol budgets underestimate removal by precipitation. Methanol concentrations in rainwater did not correlate significantly with H+, NO3-, and NSS, which suggests that the dominant source of the alcohol to rainwater is not anthropogenic. However, methanol concentrations were strongly correlated with acetaldehyde, which has a primarily biogenic input. The methanol volume-weighted concentration during the summer (2.7 ± 0.9 μM) was ~3 times that of the winter (0.9 ± 0.2 μM), further promoting biogenic emissions as the primary cause of temporal variations of methanol concentrations. Methanol concentrations peaked in rainwater collected during the time period 12 p.m.-6 p.m. Peaking during this period of optimal sunlight implies a possible relationship with photochemical methanol production, but there are also increases in biogenic activity during this time period. Rain events with terrestrial origin had greater concentrations than those of marine origin, demonstrating the significance of the continental source of methanol in rainwater.

Evaluation of dissociated and steam-reformed methanol as automotive engine fuels

NASA Technical Reports Server (NTRS)

Lalk, T. R.; Mccall, D. M.; Mccanlies, J. M.

1984-01-01

Dissociated and steam reformed methanol were evaluated as automotive engine fuels. Advantages and disadvantages in using methanol in the reformed rather than liquid state were discussed. Engine dynamometer tests were conducted with a four cylinder, 2.3 liter, spark ignition automotive engine to determine performance and emission characteristics operating on simulated dissociated and steam reformed methanol (2H2 + CO and 3H2 + CO2 respectively), and liquid methanol. Results are presented for engine performance and emissions as functions of equivalence ratio, at various throttle settings and engine speeds. Operation on dissociated and steam reformed methanol was characterized by flashback (violent propagation of a flame into the intake manifold) which limited operation to lower power output than was obtainable using liquid methanol. It was concluded that: an automobile could not be operated solely on dissociated or steam reformed methanol over the entire required power range - a supplementary fuel system or power source would be necessary to attain higher powers; the use of reformed mechanol, compared to liquid methanol, may result in a small improvement in thermal efficiency in the low power range; dissociated methanol is a better fuel than steam reformed methanol for use in a spark ignition engine; and use of dissociated or steam reformed methanol may result in lower exhaust emissions compared to liquid methanol.

Regulation of intracellular formaldehyde toxicity during methanol metabolism of the methylotrophic yeast Pichia methanolica.

PubMed

Wakayama, Keishi; Yamaguchi, Sakiko; Takeuchi, Akihito; Mizumura, Tasuku; Ozawa, Shotaro; Tomizuka, Noboru; Hayakawa, Takashi; Nakagawa, Tomoyuki

2016-11-01

In this study we found that the methylotrophic yeast Pichia methanolica showed impaired growth on high methanol medium (>5%, or 1.56 M, methanol). In contrast, P. methanolica grew well on glucose medium containing 5% methanol, but the growth defects reappeared on glucose medium supplemented with 5 mM formaldehyde. During methanol growth of P. methanolica, formaldehyde accumulated in the medium up to 0.3 mM before it was consumed rapidly based on cell growth. These findings indicate that the growth defect of P. methanolica on high methanol media is not caused directly by methanol toxicity, but rather by formaldehyde, which is a key toxic intermediate of methanol metabolism. Moreover, during methanol growth of P. methanolica, expression of enzymes in the methanol-oxidation pathway were induced before the alcohol oxidase isozymes Mod1p and Mod2p, and Mod1p expression was induced before Mod2p. These results suggest that to avoid excess accumulation of formaldehyde-the toxic intermediate of methanol metabolism-P. methanolica grown on methanol strictly regulates the order in which methanol-metabolizing enzymes are expressed. Copyright © 2016 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Infrared and reflectron time-of-flight mass spectroscopic study on the synthesis of glycolaldehyde in methanol (CH3OH) and methanol-carbon monoxide (CH3OH-CO) ices exposed to ionization radiation.

PubMed

Maity, Surajit; Kaiser, Ralf I; Jones, Brant M

2014-01-01

We present conclusive evidence on the formation of glycolaldehyde (HOCH2CHO) synthesized within astrophysically relevant ices of methanol (CH3OH) and methanol-carbon monoxide (CH3OH-CO) upon exposure to ionizing radiation at 5.5 K. The radiation induced chemical processes of the ices were monitored on line and in situ via infrared spectroscopy which was complimented by temperature programmed desorption studies post irradiation, utilizing highly sensitive reflectron time-of-flight mass spectrometry coupled with single photon fragment free photoionization (ReTOF-PI) at 10.49 eV. Specifically, glycolaldehyde was observed via the v14 band and further enhanced with the associated frequency shifts of the carbonyl stretching mode observed in irradiated isotopologue ice mixtures. Furthermore, experiments conducted with mixed isotopic ices of methanol-carbon monoxide (13CH3OH-CO, CH3(18)OH-CO, CD3OD-13CO and CH3OH-C18O) provide solid evidence of at least three competing reaction pathways involved in the formation of glycolaldehyde via non-equilibrium chemistry, which were identified as follows: (i) radical-radical recombination of HCO and CH2OH formed via decomposition of methanol--the "two methanol pathway"; (ii) via the reaction of one methanol unit (CH2OH from the decomposition of CH3OH) with one carbon monoxide unit (HCO from the hydrogenation of CO)--the "one methanol, one carbon monoxide pathway"; and (iii) formation via hydrogenation of carbon monoxide resulting in radicals of HCO and CH2OH--the "two carbon monoxide pathway". In addition, temperature programmed desorption studies revealed an increase in the amount of glycolaldehyde formed, suggesting further thermal chemistry of trapped radicals within the ice matrix. Sublimation of glycolaldehyde during the warm up was also monitored via ReTOF-PI and validated via the mutual agreement of the associated isotopic frequency shifts within the infrared band positions and the identical sublimation profiles obtained from the ReTOF spectra and infrared spectroscopy of the corresponding isotopes. In addition, an isomer of glycolaldehyde (ethene-1,2-diol) was tentatively assigned. Confirmation of the identified pathways based on infrared spectroscopy was also obtained from the observed ion signals corresponding to isotopomers of glycolaldehyde. These coupled techniques provide clear, concise evidence of the formation of a complex and astrobiologically important organic, glycolaldehyde, relevant to the icy mantles observed in the interstellar medium.

Temporal and spatial variations in rainwater methanol

NASA Astrophysics Data System (ADS)

Felix, J. D.; Jones, S. B.; Avery, G. B.; Willey, J. D.; Mead, R. N.; Kieber, R. J.

2014-01-01

This work reports the first detailed analysis of methanol concentrations in rainwater. Methanol concentrations measured in 49 rain events collected between 28 August 2007 to 10 July 2008 in Wilmington, NC, USA, ranged from below the detection limit of 6 nM to 9.3 μM with a volume weighted average concentration of 1.2 ± 0.2 μM. Methanol concentrations in rainwater were up to ~200× greater than concentrations observed in marine waters indicating wet deposition as a potential significant source to marine waters. Assuming these methanol concentrations are an appropriate proxy for global methanol rainwater concentrations the global methanol wet deposition sink is estimated as 20 Tg yr-1 which implies previous methanol budgets underestimate removal by precipitation. Methanol concentrations did not correlate with H+, NO3-, and NSS, which suggest that the dominant source of the alcohol to rainwater is not anthropogenic. However, methanol concentrations were strongly correlated with acetaldehyde which has a primarily biogenic input. Methanol volume weighted concentration during the growing season (1.5 + 0.3 μM) was more than double that of the non-growing season (0.7 + 0.1 μM), further promoting biogenic emissions as the primary cause of fluctuating methanol concentrations. Methanol concentrations peaked in rainwater collected between the time period 12:00-06:00 p.m. Peaking during this period of optimal sunlight implies a direct relationship to photochemical methanol production but there are also increases in biogenic activity during this time period. Rain events with terrestrial origins had higher concentrations than those of marine origin demonstrating the significance of the continental source of methanol in rainwater.

Design and Operation of an Electrochemical Methanol Concentration Sensor for Direct Methanol Fuel Cell Systems

NASA Technical Reports Server (NTRS)

Narayanan, S. R.; Valdez, T. I.; Chun, W.

2000-01-01

The development of a 150-Watt packaged power source based on liquid feed direct methanol fuel cells is being pursued currently at the Jet propulsion Laboratory for defense applications. In our studies we find that the concentration of methanol in the fuel circulation loop affects the electrical performance and efficiency the direct methanol fuel cell systems significantly. The practical operation of direct methanol fuel cell systems, therefore, requires accurate monitoring and control of methanol concentration. The present paper reports on the principle and demonstration of an in-house developed electrochemical sensor suitable for direct methanol fuel cell systems.

Recent Studies on Methanol Crossover in Liquid-Feed Direct Methanol Fuel Cells

NASA Technical Reports Server (NTRS)

Valdez, T. I.; Narayanan, S. R.

2000-01-01

In this work, the effects of methanol crossover and airflow rates on the cathode potential of an operating direct methanol fuel cell are explored. Techniques for quantifying methanol crossover in a fuel cell and for separating the electrical performance of each electrode in a fuel cell are discussed. The effect of methanol concentration on cathode potential has been determined to be significant. The cathode is found to be mass transfer limited when operating on low flow rate air and high concentrations of methanol. Improvements in cathode structure and operation at low methanol concentration have been shown to result in improved cell performance.

Aerobic methanol-oxidizing bacteria in soil.

PubMed

Kolb, Steffen

2009-11-01

Methanol is an atmospheric compound that is primarily released from plant polymers and impacts ozone formation. The global methanol emission rate from terrestrial ecosystems is of the same order of magnitude (4.9 x 10(12) mol year(-1)) as that of methane (10 x 10(12) mol year(-1)). The major proportion of the annual plant-released methanol does not enter the atmosphere, but may be reoxidized by biological methanol oxidation, which is catalyzed by methanol-oxidizing prokaryotes. Fifty-six aerobic methanol-oxidizing species have been isolated from soils. These methylotrophs belong to the Alpha-, Beta-, and Gammaproteobacteria, Verrucomicrobia, Firmicutes, and Actinobacteria. Their ecological niches are determined by oxygen and methanol concentration, temperature, pH, the capability to utilize nitrate as an electron acceptor, and the spectrum of nitrogen sources and utilizable multicarbon substrates. Recently discovered interactions with eukaryotes indicate that their ecological niches may not solely be defined by physicochemical parameters. Nonetheless, there are still gaps in knowledge; based on global methanol budgets, methanol oxidation in soil is important, but has not been addressed adequately by biogeochemical studies. Ratios of above-ground and soil-internal methanol oxidation are not known. The contribution to methanol-oxidation by aerobic and anaerobic methylotrophs in situ also needs further research.

Growth of Bacillus methanolicus in 2 M methanol at 50 °C: the effect of high methanol concentration on gene regulation of enzymes involved in formaldehyde detoxification by the ribulose monophosphate pathway.

PubMed

Bozdag, Ahmet; Komives, Claire; Flickinger, Michael C

2015-07-01

Bacillus methanolicus MGA3 is a Gram-positive aerobic methylotroph growing optimally at 50-53°C. Methylotrophy in B. methanolicus is encoded on pBM19 and by two chromosomal copies of the methanol dehydrogenase (mdh), hexulose phosphate synthase (hps) and phosphohexuloisomerase (phi) genes. However, there are no published studies on the regulation of methylotrophy or the dominant mechanism of detoxification of intracellular formaldehyde in response to high methanol concentration. The µ max of B. methanolicus MGA3 was assessed on methanol, mannitol and glucose. B. methanolicus achieved a µ max at 25 mM initial methanol of 0.65 ± 0.007 h(-1), which decreased to 0.231 ± 0.004 h(-1) at 2 M initial methanol. Slow growth was also observed with initial methanol concentrations of >2 M. The µ max on mannitol and glucose are 0.532 ± 0.002 and 0.336 ± 0.003 h(-1), respectively. Spiking cultures with additional methanol (100 mM) did not disturb the growth rate of methanol-grown cells, whereas, a 50 mM methanol spike halted the growth in mannitol. Surprisingly, growth in methanol was inhibited by 1 mM formaldehyde, while mannitol-grown cells tolerated 2 mM. Moreover, mannitol-grown cells removed formaldehyde faster than methanol-grown cells. Further, we show that methanol oxidation in B. methanolicus MGA3 is mainly carried out by the pBM19-encoded mdh. Formaldehyde and formate addition down-regulate the mdh and hps genes in methanol-grown cells. Similarly, they down-regulate mdh genes in mannitol-grown cells, but up-regulate hps. Phosphofructokinase (pfk) is up-regulated in both methanol and mannitol-grown cells, which suggests that pfk may be a possible synthetic methylotrophy target to reduce formaldehyde growth toxicity at high methanol concentrations.

Ecosystem-scale volatile organic compound fluxes during an extreme drought in a broadleaf temperate forest of the Missouri Ozarks (central USA)

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

Seco, Roger; Karl, Thomas; Guenther, Alex

Considerable amounts and varieties of biogenic volatile organic compounds (BVOCs) are exchanged between vegetation and the surrounding air. These BVOCs play key ecological and atmospheric roles that must be adequately represented for accurately modeling the coupled biosphere–atmosphere–climate earth system. One key uncertainty in existing models is the response of BVOC fluxes to an important global change process: drought. Here, we describe the diurnal and seasonal variation in isoprene, monoterpene, and methanol fluxes from a temperate forest ecosystem before, during, and after an extreme 2012 drought event in the Ozark region of the central USA. BVOC fluxes were dominated by isoprene,more » which attained high emission rates of up to 35.4 mg m 2 h 1 at midday. Methanol fluxes were characterized by net deposition in the morning, changing to a net emission flux through the rest of the daylight hours. Net flux of CO 2 reached its seasonal maximum approximately a month earlier than isoprenoid fluxes, which highlights the differential response of photosynthesis and isoprenoid emissions to progressing drought conditions. Nevertheless, both processes were strongly suppressed under extreme drought, although isoprene fluxes remained relatively high compared to reported fluxes from other ecosystems. Methanol exchange was less affected by drought throughout the season, confirming the complex processes driving biogenic methanol fluxes. The fraction of daytime (7–17 h) assimilated carbon released back to the atmosphere combining the three BVOCs measured was 2% of gross primary productivity (GPP) and 4.9% of net ecosystem exchange (NEE) on average for our whole measurement campaign, while exceeding 5% of GPP and 10% of NEE just before the strongest drought phase. In conclusion, the MEGANv2.1 model correctly predicted diurnal variations in fluxes driven mainly by light and temperature, although further research is needed to address model BVOC fluxes during drought events.« less

Ecosystem-scale volatile organic compound fluxes during an extreme drought in a broadleaf temperate forest of the Missouri Ozarks (central USA).

PubMed

Seco, Roger; Karl, Thomas; Guenther, Alex; Hosman, Kevin P; Pallardy, Stephen G; Gu, Lianhong; Geron, Chris; Harley, Peter; Kim, Saewung

2015-10-01

Considerable amounts and varieties of biogenic volatile organic compounds (BVOCs) are exchanged between vegetation and the surrounding air. These BVOCs play key ecological and atmospheric roles that must be adequately represented for accurately modeling the coupled biosphere-atmosphere-climate earth system. One key uncertainty in existing models is the response of BVOC fluxes to an important global change process: drought. We describe the diurnal and seasonal variation in isoprene, monoterpene, and methanol fluxes from a temperate forest ecosystem before, during, and after an extreme 2012 drought event in the Ozark region of the central USA. BVOC fluxes were dominated by isoprene, which attained high emission rates of up to 35.4 mg m(-2)  h(-1) at midday. Methanol fluxes were characterized by net deposition in the morning, changing to a net emission flux through the rest of the daylight hours. Net flux of CO2 reached its seasonal maximum approximately a month earlier than isoprenoid fluxes, which highlights the differential response of photosynthesis and isoprenoid emissions to progressing drought conditions. Nevertheless, both processes were strongly suppressed under extreme drought, although isoprene fluxes remained relatively high compared to reported fluxes from other ecosystems. Methanol exchange was less affected by drought throughout the season, confirming the complex processes driving biogenic methanol fluxes. The fraction of daytime (7-17 h) assimilated carbon released back to the atmosphere combining the three BVOCs measured was 2% of gross primary productivity (GPP) and 4.9% of net ecosystem exchange (NEE) on average for our whole measurement campaign, while exceeding 5% of GPP and 10% of NEE just before the strongest drought phase. The meganv2.1 model correctly predicted diurnal variations in fluxes driven mainly by light and temperature, although further research is needed to address model BVOC fluxes during drought events. © 2015 John Wiley & Sons Ltd.

Ecosystem-scale volatile organic compound fluxes during an extreme drought in a broadleaf temperate forest of the Missouri Ozarks (central USA)

DOE PAGES

Seco, Roger; Karl, Thomas; Guenther, Alex; ...

2015-07-07

Considerable amounts and varieties of biogenic volatile organic compounds (BVOCs) are exchanged between vegetation and the surrounding air. These BVOCs play key ecological and atmospheric roles that must be adequately represented for accurately modeling the coupled biosphere–atmosphere–climate earth system. One key uncertainty in existing models is the response of BVOC fluxes to an important global change process: drought. Here, we describe the diurnal and seasonal variation in isoprene, monoterpene, and methanol fluxes from a temperate forest ecosystem before, during, and after an extreme 2012 drought event in the Ozark region of the central USA. BVOC fluxes were dominated by isoprene,more » which attained high emission rates of up to 35.4 mg m 2 h 1 at midday. Methanol fluxes were characterized by net deposition in the morning, changing to a net emission flux through the rest of the daylight hours. Net flux of CO 2 reached its seasonal maximum approximately a month earlier than isoprenoid fluxes, which highlights the differential response of photosynthesis and isoprenoid emissions to progressing drought conditions. Nevertheless, both processes were strongly suppressed under extreme drought, although isoprene fluxes remained relatively high compared to reported fluxes from other ecosystems. Methanol exchange was less affected by drought throughout the season, confirming the complex processes driving biogenic methanol fluxes. The fraction of daytime (7–17 h) assimilated carbon released back to the atmosphere combining the three BVOCs measured was 2% of gross primary productivity (GPP) and 4.9% of net ecosystem exchange (NEE) on average for our whole measurement campaign, while exceeding 5% of GPP and 10% of NEE just before the strongest drought phase. In conclusion, the MEGANv2.1 model correctly predicted diurnal variations in fluxes driven mainly by light and temperature, although further research is needed to address model BVOC fluxes during drought events.« less

Power and Thermal Technologies for Air and Space -- Scientific Research Program. Delivery Order 0016: Developing and Processing High Energy Density Polymer Film Dielectrics for High Temperature Air Force Power Electronic Applications

DTIC Science & Technology

2010-01-01

a vacuum controller. A vacuum of < 1 µ torr was achieved with a combination of a turbo pump and a scroll pump system. The sample probing is...the polymer was reprecipitated in heptane non-solvent. The filtered polymer was washed with heptane and was finally dried in vacuum at 100ºC for three...solution was added to a large excess of methanol to precipitate the polymer. After soxhlet extraction with methanol and vacuum drying, the polymer was

Aftereffect Calculation and Prediction of Methanol Tank Leak’s Environmental Risk Accident

NASA Astrophysics Data System (ADS)

Lang, Yueting; Zheng, Lina; Chen, Henan; Wang, Qiushi; Jiang, Hui; Pan, Yiwen

2018-01-01

With the increasing frequency of environmental risk accidents, more emphasis was placed on environmental risk assessment. In this article, the aftermath of an Environmental Risk Accident on Methanol Tank Leakage occurred on a cryogenic unit area in a certain oilfield processing plant have been mainly calculated and predicted. Major hazards were identified through the major hazards identification on dangerous chemicals, which could afterwards analyze maximum credible accident and confirm source item and the source intensity. In the end, the consequence of the accident has been calculated so that the impact on surrounding environment can be predicted after the accident.

The Use of Sugar-Oximes and Other Glycosylated Drugs in Treatment against Organophosphate Poisoning

DTIC Science & Technology

1985-06-30

process on a column of silica gel (100g). The crude quarternized products were eluted from the column when the polarity of chloroform-methanol...mixture exceeded 25% of methanol. The iodide ion was exchanged with chloride by passing the crude product on a Dowex 1 anion exchange resin (30g). The... product turned out to be a very hygroscopic material). Cpd. E-357 ’H nmr: (D,0-DSS) 1.9-2.1 (12H, 4Ac); 2.6-4.0 (m, H. of the pyranose ring and CH of

Efficiency Assessment of Using Flammable Compounds from Water Treatment and Methanol Production Waste for Plasma Synthesis of Iron-Containing Pigments

NASA Astrophysics Data System (ADS)

Shekhovtsova, Anastasia P.; Karengin, Alexander G.

2016-08-01

This article describes the possibility of applying the low-temperature plasma for obtaining iron-containing pigments from water purification and flammable methanol production waste. In this paper were calculated combustion parameters of water-saltorganic compositions (WSOC) with different consists. Authors determined the modes of energy- efficient processing of the previously mentioned waste in an air plasma. Having considered the obtained results there were carried out experiments with flammable dispersed water-saltorganic compositions on laboratory plasma stand. All the experimental results are confirmed by calculations.

[Biosynthesis of the bioprotectant ectoin by aerobic methylotrophic bacteria from methanol].

PubMed

Doronina, N V; Ezhov, V A; Beschastnyĭ, A P; Trotsenko, Iu A

2010-01-01

It is shown that neutrophilic methylobacteria Methylophaga thalassica and M. marina have higher rates of growth and ectoin accumulation compared to the haloalkaliphilic species M. alcalica and M. natronia and methanotrophs Methylomicrobium alcaliphilum and M. kenyense. The conditions of M. thalassica cultivation in methanol-containing medium were optimized. The yield of this process reached 60 g/l of absolutely dry biomass containing 15-19% (9-11 g/l) ectoine. The scheme of ectoin isolation from the biomass by extraction and subsequent purification, which allowed obtaining preparations of different degree of purity, was developed.

Short Shot Tower for Silicon

NASA Technical Reports Server (NTRS)

Bates, H. E.; Hill, D. M.; Jewett, D. N.

1983-01-01

Drop length necessary to convert molten silicon to shot reduced by proposed new process. Conversion of silicon from powder or chunks to shot often simplifies processing. Shot is more easily handled in most processing equipment. Drops of liquid silicon fall through protective cloud of argon, then through rapidly cooling bath of methanol, where they quickly turn into solid shot.

40 CFR 98.240 - Definition of the source category.

Code of Federal Regulations, 2010 CFR

2010-07-01

... acrylonitrile, carbon black, ethylene, ethylene dichloride, ethylene oxide, or methanol, except as specified in... independently of an oxychlorination process to produce ethylene dichloride is not part of the petrochemical...

Biological Properties of Fucoxanthin in Oil Recovered from Two Brown Seaweeds Using Supercritical CO2 Extraction

PubMed Central

Periaswamy Sivagnanam, Saravana; Yin, Shipeng; Choi, Jae Hyung; Park, Yong Beom; Woo, Hee Chul; Chun, Byung Soo

2015-01-01

The bioactive materials in brown seaweeds hold great interest for developing new drugs and healthy foods. The oil content in brown seaweeds (Saccharina japonica and Sargassum horneri) was extracted by using environmentally friendly supercritical CO2 (SC-CO2) with ethanol as a co-solvent in a semi-batch flow extraction process and compared the results with a conventional extraction process using hexane, ethanol, and acetone mixed with methanol (1:1, v/v). The SC-CO2 method was used at a temperature of 45 °C and pressure of 250 bar. The flow rate of CO2 (27 g/min) was constant for the entire extraction period of 2 h. The obtained oil from the brown seaweeds was analyzed to determine their valuable compounds such as fatty acids, phenolic compounds, fucoxanthin and biological properties including antioxidant, antimicrobial, and antihypertension effects. The amounts of fucoxanthin extracted from the SC-CO2 oils of S. japonica and S. horneri were 0.41 ± 0.05 and 0.77 ± 0.07 mg/g, respectively. High antihypertensive activity was detected when using mixed acetone and methanol, whereas the phenolic content and antioxidant property were higher in the oil extracted by SC-CO2. The acetone–methanol mix extracts exhibited better antimicrobial activities than those obtained by other means. Thus, the SC-CO2 extraction process appears to be a good method for obtaining valuable compounds from both brown seaweeds, and showed stronger biological activity than that obtained by the conventional extraction process. PMID:26035021

Biological Properties of Fucoxanthin in Oil Recovered from Two Brown Seaweeds Using Supercritical CO2 Extraction.

PubMed

Sivagnanam, Saravana Periaswamy; Yin, Shipeng; Choi, Jae Hyung; Park, Yong Beom; Woo, Hee Chul; Chun, Byung Soo

2015-05-29

The bioactive materials in brown seaweeds hold great interest for developing new drugs and healthy foods. The oil content in brown seaweeds (Saccharina japonica and Sargassum horneri) was extracted by using environmentally friendly supercritical CO2 (SC-CO2) with ethanol as a co-solvent in a semi-batch flow extraction process and compared the results with a conventional extraction process using hexane, ethanol, and acetone mixed with methanol (1:1, v/v). The SC-CO2 method was used at a temperature of 45 °C and pressure of 250 bar. The flow rate of CO2 (27 g/min) was constant for the entire extraction period of 2 h. The obtained oil from the brown seaweeds was analyzed to determine their valuable compounds such as fatty acids, phenolic compounds, fucoxanthin and biological properties including antioxidant, antimicrobial, and antihypertension effects. The amounts of fucoxanthin extracted from the SC-CO2 oils of S. japonica and S. horneri were 0.41 ± 0.05 and 0.77 ± 0.07 mg/g, respectively. High antihypertensive activity was detected when using mixed acetone and methanol, whereas the phenolic content and antioxidant property were higher in the oil extracted by SC-CO2. The acetone-methanol mix extracts exhibited better antimicrobial activities than those obtained by other means. Thus, the SC-CO2 extraction process appears to be a good method for obtaining valuable compounds from both brown seaweeds, and showed stronger biological activity than that obtained by the conventional extraction process.

Reversible Activation of Halophilic β-lactamase from Methanol-Induced Inactive Form: Contrast to Irreversible Inactivation of Non-Halophilic Counterpart.

PubMed

Tokunaga, Hiroko; Maeda, Junpei; Arakawa, Tsutomu; Tokunaga, Masao

2017-06-01

Effects of a water-miscible organic solvent, methanol, on the structure and activity of halophilic β-lactamase derived from Chromohalobacter sp.560 (HaBla), were investigated by means of circular dichroism (CD) measurement and enzymatic activity determination. Beta-lactamase activity was enhanced about 1.2-fold in the presence of 10-20% methanol. CD measurement of HaBla revealed different structures depending on the methanol concentration: native-like active form (Form I) in 10-20% methanol and methanol-induced inactive form at higher concentration (Form II in 40-60% and Form III in 75-80% methanol). Incubation of HaBla with 40% methanol led to the complete loss of activity within ~80 min accompanied by the formation of Form II, whose activity was recovered promptly up to ~80% of full activity upon dilution of the methanol concentration to 10%. In addition, when the protein concentration was sufficiently high (e.g., 0.7 mg/ml), HaBla activity of Form III in 75% methanol could be recovered in the same way (with slightly slower recovery rate), upon dilution of the methanol concentration. In contrast, non-halophilic β-lactamase from Escherichia coli K12 strain MG1655 (EcBla) was irreversibly denatured in the presence of 40% methanol. HaBla showed remarkable ability to renature from the methanol-induced inactive states.

Effect of sorbed methanol, current, and temperature on multicomponent transport in nafion-based direct methanol fuel cells.

PubMed

Rivera, Harry; Lawton, Jamie S; Budil, David E; Smotkin, Eugene S

2008-07-24

The CO2 in the cathode exhaust of a liquid feed direct methanol fuel cell (DMFC) has two sources: methanol diffuses through the membrane electrode assembly (MEA) to the cathode where it is catalytically oxidized to CO2; additionally, a portion of the CO2 produced at the anode diffuses through the MEA to the cathode. The potential-dependent CO2 exhaust from the cathode was monitored by online electrochemical mass spectrometry (ECMS) with air and with H2 at the cathode. The precise determination of the crossover rates of methanol and CO2, enabled by the subtractive normalization of the methanol/air to the methanol/H2 ECMS data, shows that methanol decreases the membrane viscosity and thus increases the diffusion coefficients of sorbed membrane components. The crossover of CO2 initially increases linearly with the Faradaic oxidation of methanol, reaches a temperature-dependent maximum, and then decreases. The membrane viscosity progressively increases as methanol is electrochemically depleted from the anode/electrolyte interface. The crossover maximum occurs when the current dependence of the diffusion coefficients and membrane CO2 solubility dominate over the Faradaic production of CO2. The plasticizing effect of methanol is corroborated by measurements of the rotational diffusion of TEMPONE (2,2,6,6-tetramethyl-4-piperidone N-oxide) spin probe by electron spin resonance spectroscopy. A linear inverse relationship between the methanol crossover rate and current density confirms the absence of methanol electro-osmotic drag at concentrations relevant to operating DMFCs. The purely diffusive transport of methanol is explained in terms of current proton solvation and methanol-water incomplete mixing theories.

An ecosystem-scale perspective of the net land methanol flux. Synthesis of micrometeorological flux measurements

DOE PAGES

Wohlfahrt, G.; Amelynck, C.; Ammann, C.; ...

2015-07-09

Methanol is the second most abundant volatile organic compound in the troposphere and plays a significant role in atmospheric chemistry. While there is consensus about the dominant role of living plants as the major source and the reaction with OH as the major sink of methanol, global methanol budgets diverge considerably in terms of source/sink estimates, reflecting uncertainties in the approaches used to model and the empirical data used to separately constrain these terms. Here we compiled micrometeorological methanol flux data from eight different study sites and reviewed the corresponding literature in order to provide a first cross-site synthesis ofmore » the terrestrial ecosystem-scale methanol exchange and present an independent data-driven view of the land–atmosphere methanol exchange. Our study shows that the controls of plant growth on production, and thus the methanol emission magnitude, as well as stomatal conductance on the hourly methanol emission variability, established at the leaf level, hold across sites at the ecosystem level. Unequivocal evidence for bi-directional methanol exchange at the ecosystem scale is presented. Deposition, which at some sites even exceeds methanol emissions, represents an emerging feature of ecosystem-scale measurements and is likely related to environmental factors favouring the formation of surface wetness. Methanol may adsorb to or dissolve in this surface water and eventually be chemically or biologically removed from it. Management activities in agriculture and forestry are shown to increase local methanol emission by orders of magnitude; however, they are neglected at present in global budgets. While contemporary net land methanol budgets are overall consistent with the grand mean of the micrometeorological methanol flux measurements, we caution that the present approach of simulating methanol emission and deposition separately is prone to opposing systematic errors and does not allow for full advantage to be taken of the rich information content of micrometeorological flux measurements.« less

An ecosystem-scale perspective of the net land methanol flux: synthesis of micrometeorological flux measurements

PubMed Central

Wohlfahrt, G.; Amelynck, C.; Ammann, C.; Arneth, A.; Bamberger, I.; Goldstein, A. H.; Gu, L.; Guenther, A.; Hansel, A.; Heinesch, B.; Holst, T.; Hörtnagl, L.; Karl, T.; Laffineur, Q.; Neftel, A.; McKinney, K.; Munger, J. W.; Pallardy, S. G.; Schade, G. W.; Seco, R.; Schoon, N.

2015-01-01

Methanol is the second most abundant volatile organic compound in the troposphere and plays a significant role in atmospheric chemistry. While there is consensus about the dominant role of living plants as the major source and the reaction with OH as the major sink of methanol, global methanol budgets diverge considerably in terms of source/sink estimates reflecting uncertainties in the approaches used to model, and the empirical data used to separately constrain these terms. Here we compiled micrometeorological methanol flux data from eight different study sites and reviewed the corresponding literature in order to provide a first cross-site synthesis of the terrestrial ecosystem-scale methanol exchange and present an independent data-driven view of the land–atmosphere methanol exchange. Our study shows that the controls of plant growth on the production, and thus the methanol emission magnitude, and stomatal conductance on the hourly methanol emission variability, established at the leaf level, hold across sites at the ecosystem-level. Unequivocal evidence for bi-directional methanol exchange at the ecosystem scale is presented. Deposition, which at some sites even exceeds methanol emissions, represents an emerging feature of ecosystem-scale measurements and is likely related to environmental factors favouring the formation of surface wetness. Methanol may adsorb to or dissolve in this surface water and eventually be chemically or biologically removed from it. Management activities in agriculture and forestry are shown to increase local methanol emission by orders of magnitude; they are however neglected at present in global budgets. While contemporary net land methanol budgets are overall consistent with the grand mean of the micrometeorological methanol flux measurements, we caution that the present approach of simulating methanol emission and deposition separately is prone to opposing systematic errors and does not allow taking full advantage of the rich information content of micrometeorological flux measurements. PMID:25983744

40 CFR 86.1313-94 - Fuel specifications.

Code of Federal Regulations, 2011 CFR

2011-07-01

... reported in accordance with § 86.094-21(b)(3). (c) Methanol-fuel. (1) Methanol fuel used for exhaust and evaporative emission testing and in service accumulation of methanol-fueled engines shall be representative of commercially available methanol fuel and shall consist of at least 50 percent methanol by volume. (i...

Direct methanol fuel cell and system

DOEpatents

Wilson, Mahlon S.

2004-10-26

A fuel cell having an anode and a cathode and a polymer electrolyte membrane located between anode and cathode gas diffusion backings uses a methanol vapor fuel supply. A permeable polymer electrolyte membrane having a permeability effective to sustain a carbon dioxide flux equivalent to at least 10 mA/cm.sup.2 provides for removal of carbon dioxide produced at the anode by reaction of methanol with water. Another aspect of the present invention includes a superabsorpent polymer material placed in proximity to the anode gas diffusion backing to hold liquid methanol or liquid methanol solution without wetting the anode gas diffusion backing so that methanol vapor from the liquid methanol or liquid methanol-water solution is supplied to the membrane.

Fatal methanol poisoning: features of liver histopathology.

PubMed

Akhgari, Maryam; Panahianpour, Mohammad Hadi; Bazmi, Elham; Etemadi-Aleagha, Afshar; Mahdavi, Amirhosein; Nazari, Saeed Hashemi

2013-03-01

Methanol poisoning has become a considerable problem in Iran. Liver can show some features of poisoning after methanol ingestion. Therefore, our concern was to examine liver tissue histopathology in fatal methanol poisoning cases in Iranian population. In this study, 44 cases of fatal methanol poisoning were identified in a year. The histological changes of the liver were reviewed. The most striking features of liver damage by light microscopy were micro-vesicular steatosis, macro-vesicular steatosis, focal hepatocyte necrosis, mild intra-hepatocyte bile stasis, feathery degeneration and hydropic degeneration. Blood and vitreous humor methanol concentrations were examined to confirm the proposed history of methanol poisoning. The majority of cases were men (86.36%). In conclusion, methanol poisoning can cause histological changes in liver tissues. Most importantly in cases with mean blood and vitreous humor methanol levels greater than 127 ± 38.9 mg/dL more than one pathologic features were detected.

A simple preparation of very high methanol tolerant cathode electrocatalyst for direct methanol fuel cell based on polymer-coated carbon nanotube/platinum.

PubMed

Yang, Zehui; Nakashima, Naotoshi

2015-07-20

The development of a durable and methanol tolerant electrocatalyst with a high oxygen reduction reaction activity is highly important for the cathode side of direct methanol fuel cells. Here, we describe a simple and novel methodology to fabricate a practically applicable electrocatalyst with a high methanol tolerance based on poly[2,2'-(2,6-pyridine)-5,5'-bibenzimidazole]-wrapped multi-walled carbon nanotubes, on which Pt nanoparticles have been deposited, then coated with poly(vinylphosphonic acid) (PVPA). The polymer coated electrocatalyst showed an ~3.3 times higher oxygen reduction reaction activity compared to that of the commercial CB/Pt and methanol tolerance in the presence of methanol to the electrolyte due to a 50% decreased methanol adsorption on the Pt after coating with the PVPA. Meanwhile, the peroxide generation of the PVPA coated electrocatalyst was as low as 0.8% with 2 M methanol added to the electrolyte, which was much lower than those of the non-PVPA-coated electrocatalyst (7.5%) and conventional CB/Pt (20.5%). Such a high methanol tolerance is very important for the design of a direct methanol fuel cell cathode electrocatalyst with a high performance.

Integrated anode structure for passive direct methanol fuel cells with neat methanol operation

NASA Astrophysics Data System (ADS)

Wu, Huijuan; Zhang, Haifeng; Chen, Peng; Guo, Jing; Yuan, Ting; Zheng, Junwei; Yang, Hui

2014-02-01

A microporous titanium plate based integrated anode structure (Ti-IAS) suitable for passive direct methanol fuel cells (DMFCs) fueled with neat methanol is reported. This anode structure incorporates a porous titanium plate as a methanol mass transfer barrier and current collector, pervaporation film for passively vaporizing methanol, vaporous methanol cavity for evenly distributing fuel, and channels for carbon dioxide venting. With the effective control of methanol delivery rate, the Ti-IAS based DMFC allows the direct use of neat methanol as the fuel source. In the meantime, the required water for methanol-oxidation reaction at the anode can also be fully recovered from the cathode with the help of the highly hydrophobic microporous layer in the cathode. DMFCs incorporating this new anode structure exhibit a power density as high as 40 mW cm-2 and a high volumetric energy density of 489 Wh L-1 operating with neat methanol and at 25 °C. Importantly, no obvious performance degradation of the passive DMFC system is observed after more than 90 h of continuous operation. The experimental results reveal that the compact DMFC based on the Ti-IAS exhibits a substantial potential as power sources for portable applications.

Metabolite extraction from adherently growing mammalian cells for metabolomics studies: optimization of harvesting and extraction protocols.

PubMed

Dettmer, Katja; Nürnberger, Nadine; Kaspar, Hannelore; Gruber, Michael A; Almstetter, Martin F; Oefner, Peter J

2011-01-01

Trypsin/ethylenediaminetetraacetic acid (EDTA) treatment and cell scraping in a buffer solution were compared for harvesting adherently growing mammalian SW480 cells for metabolomics studies. In addition, direct scraping with a solvent was tested. Trypsinated and scraped cell pellets were extracted using seven different extraction protocols including pure methanol, methanol/water, pure acetone, acetone/water, methanol/chloroform/water, methanol/isopropanol/water, and acid-base methanol. The extracts were analyzed by GC-MS after methoximation/silylation and derivatization with propyl chloroformate, respectively. The metabolic fingerprints were compared and 25 selected metabolites including amino acids and intermediates of energy metabolism were quantitatively determined. Moreover, the influence of freeze/thaw cycles, ultrasonication and homogenization using ceramic beads on extraction yield was tested. Pure acetone yielded the lowest extraction efficiency while methanol, methanol/water, methanol/isopropanol/water, and acid-base methanol recovered similar metabolite amounts with good reproducibility. Based on overall performance, methanol/water was chosen as a suitable extraction solvent. Repeated freeze/thaw cycles, ultrasonication and homogenization did not improve overall metabolite yield of the methanol/water extraction. Trypsin/EDTA treatment caused substantial metabolite leakage proving it inadequate for metabolomics studies. Gentle scraping of the cells in a buffer solution and subsequent extraction with methanol/water resulted on average in a sevenfold lower recovery of quantified metabolites compared with direct scraping using methanol/water, making the latter one the method of choice to harvest and extract metabolites from adherently growing mammalian SW480 cells.

Systematic assessment of different solvents for the extraction of drugs of abuse and pharmaceuticals from an authentic hair pool.

PubMed

Madry, Milena M; Kraemer, Thomas; Baumgartner, Markus R

2018-01-01

Hair analysis has been established as a prevalent tool for retrospective drug monitoring. In this study, different extraction solvents for the determination of drugs of abuse and pharmaceuticals in hair were evaluated for their efficiency. A pool of authentic hair from drug users was used for extraction experiments. Hair was pulverized and extracted in triplicate with seven different solvents in a one- or two-step extraction. Three one- (methanol, acetonitrile, and acetonitrile/water) and four two-step extractions (methanol two-fold, methanol and methanol/acetonitrile/formate buffer, methanol and methanol/formate buffer, and methanol and methanol/hydrochloric acid) were tested under accurately equal experimental conditions. The extracts were directly analyzed by liquid chromatography-tandem mass spectrometry for opiates/opioids, stimulants, ketamine, selected benzodiazepines, antidepressants, antipsychotics, and antihistamines using deuterated internal standards. For most analytes, a two-step extraction with methanol did not significantly improve the yield compared to a one-step extraction with methanol. Extraction with acetonitrile alone was least efficient for most analytes. Extraction yields of acetonitrile/water, methanol and methanol/acetonitrile/formate buffer, and methanol and methanol/formate buffer were significantly higher compared to methanol. Highest efficiencies were obtained by a two-step extraction with methanol and methanol/hydrochloric acid, particularly for morphine, 6-monoacetylmorphine, codeine, 6-acetylcodeine, MDMA, zopiclone, zolpidem, amitriptyline, nortriptyline, citalopram, and doxylamine. For some analytes (e.g., tramadol, fluoxetine, sertraline), all extraction solvents, except for acetonitrile, were comparably efficient. There was no significant correlation between extraction efficiency with an acidic solvent and the pka or log P of the analyte. However, there was a significant trend for the extraction efficiency with acetonitrile to the log P of the analyte. The study demonstrates that the choice of extraction solvent has a strong impact on hair analysis outcomes. Therefore, validation protocols should include the evaluation of extraction efficiency of drugs by using authentic rather than spiked hair. Different extraction procedures may contribute to the scatter of quantitative results in inter-laboratory comparisons. Harmonization of extraction protocols is recommended, when interpretation is based on same cut-off levels. Copyright © 2017 Elsevier B.V. All rights reserved.

In vitro anti-cancer activities of Job’s tears (Coix lachryma-jobi Linn.) extracts on human colon adenocarcinoma

PubMed Central

Manosroi, Aranya; Sainakham, Mathukorn; Chankhampan, Charinya; Manosroi, Worapaka; Manosroi, Jiradej

2015-01-01

The whole seed (W), endosperm (E) and hull (H) of five cultivars of Job’s tears (Coix lachryma-jobi Linn. var. ma-yuen Stapf) including Thai Black Phayao, Thai Black Loei, Laos Black Loei, Laos White Loei and Laos Black Luang Phra Bang were processed before solvent extraction by non-cooking, roasting, boiling and steaming Each part of the Job’s tears was extracted by the cold and hot process by refluxing with methanol and hexane. The total of 330 extracts included 150 methanol extracts and 180 hexane extracts were investigated for anti-proliferative activity on human colon adenocarcinoma cell line (HT-29) by the sulforhodamine B (SRB) assay. The extracts which gave high anti-proliferative activity were tested for apoptotic activity by acridine orange and ethidium bromide double staining and anti-oxidative activities including free radical scavenging and lipid peroxidation inhibition activities. The extract from the hull of Thai Black Loei roasted before extracting by hot methanol (M-HTBL-R2) showed the highest anti-proliferative activity on HT-29 with the IC50 values of 11.61 ± 0.95 μg/ml, while the extract from the non-cooked hull of Thai Black Loei by cold methanol extraction (M-HTBL-N1) gave the highest apoptosis (8.17 ± 1.18%) with no necrosis. In addition, M-HTBL-R2 and M-HTBL-N1 indicated free radical scavenging activity at the SC50 values of 0.48 ± 0.12 and 2.47 ± 1.15 mg/ml, respectively. This study has demonstrated the anti-colorectal cancer potential of the M-HTBL-R2 and M-HTBL-N1 extracts. PMID:26981007

Biotic and abiotic controls on biogenic volatile organic compound fluxes from a subalpine forest floor

NASA Astrophysics Data System (ADS)

Gray, Christopher M.; Monson, Russell K.; Fierer, Noah

2014-04-01

Nonmethane biogenic volatile organic compounds (BVOCs) play key roles in the atmosphere, where they can influence a wide range of chemical processes, and in soils, where they can alter the rates of biogeochemical cycles and impact the growth of plants and soil organisms. However, the diversity and quantities of BVOCs released from or taken up by soils remain poorly characterized as do the biotic and abiotic controls on these fluxes. Here we used proton transfer reaction mass spectrometry to quantify BVOC flux rates from soils with and without active root systems in a subalpine coniferous forest. The total measured BVOC flux averaged 102 nmol m-2 h-1 (an estimated 2.0 µg-C m-2 h-1). The individual BVOCs with the highest net emissions from soil included monoterpenes and methanol (averaging 646 and 641 ng-C m-2 h-1, respectively) while soil represented a net sink of isoprene (-98 ng-C m-2 h-1) and formaldehyde (-37 ng-C m-2 h-1). Tree roots, directly or indirectly, contributed an average of 53% of the total carbon emitted from the soil as BVOCs, with methanol and acetaldehyde among those BVOCs most strongly associated with active root presence. The fluxes of most of the dominant BVOCs emitted from soil, including methanol, increased linearly with increasing temperature. Together the fluxes of certain BVOCs into or out of the forest floor (particularly methanol, isoprene, and monoterpenes) are likely relevant to ecosystem-level processes and belowground ecology, but these fluxes are highly variable and are strongly controlled by both root presence and soil abiotic conditions.

Optimization and kinetic modeling of esterification of the oil obtained from waste plum stones as a pretreatment step in biodiesel production.

PubMed

Kostić, Milan D; Veličković, Ana V; Joković, Nataša M; Stamenković, Olivera S; Veljković, Vlada B

2016-02-01

This study reports on the use of oil obtained from waste plum stones as a low-cost feedstock for biodiesel production. Because of high free fatty acid (FFA) level (15.8%), the oil was processed through the two-step process including esterification of FFA and methanolysis of the esterified oil catalyzed by H2SO4 and CaO, respectively. Esterification was optimized by response surface methodology combined with a central composite design. The second-order polynomial equation predicted the lowest acid value of 0.53mgKOH/g under the following optimal reaction conditions: the methanol:oil molar ratio of 8.5:1, the catalyst amount of 2% and the reaction temperature of 45°C. The predicted acid value agreed with the experimental acid value (0.47mgKOH/g). The kinetics of FFA esterification was described by the irreversible pseudo first-order reaction rate law. The apparent kinetic constant was correlated with the initial methanol and catalyst concentrations and reaction temperature. The activation energy of the esterification reaction slightly decreased from 13.23 to 11.55kJ/mol with increasing the catalyst concentration from 0.049 to 0.172mol/dm(3). In the second step, the esterified oil reacted with methanol (methanol:oil molar ratio of 9:1) in the presence of CaO (5% to the oil mass) at 60°C. The properties of the obtained biodiesel were within the EN 14214 standard limits. Hence, waste plum stones might be valuable raw material for obtaining fatty oil for the use as alternative feedstock in biodiesel production. Copyright © 2015 Elsevier Ltd. All rights reserved.

The effect of titanium nickel nitride decorated carbon nanotubes-reduced graphene oxide hybrid support for methanol oxidation

NASA Astrophysics Data System (ADS)

Liu, Gen; Pan, Zhanchang; Li, Wuyi; Yu, Ke; Xia, Guowei; Zhao, Qixiang; Shi, Shikun; Hu, Guanghui; Xiao, Chumin; Wei, Zhigang

2017-07-01

Titanium nickel nitride (TiNiN) decorated three-dimensional (3D) carbon nanotubes-reduced graphene oxide (CNT-rGO), a fancy 3D platinum (Pt)-based catalyst hybrid support, is prepared by a solvothermal process followed by a nitriding process, which is tested as anodic catalyst support for the methanol oxidation reaction (MOR). The structure, morphology and composition of the synthesized TiNiN/CNT-rGO exhibits a uniform particle dispersion with high purity and interpenetrating 3D network structure. Notably, Pt/TiNiN/CNT-rGO catalyst exhibits significantly improved catalytic activity and durability for methanol oxidation in comparison with Pt/CNT-rGO and conventional Pt/C (JM). The outstanding electrochemical performance was attributed to structure and properties. That is, the 3D CNT-rGO provided a fast transport network for charge-transfer and mass-transfer as well as TiNiN NPs with good synergistic effect and the strong electronic coupling between different domains in TiNiN/CNT-rGO, thus the catalytic activity of the novel catalyst is greatly improved. These results evidences 3D TiNiN/CNT-rGO as a promising catalyst support for a wide range of applications in fuel cells.

Influences of TiO2 phase structures on the structures and photocatalytic hydrogen production of CuOx/TiO2 photocatalysts

NASA Astrophysics Data System (ADS)

Liu, Yuanxu; Wang, Zhonglei; Huang, Weixin

2016-12-01

CuOx/TiO2 photocatalysts employing TiO2 with different phase structures as well as P25 as supports were prepared, and their structures and activity for photocatalytic H2 production in methanol/water solution under simulated solar light were comparatively studied. Structural characterization results demonstrated that the TiO2 phase structure strongly affects the CuOx-TiO2 interaction and copper species in various CuOx/TiO2 photocatalysts. The Cu2O-rutile TiO2 interaction is much stronger than the Cu2O-anatase TiO2 interaction, facilitates the interfacial charge transfer process within the Cu2O-rutile TiO2 heterojunction but disables supported Cu2O to catalyze the hole-participated methanol oxidation. The Cu2O-anatase TiO2 heterojunction with the appropriate Cu2O-anatase TiO2 interaction and thus the balancing efficiencies between the interfacial charge transfer process and hole-participated methanol oxidation is most photocatalytic active, and CuOx/P25 with the largest population of Cu2O-anatase TiO2 heterojunction exhibits the highest photocatalytic H2 production. These results provide novel insights in the applied surface science of CuOx/TiO2 photocatalysts.

Comparison of biodiesel production from sewage sludge obtained from the A²/O and MBR processes by in situ transesterification.

PubMed

Qi, Juanjuan; Zhu, Fenfen; Wei, Xiang; Zhao, Luyao; Xiong, Yiqun; Wu, Xuemin; Yan, Fawei

2016-03-01

The potential of two types of sludge obtained from the anaerobic-anoxic-oxic (A(2)/O) and membrane bioreactor (MBR) processes as lipid feedstock for biodiesel production via in situ transesterification was investigated. Experiments were conducted to determine the optimum conditions for biodiesel yield using three-factor and four-level orthogonal and single-factor tests. Several factors, namely, methanol-to-sludge mass ratio, acid concentration, and temperature, were examined. The optimum yield of biodiesel (16.6% with a fatty acid methyl ester purity of 96.7%) from A(2)/O sludge was obtained at a methanol-to-sludge mass ratio of 10:1, a temperature of 60°C, and a H2SO4 concentration of 5% (v/v). Meanwhile, the optimum yield of biodiesel (4.2% with a fatty acid methyl ester purity of 92.7%) from MBR sludge was obtained at a methanol-to-sludge mass ratio of 8:1, a temperature of 50°C, and a H2SO4 concentration of 5% (v/v). In this research, A(2)/O technology with a primary sedimentation tank is more favorable for obtaining energy from wastewater than MBR technology. Copyright © 2016 Elsevier Ltd. All rights reserved.

Development of a Process for the Spinning of Synthetic Spider Silk

DOE PAGES

Copeland, Cameron G.; Bell, Brianne E.; Christensen, Chad D.; ...

2015-06-05

Spider silks have unique mechanical properties but current efforts to duplicate those properties with recombinant proteins have been unsuccessful. Here, this study was designed to develop a single process to spin fibers with excellent and consistent mechanical properties. As-spun fibers produced were brittle, but by stretching the fibers the mechanical properties were greatly improved. A water-dip or water-stretch further increased the strength and elongation of the synthetic spider silk fibers. Given the promising results of the water stretch, a mechanical double-stretch system was developed. Both a methanol/water mixture and an isopropanol/water mixture were independently used to stretch the fibers withmore » this system. We found that the methanol mixture produced fibers with high tensile strength while the isopropanol mixture produced fibers with high elongation.« less

Hydrogen peroxide concentration by pervaporation of a ternary liquid solution in microfluidics.

PubMed

Ziemecka, Iwona; Haut, Benoît; Scheid, Benoit

2015-01-21

Pervaporation in a microfluidic device is performed on liquid ternary solutions of hydrogen peroxide-water-methanol in order to concentrate hydrogen peroxide (H2O2) by removing methanol. The quantitative analysis of the pervaporation of solutions with different initial compositions is performed, varying the operating temperature of the microfluidic device. Experimental results together with a mathematical model of the separation process are used to understand the effect of the operating conditions on the microfluidic device efficiency. The parameters influencing significantly the performance of pervaporation in the microfluidic device are determined and the limitations of the process are discussed. For the analysed system, the operating temperature of the chip has to be below the temperature at which H2O2 decomposes. Therefore, the choice of an adequate reduced operating pressure is required, depending on the expected separation efficiency.

Spatial investigation of plasma emission from laminar diffusion methanol, ethanol, and n-propanol alcohol flames using LIBS method

NASA Astrophysics Data System (ADS)

Ghezelbash, Mahsa; Majd, Abdollah Eslami; Darbani, Seyyed Mohammad Reza; Mousavi, Seyyed Jabbar; Ghasemi, Ali; Tehrani, Masoud Kavosh

2017-01-01

Laser-induced breakdown spectroscopy (LIBS) technique is used to record some plasma emissions of different laminar diffusion methanol, ethanol, and n-propanol alcohol flames, to investigate the shapes, structures (i.e., reactants and products zones), kind, and quality of burning in different areas. For this purpose, molecular bands of CH, CH*, C2, CN, and CO as well as atomic and ionic lines of C, H, N, and O are identified, simultaneously. Experimental results indicate that the CN and C2 emissions have highest intensity in LIBS spectrum of n-propanol flame and the lowest in methanol. In addition, lowest content of CO pollution and better quality of burning process in n-propanol fuel flame toward ethanol and methanol are confirmed by comparison between their CO molecular band intensities. Moreover, variation of the signal intensity from these three flames with that from a known area of burner plate is compared. Our findings in this research advance the prior results in time-integrated LIBS combustion application and suggesting that LIBS can be used successfully with the CCD detector as a non-gated analytical tool, given its simple instrumentation needs, real-time capability applications of molecular detection in laminar diffusion flame samples, requirements.

Comparison of methanol and isopropanol as wash solvents for determination of hair cortisol concentration in grizzly bears and polar bears.

PubMed

Kroshko, Thomas; Kapronczai, Luciene; Cattet, Marc R L; Macbeth, Bryan J; Stenhouse, Gordon B; Obbard, Martyn E; Janz, David M

2017-01-01

Methodological differences among laboratories are recognized as significant sources of variation in quantification of hair cortisol concentration (HCC). An important step in processing hair, particularly when collected from wildlife, is the choice of solvent used to remove or "wash" external hair shaft cortisol prior to quantification of HCC. The present study systematically compared methanol and isopropanol as wash solvents for their efficiency at removing external cortisol without extracting internal hair shaft cortisol in samples collected from free-ranging grizzly bears and polar bears. Cortisol concentrations in solvents and hair were determined in each of one to eight washes of hair with each solvent independently. •There were no significant decreases in internal hair shaft cortisol among all eight washes for either solvent, although methanol removed detectable hair surface cortisol after one wash in grizzly bear hair whereas hair surface cortisol was detected in all eight isopropanol washes.•There were no significant differences in polar bear HCC washed one to eight times with either solvent, but grizzly bear HCC was significantly greater in hair washed with isopropanol compared to methanol.•There were significant differences in HCC quantified using different commercial ELISA kits commonly used for HCC determinations.

Plasma-induced synthesis of Pt nanoparticles supported on TiO2 nanotubes for enhanced methanol electro-oxidation

NASA Astrophysics Data System (ADS)

Su, Nan; Hu, Xiulan; Zhang, Jianbo; Huang, Huihong; Cheng, Jiexu; Yu, Jinchen; Ge, Chao

2017-03-01

A Pt/C/TiO2 nanotube composite catalyst was successfully prepared for enhanced methanol electro-oxidation. Pt nanoparticles with a particle size of 2 nm were synthesized by plasma sputtering in water, and anatase TiO2 nanotubes with an inner diameter of approximately 100 nm were prepared by a simple two-step anodization method and annealing process. Field-emission scanning electron microscopy images indicated that the different morphologies of TiO2 synthesized on the surface of Ti foils were dependent on the different anodization parameters. The electrochemical performance of Pt/C/TiO2 catalysts for methanol oxidation showed that TiO2 nanotubes were more suitable for use as Pt nanoparticle support materials than irregular TiO2 short nanorods due to their tubular morphology and better electronic conductivity. X-ray photoelectron spectroscopy characterization showed that the binding energies of the Pt 4f of the Pt/C/TiO2 nanotubes exhibited a slightly positive shift caused by the relatively strong interaction between Pt and the TiO2 nanotubes, which could mitigate the poisoning of the Pt catalyst by COads, and further enhance the electrocatalytic performance. Thus, the as-obtained Pt/C/TiO2 nanotubes composites may become a promising catalyst for methanol electro-oxidation.

Cation-exchanged zeolites for the selective oxidation of methane to methanol

DOE PAGES

Kulkarni, Ambarish R.; Zhao, Zhi-Jian; Siahrostami, Samira; ...

2017-10-19

Motivated by the increasing availability of cheap natural gas resources, considerable experimental and computational research efforts have focused on identifying selective catalysts for the direct conversion of methane to methanol. One promising class of catalysts are cation-exchanged zeolites, which have steadily increased in popularity over the past decade. Here, in this article, we first present a broad overview of this field from a conceptual perspective, and highlight the role of theory in developing a molecular-level understanding of the reaction. Next, by performing and analyzing a large database of density functional theory (DFT) calculations for a wide range of transition metalmore » cations, zeolite topologies and active site motifs, we present a unifying picture of the methane activation process in terms of active site stability, C–H bond activation and methanol extraction. Based on the trade-offs of active site stability and reactivity, we propose a framework for identifying new, promising active site motifs in these systems. Further, we show that the high methanol selectivity arises due to the strong binding nature of the C–H activation products. Lastly, using the atomistic and mechanistic insight obtained from these analyses, we summarize the key challenges and future strategies for improving the performance of cation-exchanged zeolites for this industrially relevant conversion.« less

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.

Cation-exchanged zeolites for the selective oxidation of methane to methanol

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

Kulkarni, Ambarish R.; Zhao, Zhi-Jian; Siahrostami, Samira

Motivated by the increasing availability of cheap natural gas resources, considerable experimental and computational research efforts have focused on identifying selective catalysts for the direct conversion of methane to methanol. One promising class of catalysts are cation-exchanged zeolites, which have steadily increased in popularity over the past decade. Here, in this article, we first present a broad overview of this field from a conceptual perspective, and highlight the role of theory in developing a molecular-level understanding of the reaction. Next, by performing and analyzing a large database of density functional theory (DFT) calculations for a wide range of transition metalmore » cations, zeolite topologies and active site motifs, we present a unifying picture of the methane activation process in terms of active site stability, C–H bond activation and methanol extraction. Based on the trade-offs of active site stability and reactivity, we propose a framework for identifying new, promising active site motifs in these systems. Further, we show that the high methanol selectivity arises due to the strong binding nature of the C–H activation products. Lastly, using the atomistic and mechanistic insight obtained from these analyses, we summarize the key challenges and future strategies for improving the performance of cation-exchanged zeolites for this industrially relevant conversion.« less

Integrated lipase production and in situ biodiesel synthesis in a recombinant Pichia pastoris yeast: an efficient dual biocatalytic system composed of cell free enzymes and whole cell catalysts

PubMed Central

2014-01-01

Background Lipase-catalyzed biotransformation of acylglycerides or fatty acids into biodiesel via immobilized enzymes or whole cell catalysts has been considered as one of the most promising methods to produce renewable and environmentally friendly alternative liquid fuels, thus being extensively studied so far. In all previously pursued approaches, however, lipase enzymes are prepared in an independent process separated from enzymatic biodiesel production, which would unavoidably increase the cost and energy consumption during industrial manufacture of this cost-sensitive energy product. Therefore, there is an urgent need to develop novel cost-effective biocatalysts and biocatalytic processes with genuine industrial feasibility. Result Inspired by the consolidated bioprocessing of lignocellulose to generate bioethanol, an integrated process with coupled lipase production and in situ biodiesel synthesis in a recombinant P. pastoris yeast was developed in this study. The novel and efficient dual biocatalytic system based on Thermomyces lanuginosus lipase took advantage of both cell free enzymes and whole cell catalysts. The extracellular and intracellular lipases of growing yeast cells were simultaneously utilized to produce biodiesel from waste cooking oils in situ and in one pot. This integrated system effectively achieved 58% and 72% biodiesel yield via concurrent esterified-transesterified methanolysis and stepwise hydrolysis-esterification at 3:1 molar ratio between methanol and waste cooking oils, respectively. Further increasing the molar ratio of methanol to waste cooking oils to 6:1 led to an 87% biodiesel yield using the stepwise strategy. Both water tolerance and methanol tolerance of this novel system were found to be significantly improved compared to previous non-integrated biodiesel production processes using separately prepared immobilized enzymes or whole cell catalysts. Conclusion We have proposed a new concept of integrated biodiesel production. This integrated system couples lipase production to lipase-catalyzed biodiesel synthesis in one pot. The proof-of-concept was established through construction of a recombinant P. pastoris yeast strain that was able to grow, overexpress T. lanuginosus lipase, and efficiently catalyze biodiesel production from fed waste cooking oils and methanol simultaneously. This simplified single-step process represents a significant advance toward achieving economical production of biodiesel at industrial scale via a ‘green’ biocatalytic route. PMID:24713071

Improved Charge Transfer in a Mn2O3@Co1.2Ni1.8O4 Hybrid for Highly Stable Alkaline Direct Methanol Fuel Cells with Good Methanol Tolerance.

PubMed

Liu, Yan; Chen, Yuanzhen; Li, Sai; Shu, Chenyong; Fang, Yuan; Song, Bo

2018-03-21

A three-dimensional Mn 2 O 3 @Co 1.2 Ni 1.8 O 4 hybrid was synthesized via facile two-step processes and employed as a cathode catalyst in direct methanol fuel cells (DMFCs) for the first time. Because of the unique architecture with ultrathin and porous nanosheets of the Co 1.2 Ni 1.8 O 4 shell, this composite exhibits better electrochemical performance than the pristine Mn 2 O 3 . Remarkably, it shows excellent methanol tolerance, even in a high concentration solution. The DMFC was assembled with Mn 2 O 3 @Co 1.2 Ni 1.8 O 4 , polymer fiber membranes, and PtRu/C as the cathode, membrane, and anode, respectively. The power densities of 57.5 and 70.5 mW cm -2 were recorded at 18 and 28 °C, respectively, especially the former is the best result reported in the literature at such a low temperature. The stability of the Mn 2 O 3 @Co 1.2 Ni 1.8 O 4 catalyzed cathode was evaluated, and the results show that this compound possesses excellent stability in a high methanol concentration. The improved electrochemical activity could be attributed to the narrow band gap of the hybrid, which accelerates the electrons jumping from the valence band to the conduction band. Therefore, Mn III could be oxidized into Mn IV more easily, simultaneously providing an electron to the absorbed oxygen.

Enhanced methanol electro-oxidation reaction on Pt-CoOx/MWCNTs hybrid electro-catalyst

NASA Astrophysics Data System (ADS)

Nouralishahi, Amideddin; Rashidi, Ali Morad; Mortazavi, Yadollah; Khodadadi, Abbas Ali; Choolaei, Mohammadmehdi

2015-04-01

The electro-catalytic behavior of Pt-CoOx/MWCNTs in methanol electro-oxidation reaction (MOR) is investigated and compared to that of Pt/MWCNTs. The electro-catalysts were synthesized by an impregnation method using NaBH4 as the reducing agent. The morphological and physical characteristics of samples are examined by XRD, TEM, ICP and EDS techniques. In the presence of CoOx, Pt nanoparticles were highly distributed on the support with an average particle size of 2 nm, an obvious decrease from 5.1 nm for Pt/MWCNTs. Cyclic voltammetry, CO-stripping, Chronoamperometry, and electrochemical impedance spectroscopy (EIS) measurements are used to study the electrochemical behavior of the electro-catalysts. The results revealed a considerable enhancement in the oxidation kinetics of COads on Pt active sites by the participation of CoOx. Compared to Pt/MWCNTs, Pt-CoOx/MWCNTs sample has a larger electrochemical active surface area (ECSA) and higher electro-catalytic activity and stability toward methanol electro-oxidation. According to the results of cyclic voltammetry, the forward anodic peak current density enhances more than 89% at the optimum atomic ratio of Pt:Co = 2:1. Furthermore, inclusion of cobalt oxide species causes the onset potential of methanol electro-oxidation reaction to shift 84 mV to negative values compared to that on Pt/MWCNTs. Based on EIS data, dehydrogenation of methanol is the rate-determining step of MOR on both Pt/MWCNTs and Pt-CoOx/MWCNTs, at small overpotentials. However, at higher overpotentials, the oxidation of adsorbed oxygen-containing groups controls the total rate of MOR process.

Acidotolerant Bacteria and Fungi as a Sink of Methanol-Derived Carbon in a Deciduous Forest Soil

PubMed Central

Morawe, Mareen; Hoeke, Henrike; Wissenbach, Dirk K.; Lentendu, Guillaume; Wubet, Tesfaye; Kröber, Eileen; Kolb, Steffen

2017-01-01

Methanol is an abundant atmospheric volatile organic compound that is released from both living and decaying plant material. In forest and other aerated soils, methanol can be consumed by methanol-utilizing microorganisms that constitute a known terrestrial sink. However, the environmental factors that drive the biodiversity of such methanol-utilizers have been hardly resolved. Soil-derived isolates of methanol-utilizers can also often assimilate multicarbon compounds as alternative substrates. Here, we conducted a comparative DNA stable isotope probing experiment under methylotrophic (only [13C1]-methanol was supplemented) and combined substrate conditions ([12C1]-methanol and alternative multi-carbon [13Cu]-substrates were simultaneously supplemented) to (i) identify methanol-utilizing microorganisms of a deciduous forest soil (European beech dominated temperate forest in Germany), (ii) assess their substrate range in the soil environment, and (iii) evaluate their trophic links to other soil microorganisms. The applied multi-carbon substrates represented typical intermediates of organic matter degradation, such as acetate, plant-derived sugars (xylose and glucose), and a lignin-derived aromatic compound (vanillic acid). An experimentally induced pH shift was associated with substantial changes of the diversity of active methanol-utilizers suggesting that soil pH was a niche-defining factor of these microorganisms. The main bacterial methanol-utilizers were members of the Beijerinckiaceae (Bacteria) that played a central role in a detected methanol-based food web. A clear preference for methanol or multi-carbon substrates as carbon source of different Beijerinckiaceae-affiliated phylotypes was observed suggesting a restricted substrate range of the methylotrophic representatives. Apart from Bacteria, we also identified the yeasts Cryptococcus and Trichosporon as methanol-derived carbon-utilizing fungi suggesting that further research is needed to exclude or prove methylotrophy of these fungi. PMID:28790984

26 CFR 48.4041-19 - Exemption for qualified methanol and ethanol fuel.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 26 Internal Revenue 16 2011-04-01 2011-04-01 false Exemption for qualified methanol and ethanol....4041-19 Exemption for qualified methanol and ethanol fuel. (a) In general. Under section 4041(b)(2... or use of qualified methanol or ethanol fuel. (b) Qualified methanol or ethanol fuel defined. For...

26 CFR 48.4041-19 - Exemption for qualified methanol and ethanol fuel.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 26 Internal Revenue 16 2013-04-01 2013-04-01 false Exemption for qualified methanol and ethanol....4041-19 Exemption for qualified methanol and ethanol fuel. (a) In general. Under section 4041(b)(2... or use of qualified methanol or ethanol fuel. (b) Qualified methanol or ethanol fuel defined. For...

26 CFR 48.4041-19 - Exemption for qualified methanol and ethanol fuel.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 26 Internal Revenue 16 2012-04-01 2012-04-01 false Exemption for qualified methanol and ethanol....4041-19 Exemption for qualified methanol and ethanol fuel. (a) In general. Under section 4041(b)(2... or use of qualified methanol or ethanol fuel. (b) Qualified methanol or ethanol fuel defined. For...

A selective electrocatalyst–based direct methanol fuel cell operated at high concentrations of methanol

PubMed Central

Feng, Yan; Liu, Hui; Yang, Jun

2017-01-01

Owing to the serious crossover of methanol from the anode to the cathode through the polymer electrolyte membrane, direct methanol fuel cells (DMFCs) usually use dilute methanol solutions as fuel. However, the use of high-concentration methanol is highly demanded to improve the energy density of a DMFC system. Instead of the conventional strategies (for example, improving the fuel-feed system, membrane development, modification of electrode, and water management), we demonstrate the use of selective electrocatalysts to run a DMFC at high concentrations of methanol. In particular, at an operating temperature of 80°C, the as-fabricated DMFC with core-shell-shell Au@Ag2S@Pt nanocomposites at the anode and core-shell Au@Pd nanoparticles at the cathode produces a maximum power density of 89.7 mW cm−2 at a methanol feed concentration of 10 M and maintains good performance at a methanol concentration of up to 15 M. The high selectivity of the electrocatalysts achieved through structural construction accounts for the successful operation of the DMFC at high concentrations of methanol. PMID:28695199

A selective electrocatalyst-based direct methanol fuel cell operated at high concentrations of methanol.

PubMed

Feng, Yan; Liu, Hui; Yang, Jun

2017-06-01

Owing to the serious crossover of methanol from the anode to the cathode through the polymer electrolyte membrane, direct methanol fuel cells (DMFCs) usually use dilute methanol solutions as fuel. However, the use of high-concentration methanol is highly demanded to improve the energy density of a DMFC system. Instead of the conventional strategies (for example, improving the fuel-feed system, membrane development, modification of electrode, and water management), we demonstrate the use of selective electrocatalysts to run a DMFC at high concentrations of methanol. In particular, at an operating temperature of 80°C, the as-fabricated DMFC with core-shell-shell Au@Ag 2 S@Pt nanocomposites at the anode and core-shell Au@Pd nanoparticles at the cathode produces a maximum power density of 89.7 mW cm -2 at a methanol feed concentration of 10 M and maintains good performance at a methanol concentration of up to 15 M. The high selectivity of the electrocatalysts achieved through structural construction accounts for the successful operation of the DMFC at high concentrations of methanol.

Organization of Genes Required for the Oxidation of Methanol to Formaldehyde in Three Type II Methylotrophs

PubMed Central

Bastien, C.; Machlin, S.; Zhang, Y.; Donaldson, K.; Hanson, R. S.

1989-01-01

Restriction maps of genes required for the synthesis of active methanol dehydrogenase in Methylobacterium organophilum XX and Methylobacterium sp. strain AM1 have been completed and compared. In these two species of pink-pigmented, type II methylotrophs, 15 genes were identified that were required for the expression of methanol dehydrogenase activity. None of these genes were required for the synthesis of the prosthetic group of methanol dehydrogenase, pyrroloquinoline quinone. The structural gene required for the synthesis of cytochrome cL, an electron acceptor uniquely required for methanol dehydrogenase, and the genes encoding small basic peptides that copurified with methanol dehydrogenases were closely linked to the methanol dehydrogenase structural genes. A cloned 22-kilobase DNA insert from Methylsporovibrio methanica 81Z, an obligate type II methanotroph, complemented mutants that contained lesions in four genes closely linked to the methanol dehydrogenase structural genes. The methanol dehydrogenase and cytochrome cL structural genes were found to be transcribed independently in M. organophilum XX. Only two of the genes required for methanol dehydrogenase synthesis in this bacterium were found to be cotranscribed. PMID:16348074

California methanol assessment. Volume 1: Summary report

NASA Technical Reports Server (NTRS)

Otoole, R.; Dutzi, E.; Gershman, R.; Heft, R.; Kalema, W.; Maynard, D.

1983-01-01

The near term methanol industry, the competitive environment, long term methanol market, the transition period, air quality impacts of methanol, roles of the public and private sectors are considered.

Neurological Complications Resulting from Non-Oral Occupational Methanol Poisoning.

PubMed

Choi, Ji Hyun; Lee, Seung Keun; Gil, Young Eun; Ryu, Jia; Jung-Choi, Kyunghee; Kim, Hyunjoo; Choi, Jun Young; Park, Sun Ah; Lee, Hyang Woon; Yun, Ji Young

2017-02-01

Methanol poisoning results in neurological complications including visual disturbances, bilateral putaminal hemorrhagic necrosis, parkinsonism, cerebral edema, coma, or seizures. Almost all reported cases of methanol poisoning are caused by oral ingestion of methanol. However, recently there was an outbreak of methanol poisoning via non-oral exposure that resulted in severe neurological complications to a few workers at industrial sites in Korea. We present 3 patients who had severe neurological complications resulting from non-oral occupational methanol poisoning. Even though initial metabolic acidosis and mental changes were improved with hemodialysis, all of the 3 patients presented optic atrophy and ataxia or parkinsonism as neurological complications resulting from methanol poisoning. In order to manage it adequately, as well as to prevent it, physicians should recognize that methanol poisoning by non-oral exposure can cause neurologic complications.

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.

Modeling of methanol decomposition on Pt/CeO2/ZrO2 catalyst in a packed bed microreactor

NASA Astrophysics Data System (ADS)

Pohar, Andrej; Belavič, Darko; Dolanc, Gregor; Hočevar, Stanko

2014-06-01

Methanol decomposition on Pt/CeO2/ZrO2 catalyst is studied inside a packed bed microreactor in the temperature range of 300-380 °C. The microreactor is fabricated using low-temperature co-fired ceramic (LTCC) technology, which is well suited for the production of relatively complex three-dimensional structures. It is packed with 2 wt% Pt-CeO2 catalyst, which is deposited onto ZrO2 spherical particles. A 1D mathematical model, which incorporates diffusion, convection and mass transfer through the boundary layer to the catalyst particles, as well as a 3D computational fluid dynamics model, are developed to describe the methanol decomposition process inside the packed bed. The microreactor exhibits reliable operation and no catalyst deactivation was observed during three months of experimentation. A comparison between the 1D mathematical model and the 3D model, considering the full 3D geometry of the microreactor is made and the differences between the models are identified and evaluated.

Adsorbate-induced lifting of substrate relaxation is a general mechanism governing titania surface chemistry.

PubMed

Silber, David; Kowalski, Piotr M; Traeger, Franziska; Buchholz, Maria; Bebensee, Fabian; Meyer, Bernd; Wöll, Christof

2016-09-30

Under ambient conditions, almost all metals are coated by an oxide. These coatings, the result of a chemical reaction, are not passive. Many of them bind, activate and modify adsorbed molecules, processes that are exploited, for example, in heterogeneous catalysis and photochemistry. Here we report an effect of general importance that governs the bonding, structure formation and dissociation of molecules on oxidic substrates. For a specific example, methanol adsorbed on the rutile TiO 2 (110) single crystal surface, we demonstrate by using a combination of experimental and theoretical techniques that strongly bonding adsorbates can lift surface relaxations beyond their adsorption site, which leads to a significant substrate-mediated interaction between adsorbates. The result is a complex superstructure consisting of pairs of methanol molecules and unoccupied adsorption sites. Infrared spectroscopy reveals that the paired methanol molecules remain intact and do not deprotonate on the defect-free terraces of the rutile TiO 2 (110) surface.

First direct visualization of spillover species emitted from pt nanoparticles.

PubMed

Takakusagi, Satoru; Fukui, Ken-ichi; Tero, Ryugo; Asakura, Kiyotaka; Iwasawa, Yasuhiro

2010-11-02

We studied the methanol adsorption behavior of Pt nanoparticles that were vacuum-deposited on a TiO(2)(110) surface at room temperature by using an ultrahigh vacuum (UHV) scanning tunneling microscope (STM). A large number of bright spots were observed on fivefold-coordinated Ti (Ti(5c)) rows of the TiO(2)(110) surface after exposure of the Pt/TiO(2)(110) to methanol vapor. We assigned the bright spots to methoxy species. These were mobile and were found to hop along the Ti(5c) rows. In situ time-resolved STM observations of the formation and migration of the bright spots on the Pt/TiO(2)(110) were carried out in the presence of methanol. The bright spots were produced at the periphery of the Pt nanoparticles and migrated to the substrate Ti(5c) rows. We discuss the spillover process and behavior of the methoxy species on the Pt/TiO(2)(110).

Adsorbate-induced lifting of substrate relaxation is a general mechanism governing titania surface chemistry

NASA Astrophysics Data System (ADS)

Silber, David; Kowalski, Piotr M.; Traeger, Franziska; Buchholz, Maria; Bebensee, Fabian; Meyer, Bernd; Wöll, Christof

2016-09-01

Under ambient conditions, almost all metals are coated by an oxide. These coatings, the result of a chemical reaction, are not passive. Many of them bind, activate and modify adsorbed molecules, processes that are exploited, for example, in heterogeneous catalysis and photochemistry. Here we report an effect of general importance that governs the bonding, structure formation and dissociation of molecules on oxidic substrates. For a specific example, methanol adsorbed on the rutile TiO2(110) single crystal surface, we demonstrate by using a combination of experimental and theoretical techniques that strongly bonding adsorbates can lift surface relaxations beyond their adsorption site, which leads to a significant substrate-mediated interaction between adsorbates. The result is a complex superstructure consisting of pairs of methanol molecules and unoccupied adsorption sites. Infrared spectroscopy reveals that the paired methanol molecules remain intact and do not deprotonate on the defect-free terraces of the rutile TiO2(110) surface.

Cold Water Vapor in the Barnard 5 Molecular Cloud

NASA Technical Reports Server (NTRS)

Wirstrom, E. S.; Charnley, S. B.; Persson, C. M.; Buckle, J. V.; Cordiner, M. A.; Takakuwa, S.

2014-01-01

After more than 30 yr of investigations, the nature of gas-grain interactions at low temperatures remains an unresolved issue in astrochemistry. Water ice is the dominant ice found in cold molecular clouds; however, there is only one region where cold ((is) approximately 10 K) water vapor has been detected-L1544. This study aims to shed light on ice desorption mechanisms under cold cloud conditions by expanding the sample. The clumpy distribution of methanol in dark clouds testifies to transient desorption processes at work-likely to also disrupt water ice mantles. Therefore, the Herschel HIFI instrument was used to search for cold water in a small sample of prominent methanol emission peaks. We report detections of the ground-state transition of o-H2O (J = 110-101) at 556.9360 GHz toward two positions in the cold molecular cloud, Barnard 5. The relative abundances of methanol and water gas support a desorption mechanism which disrupts the outer ice mantle layers, rather than causing complete mantle removal.

Fuel droplet burning rates at high pressures

NASA Technical Reports Server (NTRS)

Canada, G. S.; Faeth, G. M.

1972-01-01

Combustion of methanol, ethanol, propanol -1, n - pentane, n - heptane and n - decane was observed in air under natural convection conditions at pressures up to 100 atm. The droplets were simulated by porous spheres with diameters in the range 0.63 - 1.90 cm. The pressure levels of the tests were high enough so that near critical combustion was observed for methanol and ethanol. Measurements were made of the burning rate and liquid surface temperatures of the fuels. The data were compared with variable property analysis of the combustion process, including a correction for natural convection. The burning rate predictions of the various theories were similar and in fair agreement with the data. The high pressure theory gave the best prediction for the liquid surface temperatures of ethanol and propanol -1 at high pressure. The experiments indicated the approach of critical burning conditions for methanol and ethanol at pressures on the order of 80 - 100 atm, which was in good agreement with the predictions of both the low and high pressure analysis.

Coke formation in a zeolite crystal during the methanol-to-hydrocarbons reaction as studied with atom probe tomography

DOE PAGES

Schmidt, Joel E.; Poplawsky, Jonathan D.; Mazumder, Baishakhi; ...

2016-08-03

Understanding the formation of carbon deposits in zeolites is vital to developing new, superior materials for various applications, including oil and gas conversion processes. Herein, atom probe tomography (APT) has been used to spatially resolve the 3D compositional changes at the sub-nm length scale in a single zeolite ZSM-5 crystal, which has been partially deactivated by the methanol-to-hydrocarbons reaction using 13C-labeled methanol. The results reveal the formation of coke in agglomerates that span length scales from tens of nanometers to atomic clusters with a median size of 30–60 13C atoms. These clusters correlate with local increases in Brønsted acid sitemore » density, demonstrating that the formation of the first deactivating coke precursor molecules occurs in nanoscopic regions enriched in aluminum. Here, this nanoscale correlation underscores the importance of carefully engineering materials to suppress detrimental coke formation.« less

Cosmos caudatus as a potential source of polyphenolic compounds: optimisation of oven drying conditions and characterisation of its functional properties.

PubMed

Mediani, Ahmed; Abas, Faridah; Khatib, Alfi; Tan, Chin Ping

2013-08-29

The aim of the study was to analyze the influence of oven thermal processing of Cosmos caudatus on the total polyphenolic content (TPC) and antioxidant capacity (DPPH) of two different solvent extracts (80% methanol, and 80% ethanol). Sonication was used to extract bioactive compounds from this herb. The results showed that the optimised conditions for the oven drying method for 80% methanol and 80% ethanol were 44.5 °C for 4 h with an IC₅₀ of 0.045 mg/mL and 43.12 °C for 4.05 h with an IC₅₀ of 0.055 mg/mL, respectively. The predicted values for TPC under the optimised conditions for 80% methanol and 80% ethanol were 16.5 and 15.8 mg GAE/100 g DW, respectively. The results obtained from this study demonstrate that Cosmos caudatus can be used as a potential source of antioxidants for food and medicinal applications.

Producing methane, methanol and electricity from organic waste of fermentation reaction using novel microbes.

PubMed

Dhiman, Saurabh Sudha; Shrestha, Namita; David, Aditi; Basotra, Neha; Johnson, Glenn R; Chadha, Bhupinder S; Gadhamshetty, Venkataramana; Sani, Rajesh K

2018-06-01

Residual solid and liquid streams from the one-pot CRUDE (Conversion of Raw and Untreated Disposal into Ethanol) process were treated with two separate biochemical routes for renewable energy transformation. The solid residual stream was subjected to thermophilic anaerobic digestion (TAD), which produced 95 ± 7 L methane kg -1 volatile solid with an overall energy efficiency of 12.9 ± 1.7%. A methanotroph, Methyloferula sp., was deployed for oxidation of mixed TAD biogas into methanol. The residual liquid stream from CRUDE process was used in a Microbial Fuel Cell (MFC) to produce electricity. Material balance calculations confirmed the integration of biochemical routes (i.e. CRUDE, TAD, and MFC) for developing a sustainable approach of energy regeneration. The current work demonstrates the utilization of different residual streams originated after food waste processing to release minimal organic load to the environment. Copyright © 2018 Elsevier Ltd. All rights reserved.

The degradation of wheat straw lignin

NASA Astrophysics Data System (ADS)

Liang, Jiaqi

2017-03-01

Lignin is a kind of formed by polymerization of aromatic alcohol, prices are lower and sources of renewable resources. Using lignin as raw material, through the push to resolve together preparation phenolic high value-added fine chemicals alkanes and aromatic hydrocarbons, such as the high grade biofuels, can partly replace fossil fuels as raw material to the production process, biomass resources is an important part of the comprehensive utilization of effective components. In lignin push solve clustering method, catalytic hydrogenolysis can directly to the lignin into liquid fuels, low oxygen content in the use of biofuels shows great potential. In this paper, through the optimization of the reaction time, reaction temperature, catalyst type and solvent type, dosage of catalyst, etc factors, determines the alcoholysis - hydrogen solution two-step degradation of lignin, the optimal process conditions: lignin alcoholysis under 50% methanol and NaOH catalyst in the solution, the lignin in methanol solution and 50% hydrogen solution under the Pd/C catalyst. In this process, the degradation of lignin yield can reach 42%.

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.

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.

Low-energy electron-induced chemistry of condensed methanol: implications for the interstellar synthesis of prebiotic molecules.

PubMed

Boamah, Mavis D; Sullivan, Kristal K; Shulenberger, Katie E; Soe, ChanMyae M; Jacob, Lisa M; Yhee, Farrah C; Atkinson, Karen E; Boyer, Michael C; Haines, David R; Arumainayagam, Christopher R

2014-01-01

In the interstellar medium, UV photolysis of condensed methanol (CH3OH), contained in ice mantles surrounding dust grains, is thought to be the mechanism that drives the formation of "complex" molecules, such as methyl formate (HCOOCH3), dimethyl ether (CH3OCH3), acetic acid (CH3COOH), and glycolaldehyde (HOCH2CHO). The source of this reaction-initiating UV light is assumed to be local because externally sourced UV radiation cannot penetrate the ice-containing dark, dense molecular clouds. Specifically, exceedingly penetrative high-energy cosmic rays generate secondary electrons within the clouds through molecular ionizations. Hydrogen molecules, present within these dense molecular clouds, are excited in collisions with these secondary electrons. It is the UV light, emitted by these electronically excited hydrogen molecules, that is generally thought to photoprocess interstellar icy grain mantles to generate "complex" molecules. In addition to producing UV light, the large numbers of low-energy (< 20 eV) secondary electrons, produced by cosmic rays, can also directly initiate radiolysis reactions in the condensed phase. The goal of our studies is to understand the low-energy, electron-induced processes that occur when high-energy cosmic rays interact with interstellar ices, in which methanol, a precursor of several prebiotic species, is the most abundant organic species. Using post-irradiation temperature-programmed desorption, we have investigated the radiolysis initiated by low-energy (7 eV and 20 eV) electrons in condensed methanol at - 85 K under ultrahigh vacuum (5 x 10(-10) Torr) conditions. We have identified eleven electron-induced methanol radiolysis products, which include many that have been previously identified as being formed by methanol UV photolysis in the interstellar medium. These experimental results suggest that low-energy, electron-induced condensed phase reactions may contribute to the interstellar synthesis of "complex" molecules previously thought to form exclusively via UV photons.

Method for making methanol

DOEpatents

Mednick, R. Lawrence; Blum, David B.

1987-01-01

Methanol is made in a liquid-phase methanol reactor by entraining a methanol-forming catalyst in an inert liquid and contacting said entrained catalyst with a synthesis gas comprising hydrogen and carbon monoxide.

Methanol incorporation in clathrate hydrates and the implications for oil and gas pipeline flow assurance and icy planetary bodies

PubMed Central

Shin, Kyuchul; Udachin, Konstantin A.; Moudrakovski, Igor L.; Leek, Donald M.; Alavi, Saman; Ratcliffe, Christopher I.; Ripmeester, John A.

2013-01-01

One of the best-known uses of methanol is as antifreeze. Methanol is used in large quantities in industrial applications to prevent methane clathrate hydrate blockages from forming in oil and gas pipelines. Methanol is also assigned a major role as antifreeze in giving icy planetary bodies (e.g., Titan) a liquid subsurface ocean and/or an atmosphere containing significant quantities of methane. In this work, we reveal a previously unverified role for methanol as a guest in clathrate hydrate cages. X-ray diffraction (XRD) and NMR experiments showed that at temperatures near 273 K, methanol is incorporated in the hydrate lattice along with other guest molecules. The amount of included methanol depends on the preparative method used. For instance, single-crystal XRD shows that at low temperatures, the methanol molecules are hydrogen-bonded in 4.4% of the small cages of tetrahydrofuran cubic structure II hydrate. At higher temperatures, NMR spectroscopy reveals a number of methanol species incorporated in hydrocarbon hydrate lattices. At temperatures characteristic of icy planetary bodies, vapor deposits of methanol, water, and methane or xenon show that the presence of methanol accelerates hydrate formation on annealing and that there is unusually complex phase behavior as revealed by powder XRD and NMR spectroscopy. The presence of cubic structure I hydrate was confirmed and a unique hydrate phase was postulated to account for the data. Molecular dynamics calculations confirmed the possibility of methanol incorporation into the hydrate lattice and show that methanol can favorably replace a number of methane guests. PMID:23661058

Methanol incorporation in clathrate hydrates and the implications for oil and gas pipeline flow assurance and icy planetary bodies.

PubMed

Shin, Kyuchul; Udachin, Konstantin A; Moudrakovski, Igor L; Leek, Donald M; Alavi, Saman; Ratcliffe, Christopher I; Ripmeester, John A

2013-05-21

One of the best-known uses of methanol is as antifreeze. Methanol is used in large quantities in industrial applications to prevent methane clathrate hydrate blockages from forming in oil and gas pipelines. Methanol is also assigned a major role as antifreeze in giving icy planetary bodies (e.g., Titan) a liquid subsurface ocean and/or an atmosphere containing significant quantities of methane. In this work, we reveal a previously unverified role for methanol as a guest in clathrate hydrate cages. X-ray diffraction (XRD) and NMR experiments showed that at temperatures near 273 K, methanol is incorporated in the hydrate lattice along with other guest molecules. The amount of included methanol depends on the preparative method used. For instance, single-crystal XRD shows that at low temperatures, the methanol molecules are hydrogen-bonded in 4.4% of the small cages of tetrahydrofuran cubic structure II hydrate. At higher temperatures, NMR spectroscopy reveals a number of methanol species incorporated in hydrocarbon hydrate lattices. At temperatures characteristic of icy planetary bodies, vapor deposits of methanol, water, and methane or xenon show that the presence of methanol accelerates hydrate formation on annealing and that there is unusually complex phase behavior as revealed by powder XRD and NMR spectroscopy. The presence of cubic structure I hydrate was confirmed and a unique hydrate phase was postulated to account for the data. Molecular dynamics calculations confirmed the possibility of methanol incorporation into the hydrate lattice and show that methanol can favorably replace a number of methane guests.

A simple preparation of very high methanol tolerant cathode electrocatalyst for direct methanol fuel cell based on polymer-coated carbon nanotube/platinum

PubMed Central

Yang, Zehui; Nakashima, Naotoshi

2015-01-01

The development of a durable and methanol tolerant electrocatalyst with a high oxygen reduction reaction activity is highly important for the cathode side of direct methanol fuel cells. Here, we describe a simple and novel methodology to fabricate a practically applicable electrocatalyst with a high methanol tolerance based on poly[2,2′-(2,6-pyridine)-5,5′-bibenzimidazole]-wrapped multi-walled carbon nanotubes, on which Pt nanoparticles have been deposited, then coated with poly(vinylphosphonic acid) (PVPA). The polymer coated electrocatalyst showed an ~3.3 times higher oxygen reduction reaction activity compared to that of the commercial CB/Pt and methanol tolerance in the presence of methanol to the electrolyte due to a 50% decreased methanol adsorption on the Pt after coating with the PVPA. Meanwhile, the peroxide generation of the PVPA coated electrocatalyst was as low as 0.8% with 2 M methanol added to the electrolyte, which was much lower than those of the non-PVPA-coated electrocatalyst (7.5%) and conventional CB/Pt (20.5%). Such a high methanol tolerance is very important for the design of a direct methanol fuel cell cathode electrocatalyst with a high performance. PMID:26192397

Methanol oxidation by temperate soils and environmental determinants of associated methylotrophs

PubMed Central

Stacheter, Astrid; Noll, Matthias; Lee, Charles K; Selzer, Mirjam; Glowik, Beate; Ebertsch, Linda; Mertel, Ralf; Schulz, Daria; Lampert, Niclas; Drake, Harold L; Kolb, Steffen

2013-01-01

The role of soil methylotrophs in methanol exchange with the atmosphere has been widely overlooked. Methanol can be derived from plant polymers and be consumed by soil microbial communities. In the current study, methanol-utilizing methylotrophs of 14 aerated soils were examined to resolve their comparative diversities and capacities to utilize ambient concentrations of methanol. Abundances of cultivable methylotrophs ranged from 106–108 gsoilDW−1. Methanol dissimilation was measured based on conversion of supplemented 14C-methanol, and occurred at concentrations down to 0.002 μmol methanol gsoilDW−1. Tested soils exhibited specific affinities to methanol (a0s=0.01 d−1) that were similar to those of other environments suggesting that methylotrophs with similar affinities were present. Two deep-branching alphaproteobacterial genotypes of mch responded to the addition of ambient concentrations of methanol (⩽0.6 μmol methanol gsoilDW−1) in one of these soils. Methylotroph community structures were assessed by amplicon pyrosequencing of genes of mono carbon metabolism (mxaF, mch and fae). Alphaproteobacteria-affiliated genotypes were predominant in all investigated soils, and the occurrence of novel genotypes indicated a hitherto unveiled diversity of methylotrophs. Correlations between vegetation type, soil pH and methylotroph community structure suggested that plant–methylotroph interactions were determinative for soil methylotrophs. PMID:23254514

Two-stage, dilute sulfuric acid hydrolysis of wood : an investigation of fundamentals

Treesearch

John F. Harris; Andrew J. Baker; Anthony H. Conner; Thomas W. Jeffries; James L. Minor; Roger C. Pettersen; Ralph W. Scott; Edward L Springer; Theodore H. Wegner; John I. Zerbe

1985-01-01

This paper presents a fundamental analysis of the processing steps in the production of methanol from southern red oak (Quercus falcata Michx.) by two-stage dilute sulfuric acid hydrolysis. Data for hemicellulose and cellulose hydrolysis are correlated using models. This information is used to develop and evaluate a process design.

Dynamic quenching study of 2-amino-3-bromo-1,4-naphthoquinone by titanium dioxide nano particles in solution (methanol).

PubMed

Pushpam, S; Kottaisamy, M; Ramakrishnan, V

2013-10-01

The dependence of fluorescence emission of 2-amino-3-bromo-1,4-naphthoquinone on titanium dioxide (TiO2) in methanol has been investigated. The increase in TiO2 concentration causes a decrease in the fluorescence intensity of 2-amino-3-bromo-1,4-naphthoquinone. A linear Stern-Volmer plot in this study indicates the presence of dynamic quenching. The quenching and association constants have been calculated. The quenching process is due to the electron transfer from 2-amino-3-bromo-1,4-naphthoquinone to TiO2. Copyright © 2013 Elsevier B.V. All rights reserved.

Evaporation and condensation at a liquid surface. II. Methanol

NASA Astrophysics Data System (ADS)

Matsumoto, Mitsuhiro; Yasuoka, Kenji; Kataoka, Yosuke

1994-11-01

The rates of evaporation and condensation of methanol under the vapor-liquid equilibrium condition at the temperature of 300 and 350 K are investigated with a molecular dynamics computer simulation. Compared with the argon system (reported in part I), the ratio of self-reflection is similar (˜10%), but the ratio of molecule exchange is several times larger than the argon, which suggests that the conventional assumption of condensation as a unimolecular process completely fails for associating fluids. The resulting total condensation coefficient is 20%-25%, and has a quantitative agreement with a recent experiment. The temperature dependence of the evaporation-condensation behavior is not significant.

Building carbon–carbon bonds using a biocatalytic methanol condensation cycle

PubMed Central

Bogorad, Igor W.; Chen, Chang-Ting; Theisen, Matthew K.; Wu, Tung-Yun; Schlenz, Alicia R.; Lam, Albert T.; Liao, James C.

2014-01-01

Methanol is an important intermediate in the utilization of natural gas for synthesizing other feedstock chemicals. Typically, chemical approaches for building C–C bonds from methanol require high temperature and pressure. Biological conversion of methanol to longer carbon chain compounds is feasible; however, the natural biological pathways for methanol utilization involve carbon dioxide loss or ATP expenditure. Here we demonstrated a biocatalytic pathway, termed the methanol condensation cycle (MCC), by combining the nonoxidative glycolysis with the ribulose monophosphate pathway to convert methanol to higher-chain alcohols or other acetyl-CoA derivatives using enzymatic reactions in a carbon-conserved and ATP-independent system. We investigated the robustness of MCC and identified operational regions. We confirmed that the pathway forms a catalytic cycle through 13C-carbon labeling. With a cell-free system, we demonstrated the conversion of methanol to ethanol or n-butanol. The high carbon efficiency and low operating temperature are attractive for transforming natural gas-derived methanol to longer-chain liquid fuels and other chemical derivatives. PMID:25355907

Is elevated creatinine a reliable marker for methanol toxicity in nitromethane-containing model fuel ingestions in children?

PubMed

Padmanabhan, Pradeep; Spiller, Henry A; Ross, Mitchell P; Bosse, George M

2011-01-01

In the absence of a rapid serum methanol level estimation, it is difficult to assess the risk from unintentional childhood ingestion of model fuels containing methanol and nitromethane (MFNM). Previous reports have documented false elevations of serum creatinine from the nitromethane in these fuels, suggesting its utility as a readily available marker of significant methanol ingestion. We performed a 2-year retrospective chart review of cases of ingestion of MFNM in children, with both a methanol level and measured creatinine level. Seven children, ages 19 months to 3 years, ingested MFNM. All seven children were seen in a hospital and had measured methanol and creatinine levels. All blood samples for methanol and creatinine were drawn within 3 hours of ingestion with methanol estimation delayed up to 24 hours. Creatinine ranged from 0.39 (0.034 mmol/l) to 10.7 mg/dl (0.95 mmol/l). All methanol levels were <10 mg/dl (0.31 mmol/l) or reported as negative. Fomepizole was initiated empirically in two patients due to delay in obtaining methanol analysis results. Transient elevations of creatinine occurred in five of the seven children. Blood urea nitrogen was within normal limits, and there was no history of renal impairment in these children, suggesting the elevated creatinine was mostly related to nitromethane ingestion. No child had a significantly elevated methanol level. Elevated creatinine level, as measured by Jaffe colorimetric method, is not a reliable marker for elevated methanol levels after unintentional ingestion of MFNM.

Thermodynamics of R-(+)-2-(4-Hydroxyphenoxy)propanoic Acid Dissolution in Methanol, Ethanol, and Methanol-Ethanol Mixture

NASA Astrophysics Data System (ADS)

Liu, Wei; Ma, Jinju; Yao, Xinding; Fang, Ruina; Cheng, Liang

2018-05-01

The solubilities of R-(+)-2-(4-hydroxyphenoxy)propanoic acid (D-HPPA) in methanol, ethanol and various methanol-ethanol mixtures are determined in the temperature range from 273.15 to 323.15 K at atmospheric pressure using a laser detecting system. The solubilities of D-HPPA increase with increasing mole fraction of ethanol in the methanol-ethanol mixtures. Experimental data were correlated with Buchowski-Ksiazczak λ h equation and modified Apelblat equation; the first one gives better approximation for the experimental results. The enthalpy, entropy and Gibbs free energy of D-HPPA dissolution in methanol, ethanol and methanol-ethanol mixtures were also calculated from the solubility data.

40 CFR 86.111-94 - Exhaust gas analytical system.

Code of Federal Regulations, 2010 CFR

2010-07-01

... hydrocarbon (THC) (hydrocarbon plus methanol in the case of methanol-fueled vehicles), methane (CH4) (for... methanol for methanol-fueled diesel-cycle vehicles) is shown as part of Figure B94-5 (or Figure B94-6... ionization detector (FID) (heated, 235 °±15 °F (113 °±8 °C) for methanol-fueled vehicles) for the...

40 CFR 86.111-94 - Exhaust gas analytical system.

Code of Federal Regulations, 2011 CFR

2011-07-01

... systems for analysis of total hydrocarbon (THC) (hydrocarbon plus methanol in the case of methanol-fueled... train (and for THC plus methanol for methanol-fueled diesel-cycle vehicles) is shown as part of Figure... B94-7, consists of a flame ionization detector (FID) (heated, 235 °±15 °F (113 °±8 °C) for methanol...

40 CFR 86.109-94 - Exhaust gas sampling system; Otto-cycle vehicles not requiring particulate emission measurements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... concentration and total flow over the test period. (2) Vehicle tailpipe to CVS Duct. For methanol-fueled... proportional samples for the bag sample, and for methanol-fueled vehicles, the methanol sample (Figure B94-2... methanol-fueled vehicles, the sample lines for the methanol and formaldehyde samples are heated to prevent...

Organization of genes required for the oxidation of methanol to formaldehyde in three type II methylotrophs

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

Bastien, C.; Machlin, S.; Zhang, Y.

Restriction maps of genes required for the synthesis of active methanol dehydrogenase in Methylobacterium organophilum XX and Methylobacterium sp. strain AM1 have been completed and compared. In these two species of pink-pigmented, type II methylotrophs, 15 genes were identified that were required for the expression of methanol dehydrogenase activity. None of these genes were required for the synthesis of the prosthetic group of methanol dehydrogenase, pyrroloquinoline quinone. The structural gene required for the synthesis of cytochrome c{sub L}, an electron acceptor uniquely required for methanol dehydrogenase, and the genes encoding small basic peptides that copurified with methanol dehydrogenases were closelymore » linked to the methanol dehydrogenase structural genes. A cloned 22-kilobase DNA insert from Methylsporovibrio methanica 81Z, an obligate type II methanotroph, complemented mutants that contained lesions in four genes closely linked to the methanol dehydrogenase structural genes. The methanol dehydrogenase and cytochrome c{sub L} structural genes were found to be transcribed independently in M. organophilum XX. Only two of the genes required for methanol dehydrogenase synthesis in this bacterium were found to be cotranscribed.« less

Upregulated Transcription of Plasmid and Chromosomal Ribulose Monophosphate Pathway Genes Is Critical for Methanol Assimilation Rate and Methanol Tolerance in the Methylotrophic Bacterium Bacillus methanolicus

PubMed Central

Jakobsen, Øyvind M.; Benichou, Aline; Flickinger, Michael C.; Valla, Svein; Ellingsen, Trond E.; Brautaset, Trygve

2006-01-01

The natural plasmid pBM19 carries the key mdh gene needed for the oxidation of methanol into formaldehyde by Bacillus methanolicus. Five more genes, glpX, fba, tkt, pfk, and rpe, with deduced roles in the cell primary metabolism, are also located on this plasmid. By using real-time PCR, we show that they are transcriptionally upregulated (6- to 40-fold) in cells utilizing methanol; a similar induction was shown for two chromosomal genes, hps and phi. These seven genes are involved in the fructose bisphosphate aldolase/sedoheptulose bisphosphatase variant of the ribulose monophosphate (RuMP) pathway for formaldehyde assimilation. Curing of pBM19 causes higher methanol tolerance and reduced formaldehyde tolerance, and the methanol tolerance is reversed to wild-type levels by reintroducing mdh. Thus, the RuMP pathway is needed to detoxify the formaldehyde produced by the methanol dehydrogenase-mediated conversion of methanol, and the in vivo transcription levels of mdh and the RuMP pathway genes reflect the methanol tolerance level of the cells. The transcriptional inducer of hps and phi genes is formaldehyde, and not methanol, and introduction of multiple copies of these two genes into B. methanolicus made the cells more tolerant of growth on high methanol concentrations. The recombinant strain also had a significantly higher specific growth rate on methanol than the wild type. While pBM19 is critical for growth on methanol and important for formaldehyde detoxification, the maintenance of this plasmid represents a burden for B. methanolicus when growing on mannitol. Our data contribute to a new and fundamental understanding of the regulation of B. methanolicus methylotrophy. PMID:16585766

A comparative study of methanol as a supplementary carbon source for enhancing denitrification in primary and secondary anoxic zones.

PubMed

Ginige, Maneesha P; Bowyer, Jocelyn C; Foley, Leah; Keller, Jürg; Yuan, Zhiguo

2009-04-01

A comparative study on the use of methanol as a supplementary carbon source to enhance denitrification in primary and secondary anoxic zones is reported. Three lab-scale sequencing batch reactors (SBR) were operated to achieve nitrogen and carbon removal from domestic wastewater. Methanol was added to the primary anoxic period of the first SBR, and to the secondary anoxic period of the second SBR. No methanol was added to the third SBR, which served as a control. The extent of improvement on the denitrification performance was found to be dependent on the reactor configuration. Addition to the secondary anoxic period is more effective when very low effluent nitrate levels are to be achieved and hence requires a relatively large amount of methanol. Adding a small amount of methanol to the secondary anoxic period may cause nitrite accumulation, which does not improve overall nitrogen removal. In the latter case, methanol should be added to the primary anoxic period. The addition of methanol can also improve biological phosphorus removal by creating anaerobic conditions and increasing the availability of organic carbon in wastewater for polyphosphate accumulating organisms. This potentially provides a cost-effective approach to phosphorus removal from wastewater with a low carbon content. New fluorescence in situ hybridisation (FISH) probes targeting methanol-utilising denitrifiers were designed using stable isotope probing. Microbial structure analysis of the sludges using the new and existing FISH probes clearly showed that the addition of methanol stimulated the growth of specific methanol-utilizing denitrifiers, which improved the capability of sludge to use methanol and ethanol for denitrification, but reduced its capability to use wastewater COD for denitrification. Unlike acetate, long-term application of methanol has no negative impact on the settling properties of the sludge.

Upregulated transcription of plasmid and chromosomal ribulose monophosphate pathway genes is critical for methanol assimilation rate and methanol tolerance in the methylotrophic bacterium Bacillus methanolicus.

PubMed

Jakobsen, Øyvind M; Benichou, Aline; Flickinger, Michael C; Valla, Svein; Ellingsen, Trond E; Brautaset, Trygve

2006-04-01

The natural plasmid pBM19 carries the key mdh gene needed for the oxidation of methanol into formaldehyde by Bacillus methanolicus. Five more genes, glpX, fba, tkt, pfk, and rpe, with deduced roles in the cell primary metabolism, are also located on this plasmid. By using real-time PCR, we show that they are transcriptionally upregulated (6- to 40-fold) in cells utilizing methanol; a similar induction was shown for two chromosomal genes, hps and phi. These seven genes are involved in the fructose bisphosphate aldolase/sedoheptulose bisphosphatase variant of the ribulose monophosphate (RuMP) pathway for formaldehyde assimilation. Curing of pBM19 causes higher methanol tolerance and reduced formaldehyde tolerance, and the methanol tolerance is reversed to wild-type levels by reintroducing mdh. Thus, the RuMP pathway is needed to detoxify the formaldehyde produced by the methanol dehydrogenase-mediated conversion of methanol, and the in vivo transcription levels of mdh and the RuMP pathway genes reflect the methanol tolerance level of the cells. The transcriptional inducer of hps and phi genes is formaldehyde, and not methanol, and introduction of multiple copies of these two genes into B. methanolicus made the cells more tolerant of growth on high methanol concentrations. The recombinant strain also had a significantly higher specific growth rate on methanol than the wild type. While pBM19 is critical for growth on methanol and important for formaldehyde detoxification, the maintenance of this plasmid represents a burden for B. methanolicus when growing on mannitol. Our data contribute to a new and fundamental understanding of the regulation of B. methanolicus methylotrophy.

Comparison of immunotoxic effects induced by the extracts from methanol and gasoline engine exhausts in vitro.

PubMed

Che, Wangjun; Liu, Guiming; Qiu, Hong; Zhang, Hao; Ran, Yun; Zeng, Xianggui; Wen, Weihua; Shu, Ya

2010-06-01

Gasoline engine exhaust has been considered as a major source of air pollution in China. Due to lower cyto- and geno-toxicity effects of methanol engine exhaust, methanol is regarded as a potential substitute for gasoline. We have previously compared cyto- and geno-toxicities of gasoline engine exhaust with that of methanol engine exhaust in A549 cells (Zhang et al., 2007).To characterize the immunotoxic effects for gasoline and methanol engine exhausts in immune cell, in this study, we further compared effects of gasoline and methanol engine exhausts on immune function in RAW264.7 cell and rabbit alveolar macrophages. Results showed that both gasoline and methanol engine exhaust could evidently inhibit RAW264.7 cell proliferation, promote RAW264.7 cell apoptosis, decrease E-rosette formation rate and inhibit anti-tumor effects of alveolar macrophages, at the same time, these effects of gasoline engine exhaust were far stronger than those of methanol engine exhaust. In addition, gasoline engine exhaust could significantly inhibit activities of ADCC of alveolar macrophages, but methanol engine exhaust could not. These results suggested that both gasoline and methanol engine exhausts might be immunotoxic atmospheric pollutants, but some effects of gasoline engine exhaust on immunotoxicities may be far stronger than that of methanol engine exhaust. Copyright 2010 Elsevier Ltd. All rights reserved.

Cobalt porphyrin-based material as methanol tolerant cathode in single chamber microbial fuel cells (SCMFCs)

NASA Astrophysics Data System (ADS)

Liu, Bingchuan; Brückner, Cristian; Lei, Yu; Cheng, Yue; Santoro, Carlo; Li, Baikun

2014-07-01

This study focused on the development of novel cathode material based on the pyrolysis of [meso-tetrakis(2-thienyl)porphyrinato]Co(II) (CoTTP) for use in single chamber microbial fuel cells (SCMFCs) to treat wastewater containing methanol. The cathodes produced at two loadings (0.5 and 1.0 mg cm-2) were examined in batch mode SCMFCs treating methanol of different concentrations (ranging from 0.005 to 0.04 M) over a 900 h operational period. Methanol was completely removed in SCMFCs, and the cycle duration was prolonged at high methanol concentrations, indicating methanol was used as fuel in SCMFCs. Methanol had more poisoning effects to the traditional platinum (Pt) cathodes than to the CoTTP cathodes. Specifically, power generations from SCMFCs with Pt cathodes gradually decreased over time, while the ones with CoTTP cathodes remained stable, even at the highest methanol concentration (0.04 M). Cathode linear sweep voltammetry (LSVs) indicated that the electrocatalytic activity of the Pt cathode was suppressed by methanol. Higher CoTTP loadings had similar open circuit potential (OCP) but higher electrocatalytic activity than lower loadings. This study demonstrated that methanol can be co-digested with wastewater and converted to power in MFCs, and a novel cathode CoTTP catalyst exhibits higher tolerance towards methanol compared with traditional Pt catalyst.

A New 95 GHz Methanol Maser Catalog. I. Data

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

Yang, Wenjin; Xu, Ye; Lu, Dengrong

The Purple Mountain Observatory 13.7 m radio telescope has been used to search for 95 GHz (8{sub 0}–7{sub 1}A{sup +}) class I methanol masers toward 1020 Bolocam Galactic Plane Survey (BGPS) sources, leading to 213 detections. We have compared the line width of the methanol and HCO{sup +} thermal emission in all of the methanol detections, and on that basis, we find that 205 of the 213 detections are very likely to be masers. This corresponds to an overall detection rate of 95 GHz methanol masers toward our BGPS sample of 20%. Of the 205 detected masers, 144 (70%) aremore » new discoveries. Combining our results with those of previous 95 GHz methanol maser searches, a total of 481 95 GHz methanol masers are now known. We have compiled a catalog listing the locations and properties of all known 95 GHz methanol masers.« less

Single-Step Syngas-to-Distillates (S2D) Process Based on Biomass-Derived Syngas – A Techno-Economic Analysis

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

Zhu, Yunhua; Jones, Susanne B.; Biddy, Mary J.

2012-08-01

This study reports the comparison of biomass gasification based syngas-to-distillate (S2D) systems using techno-economic analysis (TEA). Three cases, state of technology (SOT) case, goal case, and conventional case, were compared in terms of performance and cost. The SOT case and goal case represent technology being developed at Pacific Northwest National Laboratory for a process starting with syngas using a single-step dual-catalyst reactor for distillate generation (S2D process). The conventional case mirrors the two-step S2D process previously utilized and reported by Mobil using natural gas feedstock and consisting of separate syngas-to-methanol and methanol-to-gasoline (MTG) processes. Analysis of the three cases revealedmore » that the goal case could indeed reduce fuel production cost over the conventional case, but that the SOT was still more expensive than the conventional. The SOT case suffers from low one-pass yield and high selectivity to light hydrocarbons, both of which drive up production cost. Sensitivity analysis indicated that light hydrocarbon yield, single pass conversion efficiency, and reactor space velocity are the key factors driving the high cost for the SOT case.« less

Influence of Solvent on the Drug-Loading Process of Amphiphilic Nanogel Star Polymers.

PubMed

Carr, Amber C; Piunova, Victoria A; Maarof, Hasmerya; Rice, Julia E; Swope, William C

2018-05-31

We present an all-atom molecular dynamics study of the effect of a range of organic solvents (dichloromethane, diethyl ether, toluene, methanol, dimethyl sulfoxide, and tetrahydrofuran) on the conformations of a nanogel star polymeric nanoparticle with solvophobic and solvophilic structural elements. These nanoparticles are of particular interest for drug delivery applications. As drug loading generally takes place in an organic solvent, this work serves to provide insight into the factors controlling the early steps of that process. Our work suggests that nanoparticle conformational structure is highly sensitive to the choice of solvent, providing avenues for further study as well as predictions for both computational and experimental explorations of the drug-loading process. Our findings suggest that when used in the drug-loading process, dichloromethane, tetrahydrofuran, and toluene allow for a more extensive and increased drug-loading into the interior of nanogel star polymers of the composition studied here. In contrast, methanol is more likely to support shallow or surface loading and, consequently, faster drug release rates. Finally, diethyl ether should not work in a formulation process since none of the regions of the nanogel star polymer appear to be sufficiently solvated by it.

A novel microalgal lipid extraction method using biodiesel (fatty acid methyl esters) as an extractant.

PubMed

Huang, Wen-Can; Park, Chan Woo; Kim, Jong-Duk

2017-02-01

Although microalgae are considered promising renewable sources of biodiesel, the high cost of the downstream process is a significant obstacle in large-scale biodiesel production. In this study, a novel approach for microalgal biodiesel production was developed by using the biodiesel as an extractant. First, wet microalgae with 70% water content were incubated with a mixture of biodiesel/methanol and penetration of the mixture through the cell membrane and swelling of the lipids contained in microalgae was confirmed. Significant increases of lipid droplets were observed by confocal microscopy. Second, the swelled lipid droplets in microalgae were squeezed out using mechanical stress across the cell membrane and washed with methanol. The lipid extraction efficiency reached 68%. This process does not require drying of microalgae or solvent recovery, which the most energy-intensive step in solvent-based biodiesel production. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

Valery, N.

The calorific values of the fuels being studied were compared. Petrol is the most efficient, followed by methane in the form of LGN, then methanol and liquid hydrogen. Hydrogen is attractive only on a weight basis, but the storage problems are serious for its liquefied state. Liquid methane requires the same costly storage equipment as hydrogen, making it prohibitive for road vehicles. Methanol is a clean burning fuel and manufacturing processes are being developed. Tests are being sponsored by the Office of Coal Research and the American Gas Association and large-scale commercial plants could be capable of being onstream bymore » 1978. Synthetic crude oil has been manufactured in Sasol, South Africa since 1955. The technique is based on the Fischer-Tropsch process for synthesizing oil from coal, not only making synthetic petrol from coal but also the full range of products normally derived from crude oil. (MCW)« less

Field guide for collecting and processing stream-water samples for the National Water-Quality Assessment Program

USGS Publications Warehouse

Shelton, Larry R.

1994-01-01

The U.S. Geological Survey's National Water-Quality Assessment program includes extensive data- collection efforts to assess the quality of the Nations's streams. These studies require analyses of stream samples for major ions, nutrients, sediments, and organic contaminants. For the information to be comparable among studies in different parts of the Nation, consistent procedures specifically designed to produce uncontaminated samples for trace analysis in the laboratory are critical. This field guide describes the standard procedures for collecting and processing samples for major ions, nutrients, organic contaminants, sediment, and field analyses of conductivity, pH, alkalinity, and dissolved oxygen. Samples are collected and processed using modified and newly designed equipment made of Teflon to avoid contamination, including nonmetallic samplers (D-77 and DH-81) and a Teflon sample splitter. Field solid-phase extraction procedures developed to process samples for organic constituent analyses produce an extracted sample with stabilized compounds for more accurate results. Improvements to standard operational procedures include the use of processing chambers and capsule filtering systems. A modified collecting and processing procedure for organic carbon is designed to avoid contamination from equipment cleaned with methanol. Quality assurance is maintained by strict collecting and processing procedures, replicate sampling, equipment blank samples, and a rigid cleaning procedure using detergent, hydrochloric acid, and methanol.

Method of removing polychlorinated biphenyl from oil

DOEpatents

Cook, Gus T.; Holshouser, Stephen K.; Coleman, Richard M.; Harless, Charles E.; Whinnery, III, Walter N.

1983-01-01

Polychlorinated biphenyls are removed from oil by extracting the biphenyls into methanol. The mixture of methanol and extracted biphenyls is distilled to separate methanol therefrom, and the methanol is recycled for further use in extraction of biphenyls from oil.

Methanol Fuel Cell

NASA Technical Reports Server (NTRS)

Voecks, G. E.

1985-01-01

In proposed fuel-cell system, methanol converted to hydrogen in two places. External fuel processor converts only part of methanol. Remaining methanol converted in fuel cell itself, in reaction at anode. As result, size of fuel processor reduced, system efficiency increased, and cost lowered.

Method of removing polychlorinated biphenyl from oil

DOEpatents

Cook, G.T.; Holshouser, S.K.; Coleman, R.M.; Harless, C.E.; Whinnery, W.N. III

1982-03-17

Polychlorinated biphenyls are removed from oil by extracting the biphenyls into methanol. The mixture of methanol and extracted biphenyls is distilled to separate methanol therefrom, and the methanol is recycled for further use in extraction of biphenyls from oil.

Determination of antioxidant activities, total phenolic and flavanoid contents in Bougainvillea glabra bracts at various methanol concentrations

NASA Astrophysics Data System (ADS)

Markandan, Shalini; Abdullah, Aminah; Musa, Khalid Hamid; Subramaniam, Vimala; Stockham, Katherine

2016-11-01

The Bougainvillea glabra bract was extracted using three ratios of methanolic solvents at 50%, 70% and 100%. In this study, the methanolic extracts of B. glabra bract were evaluated for antioxidant properties and quantification of phenolics and flavanoids. Methanol at 100% was the highest extraction efficiency among three other methanolic with yield value of 38%. The content of phenolics and flavonoids of B. glabra bracts in methanol 100% were 63.92±0.90 GAE mg/100g and 249.53±26.20 QE mg/100g respectively. The antioxidant activity was measured using three different bioassays namely, DPPH, ABTS and FRAP. The results were expressed as mg Trolox equivalent per 100 g where Trolox is a vitamin E analog. Among these methanol extracts, highest antioxidant capacity was observed in the pure methanol concentration. Positive correlation was observed in B. glabra bract between DPPH assay and TPC, r2=1.00. The methanol extract at 100% was rich in polyphenolics, which indicating that the B. glabra bract has the potential to be recommended as a good dietary source of natural antioxidants.

37 GHz Methanol Masers : Horsemen of the Apocalypse for the Class II Methanol Maser Phase?

NASA Astrophysics Data System (ADS)

Ellingsen, S. P.; Breen, S. L.; Sobolev, A. M.; Voronkov, M. A.; Caswell, J. L.; Lo, N.

2011-12-01

We report the results of a search for class II methanol masers at 37.7, 38.3, and 38.5 GHz toward a sample of 70 high-mass star formation regions. We primarily searched toward regions known to show emission either from the 107 GHz class II methanol maser transition, or from the 6.035 GHz excited OH transition. We detected maser emission from 13 sources in the 37.7 GHz transition, eight of these being new detections. We detected maser emission from three sources in the 38 GHz transitions, one of which is a new detection. We find that 37.7 GHz methanol masers are only associated with the most luminous 6.7 and 12.2 GHz methanol maser sources, which in turn are hypothesized to be the oldest class II methanol sources. We suggest that the 37.7 GHz methanol masers are associated with a brief evolutionary phase (of 1000-4000 years) prior to the cessation of class II methanol maser activity in the associated high-mass star formation region.

In vitro methanol production from methyl coenzyme M using the Methanosarcina barkeri MtaABC protein complex.

PubMed

Dong, Ming; Gonzalez, Tara D; Klems, Meghan M; Steinberg, Lisa M; Chen, Wilfred; Papoutsakis, Eleftherios T; Bahnson, Brian J

2017-09-01

Methanol:coenzyme M methyltransferase is an enzyme complex composed of three subunits, MtaA, MtaB, and MtaC, found in methanogenic archaea and is needed for their growth on methanol ultimately producing methane. MtaABC catalyzes the energetically favorable methyl transfer from methanol to coenzyme M to form methyl coenzyme M. Here we demonstrate that this important reaction for possible production of methanol from the anaerobic oxidation of methane can be reversed in vitro. To this effect, we have expressed and purified the Methanosarcina barkeri MtaABC enzyme, and developed an in vitro functional assay that demonstrates MtaABC can catalyze the energetically unfavorable (ΔG° = 27 kJ/mol) reverse reaction starting from methyl coenzyme M and generating methanol as a product. Demonstration of an in vitro ability of MtaABC to produce methanol may ultimately enable the anaerobic oxidation of methane to produce methanol and from methanol alternative fuel or fuel-precursor molecules. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 33:1243-1249, 2017. © 2017 American Institute of Chemical Engineers.

The role of hydrogen bonding in the fluorescence quenching of 2,6-bis((E)-2-(benzoxazol-2-yl)vinyl)naphthalene (BBVN) in methanol

NASA Astrophysics Data System (ADS)

Hammam, Essam; Basahi, Jalal; Ismail, Iqbal; Hassan, Ibrahim; Almeelbi, Talal

2017-02-01

The excited state hydrogen bonding dynamics of BBVN in hydrogen donating methanol solvent was explored at the TD-BMK/cc-pVDZ level of theory with accounting for the bulk environment effects at the polarizable continuum model (PCM). The heteroatoms of the BBVN laser dye form hydrogen bonds with four methanol molecules. In the formed BBVN-(MeOH)4 complex, the A-type hydrogen bond (N…HO), of an average strength of 25 kJ mol- 1, is twofold stronger than the B-type (O…HO) one. Upon photon absorption, the total HB binding energy increases from 78.5 kJ mol- 1 in the ground state to 82.6 kJ mol- 1 in the first singlet (S1) excited state. In consequence of the hydrogen bonding interaction, the absorption band maximum of the BBVN-(MeOH)4 complex, which was anticipated at 398 nm (exp. 397), is redshifted by 5 nm relative to that of the free dye in methanol. The spectral shift of the stretching vibrational mode for the hydrogen bonded hydroxyl groups (with a maximum shift of 285 cm- 1) from that of the free methanol indicated the elevated strengthening of hydrogen bonds in the excited state. The vibrational modes associated with hydrogen bonding provide effective accepting modes for the dissipation of the excitation energy, thus, decreasing the fluorescence quantum yield of BBVN in alcohols as compared to that in the polar aprotic solvents. Since there is no sign of photochemistry or phosphorescence, it seems reasonable in view of the outcomes of this study to assign the major decay process of the excited singlet (S1) of BBVN in alcohols to vibronically induced internal conversion (IC) facilitated by hydrogen bonding.

40 CFR 86.117-96 - Evaporative emission enclosure calibrations.

Code of Federal Regulations, 2011 CFR

2011-07-01

... and periodic determination of enclosure background emissions (hydrocarbons and methanol); initial determination of enclosure internal volume; and periodic hydrocarbon and methanol retention check and calibration. Methanol measurements may be omitted if methanol-fueled vehicles will not be tested in the...

40 CFR 86.117-96 - Evaporative emission enclosure calibrations.

Code of Federal Regulations, 2010 CFR

2010-07-01

... and periodic determination of enclosure background emissions (hydrocarbons and methanol); initial determination of enclosure internal volume; and periodic hydrocarbon and methanol retention check and calibration. Methanol measurements may be omitted if methanol-fueled vehicles will not be tested in the...

Methanol-tolerant cathode catalyst composite for direct methanol fuel cells

DOEpatents

Zhu, Yimin; Zelenay, Piotr

2006-09-05

A direct methanol fuel cell (DMFC) having a methanol fuel supply, oxidant supply, and its membrane electrode assembly (MEA) formed of an anode electrode and a cathode electrode with a membrane therebetween, a methanol oxidation catalyst adjacent the anode electrode and the membrane, an oxidant reduction catalyst adjacent the cathode electrode and the membrane, comprises an oxidant reduction catalyst layer of Pt.sub.3Cr/C so that oxidation at the cathode of methanol that crosses from the anode through the membrane to the cathode is reduced with a concomitant increase of net electrical potential at the cathode electrode.

Methanol-Tolerant Cathode Catalyst Composite For Direct Methanol Fuel Cells

DOEpatents

Zhu, Yimin; Zelenay, Piotr

2006-03-21

A direct methanol fuel cell (DMFC) having a methanol fuel supply, oxidant supply, and its membrane electrode assembly (MEA) formed of an anode electrode and a cathode electrode with a membrane therebetween, a methanol oxidation catalyst adjacent the anode electrode and the membrane, an oxidant reduction catalyst adjacent the cathode electrode and the membrane, comprises an oxidant reduction catalyst layer of a platinum-chromium alloy so that oxidation at the cathode of methanol that crosses from the anode through the membrane to the cathode is reduced with a concomitant increase of net electrical potential at the cathode electrode.

Phenotypic characterization of ten methanol oxidation (Mox) mutant classes in methylobacterium AM1

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

Nunn, D.N.; Lidstrom, M.E.

Twenty-five methanol oxidation mutants of the facultative methylotroph Methylobacterium strain AM1 have been characterized by complementation analysis and assigned to ten complementation groups, Mox A1,A2,A3 and B-H. We have characterized each of the mutants belonging to the ten Mox complementation groups by PMS-DCPIP dye linked methanol dehydrogenase activity, by methanol-dependent whole cell oxygen consumption, by the presence or absence of methanol dehydrogenase protein by SDS-polyacrylamide gels and Western blotting, by the absorption spectra of purified mutant methanol dehydrogenase proteins and by the presence or absence of the soluble cytochrome c proteins of Methylobacterium AM1. We propose functions for each ofmore » the genes deficient in the mutants of the ten Mox complementation groups. These functions include two linked genes that encode the methanol dehydrogenase structural protein and the soluble cytochrome c/sub L/, a gene encoding a secretion function essential for the synthesis and export of methanol dehydrogenase and cytochrome c/sub L/, three gene functions responsible for the proper association of the PQQ prosthetic group with the methanol dehydrogenase apoprotein and four positive regulatory gene functions controlling the expression of the ability to oxidize methanol. 24 refs., 5 figs., 2 tabs.« less

Improving fatty acid methyl ester production yield in a lipase-catalyzed process using waste frying oils as feedstock.

PubMed

Azócar, Laura; Ciudad, Gustavo; Heipieper, Hermann J; Muñoz, Robinson; Navia, Rodrigo

2010-06-01

The application of waste frying oil (WFO) mixed with rapeseed oil as a feedstock for the effective production of fatty acid methyl esters (FAME) in a lipase-catalyzed process was investigated. The response surface methodology (RSM) was used to optimize the interaction of four variables: the percentage of WFO in the mixed feedstock, the methanol-to-oil ratio, the dosage of Novozym 435 as a catalyst and the temperature. Furthermore, the addition of methanol to the reaction mixture in a second step after 8 h was shown to effectively diminish enzyme inhibition. Using this technique, the model predicted the optimal conditions that would reach 100% FAME, including a methanol-to-oil molar ratio of 3.8:1, 100% (wt) WFO, 15% (wt) Novozym 435 and incubation at 44.5 degrees C for 12 h with agitation at 200 rpm, and verification experiments confirmed the validity of the model. According to the model, the addition of WFO increased FAME production yield, which is largely due to its higher contents of monoacylglycerols, diacylglycerols and free fatty acids (in comparison to rapeseed oil), which are more available substrates for the enzymatic catalysis. Therefore, the replacement of rapeseed oil with WFO in Novozym 435-catalyzed processes could diminish biodiesel production costs since it is a less expensive feedstock that increases the production yield and could be a potential alternative for FAME production on an industrial scale. (c) 2009 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

The Potential of Biodiesel Production derived from Fish Waste

NASA Astrophysics Data System (ADS)

Farzana Samat, Amira; Amirah Safiah Muhamad, Nor; Rasib, Nur Aziera Abd; Hassan, Siti Aminah Mohd; Sohaimi, Khairunissa Syairah Ahmad; Izzati Iberahim, Nur

2018-03-01

Petroleum based diesel is one of the largest greenhouse emitters in the worlds based on its contribution to more likely of all carbon, methane and other greenhouse emissions. Besides, the depletion of fossil fuel that indirectly increased its price has force the global oil industry not to be so dependent on the fossil fuel but instead start focusing on alternative sources. Biodiesel is recognized as a clean alternative fuel or as a fuel additive to reduce pollutant from combustion equipment. In this study, the discarded parts of mixed marine fish species were used as the raw material to produce biodiesel. Marine fish oil was extracted from the discarded part of fish and if refined through a series of pretreatment process. The refined marine fish oil undergoes esterification process to reduce the amount of free fatty acid. The oil was then transesterified with methanol and sodium hydroxide as an alkaline catalyst that will speed up the conversion of oil to methyl ester. The three process parameters considered for this study were reaction time, reaction temperature and methanol to oil molar ratio. Biodiesel obtained was then analyzed using gas chromatography (GC). Statistical analyses were performed using SPSS software. The data obtained was analyzed by using one way analysis of variance (ANOVA) repeated measure. The results obtained showed that the conversion of FAME yield is the highest at reaction time 180 minutes, reaction temperature 60°C and methanol to oil molar ratio at 15:1 with FAME yield 80.16%, 80.03% and 80.39%. Thus, it can be concluded that the conversion of biodiesel increased as the reaction time, temperature and

Chemical Evolution of Interstellar Methanol Ice Analogs upon Ultraviolet Irradiation: The Role of the Substrate

NASA Astrophysics Data System (ADS)

Ciaravella, A.; Jiménez-Escobar, A.; Cosentino, G.; Cecchi-Pestellini, C.; Peres, G.; Candia, R.; Collura, A.; Barbera, M.; Di Cicca, G.; Varisco, S.; Venezia, A. M.

2018-05-01

An important issue in the chemistry of interstellar ices is the role of dust materials. In this work, we study the effect of an amorphous water-rich magnesium silicate deposited onto ZnSe windows on the chemical evolution of ultraviolet-irradiated methanol ices. For comparison, we also irradiate similar ices deposited onto bare ZnSe windows. Silicates are produced at relatively low temperatures exploiting a sol–gel technique. The chemical composition of the synthesized material reflects the forsterite stoichiometry. Si–OH groups and magnesium carbonates are incorporated during the process. The results show that the substrate material does affect the chemical evolution of the ice. In particular, the CO2/CO ratio within the ice is larger for methanol ices deposited onto the silicate substrate as a result of concurrent effects: the photolysis of carbonates present in the adopted substrate as a source of CO2, CO, and carbon and oxygen atoms; reactions of water molecules and hydroxyl radicals released from the substrate with the CO formed in the ice by the photolysis of the methanol ice; and changes in the structure and energy of the silicate surface by ultraviolet irradiation, leading to more favorable conditions for chemical reactions or catalysis at the grain surface. The results of our experiments allow such chemical effects contributed by the various substrate material components to be disentangled.

Highly chlorinated unintentionally produced persistent organic pollutants generated during the methanol-based production of chlorinated methanes: A case study in China.

PubMed

Zhang, Lifei; Yang, Wenlong; Zhang, Linli; Li, Xiaoxiu

2015-08-01

The formation of unintentionally produced persistent organic pollutants (POPs) may occur during various chlorination processes. In this study, emissions of unintentionally produced POPs during the methanol-based production of chlorinated methanes were investigated. High concentrations of highly chlorinated compounds such as decachlorobiphenyl, octachloronaphthalene, octachlorostyrene, hexachlorobutadiene, hexachlorocyclopentadiene, hexachlorobenzene, and pentachlorobenzene were found in the carbon tetrachloride byproduct of the methanol-based production of chlorinated methanes. The total emission amounts of hexachlorocyclopentadiene, hexachlorobutadiene, polychlorinated benzenes, polychlorinated naphthalenes, octachlorostyrene, and polychlorinated biphenyls released during the production of chlorinated methanes in China in 2010 were estimated to be 10080, 7350, 5210, 427, 212, and 167 kg, respectively. Moreover, polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) were formed unintentionally during chlorinated methanes production, the emission factor for PCDDs/DFs was 364 μg toxic equivalency quotient (TEQ) t(-1) product for residues, which should be added into the UNEP toolkit for updating. It was worth noting that a high overall toxic equivalency quotient from polychlorinated naphthalenes and PCDDs/DFs was generated from the chlorinated methanes production in China in 2010. The values reached 563 and 32.8 g TEQ, respectively. The results of the study indicate that more research and improved management systems are needed to ensure that the methanol-based production of chlorinated methanes can be achieved safely. Copyright © 2015 Elsevier Ltd. All rights reserved.

Application of Mössbauer spectroscopy in industrial heterogeneous catalysis: effect of oxidant on FePO4 material phase transformations in direct methanol synthesis from methane

NASA Astrophysics Data System (ADS)

Dasireddy, Venkata D. B. C.; Khan, Faiza B.; Hanzel, Darko; Bharuth-Ram, Krish; Likozar, Blaž

2017-11-01

The effect of the FePO4 material phase transformation in the direct selective oxidation of methane to methanol was studied using various oxidants, i.e. O2, H2O and N2O. The phases of the heterogeneous catalyst applied, before and after the reactions, were characterized by M¨ossbauer spectroscopy. The main reaction products were methanol, carbon monoxide and carbon dioxide, whereas formaldehyde was produced in rather minute amounts. The Mössbauer spectra showed the change of the initial catalyst material, FePO4 (tridymite-like phase (tdm)), to the reduced metal form, iron(II) pyrophosphate, Fe2P2O7, and thereafter, the material phase change was governed by the oxidation with individual oxidizing species.Mössbauer spectroscopy measurements applied along with X-ray diffraction (XRD) studies on fresh, reduced and spent catalytic materials demonstrated a transformation of the catalyst to a mixture of phases which depended on operating process conditions. Generally, activity was low and should be a subject of further material optimization and engineering, while the selectivity towards methanol at low temperatures applied was adequate. The proceeding redox mechanism should thus play a key role in catalytic material design, while the advantage of iron-based heterogeneous catalysts primarily lies in them being comparably inexpensive and comprising non-critical raw materials only.

Effect of the components' interface on the synthesis of methanol over Cu/ZnO from CO2/H2: a microkinetic analysis based on DFT + U calculations.

PubMed

Tang, Qian-Lin; Zou, Wen-Tian; Huang, Run-Kun; Wang, Qi; Duan, Xiao-Xuan

2015-03-21

The elucidation of chemical reactions occurring on composite systems (e.g., copper (Cu)/zincite (ZnO)) from first principles is a challenging task because of their very large sizes and complicated equilibrium geometries. By combining the density functional theory plus U (DFT + U) method with microkinetic modeling, the present study has investigated the role of the phase boundary in CO2 hydrogenation to methanol over Cu/ZnO. The absence of hydrogenation locations created by the interface between the two catalyst components was revealed based on the calculated turnover frequency under realistic conditions, in which the importance of interfacial copper to provide spillover hydrogen for remote Cu(111) sites was stressed. Coupled with the fact that methanol production on the binary catalyst was recently believed to predominantly involve the bulk metallic surface, the spillover of interface hydrogen atoms onto Cu(111) facets facilitates the production process. The cooperative influence of the two different kinds of copper sites can be rationalized applying the Brönsted-Evans-Polanyi (BEP) relationship and allows us to find that the catalytic activity of ZnO-supported Cu catalysts is of volcano type with decrease in the particle size. Our results here may have useful implications in the future design of new Cu/ZnO-based materials for CO2 transformation to methanol.

Short-time microscopic dynamics of aqueous methanol solutions

NASA Astrophysics Data System (ADS)

Kalampounias, A. G.; Tsilomelekis, G.; Boghosian, S.

2012-12-01

In this paper we present the picosecond vibrational dynamics of a series of methanol aqueous solutions over a wide concentration range from dense to dilute solutions. We studied the vibrational dephasing and vibrational frequency modulation by calculating the time correlation functions of vibrational relaxation by fits in the frequency domain. This method is applied to aqueous methanol solutions xMeOH-(1 - x)H2O, where x = 0, 0.2, 0.4, 0.6, 0.8 and 1. The important finding is that the vibrational dynamics of the system become slower with increasing methanol concentration. The removal of many-body effects by having the molecules in less-crowded environments seems to be the key factor. The interpretation of the vibrational correlation function in the context of Kubo theory, which is based on the assumption that the environmental modulation arises from a single relaxation process and applied to simple liquids, is inadequate for all solutions studied. We found that the vibrational correlation functions of the solutions over the whole concentration range comply with the Rothschild approach, assuming that the environmental modulation is described by a stretched exponential decay. The evolution of the dispersion parameter α with dilution indicates the deviation of the solutions from the model simple liquid and the results are discussed in the framework of the current phenomenological status of the field.

Protection against methanol-induced retinal toxicity by LED photostimulation

NASA Astrophysics Data System (ADS)

Whelan, Harry T.; Wong-Riley, Margaret T. T.; Eells, Janis T.

2002-06-01

We have initiated experiments designed to test the hypothesis that 670-nm Light-Emitting Diode (LED) exposure will attenuate formate-induced retinal dysfunction in a rodent model of methanol toxicity. Methanol intoxication produces toxic injury to the retina. The toxic metabolite formed in methanol intoxication is formic acid, a mitochondrial toxin known to inhibit cytochrome oxidase activity. 670-nm LED light has been hypothesized to act by stimulating cytochrome oxidase activity. To test this hypothesis, one group of animals was intoxicated with methanol, a second group was intoxicated with methanol and LED-treated and a third group was untreated. LED treatment (670 nm for 1 min 45 seconds equals 50 mW/cm2, 4 joules/cm2) was administered at 5, 25, and 50 hours after the initial dose of methanol. At 72 hours of methanol intoxication, retinal function was assessed by measurement of ERG responses and retinas were prepared for histologic analysis. ERG responses recorded in methanol-intoxicated animals revealed profound attenuation of both rod-dominated and UV-cone mediated responses. In contrast, methanol- intoxicated animals exposed to LED treatment exhibited a nearly complete recovery of rod-dominated ERG responses and a slight improvement of UV-cone mediated ERG responses. LED treatment also protected the retina against the histopathologic changes produced by formate in methanol intoxication. These data provide evidence that LED phototherapy protects the retina against the cytotoxic actions of formate and are consistent with the hypothesis that LED photostimulation improves mitochondrial respiratory chain function.

Highly methanol-tolerant platinum electrocatalyst derived from poly(vinylpoyrrolidone) coating

NASA Astrophysics Data System (ADS)

Yang, Zehui; Ling, Ying; Zhang, Yunfeng; Yang, Ming

2017-02-01

The design and fabrication of a methanol-tolerant electrocatalyst is still one of the most important issues in direct methanol fuel cells (DMFCs). Here, we focus on the design of a cathodic electrocatalyst in DMFCs and describe a new methanol-tolerant electrocatalyst fabricated from poly(vinylpyrrolidone) (PVP) coating on platinum nanoparticles assisted by hydrogen bonding between PVP and polybenzimidazole (PBI). The PVP layer has a negligible effect on the oxygen reduction reaction (ORR) activity, while the methanol oxidation reaction is retarded by the PVP layer. The PVP-coated electrocatalyst shows higher ORR activity under various methanol concentrations in the electrolyte, suggesting that the PVP-coated electrocatalyst has a higher methanol tolerance. Also, the PVP-coated electrocatalyst loses only 14% of the electrochemical surface area after 5000 potential cycles from 0.6-1.0 V versus the reversible hydrogen electrode, indicating better Pt stability than non-coated (27%) and commercial (38%) electrocatalysts due to the unique sandwich structure formed by the PVP and PBI. The power density of the PVP-coated electrocatalyst is four to five times higher compared to non-coated and commercial electrocatalysts with 12 M methanol feeding to the anode side, respectively. PVP coating is important for the enhancement of Pt stability and methanol tolerance. This study offers a new method for preparing a low-cost and high-methanol-tolerant Pt electrocatalyst, and useful information for real DMFC application to eliminate the methanol crossover problem in the cathode side.

Production of carbon-13-labeled cadaverine by engineered Corynebacterium glutamicum using carbon-13-labeled methanol as co-substrate.

PubMed

Leßmeier, Lennart; Pfeifenschneider, Johannes; Carnicer, Marc; Heux, Stephanie; Portais, Jean-Charles; Wendisch, Volker F

2015-12-01

Methanol, a one-carbon compound, can be utilized by a variety of bacteria and other organisms as carbon and energy source and is regarded as a promising substrate for biotechnological production. In this study, a strain of non-methylotrophic Corynebacterium glutamicum, which was able to produce the polyamide building block cadaverine as non-native product, was engineered for co-utilization of methanol. Expression of the gene encoding NAD+-dependent methanol dehydrogenase (Mdh) from the natural methylotroph Bacillus methanolicus increased methanol oxidation. Deletion of the endogenous aldehyde dehydrogenase genes ald and fadH prevented methanol oxidation to carbon dioxide and formaldehyde detoxification via the linear formaldehyde dissimilation pathway. Heterologous expression of genes for the key enzymes hexulose-6-phosphate synthase and 6-phospho-3-hexuloisomerase of the ribulose monophosphate (RuMP) pathway in this strain restored growth in the presence of methanol or formaldehyde, which suggested efficient formaldehyde detoxification involving RuMP key enzymes. While growth with methanol as sole carbon source was not observed, the fate of 13C-methanol added as co-substrate to sugars was followed and the isotopologue distribution indicated incorporation into central metabolites and in vivo activity of the RuMP pathway. In addition, 13C-label from methanol was traced to the secreted product cadaverine. Thus, this synthetic biology approach led to a C. glutamicum strain that converted the non-natural carbon substrate methanol at least partially to the non-native product cadaverine.

Anti-Inflammatory Activity and Changes in Antioxidant Properties of Leaf and Stem Extracts from Vitex mollis Kunth during In Vitro Digestion

PubMed Central

Morales-Del-Rio, Juan Alfredo; Gutiérrez-Lomelí, Melesio; Robles-García, Miguel Angel; Aguilar, Jose Antonio; Lugo-Cervantes, Eugenia; Guerrero-Medina, Pedro Javier; Ruiz-Cruz, Saul; Cinco-Moroyoqui, Francisco J.; Wong-Corral, Francisco J.; Del-Toro-Sánchez, Carmen Lizette

2015-01-01

Vitex mollis is used in traditional Mexican medicine for the treatment of some ailments. However, there are no studies on what happens to the anti-inflammatory activity or antioxidant properties and total phenolic content of leaves and stem extracts of Vitex mollis during the digestion process; hence, this is the aim of this work. Methanolic, acetonic, and hexanic extracts were obtained from both parts of the plant. Extract yields and anti-inflammatory activity (elastase inhibition) were measured. Additionally, changes in antioxidant activity (DPPH and ABTS) and total phenols content of plant extracts before and after in vitro digestion were determined. The highest elastase inhibition to prevent inflammation was presented by hexanic extracts (leaf = 94.63% and stem = 98.30%). On the other hand, the major extract yield (16.14%), antioxidant properties (ABTS = 98.51% and DPPH = 94.47% of inhibition), and total phenols (33.70 mg GAE/g of dried sample) were showed by leaf methanolic extract. Finally, leaf and stem methanolic extracts presented an antioxidant activity increase of 35.25% and 27.22%, respectively, in comparison to their initial values after in vitro digestion process. All samples showed a decrease in total phenols at the end of the digestion. These results could be the basis to search for new therapeutic agents from Vitex mollis. PMID:26451153

Can 2,2,2-trifluoroethanol be an efficient protein denaturant than methanol and ethanol under thermal stress?

PubMed

Mohanta, Dayanidhi; Jana, Madhurima

2018-04-18

Monohydric alcohols, such as methanol (MEH), ethanol (ETH) and 2,2,2-trifluoroethanol (TFE), have significant effects on biological processes including the protein folding-unfolding phenomenon. Among the several monohydric alcohols, TFE, a fluorine-substituted alcohol, is known to induce a helical structure in proteins. In this work, we report the heterogeneous unfolding phenomenon of a small protein Chymotrypsin Inhibitor 2 in various concentrations of methanol, ethanol and TFE solutions by performing atomistic molecular dynamics simulation studies. Our study reveals that the unfolding phenomenon of CI2 under thermal stress majorly depends on the concentration and the nature of the alcohol. The presence of alcohols in general has been noted to accelerate the unfolding process compared to pure water and TFE, among them all, has been found to speed up the unfolding time scale at low concentrations. The molecular contact frequency between protein and alcohol follows the trend, MEH < ETH < TFE at low concentrations, whereas the trend becomes MEH ∼ ETH > TFE at more concentrated solutions. The differential water-mediated and self-clustering phenomena of alcohols, diverse protein-alcohol hydrogen bond strengths and the concentration dependent restricted inhomogeneous protein-water as well as protein-alcohol hydrogen bond dynamics suggest that TFE, a well known α-helix stabilizer, could be a good competitor among its class of denaturants.

Environmental stress cracking in gamma-irradiated polycarbonate - A diffusion approach

NASA Astrophysics Data System (ADS)

Silva, Pietro Paolo J. C. de O.; Araújo, Patricia L. B.; da Silveira, Leopoldo B. B.; Araújo, Elmo S.

2017-01-01

Polycarbonate (PC) is an engineering polymer which presents interesting properties. This material has been also used in medical devices, which is frequently exposed to gamma radiosterilization and to chemical agents. This may produce significant changes in polymer structure, leading to failure in service. The present work brings about a new approach on environmental stress cracking (ESC) processes elucidation in 100 kGy gamma-irradiated PC, by evaluating the diffusion process of methanol or 2-propanol in test specimens and determining the diffusion parameters on solvent-irradiated polymer systems. A comparison of diffusion parameters for both solvents indicated that methanol has a considerable ESC action on PC, with diffusion parameter of 7.5×10-14±1% m2 s-1 for non-irradiated PC and 7.8×10-14±2.8% m2 s-1 for PC irradiated at 100 kGy. In contrast, 2-propanol did not act as an ESC agent, as it did promote neither swelling nor cracks in the test specimens. These results were confirmed by visual analysis and optical microscopy. Unexpectedly, structural damages evidenced in tensile strength tests suggested that 2-propanol is as aggressive as methanol chemical for PC. Moreover, although some manufacturers indicate the use of 2-propanol as a cleaning product for PC artifacts, such use should be avoided in parts under mechanical stress.

Electro-oxidation of methanol in alkaline conditions using Pd-Ni nanoparticles prepared from organometallic precursors and supported on carbon vulcan

NASA Astrophysics Data System (ADS)

Manzo-Robledo, A.; Costa, Natália J. S.; Philippot, K.; Rossi, Liane M.; Ramírez-Meneses, E.; Guerrero-Ortega, L. P. A.; Ezquerra-Quiroga, S.

2015-12-01

Oxidation of low-molecular weight alcohols as energy sources using metal nanoparticles has attracted considerable interest for use as a power source in portable electronic devices. In this work, a series of mono- and bimetallic nanoparticles based on palladium and nickel (Pd, Pd90Ni10, Pd50Ni50, Pd10Ni90, and Ni) have been synthesized from organometallic precursors, namely tris(dibenzylideneacetone) dipalladium(0), Pd2(dba)3, and bis(1,5-cyclooctadiene)nickel(0), Ni(cod)2. Well-defined metal particles in the nanometric scale from 4.2 to 6.3 nm were observed by transmission electron microscopy. The as-prepared nanoparticles were mixed with a carbon Vulcan matrix (10 % wt. of the catalyst in turn) for investigation as electrocatalysts in methanol oxidation reaction (MOR) in alkaline conditions. The i- E profiles from cyclic voltammetry for the monometallic systems indicated a redox process attributed only to palladium or nickel, as expected. With the bimetallic nanomaterials, the redox process and the i- E characteristics are functions of the amount of nickel associated to palladium. From a fundamental point of view, it has been established that the OH ions' interfacial interaction and the MOR kinetics are affected by the presence of nickel (decreasing the faradic current) as supported by the current versus potential profiles obtained as a function of methanol concentration and with temperature variation.

Soil moisture by extraction and gas chromatography

NASA Technical Reports Server (NTRS)

Merek, E. L.; Carle, G. C.

1973-01-01

To determine moisture content of soils rapidly and conveniently extract moisture with methanol and determine water content of methanol extract by gas chromatography. Moisture content of sample is calculated from weight of water and methanol in aliquot and weight of methanol added to sample.

Degreasing of titanium to minimize stress corrosion

NASA Technical Reports Server (NTRS)

Carpenter, S. R.

1967-01-01

Stress corrosion of titanium and its alloys at elevated temperatures is minimized by replacing trichloroethylene with methanol or methyl ethyl ketone as a degreasing agent. Wearing cotton gloves reduces stress corrosion from perspiration before the metal components are processed.

Report on Investigation of Alcohol Combustion Associated Wear in Spark Ignition Engines, Mechanisms and Lubricant Effects.

DTIC Science & Technology

1984-12-01

investigated four - alcohol -containing fuels: pure methanol , pure ethanol, methanol in unleaded gaso- line, and ethanol in unleaded gasoline (gasohol...testing indicated that pure alcohol fuels reduced the buildup of engine .. deposits. Also neat methanol greatly increased engine wear rates at engine...results from reactions between methanol combustion products and the cast-iron cylinder liner, where the presence of liquid methanol in the combustion

Methanol production from Eucalyptus wood chips. Final report

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

Fishkind, H.H.

This feasibility study includes all phases of methanol production from seedling to delivery of finished methanol. The study examines: production of 55 million, high quality, Eucalyptus seedlings through tissue culture; establishment of a Eucalyptus energy plantation on approximately 70,000 acres; engineering for a 100 million gallon-per-day methanol production facility; potential environmental impacts of the whole project; safety and health aspects of producing and using methanol; and development of site specific cost estimates.

Short-term inhalation toxicity of methanol, gasoline, and methanol/gasoline in the rat.

PubMed

Poon, R; Chu, I; Bjarnason, S; Vincent, R; Potvin, M; Miller, R B; Valli, V E

1995-01-01

Four- to five-week-old male and female Sprague Dawley rats were exposed to vapors of methanol (2500 ppm), gasoline (3200 ppm), and methanol/gasoline (2500/3200 ppm, 570/3200 ppm) six hours per day, five days per week for four weeks. Control animals were exposed to filtered room air only. Depression in body weight gain and reduced food consumption were observed in male rats, and increased relative liver weight was detected in rats of both sexes exposed to gasoline or methanol/gasoline mixtures. Rats of both sexes exposed to methanol/gasoline mixtures had increased relative kidney weight and females exposed to gasoline and methanol/gasoline mixtures had increased kidney weight. Decreased serum glucose and cholesterol were detected in male rats exposed to gasoline and methanol/gasoline mixtures. Decreased hemoglobin was observed in females inhaling vapors of gasoline and methanol/gasoline at 570/3200 ppm. Urine from rats inhaling gasoline or methanol/gasoline mixtures had up to a fourfold increase in hippuric acid, a biomarker of exposure to the toluene constituent of gasoline, and up to a sixfold elevation in ascorbic acid, a noninvasive biomarker of hepatic response. Hepatic mixed-function oxidase (aniline hydroxylase, aminopyrine N-demethylase and ethoxyresorufin O-deethylase) activities and UDP-glucuronosyltransferase activity were elevated in rats exposed to gasoline and methanol/gasoline mixtures. Histopathological changes were confined to very mild changes in the nasal passages and in the uterus, where decreased incidence or absence of mucosal and myometrial eosinophilia was observed in females inhaling gasoline and methanol/gasoline at 570/3200 ppm. It was concluded that gasoline was largely responsible for the adverse effects, the most significant of which included depression in weight gain in the males, increased liver weight and hepatic microsomal enzyme activities in both sexes, and suppression of uterine eosinophilia. No apparent interactive effects between methanol and gasoline were observed.

Air breathing direct methanol fuel cell

DOEpatents

Ren, Xiaoming

2002-01-01

An air breathing direct methanol fuel cell is provided with a membrane electrode assembly, a conductive anode assembly that is permeable to air and directly open to atmospheric air, and a conductive cathode assembly that is permeable to methanol and directly contacting a liquid methanol source.

40 CFR 63.2262 - How do I conduct performance tests and establish operating requirements?

Code of Federal Regulations, 2011 CFR

2011-07-01

... or documentation of inlet methanol or formaldehyde concentration is required) and outlet of the... HAP, formaldehyde, methanol, or total hydrocarbon (THC) emission rates. (2) When showing compliance... acetaldehyde, acrolein, formaldehyde, methanol, phenol, and propionaldehyde), THC, formaldehyde, or methanol in...

40 CFR 63.2262 - How do I conduct performance tests and establish operating requirements?

Code of Federal Regulations, 2010 CFR

2010-07-01

... or documentation of inlet methanol or formaldehyde concentration is required) and outlet of the... HAP, formaldehyde, methanol, or total hydrocarbon (THC) emission rates. (2) When showing compliance... acetaldehyde, acrolein, formaldehyde, methanol, phenol, and propionaldehyde), THC, formaldehyde, or methanol in...

Engineering the biological conversion of methanol to specialty chemicals in Escherichia coli

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

Whitaker, W. Brian; Jones, J. Andrew; Bennett, R. Kyle

Methanol is an attractive substrate for biological production of chemicals and fuels. Engineering methylotrophic Escherichia coli as a platform organism for converting methanol to metabolites is desirable. Prior efforts to engineer methylotrophic E. coli were limited by methanol dehydrogenases (Mdhs) with unfavorable enzyme kinetics. We engineered E. coli to utilize methanol using a superior NAD-dependent Mdh from Bacillus stearothermophilus and ribulose monophosphate (RuMP) pathway enzymes from B. methanolicus. Using 13C-labeling, we demonstrate this E. coli strain converts methanol into biomass components. For example, the key TCA cycle intermediates, succinate and malate, exhibit labeling up to 39%, while the lower glycolyticmore » intermediate, 3-phosphoglycerate, up to 53%. Multiple carbons are labeled for each compound, demonstrating a cycling RuMP pathway for methanol assimilation to support growth. In conclusion, by incorporating the pathway to synthesize the flavanone naringenin, we demonstrate the first example of in vivo conversion of methanol into a specialty chemical in E. coli.« less

Carbon nanotubes based methanol sensor for fuel cells application.

PubMed

Kim, D W; Lee, J S; Lee, G S; Overzet, L; Kozlov, M; Aliev, A E; Park, Y W; Yang, D J

2006-11-01

An electrochemical sensor is built using vertically grown multi-walled carbon nanotubes (MWNTs) micro-array to detect methanol concentration in water. This study is done for the potential use of the array as methanol sensor for portable units of direct methanol fuel cells (DMFCs). Platinum (Pt) nanoparticles electro-deposited CNTs (Pt/CNTs) electrode shows high sensitivity in the measurement of methanol concentration in water with cyclic voltammetry (CV) measurement at room temperature. Further investigation has also been undertaken to measure the concentration by changing the amount of the mixture of methanol and formic acid in water. We compared the performance of our micro array sensor built with Pt/CNTs electrodes versus that of Pt wire electrode using CV measurement. We found that our Pt/CNTs array sensor shows high sensitivity and detects methanol concentrations in the range of 0.04 M to 0.10 M. In addition, we found that co-use of formic acid as electrolyte enables us to measure up to 1.0 M methanol concentration.

Engineering the biological conversion of methanol to specialty chemicals in Escherichia coli

DOE PAGES

Whitaker, W. Brian; Jones, J. Andrew; Bennett, R. Kyle; ...

2016-11-01

Methanol is an attractive substrate for biological production of chemicals and fuels. Engineering methylotrophic Escherichia coli as a platform organism for converting methanol to metabolites is desirable. Prior efforts to engineer methylotrophic E. coli were limited by methanol dehydrogenases (Mdhs) with unfavorable enzyme kinetics. We engineered E. coli to utilize methanol using a superior NAD-dependent Mdh from Bacillus stearothermophilus and ribulose monophosphate (RuMP) pathway enzymes from B. methanolicus. Using 13C-labeling, we demonstrate this E. coli strain converts methanol into biomass components. For example, the key TCA cycle intermediates, succinate and malate, exhibit labeling up to 39%, while the lower glycolyticmore » intermediate, 3-phosphoglycerate, up to 53%. Multiple carbons are labeled for each compound, demonstrating a cycling RuMP pathway for methanol assimilation to support growth. In conclusion, by incorporating the pathway to synthesize the flavanone naringenin, we demonstrate the first example of in vivo conversion of methanol into a specialty chemical in E. coli.« less

Engineering the biological conversion of methanol to specialty chemicals in Escherichia coli.

PubMed

Whitaker, W Brian; Jones, J Andrew; Bennett, R Kyle; Gonzalez, Jacqueline E; Vernacchio, Victoria R; Collins, Shannon M; Palmer, Michael A; Schmidt, Samuel; Antoniewicz, Maciek R; Koffas, Mattheos A; Papoutsakis, Eleftherios T

2017-01-01

Methanol is an attractive substrate for biological production of chemicals and fuels. Engineering methylotrophic Escherichia coli as a platform organism for converting methanol to metabolites is desirable. Prior efforts to engineer methylotrophic E. coli were limited by methanol dehydrogenases (Mdhs) with unfavorable enzyme kinetics. We engineered E. coli to utilize methanol using a superior NAD-dependent Mdh from Bacillus stearothermophilus and ribulose monophosphate (RuMP) pathway enzymes from B. methanolicus. Using 13 C-labeling, we demonstrate this E. coli strain converts methanol into biomass components. For example, the key TCA cycle intermediates, succinate and malate, exhibit labeling up to 39%, while the lower glycolytic intermediate, 3-phosphoglycerate, up to 53%. Multiple carbons are labeled for each compound, demonstrating a cycling RuMP pathway for methanol assimilation to support growth. By incorporating the pathway to synthesize the flavanone naringenin, we demonstrate the first example of in vivo conversion of methanol into a specialty chemical in E. coli. Copyright © 2016 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

Biological conversion of biogas to methanol using methanotrophs isolated from solid-state anaerobic digestate.

PubMed

Sheets, Johnathon P; Ge, Xumeng; Li, Yueh-Fen; Yu, Zhongtang; Li, Yebo

2016-02-01

The aim of this work was to isolate methanotrophs (methane oxidizing bacteria) that can directly convert biogas produced at a commercial anaerobic digestion (AD) facility to methanol. A methanotrophic bacterium was isolated from solid-state anaerobic digestate. The isolate had characteristics comparable to obligate methanotrophs from the genus Methylocaldum. This newly isolated methanotroph grew on biogas or purified CH4 and successfully converted biogas from AD to methanol. Methanol production was achieved using several methanol dehydrogenase (MDH) inhibitors and formate as an electron donor. The isolate also produced methanol using phosphate with no electron donor or using formate with no MDH inhibitor. The maximum methanol concentration (0.43±0.00gL(-1)) and 48-h CH4 to methanol conversion (25.5±1.1%) were achieved using biogas as substrate and a growth medium containing 50mM phosphate and 80mM formate. Copyright © 2015 Elsevier Ltd. All rights reserved.

Feasibility investigations on multi-cutter milling process: A novel fabrication method for microreactors with multiple microchannels

NASA Astrophysics Data System (ADS)

Pan, Minqiang; Zeng, Dehuai; Tang, Yong

A novel multi-cutter milling process for multiple parallel microchannels with manifolds is proposed to address the challenge of mass manufacture as required for cost-effective commercial applications. Several slotting cutters are stacked together to form a composite tool for machining microchannels simultaneously. The feasibility of this new fabrication process is experimentally investigated under different machining conditions and reaction characteristics of methanol steam reforming for hydrogen production. The influences of cutting parameters and the composite tool on the microchannel qualities and burr formation are analyzed. Experimental results indicate that larger cutting speed, smaller feed rate and cutting depth are in favor of obtaining relatively good microchannel qualities and small burrs. Of all the cutting parameters considered in these experiments, 94.2 m min -1 cutting speed, 23.5 mm min -1 feed rate and 0.5 mm cutting depth are found to be the optimum value. According to the comparisons of experimental results of multi-cutter milling process and estimated one of other alternative methods, it is found that multi-cutter milling process shows much shorter machining time and higher work removal rate than that of other alternative methods. Reaction characteristics of methanol steam reforming in microchannels also indicate that multi-cutter milling process is probably suitable for a commercial application.

Dissimilation of [(13)C]methanol by continuous cultures of Bacillus methanolicus MGA3 at 50 degrees C studied by (13)C NMR and isotope-ratio mass spectrometry.

PubMed

Pluschkell, Stefanie B; Flickinger, Michael C

2002-10-01

Using a continuous culture of Bacillus methanolicus MGA3 limited by 100 mM methanol in the feed and growing at a dilution rate D=0.25 h(-1), transients in dissolved methanol were studied to determine the effects of methanol toxicity and the pathway of methanol dissimilation to CO(2). Steady-state cultures were disturbed by pulses of methanol resulting in a rapid change in concentration of 6.4-12.8 mM. B. methanolicus MGA3 responded to a sudden increase in available methanol by a transient decline in the biomass concentration in the reactor. In most cases the culture returned to steady state between 4 and 12 h after pulse addition. However, at a methanol pulse of 12.8 mM, complete biomass washout occurred and the culture did not return to steady state. Integrating the response curves of the dry biomass concentration over a 12 h time period showed that a methanol pulse can cause an average transient decline in the biomass yield of up to 22%. (13)C NMR experiments using labelled methanol indicated that the transient partial or complete biomass washout was probably caused by toxic accumulation of formaldehyde in the culture. These experiments also showed accumulation of formate, indicating that B. methanolicus possesses formaldehyde dehydrogenase and formate dehydrogenase activity resulting in a methanol dissimilation pathway via formate to CO(2). Studies using isotope-ratio mass spectrometry provided further evidence of a methanol dissimilation pathway via formate. B. methanolicus MGA3, growing continuously under methanol limitation, consumed added formate at a rate of approximately 0.85 mmol l(-1) h(-1). Furthermore, significant accumulation of (13)CO(2) in the reactor exhaust gas was measured in response to a pulse addition of [(13)C]formic acid to the bioreactor. This indicates that B. methanolicus dissimilates methanol carbon to CO(2) in order to detoxify formaldehyde by both a linear pathway to formate and a cyclic mechanism as part of the RuMP pathway.

Probing the nuclear susceptibility of mesoionic compounds using two-beam coupling with chirp-controlled pulses

NASA Astrophysics Data System (ADS)

Bosco, Carlos A. C.; Maciel, Glauco S.; Rakov, Nikifor; de Araújo, Cid B.; Acioli, Lúcio H.; Simas, Alfredo M.; Athayde-Filho, Petrônio F.; Miller, Joseph

2007-11-01

The third-order non-linear optical response of mesoionic compounds (MIC) in dimethylsulfoxide (DMSO) and methanol solutions was investigated by use of collinear pump and probe technique with chirp-controlled femtosecond pulses. The experiments allowed the investigation of non-instantaneous nuclear processes and thermal effects induced by two-photon absorption (TPA). We found that the nuclear non-linearity of MIC in DMSO is ˜1/5 the benzene, which was used as a reference material. This result is attributed to the large inertia of MIC to rotation, compared to benzene. The results for MIC in methanol indicate the influence of thermal effects due to TPA.

Thin Film Catalyst Layers for Direct Methanol Fuel Cells

NASA Technical Reports Server (NTRS)

Witham, C. K.; Chun, W.; Ruiz, R.; Valdez, T. I.; Narayanan, S. R.

2000-01-01

One of the primary obstacles to the widespread use of the direct methanol fuel cell (DMFC) is the high cost of the catalyst. Therefore, reducing the catalyst loading well below the current level of 8-12 mg/cm 2 would be important to commercialization. The current methods for preparation of catalyst layers consisting of catalyst, ionomer and sometimes a hydrophobic additive are applied by either painting, spraying, decal transfer or screen printing processes. Sputter deposition is a coating technique widely used in manufacturing and therefore particularly attractive. In this study we have begun to explore sputtering as a method for catalyst deposition. Present experiments focus on Pt-Ru catalyst layers for the anode.

Controllable pt nanoparticle deposition on carbon nanotubes as an anode catalyst for direct methanol fuel cells.

PubMed

Mu, Yongyan; Liang, Hanpu; Hu, Jinsong; Jiang, Li; Wan, Lijun

2005-12-01

We report a novel process to prepare well-dispersed Pt nanoparticles on CNTs. Pt nanoparticles, which were modified by the organic molecule triphenylphosphine, were deposited on multiwalled carbon nanotubes by the organic molecule, which acts as a cross linker. By manipulating the relative ratio of Pt nanoparticles and multiwalled carbon nanotubes in solution, Pt/CNT composites with different Pt content were achieved. The so-prepared Pt/CNT composite materials show higher electrocatalytic activity and better tolerance to poisoning species in methanol oxidation than the commercial E-TEK catalyst, which can be ascribed to the high dispersion of Pt nanoparticles on the multiwalled carbon nanotube surface.

Evaluation of co-metabolic removal of trichloroethylene in a biotrickling filter under acidic conditions.

PubMed

Chheda, Dhawal; Sorial, George A

2017-07-01

This study investigated the removal of hydrophobic trichloroethylene (TCE) in the presence of methanol (co-metabolite) in a biotrickling filter, which was seeded with fungi at pH4. Starvation was chosen as the biomass control strategy. Two systems, Biofilter I (methanol:TCE 70:30) and Biofilter II (methanol:TCE 80:20) were run in parallel, each with varying composition ratios. The TCE loading rates for both biofilters ranged from 3.22 to 12.88g/m 3 /hr. Depending on the ratio, methanol concentrations varied from 4.08 to 27.95g/m 3 /hr. The performance of the systems was evaluated and compared by calculating removal kinetics, carbon mass balance, efficiencies and elimination capacities. Methanol was observed to enhance TCE removal during the initial loading rate. However, methanol later inhibited TCE degradation above 6.44g TCE/m 3 /hr (Biofilter I) and 3.22g TCE/m 3 /hr (Biofilter II). Conversely, TCE did not impede methanol removal because over 95% methanol elimination was consistently achieved. Overall, Biofilter I was able to outperform Biofilter II due to its greater resistance towards methanol competition. Copyright © 2016. Published by Elsevier B.V.

Improvement in methanol production by regulating the composition of synthetic gas mixture and raw biogas.

PubMed

Patel, Sanjay K S; Mardina, Primata; Kim, Dongwook; Kim, Sang-Yong; Kalia, Vipin C; Kim, In-Won; Lee, Jung-Kul

2016-10-01

Raw biogas can be an alternative feedstock to pure methane (CH4) for methanol production. In this investigation, we evaluated the methanol production potential of Methylosinus sporium from raw biogas originated from an anaerobic digester. Furthermore, the roles of different gases in methanol production were investigated using synthetic gas mixtures of CH4, carbon dioxide (CO2), and hydrogen (H2). Maximum methanol production was 5.13, 4.35, 6.28, 7.16, 0.38, and 0.36mM from raw biogas, CH4:CO2, CH4:H2, CH4:CO2:H2, CO2, and CO2:H2, respectively. Supplementation of H2 into raw biogas increased methanol production up to 3.5-fold. Additionally, covalent immobilization of M. sporium on chitosan resulted in higher methanol production from raw biogas. This study provides a suitable approach to improve methanol production using low cost raw biogas as a feed containing high concentrations of H2S (0.13%). To our knowledge, this is the first report on methanol production from raw biogas, using immobilized cells of methanotrophs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Self-ignition of S.I. engine model fuels: A shock tube investigation at high pressure

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

Fieweger, K.; Blumenthal, R.; Adomeit, G.

1997-06-01

The self-ignition of several spark-ignition (SI) engine fuels (iso-octane, methanol, methyl tert-butyl ether and three different mixtures of iso-octane and n-heptane), mixed with air, was investigated experimentally under relevant engine conditions by the shock tube technique. Typical modes of the self-ignition process were registered cinematographically. For temperatures relevant to piston engine combustion, the self-ignition process always starts as an inhomogeneous, deflagrative mild ignition. This instant is defined by the ignition delay time, {tau}{sub defl}. The deflagration process in most cases is followed by a secondary explosion (DDT). This transition defines a second ignition delay time, {tau}{sub DDT}, which is amore » suitable approximation for the chemical ignition delay time, if the change of the thermodynamic conditions of the unburned test gas due to deflagration is taken into account. For iso-octane at p = 40 bar, a NTC (negative temperature coefficient), behavior connected with a two step (cool flame) self-ignition at low temperatures was observed. This process was very pronounced for rich and less pronounced for stoichiometric mixtures. The results of the {tau}{sub DDT} delays of the stoichiometric mixtures were shortened by the primary deflagration process in the temperature range between 800 and 1,000 K. Various mixtures of iso-octane and n-heptane were investigated. The results show a strong influence of the n-heptane fraction in the mixture, both on the ignition delay time and on the mode of self-ignition. The self-ignition of methanol and MTBE (methyl tert-butyl ether) is characterized by a very pronounced initial deflagration. For temperatures below 900 K (methanol: 800 K), no secondary explosion occurs. Taking into account the pressure increase due to deflagration, the measured delays {tau}{sub DDT} of the secondary explosion are shortened by up to one order of magnitude.« less

Methanol Oxidation on Pt3Sn(111) for Direct Methanol Fuel Cells: Methanol Decomposition.

PubMed

Lu, Xiaoqing; Deng, Zhigang; Guo, Chen; Wang, Weili; Wei, Shuxian; Ng, Siu-Pang; Chen, Xiangfeng; Ding, Ning; Guo, Wenyue; Wu, Chi-Man Lawrence

2016-05-18

PtSn alloy, which is a potential material for use in direct methanol fuel cells, can efficiently promote methanol oxidation and alleviate the CO poisoning problem. Herein, methanol decomposition on Pt3Sn(111) was systematically investigated using periodic density functional theory and microkinetic modeling. The geometries and energies of all of the involved species were analyzed, and the decomposition network was mapped out to elaborate the reaction mechanisms. Our results indicated that methanol and formaldehyde were weakly adsorbed, and the other derivatives (CHxOHy, x = 1-3, y = 0-1) were strongly adsorbed and preferred decomposition rather than desorption on Pt3Sn(111). The competitive methanol decomposition started with the initial O-H bond scission followed by successive C-H bond scissions, (i.e., CH3OH → CH3O → CH2O → CHO → CO). The Brønsted-Evans-Polanyi relations and energy barrier decomposition analyses identified the C-H and O-H bond scissions as being more competitive than the C-O bond scission. Microkinetic modeling confirmed that the vast majority of the intermediates and products from methanol decomposition would escape from the Pt3Sn(111) surface at a relatively low temperature, and the coverage of the CO residue decreased with an increase in the temperature and decrease in partial methanol pressure.

Competition between rice (Oryza sativa L.) and (barnyardgrass (Echinochloa crus-galli (L.) P. Beauv.) as affected by methanol foliar application.

PubMed

Rezaeieh, Alireza D; Aminpanah, Hashem; Sadeghi, Seyed M

2015-01-01

Pot experiment was conducted in Iran, to evaluate the effect of methanol on competition between rice (Oryza sativa) and barnyardgrass (Echinochloa crus-galli). The experiment was conducted as a randomized complete block design with a factorial treatment arrangement and three replicates. Factors were two aqueous methanol foliar applications (0, and 14% v/v) and five rice: barnyardgrass ratios (100:0, 75:25, 50:50, 25:6, and 0:100). Replacement series diagrams for aboveground dry weight illustrated that 'Shiroudi' was more competitive than barnyardgrass as averaged across methanol foliar applications. When methanol was not sprayed, the lines for 'Shiroudi' and barnyardgrass intersected at 75:25 rice: barnyardgrass ratio, but when methanol was sprayed at 14% v/v, the lines for 'Shiroudi' and barnyardgrass intersect at the left of the 75:25 rice: barnyardgrass mixture proportion. These indicate that methanol application reduced competitive ability of 'Shiroudi' against barnyardgrass for aboveground biomass accumulation. At the same time, Methanol foliar application significantly reduced the relative crowding coefficient of 'Shiroudi' while simultaneously it significantly increased the relative crowding coefficient of barnyard grass. This indicates that methanol foliar application reduced the competitive ability of 'Shiroudi' against barnyardgrass for shoot biomass accumulation. This experiment illustrated that foliar spray of aqueous methanol can not be recommended for rice under weedy conditions.

Evaluation of the dust and methanol extracts of Garcinia kolae for the control of Callosobruchus maculatus (F.) and Sitophilus zeamais (Mots)

PubMed Central

Ogunleye, R.F.; Adefemi, S.O.

2007-01-01

Insecticidal effects of different doses of the dust and methanol extracts of Garcinia kolae on Callosobruchus maculatus and Sitophilus zeamais were tested. The dust had no significant effect on the two insects; none of them died even at 3 d after treatment. The methanol extracts, however, had rapid lethal effects on both C. maculatus and S. zeamais. The mortality of C. maculatus by the lowest concentration of methanol extracts ranged from 95%~100% whereas in S. zeamais, the mortality ranged from 87.5%~100% and 70%~100% in concentrations of 1 g extract+3 ml methanol and 1 g extract+5 ml methanol, respectively, from 24 to 48 h. The least concentration of 1 g extract+15 ml methanol had no significant lethal effect on Sitophilus zeamais. PMID:18257127

A karyotype comparison between two species of bordered plant bugs (Hemiptera, Heteroptera, Largidae) by conventional chromosome staining, C-banding and rDNA-FISH.

PubMed

Salanitro, Lucila Belén; Massaccesi, Anabella Cecilia; Urbisaglia, Santiago; Bressa, María José; Chirino, Mónica Gabriela

2017-01-01

A cytogenetic characterization, including heterochromatin content, and the analysis of the location of rDNA genes, was performed in Largus fasciatus Blanchard, 1843 and L. rufipennis Laporte, 1832. Mitotic and meiotic analyses revealed the same diploid chromosome number 2n = 12 + X0/XX (male/female). Heterochromatin content, very scarce in both species, revealed C-blocks at both ends of autosomes and X chromosome. The most remarkable cytological feature observed between both species was the different chromosome position of the NORs. This analysis allowed us to use the NORs as a cytological marker because two clusters of rDNA genes are located at one end of one pair of autosomes in L. fasciatus , whereas a single rDNA cluster is located at one terminal region of the X chromosome in L. rufipennis . Taking into account our results and previous data obtained in other heteropteran species, the conventional staining, chromosome bandings, and rDNA-FISH provide important chromosome markers for cytotaxonomy, karyotype evolution, and chromosome structure and organization studies.

Influence of liquid medium on the activity of a low-alpha Fischer-Tropsch catalyst

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

Gormley, R.J.; Zarochak, M.F.; Deffenbaugh, P.W.

1995-12-31

The purpose of this research was to measure activity, selectivity, and the maintenance of these properties in slurry autoclave experiments with a Fischer-Tropsch (FT) catalyst that was used in the {open_quotes}FT II{close_quotes} bubble-column test, conducted at the Alternative Fuels Development Unit (AFDU) at LaPorte, Texas during May 1994. The catalyst contained iron, copper, and potassium and was formulated to produce mainly hydrocarbons in the gasoline range with lesser production of diesel-range products and wax. The probability of chain growth was thus deliberately kept low. Principal goals of the autoclave work have been to find the true activity of this catalystmore » in a stirred tank reactor, unhindered by heat or mass transfer effects, and to obtain a steady conversion and selectivity over the approximately 15 days of each test. Slurry autoclave testing of the catalyst in heavier waxes also allows insight into operation of larger slurry bubble column reactors. The stability of reactor operation in these experiments, particularly at loadings exceeding 20 weight %, suggests the likely stability of operations on a larger scale.« less

Technology development for iron Fischer-Tropsch catalysts

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

O`Brien, R.J.; Raje, A.; Keogh, R.A.

1995-12-31

The objective of this research project is to develop the technology for the production of physically robust iron-based Fischer-Tropsch catalysts that have suitable activity, selectivity and stability to be used in the slurry phase synthesis reactor development. The catalysts that are developed shall be suitable for testing in the Advanced Fuels Development Facility at LaPorte, Texas, to produce either low-or high-alpha product distributions. Previous work by the offeror has produced a catalyst formulation that is 1.5 times as active as the {open_quotes}standard-catalyst{close_quotes} developed by German workers for slurry phase synthesis. In parallel, work will be conducted to design a high-alphamore » iron catalyst this is suitable for slurry phase synthesis. Studies will be conducted to define the chemical phases present at various stages of the pretreatment and synthesis stages and to define the course of these changes. The oxidation/reduction cycles that are anticipated to occur in large, commercial reactors will be studied at the laboratory scale. Catalyst performance will be determined for catalysts synthesized in this program for activity, selectivity and aging characteristics.« less

Methanol exchange dynamics between a temperate cropland soil and the atmosphere

NASA Astrophysics Data System (ADS)

Bachy, A.; Aubinet, M.; Amelynck, C.; Schoon, N.; Bodson, B.; Moureaux, C.; Delaplace, P.; De Ligne, A.; Heinesch, B.

2018-03-01

Soil methanol (CH3OH) exchange is often considered as several orders of magnitude smaller than plant methanol exchange. However, for some ecosystems, it is significant in regard with plant exchange and worth thus better consideration. Our study sought to gain a better understanding of soil exchange. Methanol flux was measured at the ecosystem scale on a bare agricultural soil over two contrasted periods using the disjunct eddy covariance by mass scanning technique. A proton-transfer-reaction mass spectrometer was used for the methanol ambient mixing ratio measurements. Bi-directional exchange dynamics were observed. Methanol emission occurred under dry and warm conditions and correlated best with soil surface temperature, whereas methanol uptake occurred under wet and mild conditions and correlated well with the methanol ambient concentration. After having tested a physical adsorption-desorption model and by confronting our data with the literature, we propose that the exchange was ruled by both a physical adsorption/desorption mechanism and by a methanol source, which still needs to be identified. The soil emission decreased when the vegetation developed. The reasons for the decrease still need to be determined. Overall, the dynamics observed at our site were similar to those reported by other studies for both cropland and forest ecosystems. The mechanism proposed in our work can thus be possibly applied to other sites or ecosystems. In addition, the methanol exchange rate was in the upper range of the exchange rates reported by other soil studies, suggesting that cropland soils are more important methanol exchangers than those in other ecosystems and should therefore be further investigated.

Methanol exposure interferes with morphological cell movements in the Drosophila embryo and causes increased apoptosis in the CNS.

PubMed

Mellerick, Dervla M; Liu, Heather

2004-09-05

Despite the significant contributions of tissue culture and bacterial models to toxicology, whole animal models for developmental neurotoxins are limited in availability and ease of experimentation. Because Drosophila is a well understood model for embryonic development that is highly accessible, we asked whether it could be used to study methanol developmental neurotoxicity. In the presence of 4% methanol, approximately 35% of embryos die and methanol exposure leads to severe CNS defects in about half those embryos, where the longitudinal connectives are dorsally displaced and commissure formation is severely reduced. In addition, a range of morphological defects in other germ layers is seen, and cell movement is adversely affected by methanol exposure. Although we did not find any evidence to suggest that methanol exposure affects the capacity of neuroblasts to divide or induces inappropriate apoptosis in these cells, in the CNS of germ band retracted embryos, the number of apoptotic nuclei is significantly increased in methanol-exposed embryos in comparison to controls, particularly in and adjacent to the ventral midline. Apoptosis contributes significantly to methanol neurotoxicity because embryos lacking the cell death genes grim, hid, and reaper have milder CNS defects resulting from methanol exposure than wild-type embryos. Our data suggest that when neurons and glia are severely adversely affected by methanol exposure, the damaged cells are cleared by apoptosis, leading to embryonic death. Thus, the Drosophila embryo may prove useful in identifying and unraveling mechanistic aspects of developmental neurotoxicity, specifically in relation to methanol toxicity.

Novel crosslinked membranes based on sulfonated poly(ether ether ketone) for direct methanol fuel cells.

PubMed

Zhu, Yuanqin; Zieren, Shelley; Manthiram, Arumugam

2011-07-14

Novel covalently crosslinked membranes based on sulfonated poly(ether ether ketone) and carboxylated polysulfone exhibit much lower methanol crossover and better performance in direct methanol fuel cells at 65 °C in 1 and 2 M methanol solutions compared to Nafion 115 membranes.

(14)C METHANOL INCORPORATION INTO DNA AND SPECIFIC PROTEINS OF ORGANOGENESIS STAGE MOUSE EMBRYOS IN VITRO

EPA Science Inventory

Methanol (MeOH), a widely used industrial solvent and alternative motor fuel, has been shown to be mutagenic and teratogenic. We have demonstrated that methanol is teratogenic in mice in vivo and causes dysmorphogenesis in cultured organogenesis stage mouse embryos. Methanol is ...

40 CFR 721.4880 - Methanol, trichloro-, carbonate (2:1).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Methanol, trichloro-, carbonate (2:1... Substances § 721.4880 Methanol, trichloro-, carbonate (2:1). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as methanol, trichloro-, carbonate (2:1) (CAS...

40 CFR 86.1227-96 - Test procedures; overview.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Methanol-Fueled Heavy-Duty Vehicles § 86.1227-96 Test procedures; overview. (a) The overall test consists... petroleum gas-fueled, and methanol-fueled vehicles) is designed to determine hydrocarbon and/or methanol... operation, which result in hydrocarbon and/or methanol vapor losses. The test procedure is designed to...

40 CFR 721.4880 - Methanol, trichloro-, carbonate (2:1).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Methanol, trichloro-, carbonate (2:1... Substances § 721.4880 Methanol, trichloro-, carbonate (2:1). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as methanol, trichloro-, carbonate (2:1) (CAS...