Research and evaluation of biomass resources/conversion/utilization systems. Biomass allocation model. Volume 1: Test and appendices A & B

NASA Astrophysics Data System (ADS)

Stringer, R. P.; Ahn, Y. K.; Chen, H. T.; Helm, R. W.; Nelson, E. T.; Shields, K. J.

1981-08-01

A biomass allocation model was developed to show the most profitable combination of biomass feedstocks, thermochemical conversion processes, and fuel products to serve the seasonal conditions in a regional market. This optimization model provides a tool for quickly calculating which of a large number of potential biomass missions is the most profitable mission. Other components of the system serve as a convenient storage and retrieval mechanism for biomass marketing and thermochemical conversion processing data. The system can be accessed through the use of a computer terminal, or it could be adapted to a microprocessor. A User's Manual for the system is included. Biomass derived fuels included in the data base are the following: medium Btu gas, low Btu gas, substitute natural gas, ammonia, methanol, electricity, gasoline, and fuel oil.

Thermo-Chemical Conversion of Microwave Activated Biomass Mixtures

NASA Astrophysics Data System (ADS)

Barmina, I.; Kolmickovs, A.; Valdmanis, R.; Vostrikovs, S.; Zake, M.

2018-05-01

Thermo-chemical conversion of microwave activated wheat straw mixtures with wood or peat pellets is studied experimentally with the aim to provide more effective application of wheat straw for heat energy production. Microwave pre-processing of straw pellets is used to provide a partial decomposition of the main constituents of straw and to activate the thermo-chemical conversion of wheat straw mixtures with wood or peat pellets. The experimental study includes complex measurements of the elemental composition of biomass pellets (wheat straw, wood, peat), DTG analysis of their thermal degradation, FTIR analysis of the composition of combustible volatiles entering the combustor, the flame temperature, the heat output of the device and composition of the products by comparing these characteristics for mixtures with unprocessed and mw pre-treated straw pellets. The results of experimental study confirm that mw pre-processing of straw activates the thermal decomposition of mixtures providing enhanced formation of combustible volatiles. This leads to improvement of the combustion conditions in the flame reaction zone, completing thus the combustion of volatiles, increasing the flame temperature, the heat output from the device, the produced heat energy per mass of burned mixture and decreasing at the same time the mass fraction of unburned volatiles in the products.

Thermochemical water decomposition. [hydrogen separation for energy applications

NASA Technical Reports Server (NTRS)

Funk, J. E.

1977-01-01

At present, nearly all of the hydrogen consumed in the world is produced by reacting hydrocarbons with water. As the supply of hydrocarbons diminishes, the problem of producing hydrogen from water alone will become increasingly important. Furthermore, producing hydrogen from water is a means of energy conversion by which thermal energy from a primary source, such as solar or nuclear fusion of fission, can be changed into an easily transportable and ecologically acceptable fuel. The attraction of thermochemical processes is that they offer the potential for converting thermal energy to hydrogen more efficiently than by water electrolysis. A thermochemical hydrogen-production process is one which requires only water as material input and mainly thermal energy, or heat, as an energy input. Attention is given to a definition of process thermal efficiency, the thermodynamics of the overall process, the single-stage process, the two-stage process, multistage processes, the work of separation and a process evaluation.

2011 Biomass Program Platform Peer Review. Thermochemical Conversion

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

Grabowski, Paul E.

This document summarizes the recommendations and evaluations provided by an independent external panel of experts at the 2011 U.S. Department of Energy Biomass Program’s Thermochemical Conversion Platform Review meeting.

Characterisation of agroindustrial solid residues as biofuels and potential application in thermochemical processes.

PubMed

Virmond, Elaine; De Sena, Rennio F; Albrecht, Waldir; Althoff, Christine A; Moreira, Regina F P M; José, Humberto J

2012-10-01

In the present work, selected agroindustrial solid residues from Brazil - biosolids from meat processing wastewater treatment and mixture of sawdust with these biosolids; residues from apple and orange juice industries; sugarcane bagasse; açaí kernels (Euterpe oleracea) and rice husk - were characterised as solid fuels and an evaluation of their properties, including proximate and ultimate composition, energy content, thermal behaviour, composition and fusibility of the ashes was performed. The lower heating value of the biomasses ranged from 14.31 MJkg(-1) to 29.14 MJkg(-1), on a dry and ash free basis (daf), all presenting high volatile matter content, varying between 70.57 wt.% and 85.36 wt.% (daf) what improves the thermochemical conversion of the solids. The fouling and slagging tendency of the ashes was predicted based on the fuel ash composition and on the ash fusibility correlations proposed in the literature, which is important to the project and operation of biomass conversion systems. The potential for application of the Brazilian agroindustrial solid residues studied as alternative energy sources in thermochemical processes has been identified, especially concerning direct combustion for steam generation. Copyright © 2012 Elsevier Ltd. All rights reserved.

Turning manure into biochar through thermochemical conversion has the potential to become an exciting new way to handle waste

USDA-ARS?s Scientific Manuscript database

The livestock sector remains vigilant to address effective manure treatment that also safeguards natural resources. Livestock operations must balance business concerns, efficient energy management and environmental stewardship. Fortunately, thermochemical conversion technologies for converting lives...

Analysis of Efficiency of the Ship Propulsion System with Thermochemical Recuperation of Waste Heat

NASA Astrophysics Data System (ADS)

Cherednichenko, Oleksandr; Serbin, Serhiy

2018-03-01

One of the basic ways to reduce polluting emissions of ship power plants is application of innovative devices for on-board energy generation by means of secondary energy resources. The combined gas turbine and diesel engine plant with thermochemical recuperation of the heat of secondary energy resources has been considered. It is suggested to conduct the study with the help of mathematical modeling methods. The model takes into account basic physical correlations, material and thermal balances, phase equilibrium, and heat and mass transfer processes. The paper provides the results of mathematical modeling of the processes in a gas turbine and diesel engine power plant with thermochemical recuperation of the gas turbine exhaust gas heat by converting a hydrocarbon fuel. In such a plant, it is possible to reduce the specific fuel consumption of the diesel engine by 20%. The waste heat potential in a gas turbine can provide efficient hydrocarbon fuel conversion at the ratio of powers of the diesel and gas turbine engines being up to 6. When the diesel engine and gas turbine operate simultaneously with the use of the LNG vapor conversion products, the efficiency coefficient of the plant increases by 4-5%.

Application of Metal Catalysts for High Selectivity of Glycerol Conversion to Alcohols

DOT National Transportation Integrated Search

2010-11-01

The objective of this project is to determine the applicability of metal-based catalysts and optimize the process conditions for thermochemically producing primary alcohols. Metal catalysts were evaluated for their selectivities for producing alcohol...

Development of a practical photochemical energy storage system. Quarterly report. [Interconversion between norbornadiene and quadricyclene for thermochemical heat storage

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

Hautala, R.R.; Kutal, C.R.

1977-06-15

Research on polymeric organic sensitizers and polymeric inorganic sensitizers for the conversion of norbornadine to quadricyclene and catalysts for the conversion of quadricyclene to norbornadine is described. The interconversion of norbornadine and quadricyclene is studied for its possible use for thermochemical solar energy storage. (WHK)

Climate Impact and Economic Feasibility of Solar Thermochemical Jet Fuel Production.

PubMed

Falter, Christoph; Batteiger, Valentin; Sizmann, Andreas

2016-01-05

Solar thermochemistry presents a promising option for the efficient conversion of H2O and CO2 into liquid hydrocarbon fuels using concentrated solar energy. To explore the potential of this fuel production pathway, the climate impact and economic performance are analyzed. Key drivers for the economic and ecological performance are thermochemical energy conversion efficiency, the level of solar irradiation, operation and maintenance, and the initial investment in the fuel production plant. For the baseline case of a solar tower concentrator with CO2 capture from air, jet fuel production costs of 2.23 €/L and life cycle greenhouse gas (LC GHG) emissions of 0.49 kgCO2-equiv/L are estimated. Capturing CO2 from a natural gas combined cycle power plant instead of the air reduces the production costs by 15% but leads to LC GHG emissions higher than that of conventional jet fuel. Favorable assumptions for all involved process steps (30% thermochemical energy conversion efficiency, 3000 kWh/(m(2) a) solar irradiation, low CO2 and heliostat costs) result in jet fuel production costs of 1.28 €/L at LC GHG emissions close to zero. Even lower production costs may be achieved if the commercial value of oxygen as a byproduct is considered.

Thermogravimetric characterization of irrigated bermudagrass as a combustion feedstock

USDA-ARS?s Scientific Manuscript database

The bioenergy production industry can benefit from a greater understanding of potential differences among the various feedstock materials and production influences on thermochemical conversion processes such as combustion. The thermal degradation of biomass during combustion can quickly be assessed ...

Effects of hot-water extraction on the thermochemical conversion of shrub willow via fast pyrolysis

USDA-ARS?s Scientific Manuscript database

Hot-water extraction (TM) (HWE) is a pretreatment technology designed to facilitate the subsequent hydrolysis of cellulose by removing the majority of the hemicellulose and ash content from the solid biomass. The HWE process generates salable sugars and other products as part of the process. The bio...

Dairy manure biochar as a phosphorus fertilizer

USDA-ARS?s Scientific Manuscript database

Future manure management practices will need to remove large amounts of organic waste as well as harness energy to generate value-added products. Manures can be processed using thermochemical conversion technologies to generate a solid product called biochar. Dairy manure biochars contain sufficient...

Selected global examples of cellulosic cropping system trends

USDA-ARS?s Scientific Manuscript database

Plant biomass has been recognized globally as an important link to a sustainable energy future because it can be grown universally and converted into liquid transportation fuels or other material through biochemical, thermochemical, or catalytic conversion processes. A key challenge is that cellulos...

Research and evaluation of biomass resources/conversion/utilization systems (market/experimental analysis for development of a data base for a fuels from biomass model. Volume I. Biomass allocation model. Technical progress report for the period ending September 30, 1980

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

Ahn, Y.K.; Chen, H.T.; Helm, R.W.

1980-01-01

A biomass allocation model has been developed to show the most profitable combination of biomass feedstocks thermochemical conversion processes, and fuel products to serve the seasonal conditions in a regional market. This optimization model provides a tool for quickly calculating the most profitable biomass missions from a large number of potential biomass missions. Other components of the system serve as a convenient storage and retrieval mechanism for biomass marketing and thermochemical conversion processing data. The system can be accessed through the use of a computer terminal, or it could be adapted to a portable micro-processor. A User's Manual for themore » system has been included in Appendix A of the report. The validity of any biomass allocation solution provided by the allocation model is dependent on the accuracy of the data base. The initial data base was constructed from values obtained from the literature, and, consequently, as more current thermochemical conversion processing and manufacturing costs and efficiencies become available, the data base should be revised. Biomass derived fuels included in the data base are the following: medium Btu gas low Btu gas, substitute natural gas, ammonia, methanol, electricity, gasoline, and fuel oil. The market sectors served by the fuels include: residential, electric utility, chemical (industrial), and transportation. Regional/seasonal costs and availabilities and heating values for 61 woody and non-woody biomass species are included. The study has included four regions in the United States which were selected because there was both an availability of biomass and a commercial demand for the derived fuels: Region I: NY, WV, PA; Region II: GA, AL, MS; Region III: IN, IL, IA; and Region IV: OR, WA.« less

Continuous thermochemical conversion process to produce oil from swine manure

USGS Publications Warehouse

Ocfemia, K.; Zhang, Y.; Funk, T.; Christianson, L.; Chen, S.

2004-01-01

Thermochemical conversion (TCC) of livestock manure is a novel technology that has shown very promising results in treating waste and producing oil. A batch TCC system that was previously developed successfully converted 70% of swine manure volatile solids to oil and reduced manure chemical oxygen demand by ??? 75%. The necessary retention time to achieve an oil product was largely dependent on the operating temperature. The highest oil production efficiency was 80% of the volatile solids (or 70 wt % of the total solids). The average carbon and hydrogen contents were ??? 72 and 9%, respectively. The heating values for 80% of the oil products ranged from 32,000 to 36,700 kJ/kg. This is an abstract of a paper presented at the AWMA 97th Annual Conference and Exhibition (Indianapolis, IN 6/22-25/2004).

Sustainable conversion of coffee and other crop wastes to biofuels and bioproducts using combined biochemical and thermochemical processes in a multi-stage biorefinery concept

USDA-ARS?s Scientific Manuscript database

The environmental impact of agricultural waste from processing of food and feed crops is an increasing concern worldwide. Concerted efforts are underway to develop sustainable practices for the disposal of residues from processing of such crops as coffee, sugarcane, or corn. Coffee is crucial to the...

Laser beam heat method reported

NASA Astrophysics Data System (ADS)

Tsuchiya, Hachiro; Goto, Hidekazu

1988-07-01

An outline of research involving the processing method utilizing laser-induced thermochemistry was presented, with the CO2 laser processing of ceramics in CF4 gas used as a practical processing example. It has become clear that it will be possible to conduct laser proccessing of ceramics with high efficiency and high precision by utilizing the thermochemical processes, but it is not believed that the present method is the best one and it is not clear that it can be applied to commercial processing. It is thought that the processing characteristics of this method will be greatly changed by the combination of the atmospheric gas and the material, and it is important to conduct tests on various combinations. However, it is believed that the improvement and development will become possible by theoretically confirming the basic process of the processing, especially of the the thermochemical process between the solid surface and the atmospheric gas molecule. Actually, it is believed that the thermochemical process on the solid surface is quite complicated. For example, it was confirmed that when thermochemical processing the Si monocrystal in the CF4 gas, the processing speed would change by at least 10 times through changing the gas pressure and the mixing O2 gas density. However, conversely speaking, it is believed that the fact that this method is complicated, with many unexplained points and room for research, conceals the possibility of its being applied to various fields, and also, in this sense, the quantitative confirmation of its basic process in an important problem to be solved in the future.

Response of maize germination and growth to HTC filtrate type and concentration

USDA-ARS?s Scientific Manuscript database

Hydrothermal carbonization (HTC) is a thermochemical treatment process that allows for the conversion of biomass slurries into value added products. The option of using HTC filtrate as a liquid based fertilizer for agricultural crop production was evaluated through germination and plant growth studi...

THERMOCHEMICAL CONVERSION OF FERMENTATION-DERIVED OXYGENATES TO FUELS

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

Ramasamy, Karthikeyan K.; Wang, Yong

2013-06-01

At present ethanol generated from renewable resources through fermentation process is the dominant biofuel. But ethanol suffers from undesirable fuel properties such as low energy density and high water solubility. The production capacity of fermentation derived oxygenates are projected to rise in near future beyond the current needs. The conversion of oxygenates to hydrocarbon compounds that are similar to gasoline, diesel and jet fuel is considered as one of the viable option. In this chapter the thermo catalytic conversion of oxygenates generated through fermentation to fuel range hydrocarbons will be discussed.

Pelletizing properties of torrefied spruce

Treesearch

Wolfgang Stelte; Craig Clemons; Jens K. Holm; Anand R. Sanadi; Jesper Ahrenfeldt; Lei Shang; Ulrik B. Henriksen

2011-01-01

Torrefaction is a thermo-chemical conversion process improving the handling, storage and combustion properties of wood. To save storage space and transportation costs, it can be compressed into fuel pellets of high physical and energetic density. The resulting pellets are relatively resistant to moisture uptake, microbiological decay and easy to comminute into small...

Depolymerization of lignin via co-pyrolysis with 1,4-butanediol in a microwave reactor

USDA-ARS?s Scientific Manuscript database

The production of valuable compounds from low cost but abundant residual lignin has proven to be challenging. The lack of effective biochemical lignin depolymerization processes has led many to focus on thermochemical conversion methods. Bench scale microwave pyrolysis of lignin has been performed...

Impact of two hydrothermal carbonization filtrates on soil greenhouse production

USDA-ARS?s Scientific Manuscript database

Hydrothermal carbonization (HTC) is a thermochemical treatment process that allows for the conversion of wet biomass slurries to new liquid and solid products. A majority of the research to date has focused on the solid HTC product (hydrochar). Less attention has been paid to the utilization of the ...

Experimental aspects of the thermochemical conversion of solar energy - Decarbonation of CaCO3

NASA Astrophysics Data System (ADS)

Flamant, G.; Hernandez, D.; Bonet, C.; Traverse, J.-P.

1980-01-01

The feasibility of thermochemical conversion of concentrated solar energy is investigated. Consideration is given to heterogeneous systems in the range 500-1500 C. A reaction volume is on a laboratory scale about 30 cu cm. An experimental set-up selected is a fluid bed and a rotary kiln. An endothermal reaction, namely, decarbonation of CaCO3, is selected as a possible application for solar power plants.

Development of efficient, integrated cellulosic biorefineries : LDRD final report.

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

Teh, Kwee-Yan; Hecht, Ethan S.; Shaddix, Christopher R.

2010-09-01

Cellulosic ethanol, generated from lignocellulosic biomass sources such as grasses and trees, is a promising alternative to conventional starch- and sugar-based ethanol production in terms of potential production quantities, CO{sub 2} impact, and economic competitiveness. In addition, cellulosic ethanol can be generated (at least in principle) without competing with food production. However, approximately 1/3 of the lignocellulosic biomass material (including all of the lignin) cannot be converted to ethanol through biochemical means and must be extracted at some point in the biochemical process. In this project we gathered basic information on the prospects for utilizing this lignin residue material inmore » thermochemical conversion processes to improve the overall energy efficiency or liquid fuel production capacity of cellulosic biorefineries. Two existing pretreatment approaches, soaking in aqueous ammonia (SAA) and the Arkenol (strong sulfuric acid) process, were implemented at Sandia and used to generated suitable quantities of residue material from corn stover and eucalyptus feedstocks for subsequent thermochemical research. A third, novel technique, using ionic liquids (IL) was investigated by Sandia researchers at the Joint Bioenergy Institute (JBEI), but was not successful in isolating sufficient lignin residue. Additional residue material for thermochemical research was supplied from the dilute-acid simultaneous saccharification/fermentation (SSF) pilot-scale process at the National Renewable Energy Laboratory (NREL). The high-temperature volatiles yields of the different residues were measured, as were the char combustion reactivities. The residue chars showed slightly lower reactivity than raw biomass char, except for the SSF residue, which had substantially lower reactivity. Exergy analysis was applied to the NREL standard process design model for thermochemical ethanol production and from a prototypical dedicated biochemical process, with process data supplied by a recent report from the National Research Council (NRC). The thermochemical system analysis revealed that most of the system inefficiency is associated with the gasification process and subsequent tar reforming step. For the biochemical process, the steam generation from residue combustion, providing the requisite heating for the conventional pretreatment and alcohol distillation processes, was shown to dominate the exergy loss. An overall energy balance with different potential distillation energy requirements shows that as much as 30% of the biomass energy content may be available in the future as a feedstock for thermochemical production of liquid fuels.« less

Influence of feedstock particle size on lignocellulose conversion--a review.

PubMed

Vidal, Bernardo C; Dien, Bruce S; Ting, K C; Singh, Vijay

2011-08-01

Feedstock particle sizing can impact the economics of cellulosic ethanol commercialization through its effects on conversion yield and energy cost. Past studies demonstrated that particle size influences biomass enzyme digestibility to a limited extent. Physical size reduction was able to increase conversion rates to maximum of ≈ 50%, whereas chemical modification achieved conversions of >70% regardless of biomass particle size. This suggests that (1) mechanical pretreatment by itself is insufficient to attain economically feasible biomass conversion, and, therefore, (2) necessary particle sizing needs to be determined in the context of thermochemical pretreatment employed for lignocellulose conversion. Studies of thermochemical pretreatments that have taken into account particle size as a factor have exhibited a wide range of maximal sizes (i.e., particle sizes below which no increase in pretreatment effectiveness, measured in terms of the enzymatic conversion resulting from the pretreatment, were observed) from <0.15 to 50 mm. Maximal sizes as defined above were dependent on the pretreatment employed, with maximal size range decreasing as follows: steam explosion > liquid hot water > dilute acid and base pretreatments. Maximal sizes also appeared dependent on feedstock, with herbaceous or grassy biomass exhibiting lower maximal size range (<3 mm) than woody biomass (>3 mm). Such trends, considered alongside the intensive energy requirement of size reduction processes, warrant a more systematic study of particle size effects across different pretreatment technologies and feedstock, as a requisite for optimizing the feedstock supply system.

NREL's Thermochemical Conversion Facility Video Text Version | Bioenergy |

Science.gov Websites

steady-state. We use a tandem fast pyrolysis reactor and Davison recirculating reactor system to study ex be continually added and withdrawn so we can study catalyst activity and product composition at catalyst. Here we can study the impact of catalyst formulation and processing conditions on bio-oil

Green technology for conversion of renewable hydrocarbon based on plasma-catalytic approach

NASA Astrophysics Data System (ADS)

Fedirchyk, Igor; Nedybaliuk, Oleg; Chernyak, Valeriy; Demchina, Valentina

2016-09-01

The ability to convert renewable biomass into fuels and chemicals is one of the most important steps on our path to green technology and sustainable development. However, the complex composition of biomass poses a major problem for established conversion technologies. The high temperature of thermochemical biomass conversion often leads to the appearance of undesirable byproducts and waste. The catalytic conversion has reduced yield and feedstock range. Plasma-catalytic reforming technology opens a new path for biomass conversion by replacing feedstock-specific catalysts with free radicals generated in the plasma. We studied the plasma-catalytic conversion of several renewable hydrocarbons using the air plasma created by rotating gliding discharge. We found that plasma-catalytic hydrocarbon conversion can be conducted at significantly lower temperatures (500 K) than during the thermochemical ( 1000 K) and catalytic (800 K) conversion. By using gas chromatography, we determined conversion products and found that conversion efficiency of plasma-catalytic conversion reaches over 85%. We used obtained data to determine the energy yield of hydrogen in case of plasma-catalytic reforming of ethanol and compared it with other plasma-based hydrogen-generating systems.

Co-generated fast pyrolysis biochar mitigates green-house gas emissions and increases carbon sequestration in temperate soils

USDA-ARS?s Scientific Manuscript database

Biochar (BC) is a product of thermochemical conversion of biomass via pyrolysis, together with gas (syngas), liquid (bio-oil), and heat. Fast pyrolysis is a promising process for bio-oil generation, which leaves 10-30% of the original biomass as char. When applied to soils, BC may increase soil C s...

A Commercialization Roadmap for Carbon-Negative Energy Systems

NASA Astrophysics Data System (ADS)

Sanchez, D.

2016-12-01

The Intergovernmental Panel on Climate Change (IPCC) envisages the need for large-scale deployment of net-negative CO2 emissions technologies by mid-century to meet stringent climate mitigation goals and yield a net drawdown of atmospheric carbon. Yet there are few commercial deployments of BECCS outside of niche markets, creating uncertainty about commercialization pathways and sustainability impacts at scale. This uncertainty is exacerbated by the absence of a strong policy framework, such as high carbon prices and research coordination. Here, we propose a strategy for the potential commercial deployment of BECCS. This roadmap proceeds via three steps: 1) via capture and utilization of biogenic CO2 from existing bioenergy facilities, notably ethanol fermentation, 2) via thermochemical co-conversion of biomass and fossil fuels, particularly coal, and 3) via dedicated, large-scale BECCS. Although biochemical conversion is a proven first market for BECCS, this trajectory alone is unlikely to drive commercialization of BECCS at the gigatonne scale. In contrast to biochemical conversion, thermochemical conversion of coal and biomass enables large-scale production of fuels and electricity with a wide range of carbon intensities, process efficiencies and process scales. Aside from systems integration, primarily technical barriers are involved in large-scale biomass logistics, gasification and gas cleaning. Key uncertainties around large-scale BECCS deployment are not limited to commercialization pathways; rather, they include physical constraints on biomass cultivation or CO2 storage, as well as social barriers, including public acceptance of new technologies and conceptions of renewable and fossil energy, which co-conversion systems confound. Despite sustainability risks, this commercialization strategy presents a pathway where energy suppliers, manufacturers and governments could transition from laggards to leaders in climate change mitigation efforts.

Thermochemical hydrolysis of macroalgae Ulva for biorefinery: Taguchi robust design method

PubMed Central

Jiang, Rui; Linzon, Yoav; Vitkin, Edward; Yakhini, Zohar; Chudnovsky, Alexandra; Golberg, Alexander

2016-01-01

Understanding the impact of all process parameters on the efficiency of biomass hydrolysis and on the final yield of products is critical to biorefinery design. Using Taguchi orthogonal arrays experimental design and Partial Least Square Regression, we investigated the impact of change and the comparative significance of thermochemical process temperature, treatment time, %Acid and %Solid load on carbohydrates release from green macroalgae from Ulva genus, a promising biorefinery feedstock. The average density of hydrolysate was determined using a new microelectromechanical optical resonator mass sensor. In addition, using Flux Balance Analysis techniques, we compared the potential fermentation yields of these hydrolysate products using metabolic models of Escherichia coli, Saccharomyces cerevisiae wild type, Saccharomyces cerevisiae RN1016 with xylose isomerase and Clostridium acetobutylicum. We found that %Acid plays the most significant role and treatment time the least significant role in affecting the monosaccharaides released from Ulva biomass. We also found that within the tested range of parameters, hydrolysis with 121 °C, 30 min 2% Acid, 15% Solids could lead to the highest yields of conversion: 54.134–57.500 gr ethanol kg−1 Ulva dry weight by S. cerevisiae RN1016 with xylose isomerase. Our results support optimized marine algae utilization process design and will enable smart energy harvesting by thermochemical hydrolysis. PMID:27291594

Thermochemical hydrolysis of macroalgae Ulva for biorefinery: Taguchi robust design method

NASA Astrophysics Data System (ADS)

Jiang, Rui; Linzon, Yoav; Vitkin, Edward; Yakhini, Zohar; Chudnovsky, Alexandra; Golberg, Alexander

2016-06-01

Understanding the impact of all process parameters on the efficiency of biomass hydrolysis and on the final yield of products is critical to biorefinery design. Using Taguchi orthogonal arrays experimental design and Partial Least Square Regression, we investigated the impact of change and the comparative significance of thermochemical process temperature, treatment time, %Acid and %Solid load on carbohydrates release from green macroalgae from Ulva genus, a promising biorefinery feedstock. The average density of hydrolysate was determined using a new microelectromechanical optical resonator mass sensor. In addition, using Flux Balance Analysis techniques, we compared the potential fermentation yields of these hydrolysate products using metabolic models of Escherichia coli, Saccharomyces cerevisiae wild type, Saccharomyces cerevisiae RN1016 with xylose isomerase and Clostridium acetobutylicum. We found that %Acid plays the most significant role and treatment time the least significant role in affecting the monosaccharaides released from Ulva biomass. We also found that within the tested range of parameters, hydrolysis with 121 °C, 30 min 2% Acid, 15% Solids could lead to the highest yields of conversion: 54.134-57.500 gr ethanol kg-1 Ulva dry weight by S. cerevisiae RN1016 with xylose isomerase. Our results support optimized marine algae utilization process design and will enable smart energy harvesting by thermochemical hydrolysis.

Effect of various types of thermochemical processing of sewage sludges on phosphorus speciation, solubility, and fertilization performance.

PubMed

Steckenmesser, Daniel; Vogel, Christian; Adam, Christian; Steffens, Diedrich

2017-04-01

Sewage sludge has one of the highest phosphorus (P) recovery potentials of all waste materials. Therefore, P-recycling from sewage sludge could contribute to closing the P-cycle. Recently, various thermal processes for P-recovery have been developed, but there is still a demand for information on the effect of different process parameters (e.g. additives and temperature) on P-speciation and especially on the fertilization performance. In the present study, two common methods (low-temperature conversion at 400-500°C and thermochemical treatment at 950°C) were investigated and combined to produce highly bioavailable P-fertilizers from two different types of sewage sludge based on chemical phosphorus precipitation (Chem-P) and enhanced biological phosphorus removal (Bio-P). The results of P-fractionation, X-ray diffraction analysis, and pot experiments with maize showed that Bio-P sludges attain high P-plant-availability after treatment at low temperatures (400°C). In contrast, Chem-P sludges can adequately be treated at higher temperatures under reductive conditions with sodium additives to form highly bioavailable calcium-sodium-phosphate. Additionally, also highly heavy-metal contaminated sludges can be thermochemically treated at high temperatures to achieve the legal requirements for fertilizers. Copyright © 2017 Elsevier Ltd. All rights reserved.

Comparative studies on thermochemical characterization of corn stover pretreated by white-rot and brown-rot fungi.

PubMed

Zeng, Yelin; Yang, Xuewei; Yu, Hongbo; Zhang, Xiaoyu; Ma, Fuying

2011-09-28

The effects of white-rot and brown-rot fungal pretreatment on the chemical composition and thermochemical conversion of corn stover were investigated. Fungus-pretreated corn stover was analyzed by Fourier transform infrared spectroscopy and X-ray diffraction analysis to characterize the changes in chemical composition. Differences in thermochemical conversion of corn stover after fungal pretreatment were investigated using thermogravimetric and pyrolysis analysis. The results indicated that the white-rot fungus Irpex lacteus CD2 has great lignin-degrading ability, whereas the brown-rot fungus Fomitopsis sp. IMER2 preferentially degrades the amorphous regions of the cellulose. The biopretreatment favors thermal decomposition of corn stover. The weight loss of IMER2-treated acid detergent fiber became greater, and the oil yield increased from 32.7 to 50.8%. After CD2 biopretreatment, 58% weight loss of acid detergent lignin was achieved and the oil yield increased from 16.8 to 26.8%.

Thermochemical Wastewater Valorization via Enhanced Microbial Toxicity Tolerance

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

Beckham, Gregg T; Thelhawadigedara, Lahiru Niroshan Jayakody; Johnson, Christopher W

Thermochemical (TC) biomass conversion processes such as pyrolysis and liquefaction generate considerable amounts of wastewater, which often contains highly toxic compounds that are incredibly challenging to convert via standard wastewater treatment approaches such as anaerobic digestion. These streams represent a cost for TC biorefineries, and a potential valorization opportunity, if effective conversion methods are developed. The primary challenge hindering microbial conversion of TC wastewater is toxicity. In this study, we employ a robust bacterium, Pseudomonas putida, with TC wastewater streams to demonstrate that aldehydes are the most inhibitory compounds in these streams. Proteomics, transcriptomics, and fluorescence-based immunoassays of P. putidamore » grown in a representative wastewater stream indicate that stress results from protein damage, which we hypothesize is a primary toxicity mechanism. Constitutive overexpression of the chaperone genes, groEL, groES, and clpB, in a genome-reduced P. putida strain improves the tolerance towards multiple TC wastewater samples up to 200-fold. Moreover, the concentration ranges of TC wastewater are industrially relevant for further bioprocess development for all wastewater streams examined here, representing different TC process configurations. Furthermore, we demonstrate proof-of-concept polyhydroxyalkanoate production from the usable carbon in an exemplary TC wastewater stream. Overall, this study demonstrates that protein quality control machinery and repair mechanisms can enable substantial gains in microbial tolerance to highly toxic substrates, including heterogeneous waste streams. When coupled to other metabolic engineering advances such as expanded substrate utilization and enhanced product accumulation, this study generally enables new strategies for biological conversion of highly-toxic, organic-rich wastewater via engineered aerobic monocultures or designer consortia.« less

Thermal decomposition of sewage sludge under N2, CO2 and air: Gas characterization and kinetic analysis.

PubMed

Hernández, Ana Belén; Okonta, Felix; Freeman, Ntuli

2017-07-01

Thermochemical valorisation processes that allow energy to be recovered from sewage sludge, such as pyrolysis and gasification, have demonstrated great potential as convenient alternatives to conventional sewage sludge disposal technologies. Moreover, these processes may benefit from CO 2 recycling. Today, the scaling up of these technologies requires an advanced knowledge of the reactivity of sewage sludge and the characteristics of the products, specific to the thermochemical process. In this study the behaviour of sewage sludge during thermochemical conversion, under different atmospheres (N 2 , CO 2 and air), was studied, using TGA-FTIR, in order to understand the effects of different atmospheric gases on the kinetics of degradation and on the gaseous products. The different steps observed during the solid degradation were related with the production of different gaseous compounds. A higher oxidative degree of the atmosphere surrounding the sample resulted in higher reaction rates and a shift of the degradation mechanisms to lower temperatures, especially for the mechanisms taking place at temperatures above 400 °C. Finally, a multiple first-order reaction model was proposed to compare the kinetic parameters obtained under different atmospheres. Overall, the highest activation energies were obtained for combustion. This work proves that CO 2 , an intermediate oxidative atmosphere between N 2 and air, results in an intermediate behaviour (intermediate peaks in the derivative thermogravimetric curves and intermediate activation energies) during the thermochemical decomposition of sewage sludge. Overall, it can be concluded that the kinetics of these different processes require a different approach for their scaling up and specific consideration of their characteristic reaction temperatures and rates should be evaluated. Copyright © 2017 Elsevier Ltd. All rights reserved.

Revisiting the BaO2/BaO redox cycle for solar thermochemical energy storage.

PubMed

Carrillo, A J; Sastre, D; Serrano, D P; Pizarro, P; Coronado, J M

2016-03-21

The barium peroxide-based redox cycle was proposed in the late 1970s as a thermochemical energy storage system. Since then, very little attention has been paid to such redox couples. In this paper, we have revisited the use of reduction-oxidation reactions of the BaO2/BaO system for thermochemical heat storage at high temperatures. Using thermogravimetric analysis, reduction and oxidation reactions were studied in order to find the main limitations associated with each process. Furthermore, the system was evaluated through several charge-discharge stages in order to analyse its possible degradation after repeated cycling. Through differential scanning calorimetry the heat stored and released were also determined. Oxidation reaction, which was found to be slower than reduction, was studied in more detail using isothermal tests. It was observed that the rate-controlling step of BaO oxidation follows zero-order kinetics, although at high temperatures a deviation from Arrhenius behaviour was observed probably due to hindrances to anionic oxygen diffusion caused by the formation of an external layer of BaO2. This redox couple was able to withstand several redox cycles without deactivation, showing reaction conversions close to 100% provided that impurities are previously eliminated through thermal pre-treatment, demonstrating the feasibility of this system for solar thermochemical heat storage.

Noncatalytic transformation of the crude lipid of ChlorellaI vulgaris into fatty acid methyl ester (FAME) with charcoal via a thermo-chemical process.

PubMed

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

2013-02-01

The noncatalytic transformation of the crude lipid of Chlorella vulgaris (C. vulgaris) into fatty acid methyl ester (FAME) via a thermo-chemical process was mainly investigated in this work. The crude lipid of C. vulgaris was recovered by means of solvent extraction from C. vulgaris cultivated in a raceway pond. The conventional catalyzed transesterification of crude lipid of C. vulgaris is notably inhibited by the impurities contained in the crude lipid of C. vulgaris. These impurities are inevitably derived from the solvent extraction process for C. vulgaris. However, this work presents the noncatalytic transesterification of microalgal lipid into FAME, which could be an alternative option. For example, the noncatalytic transformation of microalgal lipid into FAME provides evidence that the esterification of free fatty acids (FFAs) and the transesterification of triglycerides can be combined into a single step less susceptible to the impurities and with a high conversion efficiency (∼97%). Copyright © 2012 Elsevier Ltd. All rights reserved.

A pyrolysis study for the thermal and kinetic characteristics of an agricultural waste with two different plastic wastes.

PubMed

Çepelioğullar, Özge; Pütün, Ayşe E

2014-10-01

In this study, thermochemical conversion of plastic wastes (PET and PVC) together with an agricultural waste (hazelnut shell) was investigated. In order to determine the thermal and kinetic behaviours, pyrolysis experiments were carried out from room temperature to 800 °C, with a heating rate of 10 °C min(-1) in the presence of a N2 atmosphere in a thermogravimetric analyzer. With the obtained thermogravimetric data, an appropriate temperature was specified for the pyrolysis of biomass-plastic wastes in a fixed-bed reactor. At the second step, pyrolysis experiments were carried out at the same conditions with the thermogravimetric analyzer, except the final temperature which was up to 500 °C in this case. After pyrolysis experiments, pyrolysis yields were calculated and characterization studies for bio-oil were investigated. Experimental results showed that co-pyrolysis has an important role in the determination of the pyrolysis mechanism and the process conditions while designing/implementing a thermochemical conversion method where biomass-plastic materials were preferred as raw materials. © The Author(s) 2014.

Thermochemical Users Facility | Bioenergy | NREL

Science.gov Websites

collaborate on research and development efforts or to use our equipment to test their materials and processes NREL's thermochemical process integration, scale-up, and piloting research. Schematic diagram of NRELs about NREL's thermochemical process integration, scale-up, and piloting research. Thermochemical

Development of life cycle water footprints for the production of fuels and chemicals from algae biomass.

PubMed

Nogueira Junior, Edson; Kumar, Mayank; Pankratz, Stan; Oyedun, Adetoyese Olajire; Kumar, Amit

2018-09-01

This study develops life cycle water footprints for the production of fuels and chemicals via thermochemical conversion of algae biomass. This study is based on two methods of feedstock production - ponds and photobioreactors (PBRs) - and four conversion pathways - fast pyrolysis, hydrothermal liquefaction (HTL), conventional gasification, and hydrothermal gasification (HTG). The results show the high fresh water requirement for algae production and the necessity to recycle harvested water or use alternative water sources. To produce 1 kg of algae through ponds, 1564 L of water are required. When PBRs are used, only 372 L water are required; however, the energy requirements for PBRs are about 30 times higher than for ponds. From a final product perspective, the pathway based on the gasification of algae biomass was the thermochemical conversion method that required the highest amount of water per MJ produced (mainly due to its low hydrogen yield), followed by fast pyrolysis and HTL. On the other hand, HTG has the lowest water footprint, mainly because the large amount of electricity generated as part of the process compensates for the electricity used by the system. Performance in all pathways can be improved through recycling channels. Copyright © 2018 Elsevier Ltd. All rights reserved.

Thermochemical energy storage: Proceedings from the International Seminar on hermochemical Energy Storage

NASA Astrophysics Data System (ADS)

Wettermark, G.

1980-10-01

Energy storage problems are explored. Tomorrow's energy sources will provide a continuous flow of energy. Matching supply and demand will necessitate a wide range of storage capabilities. For storing heat thermochemical and economic solutions may take advantage of the various options inherent in this kind of storage, namely heat pumping, transport of heat and direct conversion to other desired forms of energy such as electricity and mechanical work. There is a need to regularly summarize the knowledge and research in the field of thermochemical energy storage in different parts of the world.

Energy Conversion and Storage Program

NASA Astrophysics Data System (ADS)

Cairns, E. J.

1993-06-01

This report is the 1992 annual progress report for the Energy Conversion and Storage Program, a part of the Energy and Environment Division of the Lawrence Berkeley Laboratory. Work described falls into three broad areas: electrochemistry; chemical applications; and materials applications. The Energy Conversion and Storage Program applies principles of chemistry and materials science to solve problems in several areas: (1) production of new synthetic fuels, (2) development of high-performance rechargeable batteries and fuel cells, (3) development of advanced thermochemical processes for energy conversion, (4) characterization of complex chemical processes and chemical species, and (5) study and application of novel materials for energy conversion and transmission. Projects focus on transport-process principles, chemical kinetics, thermodynamics, separation processes, organic and physical chemistry, novel materials, and advanced methods of analysis. Electrochemistry research aims to develop advanced power systems for electric vehicle and stationary energy storage applications. Chemical applications research includes topics such as separations, catalysis, fuels, and chemical analyses. Included in this program area are projects to develop improved, energy-efficient methods for processing product and waste streams from synfuel plants, coal gasifiers, and biomass conversion processes. Materials applications research includes evaluation of the properties of advanced materials, as well as development of novel preparation techniques. For example, techniques such as sputtering, laser ablation, and poised laser deposition are being used to produce high-temperature superconducting films.

An evaluation of negative-emission transportation-energy systems for the US

NASA Astrophysics Data System (ADS)

Larson, E. D.; Meerman, J. C.

2017-12-01

We present technical, economic, and carbon footprint evaluations of alternative technological pathways for negative emissions transportation energy from sustainably-sourced lignocellulosic biomass in the U.S. We combine the understanding of alternative technological pathways with spatially-resolved projections of the sustainable supply of lignocellulosic biomass and with future demands for transportation services to provide insights on the extent to which biomass-based energy might be able to help meet mid-century U.S. transportation energy needs and carbon mitigation targets. Biomass conversion routes included in our evaluations are biochemical, biocatalytic, thermocatalytic hydropyrolysis, and thermochemical gasification/synthesis to produce liquid fuels fungible with petroleum-derived fuels, and thermochemical conversion to hydrogen (for fuel cell vehicles) or electricity (for battery electric vehicles). Lifecycle net negative emissions are achieved for each system via soil carbon buildup during biomass production and/or capture of CO2 at the conversion facility and underground storage. Co-processing of some fossil fuel is considered in some cases to improve economics. For self-consistency in the analysis across systems, a common set of technical, economic and carbon footprint input parameters are adopted. Capital cost estimates are harmonized by taking into account scale of facilities, level of engineering details available in generating a cost estimate, and the technology readiness level (TRL) of components and the process as a whole. Implications for economics of future commercial plants are investigated, considering alternative prospective reductions in capital and operating costs (via "learning by doing") and alternative carbon mitigation policies.

Independent Assessment of Technology Characterizations to Support the Biomass Program Annual State-of-Technology Assessments

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

Yeh, B.

2011-03-01

This report discusses an investigation that addressed two thermochemical conversion pathways for the production of liquid fuels and addressed the steps to the process, the technology providers, a method for determining the state of technology and a tool to continuously assess the state of technology. This report summarizes the findings of the investigation as well as recommendations for improvements for future studies.

Renewable energy from corn residues by thermochemical conversion

NASA Astrophysics Data System (ADS)

Yu, Fei

Declining fossil oil reserve, skyrocket price, unsecured supplies, and environment pollution are among the many energy problems we are facing today. It is our conviction that renewable energy is a solution to these problems. The long term goal of the proposed research is to develop commercially practical technologies to produce energy from renewable resources. The overall objective of my research is to study and develop thermochemical processes for converting bulky and low-energy-density biomass materials into bio-fuels and value-added bio-products. The rationale for the proposed research is that, once such processes are developed, processing facility can be set up on or near biomass product sites, reducing the costs associated with transport of bulky biomass which is a key technical barrier to biomass conversion. In my preliminary research, several conversion technologies including atmospheric pressure liquefaction, high pressure liquefaction, and microwave pyrolysis have been evaluated. Our data indicated that microwave pyrolysis had the potential to become a simple and economically viable biomass conversion technology. Microwave pyrolysis is an innovative process that provides efficient and uniform heating, and are robust to type, size and uniformity of feedstock and therefore suitable for almost any waste materials without needing to reduce the particle size. The proposed thesis focused on in-depth investigations of microwave pyrolysis of corn residues. My first specific aim was to examine the effects of processing parameters on product yields. The second specific research aim was to characterize the products (gases, bio-oils, and solid residues), which was critical to process optimization and product developments. Other research tasks included conducting kinetic modeling and preliminary mass and energy balance. This study demonstrated that microwave pyrolysis could be optimized to produce high value syngas, liquid fuels and pyrolytic carbons, and had a great potential to become a commercial process according to the mass and energy balance. One-step global model and two-step consecutive-reaction kinetic model offered a clue to the key mechanistic steps in the overall pyrolysis of corn residues. These results should have a positive impact on advancing renewable energy technologies and establishing the University's leadership status in the area of renewable energy development.

Copper(II)-mediated thermolysis of alginates: a model kinetic study on the influence of metal ions in the thermochemical processing of macroalgae

PubMed Central

Rowbotham, J. S.; Dyer, P. W.; Greenwell, H. C.; Selby, D.; Theodorou, M. K.

2013-01-01

Thermochemical processing methods such as pyrolysis are of growing interest as a means of converting biomass into fuels and commodity chemicals in a sustainable manner. Macroalgae, or seaweed, represent a novel class of feedstock for pyrolysis that, owing to the nature of the environments in which they grow coupled with their biochemistry, naturally possess high metal contents. Although the impact of metals upon the pyrolysis of terrestrial biomass is well documented, their influence on the thermochemical conversion of marine-derived feeds is largely unknown. Furthermore, these effects are inherently difficult to study, owing to the heterogeneous character of natural seaweed samples. The work described in this paper uses copper(II) alginate, together with alginic acid and sodium alginate as model compounds for exploring the effects of metals upon macroalgae thermolysis. A thermogravimetric analysis–Fourier transform infrared spectroscopic study revealed that, unusually, Cu2+ ions promote the onset of pyrolysis in the alginate polymer, with copper(II) alginate initiating rapid devolatilization at 143°C, 14°C lower than alginic acid and 61°C below the equivalent point for sodium alginate. Moreover, this effect was mirrored in a sample of wild Laminaria digitata that had been doped with Cu2+ ions prior to pyrolysis, thus validating the use of alginates as model compounds with which to study the thermolysis of macroalgae. These observations indicate the varying impact of different metal species on thermochemical behaviour of seaweeds and offer an insight into the pyrolysis of brown macroalgae used in phytoremediation of metal-containing waste streams. PMID:24427515

Lignin structural alterations in thermochemical pretreatments with limited delignification

DOE PAGES

Pu, Yunqiao; Hu, Fan; Huang, Fang; ...

2015-08-02

Lignocellulosic biomass has a complex and rigid cell wall structure that makes biomass recalcitrant to biological and chemical degradation. Among the three major structural biopolymers (i.e., cellulose, hemicellulose and lignin) in plant cell walls, lignin is considered the most recalcitrant component and generally plays a negative role in the biochemical conversion of biomass to biofuels. The conversion of biomass to biofuels through a biochemical platform usually requires a pretreatment stage to reduce the recalcitrance. Pretreatment renders compositional and structural changes of biomass with these changes ultimately govern the efficiency of the subsequent enzymatic hydrolysis. Dilute acid, hot water, steam explosion,more » and ammonia fiber expansion pretreatments are among the leading thermochemical pretreatments with a limited delignification that can reduce biomass recalcitrance. Practical applications of these pretreatment are rapidly developing as illustrated by recent commercial scale cellulosic ethanol plants. While these thermochemical pretreatments generally lead to only a limited delignification and no significant change of lignin content in the pretreated biomass, the lignin transformations that occur during these pretreatments and the roles they play in recalcitrance reduction is an important research aspect. This review highlights recent advances in our understanding of lignin alterations during these limited delignification thermochemical pretreatments, with emphasis on lignin chemical structures, molecular weights, and redistributions in the pretreated biomass.« less

Comparative TEA for Indirect Liquefaction Pathways to Distillate-Range Fuels via Oxygenated Intermediates

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

Tan, Eric; Snowden-Swan, Lesley J.; Talmadge, Michael

This paper presents a comparative techno-economic analysis of five conversion pathways from biomass to gasoline-, jet-, and diesel-range hydrocarbons via indirect liquefaction with specific focus on pathways utilizing oxygenated intermediates (derived either via thermochemical or biochemical conversion steps). The four emerging pathways of interest are compared with one conventional pathway (Fischer-Tropsch) for the production of the hydrocarbon blendstocks. The processing steps of the four emerging pathways include: biomass-to-syngas via indirect gasification, gas cleanup, conversion of syngas to alcohols/oxygenates, followed by conversion of alcohols/oxygenates to hydrocarbon blendstocks via dehydration, oligomerization, and hydrogenation. We show that the emerging pathways via oxygenated intermediatesmore » have the potential to be cost competitive with the conventional Fischer-Tropsch process. The evaluated pathways and the benchmark process generally exhibit similar fuel yields and carbon conversion efficiencies. The resulting minimum fuel selling prices are comparable to the benchmark at approximately $3.60 per gallon-gasoline equivalent, with potential for two new pathways to be more economically competitive. Additionally, the coproduct values can play an important role in the economics of the processes with oxygenated intermediates derived via syngas fermentation. Major cost drivers for the integrated processes are tied to achievable fuel yields and conversion efficiency of the intermediate steps, i.e., the production of oxygenates/alcohols from syngas and the conversion of oxygenates/alcohols to hydrocarbon fuels.« less

University Capstone Project: Enhanced Initiation Techniques for Thermochemical Energy Conversion

DTIC Science & Technology

2013-03-01

technologies such as scramjets, gas turbine engines (relight and afterburner ignition), and pulsed detonation engines ( PDEs ) because of the limited...events in a flow tube were recorded, and the PDE engine was fired while monitoring ignition time and wave speed throughout the detonation process...long steel tube fitted with a 36” long, 2” x 2” square polycarbonate test section is used in place of the instrumented detonation tube. The PDE

System and process for producing fuel with a methane thermochemical cycle

DOEpatents

Diver, Richard B.

2015-12-15

A thermochemical process and system for producing fuel are provided. The thermochemical process includes reducing an oxygenated-hydrocarbon to form an alkane and using the alkane in a reforming reaction as a reducing agent for water, a reducing agent for carbon dioxide, or a combination thereof. Another thermochemical process includes reducing a metal oxide to form a reduced metal oxide, reducing an oxygenated-hydrocarbon with the reduced metal oxide to form an alkane, and using the alkane in a reforming reaction as a reducing agent for water, a reducing agent for carbon dioxide, or a combination thereof. The system includes a reformer configured to perform a thermochemical process.

Mission analysis for the federal fuels from biomass program. Volume IV. Termochemical conversion of biomass to fuels and chemicals

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

Kohan, S.M.; Barkhordar, P.M.

1979-01-01

The thermochemical conversion of biomass feedstocks generally denotes technologies that use elevated temperatures to convert the fixed carbon content of biomass materials to produce other, more useful energy forms. Examples are combustion to produce heat, steam, electricity, or combinations of these; pyrolysis to produce gas (low- or intermediate-Btu), pyrolytic liquids and chemicals, and char; gasification to produce low or intermediate Btu gas (and, from IBG, additional products such as SNG, ammonia, methanol, or Fischer-Tropsch liquids); and liquefaction to produce heavy fuel oil or, with upgrading, lighter-boiling liquid products such as distillates, light fuel oils, or gasoline. This section discusses themore » selection of the feedstock used in the analysis of thermochemical conversion technologies. The following sections present detailed technical and economic evaluations of biomass conversion to electricity and steam by combustion, SNG by gasification and methanation, methanol by gasification and synthesis, oil by catalytic liquefaction, oil and char by pyrolysis, and ammonia by gasification and synthesis. The conversion options were reviewed with DOE for approval at the start of the project.« less

Technician's Perspective on an Ever-Changing Research Environment: Catalytic Conversion of Biomass to Fuels

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

Thibodeaux, J.; Hensley, J.

2013-01-01

The biomass thermochemical conversion platform at the National Renewable Energy Laboratory (NREL) develops and demonstrates processes for the conversion of biomass to fuels and chemicals including gasification, pyrolysis, syngas clean-up, and catalytic synthesis of alcohol and hydrocarbon fuels. In this talk, I will discuss the challenges of being a technician in this type of research environment, including handling and working with catalytic materials and hazardous chemicals, building systems without being given all of the necessary specifications, pushing the limits of the systems through ever-changing experiments, and achieving two-way communication with engineers and supervisors. I will do this by way ofmore » two examples from recent research. First, I will describe a unique operate-to-failure experiment in the gasification of chicken litter that resulted in the formation of a solid plug in the gasifier, requiring several technicians to chisel the material out. Second, I will compare and contrast bench scale and pilot scale catalyst research, including instances where both are conducted simultaneously from common upstream equipment. By way of example, I hope to illustrate the importance of researchers 1) understanding the technicians' perspective on tasks, 2) openly communicating among all team members, and 3) knowing when to voice opinions. I believe the examples in this talk will highlight the crucial role of a technical staff: skills attained by years of experience to build and operate research and production systems. The talk will also showcase the responsibilities of NREL technicians and highlight some interesting behind-the-scenes work that makes data generation from NREL's thermochemical process development unit possible.« less

Adam Bratis, Ph.D. | NREL

Science.gov Websites

Sciences & Technology Adam.Bratis@nrel.gov | 303-384-7852 Areas of Expertise Adam Bratis joined the managerial oversight in the areas of biochemical conversion, thermochemical conversion, algal biofuels with 11 years of experience with ExxonMobil in the areas of research and development, corporate

Impact of feedstock quality and variation on biochemical and thermochemical conversion

DOE PAGES

Li, Chenlin; Aston, John E.; Lacey, Jeffrey A.; ...

2016-07-21

The production of biofuels from lignocellulosic feedstock is attracting considerable attention in the United States and globally as a strategy to diversify energy resources, spur regional economic development and reduce greenhouse gas emissions. Because of the wide variation in feedstock types, compositions and content of convertible organics, there is a growing need to better understand correlations among feedstock quality attributes and conversion performance. Knowledge of the feedstock impact on conversion is essential to supply quality controlled, uniform and on-spec feedstocks to biorefineries. This review paper informs the development of meaningful feedstock quality specifications for different conversion processes. Discussions are focusedmore » on how compositional properties of feedstocks affect various unit operations in biochemical conversion processes, fast pyrolysis and hydrothermal liquefaction. In addition, future perspectives are discussed that focus on the challenges and prospects of addressing compositionally intrinsic inhibitors through feedstock preprocessing at regionally distributed depots. As a result, such preprocessing depots may allow for the commoditization of lignocellulosic feedstock and realization of stable, cost-effective and quality controlled biomass supply systems.« less

Impact of feedstock quality and variation on biochemical and thermochemical conversion

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

Li, Chenlin; Aston, John E.; Lacey, Jeffrey A.

The production of biofuels from lignocellulosic feedstock is attracting considerable attention in the United States and globally as a strategy to diversify energy resources, spur regional economic development and reduce greenhouse gas emissions. Because of the wide variation in feedstock types, compositions and content of convertible organics, there is a growing need to better understand correlations among feedstock quality attributes and conversion performance. Knowledge of the feedstock impact on conversion is essential to supply quality controlled, uniform and on-spec feedstocks to biorefineries. This review paper informs the development of meaningful feedstock quality specifications for different conversion processes. Discussions are focusedmore » on how compositional properties of feedstocks affect various unit operations in biochemical conversion processes, fast pyrolysis and hydrothermal liquefaction. In addition, future perspectives are discussed that focus on the challenges and prospects of addressing compositionally intrinsic inhibitors through feedstock preprocessing at regionally distributed depots. As a result, such preprocessing depots may allow for the commoditization of lignocellulosic feedstock and realization of stable, cost-effective and quality controlled biomass supply systems.« less

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

Li, Mi; Pu, Yunqiao; Yoo, Chang Geun

The native recalcitrance of plants hinders the biomass conversion process using current biorefinery techniques. Down-regulation of the caffeic acid O-methyltransferase (COMT) gene in the lignin biosynthesis pathway of switchgrass reduced the thermochemical and biochemical conversion recalcitrance of biomass. Due to potential environmental influences on lignin biosynthesis and deposition, studying the consequences of physicochemical changes in field-grown plants without pretreatment is essential to evaluate the performance of lignin-altered plants. In this study, we determined the chemical composition, cellulose crystallinity and the degree of its polymerization, molecular weight of hemicellulose, and cellulose accessibility of cell walls in order to better understand themore » fundamental features of why biomass is recalcitrant to conversion without pretreatment. The most important is to investigate whether traits and features are stable in the dynamics of field environmental effects over multiple years.« less

Bio-Oil Separation and Stabilization by Supercritical Fluid Fractionation. 2014 Final Report

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

Agblevor, Foster; Petkovic, Lucia; Bennion, Edward

The objective of this project is to use supercritical fluids to separate and fractionate algal-based bio-oils into stable products that can be subsequently upgraded to produce drop-in renewable fuels. To accomplish this objective, algae was grown and thermochemically converted to bio-oils using hydrothermal liquefaction (HTL), pyrolysis, and catalytic pyrolysis. The bio-oils were separated into an extract and a raffinate using near-critical propane or carbon dioxide. The fractions were then subjected to thermal aging studies to determine if the extraction process had stabilized the products. It was found that the propane extract fraction was twice as stable as the parent catalyticmore » pyrolysis bio-oils as measured by the change in viscosity after two weeks of accelerated aging at 80°C. Further, in-situ NMR aging studies found that the propane extract was chemically more stable than the parent bio-oil. Thus the milestone of stabilizing the product was met. A preliminary design of the extraction plant was prepared. The design was based on a depot scale plant processing 20,000,000 gallons per year of bio-oil. It was estimated that the capital costs for such a plant would be $8,700,000 with an operating cost of $3,500,000 per year. On a per gallon of product cost and a 10% annual rate of return, capital costs would represent $0.06 per gallon and operating costs would amount to $0.20 per gallon. Further, it was found that the energy required to run the process represented 6.2% of the energy available in the bio-oil, meeting the milestone of less than 20%. Life cycle analysis and greenhouse gas (GHG) emission analysis found that the energy for running the critical fluid separation process and the GHG emissions were minor compared to all the inputs to the overall well to pump system. For the well to pump system boundary, energetics in biofuel conversion are typically dominated by energy demands in the growth, dewater, and thermochemical process. Bio-oil stabilization by near critical propane extraction had minimal impact in the overall energetics of the process with NER contributions of 0.03. Based on the LCA, the overall conversion pathways were found to be energy intensive with a NER of about 2.3 and 1.2 for catalytic pyrolysis and HTL, respectively. GHG emissions for the catalytic pyrolysis process were greater than that of petroleum diesel at 210 g CO2 eq compared to 18.9 g CO2 eq. Microalgae bio-oil based diesel with thermochemical conversion through HTL meets renewable fuel standards with favorable emission reductions of -10.8 g CO2 eq. The importance of the outcomes is that the critical fluid extraction and stabilization process improved product stability and did so with minimal energy inputs and processing costs. The LCA and GHG emission calculations point toward the HTL pathway as the more favorable thermochemical route towards upgrading algae to bio-fuels. Since the quality of the HTL oil was significantly lower than that of the catalytic pyrolysis bio-oil, the next steps point toward improving the quality of the HTL oils from algae biomass and focusing the critical fluid stabilization on that bio-oil product.« less

Baking sunflower hulls within an aluminum envelope in a common laboratory oven yields charcoal.

PubMed

Arnal, Pablo Maximiliano

2015-01-01

Charcoals have been widely used by scientist to research the removal of contaminants from water and air. One key feature of charcoal is that it keeps macropores from the parent material - though anisotropically contracted - and can even develop meso- and micropores. However, the controlled thermochemical conversion of biomass into charcoal at laboratory scale normally requires special setups which involve either vacuum or inert gas. Those setups may not be affordable in research groups or educational institutions where the research of charcoals would be highly welcome. In this work, I propose a simple and effective method to steer the thermochemical process that converts sunflower hulls (SFH) into charcoal with basic laboratory resources. The carbonization method: •Place SFH in an airtight aluminum envelope.•Thermally treat SFH within the envelope in a common laboratory oven.•Open the envelope to obtain the carbonized sunflower hulls.

Power efficiency improvements of the industrial processes at application of thermochemical recuperation of heath of the leaving gases with use of microchannel reactors

NASA Astrophysics Data System (ADS)

Tararykov, A. V.; Garyaev, A. B.

2017-11-01

The possibility of increasing the energy efficiency of production processes by converting the initial fuel - natural gas to synthesized fuel using the heat of the exhaust gases of plants involved in production is considered. Possible applications of this technology are given. A mathematical model of the processes of heat and mass transfer occurring in a thermochemical reactor is developed taking into account the nonequilibrium nature of the course of chemical reactions of fuel conversion. The possibility of using microchannel reaction elements and facilities for methane conversion in order to intensify the process and reduce the overall dimensions of plants is considered. The features of the course of heat and mass transfer processes under flow conditions in microchannel reaction elements are described. Additions have been made to the mathematical model, which makes it possible to use it for microchannel installations. With the help of a mathematical model, distribution of the parameters of mixtures along the length of the reaction element of the reactor-temperature, the concentration of the reacting components, the velocity, and the values of the heat fluxes are obtained. The calculations take into account the change in the thermophysical properties of the mix-ture, the type of the catalytic element, the rate of the reactions, the heat exchange processes by radiation, and the lon-gitudinal heat transfer along the flow of the reacting mixture. The reliability of the results of the application of the mathematical model is confirmed by their comparison with the experimental data obtained by Grasso G., Schaefer G., Schuurman Y., Mirodatos C., Kuznetsov V.V., Vitovsky O.V. on similar installations.

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

Price, H.L.

Much of the polymer composites industry is built around the thermochemical conversion of raw material into useful composites. The raw materials (molding compound, prepreg) often are made up of thermosetting resins and small fibers or particles. While this conversion can follow a large number of paths, only a few paths are efficient, economical and lead to desirable composite properties. Processing instrument (P/I) technology enables a computer to sense and interpret changes taking place during the cure of prepreg or molding compound. P/I technology has been used to make estimates of gel time and cure time, thermal diffusivity measurements and transitionmore » temperature measurements. Control and sensing software is comparatively straightforward. The interpretation of results with appropriate software is under development.« less

Investigation of thermochemical biorefinery sizing and environmental sustainability impacts for conventional supply system and distributed pre-processing supply system designs

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

David J. Muth, Jr.; Matthew H. Langholtz; Eric C. D. Tan

The 2011 US Billion-Ton Update estimates that by 2030 there will be enough agricultural and forest resources to sustainably provide at least one billion dry tons of biomass annually, enough to displace approximately 30% of the country's current petroleum consumption. A portion of these resources are inaccessible at current cost targets with conventional feedstock supply systems because of their remoteness or low yields. Reliable analyses and projections of US biofuels production depend on assumptions about the supply system and biorefinery capacity, which, in turn, depend upon economic value, feedstock logistics, and sustainability. A cross-functional team has examined combinations of advancesmore » in feedstock supply systems and biorefinery capacities with rigorous design information, improved crop yield and agronomic practices, and improved estimates of sustainable biomass availability. A previous report on biochemical refinery capacity noted that under advanced feedstock logistic supply systems that include depots and pre-processing operations there are cost advantages that support larger biorefineries up to 10 000 DMT/day facilities compared to the smaller 2000 DMT/day facilities. This report focuses on analyzing conventional versus advanced depot biomass supply systems for a thermochemical conversion and refinery sizing based on woody biomass. The results of this analysis demonstrate that the economies of scale enabled by advanced logistics offsets much of the added logistics costs from additional depot processing and transportation, resulting in a small overall increase to the minimum ethanol selling price compared to the conventional logistic supply system. While the overall costs do increase slightly for the advanced logistic supply systems, the ability to mitigate moisture and ash in the system will improve the storage and conversion processes. In addition, being able to draw on feedstocks from further distances will decrease the risk of biomass supply to the conversion facility.« less

High Efficiency Solar Thermochemical Reactor for Hydrogen Production.

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

McDaniel, Anthony H.

2017-09-30

This research and development project is focused on the advancement of a technology that produces hydrogen at a cost that is competitive with fossil-based fuels for transportation. A twostep, solar-driven WS thermochemical cycle is theoretically capable of achieving an STH conversion ratio that exceeds the DOE target of 26% at a scale large enough to support an industrialized economy [1]. The challenge is to transition this technology from the laboratory to the marketplace and produce hydrogen at a cost that meets or exceeds DOE targets.

Energy conversion and storage program

NASA Astrophysics Data System (ADS)

Cairns, E. J.

1992-03-01

The Energy Conversion and Storage Program applies chemistry and materials science principles to solve problems in: (1) production of new synthetic fuels; (2) development of high-performance rechargeable batteries and fuel cells; (3) development of advanced thermochemical processes for energy conversion; (4) characterization of complex chemical processes; and (5) application of novel materials for energy conversion and transmission. Projects focus on transport-process principles, chemical kinetics, thermodynamics, separation processes, organic and physical chemistry, novel materials, and advanced methods of analysis. Electrochemistry research aims to develop advanced power systems for electric vehicle and stationary energy storage applications. Topics include identification of new electrochemical couples for advanced rechargeable batteries, improvements in battery and fuel-cell materials, and the establishment of engineering principles applicable to electrochemical energy storage and conversion. Chemical Applications research includes topics such as separations, catalysis, fuels, and chemical analyses. Included in this program area are projects to develop improved, energy-efficient methods for processing waste streams from synfuel plants and coal gasifiers. Other research projects seek to identify and characterize the constituents of liquid fuel-system streams and to devise energy-efficient means for their separation. Materials Applications research includes the evaluation of the properties of advanced materials, as well as the development of novel preparation techniques. For example, the use of advanced techniques, such as sputtering and laser ablation, are being used to produce high-temperature superconducting films.

Production of hydrogen from biomass by catalytic steam reforming of fast pyrolysis oil

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

Czernik, S.; Wang, D.; Chornet, E.

1998-08-01

Hydrogen is the prototype of the environmentally cleanest fuel of interest for power generation using fuel cells and for transportation. The thermochemical conversion of biomass to hydrogen can be carried out through two distinct strategies: (a) gasification followed by water-gas shift conversion, and (b) catalytic steam reforming of specific fractions derived from fast pyrolysis and aqueous/steam processes of biomass. This paper presents the latter route that begins with fast pyrolysis of biomass to produce bio-oil. This oil (as a whole or its selected fractions) can be converted to hydrogen via catalytic steam reforming followed by a water-gas shift conversion step.more » Such a process has been demonstrated at the bench scale using model compounds, poplar oil aqueous fraction, and the whole pyrolysis oil with commercial Ni-based steam reforming catalysts. Hydrogen yields as high as 85% have been obtained. Catalyst initial activity can be recovered through regeneration cycles by steam or CO{sub 2} gasification of carbonaceous deposits.« less

High yielding tropical energy crops for bioenergy production: Effects of plant components, harvest years and locations on biomass composition.

PubMed

Surendra, K C; Ogoshi, Richard; Zaleski, Halina M; Hashimoto, Andrew G; Khanal, Samir Kumar

2018-03-01

The composition of lignocellulosic feedstock, which depends on crop type, crop management, locations and plant parts, significantly affects the conversion efficiency of biomass into biofuels and biobased products. Thus, this study examined the composition of different parts of two high yielding tropical energy crops, Energycane and Napier grass, collected across three locations and years. Significantly higher fiber content was found in the leaves of Energycane than stems, while fiber content was significantly higher in the stems than the leaves of Napier grass. Similarly, fiber content was higher in Napier grass than Energycane. Due to significant differences in biomass composition between the plant parts within a crop type, neither biological conversion, including anaerobic digestion, nor thermochemical pretreatment alone is likely to efficiently convert biomass components into biofuels and biobased products. However, combination of anaerobic digestion with thermochemical conversion technologies could efficiently utilize biomass components in generating biofuels and biobased products. Copyright © 2017 Elsevier Ltd. All rights reserved.

Marc Pomeroy | NREL

Science.gov Websites

sampling of on-stream components of thermochemical biomass conversion in real-time Affiliated Research Integration, Scale-Up, and Piloting Areas of Expertise Analytical sampling of hot gas and vapor phase products

Next-generation cellulosic ethanol technologies and their contribution to a sustainable Africa

PubMed Central

van Zyl, W. H.; Chimphango, A. F. A.; den Haan, R.; Görgens, J. F.; Chirwa, P. W. C.

2011-01-01

The world is currently heavily dependent on oil, especially in the transport sector. However, rising oil prices, concern about environmental impact and supply instability are among the factors that have led to greater interest in renewable fuel and green chemistry alternatives. Lignocellulose is the only foreseeable renewable feedstock for sustainable production of transport fuels. The main technological impediment to more widespread utilization of lignocellulose for production of fuels and chemicals in the past has been the lack of low-cost technologies to overcome the recalcitrance of its structure. Both biological and thermochemical second-generation conversion technologies are currently coming online for the commercial production of cellulosic ethanol concomitantly with heat and electricity production. The latest advances in biological conversion of lignocellulosics to ethanol with a focus on consolidated bioprocessing are highlighted. Furthermore, integration of cellulosic ethanol production into existing bio-based industries also using thermochemical processes to optimize energy balances is discussed. Biofuels have played a pivotal yet suboptimal role in supplementing Africa's energy requirements in the past. Capitalizing on sub-Saharan Africa's total biomass potential and using second-generation technologies merit a fresh look at the potential role of bioethanol production towards developing a sustainable Africa while addressing food security, human needs and local wealth creation. PMID:22482027

Thermochemical and kinetic aspects of the sulfurization of Cu-Sb and Cu-Bi thin films

NASA Astrophysics Data System (ADS)

Colombara, Diego; Peter, Laurence M.; Rogers, Keith D.; Hutchings, Kyle

2012-02-01

CuSbS2 and Cu3BiS3 are being investigated as part of a search for new absorber materials for photovoltaic devices. Thin films of these chalcogenides were produced by conversion of stacked and co-electroplated metal precursor layers in the presence of elemental sulfur vapour. Ex-situ XRD and SEM/EDS analyses of the processed samples were employed to study the reaction sequence with the aim of achieving compact layer morphologies. A new “Time-Temperature-Reaction” (TTR) diagram and modified Pilling-Bedworth coefficients have been introduced for the description and interpretation of the reaction kinetics. For equal processing times, the minimum temperature required for CuSbS2 to appear is substantially lower than for Cu3BiS3, suggesting that interdiffusion across the interfaces between the binary sulfides is a key step in the formation of the ternary compounds. The effects of the heating rate and sulfur partial pressure on the phase evolution as well as the potential losses of Sb and Bi during the processes have been investigated experimentally and the results related to the equilibrium pressure diagrams obtained via thermochemical computation.

Investigation of thermochemical biorefinery sizing and environmental sustainability impacts for conventional supply system and distributed preprocessing supply system designs

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

Muth, jr., David J.; Langholtz, Matthew H.; Tan, Eric

2014-03-31

The 2011 US Billion-Ton Update estimates that by 2030 there will be enough agricultural and forest resources to sustainably provide at least one billion dry tons of biomass annually, enough to displace approximately 30% of the country's current petroleum consumption. A portion of these resources are inaccessible at current cost targets with conventional feedstock supply systems because of their remoteness or low yields. Reliable analyses and projections of US biofuels production depend on assumptions about the supply system and biorefinery capacity, which, in turn, depend upon economic value, feedstock logistics, and sustainability. A cross-functional team has examined combinations of advancesmore » in feedstock supply systems and biorefinery capacities with rigorous design information, improved crop yield and agronomic practices, and improved estimates of sustainable biomass availability. A previous report on biochemical refinery capacity noted that under advanced feedstock logistic supply systems that include depots and pre-processing operations there are cost advantages that support larger biorefineries up to 10 000 DMT/day facilities compared to the smaller 2000 DMT/day facilities. This report focuses on analyzing conventional versus advanced depot biomass supply systems for a thermochemical conversion and refinery sizing based on woody biomass. The results of this analysis demonstrate that the economies of scale enabled by advanced logistics offsets much of the added logistics costs from additional depot processing and transportation, resulting in a small overall increase to the minimum ethanol selling price compared to the conventional logistic supply system. While the overall costs do increase slightly for the advanced logistic supply systems, the ability to mitigate moisture and ash in the system will improve the storage and conversion processes. In addition, being able to draw on feedstocks from further distances will decrease the risk of biomass supply to the conversion facility.« less

Study of traits and recalcitrance reduction of field-grown COMT down-regulated switchgrass

DOE PAGES

Li, Mi; Pu, Yunqiao; Yoo, Chang Geun; ...

2017-01-03

The native recalcitrance of plants hinders the biomass conversion process using current biorefinery techniques. Down-regulation of the caffeic acid O-methyltransferase (COMT) gene in the lignin biosynthesis pathway of switchgrass reduced the thermochemical and biochemical conversion recalcitrance of biomass. Due to potential environmental influences on lignin biosynthesis and deposition, studying the consequences of physicochemical changes in field-grown plants without pretreatment is essential to evaluate the performance of lignin-altered plants. In this study, we determined the chemical composition, cellulose crystallinity and the degree of its polymerization, molecular weight of hemicellulose, and cellulose accessibility of cell walls in order to better understand themore » fundamental features of why biomass is recalcitrant to conversion without pretreatment. The most important is to investigate whether traits and features are stable in the dynamics of field environmental effects over multiple years.« less

Physico-chemical and thermochemical studies of the hydrolytic conversion of amorphous tricalcium phosphate into apatite

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

Somrani, Saida; Banu, Mihai; Jemal, Mohamed

2005-05-15

The conversion of amorphous tricalcium phosphate with different hydration ratio into apatite in water at 25 deg. C has been studied by microcalorimetry and several physical-chemical methods. The hydrolytic transformation was dominated by two strong exothermic events. A fast, relatively weak, wetting process and a very slow but strong heat release assigned to a slow internal rehydration and the crystallization of the amorphous phase into an apatite. The exothermic phenomenon related to the rehydration exceeded the crystalline transformation enthalpy. Rehydration occurred before the conversion of the amorphous phase into apatite and determined the advancement of the hydrolytic reaction. The apatiticmore » phases formed evolved slightly with time after their formation. The crystallinity increased whereas the amount of HPO{sub 4}{sup 2-} ion decreased. These data allow a better understanding of the behavior of biomaterials involving amorphous phases such as hydroxyapatite plasma-sprayed coatings.« less

Applications of de-oiled microalgal biomass towards development of sustainable biorefinery.

PubMed

Maurya, Rahulkumar; Paliwal, Chetan; Ghosh, Tonmoy; Pancha, Imran; Chokshi, Kaumeel; Mitra, Madhusree; Ghosh, Arup; Mishra, Sandhya

2016-08-01

In view of commercialization of microalgal biofuel, the de-oiled microalgal biomass (DMB) is a surplus by-product in the biorefinery process that needs to be exploited to make the process economically attractive and feasible. This DMB, rich in carbohydrates, proteins, and minerals, can be used as feed, fertilizer, and substrate for the production of bioethanol/bio-methane. Further, thermo-chemical conversion of DMB results into fuels and industrially important chemicals. Future prospects of DMB also lie with its conversion into novel biomaterials like nanoparticles and carbon-dot which have biomedical importance. The lowest valued application of DMB is to use it for adsorption of dyes and heavy metals from industrial effluents. This study reviews how DMB can be utilized for different applications and in the generation of valuable co-products. The value addition of DMB would thereby improve the overall cost economics of the microalgal bio-refinery. Copyright © 2016 Elsevier Ltd. All rights reserved.

Sugarcane-Biorefinery.

PubMed

Vaz, Sílvio

2017-03-17

Concepts such as biorefinery and green chemistry focus on the usage of biomass, as with the oil value chain. However, it can cause less negative impact on the environment. A biorefinery based on sugarcane (Saccharum spp.) as feedstock is an example, because it can integrate into the same physical space, of processes for obtaining biofuels (ethanol), chemicals (from sugars or ethanol), electricity, and heat.The use of sugarcane as feedstock for biorefineries is dictated by its potential to supply sugars, ethanol, natural polymers or macromolecules, organic matter, and other compounds and materials. By means of conversion processes (chemical, biochemical, and thermochemical), sugarcane biomass can be transformed into high-value bioproducts to replace petrochemicals, as a bioeconomy model.

Biomass thermochemical gasification: Experimental studies and modeling

NASA Astrophysics Data System (ADS)

Kumar, Ajay

The overall goals of this research were to study the biomass thermochemical gasification using experimental and modeling techniques, and to evaluate the cost of industrial gas production and combined heat and power generation. This dissertation includes an extensive review of progresses in biomass thermochemical gasification. Product gases from biomass gasification can be converted to biopower, biofuels and chemicals. However, for its viable commercial applications, the study summarizes the technical challenges in the gasification and downstream processing of product gas. Corn stover and dried distillers grains with solubles (DDGS), a non-fermentable byproduct of ethanol production, were used as the biomass feedstocks. One of the objectives was to determine selected physical and chemical properties of corn stover related to thermochemical conversion. The parameters of the reaction kinetics for weight loss were obtained. The next objective was to investigate the effects of temperature, steam to biomass ratio and equivalence ratio on gas composition and efficiencies. DDGS gasification was performed on a lab-scale fluidized-bed gasifier with steam and air as fluidizing and oxidizing agents. Increasing the temperature resulted in increases in hydrogen and methane contents and efficiencies. A model was developed to simulate the performance of a lab-scale gasifier using Aspen Plus(TM) software. Mass balance, energy balance and minimization of Gibbs free energy were applied for the gasification to determine the product gas composition. The final objective was to optimize the process by maximizing the net energy efficiency, and to estimate the cost of industrial gas, and combined heat and power (CHP) at a biomass feedrate of 2000 kg/h. The selling price of gas was estimated to be 11.49/GJ for corn stover, and 13.08/GJ for DDGS. For CHP generation, the electrical and net efficiencies were 37 and 86%, respectively for corn stover, and 34 and 78%, respectively for DDGS. For corn stover, the selling price of electricity was 0.1351/kWh. For DDGS, the selling price of electricity was 0.1287/kWh.

High-flux solar-driven thermochemical dissociation of CO2 and H2O using nonstoichiometric ceria.

PubMed

Chueh, William C; Falter, Christoph; Abbott, Mandy; Scipio, Danien; Furler, Philipp; Haile, Sossina M; Steinfeld, Aldo

2010-12-24

Because solar energy is available in large excess relative to current rates of energy consumption, effective conversion of this renewable yet intermittent resource into a transportable and dispatchable chemical fuel may ensure the goal of a sustainable energy future. However, low conversion efficiencies, particularly with CO(2) reduction, as well as utilization of precious materials have limited the practical generation of solar fuels. By using a solar cavity-receiver reactor, we combined the oxygen uptake and release capacity of cerium oxide and facile catalysis at elevated temperatures to thermochemically dissociate CO(2) and H(2)O, yielding CO and H(2), respectively. Stable and rapid generation of fuel was demonstrated over 500 cycles. Solar-to-fuel efficiencies of 0.7 to 0.8% were achieved and shown to be largely limited by the system scale and design rather than by chemistry.

An evaluation of tannery industry wastewater treatment sludge gasification by artificial neural network modeling.

PubMed

Ongen, Atakan; Ozcan, H Kurtulus; Arayıcı, Semiha

2013-12-15

This paper reports on the calorific value of synthetic gas (syngas) produced by gasification of dewatered sludge derived from treatment of tannery wastewater. Proximate and ultimate analyses of samples were performed. Thermochemical conversion alters the chemical structure of the waste. Dried air was used as a gasification agent at varying flow rates, which allowed the feedstock to be quickly converted into gas by means of different heterogeneous reactions. A lab-scale updraft fixed-bed steel reactor was used for thermochemical conversion of sludge samples. Artificial neural network (ANN) modeling techniques were used to observe variations in the syngas related to operational conditions. Modeled outputs showed that temporal changes of model predictions were in close accordance with real values. Correlation coefficients (r) showed that the ANN used in this study gave results with high sensitivity. Copyright © 2013 Elsevier B.V. All rights reserved.

Lignin plays a negative role in the biochemical process for producing lignocellulosic biofuels.

PubMed

Zeng, Yining; Zhao, Shuai; Yang, Shihui; Ding, Shi-You

2014-06-01

A biochemical platform holds the most promising route toward lignocellulosic biofuels, in which polysaccharides are hydrolyzed by cellulase enzymes into simple sugars and fermented to ethanol by microbes. However, these polysaccharides are cross-linked in the plant cell walls with the hydrophobic network of lignin that physically impedes enzymatic deconstruction. A thermochemical pretreatment process is often required to remove or delocalize lignin, which may also generate inhibitors that hamper enzymatic hydrolysis and fermentation. Here we review recent advances in understanding lignin structure in the plant cell walls and the negative roles of lignin in the processes of converting biomass to biofuels. Perspectives and future directions to improve the biomass conversion process are also discussed. Copyright © 2013. Published by Elsevier Ltd.

Solar to fuels conversion technologies: a perspective.

PubMed

Tuller, Harry L

2017-01-01

To meet increasing energy needs, while limiting greenhouse gas emissions over the coming decades, power capacity on a large scale will need to be provided from renewable sources, with solar expected to play a central role. While the focus to date has been on electricity generation via photovoltaic (PV) cells, electricity production currently accounts for only about one-third of total primary energy consumption. As a consequence, solar-to-fuel conversion will need to play an increasingly important role and, thereby, satisfy the need to replace high energy density fossil fuels with cleaner alternatives that remain easy to transport and store. The solar refinery concept (Herron et al. in Energy Environ Sci 8:126-157, 2015), in which captured solar radiation provides energy in the form of heat, electricity or photons, used to convert the basic chemical feedstocks CO 2 and H 2 O into fuels, is reviewed as are the key conversion processes based on (1) combined PV and electrolysis, (2) photoelectrochemically driven electrolysis and (3) thermochemical processes, all focused on initially converting H 2 O and CO 2 to H 2 and CO. Recent advances, as well as remaining challenges, associated with solar-to-fuel conversion are discussed, as is the need for an intensive research and development effort to bring such processes to scale.

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

Johnson, Terry Alan; Hogan, Roy E., Jr.; McDaniel, Anthony H.

Two of the most daunting problems facing humankind in the twenty-first century are energy security and climate change. This report summarizes work accomplished towards addressing these problems through the execution of a Grand Challenge LDRD project (FY09-11). The vision of Sunshine to Petrol is captured in one deceptively simple chemical equation: Solar Energy + xCO{sub 2} + (x+1)H{sub 2}O {yields} C{sub x}H{sub 2x+2}(liquid fuel) + (1.5x+.5)O{sub 2} Practical implementation of this equation may seem far-fetched, since it effectively describes the use of solar energy to reverse combustion. However, it is also representative of the photosynthetic processes responsible for much ofmore » life on earth and, as such, summarizes the biomass approach to fuels production. It is our contention that an alternative approach, one that is not limited by efficiency of photosynthesis and more directly leads to a liquid fuel, is desirable. The development of a process that efficiently, cost effectively, and sustainably reenergizes thermodynamically spent feedstocks to create reactive fuel intermediates would be an unparalleled achievement and is the key challenge that must be surmounted to solve the intertwined problems of accelerating energy demand and climate change. We proposed that the direct thermochemical conversion of CO{sub 2} and H{sub 2}O to CO and H{sub 2}, which are the universal building blocks for synthetic fuels, serve as the basis for this revolutionary process. To realize this concept, we addressed complex chemical, materials science, and engineering problems associated with thermochemical heat engines and the crucial metal-oxide working-materials deployed therein. By project's end, we had demonstrated solar-driven conversion of CO{sub 2} to CO, a key energetic synthetic fuel intermediate, at 1.7% efficiency.« less

Process Design and Economics for the Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels. Thermochemical Research Pathways with In Situ and Ex Situ Upgrading of Fast Pyrolysis Vapors

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

Dutta, Abhijit; Sahir, Asad; Tan, Eric

This report was developed as part of the U.S. Department of Energy’s Bioenergy Technologies Office’s efforts to enable the development of technologies for the production of infrastructurecompatible, cost-competitive liquid hydrocarbon fuels from biomass. Specifically, this report details two conceptual designs based on projected product yields and quality improvements via catalyst development and process integration. It is expected that these research improvements will be made within the 2022 timeframe. The two conversion pathways detailed are (1) in situ and (2) ex situ upgrading of vapors produced from the fast pyrolysis of biomass. While the base case conceptual designs and underlying assumptionsmore » outline performance metrics for feasibility, it should be noted that these are only two of many other possibilities in this area of research. Other promising process design options emerging from the research will be considered for future techno-economic analysis.« less

Design and commissioning of a multi-mode prototype for thermochemical conversion of human faeces.

PubMed

Jurado, Nelia; Somorin, Tosin; Kolios, Athanasios J; Wagland, Stuart; Patchigolla, Kumar; Fidalgo, Beatriz; Parker, Alison; McAdam, Ewan; Williams, Leon; Tyrrel, Sean

2018-05-01

This article describes the design and commissioning of a micro-combustor for energy recovery from human faeces, which can operate both in updraft and downdraft modes. Energy recovery from faecal matter via thermochemical conversion has recently been identified as a feasible solution for sanitation problems in low income countries and locations of high income countries where access to sewage infrastructures is difficult or not possible. This technology can be applied to waterless toilets with the additional outcome of generating heat and power that can be used to pre-treat the faeces before their combustion and to ensure that the entire system is self-sustaining. The work presented here is framed within the Nano Membrane Toilet (NMT) project that is being carried out at Cranfield University, as part of the Reinvent the Toilet Challenge of the Bill and Melinda Gates Foundation. For this study, preliminary trials using simulant faeces pellets were first carried out to find out the optimum values for the main operating variables at the scale required by the process, i.e. a fuel flowrate between 0.4 and 1.2 g/min of dry faeces. Parameters such as ignition temperature, residence time, and maximum temperature reached, were determined and used for the final design of the bench-scale combustor prototype. The prototype was successfully commissioned and the first experimental results, using real human faeces, are discussed in the paper.

Analysis of medium-BTU gasification condensates, June 1985-June 1986

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

Elliott, D.C.

1987-05-01

This report provides the final results of chemical and physical analysis of condensates from biomass gasification systems which are part of the US Department of Energy Biomass Thermochemical Conversion Program. The work described in detail in this report involves extensive analysis of condensates from four medium-BTU gasifiers. The analyses include elemental analysis, ash, moisture, heating value, density, specific chemical analysis, ash, moisture, heating value, density, specific chemical analysis (gas chromatography/mass spectrometry, infrared spectrophotometry, Carbon-13 nuclear magnetic resonance spectrometry) and Ames Assay. This work was an extension of a broader study earlier completed of the condensates of all the gasifers andmore » pyrolyzers in the Biomass Thermochemical Conversion Program. The analytical data demonstrates the wide range of chemical composition of the organics recoverd in the condensates and suggests a direct relationship between operating temperature and chemical composition of the condensates. A continuous pathway of thermal degradation of the tar components as a function of temperature is proposed. Variations in the chemical composition of the organic in the tars are reflected in the physical properties of tars and phase stability in relation to water in the condensate. The biological activity appears to be limited to the tars produced at high temperatures as a result of formation of polycyclic aromatic hydrocarbons in high concentrations. Future studies of the time/temperature relationship to tar composition and the effect of processing atmosphere should be undertaken. Further processing of the condensates either as wastewater treatment or upgrading of the organics to useful products is also recommended. 15 refs., 4 figs., 4 tabs.« less

Lignin: Characterization of a Multifaceted Crop Component

PubMed Central

2013-01-01

Lignin is a plant component with important implications for various agricultural disciplines. It confers rigidity to cell walls, and is therefore associated with tolerance to abiotic and biotic stresses and the mechanical stability of plants. In animal nutrition, lignin is considered an antinutritive component of forages as it cannot be readily fermented by rumen microbes. In terms of energy yield from biomass, the role of lignin depends on the conversion process. It contains more gross energy than other cell wall components and therefore confers enhanced heat value in thermochemical processes such as direct combustion. Conversely, it negatively affects biological energy conversion processes such as bioethanol or biogas production, as it inhibits microbial fermentation of the cell wall. Lignin from crop residues plays an important role in the soil organic carbon cycling, as it constitutes a recalcitrant carbon pool affecting nutrient mineralization and carbon sequestration. Due to the significance of lignin in several agricultural disciplines, the modification of lignin content and composition by breeding is becoming increasingly important. Both mapping of quantitative trait loci and transgenic approaches have been adopted to modify lignin in crops. However, breeding goals must be defined considering the conflicting role of lignin in different agricultural disciplines. PMID:24348159

Biomass energy: a monograph

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

Hiler, E.A.; Stout, B.A.

1985-01-01

This monograph presents a review of the status of biomass as an alternative energy source, with particular emphasis on the energy research programs of the Texas A and M University System. Eight chapters include joint research efforts in thermochemical conversion (combustion, gasification, pyrolysis), biological conversion (anaerobic digestion, fermentation), and plant oil extraction (physical expelling, solvent extraction). Six chapters are indexed separately for inclusion in the Energy Data Base and in Energy Abstracts for Policy Analysis.

Biomass waste-to-energy valorisation technologies: a review case for banana processing in Uganda.

PubMed

Gumisiriza, Robert; Hawumba, Joseph Funa; Okure, Mackay; Hensel, Oliver

2017-01-01

Uganda's banana industry is heavily impeded by the lack of cheap, reliable and sustainable energy mainly needed for processing of banana fruit into pulp and subsequent drying into chips before milling into banana flour that has several uses in the bakery industry, among others. Uganda has one of the lowest electricity access levels, estimated at only 2-3% in rural areas where most of the banana growing is located. In addition, most banana farmers have limited financial capacity to access modern solar energy technologies that can generate sufficient energy for industrial processing. Besides energy scarcity and unreliability, banana production, marketing and industrial processing generate large quantities of organic wastes that are disposed of majorly by unregulated dumping in places such as swamps, thereby forming huge putrefying biomass that emit green house gases (methane and carbon dioxide). On the other hand, the energy content of banana waste, if harnessed through appropriate waste-to-energy technologies, would not only solve the energy requirement for processing of banana pulp, but would also offer an additional benefit of avoiding fossil fuels through the use of renewable energy. The potential waste-to-energy technologies that can be used in valorisation of banana waste can be grouped into three: Thermal (Direct combustion and Incineration), Thermo-chemical (Torrefaction, Plasma treatment, Gasification and Pyrolysis) and Biochemical (Composting, Ethanol fermentation and Anaerobic Digestion). However, due to high moisture content of banana waste, direct application of either thermal or thermo-chemical waste-to-energy technologies is challenging. Although, supercritical water gasification does not require drying of feedstock beforehand and can be a promising thermo-chemical technology for gasification of wet biomass such as banana waste, it is an expensive technology that may not be adopted by banana farmers in Uganda. Biochemical conversion technologies are reported to be more eco-friendly and appropriate for waste biomass with high moisture content such as banana waste. Uganda's banana industrialisation is rural based with limited technical knowledge and economic capability to setup modern solar technologies and thermo-conversions for drying banana fruit pulp. This review explored the advantages of various waste-to-energy technologies as well as their shortfalls. Anaerobic digestion stands out as the most feasible and appropriate waste-to-energy technology for solving the energy scarcity and waste burden in banana industry. Finally, potential options for the enhancement of anaerobic digestion of banana waste were also elucidated.

Sustainable conversion of coffee and other crop wastes to biofuels and bioproducts using coupled biochemical and thermochemical processes in a multi-stage biorefinery concept.

PubMed

Hughes, Stephen R; López-Núñez, Juan Carlos; Jones, Marjorie A; Moser, Bryan R; Cox, Elby J; Lindquist, Mitch; Galindo-Leva, Luz Angela; Riaño-Herrera, Néstor M; Rodriguez-Valencia, Nelson; Gast, Fernando; Cedeño, David L; Tasaki, Ken; Brown, Robert C; Darzins, Al; Brunner, Lane

2014-10-01

The environmental impact of agricultural waste from the processing of food and feed crops is an increasing concern worldwide. Concerted efforts are underway to develop sustainable practices for the disposal of residues from the processing of such crops as coffee, sugarcane, or corn. Coffee is crucial to the economies of many countries because its cultivation, processing, trading, and marketing provide employment for millions of people. In coffee-producing countries, improved technology for treatment of the significant amounts of coffee waste is critical to prevent ecological damage. This mini-review discusses a multi-stage biorefinery concept with the potential to convert waste produced at crop processing operations, such as coffee pulping stations, to valuable biofuels and bioproducts using biochemical and thermochemical conversion technologies. The initial bioconversion stage uses a mutant Kluyveromyces marxianus yeast strain to produce bioethanol from sugars. The resulting sugar-depleted solids (mostly protein) can be used in a second stage by the oleaginous yeast Yarrowia lipolytica to produce bio-based ammonia for fertilizer and are further degraded by Y. lipolytica proteases to peptides and free amino acids for animal feed. The lignocellulosic fraction can be ground and treated to release sugars for fermentation in a third stage by a recombinant cellulosic Saccharomyces cerevisiae, which can also be engineered to express valuable peptide products. The residual protein and lignin solids can be jet cooked and passed to a fourth-stage fermenter where Rhodotorula glutinis converts methane into isoprenoid intermediates. The residues can be combined and transferred into pyrocracking and hydroformylation reactions to convert ammonia, protein, isoprenes, lignins, and oils into renewable gas. Any remaining waste can be thermoconverted to biochar as a humus soil enhancer. The integration of multiple technologies for treatment of coffee waste has the potential to contribute to economic and environmental sustainability.

Evaluation of biochars by temperature programmed oxidation/mass spectroscopy

USDA-ARS?s Scientific Manuscript database

Biochar from the thermochemical conversion of biomass was evaluated by Temperature Programmed Oxidation (TPO) coupled with mass spectroscopy. This technique can be used to assess the oxidative reactivity of carbonaceous solids where higher temperature reactivity indicates greater structural order. ...

An analysis of hydrogen production via closed-cycle schemes. [thermochemical processings from water

NASA Technical Reports Server (NTRS)

Chao, R. E.; Cox, K. E.

1975-01-01

A thermodynamic analysis and state-of-the-art review of three basic schemes for production of hydrogen from water: electrolysis, thermal water-splitting, and multi-step thermochemical closed cycles is presented. Criteria for work-saving thermochemical closed-cycle processes are established, and several schemes are reviewed in light of such criteria. An economic analysis is also presented in the context of energy costs.

Small Scale Gasification Application and Perspectives in Circular Economy

NASA Astrophysics Data System (ADS)

Klavins, Maris; Bisters, Valdis; Burlakovs, Juris

2018-06-01

Gasification is the process converting solid fuels as coal and organic plant matter, or biomass into combustible gas, called syngas. Gasification is a thermal conversion process using carbonaceous fuel, and it differs substantially from other thermal processes such as incineration or pyrolysis. The process can be used with virtually any carbonaceous fuel. It is an endothermic thermal conversion process, with partial oxidation being the dominant feature. Gasification converts various feedstock including waste to a syngas. Instead of producing only heat and electricity, synthesis gas produced by gasification may be transformed into commercial products with higher value as transport fuels, fertilizers, chemicals and even to substitute natural gas. Thermo-chemical conversion of biomass and solid municipal waste is developing as a tool to promote the idea of energy system without fossil fuels to a reality. In municipal solid waste management, gasification does not compete with recycling, moreover it enhances recycling programs. Pre-processing and after-processing must increase the amount of recyclables in the circular economy. Additionally, end of life plastics can serve as an energy feedstock for gasification as otherwise it cannot be sorted out and recycled. There is great potential for application of gasification technology within the biomass waste and solid waste management sector. Industrial self-consumption in the mode of combined heat and power can contribute to sustainable economic development within a circular economy.

Hydrothermal conversion of xylose, glucose, and cellulose under the catalysis of transition metal sulfates.

PubMed

Cao, Xuefei; Peng, Xinwen; Sun, Shaoni; Zhong, Linxin; Chen, Wei; Wang, Sha; Sun, Run-Cang

2015-03-15

Hydrothermal conversion (HTC) is an important thermochemical process to upgrade low-cost biomass into valuable chemicals or fuels. As compared with non-catalytic HTC, catalytic HTC shows high energy efficiency on biomass upgradation. In this work, the catalytic performances of various transition metal sulfates (Mn(2+), Fe(2+), Fe(3+), Co(2+), Ni(2+), Cu(2+), and Zn(2+)) in the HTCs of xylose, glucose, and cellulose under different conditions were explored. Among these catalysts, Zn(2+) and Ni(2+) showed obvious effects on the conversions of xylose, glucose, and cellulose into lactic acid, while Cu(2+) and Fe(3+), which could significantly accelerate the hydrolysis of cellulose into glucose at 200°C, displayed high efficiency on converting glucose and cellulose into levulinic acid and formic acid at high temperature. Additionally, significant positive correlative relationships among xylose, glucose, and cellulose degradations were observed. This study is helpful for screening appropriate catalysts for biomass upgradation through catalytic HTC of monosaccharide. Copyright © 2014 Elsevier Ltd. All rights reserved.

Biomass recalcitrance: a multi-scale, multi-factor, and conversion-specific property.

PubMed

McCann, Maureen C; Carpita, Nicholas C

2015-07-01

Recalcitrance of plant biomass to enzymatic hydrolysis for biofuel production is thought to be a property conferred by lignin or lignin-carbohydrate complexes. However, chemical catalytic and thermochemical conversion pathways, either alone or in combination with biochemical and fermentative pathways, now provide avenues to utilize lignin and to expand the product range beyond ethanol or butanol. To capture all of the carbon in renewable biomass, both lignin-derived aromatics and polysaccharide-derived sugars need to be transformed by catalysts to liquid hydrocarbons and high-value co-products. We offer a new definition of recalcitrance as those features of biomass which disproportionately increase energy requirements in conversion processes, increase the cost and complexity of operations in the biorefinery, and/or reduce the recovery of biomass carbon into desired products. The application of novel processing technologies applied to biomass reveal new determinants of recalcitrance that comprise a broad range of molecular, nanoscale, and macroscale factors. Sampling natural genetic diversity within a species, transgenic approaches, and synthetic biology approaches are all strategies that can be used to select biomass for reduced recalcitrance in various pretreatments and conversion pathways. © The Author 2015. Published by Oxford University Press on behalf of the Society for Experimental Biology. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Contributions of pyrogenic materials on the accumulation of soil organic matter

USDA-ARS?s Scientific Manuscript database

Soil amendment of charcoal co-product (HHVdb as high as coal) from thermochemical waste biomass-to-energy conversion (slow/fast pyrolysis and gasification) has received considerable interests for both contaminated and agricultural lands. Biochar amendment not only increases soil organic carbon cont...

Hybrid Thermochemical/Biological Processing

NASA Astrophysics Data System (ADS)

Brown, Robert C.

The conventional view of biorefineries is that lignocellulosic plant material will be fractionated into cellulose, hemicellulose, lignin, and terpenes before these components are biochemically converted into market products. Occasionally, these plants include a thermochemical step at the end of the process to convert recalcitrant plant components or mixed waste streams into heat to meet thermal energy demands elsewhere in the facility. However, another possibility for converting high-fiber plant materials is to start by thermochemically processing it into a uniform intermediate product that can be biologically converted into a bio-based product. This alternative route to bio-based products is known as hybrid thermochemical/biological processing. There are two distinct approaches to hybrid processing: (a) gasification followed by fermentation of the resulting gaseous mixture of carbon monoxide (CO), hydrogen (H2), and carbon dioxide (CO2) and (b) fast pyrolysis followed by hydrolysis and/or fermentation of the anhydrosugars found in the resulting bio-oil. This article explores this "cart before the horse" approach to biorefineries.

Catalytic Upgrading of Thermochemical Intermediates to Hydrocarbons: Conversion of Lignocellulosic Feedstocks to Aromatic Fuels and High Value Chemicals

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

Cortright, Randy; Rozmiarek, Bob; Van Straten, Matt

The principal objective of this project was to develop a fully integrated catalytic process that efficiently converts lignocellulosic feedstocks (e.g. bagasse, corn stover, and loblolly pine) into aromatic-rich fuels and chemicals. Virent led this effort with key feedstock support from Iowa State University. Within this project, Virent leveraged knowledge of catalytic processing of sugars and biomass to investigate two liquefaction technologies (Reductive Catalytic Liquefaction (USA Patent No. 9,212,320, 2015) and Solvolysis (USA Patent No. 9,157,030, 2015) (USA Patent No. 9,157,031, 2015)) that take advantage of proprietary catalysts at temperatures less than 300°C in the presence of unique solvent molecules generatedmore » in-situ within the liquefaction processes.« less

Testing of an advanced thermochemical conversion reactor system

NASA Astrophysics Data System (ADS)

1990-01-01

This report presents the results of work conducted by MTCI to verify and confirm experimentally the ability of the MTCI gasification process to effectively generate a high-quality, medium-Btu gas from a wider variety of feedstock and waste than that attainable in air-blown, direct gasification systems. The system's overall simplicity, due to the compact nature of the pulse combustor, and the high heat transfer rates attainable within the pulsating flow resonance tubes, provide a decided and near-term potential economic advantage for the MTCI indirect gasification system. The primary objective was the design, construction, and testing of a Process Design Verification System for an indirectly heated, thermochemical fluid-bed reactor and a pulse combustor an an integrated system that can process alternative renewable sources of energy such as biomass, black liquor, municipal solid waste and waste hydrocarbons, including heavy oils into a useful product gas. The test objectives for the biomass portion of this program were to establish definitive performance data on biomass feedstocks covering a wide range of feedstock qualities and characteristics. The test objectives for the black liquor portion of this program were to verify the operation of the indirect gasifier on commercial black liquor containing 65 percent solids at several temperature levels and to characterize the bed carbon content, bed solids particle size and sulfur distribution as a function of gasification conditions.

Techno-Economic, Sustainability, and Market Analysis | Bioenergy | NREL

Science.gov Websites

Techno-Economic, Sustainability, and Market Analysis Techno-Economic, Sustainability, and Market Analysis NREL conducts techno-economic analyses (TEAs) for algal biofuels, thermochemical conversion, and agitating the liquid as it flows around. Algal Biofuels Techno-Economic Analysis NREL's Algae Techno

Across-phase biomass pyrolysis stoichiometry, energy balance, and product formation kinetics

USDA-ARS?s Scientific Manuscript database

Predictive correlations between reactions occurring in the gas-, liquid- and solid-phases are necessary to economically utilize the thermochemical conversion of agricultural wastes impacting the food, water, and energy nexus. On the basis of an empirical mass balance (99.7%), this study established...

Conversion of sweet sorghum bagasse into value-added biochar

USDA-ARS?s Scientific Manuscript database

Sweet sorghum bagasse is an untapped resourceful carbon-rich material that can be thermochemically converted into value-added biochars. These biochars can be applied to the field as soil amendment for soil health enhancement, improved soil carbon content, water holding capacity, soil drainage and a...

Evaluation of Brazilian biomasses as potential feedstocks for fuel production via fast pyrolysis

USDA-ARS?s Scientific Manuscript database

The utilization of lignocellulosic materials to generate energy is constantly expanding around the world. In addition to the well-known biofuels such as ethanol and biodiesel, advanced biofuels obtained by thermochemical conversion routes have been explored, including pyrolysis oil, biochar and syng...

Evaluation of biochars by temperature programmed oxidation/mass spectrometry

Treesearch

Michael Jackson; Thomas Eberhardt; Akwasi Boateng; Charles Mullen; Les Groom

2013-01-01

Biochars produced from thermochemical conversions of biomass were evaluated by temperature programmed oxidation (TPO). This technique, used to characterize carbon deposits on petroleum cracking catalysts, provides information on the oxidative stability of carbonaceous solids, where higher temperature reactivity indicates greater structural order, an important property...

Improved conversion of herbaceous biomass to biofuels: Potential for modification of key plant characteristics

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

Sladden, S.E.; Bransby, D.I.

1989-10-01

Biomass crops are converted to fuels via biochemical and thermochemical processes. The process preferred depends on properties and cost of available feedstocks, and on the specific products desired. Since most mature biomass crops are composed of up to 80% cell wall fibers, the properties of these fibers determine, to a large degree, the conversion potential of the crop. However, biomass crops also contain small amounts of proteins, soluble carbohydrates and interfering materials (e.g., tannins and silica) which also influence the desirability of the feedstock in specific conversion processes. Fortunately, wide variation exists in the chemical composition of potential biomass crops.more » Although the chemical composition of feedstocks can be influenced significantly with judicious management has species selection, some traits are sufficiently heritable to permit breeding for improved feedstock composition. In addition to breeding for specific compositional traits directly, selection for in vitro digestibility or for easily-measured canopy or physiological traits may lead to more rapid and efficient progress in feedstock improvement, provided those measurements are highly-correlated with desirable feedstock composition. At the same time breeders must improve, or at least avoid damaging, stand longevity, tendency of plants to lodge, and establishment traits (e.g., disease resistance and seedling vigor). 46 refs., 8 tabs.« less

Thermochemical characterization of pigeon pea stalk for its efficient utilization as an energy source

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

Katyal, S.K.; Iyer, P.V.R.

2000-05-01

Pigeon pea stalk is a widely available biomass species in India. In this article the potential use of pigeon pea stalk as a fuel source through thermochemical conversion methods such as combustion, gasification, and pyrolysis has been investigated through experimentation using a thermogravimetric analyzer and pilot-plant-scale equipment. It has been proposed that pigeon pea stalks can be effectively utilized in two ways. The first is to pyrolyze the material to produce value-added products such as char, tar, and fuel gas. The second alternative is to partially pyrolyze the material to remove tar-forming volatiles, followed by gasification of reactive char tomore » generate producer gas.« less

Hydrogen as an energy medium

NASA Technical Reports Server (NTRS)

Cox, K. E.

1976-01-01

Coal, though abundant in certain geographical locations of the USA poses environmental problems associated with its mining and combustion. Also, nuclear fission energy appears to have problems regarding safety and radioactive waste disposal that are as yet unresolved. The paper discusses hydrogen use and market projection along with energy sources for hydrogen production. Particular attention is given to hydrogen production technology as related to electrolysis and thermochemical water decomposition. Economics of hydrogen will ultimately be determined by the price and availability of future energy carriers such as electricity and synthetic natural gas. Thermochemical methods of hydrogen production appear to offer promise largely in the efficiency of energy conversion and in capital costs over electrolytic methods.

Catalytic thermal cracking of postconsumer waste plastics to fuels. 2. Pilot-scale thermochemical conversion

USDA-ARS?s Scientific Manuscript database

Synthetic gasoline and diesel fuels were prepared via catalytic and noncatalytic pyrolysis of waste polyethylene and polypropylene plastics followed by distillation of plastic crude oils. Reaction conditions optimized using a 2 L batch reactor were applied to pilot-scale production of plastic crude ...

Hydrothermal carbonization of municipal solid waste for carbon sequestration and energy generation

USDA-ARS?s Scientific Manuscript database

A fairly new, innovative technique, called hydrothermal carbonization (HTC), has the potential to change the way municipal solid waste (MSW) is managed. HTC is a wet, low temperature (180-350°C), low pressure (in a closed system) thermochemical waste treatment/conversion technology that has been sho...

Heterogeneous Catalysis for Thermochemical Conversion | Bioenergy | NREL

Science.gov Websites

redox Ce-ZrO2 support. This article discusses research findings that appropriately frame the challenges to aid in bridging the findings of theoretical and experimental catalysis research, and transforming zeolite active site design from an empirical endeavor into a more predictable science founded on validated

Thermo-chemical and biological conversion potential of various biomass feedstocks to ethanol

USDA-ARS?s Scientific Manuscript database

The goal of this study is to evaluate the potential and the economy of producing ethanol from gasification-fermentation of various biomass feedstocks. The biomass feedstocks include winter cover crops (wheat, rye, clover, hairy betch), summer cover crop (sunhemp), chicken litter, and woody biomass. ...

Thermochemical conversion technologies for production of renewable energy and value-added char from animal manures

USDA-ARS?s Scientific Manuscript database

Confined animal feeding operations (CAFOs) in the USA and many other countries have undergone extensive expansions and consolidations for the last few decades. This shift in animal production agriculture toward fewer, but larger operations has created serious environmental concerns in recycling and ...

Reversible and irreversible sorption of agrochemicals in biochar amended soils: synergistic effects of heavy metals

USDA-ARS?s Scientific Manuscript database

Soil amendment of biochar products from thermochemical waste-to-energy conversion (slow/fast pyrolysis and gasification) of biomass has received considerable interests for both contaminated and agricultural sites. Recalcitrant nature of biochar manifests in their decade-long effectiveness in soil a...

Valorization of guayule as a feedstock for lignocellulosic biorefineries using ammonia fiber expansion (AFEX) pretreatment

USDA-ARS?s Scientific Manuscript database

Natural rubber latex extraction from guayule leaves behind greater than 80% (by weight) of agricultural residue as a feedstock suitable for conversion to biofuels via a thermochemical or biochemical route. Untreated guayule shrub and bagasse (after latex extraction) has shown to be very recalcitrant...

Chemical state of chromium in sewage sludge ash based phosphorus-fertilisers.

PubMed

Vogel, Christian; Adam, Christian; Kappen, Peter; Schiller, Tara; Lipiec, Ewelina; McNaughton, Don

2014-05-01

Sewage sludge ash (SSA) based P-fertilisers were produced by thermochemical treatment of SSA with Cl-donors at approximately 1000°C. During this thermochemical process heavy metals are separated as heavy metal chlorides via the gas phase. Chromium cannot be separated under normal conditions. The risk of the development of toxic Cr(VI) during the thermochemical process was investigated. X-ray Absorption Spectroscopy measurements showed that SSA and thermochemically treated SSA with CaCl2, MgCl2 and NaCl contain Cr(III) compounds only. In contrast, treating SSA with elevated quantities of Na2CO3, to enhance the plant-availability of the phosphate phases of the fertiliser, developed approximately 10-15% Cr(VI). Furthermore, Raman microspectroscopy showed that using Mg-carbonate reduces the risk of a Cr(VI) development during thermochemical treatment. Additionally, leaching tests showed that only a Cr-water solubility>10% is an indicator for Cr(VI) in SSA based P-fertilisers. Copyright © 2013 Elsevier Ltd. All rights reserved.

Conversion and assimilation of furfural and 5-(hydroxymethyl)furfural by Pseudomonas putida KT2440

DOE PAGES

Guarnieri, Michael T.; Franden, Mary Ann; Johnson, Christopher W.; ...

2017-02-08

The sugar dehydration products, furfural and 5-(hydroxymethyl)furfural (HMF), are commonly formed during high-temperature processing of lignocellulose, most often in thermochemical pretreatment, liquefaction, or pyrolysis. Typically, these two aldehydes are considered major inhibitors in microbial conversion processes. Many microbes can convert these compounds to their less toxic, dead-end alcohol counterparts, furfuryl alcohol and 5-(hydroxymethyl)furfuryl alcohol. Recently, the genes responsible for aerobic catabolism of furfural and HMF were discovered in Cupriavidus basilensis HMF14 to enable complete conversion of these compounds to the TCA cycle intermediate, 2-oxo-glutarate. In this work, we engineer the robust soil microbe, Pseudomonas putida KT2440, to utilize furfural andmore » HMF as sole carbon and energy sources via complete genomic integration of the 12 kB hmf gene cluster previously reported from Burkholderia phytofirmans. The common intermediate, 2-furoic acid, is shown to be a bottleneck for both furfural and HMF metabolism. When cultured on biomass hydrolysate containing representative amounts of furfural and HMF from dilute-acid pretreatment, the engineered strain outperforms the wild type microbe in terms of reduced lag time and enhanced growth rates due to catabolism of furfural and HMF. Overall, this study demonstrates that an approach for biological conversion of furfural and HMF, relative to the typical production of dead-end alcohols, enables both enhanced carbon conversion and substantially improves tolerance to hydrolysate inhibitors. Furthermore, this approach should find general utility both in emerging aerobic processes for the production of fuels and chemicals from biomass-derived sugars and in the biological conversion of high-temperature biomass streams from liquefaction or pyrolysis where furfural and HMF are much more abundant than in biomass hydrolysates from pretreatment.« less

Conversion and assimilation of furfural and 5-(hydroxymethyl)furfural by Pseudomonas putida KT2440

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

Guarnieri, Michael T.; Franden, Mary Ann; Johnson, Christopher W.

The sugar dehydration products, furfural and 5-(hydroxymethyl)furfural (HMF), are commonly formed during high-temperature processing of lignocellulose, most often in thermochemical pretreatment, liquefaction, or pyrolysis. Typically, these two aldehydes are considered major inhibitors in microbial conversion processes. Many microbes can convert these compounds to their less toxic, dead-end alcohol counterparts, furfuryl alcohol and 5-(hydroxymethyl)furfuryl alcohol. Recently, the genes responsible for aerobic catabolism of furfural and HMF were discovered in Cupriavidus basilensis HMF14 to enable complete conversion of these compounds to the TCA cycle intermediate, 2-oxo-glutarate. In this work, we engineer the robust soil microbe, Pseudomonas putida KT2440, to utilize furfural andmore » HMF as sole carbon and energy sources via complete genomic integration of the 12 kB hmf gene cluster previously reported from Burkholderia phytofirmans. The common intermediate, 2-furoic acid, is shown to be a bottleneck for both furfural and HMF metabolism. When cultured on biomass hydrolysate containing representative amounts of furfural and HMF from dilute-acid pretreatment, the engineered strain outperforms the wild type microbe in terms of reduced lag time and enhanced growth rates due to catabolism of furfural and HMF. Overall, this study demonstrates that an approach for biological conversion of furfural and HMF, relative to the typical production of dead-end alcohols, enables both enhanced carbon conversion and substantially improves tolerance to hydrolysate inhibitors. Furthermore, this approach should find general utility both in emerging aerobic processes for the production of fuels and chemicals from biomass-derived sugars and in the biological conversion of high-temperature biomass streams from liquefaction or pyrolysis where furfural and HMF are much more abundant than in biomass hydrolysates from pretreatment.« less

Conversion and assimilation of furfural and 5-(hydroxymethyl)furfural by Pseudomonas putida KT2440.

PubMed

Guarnieri, Michael T; Ann Franden, Mary; Johnson, Christopher W; Beckham, Gregg T

2017-06-01

The sugar dehydration products, furfural and 5-(hydroxymethyl)furfural (HMF), are commonly formed during high-temperature processing of lignocellulose, most often in thermochemical pretreatment, liquefaction, or pyrolysis. Typically, these two aldehydes are considered major inhibitors in microbial conversion processes. Many microbes can convert these compounds to their less toxic, dead-end alcohol counterparts, furfuryl alcohol and 5-(hydroxymethyl)furfuryl alcohol. Recently, the genes responsible for aerobic catabolism of furfural and HMF were discovered in Cupriavidus basilensis HMF14 to enable complete conversion of these compounds to the TCA cycle intermediate, 2-oxo-glutarate. In this work, we engineer the robust soil microbe, Pseudomonas putida KT2440, to utilize furfural and HMF as sole carbon and energy sources via complete genomic integration of the 12 kB hmf gene cluster previously reported from Burkholderia phytofirmans . The common intermediate, 2-furoic acid, is shown to be a bottleneck for both furfural and HMF metabolism. When cultured on biomass hydrolysate containing representative amounts of furfural and HMF from dilute-acid pretreatment, the engineered strain outperforms the wild type microbe in terms of reduced lag time and enhanced growth rates due to catabolism of furfural and HMF. Overall, this study demonstrates that an approach for biological conversion of furfural and HMF, relative to the typical production of dead-end alcohols, enables both enhanced carbon conversion and substantially improves tolerance to hydrolysate inhibitors. This approach should find general utility both in emerging aerobic processes for the production of fuels and chemicals from biomass-derived sugars and in the biological conversion of high-temperature biomass streams from liquefaction or pyrolysis where furfural and HMF are much more abundant than in biomass hydrolysates from pretreatment.

Biomass Supply Chain and Conversion Economics of Cellulosic Ethanol

NASA Astrophysics Data System (ADS)

Gonzalez, Ronalds W.

2011-12-01

Cellulosic biomass is a potential and competitive source for bioenergy production, reasons for such acclamation include: biomass is one the few energy sources that can actually be utilized to produce several types of energy (motor fuel, electricity, heat) and cellulosic biomass is renewable and relatively found everywhere. Despite these positive advantages, issues regarding cellulosic biomass availability, supply chain, conversion process and economics need a more comprehensive understanding in order to identify the near short term routes in biomass to bioenergy production. Cellulosic biomass accounts for around 35% to 45% of cost share in cellulosic ethanol production, in addition, different feedstock have very different production rate, (dry ton/acre/year), availability across the year, and chemical composition that affect process yield and conversion costs as well. In the other hand, existing and brand new conversion technologies for cellulosic ethanol production offer different advantages, risks and financial returns. Ethanol yield, financial returns, delivered cost and supply chain logistic for combinations of feedstock and conversion technology are investigated in six studies. In the first study, biomass productivity, supply chain and delivered cost of fast growing Eucalyptus is simulated in economic and supply chain models to supply a hypothetic ethanol biorefinery. Finding suggests that Eucalyptus can be a potential hardwood grown specifically for energy. Delivered cost is highly sensitive to biomass productivity, percentage of covered area. Evaluated at different financial expectations, delivered cost can be competitive compared to current forest feedstock supply. In the second study, Eucalyptus biomass conversion into cellulosic ethanol is simulated in the dilute acid pretreatment, analysis of conversion costs, cost share, CAPEX and ethanol yield are examined. In the third study, biomass supply and delivered cost of loblolly pine is simulated in economic and supply chain models specifically for biomass to bioenergy production. The study suggest that this species can be profitably managed for biomass production with rotation length of 11 to 12 years and with a stand tree density of 1,200 trees per acre. Optimum rotation length is greatly affected by seedlings costs and biomass productivity. In the fourth study, a evaluation of seven different feedstocks (loblolly pine, natural mixed hardwood, Eucalyptus, switchgrass, miscanthus, corn stover and sweet sorghum) is made in terms of supply chain, biomass delivered costs, dollar per ton of carbohydrate and dollar per million BTU delivered to a biorefinery. Forest feedstocks present better advantages in terms of a well established supply chain, year round supply and no need for biomass storage. In the same context biomass delivered costs, as well as cost to delivered one ton of carbohydrate and one million BTU is lower in forest feedstocks. In the fifth study, conversion costs, profitability and sensitivity analysis for a novel pretreatment process, green liquor, are modeled for ethanol production with loblolly pine, natural mixed hardwood and Eucalyptus as feedstocks, evaluated in two investment scenarios: green field and repurposing of an old kraft pulp mill. Better financial returns are perceived in the natural hardwood - repurposing scenario, mainly due to lower CAPEX and lower enzyme charge and cost. In the sixth study, conversion cost, CAPEX, ethanol yield and profitability for the thermochemical process (indirect gasification and production of mixed alcohol) is simulated for loblolly pine, natural hardwood, eucalyptus, corn stover and switchgrass. Higher ethanol yield with forest feedstock (due to higher content of %C and %H) result in better economic performance, when compare to agriculture biomass. This research indicates that forest feedstock outperform agriculture biomass in terms of delivered costs, supply chain, ethanol yield and process profitability. Loblolly pine seems to be more suitable for thermochemical processes, while hardwood suit better for biochemical conversion (based on the technologies studied).

Life-Cycle Assessment of a Distributed-Scale Thermochemical Bioenergy Conversion System

Treesearch

Hongmei Gu; Richard Bergman

2016-01-01

Expanding bioenergy production from woody biomass has the potential to decrease net greenhouse gas (GHG) emissions and improve the energy security of the United States. Science-based and internationally accepted life-cycle assessment (LCA) is an effective tool for policy makers to make scientifically informed decisions on expanding renewable energy production from...

Fate of higher-mass elements and surface functional groups during the pyrolysis of waste pecan shell

USDA-ARS?s Scientific Manuscript database

Thermochemical conversion of agricultural wastes to bioenergy has a potential to play forefront roles within the context of food, energy, and water nexus. Biochar solid product of pyrolysis is a promising tool to manage food crop production and water resources by means of soil amendment. The goal ...

Financial performance of a mobile pyrolysis system used to produce biochar from sawmill residues

Treesearch

Dongyeob Kim; Nathaniel McLean Anderson; Woodam Chung

2015-01-01

Primary wood products manufacturers generate significant amounts of woody biomass residues that can be used as feedstocks for distributed-scale thermochemical conversion systems that produce valuable bioenergy and bioproducts. However, private investment in these technologies is driven primarily by financial performance, which is often unknown for new technologies with...

Estimating GHG Emissions from the Manufacturing of Field-Applied Biochar Pellets

Treesearch

Richard D. Bergman; Hanwen Zhang; Karl Englund; Keith Windell; Hongmei Gu

2016-01-01

Biochar application to forest soils can provide direct and indirect benefits, including carbon sequestration. Biochar, the result of thermochemical conversion of biomass, can have positive environmental climate benefits and can be more stable when field-applied to forest soils than wood itself. Categorizing greenhouse gas (GHG) emissions and carbon sequestration...

Thermochemical conversion of biomass in smouldering combustion across scales: The roles of heterogeneous kinetics, oxygen and transport phenomena.

PubMed

Huang, Xinyan; Rein, Guillermo

2016-05-01

The thermochemical conversion of biomass in smouldering combustion is investigated here by combining experiments and modeling at two scales: matter (1mg) and bench (100g) scales. Emphasis is put on the effect of oxygen (0-33vol.%) and oxidation reactions because these are poorly studied in the literature in comparison to pyrolysis. The results are obtained for peat as a representative biomass for which there is high-quality experimental data published previously. Three kinetic schemes are explored, including various steps of drying, pyrolysis and oxidation. The kinetic parameters are found using the Kissinger-Genetic Algorithm method, and then implemented in a one-dimensional model of heat and mass transfer. The predictions are validated with thermogravimetric and bench-scale experiments and then analyzed to unravel the role of heterogeneous reaction. This is the first time that the influence of oxygen on biomass smouldering is explained in terms of both chemistry and transport phenomena across scales. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Thermochemical pretreatment of lignocellulose residues: assessment of the effect on operational conditions and their interactions on the characteristics of leachable fraction.

PubMed

Vásquez, Denisse; Contreras, Elsa; Palma, Carolyn; Carvajal, Andrea

2015-01-01

Annually, large amounts of agricultural residues are produced in Chile, which can be turned into a good opportunity to diversify the energy matrix. These residues have a slow hydrolysis stage during anaerobic digestion; therefore, the application of a pretreatment seems to be an alternative to improve the process. This work focused on applying a thermochemical pretreatment with NaOH on two lignocellulosic residues. The experiments were performed according to a 2(4) factorial design. The factors studied in a 2(4) factorial design were: temperature (60 and 120 °C), pretreatment time (10 and 30 minutes), NaOH dose (2 and 4%), and residue size (<1 and 1-3 mm for wheat straw; 1-5 and 5-10 mm for corn stover). The analyzed response variables were the solubilization of organic matter, and the biodegradability of the lignocellulose hydrolysate. The statistical analysis of the data allowed the identification of the experimental conditions that maximized solubilization of organic matter and biodegradability. The main results showed that more aggressive experimental conditions could increase the breaking down of the structure; in addition, the time of pretreatment was not significant. Conversely, the less aggressive experimental conditions, regarding regent dosage and downsizing, favored the release of biodegradable organic matter. The main conclusion of this study was the identification of the operational conditions of the thermochemical pretreatment that promote maximum biogas production, which was caused due to the solubilization of a large amount of organic matter, but not because of the increase in biodegradability of the released organic matter.

Characterisation of chemical composition and energy content of green waste and municipal solid waste from Greater Brisbane, Australia.

PubMed

Hla, San Shwe; Roberts, Daniel

2015-07-01

The development and deployment of thermochemical waste-to-energy systems requires an understanding of the fundamental characteristics of waste streams. Despite Australia's growing interest in gasification of waste streams, no data are available on their thermochemical properties. This work presents, for the first time, a characterisation of green waste and municipal solid waste in terms of chemistry and energy content. The study took place in Brisbane, the capital city of Queensland. The municipal solid waste was hand-sorted and classified into ten groups, including non-combustibles. The chemical properties of the combustible portion of municipal solid waste were measured directly and compared with calculations made based on their weight ratios in the overall municipal solid waste. The results obtained from both methods were in good agreement. The moisture content of green waste ranged from 29% to 46%. This variability - and the tendency for soil material to contaminate the samples - was the main contributor to the variation of samples' energy content, which ranged between 7.8 and 10.7MJ/kg. The total moisture content of food wastes and garden wastes was as high as 70% and 60%, respectively, while the total moisture content of non-packaging plastics was as low as 2.2%. The overall energy content (lower heating value on a wet basis, LHVwb) of the municipal solid waste was 7.9MJ/kg, which is well above the World Bank-recommended value for utilisation in thermochemical conversion processes. Copyright © 2015 Elsevier Ltd. All rights reserved.

Method for Hot Real-Time Sampling of Gasification Products

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

Pomeroy, Marc D

The Thermochemical Process Development Unit (TCPDU) at the National Renewable Energy Laboratory (NREL) is a highly instrumented half-ton/day pilot scale plant capable of demonstrating industrially relevant thermochemical technologies from lignocellulosic biomass conversion, including gasification. Gasification creates primarily Syngas (a mixture of Hydrogen and Carbon Monoxide) that can be utilized with synthesis catalysts to form transportation fuels and other valuable chemicals. Biomass derived gasification products are a very complex mixture of chemical components that typically contain Sulfur and Nitrogen species that can act as catalysis poisons for tar reforming and synthesis catalysts. Real-time hot online sampling techniques, such as Molecular Beammore » Mass Spectrometry (MBMS), and Gas Chromatographs with Sulfur and Nitrogen specific detectors can provide real-time analysis providing operational indicators for performance. Sampling typically requires coated sampling lines to minimize trace sulfur interactions with steel surfaces. Other materials used inline have also shown conversion of sulfur species into new components and must be minimized. Sample line Residence time within the sampling lines must also be kept to a minimum to reduce further reaction chemistries. Solids from ash and char contribute to plugging and must be filtered at temperature. Experience at NREL has shown several key factors to consider when designing and installing an analytical sampling system for biomass gasification products. They include minimizing sampling distance, effective filtering as close to source as possible, proper line sizing, proper line materials or coatings, even heating of all components, minimizing pressure drops, and additional filtering or traps after pressure drops.« less

Syngas Production By Thermochemical Conversion Of H2o And Co2 Mixtures Using A Novel Reactor Design

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

Pearlman, Howard; Chen, Chien-Hua

The Department of Energy awarded Advanced Cooling Technologies, Inc. (ACT) an SBIR Phase II contract (#DE-SC0004729) to develop a high-temperature solar thermochemical reactor for syngas production using water and/or carbon dioxide as feedstocks. The technology aims to provide a renewable and sustainable alternative to fossil fuels, promote energy independence and mitigate adverse issues associated with climate change by essentially recycling carbon from carbon dioxide emitted by the combustion of hydrocarbon fuels. To commercialize the technology and drive down the cost of solar fuels, new advances are needed in materials development and reactor design, both of which are integral elements inmore » this program.« less

Updraft gasification of poultry litter at farm-scale--A case study.

PubMed

Taupe, N C; Lynch, D; Wnetrzak, R; Kwapinska, M; Kwapinski, W; Leahy, J J

2016-04-01

Farm and animal wastes are increasingly being investigated for thermochemical conversion, such as gasification, due to the urgent necessity of finding new waste treatment options. We report on an investigation of the use of a farm-scale, auto-thermal gasification system for the production of a heating gas using poultry litter (PL) as a feedstock. The gasification process was robust and reliable. The PL's ash melting temperature was 639°C, therefore the reactor temperature was kept around this value. As a result of the low reactor temperature the process performance parameters were low, with a cold gas efficiency (CGE) of 0.26 and a carbon conversion efficiency (CCE) of 0.44. The calorific value of the clean product gas was 3.39 MJ m(-3)N (LHV). The tar was collected as an emulsion containing 87 wt.% water and the extracted organic compounds were identified. The residual char exceeds thresholds for Zn and Cu to obtain European biochar certification; however, has potential to be classified as a pyrogenic carbonaceous material (PCM), which resembles a high nutrient biochar. Copyright © 2016 Elsevier Ltd. All rights reserved.

Towards a carbon-negative sustainable bio-based economy.

PubMed

Vanholme, Bartel; Desmet, Tom; Ronsse, Frederik; Rabaey, Korneel; Van Breusegem, Frank; De Mey, Marjan; Soetaert, Wim; Boerjan, Wout

2013-01-01

The bio-based economy relies on sustainable, plant-derived resources for fuels, chemicals, materials, food and feed rather than on the evanescent usage of fossil resources. The cornerstone of this economy is the biorefinery, in which renewable resources are intelligently converted to a plethora of products, maximizing the valorization of the feedstocks. Innovation is a prerequisite to move a fossil-based economy toward sustainable alternatives, and the viability of the bio-based economy depends on the integration between plant (green) and industrial (white) biotechnology. Green biotechnology deals with primary production through the improvement of biomass crops, while white biotechnology deals with the conversion of biomass into products and energy. Waste streams are minimized during these processes or partly converted to biogas, which can be used to power the processing pipeline. The sustainability of this economy is guaranteed by a third technology pillar that uses thermochemical conversion to valorize waste streams and fix residual carbon as biochar in the soil, hence creating a carbon-negative cycle. These three different multidisciplinary pillars interact through the value chain of the bio-based economy.

Towards a carbon-negative sustainable bio-based economy

PubMed Central

Vanholme, Bartel; Desmet, Tom; Ronsse, Frederik; Rabaey, Korneel; Breusegem, Frank Van; Mey, Marjan De; Soetaert, Wim; Boerjan, Wout

2013-01-01

The bio-based economy relies on sustainable, plant-derived resources for fuels, chemicals, materials, food and feed rather than on the evanescent usage of fossil resources. The cornerstone of this economy is the biorefinery, in which renewable resources are intelligently converted to a plethora of products, maximizing the valorization of the feedstocks. Innovation is a prerequisite to move a fossil-based economy toward sustainable alternatives, and the viability of the bio-based economy depends on the integration between plant (green) and industrial (white) biotechnology. Green biotechnology deals with primary production through the improvement of biomass crops, while white biotechnology deals with the conversion of biomass into products and energy. Waste streams are minimized during these processes or partly converted to biogas, which can be used to power the processing pipeline. The sustainability of this economy is guaranteed by a third technology pillar that uses thermochemical conversion to valorize waste streams and fix residual carbon as biochar in the soil, hence creating a carbon-negative cycle. These three different multidisciplinary pillars interact through the value chain of the bio-based economy. PMID:23761802

Biochar potential evaluation of palm oil wastes through slow pyrolysis: Thermochemical characterization and pyrolytic kinetic studies.

PubMed

Lee, Xin Jiat; Lee, Lai Yee; Gan, Suyin; Thangalazhy-Gopakumar, Suchithra; Ng, Hoon Kiat

2017-07-01

This research investigated the potential of palm kernel shell (PKS), empty fruit bunch (EFB) and palm oil sludge (POS), abundantly available agricultural wastes, as feedstock for biochar production by slow pyrolysis (50mLmin -1 N 2 at 500°C). Various characterization tests were performed to establish the thermochemical properties of the feedstocks and obtained biochars. PKS and EFB had higher lignin, volatiles, carbon and HHV, and lower ash than POS. The thermochemical conversion had enhanced the biofuel quality of PKS-char and EFB-char exhibiting increased HHV (26.18-27.50MJkg -1 ) and fixed carbon (53.78-59.92%), and decreased moisture (1.03-2.26%). The kinetics of pyrolysis were evaluated by thermogravimetry at different heating rates (10-40°C). The activation energies determined by Kissinger-Akahira-Sunose and Flynn-Wall-Ozawa models were similar, and comparable with literature data. The findings implied that PKS and EFB are very promising sources for biochars synthesis, and the obtained chars possessed significant biofuel potential. Copyright © 2017 Elsevier Ltd. All rights reserved.

Process development for elemental recovery from PGM tailings by thermochemical treatment: Preliminary major element extraction studies using ammonium sulphate as extracting agent.

PubMed

Mohamed, Sameera; van der Merwe, Elizabet M; Altermann, Wladyslaw; Doucet, Frédéric J

2016-04-01

Mine tailings can represent untapped secondary resources of non-ferrous, ferrous, precious, rare and trace metals. Continuous research is conducted to identify opportunities for the utilisation of these materials. This preliminary study investigated the possibility of extracting major elements from South African tailings associated with the mining of Platinum Group Metals (PGM) at the Two Rivers mine operations. These PGM tailings typically contain four major elements (11% Al2O3; 12% MgO; 22% Fe2O3; 34% Cr2O3), with lesser amounts of SiO2 (18%) and CaO (2%). Extraction was achieved via thermochemical treatment followed by aqueous dissolution, as an alternative to conventional hydrometallurgical processes. The thermochemical treatment step used ammonium sulphate, a widely available, low-cost, recyclable chemical agent. Quantification of the efficiency of the thermochemical process required the development and optimisation of the dissolution technique. Dissolution in water promoted the formation of secondary iron precipitates, which could be prevented by leaching thermochemically-treated tailings in 0.6M HNO3 solution. The best extraction efficiencies were achieved for aluminium (ca. 60%) and calcium (ca. 80%). 35% iron and 32% silicon were also extracted, alongside chromium (27%) and magnesium (25%). Thermochemical treatment using ammonium sulphate may therefore represent a promising technology for extracting valuable elements from PGM tailings, which could be subsequently converted to value-added products. However, it is not element-selective, and major elements were found to compete with the reagent to form water-soluble sulphate-metal species. Further development of this integrated process, which aims at achieving the full potential of utilisation of PGM tailings, is currently underway. Copyright © 2016 Elsevier Ltd. All rights reserved.

Evaluation of the Relative Merits of Herbaceous and Woody Crops for Use in Tunable Thermochemical Processing

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

Park, Joon-Hyun; Martinalbo, Ilya

This report summarizes the work and findings of the grant work conducted from January 2009 until September 2011 under the collaboration between Ceres, Inc. and Choren USA, LLC. This DOE-funded project involves a head-to-head comparison of two types of dedicated energy crops in the context of a commercial gasification conversion process. The main goal of the project was to gain a better understanding of the differences in feedstock composition between herbaceous and woody species, and how these differences may impact a commercial gasification process. In this work, switchgrass was employed as a model herbaceous energy crop, and willow as amore » model short-rotation woody crop. Both crops are species native to the U.S. with significant potential to contribute to U.S. goals for renewable liquid fuel production, as outlined in the DOE Billion Ton Update (http://www1.eere.energy.gov/biomass/billion_ton_update.html, 2011). In some areas of the U.S., switching between woody and herbaceous feedstocks or blending of the two may be necessary to keep a large-scale gasifier operating near capacity year round. Based on laboratory tests and process simulations it has been successfully shown that suitable high yielding switchgrass and willow varieties exist that meet the feedstock specifications for large scale entrained flow biomass gasification. This data provides the foundation for better understanding how to use both materials in thermochemical processes. It has been shown that both switchgrass and willow varieties have comparable ranges of higher heating value, BTU content and indistinguishable hydrogen/carbon ratios. Benefits of switchgrass, and other herbaceous feedstocks, include its low moisture content, which reduce energy inputs and costs for drying feedstock. Compared to the typical feedstock currently being used in the Carbo-V® process, switchgrass has a higher ash content, combined with a lower ash melting temperature. Whether or not this may cause inefficiencies in the process, needs to be verified by long term test runs. Currently, there are not sufficient operational test data available for the Carbo-V® process for the utilization of higher ash content feedstocks. The application of currently evolving biomass pretreatment technologies, such as pelletization and torrefaction, will be able to expand the portfolio of biomass varieties and species acceptable in gasification processes. Tests showed that 6 mm diameter pellets of switchgrass were superior to 8 mm diameter pellets produced in a flat dye press, and that torrefaction of switchgrass produced an excellent (but currently costly) feedstock that could be handled, crushed, and combusted in a manner compatible with any coal-fed gasification facility. Ceres will use this information in the development of high yielding, dedicated energy crops specifically tailored for thermochemical conversion. CHOREN will make use of the information for improvement or development of low cost, highly efficient biomass gasification processes that convert a wide variety of biomass feedstocks to fuels, chemicals, heat and power via the production of tar free green syngas on an industrial scale.« less

Chemistry of sustainability-Part I: Carbon dioxide as an organic synthon and Part II: Study of thermodynamics of cation exchange reactions in semiconductor nanocrystals

NASA Astrophysics Data System (ADS)

Sathe, Ajay A.

Sustainability is an important part of the design and development of new chemical and energy conversion processes. Simply put sustainability is the ability to meet our needs without sacrificing the ability of the next generations to meet theirs. This thesis describes our efforts in developing two orthogonal strategies for the fixation of CO2 by utilizing high energy intermediates which are generated via oxidative or reductive processes on common organic substrates and of thermochemical measurements of cation exchange reactions which will aid the development of new materials relevant for energy conversion and storage. The first chapter lays a background for the challenges and opportunities for the use of CO2 in organic synthesis. The rapidly growing field of continuous flow processing in organic synthesis is introduced, and its importance in the development of sustainable chemical conversions is highlighted. The second chapter describes the development of a novel route to alpha-amino acids via reductive carboxylation of imines. A mechanistic proposal is presented and the reaction is shown to proceed through the intermediacy of alpha-amino alkyl metal species. Possible strategies for designing catalytic and enantioselective variants of the reaction are presented. The third chapter describes the development of a catalytic oxidative carboxylation of olefins to yield cyclic carbonates. The importance of flow chemistry and membrane separation is demonstrated by allowing the combination of mutually incompatible reagents in a single reaction sequence. While the use of carbon dioxide for synthesis of organic fine chemicals is not expected to help reduce the atmospheric carbon dioxide levels, or tackle climate change, it certainly has the potential to reduce our dependence on non-sustainable carbon feedstocks, and help achieve a carbon neutral chemical life cycle. Having described the use of carbon dioxide and flow chemistry for sustainable chemical conversion, the fourth chapter introduces the role of nanomaterials in sustainable solar energy conversion and storage. The use of cation exchange reactions in nanocrystals to access novel materials is highlighted. Despite having shown tremendous promise in the synthetic applications, the fundamental measurements of the thermodynamic and kinetic parameters of a cation exchange reaction are largely non-existent. This impedes the future growth of this powerful methodology. The technique of isothermal titration calorimetry is introduced, and its importance to studying the thermochemical changes occurring during cation exchange is outlined. The final chapter presents results obtained from the isothermal titration calorimetry on the prototypical cation exchange reaction between cadmium selenide and silver ions. The role of nanoparticle size, identity of the silver salt, solvent, surface ligands and temperature is studied. Recommendations for future investigations using ITC as well as other characterization techniques for discerning the kinetics of cation exchange are presented. I believe that a more unified mechanistic understanding of the cation exchange process in nanomaterials will aid the development of more efficient and robust materials for applications in a wide variety of fields.

Impact of harvest time and switchgrass cultivar on conversion to sugars and pyrolysis oils using biochemical and thermochemical routes

USDA-ARS?s Scientific Manuscript database

Switchgrass (Panicum virgatum L.), a perennial grass native to much of North America, is undergoing development as a dedicated energy crop. While high-biomass yield is necessary for the development of switchgrass as a bioenergy crop, composition of the biomass and nutrient content as they relate to...

Torrefaction? What’s that?

Treesearch

D. Mitchell; T. Elder

2010-01-01

Torrefaction is a thermo-chemical process that reduces the moisture content of wood and transforms it into a brittle, char-type material. The thermo-chemical process can reduce the mass of wood by 20-30% resulting in a denser, higher-valued product that can be transported more economically than traditional wood chips. Through torrefaction, wood may retain 90% of the...

Thermochemical analyses of the oxidative vaporization of metals and oxides by oxygen molecules and atoms

NASA Technical Reports Server (NTRS)

Kohl, F. J.; Leisz, D. M.; Fryburg, G. C.; Stearns, C. A.

1977-01-01

Equilibrium thermochemical analyses are employed to describe the vaporization processes of metals and metal oxides upon exposure to molecular and atomic oxygen. Specific analytic results for the chromium-, platinum-, aluminum-, and silicon-oxygen systems are presented. Maximum rates of oxidative vaporization predicted from the thermochemical considerations are compared with experimental results for chromium and platinum. The oxidative vaporization rates of chromium and platinum are considerably enhanced by oxygen atoms.

Hydrogen production from solar energy

NASA Technical Reports Server (NTRS)

Eisenstadt, M. M.; Cox, K. E.

1975-01-01

Three alternatives for hydrogen production from solar energy have been analyzed on both efficiency and economic grounds. The analysis shows that the alternative using solar energy followed by thermochemical decomposition of water to produce hydrogen is the optimum one. The other schemes considered were the direct conversion of solar energy to electricity by silicon cells and water electrolysis, and the use of solar energy to power a vapor cycle followed by electrical generation and electrolysis. The capital cost of hydrogen via the thermochemical alternative was estimated at $575/kW of hydrogen output or $3.15/million Btu. Although this cost appears high when compared with hydrogen from other primary energy sources or from fossil fuel, environmental and social costs which favor solar energy may prove this scheme feasible in the future.

Solar thermochemical splitting of water to generate hydrogen

PubMed Central

Rao, C. N. R.; Dey, Sunita

2017-01-01

Solar photochemical means of splitting water (artificial photosynthesis) to generate hydrogen is emerging as a viable process. The solar thermochemical route also promises to be an attractive means of achieving this objective. In this paper we present different types of thermochemical cycles that one can use for the purpose. These include the low-temperature multistep process as well as the high-temperature two-step process. It is noteworthy that the multistep process based on the Mn(II)/Mn(III) oxide system can be carried out at 700 °C or 750 °C. The two-step process has been achieved at 1,300 °C/900 °C by using yttrium-based rare earth manganites. It seems possible to render this high-temperature process as an isothermal process. Thermodynamics and kinetics of H2O splitting are largely controlled by the inherent redox properties of the materials. Interestingly, under the conditions of H2O splitting in the high-temperature process CO2 can also be decomposed to CO, providing a feasible method for generating the industrially important syngas (CO+H2). Although carbonate formation can be addressed as a hurdle during CO2 splitting, the problem can be avoided by a suitable choice of experimental conditions. The choice of the solar reactor holds the key for the commercialization of thermochemical fuel production. PMID:28522461

Thermochemical water decomposition processes

NASA Technical Reports Server (NTRS)

Chao, R. E.

1974-01-01

Thermochemical processes which lead to the production of hydrogen and oxygen from water without the consumption of any other material have a number of advantages when compared to other processes such as water electrolysis. It is possible to operate a sequence of chemical steps with net work requirements equal to zero at temperatures well below the temperature required for water dissociation in a single step. Various types of procedures are discussed, giving attention to halide processes, reverse Deacon processes, iron oxide and carbon oxide processes, and metal and alkali metal processes. Economical questions are also considered.

Cyclic thermochemical process for producing hydrogen using cerium-titanium compounds

DOEpatents

Bamberger, Carlos E.

1980-01-01

A thermochemical cyclic process for producing hydrogen employs the reaction between ceric oxide and titanium dioxide to form cerium titanate and oxygen. The titanate is treated with an alkali metal hydroxide to give hydrogen, ceric oxide, an alkali metal titanate and water. Alkali metal titanate and water are boiled to give titanium dioxide which, along with ceric oxide, is recycled.

Cyclic thermochemical process for producing hydrogen using cerium-titanium compounds

DOEpatents

Bamberger, C.E.

A thermochemical cyclic process for producing hydrogen employs the reaction between ceric oxide and titanium dioxide to form cerium titanate and oxygen. The titanate is treated with an alkali metal hydroxide to give hydrogen, ceric oxide, an alkali metal titanate and water. Alkali metal titanate and water are boiled to give titanium dioxide which, along with ceric oxide, is recycled.

Thermochemical valorization and characterization of household biowaste.

PubMed

Vakalis, S; Sotiropoulos, A; Moustakas, K; Malamis, D; Vekkos, K; Baratieri, M

2017-12-01

Valorization of municipal solid waste (MSW), by means of energy and material recovery, is considered to be a crucial step for sustainable waste management. A significant fraction of MSW is comprised from food waste, the treatment of which is still a challenge. Therefore, the conventional disposal of food waste in landfills is being gradually replaced by recycling aerobic treatment, anaerobic digestion and waste-to-energy. In principle, thermal processes like combustion and gasification are preferred for the recovery of energy due to the higher electrical efficiency and the significantly less time required for the process to be completed when compared to biological process, i.e. composting, anaerobic digestion and transesterification. Nonetheless, the high water content and the molecular structure of biowaste are constraining factors in regard to the application of thermal conversion pathways. Investigating alternative solutions for the pre-treatment and more energy efficient handling of this waste fraction may provide pathways for the optimization of the whole process. In this study, by means of utilizing drying/milling as an intermediate step, thermal treatment of household biowaste has become possible. Household biowaste has been thermally processed in a bench scale reactor by means of torrefaction, carbonization and high temperature pyrolysis. According to the operational conditions, fluctuating fractions of biochar, bio-oil (tar) and syngas were recovered. The thermochemical properties of the feedstock and products were analyzed by means of Simultaneous Thermal Analysis (STA), Ultimate and Proximate analysis and Attenuated Total Reflectance (ATR). The analysis of the products shows that torrefaction of dried household biowaste produces an energy dense fuel and high temperature pyrolysis produces a graphite-like material with relatively high yield. Copyright © 2016 Elsevier Ltd. All rights reserved.

Combined Ceria Reduction and Methane Reforming in a Solar-Driven Particle-Transport Reactor.

PubMed

Welte, Michael; Warren, Kent; Scheffe, Jonathan R; Steinfeld, Aldo

2017-09-20

We report on the experimental performance of a solar aerosol reactor for carrying out the combined thermochemical reduction of CeO 2 and reforming of CH 4 using concentrated radiation as the source of process heat. The 2 kW th solar reactor prototype utilizes a cavity receiver enclosing a vertical Al 2 O 3 tube which contains a downward gravity-driven particle flow of ceria particles, either co-current or counter-current to a CH 4 flow. Experimentation under a peak radiative flux of 2264 suns yielded methane conversions up to 89% at 1300 °C for residence times under 1 s. The maximum extent of ceria reduction, given by the nonstoichiometry δ (CeO 2-δ ), was 0.25. The solar-to-fuel energy conversion efficiency reached 12%. The syngas produced had a H 2 :CO molar ratio of 2, and its calorific value was solar-upgraded by 24% over that of the CH 4 reformed.

Combined Ceria Reduction and Methane Reforming in a Solar-Driven Particle-Transport Reactor

PubMed Central

2017-01-01

We report on the experimental performance of a solar aerosol reactor for carrying out the combined thermochemical reduction of CeO2 and reforming of CH4 using concentrated radiation as the source of process heat. The 2 kWth solar reactor prototype utilizes a cavity receiver enclosing a vertical Al2O3 tube which contains a downward gravity-driven particle flow of ceria particles, either co-current or counter-current to a CH4 flow. Experimentation under a peak radiative flux of 2264 suns yielded methane conversions up to 89% at 1300 °C for residence times under 1 s. The maximum extent of ceria reduction, given by the nonstoichiometry δ (CeO2−δ), was 0.25. The solar-to-fuel energy conversion efficiency reached 12%. The syngas produced had a H2:CO molar ratio of 2, and its calorific value was solar-upgraded by 24% over that of the CH4 reformed. PMID:28966440

Food waste-to-energy conversion technologies: current status and future directions.

PubMed

Pham, Thi Phuong Thuy; Kaushik, Rajni; Parshetti, Ganesh K; Mahmood, Russell; Balasubramanian, Rajasekhar

2015-04-01

Food waste represents a significantly fraction of municipal solid waste. Proper management and recycling of huge volumes of food waste are required to reduce its environmental burdens and to minimize risks to human health. Food waste is indeed an untapped resource with great potential for energy production. Utilization of food waste for energy conversion currently represents a challenge due to various reasons. These include its inherent heterogeneously variable compositions, high moisture contents and low calorific value, which constitute an impediment for the development of robust, large scale, and efficient industrial processes. Although a considerable amount of research has been carried out on the conversion of food waste to renewable energy, there is a lack of comprehensive and systematic reviews of the published literature. The present review synthesizes the current knowledge available in the use of technologies for food-waste-to-energy conversion involving biological (e.g. anaerobic digestion and fermentation), thermal and thermochemical technologies (e.g. incineration, pyrolysis, gasification and hydrothermal oxidation). The competitive advantages of these technologies as well as the challenges associated with them are discussed. In addition, the future directions for more effective utilization of food waste for renewable energy generation are suggested from an interdisciplinary perspective. Copyright © 2014 Elsevier Ltd. All rights reserved.

Prospects for energy recovery during hydrothermal and biological processing of waste biomass.

PubMed

Gerber Van Doren, Léda; Posmanik, Roy; Bicalho, Felipe A; Tester, Jefferson W; Sills, Deborah L

2017-02-01

Thermochemical and biological processes represent promising technologies for converting wet biomasses, such as animal manure, organic waste, or algae, to energy. To convert biomass to energy and bio-chemicals in an economical manner, internal energy recovery should be maximized to reduce the use of external heat and power. In this study, two conversion pathways that couple hydrothermal liquefaction with anaerobic digestion or catalytic hydrothermal gasification were compared. Each of these platforms is followed by two alternative processes for gas utilization: 1) combined heat and power; and 2) combustion in a boiler. Pinch analysis was applied to integrate thermal streams among unit processes and improve the overall system efficiency. A techno-economic analysis was conducted to compare the feasibility of the four modeled scenarios under different market conditions. Our results show that a systems approach designed to recover internal heat and power can reduce external energy demands and increase the overall process sustainability. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of hydrothermal liquefaction aqueous phase recycling on bio-crude yields and composition.

PubMed

Biller, Patrick; Madsen, René B; Klemmer, Maika; Becker, Jacob; Iversen, Bo B; Glasius, Marianne

2016-11-01

Hydrothermal liquefaction (HTL) is a promising thermo-chemical processing technology for the production of biofuels but produces large amounts of process water. Therefore recirculation of process water from HTL of dried distillers grains with solubles (DDGS) is investigated. Two sets of recirculation on a continuous reactor system using K2CO3 as catalyst were carried out. Following this, the process water was recirculated in batch experiments for a total of 10 rounds. To assess the effect of alkali catalyst, non-catalytic HTL process water recycling was performed with 9 recycle rounds. Both sets of experiments showed a large increase in bio-crude yields from approximately 35 to 55wt%. The water phase and bio-crude samples from all experiments were analysed via quantitative gas chromatography-mass spectrometry (GC-MS) to investigate their composition and build-up of organic compounds. Overall the results show an increase in HTL conversion efficiency and a lower volume, more concentrated aqueous by-product following recycling. Copyright © 2016 Elsevier Ltd. All rights reserved.

Recovery Act. Demonstration of a Pilot Integrated Biorefinery for the Efficient, Direct Conversion of Biomass to Diesel Fuel

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

Schuetzle, Dennis; Tamblyn, Greg; Caldwell, Matt

2015-05-12

The Renewable Energy Institute International, in collaboration with Greyrock Energy and Red Lion Bio-Energy (RLB) has successfully demonstrated operation of a 25 ton per day (tpd) nameplate capacity, pilot, pre-commercial-scale integrated biorefinery (IBR) plant for the direct production of premium, “drop-in”, synthetic fuels from agriculture and forest waste feedstocks using next-generation thermochemical and catalytic conversion technologies. The IBR plant was built and tested at the Energy Center, which is located in the University of Toledo Medical Campus in Toledo, Ohio.

Bioconversion study conducted by JPL

NASA Technical Reports Server (NTRS)

Kalvinskas, J.

1978-01-01

The Jet Propulsion Laboratory (JPL) of Caltech conducted a study of bioconversion as a means of identifying the role of biomass for meeting the national energy fuel and chemical requirements and the role and means for JPL-Caltech involvement in bioconversion. The bioconversion study included the following categories; biomass sources, chemicals from biomass, thermochemical conversion of biomass to fuels, biological conversion of biomass to fuels and chemicals, and basic bioconversion sciences. A detailed review is included of the bioconversion fields cited with specific conclusions and recommendations given for future research and development and overall biomass system engineering and economic studies.

Materials-Related Aspects of Thermochemical Water and Carbon Dioxide Splitting: A Review

PubMed Central

Roeb, Martin; Neises, Martina; Monnerie, Nathalie; Call, Friedemann; Simon, Heike; Sattler, Christian; Schmücker, Martin; Pitz-Paal, Robert

2012-01-01

Thermochemical multistep water- and CO2-splitting processes are promising options to face future energy problems. Particularly, the possible incorporation of solar power makes these processes sustainable and environmentally attractive since only water, CO2 and solar power are used; the concentrated solar energy is converted into storable and transportable fuels. One of the major barriers to technological success is the identification of suitable active materials like catalysts and redox materials exhibiting satisfactory durability, reactivity and efficiencies. Moreover, materials play an important role in the construction of key components and for the implementation in commercial solar plants. The most promising thermochemical water- and CO2-splitting processes are being described and discussed with respect to further development and future potential. The main materials-related challenges of those processes are being analyzed. Technical approaches and development progress in terms of solving them are addressed and assessed in this review.

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

Biomass Conversion to Produce Hydrocarbon Liquid Fuel Via Hot-vapor Filtered Fast Pyrolysis and Catalytic Hydrotreating.

PubMed

Wang, Huamin; Elliott, Douglas C; French, Richard J; Deutch, Steve; Iisa, Kristiina

2016-12-25

Lignocellulosic biomass conversion to produce biofuels has received significant attention because of the quest for a replacement for fossil fuels. Among the various thermochemical and biochemical routes, fast pyrolysis followed by catalytic hydrotreating is considered to be a promising near-term opportunity. This paper reports on experimental methods used 1) at the National Renewable Energy Laboratory (NREL) for fast pyrolysis of lignocellulosic biomass to produce bio-oils in a fluidized-bed reactor and 2) at Pacific Northwest National Laboratory (PNNL) for catalytic hydrotreating of bio-oils in a two-stage, fixed-bed, continuous-flow catalytic reactor. The configurations of the reactor systems, the operating procedures, and the processing and analysis of feedstocks, bio-oils, and biofuels are described in detail in this paper. We also demonstrate hot-vapor filtration during fast pyrolysis to remove fine char particles and inorganic contaminants from bio-oil. Representative results showed successful conversion of biomass feedstocks to fuel-range hydrocarbon biofuels and, specifically, the effect of hot-vapor filtration on bio-oil production and upgrading. The protocols provided in this report could help to generate rigorous and reliable data for biomass pyrolysis and bio-oil hydrotreating research.

Biomass Conversion to Produce Hydrocarbon Liquid Fuel Via Hot-vapor Filtered Fast Pyrolysis and Catalytic Hydrotreating

PubMed Central

Wang, Huamin; Elliott, Douglas C.; French, Richard J.; Deutch, Steve; Iisa, Kristiina

2016-01-01

Lignocellulosic biomass conversion to produce biofuels has received significant attention because of the quest for a replacement for fossil fuels. Among the various thermochemical and biochemical routes, fast pyrolysis followed by catalytic hydrotreating is considered to be a promising near-term opportunity. This paper reports on experimental methods used 1) at the National Renewable Energy Laboratory (NREL) for fast pyrolysis of lignocellulosic biomass to produce bio-oils in a fluidized-bed reactor and 2) at Pacific Northwest National Laboratory (PNNL) for catalytic hydrotreating of bio-oils in a two-stage, fixed-bed, continuous-flow catalytic reactor. The configurations of the reactor systems, the operating procedures, and the processing and analysis of feedstocks, bio-oils, and biofuels are described in detail in this paper. We also demonstrate hot-vapor filtration during fast pyrolysis to remove fine char particles and inorganic contaminants from bio-oil. Representative results showed successful conversion of biomass feedstocks to fuel-range hydrocarbon biofuels and, specifically, the effect of hot-vapor filtration on bio-oil production and upgrading. The protocols provided in this report could help to generate rigorous and reliable data for biomass pyrolysis and bio-oil hydrotreating research. PMID:28060311

Livestock waste-to-bioenergy generation opportunities.

PubMed

Cantrell, Keri B; Ducey, Thomas; Ro, Kyoung S; Hunt, Patrick G

2008-11-01

The use of biological and thermochemical conversion (TCC) technologies in livestock waste-to-bioenergy treatments can provide livestock operators with multiple value-added, renewable energy products. These products can meet heating and power needs or serve as transportation fuels. The primary objective of this work is to present established and emerging energy conversion opportunities that can transform the treatment of livestock waste from a liability to a profit center. While biological production of methanol and hydrogen are in early research stages, anaerobic digestion is an established method of generating between 0.1 to 1.3m3m(-3)d(-1) of methane-rich biogas. The TCC processes of pyrolysis, direct liquefaction, and gasification can convert waste into gaseous fuels, combustible oils, and charcoal. Integration of biological and thermal-based conversion technologies in a farm-scale hybrid design by combining an algal CO2-fixation treatment requiring less than 27,000m2 of treatment area with the energy recovery component of wet gasification can drastically reduce CO2 emissions and efficiently recycle nutrients. These designs have the potential to make future large scale confined animal feeding operations sustainable and environmentally benign while generating on-farm renewable energy.

Succinic acid production on xylose-enriched biorefinery streams by Actinobacillus succinogenes in batch fermentation

DOE PAGES

Salvachua, Davinia; Mohagheghi, Ali; Smith, Holly; ...

2016-02-02

Co-production of chemicals from lignocellulosic biomass alongside fuels holds promise for improving the economic outlook of integrated biorefineries. In current biochemical conversion processes that use thermochemical pretreatment and enzymatic hydrolysis, fractionation of hemicellulose-derived and cellulose-derived sugar streams is possible using hydrothermal or dilute acid pretreatment (DAP), which then offers a route to parallel trains for fuel and chemical production from xylose- and glucose-enriched streams. Succinic acid (SA) is a co-product of particular interest in biorefineries because it could potentially displace petroleum-derived chemicals and polymer precursors for myriad applications. Furthermore, SA production from biomass-derived hydrolysates has not yet been fully exploredmore » or developed.« less

The influence of Ag content and annealing time on structural and optical properties of SGS antimony-germanate glass doped with Er3+ ions

NASA Astrophysics Data System (ADS)

Zmojda, J.; Kochanowicz, M.; Miluski, P.; Baranowska, A.; Basa, A.; Jadach, R.; Sitarz, M.; Dorosz, D.

2018-05-01

A series of erbium doped SGS antimony-germanate glass embedding silver (Ag0) nanoparticles have been synthesized by a one-step melt-quench thermochemical reduction technique. The effect of NPs concentration and annealing time on the structural and photoluminescent (PL) properties were investigated. The Raman spectra as a function of temperature measured in-situ allow to determine the structural changes in vicinity of Ag+ ions and confirmed thermochemical reduction of Ag+ ions by Sb3+ ions. The surface plasmon resonance absorption band was evidenced near 450 nm. The impact of local field effect generated by Ag0 nanoparticles (NPs) and energy transfer from surface of silver NPs to trivalent erbium ions on near-infrared and up-conversion luminescence was described in terms of enhancement and quench phenomena.

Combining mineral physics with seismic observations: What can we deduce about the thermochemical structure of the Earth's deep interior?

NASA Astrophysics Data System (ADS)

Cobden, L. J.

2017-12-01

Mineral physics provides the essential link between seismic observations of the Earth's interior, and laboratory (or computer-simulated) measurements of rock properties. In this presentation I will outline the procedure for quantitative conversion from thermochemical structure to seismic structure (and vice versa) using the latest datasets from seismology and mineralogy. I will show examples of how this method can allow us to infer major chemical and dynamic properties of the deep mantle. I will also indicate where uncertainties and limitations in the data require us to exercise caution, in order not to "over-interpret" seismic observations. Understanding and modelling these uncertainties serves as a useful guide for mineralogists to ascertain which mineral parameters are most useful in seismic interpretation, and enables seismologists to optimise their data assembly and inversions for quantitative interpretations.

Renewable hydrogen production via thermochemical/electrochemical coupling

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

Ambrosini, Andrea; Babiniec, Sean Michael; Miller, James E.

A coupled electrochemical/thermochemical cycle was investigated to produce hydrogen from renewable resources. Like a conventional thermochemical cycle, this cycle leverages chemical energy stored in a thermochemical working material that is reduced thermally by solar energy. However, in this concept, the stored chemical energy only needs to be partially, but not fully, capable of splitting steam to produce hydrogen. To complete the process, a proton-conducting membrane is driven to separate hydrogen as it is produced, thus shifting the thermodynamics toward further hydrogen production. This novel coupled-cycle concept provides several benefits. First, the required oxidation enthalpy of the reversible thermochemical material ismore » reduced, enabling the process to occur at lower temperatures. Second, removing the requirement for spontaneous steam-splitting widens the scope of materials compositions, allowing for less expensive/more abundant elements to be used. Lastly, thermodynamics calculations suggest that this concept can potentially reach higher efficiencies than photovoltaic-to-electrolysis hydrogen production methods. This Exploratory Express LDRD involved assessing the practical feasibility of the proposed coupled cycle. A test stand was designed and constructed and proton-conducting membranes were synthesized. While the full proof of concept was not achieved, the individual components of the experiment were validated and new capabilities that can be leveraged by a variety of programs were developed.« less

Quantitative Thermochemical Measurements in High-Pressure Gaseous Combustion

NASA Technical Reports Server (NTRS)

Kojima, Jun J.; Fischer, David G.

2012-01-01

We present our strategic experiment and thermochemical analyses on combustion flow using a subframe burst gating (SBG) Raman spectroscopy. This unconventional laser diagnostic technique has promising ability to enhance accuracy of the quantitative scalar measurements in a point-wise single-shot fashion. In the presentation, we briefly describe an experimental methodology that generates transferable calibration standard for the routine implementation of the diagnostics in hydrocarbon flames. The diagnostic technology was applied to simultaneous measurements of temperature and chemical species in a swirl-stabilized turbulent flame with gaseous methane fuel at elevated pressure (17 atm). Statistical analyses of the space-/time-resolved thermochemical data provide insights into the nature of the mixing process and it impact on the subsequent combustion process in the model combustor.

Thermodynamic Analysis of the Use a Chemical Heat Pump to Link a Supercritical Water-Cooled Nuclear Reactor and a Thermochemical Water-Splitting Cycle for Hydrogen Production

NASA Astrophysics Data System (ADS)

Granovskii, Mikhail; Dincer, Ibrahim; Rosen, Marc A.; Pioro, Igor

Increases in the power generation efficiency of nuclear power plants (NPPs) are mainly limited by the permissible temperatures in nuclear reactors and the corresponding temperatures and pressures of the coolants in reactors. Coolant parameters are limited by the corrosion rates of materials and nuclear-reactor safety constraints. The advanced construction materials for the next generation of CANDU reactors, which employ supercritical water (SCW) as a coolant and heat carrier, permit improved “steam” parameters (outlet temperatures up to 625°C and pressures of about 25 MPa). An increase in the temperature of steam allows it to be utilized in thermochemical water splitting cycles to produce hydrogen. These methods are considered by many to be among the most efficient ways to produce hydrogen from water and to have advantages over traditional low-temperature water electrolysis. However, even lower temperature water splitting cycles (Cu-Cl, UT-3, etc.) require an intensive heat supply at temperatures higher than 550-600°C. A sufficient increase in the heat transfer from the nuclear reactor to a thermochemical water splitting cycle, without jeopardizing nuclear reactor safety, might be effectively achieved by application of a heat pump, which increases the temperature of the heat supplied by virtue of a cyclic process driven by mechanical or electrical work. Here, a high-temperature chemical heat pump, which employs the reversible catalytic methane conversion reaction, is proposed. The reaction shift from exothermic to endothermic and back is achieved by a change of the steam concentration in the reaction mixture. This heat pump, coupled with the second steam cycle of a SCW nuclear power generation plant on one side and a thermochemical water splitting cycle on the other, increases the temperature of the “nuclear” heat and, consequently, the intensity of heat transfer into the water splitting cycle. A comparative preliminary thermodynamic analysis is conducted of the combined system comprising a SCW nuclear power generation plant and a chemical heat pump, which provides high-temperature heat to a thermochemical water splitting cycle for hydrogen production. It is concluded that the proposed chemical heat pump permits the utilization efficiency of nuclear energy to be improved by at least 2% without jeopardizing nuclear reactor safety. Based on this analysis, further research appears to be merited on the proposed advanced design of a nuclear power generation plant combined with a chemical heat pump, and implementation in appropriate applications seems worthwhile.

A Study of Upgraded Phenolic Curing for RSRM Nozzle Rings

NASA Technical Reports Server (NTRS)

Smartt, Ziba

2000-01-01

A thermochemical cure model for predicting temperature and degree of cure profiles in curing phenolic parts was developed, validated and refined over several years. The model supports optimization of cure cycles and allows input of properties based upon the types of material and the process by which these materials are used to make nozzle components. The model has been refined to use sophisticated computer graphics to demonstrate the changes in temperature and degree of cure during the curing process. The effort discussed in the paper will be the conversion from an outdated solid modeling input program and SINDA analysis code to an integrated solid modeling and analysis package (I-DEAS solid model and TMG). Also discussed will be the incorporation of updated material properties obtained during full scale curing tests into the cure models and the results for all the Reusable Solid Rocket Motor (RSRM) nozzle rings.

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

Sievers, David A.; Lischeske, James J.; Biddy, Mary J.

Solid-liquid separation of intermediate process slurries is required in some process configurations for the conversion of lignocellulosic biomass to transportation fuels. Thermochemically pretreated and enzymatically hydrolyzed corn stover slurries have proven difficult to filter due to formation of very low permeability cakes that are rich in lignin. Treatment of two different slurries with polyelectrolyte flocculant was demonstrated to increase mean particle size and filterability. Filtration flux was greatly improved, and thus scaled filter unit capacity was increased approximately 40-fold compared with unflocculated slurry. Although additional costs were accrued using polyelectrolyte, techno-economic analysis revealed that the increase in filter capacity significantlymore » reduced overall production costs. Fuel production cost at 95% sugar recovery was reduced by $1.35 US per gallon gasoline equivalent for dilute-acid pretreated and enzymatically hydrolyzed slurries and $3.40 for slurries produced using an additional alkaline de-acetylation preprocessing step that is even more difficult to natively filter.« less

Ab Initio Computations and Active Thermochemical Tables Hand in Hand: Heats of Formation of Core Combustion Species.

PubMed

Klippenstein, Stephen J; Harding, Lawrence B; Ruscic, Branko

2017-09-07

The fidelity of combustion simulations is strongly dependent on the accuracy of the underlying thermochemical properties for the core combustion species that arise as intermediates and products in the chemical conversion of most fuels. High level theoretical evaluations are coupled with a wide-ranging implementation of the Active Thermochemical Tables (ATcT) approach to obtain well-validated high fidelity predictions for the 0 K heat of formation for a large set of core combustion species. In particular, high level ab initio electronic structure based predictions are obtained for a set of 348 C, N, O, and H containing species, which corresponds to essentially all core combustion species with 34 or fewer electrons. The theoretical analyses incorporate various high level corrections to base CCSD(T)/cc-pVnZ analyses (n = T or Q) using H 2 , CH 4 , H 2 O, and NH 3 as references. Corrections for the complete-basis-set limit, higher-order excitations, anharmonic zero-point energy, core-valence, relativistic, and diagonal Born-Oppenheimer effects are ordered in decreasing importance. Independent ATcT values are presented for a subset of 150 species. The accuracy of the theoretical predictions is explored through (i) examination of the magnitude of the various corrections, (ii) comparisons with other high level calculations, and (iii) through comparison with the ATcT values. The estimated 2σ uncertainties of the three methods devised here, ANL0, ANL0-F12, and ANL1, are in the range of ±1.0-1.5 kJ/mol for single-reference and moderately multireference species, for which the calculated higher order excitations are 5 kJ/mol or less. In addition to providing valuable references for combustion simulations, the subsequent inclusion of the current theoretical results into the ATcT thermochemical network is expected to significantly improve the thermochemical knowledge base for less-well studied species.

Ab Initio Computations and Active Thermochemical Tables Hand in Hand: Heats of Formation of Core Combustion Species

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

Klippenstein, Stephen J.; Harding, Lawrence B.; Ruscic, Branko

Here, the fidelity of combustion simulations is strongly dependent on the accuracy of the underlying thermochemical properties for the core combustion species that arise as intermediates and products in the chemical conversion of most fuels. High level theoretical evaluations are coupled with a wide-ranging implementation of the Active Thermochemical Tables (ATcT) approach to obtain well-validated high fidelity predictions for the 0 K heat of formation for a large set of core combustion species. In particular, high level ab initio electronic structure based predictions are obtained for a set of 348 C, N, O, and H containing species, which corresponds tomore » essentially all core combustion species with 34 or fewer electrons. The theoretical analyses incorporate various high level corrections to base CCSD(T)/cc-pVnZ analyses (n = T or Q) using H 2, CH 4, H 2O, and NH 3 as references. Corrections for the complete-basis-set limit, higher-order excitations, anharmonic zeropoint energy, core–valence, relativistic, and diagonal Born–Oppenheimer effects are ordered in decreasing importance. Independent ATcT values are presented for a subset of 150 species. The accuracy of the theoretical predictions is explored through (i) examination of the magnitude of the various corrections, (ii) comparisons with other high level calculations, and (iii) through comparison with the ATcT values. The estimated 2σ uncertainties of the three methods devised here, ANL0, ANL0-F12, and ANL1, are in the range of ±1.0–1.5 kJ/mol for single-reference and moderately multireference species, for which the calculated higher order excitations are 5 kJ/mol or less. In addition to providing valuable references for combustion simulations, the subsequent inclusion of the current theoretical results into the ATcT thermochemical network is expected to significantly improve the thermochemical knowledge base for less-well studied species.« less

Ab Initio Computations and Active Thermochemical Tables Hand in Hand: Heats of Formation of Core Combustion Species

DOE PAGES

Klippenstein, Stephen J.; Harding, Lawrence B.; Ruscic, Branko

2017-07-31

Here, the fidelity of combustion simulations is strongly dependent on the accuracy of the underlying thermochemical properties for the core combustion species that arise as intermediates and products in the chemical conversion of most fuels. High level theoretical evaluations are coupled with a wide-ranging implementation of the Active Thermochemical Tables (ATcT) approach to obtain well-validated high fidelity predictions for the 0 K heat of formation for a large set of core combustion species. In particular, high level ab initio electronic structure based predictions are obtained for a set of 348 C, N, O, and H containing species, which corresponds tomore » essentially all core combustion species with 34 or fewer electrons. The theoretical analyses incorporate various high level corrections to base CCSD(T)/cc-pVnZ analyses (n = T or Q) using H 2, CH 4, H 2O, and NH 3 as references. Corrections for the complete-basis-set limit, higher-order excitations, anharmonic zeropoint energy, core–valence, relativistic, and diagonal Born–Oppenheimer effects are ordered in decreasing importance. Independent ATcT values are presented for a subset of 150 species. The accuracy of the theoretical predictions is explored through (i) examination of the magnitude of the various corrections, (ii) comparisons with other high level calculations, and (iii) through comparison with the ATcT values. The estimated 2σ uncertainties of the three methods devised here, ANL0, ANL0-F12, and ANL1, are in the range of ±1.0–1.5 kJ/mol for single-reference and moderately multireference species, for which the calculated higher order excitations are 5 kJ/mol or less. In addition to providing valuable references for combustion simulations, the subsequent inclusion of the current theoretical results into the ATcT thermochemical network is expected to significantly improve the thermochemical knowledge base for less-well studied species.« less

Process simulation and cost analysis for removing inorganics from wood chips using combined mechanical and chemical preprocessing

DOE PAGES

Hu, Hongqiang; Westover, Tyler L.; Cherry, Robert; ...

2016-10-03

Inorganic species (ash) in biomass feedstocks negatively impact thermochemical and biochemical energy conversion processes. In this work, a process simulation model is developed to model the reduction in ash content of loblolly logging residues using a combination of air classification and dilute-acid leaching. Various scenarios are considered, and it is found that costs associated with discarding high-ash material from air classification are substantial. The costs of material loss can be reduced by chemical leaching the high-ash fraction obtained from air classification. The optimal leaching condition is found to be approximately 0.1 wt% sulfuric acid at 24°C. In example scenarios, totalmore » process costs in the range of $10-12/dry tonnes of product are projected that result in a removal of 11, 66, 53 and 86% of organics, total ash (inorganics), alkaline earth metals and phosphorus (AAEMS+P), and silicon, respectively. Here, sensitivity analyses indicate that costs associated with loss of organic material during processing (yield losses), brine disposal, and labor have the greatest potential to impact the total processing cost.« less

Effects of Impurities and Processing on Silicon Solar Cells, Phase 3

NASA Technical Reports Server (NTRS)

Hopkins, R. H.; Davis, J. R.; Blais, P. D.; Rohatgi, A.; Campbell, R. B.; Rai-Choudhury, P.; Stapleton, R. E.; Mollenkopf, H. C.; Mccormick, J. R.

1979-01-01

Results of the 14th quarterly report are presented for a program designed to assess the effects of impurities, thermochemical processes and any impurity process interactions on the performance of terrestrial silicon solar cells. The Phase 3 effort encompasses: (1) potential interactions between impurities and thermochemical processing of silicon; (2) impurity-cell performance relationships in n-base silicon; (3) effect of contaminants introduced during silicon production, refining or crystal growth on cell performance; (4) effects of nonuniform impurity distributions in large area silicon wafers; and (5) a preliminary study of the permanence of impurity effects in silicon solar cells.

Development of the hybrid sulfur cycle for use with concentrated solar heat. I. Conceptual design

DOE PAGES

Gorensek, Maximilian B.; Corgnale, Claudio; Summers, William A.

2017-07-27

We propose a detailed conceptual design of a solar hybrid sulfur (HyS) cycle. Numerous design tradeoffs, including process operating conditions and strategies, methods of integration with solar energy sources, and solar design options were considered. A baseline design was selected, and process flowsheets were developed. Pinch analyses were performed to establish the limiting energy efficiency. Detailed material and energy balances were completed, and a full stream table prepared. Design assumptions include use of: location in the southwest US desert, falling particle concentrated solar receiver, indirect heat transfer via pressurized helium, continuous operation with thermal energy storage, liquid-fed electrolyzer with PBImore » membrane, and bayonet-type acid decomposer. Thermochemical cycle efficiency for the HyS process was estimated to be 35.0%, LHV basis. The solar-to-hydrogen (STH) energy conversion ratio was 16.9%. This thus exceeds the Year 2015 DOE STCH target of STH >10%, and shows promise for meeting the Year 2020 target of 20%.« less

Development of the hybrid sulfur cycle for use with concentrated solar heat. I. Conceptual design

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

Gorensek, Maximilian B.; Corgnale, Claudio; Summers, William A.

We propose a detailed conceptual design of a solar hybrid sulfur (HyS) cycle. Numerous design tradeoffs, including process operating conditions and strategies, methods of integration with solar energy sources, and solar design options were considered. A baseline design was selected, and process flowsheets were developed. Pinch analyses were performed to establish the limiting energy efficiency. Detailed material and energy balances were completed, and a full stream table prepared. Design assumptions include use of: location in the southwest US desert, falling particle concentrated solar receiver, indirect heat transfer via pressurized helium, continuous operation with thermal energy storage, liquid-fed electrolyzer with PBImore » membrane, and bayonet-type acid decomposer. Thermochemical cycle efficiency for the HyS process was estimated to be 35.0%, LHV basis. The solar-to-hydrogen (STH) energy conversion ratio was 16.9%. This thus exceeds the Year 2015 DOE STCH target of STH >10%, and shows promise for meeting the Year 2020 target of 20%.« less

Effect of torrefaction on yield and quality of pyrolytic products of arecanut husk: An agro-processing wastes.

PubMed

Gogoi, Debajeet; Bordoloi, Neonjyoti; Goswami, Ritusmita; Narzari, Rumi; Saikia, Ruprekha; Sut, Debashis; Gogoi, Lina; Kataki, Rupam

2017-10-01

In the present study, arecanut husk, an agro-processing waste of areca plam industry highly prevalent in the north-eastern region of India, was investigated for its suitability as a prospective bioenergy feedstock for thermo-chemical conversion. Pretreatment of areca husk using torrefaction was performed in a fixed bed reactor with varying reaction temperature (200, 225, 250 and 275°C). The torrefied areca husk was subsequently pyrolyzed from temperature range of 300-600°C with heating rate of 40°C/min to obtain biooil and biochar. The torrefied areca husk, pyrolysis products were characterized by using different techniques. The energy and mass yield of torrefied biomass were found to be decreased with an increase in the torrefaction temperature. Further, biochar were found to be effective in removal of As (V) from aqueous solutions but efficiency of removal was better in case of torrefied biochar. Chemical composition of bio-oil is also influenced by torrefaction process. Copyright © 2017 Elsevier Ltd. All rights reserved.

A low-cost solid–liquid separation process for enzymatically hydrolyzed corn stover slurries

DOE PAGES

Sievers, David A.; Lischeske, James J.; Biddy, Mary J.; ...

2015-07-01

Solid-liquid separation of intermediate process slurries is required in some process configurations for the conversion of lignocellulosic biomass to transportation fuels. Thermochemically pretreated and enzymatically hydrolyzed corn stover slurries have proven difficult to filter due to formation of very low permeability cakes that are rich in lignin. Treatment of two different slurries with polyelectrolyte flocculant was demonstrated to increase mean particle size and filterability. Filtration flux was greatly improved, and thus scaled filter unit capacity was increased approximately 40-fold compared with unflocculated slurry. Although additional costs were accrued using polyelectrolyte, techno-economic analysis revealed that the increase in filter capacity significantlymore » reduced overall production costs. Fuel production cost at 95% sugar recovery was reduced by $1.35 US per gallon gasoline equivalent for dilute-acid pretreated and enzymatically hydrolyzed slurries and $3.40 for slurries produced using an additional alkaline de-acetylation preprocessing step that is even more difficult to natively filter.« less

Combined theoretical and experimental analysis of processes determining cathode performance in solid oxide fuel cells.

PubMed

Kuklja, M M; Kotomin, E A; Merkle, R; Mastrikov, Yu A; Maier, J

2013-04-21

Solid oxide fuel cells (SOFC) are under intensive investigation since the 1980's as these devices open the way for ecologically clean direct conversion of the chemical energy into electricity, avoiding the efficiency limitation by Carnot's cycle for thermochemical conversion. However, the practical development of SOFC faces a number of unresolved fundamental problems, in particular concerning the kinetics of the electrode reactions, especially oxygen reduction reaction. We review recent experimental and theoretical achievements in the current understanding of the cathode performance by exploring and comparing mostly three materials: (La,Sr)MnO3 (LSM), (La,Sr)(Co,Fe)O3 (LSCF) and (Ba,Sr)(Co,Fe)O3 (BSCF). Special attention is paid to a critical evaluation of advantages and disadvantages of BSCF, which shows the best cathode kinetics known so far for oxides. We demonstrate that it is the combined experimental and theoretical analysis of all major elementary steps of the oxygen reduction reaction which allows us to predict the rate determining steps for a given material under specific operational conditions and thus control and improve SOFC performance.

Conceptual design of an integrated hydrothermal liquefaction and biogas plant for sustainable bioenergy production.

PubMed

Hoffmann, Jessica; Rudra, Souman; Toor, Saqib S; Holm-Nielsen, Jens Bo; Rosendahl, Lasse A

2013-02-01

Initial process studies carried out in Aspen Plus on an integrated thermochemical conversion process are presented herein. In the simulations, a hydrothermal liquefaction (HTL) plant is combined with a biogas plant (BP), such that the digestate from the BP is converted to a biocrude in the HTL process. This biorefinery concept offers a sophisticated and sustainable way of converting organic residuals into a range of high-value biofuel streams in addition to combined heat and power (CHP) production. The primary goal of this study is to provide an initial estimate of the feasibility of such a process. By adding a diesel-quality-fuel output to the process, the product value is increased significantly compared to a conventional BP. An input of 1000 kg h(-1) manure delivers approximately 30-38 kg h(-1) fuel and 38-61 kg h(-1) biogas. The biogas can be used to upgrade the biocrude, to supply the gas grid or for CHP. An estimated 62-84% of the biomass energy can be recovered in the biofuels. Copyright © 2012 Elsevier Ltd. All rights reserved.

Biomass conversion to produce hydrocarbon liquid fuel via hot-vapor filtered fast pyrolysis and catalytic hydrotreating

DOE PAGES

Wang, Huamin; Elliott, Douglas C.; French, Richard J.; ...

2016-12-25

Lignocellulosic biomass conversion to produce biofuels has received significant attention because of the quest for a replacement for fossil fuels. Among the various thermochemical and biochemical routes, fast pyrolysis followed by catalytic hydrotreating is considered to be a promising near-term opportunity. This paper reports on experimental methods used 1) at the National Renewable Energy Laboratory (NREL) for fast pyrolysis of lignocellulosic biomass to produce bio-oils in a fluidized-bed reactor and 2) at Pacific Northwest National Laboratory (PNNL) for catalytic hydrotreating of bio-oils in a two-stage, fixed-bed, continuous-flow catalytic reactor. The configurations of the reactor systems, the operating procedures, and themore » processing and analysis of feedstocks, bio-oils, and biofuels are described in detail in this paper. We also demonstrate hot-vapor filtration during fast pyrolysis to remove fine char particles and inorganic contaminants from bio-oil. Representative results showed successful conversion of biomass feedstocks to fuel-range hydrocarbon biofuels and, specifically, the effect of hot-vapor filtration on bio-oil production and upgrading. As a result, the protocols provided in this report could help to generate rigorous and reliable data for biomass pyrolysis and bio-oil hydrotreating research.« less

Biomass conversion to produce hydrocarbon liquid fuel via hot-vapor filtered fast pyrolysis and catalytic hydrotreating

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

Wang, Huamin; Elliott, Douglas C.; French, Richard J.

Lignocellulosic biomass conversion to produce biofuels has received significant attention because of the quest for a replacement for fossil fuels. Among the various thermochemical and biochemical routes, fast pyrolysis followed by catalytic hydrotreating is considered to be a promising near-term opportunity. This paper reports on experimental methods used 1) at the National Renewable Energy Laboratory (NREL) for fast pyrolysis of lignocellulosic biomass to produce bio-oils in a fluidized-bed reactor and 2) at Pacific Northwest National Laboratory (PNNL) for catalytic hydrotreating of bio-oils in a two-stage, fixed-bed, continuous-flow catalytic reactor. The configurations of the reactor systems, the operating procedures, and themore » processing and analysis of feedstocks, bio-oils, and biofuels are described in detail in this paper. We also demonstrate hot-vapor filtration during fast pyrolysis to remove fine char particles and inorganic contaminants from bio-oil. Representative results showed successful conversion of biomass feedstocks to fuel-range hydrocarbon biofuels and, specifically, the effect of hot-vapor filtration on bio-oil production and upgrading. As a result, the protocols provided in this report could help to generate rigorous and reliable data for biomass pyrolysis and bio-oil hydrotreating research.« less

Synfuels from fusion: using the tandem mirror reactor and a thermochemical cycle to produce hydrogen

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

Werner, R.W.

1982-11-01

This study is concerned with the following area: (1) the tandem mirror reactor and its physics; (2) energy balance; (3) the lithium oxide canister blanket system; (4) high-temperature blanket; (5) energy transport system-reactor to process; (6) thermochemical hydrogen processes; (7) interfacing the GA cycle; (8) matching power and temperature demands; (9) preliminary cost estimates; (10) synfuels beyond hydrogen; and (11) thermodynamics of the H/sub 2/SO/sub 4/-H/sub 2/O system. (MOW)

Report of National Institute for Resources and Environment. No. 5: Study on direct liquefaction of woody biomass

NASA Astrophysics Data System (ADS)

Ogi, Tomoko; Yokoyama, Shinya; Minowa, Tomoaki; Dote, Yutaka; Koguchi, Katsuya

1993-03-01

Various researches on the production of liquid fuels from biomass were undertaken. Carbon monoxide and/or hydrogen were used in most cases, while processes using a little or none of these reducing gas were investigated. The following results on thermochemical conversion of wood biomass are presented, in which wood is reacted in aqueous solution in the presence of an alkali catalyst without reducing gases, which yielded a liquid product: (1) the optimum reaction condition is determined from systematic studies carried out with reaction parameter and variety of catalyst; (2) the optimum organic solvents are determined from investigations concerning production of heavy oil which is easily separable from an aqueous layer; (3) the effectiveness of the repeated use of reaction solvent is indicated by experiments in which water or a 2-propanol/water mixture is used repeatedly as a reaction solvent; and (4) heavy oil obtained by the liquefaction process was analyzed by (1) H-NMR (Nuclear Magnetic Resonance), GC (Gas Chromatography) - MS (Mass Spectrometry), and acid-base extraction. The liquefaction technology may be evaluated as one of the highly promising biomass conversion technologies, although some technical problems, such as separation or upgrading of heavy oils need to be solved. For the promotion of a total system, in which biomass is planted and grown and then the biomass is used as fuel and/or chemicals, further development of technologies are needed not only for conversion itself but also for plantation, afforestation, and irrigation.

Accelerating Commercialization of Algal Biofuels Through Partnerships (Brochure)

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

Not Available

2011-10-01

This brochure describes National Renewable Energy Laboratory's (NREL's) algal biofuels research capabilities and partnership opportunities. NREL is accelerating algal biofuels commercialization through: (1) Advances in applied biology; (2) Algal strain development; (3) Development of fuel conversion pathways; (4) Techno-economic analysis; and (5) Development of high-throughput lipid analysis methodologies. NREL scientists and engineers are addressing challenges across the algal biofuels value chain, including algal biology, cultivation, harvesting and extraction, and fuel conversion. Through partnerships, NREL can share knowledge and capabilities in the following areas: (1) Algal Biology - A fundamental understanding of algal biology is key to developing cost-effective algal biofuelsmore » processes. NREL scientists are experts in the isolation and characterization of microalgal species. They are identifying genes and pathways involved in biofuel production. In addition, they have developed a high-throughput, non-destructive technique for assessing lipid production in microalgae. (2) Cultivation - NREL researchers study algal growth capabilities and perform compositional analysis of algal biomass. Laboratory-scale photobioreactors and 1-m2 open raceway ponds in an on-site greenhouse allow for year-round cultivation of algae under a variety of conditions. A bioenergy-focused algal strain collection is being established at NREL, and our laboratory houses a cryopreservation system for long-term maintenance of algal cultures and preservation of intellectual property. (3) Harvesting and Extraction - NREL is investigating cost-effective harvesting and extraction methods suitable for a variety of species and conditions. Areas of expertise include cell wall analysis and deconstruction and identification and utilization of co-products. (4) Fuel Conversion - NREL's excellent capabilities and facilities for biochemical and thermochemical conversion of biomass to biofuels are being applied to algal biofuels processes. Analysts are also testing algal fuel properties to measure energy content and ensure compatibility with existing fueling infrastructure. (5) Cross-Cutting Analysis - NREL scientists and engineers are conducting rigorous techno-economic analyses of algal biofuels processes. In addition, they are performing a full life cycle assessment of the entire algae-to-biofuels process.« less

EDITORIAL: Non-thermal plasma-assisted fuel conversion for green chemistry Non-thermal plasma-assisted fuel conversion for green chemistry

NASA Astrophysics Data System (ADS)

Nozaki, Tomohiro; Gutsol, Alexander

2011-07-01

This special issue is based on the symposium on Non-thermal Plasma Assisted Fuel Conversion for Green Chemistry, a part of the 240th ACS National Meeting & Exposition held in Boston, MA, USA, 22-26 August 2010. Historically, the Division of Fuel Chemistry of the American Chemical Society (ACS) has featured three plasma-related symposia since 2000, and has launched special issues in Catalysis Today on three occasions: 'Catalyst Preparation using Plasma Technologies', Fall Meeting, Washington DC, USA, 2000. Special issue in Catalysis Today 72 (3-4) with 12 peer-reviewed articles. 'Plasma Technology and Catalysis', Spring Meeting, New Orleans, LA, USA, 2003. Special issue in Catalysis Today 89 (1-2) with more than 30 peer-reviewed articles. 'Utilization of Greenhouse Gases II' (partly focused on plasma-related technologies), Spring Meeting, Anaheim, CA, USA, 2004. Special issue in Catalysis Today 98 (4) with 25 peer-reviewed articles. This time, selected presentations are published in this Journal of Physics D: Applied Physics special issue. An industrial material and energy conversion technology platform is established on thermochemical processes including various catalytic reactions. Existing industry-scale technology is already well established; nevertheless, further improvement in energy efficiency and material saving has been continuously demanded. Drastic reduction of CO2 emission is also drawing keen attention with increasing recognition of energy and environmental issues. Green chemistry is a rapidly growing research field, and frequently highlights renewable bioenergy, bioprocesses, solar photocatalysis of water splitting, and regeneration of CO2 into useful chemicals. We would also like to emphasize 'plasma catalysis' of hydrocarbon resources as an important part of the innovative next-generation green technologies. The peculiarity of non-thermal plasma is that it can generate reactive species almost independently of reaction temperature. Plasma-generated reactive species are used to initiate chemical reactions at unexpectedly lower temperatures than conventional thermochemical reactions, leading to non-equilibrium product distribution or creating unconventional reaction pathways. When non-thermal plasma is combined with catalysts, a synergistic effect is frequently observed. Such unique properties of non-thermal plasma are expected to contribute excellent control over process parameters that meet the need for energy saving, environment protection, and material preservation. This special issue consists of eleven peer-reviewed papers including two invited publications. Professors Alexander Fridman and Alexander Rabinovich from Drexel University, and Dr Gutsol from the Chevron Energy Technology Company present a critical review of various industry-oriented practical plasma fuel conversion processes. Professor Richard Mallinson from University of Oklahoma describes his recent project on E85 (85%-ethanol/15%-gasoline) upgrading using non-thermal plasma and catalyst hybrid reactor, and highlights the synergistic effect on fuel conversion processes. Other papers focus on plasma/catalyst hybrid reactions for methane dry (CO2) reforming, plasma synthesis of carbon suboxide polymer from CO, the gas-to-liquid (GTL) process using a non-thermal plasma-combined micro-chemical reactor, and molecular beam characterization of plasma-generated reactive species. Much research regarding plasma catalysis is ongoing worldwide, but there is plenty of room for further development of plasma fuel processing, which could eventually provide a viable and flexible solution in future energy and material use. Finally, we would like to thank all symposium participants for their active discussion. We appreciate the sponsorship of the Division of Fuel Chemistry of the American Chemical Society. We express special thanks to the program chair of the Fuel Chemistry Division, Professor Chang-jun Liu at Tianjin University, for his dedication to the success of the symposium. We particularly express our appreciation to the Editorial Board of Journal of Physics D: Applied Physics for publication of the special issue.

Heterogeneous Catalysis for Thermochemical Conversion Publications |

Science.gov Websites

pentagons is an upside-down Y shape and H2 +with a sideways Y shape with two lines at the base. A gold arrow a photo of woody biomass. In the center is a diamond shape composed of four outer triangle sections blue spheres. In the upper left is a large molecule shape made up of a hexagon of black spheres

Evaluation energy efficiency of bioconversion knot rejects to ethanol in comparison to other thermochemically pretreated biomass

Treesearch

Zhaojiang Wang; Menghua Qin; J.Y. Zhu; Guoyu Tian; Zongquan Li

2013-01-01

Rejects from sulfite pulp mill that otherwise would be disposed of by incineration were converted to ethanol by a combined physical–biological process that was comprised of physical refining and simultaneous saccharification and fermentation (SSF). The energy efficiency was evaluated with comparison to thermochemically pretreated biomass, such as those pretreated by...

Pretreatment of Hardwood and Miscanthus with Trametes versicolor for Bioenergy Conversion and Densification Strategies.

PubMed

Kalinoski, Ryan M; Flores, Hector D; Thapa, Sunil; Tuegel, Erin R; Bilek, Michael A; Reyes-Mendez, Evelin Y; West, Michael J; Dumonceaux, Tim J; Canam, Thomas

2017-12-01

The pretreatment of plant biomass negatively impacts the economics of many bioenergy and bioproduct processes due to the thermochemical requirements for deconstruction of lignocelluluose. An effective strategy to reduce these severity requirements is to pretreat the biomass with white-rot fungi, such as Trametes versicolor, which have the innate ability to deconstruct lignocellulose with a suite of specialized enzymes. In the present study, the effects of 12 weeks of pretreatment with a wild-type strain (52J) and a cellobiose dehydrogenase-deficient strain (m4D) of T. versicolor on hardwood and Miscanthus were explored. Both strains of T. versicolor led to significant decreases of insoluble lignin and significant increases of soluble lignin after acid hydrolysis, which suggests improved lignin extractability. The glucose yields after saccharification using an enzyme cocktail containing chitinase were similar or significantly higher with 52J-treated biomass compared to untreated hardwood and Miscanthus, respectively. The fungal treated biomass, regardless of the strain used, also showed significant increases in energy content and compressive strength of pellets. Overall, the use of T. versicolor as a pretreatment agent for hardwood and Miscanthus could be an environmentally friendly strategy for conversion technologies that require delignification and saccharification, and/or processes that require densification and transport.

Surface thermochemical effects on TPS-coupled aerothermodynamics in hypersonic Martian gas flow

NASA Astrophysics Data System (ADS)

Yang, Xiaofeng; Gui, Yewei; Tang, Wei; Du, Yanxia; Liu, Lei; Xiao, Guangming; Wei, Dong

2018-06-01

This paper deals with the surface thermochemical effects on TPS-coupled aerothermodynamics in hypersonic Martian gas flow. An interface condition with finite-rate thermochemistry was established to balance the three-dimensional Navier-Stokes solver and TPS thermal response solver, and a series of coupled simulations of chemical non-equilibrium aerothermodynamics and structure heat transfer with various surface catalycities were performed for hypersonic Mars entries. The analysis of surface thermochemistry reveals that the surface chemical reactions have great contribution to aerodynamic heating, and the temperature-dependence of finite-rate catalysis highly influences the evolution of the coupling aerodynamic heating in the coupling process. For fixed free stream parameters with proper catalytic excitation energy, a "leap" phenomenon of the TPS-coupled heat flux with the coupling time appears in the initial stage of the coupling process, due to the strong thermochemical effects on the TPS surface.

Pie waste - A component of food waste and a renewable substrate for producing ethanol.

PubMed

Magyar, Margaret; da Costa Sousa, Leonardo; Jayanthi, Singaram; Balan, Venkatesh

2017-04-01

Sugar-rich food waste is a sustainable feedstock that can be converted into ethanol without an expensive thermochemical pretreatment that is commonly used in first and second generation processes. In this manuscript we have outlined the pie waste conversion to ethanol through a two-step process, namely, enzyme hydrolysis using commercial enzyme products mixtures and microbial fermentation using yeast. Optimized enzyme cocktail was found to be 45% alpha amylase, 45% gamma amylase, and 10% pectinase at 2.5mg enzyme protein/g glucan produced a hydrolysate with high glucose concentration. All three solid loadings (20%, 30%, and 40%) produced sugar-rich hydrolysates and ethanol with little to no enzyme or yeast inhibition. Enzymatic hydrolysis and fermentation process mass balance was carried out using pie waste on a 1000g dry weight basis that produced 329g ethanol at 20% solids loading. This process clearly demonstrate how food waste could be efficiently converted to ethanol that could be used for making biodiesel by reacting with waste cooking oil. Copyright © 2017 Elsevier Ltd. All rights reserved.

Solar thermochemical processing system and method

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

Wegeng, Robert S.; Humble, Paul H.; Krishnan, Shankar

A solar thermochemical processing system is disclosed. The system includes a first unit operation for receiving concentrated solar energy. Heat from the solar energy is used to drive the first unit operation. The first unit operation also receives a first set of reactants and produces a first set of products. A second unit operation receives the first set of products from the first unit operation and produces a second set of products. A third unit operation receives heat from the second unit operation to produce a portion of the first set of reactants.

Thermodynamic analysis of a combined-cycle solar thermal power plant with manganese oxide-based thermochemical energy storage

NASA Astrophysics Data System (ADS)

Lei, Qi; Bader, Roman; Kreider, Peter; Lovegrove, Keith; Lipiński, Wojciech

2017-11-01

We explore the thermodynamic efficiency of a solar-driven combined cycle power system with manganese oxide-based thermochemical energy storage system. Manganese oxide particles are reduced during the day in an oxygen-lean atmosphere obtained with a fluidized-bed reactor at temperatures in the range of 750-1600°C using concentrated solar energy. Reduced hot particles are stored and re-oxidized during night-time to achieve continuous power plant operation. The steady-state mass and energy conservation equations are solved for all system components to calculate the thermodynamic properties and mass flow rates at all state points in the system, taking into account component irreversibilities. The net power block and overall solar-to-electric energy conversion efficiencies, and the required storage volumes for solids and gases in the storage system are predicted. Preliminary results for a system with 100 MW nominal solar power input at a solar concentration ratio of 3000, designed for constant round-the-clock operation with 8 hours of on-sun and 16 hours of off-sun operation and with manganese oxide particles cycled between 750 and 1600°C yield a net power block efficiency of 60.0% and an overall energy conversion efficiency of 41.3%. Required storage tank sizes for the solids are estimated to be approx. 5-6 times smaller than those of state-of-the-art molten salt systems.

Perovskite nanocomposites as effective CO2-splitting agents in a cyclic redox scheme

PubMed Central

Zhang, Junshe; Haribal, Vasudev; Li, Fanxing

2017-01-01

We report iron-containing mixed-oxide nanocomposites as highly effective redox materials for thermochemical CO2 splitting and methane partial oxidation in a cyclic redox scheme, where methane was introduced as an oxygen “sink” to promote the reduction of the redox materials followed by reoxidation through CO2 splitting. Up to 96% syngas selectivity in the methane partial oxidation step and close to complete conversion of CO2 to CO in the CO2-splitting step were achieved at 900° to 980°C with good redox stability. The productivity and production rate of CO in the CO2-splitting step were about seven times higher than those in state-of-the-art solar-thermal CO2-splitting processes, which are carried out at significantly higher temperatures. The proposed approach can potentially be applied for acetic acid synthesis with up to 84% reduction in CO2 emission when compared to state-of-the-art processes. PMID:28875171

Thermo-electrochemical production of compressed hydrogen from methane with near-zero energy loss

NASA Astrophysics Data System (ADS)

Malerød-Fjeld, Harald; Clark, Daniel; Yuste-Tirados, Irene; Zanón, Raquel; Catalán-Martinez, David; Beeaff, Dustin; Morejudo, Selene H.; Vestre, Per K.; Norby, Truls; Haugsrud, Reidar; Serra, José M.; Kjølseth, Christian

2017-11-01

Conventional production of hydrogen requires large industrial plants to minimize energy losses and capital costs associated with steam reforming, water-gas shift, product separation and compression. Here we present a protonic membrane reformer (PMR) that produces high-purity hydrogen from steam methane reforming in a single-stage process with near-zero energy loss. We use a BaZrO3-based proton-conducting electrolyte deposited as a dense film on a porous Ni composite electrode with dual function as a reforming catalyst. At 800 °C, we achieve full methane conversion by removing 99% of the formed hydrogen, which is simultaneously compressed electrochemically up to 50 bar. A thermally balanced operation regime is achieved by coupling several thermo-chemical processes. Modelling of a small-scale (10 kg H2 day-1) hydrogen plant reveals an overall energy efficiency of >87%. The results suggest that future declining electricity prices could make PMRs a competitive alternative for industrial-scale hydrogen plants integrating CO2 capture.

Solar thermochemical process interface study

NASA Technical Reports Server (NTRS)

1984-01-01

The design and analyses of a subsystem of a hydrogen production process are described. The process is based on solar driven thermochemical reactions. The subject subsystem receives sulfuric acid of 60% concentration at 100 C, 1 atm pressure. The acid is further concentrated, vaporized, and decomposed (at a rate of 122 g moles/sec H2SO4) into SO2, O2, and water. The produce stream is cooled to 100 C. Three subsystem options, each being driven by direct solar energy, were designed and analyzed. The results are compared with a prior study case in which solar energy was provided indirectly through a helium loop.

Effect of mechanical disruption on the effectiveness of three reactors used for dilute acid pretreatment of corn stover Part 2: morphological and structural substrate analysis

PubMed Central

2014-01-01

Background Lignocellulosic biomass is a renewable, naturally mass-produced form of stored solar energy. Thermochemical pretreatment processes have been developed to address the challenge of biomass recalcitrance, however the optimization, cost reduction, and scalability of these processes remain as obstacles to the adoption of biofuel production processes at the industrial scale. In this study, we demonstrate that the type of reactor in which pretreatment is carried out can profoundly alter the micro- and nanostructure of the pretreated materials and dramatically affect the subsequent efficiency, and thus cost, of enzymatic conversion of cellulose. Results Multi-scale microscopy and quantitative image analysis was used to investigate the impact of different biomass pretreatment reactor configurations on plant cell wall structure. We identify correlations between enzymatic digestibility and geometric descriptors derived from the image data. Corn stover feedstock was pretreated under the same nominal conditions for dilute acid pretreatment (2.0 wt% H2SO4, 160°C, 5 min) using three representative types of reactors: ZipperClave® (ZC), steam gun (SG), and horizontal screw (HS) reactors. After 96 h of enzymatic digestion, biomass treated in the SG and HS reactors achieved much higher cellulose conversions, 88% and 95%, respectively, compared to the conversion obtained using the ZC reactor (68%). Imaging at the micro- and nanoscales revealed that the superior performance of the SG and HS reactors could be explained by reduced particle size, cellular dislocation, increased surface roughness, delamination, and nanofibrillation generated within the biomass particles during pretreatment. Conclusions Increased cellular dislocation, surface roughness, delamination, and nanofibrillation revealed by direct observation of the micro- and nanoscale change in accessibility explains the superior performance of reactors that augment pretreatment with physical energy. PMID:24690534

Gasification: An alternative solution for energy recovery and utilization of vegetable market waste.

PubMed

Narnaware, Sunil L; Srivastava, Nsl; Vahora, Samir

2017-03-01

Vegetables waste is generally utilized through a bioconversion process or disposed of at municipal landfills, dumping sites or dumped on open land, emitting a foul odor and causing health hazards. The presents study deals with an alternative way to utilize solid vegetable waste through a thermochemical route such as briquetting and gasification for its energy recovery and subsequent power generation. Briquettes of 50 mm diameter were produced from four different types of vegetable waste. The bulk density of briquettes produced was increased 10 to 15 times higher than the density of the dried vegetable waste in loose form. The lower heating value (LHV) of the briquettes ranged from 10.26 MJ kg -1 to 16.60 MJ kg -1 depending on the type of vegetable waste. The gasification of the briquettes was carried out in an open core downdraft gasifier, which resulted in syngas with a calorific value of 4.71 MJ Nm -3 at the gasification temperature between 889°C and 1011°C. A spark ignition, internal combustion engine was run on syngas and could generate a maximum load up to 10 kW e . The cold gas efficiency and the hot gas efficiency of the gasifier were measured at 74.11% and 79.87%, respectively. Energy recovery from the organic vegetable waste was possible through a thermochemical conversion route such as briquetting and subsequent gasification and recovery of the fuel for small-scale power generation.

Numerical simulation of waste tyres gasification.

PubMed

Janajreh, Isam; Raza, Syed Shabbar

2015-05-01

Gasification is a thermochemical pathway used to convert carbonaceous feedstock into syngas (CO and H2) in a deprived oxygen environment. The process can accommodate conventional feedstock such as coal, discarded waste including plastics, rubber, and mixed waste owing to the high reactor temperature (1000 °C-1600 °C). Pyrolysis is another conversion pathway, yet it is more selective to the feedstock owing to the low process temperature (350 °C-550 °C). Discarded tyres can be subjected to pyrolysis, however, the yield involves the formation of intermediate radicals additional to unconverted char. Gasification, however, owing to the higher temperature and shorter residence time, is more opted to follow quasi-equilibrium and being predictive. In this work, tyre crumbs are subjected to two levels of gasification modelling, i.e. equilibrium zero dimension and reactive multi-dimensional flow. The objective is to investigate the effect of the amount of oxidising agent on the conversion of tyre granules and syngas composition in a small 20 kW cylindrical gasifier. Initially the chemical compositions of several tyre samples are measured following the ASTM procedures for proximate and ultimate analysis as well as the heating value. The measured data are used to carry out equilibrium-based and reactive flow gasification. The result shows that both models are reasonably predictive averaging 50% gasification efficiency, the devolatilisation is less sensitive than the char conversion to the equivalence ratio as devolatilisation is always complete. In view of the high attained efficiency, it is suggested that the investigated tyre gasification system is economically viable. © The Author(s) 2015.

Hydrothermal Liquefaction of Wastewater Treatment Plant Solids

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

Billing, Justin M.

2016-10-16

Feedstock cost is the greatest barrier to the commercial production of biofuels. The merits of any thermochemical or biological conversion process are constrained by their applicability to the lowest cost feedstocks. At PNNL, a recent resource assessment of wet waste feedstocks led to the identification of waste water treatment plant (WWTP) solids as a cost-negative source of biomass. WWTP solids disposal is a growing environmental concern [1, 2] and can account for up to half of WWTP operating costs. The high moisture content is well-suited for hydrothermal liquefaction (HTL), avoiding the costs and parasitic energy losses associated with drying themore » feedstock for incineration. The yield and quality of biocrude and upgraded biocrude from WWTP solids is comparable to that obtained from algae feedstocks but the feedstock cost is $500-1200 less per dry ton. A collaborative project was initiated and directed by the Water Environment & Reuse Foundation (WERF) and included feedstock identification, dewatering, shipping to PNNL, conversion to biocrude by HTL, and catalytic hydrothermal gasification of the aqueous byproduct. Additional testing at PNNL included biocrude upgrading by catalytic hydrotreatment, characterization of the hydrotreated product, and a preliminary techno-economic analysis (TEA) based on empirical results. This short article will cover HTL conversion and biocrude upgrading. The WERF project report with complete HTL results is now available through the WERF website [3]. The preliminary TEA is available as a PNNL report [4].« less

Matthew Oliver | NREL

Science.gov Websites

Process Development Unit. NREL's Thermal and Catalytic Process Development Unit can process 1/2 ton per biomass to fuels and chemicals Affiliated Research Programs Thermochemical Process Integration, Scale-Up

Carboxylate platform: the MixAlco process part 1: comparison of three biomass conversion platforms.

PubMed

Holtzapple, Mark T; Granda, Cesar B

2009-05-01

To convert biomass to liquid fuels, three platforms are compared: thermochemical, sugar, and carboxylate. To create a common basis, each platform is fed "ideal biomass," which contains polysaccharides (68.3%) and lignin (31.7%). This ratio is typical of hardwood biomass and was selected so that when gasified and converted to hydrogen, the lignin has sufficient energy to produce ethanol from the carboxylic acids produced by the carboxylate platform. Using balanced chemical reactions, the theoretical yield and energy efficiency were determined for each platform. For all platforms, the ethanol yield can be increased by 71% to 107% by supplying external hydrogen produced from other sources (e.g., solar, wind, nuclear, fossil fuels). The alcohols can be converted to alkanes with a modest loss of energy efficiency (3 to 5 percentage points). Of the three platforms considered, the carboxylate platform has demonstrated the highest product yields.

Analysis of Hydrogen Generation through Thermochemical Gasification of Coconut Shell Using Thermodynamic Equilibrium Model Considering Char and Tar

PubMed Central

Rupesh, Shanmughom; Muraleedharan, Chandrasekharan; Arun, Palatel

2014-01-01

This work investigates the potential of coconut shell for air-steam gasification using thermodynamic equilibrium model. A thermodynamic equilibrium model considering tar and realistic char conversion was developed using MATLAB software to predict the product gas composition. After comparing it with experimental results the prediction capability of the model is enhanced by multiplying equilibrium constants with suitable coefficients. The modified model is used to study the effect of key process parameters like temperature, steam to biomass ratio, and equivalence ratio on product gas yield, composition, and heating value of syngas along with gasification efficiency. For a steam to biomass ratio of unity, the maximum mole fraction of hydrogen in the product gas is found to be 36.14% with a lower heating value of 7.49 MJ/Nm3 at a gasification temperature of 1500 K and equivalence ratio of 0.15. PMID:27433487

Analysis of Hydrogen Generation through Thermochemical Gasification of Coconut Shell Using Thermodynamic Equilibrium Model Considering Char and Tar.

PubMed

Rupesh, Shanmughom; Muraleedharan, Chandrasekharan; Arun, Palatel

2014-01-01

This work investigates the potential of coconut shell for air-steam gasification using thermodynamic equilibrium model. A thermodynamic equilibrium model considering tar and realistic char conversion was developed using MATLAB software to predict the product gas composition. After comparing it with experimental results the prediction capability of the model is enhanced by multiplying equilibrium constants with suitable coefficients. The modified model is used to study the effect of key process parameters like temperature, steam to biomass ratio, and equivalence ratio on product gas yield, composition, and heating value of syngas along with gasification efficiency. For a steam to biomass ratio of unity, the maximum mole fraction of hydrogen in the product gas is found to be 36.14% with a lower heating value of 7.49 MJ/Nm(3) at a gasification temperature of 1500 K and equivalence ratio of 0.15.

A demonstration of glass bonding using patterned nanocomposite thermites deposited from fluid

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

Rodriguez, Juan Carlos

2015-01-01

Ceramics and other nonmetals are widely used in industrial and research applications. Although these materials provide many advantages, they often pose unique challenges during bonding. This work aims to expand on current processes, which have much narrower applications, to nd a more universal method for nonmetal bonding. We utilize inks comprised of aluminum-based nanoenergetics, (a heat source) and tin (a bonding agent). Requirements for successful bonding are explored and four key criteria are established. Through statistical simulation and thermochemical equilibrium calculations, we conclude that the presence of a diluent in large percentages negatively impacts reaction kinetics. Conversely, we show smallmore » percentages of added tin enhance gas generation and drive faster reaction rates. The bulk bonding material, thermite plus tin, forms a continuous structure during reaction, adhering well to the substrate surface. In some cases, these bonds failed above 1200 kPa.« less

Hydrogen production from algal biomass - Advances, challenges and prospects.

PubMed

Show, Kuan-Yeow; Yan, Yuegen; Ling, Ming; Ye, Guoxiang; Li, Ting; Lee, Duu-Jong

2018-06-01

Extensive effort is being made to explore renewable energy in replacing fossil fuels. Biohydrogen is a promising future fuel because of its clean and high energy content. A challenging issue in establishing hydrogen economy is sustainability. Biohydrogen has the potential for renewable biofuel, and could replace current hydrogen production through fossil fuel thermo-chemical processes. A promising source of biohydrogen is conversion from algal biomass, which is abundant, clean and renewable. Unlike other well-developed biofuels such as bioethanol and biodiesel, production of hydrogen from algal biomass is still in the early stage of development. There are a variety of technologies for algal hydrogen production, and some laboratory- and pilot-scale systems have demonstrated a good potential for full-scale implementation. This work presents an elucidation on development in biohydrogen encompassing biological pathways, bioreactor designs and operation and techno-economic evaluation. Challenges and prospects of biohydrogen production are also outlined. Copyright © 2018 Elsevier Ltd. All rights reserved.

A high temperature drop-tube and packed-bed solar reactor for continuous biomass gasification

NASA Astrophysics Data System (ADS)

Bellouard, Quentin; Abanades, Stéphane; Rodat, Sylvain; Dupassieux, Nathalie

2017-06-01

Biomass gasification is an attractive process to produce high-value syngas. Utilization of concentrated solar energy as the heat source for driving reactions increases the energy conversion efficiency, saves biomass resource, and eliminates the needs for gas cleaning and separation. A high-temperature tubular solar reactor combining drop tube and packed bed concepts was used for continuous solar-driven gasification of biomass. This 1 kW reactor was experimentally tested with biomass feeding under real solar irradiation conditions at the focus of a 2 m-diameter parabolic solar concentrator. Experiments were conducted at temperatures ranging from 1000°C to 1400°C using wood composed of a mix of pine and spruce (bark included) as biomass feedstock. The aim of this study was to demonstrate the feasibility of syngas production in this reactor concept and to prove the reliability of continuous biomass gasification processing using solar energy. The study first consisted of a parametric study of the gasification conditions to obtain an optimal gas yield. The influence of temperature and oxidizing agent (H2O or CO2) on the product gas composition was investigated. The study then focused on solar gasification during continuous biomass particle injection for demonstrating the feasibility of a continuous process. Regarding the energy conversion efficiency of the lab scale reactor, energy upgrade factor of 1.21 and solar-to-fuel thermochemical efficiency up to 28% were achieved using wood heated up to 1400°C.

Bio-oil production via subcritical hydrothermal liquefaction of biomass

NASA Astrophysics Data System (ADS)

Durak, Halil

2017-04-01

Biomass based raw materials can be converted into the more valued energy forms using biochemical methods such as ethanol fermentation, methane fermentation and the thermochemical methods such as direct combustion, pyrolysis, gasification, liquefaction. The bio-oil obtained from the biomass has many advantages than traditional use. Firstly, it has features such as high energy density, easy storage and easy transportation. Bio-oil can be used as a fuel in engines, turbines and burning units directly. Besides, it can be converted into products in higher quality and volume via catalytic cracking, hydrodexygenation, emulsification, and steam reforming [1,2]. Many organic solvents such as acetone, ethanol, methanol, isopropanol are used in the supercritical liquefaction processes. When we think about the cost and effects of the organic solvent on nature, it will be understood better that it is necessary to find solvent that are more sensitive against nature. Here, water must have an important place because of its features. Most important solvent of the world water is named as "universal solvent" because none of the liquids can dissolve the materials as much as done by water. Water is found much at the nature and cost of it is very few when compared with the other solvent. Hydrothermal liquefaction, a thermochemical conversion process is an effective method used for converting biomass into the liquid products. General reaction conditions for hydrothermal liquefaction process are the 250-374 °C temperature range and 4 - 22 Mpa pressure values range, besides, the temperature values can be higher according to the product that is expected to be obtained [3,4]. In this study, xanthium strumarium plant stems have been used as biomass source. The experiments have been carried out using a cylindrical reactor (75 mL) at the temperatures of 300 °C. The produced liquids at characterized by elemental analysis, GC-MS and FT-IR. According to the analysis, different types of compounds were identified by GC-MS.

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

Fitzpatrick, Stephen W.

This project involved a three-year program managed by BioMetics, Inc. (Waltham, MA) to demonstrate the commercial feasibility of Biofine thermochemical process technology for conversion of cellulose-containing wastes or renewable materials into levulinic acid, a versatile platform chemical. The program, commencing in October 1995, involved the design, procurement, construction and operation of a plant utilizing the Biofine process to convert 1 dry ton per day of paper sludge waste. The plant was successfully designed, constructed, and commissioned in 1997. It was operated for a period of one year on paper sludge from a variety of source paper mills to collect datamore » to verify the design for a commercial scale plant. Operational results were obtained for four different feedstock varieties. Stable, continuous operation was achieved for two of the feedstocks. Continuous operation of the plant at demonstration scale provided the opportunity for process optimization, development of operational protocols, operator training and identification of suitable materials of construction for scale up to commercial operation . Separated fiber from municipal waster was also successfully processed. The project team consisted of BioMetics Inc., Great Lakes Chemical Corporation (West Lafayette, IN), and New York State Energy Research and Development Authority (Albany, NY).« less

Recent developments of post-modification of biochar for electrochemical energy storage.

PubMed

Cheng, Bin-Hai; Zeng, Raymond J; Jiang, Hong

2017-12-01

Biochar is a common byproduct from thermochemical conversion of biomass to produce bioenergy. However, the biochar features, such as morphology, porosity and surface chemistry, cannot be well controlled in conventional conversion approaches, limiting the wide application of raw biochar. Aiming to meet the specific requirements, post-modification of raw biochar was frequently conducted to improve the quality. In this review, recent developments regarding post-modification methods of biochar are presented and discussed. Progresses on the applications of post modified biochar as electrode materials for supercapacitors are intensively summarized. This review aims to reveal the key factors that affecting the performance of biochar-based supercapacitors, and provide guidance for rationalizing the modification methods to expand the applications of biochar-based functional materials in supercapacitors. Copyright © 2017 Elsevier Ltd. All rights reserved.

Catalytic Deoxygenation of Biomass Pyrolysis Vapors to Improve Bio-oil Stability

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

Dayton, David C.

2016-12-22

The President’s Advanced Energy Initiative called for a change in the way Americans fuel their vehicles to promote improved energy security. Increasing biofuels production from domestic lignocellulosic resources requires advanced technology development to achieve the aggressive targets set forth to reduce motor gasoline consumption by 20% in ten years (by 2017). The U.S. Department of Energy (USDOE) Office of the Biomass Program (currently Bioenergy Technologies Office) is actively funding research and development in both biochemical and thermochemical conversion technologies to accelerate the deployment of biofuels technologies in the near future to meet the goals of the Advanced Energy Initiative. Thermochemicalmore » conversion technology options include both gasification and pyrolysis to enable the developing lignocellulosic biorefineries and maximize biomass resource utilization for production of biofuels.« less

Study of combustion and emission characteristics of fuel derived from waste plastics by various waste to energy (W-t-E) conversion processes

NASA Astrophysics Data System (ADS)

Hazrat, M. A.; Rasul, M. G.; Khan, M. M. K.

2016-07-01

Reduction of plastic wastes by means of producing energy can be treated as a good investment in the waste management and recycling sectors. In this article, conversion of plastics into liquid fuel by two thermo-chemical processes, pyrolysis and gasification, are reviewed. The study showed that the catalytic pyrolysis of homogenous waste plastics produces better quality and higher quantity of liquefied fuel than that of non-catalytic pyrolysis process at a lower operating temperature. The syngas produced from gasification process, which occurs at higher temperature than the pyrolysis process, can be converted into diesel by the Fischer-Tropsch (FT) reaction process. Conducive bed material like Olivine in the gasification conversion process can remarkably reduce the production of tar. The waste plastics pyrolysis oil showed brake thermal efficiency (BTE) of about 27.75%, brake specific fuel consumption (BSFC) of 0.292 kg/kWh, unburned hydrocarbon emission (uHC) of 91 ppm and NOx emission of 904 ppm in comparison with the diesel for BTE of 28%, BSFC of 0.276 kg/kWh, uHC of 57 ppm and NOx of 855 ppm. Dissolution of Polystyrene (PS) into biodiesel also showed the potential of producing alternative transport fuel. It has been found from the literature that at higher engine speed, increased EPS (Expanded Polystyrene) quantity based biodiesel blends reduces CO, CO2, NOx and smoke emission. EPS-biodiesel fuel blend increases the brake thermal efficiency by 7.8%, specific fuel consumption (SFC) by 7.2% and reduces brake power (Pb) by 3.2%. More study using PS and EPS with other thermoplastics is needed to produce liquid fuel by dissolving them into biodiesel and to assess their suitability as a transport fuel. Furthermore, investigation to find out most suitable W-t-E process for effective recycling of the waste plastics as fuel for internal combustion engines is necessary to reduce environmental pollution and generate revenue which will be addressed in this article.

Innovative solar thermochemical water splitting.

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

Hogan, Roy E. Jr.; Siegel, Nathan P.; Evans, Lindsey R.

2008-02-01

Sandia National Laboratories (SNL) is evaluating the potential of an innovative approach for splitting water into hydrogen and oxygen using two-step thermochemical cycles. Thermochemical cycles are heat engines that utilize high-temperature heat to produce chemical work. Like their mechanical work-producing counterparts, their efficiency depends on operating temperature and on the irreversibility of their internal processes. With this in mind, we have invented innovative design concepts for two-step solar-driven thermochemical heat engines based on iron oxide and iron oxide mixed with other metal oxides (ferrites). The design concepts utilize two sets of moving beds of ferrite reactant material in close proximitymore » and moving in opposite directions to overcome a major impediment to achieving high efficiency--thermal recuperation between solids in efficient counter-current arrangements. They also provide inherent separation of the product hydrogen and oxygen and are an excellent match with high-concentration solar flux. However, they also impose unique requirements on the ferrite reactants and materials of construction as well as an understanding of the chemical and cycle thermodynamics. In this report the Counter-Rotating-Ring Receiver/Reactor/Recuperator (CR5) solar thermochemical heat engine and its basic operating principals are described. Preliminary thermal efficiency estimates are presented and discussed. Our ferrite reactant material development activities, thermodynamic studies, test results, and prototype hardware development are also presented.« less

Biological lignocellulose solubilization: Comparative evaluation of biocatalysts and enhancement via cotreatment

DOE PAGES

Paye, Julie M. D.; Guseva, Anna; Hammer, Sarah K.; ...

2016-01-12

Feedstock recalcitrance is the most important barrier impeding cost-effective production of cellulosic biofuels. Pioneer commercial cellulosic ethanol facilities employ thermochemical pretreatment and addition of fungal cellulase, reflecting the main research emphasis in the field. However, it has been suggested that it may be possible to process cellulosic biomass without thermochemical pretreatment using thermophilic, cellulolytic bacteria. Thus, to further explore this idea, we examine the ability of various biocatalysts to solubilize autoclaved but otherwise unpretreated cellulosic biomass under controlled but not industrial conditions.

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

Das, K. C., Adams; Thomas, T; Eiteman, Mark A

In this project we focused on several aspects of technology development that advances the formation of an integrated biorefinery. These focus areas include: [ 1] pretreatment of biomass to enhance quality of products from thermochemical conversion; [2] characterization of and development of coproduct uses; [3] advancement in fermentation of lignocellulosics and particularly C5 and C6 sugars simultaneously, and [ 4] development of algal biomass as a potential substrate for the biorefinery. These advancements are intended to provide a diverse set of product choices within the biorefinery, thus improving the cost effectiveness of the system. Technical effectiveness was demonstrated in themore » thermochemical product quality in the form of lower tar production, simultaneous of use of multiple sugars in fermentation, use ofbiochar in environmental (ammonia adsorption) and agricultural applications, and production of algal biomass in wastewaters. Economic feasibility of algal biomass production systems seems attractive, relative to the other options. However, further optimization in all paths, and testing/demonstration at larger scales are required to fully understand the economic viabilities. The coproducts provide a clear picture that multiple streams of value can be generated within an integrated biorefinery, and these include fuels and products.« less

Use of Tabulated Thermochemical Data for Pure Compounds

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.

1999-01-01

Thermodynamic data for inorganic compounds is found in a variety of tabulations and computer databases. An extensive listing of sources of inorganic thermodynamic data is provided. The three major tabulations are the JANAF tables. Thermodynamic Properties of Individual Substances, and the tabulation by Barin. The notation and choice of standard states is different in each of these tabulations, so combining data from the different tabulations is often a problem. By understanding the choice of standard states, it is possible to develop simple equations for conversion of the data from one form to another.

The thermochemical structure and evolution of Earth's mantle: constraints and numerical models.

PubMed

Tackley, Paul J; Xie, Shunxing

2002-11-15

Geochemical observations place several constraints on geophysical processes in the mantle, including a requirement to maintain several distinct reservoirs. Geophysical constraints limit plausible physical locations of these reservoirs to a thin basal layer, isolated deep 'piles' of material under large-scale mantle upwellings, high-viscosity blobs/plums or thin strips throughout the mantle, or some combination of these. A numerical model capable of simulating the thermochemical evolution of the mantle is introduced. Preliminary simulations are more differentiated than Earth but display some of the proposed thermochemical processes, including the generation of a high-mu mantle reservoir by recycling of crust, and the generation of a high-(3)He/(4)He reservoir by recycling of residuum, although the resulting high-(3)He/(4)He material tends to aggregate near the top, where mid-ocean-ridge melting should sample it. If primitive material exists as a dense basal layer, it must be much denser than subducted crust in order to retain its primitive (e.g. high-(3)He) signature. Much progress is expected in the near future.

Catalytic hydrothermal upgrading of crude bio-oils produced from different thermo-chemical conversion routes of microalgae.

PubMed

Duan, Peigao; Wang, Bing; Xu, Yuping

2015-06-01

This study presents experimental results that compare the use of hydrothermal liquefaction (HTL), alcoholysis (Al), pyrolysis (Py) and hydropyrolysis (HPy) for the production of bio-oil from a microalga (Chlorella pyrenoidosa) and the catalytic hydrothermal upgrading of crude bio-oils produced by these four conversion routes. The yields and compositions of bio-oil, solid residue, and gases were evaluated and compared. HTL resulted in a bio-oil that has a higher energy density and superior fuel properties, such as thermal and storage stabilities, compared with the other three conversion routes. The N in crude bio-oils produced from Py and HPy is more easily removed than that in the bio-oils produced from HTL and Al. The upgraded bio-oils contain reduced amounts of certain O-containing and N-containing compounds and significantly increased saturated hydrocarbon contents. All of the upgraded bio-oils have a larger fraction boiling below 350°C than their corresponding crude bio-oils. Copyright © 2015 Elsevier Ltd. All rights reserved.

Polyurethane foams based on crude glycerol-derived biopolyols: One-pot preparation of biopolyols with branched fatty acid ester chains and its effects on foam formation and properties

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

Li, Cong; Luo, Xiaolan; Li, Tao

2014-01-01

Environmentally friendly biopolyols have been produced with crude glycerol as the sole feedstock using a one-pot thermochemical conversion process without the addition of extra catalysts and reagents. Structural features of these biopolyols were characterized by rheology analysis. Rigid polyurethane (PU) foams were obtained from these crude glycerol-based biopolyols and the foaming mechanism was explored. Investigations revealed that partial carbonyl groups hydrogen-bonded with NeH were replaced by aromatic rings after the introduction of branched fatty acid ester chains in the “urea rich” phase, and that distinct microphases had formed in the foams. Studies showed that branched fatty acid ester chains inmore » the biopolyols played an important role in reducing the degree of microphase separation and stabilizing bubbles during foaming processes. PU foams with thermal conductivity comparable to commercial products made from petroleum-based polyols were obtained. These studies show the potential for development of PU foams based on crude glycerol, a renewable resource.« less

Evaluating Indicators and Life Cycle Inventories for Processes in Early Stages of Technical Readiness

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

Tan, Eric C; Smith, Raymond; Ruiz-Mercado, Gerardo

This presentation examines different methods for analyzing manufacturing processes in the early stages of technical readiness. Before developers know much detail about their processes, it is valuable to apply various assessments to evaluate their performance. One type of assessment evaluates performance indicators to describe how closely processes approach desirable objectives. Another type of assessment determines the life cycle inventories (LCI) of inputs and outputs for processes, where for a functional unit of product, the user evaluates the resources used and the releases to the environment. These results can be compared to similar processes or combined with the LCI of othermore » processes to examine up-and down-stream chemicals. The inventory also provides a listing of the up-stream chemicals, which permits study of the whole life cycle. Performance indicators are evaluated in this presentation with the U.S. Environmental Protection Agency's GREENSCOPE (Gauging Reaction Effectiveness for ENvironmental Sustainability with a multi-Objective Process Evaluator) methodology, which evaluates processes in four areas: Environment, Energy, Economics, and Efficiency. The method develops relative scores for indicators that allow comparisons across various technologies. In this contribution, two conversion pathways for producing cellulosic ethanol from biomass, via thermochemical and biochemical routes, are studied. The information developed from the indicators and LCI can be used to inform the process design and the potential life cycle effects of up- and down-stream chemicals.« less

Performance assessment of dilute-acid leaching to improve corn stover quality for thermochemical conversion

DOE PAGES

Aston, John E.; Thompson, David N.; Westover, Tyler L.

2016-08-30

Lignocellulosic biomass is a sustainable energy source that can help meet the increasing demand for biofuels in the United States. However, the quality and availability of such feedstocks greatly affects their suitability for downstream conversion. This work reports the effects of dilute-acid leaching at various solid loadings, temperatures and acid loadings on the quality of a traditional biochemical feedstock, corn stover, as a potential feedstock for thermochemical conversions. At 5 wt% solids, dilute-acid leaching was observed to effectively remove 97.3% of the alkali metals and alkaline earth metals that can negatively affect degradation pathways during pyrolysis and result in greatermore » yield of non-condensable gases. In addition, up to 98.4% of the chlorine and 88.8% of the phosphorus, which can cause equipment corrosion and foul upgrading catalysts, respectively, were removed. At 25°C in the absence of acid, only 6.8% of the alkali metals and alkaline earth metals were removed; however 88.0% of chloride was still removed. The ratio of alkaline/acidic ash species has been suggested to proportionately relate to slagging in biopower applications. The initial alkali/acid ratio of the ash species present in the untreated corn stover was 0.38 (significant slagging risk). At 5 wt% solids, this ratio was decreased to 0.18 (moderate slagging risk) at 0 wt% acid and 90°C, and was decreased to 0.07, 0.08 and 0.06 at 0.5 wt% acid at 25°C, 50°C and 90°C, respectively (little or no slagging risk). Increasing the acid loading to 1.0% only slightly decreased the measured alkali/acid ratio of remaining ash species. Lastly, the results presented here show that a water wash or dilute-acid preprocessing step can improve corn stover quality for pyrolysis, hydrothermal liquefaction and biopower.« less

Performance assessment of dilute-acid leaching to improve corn stover quality for thermochemical conversion

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

Aston, John E.; Thompson, David N.; Westover, Tyler L.

Lignocellulosic biomass is a sustainable energy source that can help meet the increasing demand for biofuels in the United States. However, the quality and availability of such feedstocks greatly affects their suitability for downstream conversion. This work reports the effects of dilute-acid leaching at various solid loadings, temperatures and acid loadings on the quality of a traditional biochemical feedstock, corn stover, as a potential feedstock for thermochemical conversions. At 5 wt% solids, dilute-acid leaching was observed to effectively remove 97.3% of the alkali metals and alkaline earth metals that can negatively affect degradation pathways during pyrolysis and result in greatermore » yield of non-condensable gases. In addition, up to 98.4% of the chlorine and 88.8% of the phosphorus, which can cause equipment corrosion and foul upgrading catalysts, respectively, were removed. At 25°C in the absence of acid, only 6.8% of the alkali metals and alkaline earth metals were removed; however 88.0% of chloride was still removed. The ratio of alkaline/acidic ash species has been suggested to proportionately relate to slagging in biopower applications. The initial alkali/acid ratio of the ash species present in the untreated corn stover was 0.38 (significant slagging risk). At 5 wt% solids, this ratio was decreased to 0.18 (moderate slagging risk) at 0 wt% acid and 90°C, and was decreased to 0.07, 0.08 and 0.06 at 0.5 wt% acid at 25°C, 50°C and 90°C, respectively (little or no slagging risk). Increasing the acid loading to 1.0% only slightly decreased the measured alkali/acid ratio of remaining ash species. Lastly, the results presented here show that a water wash or dilute-acid preprocessing step can improve corn stover quality for pyrolysis, hydrothermal liquefaction and biopower.« less

A Review: Using Pyrolysis and its Bioproducts to Help Close the Loop in Sustainable Life Support Systems

NASA Technical Reports Server (NTRS)

McCoy, LaShelle E.

2013-01-01

The next step in human exploration of space is beyond low Earth orbit and possibly to sites such as the Moon and Mars. Resupply of critical life support components for missions such as these are difficult or impossible. Life support processes for closing the loop of water, oxygen and carbon have to be identified. Currently, there are many technologies proposed for terrestrial missions for waste, water, air processing. and the creation of consumables. There are a variety of different approaches, but few address all of these issues simultaneously. One candidate is pyrolysis; a method where waste streams can be heated in the absence of oxygen to undergo a thermochemical conversion producing a series of bioproducts. Bioproducts like biochar made from non-edible biomass and human solid waste can possibly provide valuable benefits such as waste reduction, regolith fertilization for increased food production, and become a consumable for water processing and air revitalization systems. Syngas containing hydrogen, carbon monoxide and carbon dioxide, can be converted to methane and dimethyl ether to create propellants. Bio-oils can be utilized as a heating fuel or fed to bioreactors that utilize oil-eating microbes.

Lance Wheeler | NREL

Science.gov Websites

solution-phase phenomena of nanomaterials Switchable photovoltaics Solar thermochemical fuel production methylammonium lead halide perovskites during thermal processing from solution," Energy & Environmental

Study of Catalyst Variation Effect in Glycerol Conversion Process to Hydrogen Gas by Steam Reforming

NASA Astrophysics Data System (ADS)

Widayat; Hartono, R.; Elizabeth, E.; Annisa, A. N.

2018-04-01

Along with the economic development, needs of energy being increase too. Hydrogen as alternative energy has many usages. Besides that, hydrogen is one source of energy that is a clean fuel, but process production of hydrogen from natural gas as a raw material has been used for a long time. Therefore, there is need new invention to produce hydrogen from the others raw material. Glycerol, a byproduct of biodiesel production, is a compound which can be used as a raw material for hydrogen production. By using glycerol as a raw material of hydrogen production, we can get added value of glycerol as well as an energy source solution. The process production of hydrogen by steam reforming is a thermochemical process with efficiency 70%. This process needs contribution of catalyst to improve its efficiency and selectivity of the process. In this study will be examined the effect variation of catalyst for glycerol conversion process to hydrogen by steam reforming. The method for catalyst preparation was variation of catalyst impregnation composition, catalyst calcined with difference concentration of hydrochloric acid and calcined with difference hydrochloric acid ratio. After that, all of catalyst which have been prepared, used for steam reforming process for hydrogen production from glycerol as a raw material. From the study, the highest yield of hydrogen gas showed in the process production by natural zeolite catalyst with 1:15 Hydrochloric acid ratio was 42.28%. Hydrogen yield for 2M calcined natural zeolite catalyst was 38.37%, for ZSM-5 catalyst was 15.83%, for 0.5M calcined natural zeolite was 13.09% and for ultrasonic natural zeolite was 11.43%. The lowest yield of hydrogen gas showed in catalyst 2Zn/ZSM-5 with 11.22%. This result showed that hydrogen yield product was affected by catalyst variation because of the catalyst has difference characteristic and difference catalytic activity after the catalyst preparation process.

Thermochemical energy storage for a lunar base

NASA Technical Reports Server (NTRS)

Perez-Davis, Marla E.; Mckissock, Barbara I.; Difilippo, Frank

1992-01-01

A thermochemical solar energy storage concept involving the reversible reaction CaO + H2O yields Ca(OH)2 is proposed as a power system element for a lunar base. The operation and components of such a system are described. The CaO/H2O system is capable of generating electric power during both the day and night. Mass of the required amount of CaO is neglected since it is obtained from lunar soil. Potential technical problems, such as reactor design and lunar soil processing, are reviewed.

Phylogeny in Defining Model Plants for Lignocellulosic Ethanol Production: A Comparative Study of Brachypodium distachyon, Wheat, Maize, and Miscanthus x giganteus Leaf and Stem Biomass

PubMed Central

Meineke, Till; Manisseri, Chithra; Voigt, Christian A.

2014-01-01

The production of ethanol from pretreated plant biomass during fermentation is a strategy to mitigate climate change by substituting fossil fuels. However, biomass conversion is mainly limited by the recalcitrant nature of the plant cell wall. To overcome recalcitrance, the optimization of the plant cell wall for subsequent processing is a promising approach. Based on their phylogenetic proximity to existing and emerging energy crops, model plants have been proposed to study bioenergy-related cell wall biochemistry. One example is Brachypodium distachyon, which has been considered as a general model plant for cell wall analysis in grasses. To test whether relative phylogenetic proximity would be sufficient to qualify as a model plant not only for cell wall composition but also for the complete process leading to bioethanol production, we compared the processing of leaf and stem biomass from the C3 grasses B. distachyon and Triticum aestivum (wheat) with the C4 grasses Zea mays (maize) and Miscanthus x giganteus, a perennial energy crop. Lambda scanning with a confocal laser-scanning microscope allowed a rapid qualitative analysis of biomass saccharification. A maximum of 108–117 mg ethanol·g−1 dry biomass was yielded from thermo-chemically and enzymatically pretreated stem biomass of the tested plant species. Principal component analysis revealed that a relatively strong correlation between similarities in lignocellulosic ethanol production and phylogenetic relation was only given for stem and leaf biomass of the two tested C4 grasses. Our results suggest that suitability of B. distachyon as a model plant for biomass conversion of energy crops has to be specifically tested based on applied processing parameters and biomass tissue type. PMID:25133818

Soot and Spectral Radiation Modeling in ECN Spray A and in Engines

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

Haworth, Daniel C; Ferreyro-Fernandez, Sebastian; Paul, Chandan

The amount of soot formed in a turbulent combustion system is determined by a complex system of coupled nonlinear chemical and physical processes. Different physical subprocesses can dominate, depending on the hydrodynamic and thermochemical environments. Similarly, the relative importance of reabsorption, spectral radiation properties, and molecular gas radiation versus soot radiation varies with thermochemical conditions, and in ways that are difficult to predict for the highly nonhomogeneous in-cylinder mixtures in engines. Here it is shown that transport and mixing play relatively more important roles as rate-determining processes in soot formation at engine-relevant conditions. It is also shown that molecular gasmore » radiation and spectral radiation properties are important for engine-relevant conditions.« less

Entropy production in mesoscopic stochastic thermodynamics: nonequilibrium kinetic cycles driven by chemical potentials, temperatures, and mechanical forces

NASA Astrophysics Data System (ADS)

Qian, Hong; Kjelstrup, Signe; Kolomeisky, Anatoly B.; Bedeaux, Dick

2016-04-01

Nonequilibrium thermodynamics (NET) investigates processes in systems out of global equilibrium. On a mesoscopic level, it provides a statistical dynamic description of various complex phenomena such as chemical reactions, ion transport, diffusion, thermochemical, thermomechanical and mechanochemical fluxes. In the present review, we introduce a mesoscopic stochastic formulation of NET by analyzing entropy production in several simple examples. The fundamental role of nonequilibrium steady-state cycle kinetics is emphasized. The statistical mechanics of Onsager’s reciprocal relations in this context is elucidated. Chemomechanical, thermomechanical, and enzyme-catalyzed thermochemical energy transduction processes are discussed. It is argued that mesoscopic stochastic NET in phase space provides a rigorous mathematical basis of fundamental concepts needed for understanding complex processes in chemistry, physics and biology. This theory is also relevant for nanoscale technological advances.

Ethanol extraction of phytosterols from corn fiber

DOEpatents

Abbas, Charles; Beery, Kyle E.; Binder, Thomas P.; Rammelsberg, Anne M.

2010-11-16

The present invention provides a process for extracting sterols from a high solids, thermochemically hydrolyzed corn fiber using ethanol as the extractant. The process includes obtaining a corn fiber slurry having a moisture content from about 20 weight percent to about 50 weight percent solids (high solids content), thermochemically processing the corn fiber slurry having high solids content of 20 to 50% to produce a hydrolyzed corn fiber slurry, dewatering the hydrolyzed corn fiber slurry to achieve a residual corn fiber having a moisture content from about 30 to 80 weight percent solids, washing the residual corn fiber, dewatering the washed, hydrolyzed corn fiber slurry to achieve a residual corn fiber having a moisture content from about 30 to 80 weight percent solids, and extracting the residual corn fiber with ethanol and separating at least one sterol.

Nuclear driven water decomposition plant for hydrogen production

NASA Technical Reports Server (NTRS)

Parker, G. H.; Brecher, L. E.; Farbman, G. H.

1976-01-01

The conceptual design of a hydrogen production plant using a very-high-temperature nuclear reactor (VHTR) to energize a hybrid electrolytic-thermochemical system for water decomposition has been prepared. A graphite-moderated helium-cooled VHTR is used to produce 1850 F gas for electric power generation and 1600 F process heat for the water-decomposition process which uses sulfur compounds and promises performance superior to normal water electrolysis or other published thermochemical processes. The combined cycle operates at an overall thermal efficiency in excess of 45%, and the overall economics of hydrogen production by this plant have been evaluated predicated on a consistent set of economic ground rules. The conceptual design and evaluation efforts have indicated that development of this type of nuclear-driven water-decomposition plant will permit large-scale economic generation of hydrogen in the 1990s.

Thermo-chemical pretreatment of rice straw for further processing for levulinic acid production.

PubMed

Elumalai, Sasikumar; Agarwal, Bhumica; Sangwan, Rajender S

2016-10-01

A variety of pretreatment protocols for rice straw fiber reconstruction were evaluated under mild conditions (upto 0.2%wt. and 121°C) with the object of improving polymer susceptibility to chemical attack while preserving carbohydrate sugars for levulinic acid (LA) production. Each of the protocols tested significantly enhanced pretreatment recoveries of carbohydrate sugars and lignin, and a NaOH protocol showed the most promise, with enhanced carbohydrate preservation (upto 20% relative to the other protocols) and more effective lignin dissolution (upto 60%). Consequently, post-pretreatment fibers were evaluated for LA preparation using an existing co-solvent system consisting of HCl and THF, in addition supplementation of DMSO was attempted, in order to improve final product recovery. In contrast to pretreatment response, H2SO4 protocol fibers yielded highest LA conc. (21%wt. with 36% carbohydrate conversion efficiency) under the modest reaction conditions. Apparent spectroscopic analysis witnessed for fiber destruction and delocalization of inherent constituents during pretreatment protocols. Copyright © 2016 Elsevier Ltd. All rights reserved.

Synergistic effect on thermal behavior during co-pyrolysis of lignocellulosic biomass model components blend with bituminous coal.

PubMed

Wu, Zhiqiang; Wang, Shuzhong; Zhao, Jun; Chen, Lin; Meng, Haiyu

2014-10-01

Co-thermochemical conversion of lignocellulosic biomass and coal has been investigated as an effective way to reduce the carbon footprint. Successful evaluating on thermal behavior of the co-pyrolysis is prerequisite for predicting performance and optimizing efficiency of this process. In this paper, pyrolysis and kinetics characteristics of three kinds of lignocellulosic biomass model components (cellulose, hemicellulose, and lignin) blended with a kind of Chinese bituminous coal were explored by thermogravimetric analyzer and Kissinger-Akahira-Sunose method. The results indicated that the addition of model compounds had different synergistic effects on thermal behavior of the bituminous coal. The cellulose showed positive synergistic effects on the thermal decomposition of the coal bituminous coal with lower char yield than calculated value. For hemicellulose and lignin, whether positive or negative synergistic was related to the mixed ratio and temperature range. The distribution of the average activation energy values for the mixtures showed nonadditivity performance. Copyright © 2014 Elsevier Ltd. All rights reserved.

Utilization of grasses for potential biofuel production and phytoremediation of heavy metal contaminated soils.

PubMed

Balsamo, Ronald A; Kelly, William J; Satrio, Justinus A; Ruiz-Felix, M Nydia; Fetterman, Marisa; Wynn, Rodd; Hagel, Kristen

2015-01-01

This research focuses on investigating the use of common biofuel grasses to assess their potential as agents of long-term remediation of contaminated soils using lead as a model heavy metal ion. We present evidence demonstrating that switch grass and Timothy grass may be potentially useful for long-term phytoremediation of heavy metal contaminated soils and describe novel techniques to track and remove contaminants from inception to useful product. Enzymatic digestion and thermochemical approaches are being used to convert this lignocellulosic feedstock into useful product (sugars, ethanol, biocrude oil+biochar). Preliminary studies on enzymatic hydrolysis and fast pyrolysis of the Switchgrass materials that were grown in heavy metal contaminated soil and non-contaminated soils show that the presence of lead in the Switchgrass material feedstock does not adversely affect the outcomes of the conversion processes. These results indicate that the modest levels of contaminant uptake allow these grass species to serve as phytoremediation agents as well as feedstocks for biofuel production in areas degraded by industrial pollution.

Project Independence: Construction of an Integrated Biorefinery for Production of Renewable Biofuels at an Existing Pulp and Paper Mill

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

Freeman, Douglas

2012-06-01

Project Independence proposed to construct a demonstration biomass-to-liquids (BTL) biorefinery in Wisconsin Rapids, isconsin. The biorefinery was to be co-located at the existing pulp and paper mill, NewPage Wisconsin System Incorporated’s Wisconsin Rapids Mill, and when in full operation would both generate renewable energy for Wisconsin Rapids Mill and produce liquid fuels from abundant and renewable lignocellulosic biomass. The biorefinery would serve to validate the thermochemical pathway and economic models for BTL production using forest residuals and wood waste, providing a basis for proliferating BTL conversion technologies throughout the United States. It was a project goal to create a compellingmore » new business model for the pulp and paper industry, and support the nation’s goal for increasing renewable fuels production and reducing its dependence on foreign oil. NewPage Corporation planned to replicate this facility at other NewPage Corporation mills after this first demonstration scale plant was operational and had proven technical and economic feasibility. An overview of the process begins with biomass being harvested, sized, conditioned and fed into a ThermoChem Recovery International (TRI) steam reformer where it is converted to high quality synthetic gas (syngas). The syngas is then cleaned, compressed, scrubbed, polished and fed into the Fischer-Tropsch (F-T) catalytic reactors where the gas is converted into two, sulfur-free, clean crude products which will be marketed as revenue generating streams. Additionally, the Fischer-Tropsch products could be upgraded for use in automotive, aviation and chemical industries as valuable products, if desired. As the Project Independence project set out to prove forest products could be used to commercially produce biofuels, they planned to address and mitigate issues as they arose. In the early days of the Project Independence project, the plant was sized to process 500 dry tons of biomass per day but would generate a blend of synthesis gas for the lime kiln and a minimum of Fischer-Tropsch liquids for sale. This was to be done using a single stage of Fischer-Tropsch reaction at roughly a 70% yield. The capability of the Wisconsin Rapids Mill lime kiln to run on the relatively low heating value of the product synthesis gas was problematic. The design was then changed to maximize Fischer-Tropsch liquids production using a two stage Fischer-Tropsch process. Project Independence progressed with the design of the mill as ThermoChem Recovery International worked on the technical details of the project as well as develop information from their pilot plant. The pilot plant work uncovered several problems with the synthesis gas clean-up that solutions. ThermoChem Recovery International found these solutions and developed a very good path forward on the technical side. The technical solutions were demonstrated in the pilot plant to everyone’s satisfaction. In July 2010, NewPage Corporation had been severely affected by the downturn in the economy and actively went to find a strategic partner. By April 2011 the Abell Foundation entered the picture as this strategic partner. The Abell Foundation would join forces as Project Independence Inc. to build the 500 dry ton per day Project Independence plant. The design of this facility progress even after NewPage Corporation declared Chapter 11 Bankruptcy protection in September, 2011. This continued until April 2012 when NewPage Corporation determined that continued work on Project Independence Inc. presented too much risk with little reward for NewPage Corporation. The project was terminated at this point.« less

Pyrolysis of triglyceride materials for the production of renewable fuels and chemicals.

PubMed

Maher, K D; Bressler, D C

2007-09-01

Conversion of vegetable oils and animal fats composed predominantly of triglycerides using pyrolysis type reactions represents a promising option for the production of renewable fuels and chemicals. The purpose of this article was to collect and review literature on the thermo-chemical conversion of triglyceride based materials. The literature was divided and discussed as (1) direct thermal cracking and (2) combination of thermal and catalytic cracking. Typically, four main catalyst types are used including transition metal catalysts, molecular sieve type catalysts, activated alumina, and sodium carbonate. Reaction products are heavily dependant on the catalyst type and reaction conditions and can range from diesel like fractions to gasoline like fractions. Research in this area is not as advanced as bio-oil and bio-diesel research and there is opportunity for further study in the areas of reaction optimization, detailed characterization of products and properties, and scale-up.

System for thermochemical hydrogen production

DOEpatents

Werner, R.W.; Galloway, T.R.; Krikorian, O.H.

1981-05-22

Method and apparatus are described for joule boosting a SO/sub 3/ decomposer using electrical instead of thermal energy to heat the reactants of the high temperature SO/sub 3/ decomposition step of a thermochemical hydrogen production process driven by a tandem mirror reactor. Joule boosting the decomposer to a sufficiently high temperature from a lower temperature heat source eliminates the need for expensive catalysts and reduces the temperature and consequent materials requirements for the reactor blanket. A particular decomposer design utilizes electrically heated silicon carbide rods, at a temperature of 1250/sup 0/K, to decompose a cross flow of SO/sub 3/ gas.

Study of TLIPSS formation on different metals and alloys and their selective etching

NASA Astrophysics Data System (ADS)

Dostovalov, Alexandr V.; Korolkov, Victor P.; Terentiev, Vadim S.; Okotrub, Konstantin A.; Dultsev, Fedor N.; Nemykin, Anton; Babin, Sergey A.

2017-02-01

Experimental investigation of thermochemical laser-induced periodic surface structures (TLIPSS) formation on metal films (Ti, Cr, Ni, NiCr) at different processing conditions is presented. The hypothesis that the TLIPSS formation depends significantly on parabolic rate constant for oxide thin film growth is discussed. Evidently, low value of this parameter for Ni is the reason of TLIPSS absence on Ni and NiCr film with low Cr content. The effect of simultaneous ablative (with period ≍λ) and thermochemical (with period ≍λ) LIPSS formation was observed. The formation of structures after TLIPSS selective etching was demonstrated.

Strategic supply system design - a holistic evaluation of operational and production cost for a biorefinery supply chain

DOE PAGES

Lamers, Patrick; Tan, Eric C. D.; Searcy, Erin M.; ...

2015-08-20

Here, pioneer cellulosic biorefineries across the United States rely on a conventional feedstock supply system based on one-year contracts with local growers, who harvest, locally store, and deliver feed-stock in low-density format to the conversion facility. While the conventional system is designed for high biomass yield areas, pilot scale operations have experienced feedstock supply shortages and price volatilities due to reduced harvests and competition from other industries. Regional supply dependency and the inability to actively manage feedstock stability and quality, provide operational risks to the biorefinery, which translate into higher investment risk. The advanced feedstock supply system based on amore » network of depots can mitigate many of these risks and enable wider supply system benefits. This paper compares the two concepts from a system-level perspective beyond mere logistic costs. It shows that while processing operations at the depot increase feedstock supply costs initially, they enable wider system benefits including supply risk reduction (leading to lower interest rates on loans), industry scale-up, conversion yield improvements, and reduced handling equipment and storage costs at the biorefinery. When translating these benefits into cost reductions per liter of gasoline equivalent (LGE), we find that total cost reductions between -0.46 to -0.21 per LGE for biochemical and -0.32 to -0.12 per LGE for thermochemical conversion pathways are possible. Naturally, these system level benefits will differ between individual actors along the feedstock supply chain. Further research is required with respect to depot sizing, location, and ownership structures.« less

Strategic supply system design - a holistic evaluation of operational and production cost for a biorefinery supply chain

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

Lamers, Patrick; Tan, Eric C. D.; Searcy, Erin M.

Here, pioneer cellulosic biorefineries across the United States rely on a conventional feedstock supply system based on one-year contracts with local growers, who harvest, locally store, and deliver feed-stock in low-density format to the conversion facility. While the conventional system is designed for high biomass yield areas, pilot scale operations have experienced feedstock supply shortages and price volatilities due to reduced harvests and competition from other industries. Regional supply dependency and the inability to actively manage feedstock stability and quality, provide operational risks to the biorefinery, which translate into higher investment risk. The advanced feedstock supply system based on amore » network of depots can mitigate many of these risks and enable wider supply system benefits. This paper compares the two concepts from a system-level perspective beyond mere logistic costs. It shows that while processing operations at the depot increase feedstock supply costs initially, they enable wider system benefits including supply risk reduction (leading to lower interest rates on loans), industry scale-up, conversion yield improvements, and reduced handling equipment and storage costs at the biorefinery. When translating these benefits into cost reductions per liter of gasoline equivalent (LGE), we find that total cost reductions between -0.46 to -0.21 per LGE for biochemical and -0.32 to -0.12 per LGE for thermochemical conversion pathways are possible. Naturally, these system level benefits will differ between individual actors along the feedstock supply chain. Further research is required with respect to depot sizing, location, and ownership structures.« less

Anisotropic diamond etching through thermochemical reaction between Ni and diamond in high-temperature water vapour.

PubMed

Nagai, Masatsugu; Nakanishi, Kazuhiro; Takahashi, Hiraku; Kato, Hiromitsu; Makino, Toshiharu; Yamasaki, Satoshi; Matsumoto, Tsubasa; Inokuma, Takao; Tokuda, Norio

2018-04-27

Diamond possesses excellent physical and electronic properties, and thus various applications that use diamond are under development. Additionally, the control of diamond geometry by etching technique is essential for such applications. However, conventional wet processes used for etching other materials are ineffective for diamond. Moreover, plasma processes currently employed for diamond etching are not selective, and plasma-induced damage to diamond deteriorates the device-performances. Here, we report a non-plasma etching process for single crystal diamond using thermochemical reaction between Ni and diamond in high-temperature water vapour. Diamond under Ni films was selectively etched, with no etching at other locations. A diamond-etching rate of approximately 8.7 μm/min (1000 °C) was successfully achieved. To the best of our knowledge, this rate is considerably greater than those reported so far for other diamond-etching processes, including plasma processes. The anisotropy observed for this diamond etching was considerably similar to that observed for Si etching using KOH.

Static Thermochemical Model of COREX Melter Gasifier

NASA Astrophysics Data System (ADS)

Srishilan, C.; Shukla, Ajay Kumar

2018-02-01

COREX is one of the commercial smelting reduction processes. It uses the finer size ore and semi-soft coal instead of metallurgical coke to produce hot metal from iron ore. The use of top gas with high calorific value as a by-product export gas makes the process economical and green. The predictive thermochemical model of the COREX process presented here enables rapid computation of process parameters such as (1) required amount of ore, coal, and flux; (2) amount of slag and gas generated; and (3) gas compositions (based on the raw material and desired hot metal quality). The model helps in predicting the variations in process parameters with respect to the (1) degree of metallization and (2) post-combustion ratio for given raw material conditions. In general reduction in coal, flux, and oxygen, the requirement is concomitant with an increase in the degree of metallization and post-combustion ratio. The model reported here has been benchmarked using industrial data obtained from the JSW Steel Plant, India.

Process Simulation and Techno-Economic Evaluation of Alternative Biorefinery Scenarios

NASA Astrophysics Data System (ADS)

Aizpurua Gonzalez, Carlos Ernesto

A biorefinery is a complex processing facility that uses sustainably produced biomass as feedstock to generate biofuels and chemical products using a wide variety of alternative conversion pathways. The alternative conversion pathways can be generally classified as either biochemical or thermochemical conversion. A biorefinery is commonly based on a core biomass conversion technology (pretreatment, hydrolysis, pyrolysis, etc.) followed by secondary processing stages that determine the specific product, and its recovery. In this study, techno-economic analysis of several different lignocellulosic biomass conversion pathways have been performed. First, a novel biochemical conversion, which used electron beam and steam explosion pretreatments for ethanol production was evaluated. This evaluation include both laboratory work and process modeling. Encouraging experimental results are obtained that showed the biomass had enhanced reactivity to the enzyme hydrolysis. The total sugar recovery for the hardwood species was 72% using 5 FPU/g enzyme dosage. The combination of electron beam and steam explosion provides an improvement in sugar conversion of more than 20% compared to steam explosion alone. This combination of pretreatments was modeled along with a novel ethanol dehydration process that is based on vapor permeation membranes. The economic feasibility of this novel pretreatment-dehydration technology was evaluated and compared with the dilute acid process proposed by NREL in 2011. Overall, the pretreatment-dehydration technology process produces the same ethanol yields (81 gal/bdton). However, the economics of this novel process does not look promising since the minimum ethanol selling price (MESP) to generate an internal rate of return of 10% is of 3.09 /gal, compared to 2.28 /gal for the base case. To enhance the economic potential of a biorefinery, the isolation of value-added co-products was incorporated into the base dilute acid biorefinery process. In this case the work focused on the ethanol extraction of the non-structural components of switchgrass prior to pretreatment and enzymatic hydrolysis. Promising results obtained with an Aspen PlusRTM model showed that a MESP of 2.5 /gal along with an assumed co-product selling price of 1 /Kg generated an 18% internal rate of return (IRR). In a second series of studies biomass fast pyrolysis and the bio-oil upgrading for the production of drop-in fuels was analyzed. Again, an Aspen PlusRTM based process model was used to evaluate the impacts of different biomass feedstock composition on the biofuel product. In this case the biofuel produced both a gasoline and diesel fraction. Model results showed that both the carbon and ash content of the biomass had an impact on the amount and price of the biofuel products. The highest biofuel yield were obtained with the hardwood (red maple) and perennial (switchgrass) feedstocks at about 48 gal/bdton of biomass, while the softwood (loblolly pine) provided 46 gal/bdton. Bark (acacia), the feedstock with the highest ash content, only provided 39 gal/bdton. But when the cost of these feedstocks was included the softwood is predicted to provide the lowest cost fuel, followed by the bark. As expected overall cost of the biofuel was dramatically impacted by the cost of the feedstock, and also by the use of a fraction of the intermediate bio-oil as the source of the hydrogen needed for upgrading the bio-oil to a hydrocarbon fuel product. Using hydrogen from natural gas instead of hydrogen from reforming the intermediate bio-oil reduced the estimated cost of the fuel product by $1.20/gal.

Microreactor System Design for a NASA In Situ Propellant Production Plant on Mars

NASA Technical Reports Server (NTRS)

TeGrotenhuis, W. E.; Wegeng, R. S.; Vanderwiel, D. P.; Whyatt, G. A.; Viswanathan, V. V.; Schielke, K. P.; Sanders, G. B.; Peters, T. A.; Nicholson, Leonard S. (Technical Monitor)

2000-01-01

The NASA In Situ Resource Utilization (ISRU) program is planning near-term missions to Mars that will include chemical processes for converting the carbon dioxide (CO2) and possibly water from the Martian environment to propellants, oxygen, and other useful chemicals. The use of indigenous resources reduces the size and weight of the payloads from Earth significantly, representing enormous cost savings that make human exploration of Mars affordable. Extraterrestrial chemical processing plants will need to be compact, lightweight, highly efficient under reduced gravity, and extraordinarily reliable for long periods. Microchemical and thermal systems represent capability for dramatic reduction in size and weight, while offering high reliability through massive parallelization. In situ propellant production (ISPP), one aspect of the ISRU program, involves collecting and pressurizing atmospheric CO2, conversion reactions, chemical separations, heat exchangers, and cryogenic storage. A preliminary system design of an ISPP plant based on microtechnology has demonstrated significant size, weight, and energy efficiency gains over the current NASA baseline. Energy management is a strong driver for Mars-based processes, not only because energy is a scarce resource, but because heat rejection is problematic; the low pressure environment makes convective heat transfer ineffective. Energy efficiency gains are largely achieved in the microchemical plant through extensive heat recuperation and energy cascading, which has a small size and weight penalty because the added micro heat exchangers are small. This leads to additional size and weight gains by reducing the required area of waste heat radiators. The microtechnology-based ISPP plant is described in detail, including aspects of pinch analysis for optimizing the heat exchanger network. Three options for thermochemical compression Of CO2 from the Martian atmosphere, adsorption, absorption, and cryogenic freezing, are presented, as well as three options for water decomposition, low temperature electrolysis, high temperature electrolysis, and thermochemical decomposition. Other elements of the plant include Sabatier and reverse water gas shift reactors, water recovery, chemical separations, and cryogenic storage. Data are presented supporting preliminary sizing of components, and results of the system design are compared to the existing NASA baseline that is based on conventional technologies.

Comparative study of thermochemical processes for hydrogen production from biomass fuels.

PubMed

Biagini, Enrico; Masoni, Lorenzo; Tognotti, Leonardo

2010-08-01

Different thermochemical configurations (gasification, combustion, electrolysis and syngas separation) are studied for producing hydrogen from biomass fuels. The aim is to provide data for the production unit and the following optimization of the "hydrogen chain" (from energy source selection to hydrogen utilization) in the frame of the Italian project "Filiera Idrogeno". The project focuses on a regional scale (Tuscany, Italy), renewable energies and automotive hydrogen. Decentred and small production plants are required to solve the logistic problems of biomass supply and meet the limited hydrogen infrastructures. Different options (gasification with air, oxygen or steam/oxygen mixtures, combustion, electrolysis) and conditions (varying the ratios of biomass and gas input) are studied by developing process models with uniform hypothesis to compare the results. Results obtained in this work concern the operating parameters, process efficiencies, material and energetic needs and are fundamental to optimize the entire hydrogen chain. Copyright 2010 Elsevier Ltd. All rights reserved.

Evaluation energy efficiency of bioconversion knot rejects to ethanol in comparison to other thermochemically pretreated biomass.

PubMed

Wang, Zhaojiang; Qin, Menghua; Zhu, J Y; Tian, Guoyu; Li, Zongquan

2013-02-01

Rejects from sulfite pulp mill that otherwise would be disposed of by incineration were converted to ethanol by a combined physical-biological process that was comprised of physical refining and simultaneous saccharification and fermentation (SSF). The energy efficiency was evaluated with comparison to thermochemically pretreated biomass, such as those pretreated by dilute acid (DA) and sulfite pretreatment to overcome recalcitrance of lignocelluloses (SPORL). It was observed that the structure deconstruction of rejects by physical refining was indispensable to effective bioconversion but more energy intensive than that of thermochemically pretreated biomass. Fortunately, the energy consumption was compensated by the reduced enzyme dosage and the elevated ethanol yield. Furthermore, adjustment of disk-plates gap led to reduction in energy consumption with negligible influence on ethanol yield. In this context, energy efficiency up to 717.7% was achieved for rejects, much higher than that of SPORL sample (283.7%) and DA sample (152.8%). Copyright © 2012 Elsevier Ltd. All rights reserved.

Thermochemical hydrogen production based on magnetic fusion

NASA Astrophysics Data System (ADS)

Krikorian, O. H.; Brown, L. C.

Preliminary results of a DoE study to define the configuration and production costs for a Tandem Mirror Reactor (TMR) heat source H2 fuel production plant are presented. The TMR uses the D-T reaction to produce thermal energy and dc electrical current, with an Li blanket employed to breed more H-3 for fuel. Various blanket designs are being considered, and the coupling of two of them, a heat pipe blanket to a Joule-boosted decomposer, and a two-temperature zone blanket to a fluidized bed decomposer, are discussed. The thermal energy would be used in an H2SO4 thermochemical cycler to produce the H2. The Joule-boosted decomposer, involving the use of electrically heated commercial SiC furnace elements to transfer process heat to the thermochemical H2 cycle, is found to yield H2 fuel at a cost of $12-14/GJ, which is the projected cost of fossil fuels in 30-40 yr, when the TMR H2 production facility would be operable.

Supercritical Fluids Processing of Biomass to Chemicals and Fuels

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

Olson, Norman K.

2011-09-28

The main objective of this project is to develop and/or enhance cost-effective methodologies for converting biomass into a wide variety of chemicals, fuels, and products using supercritical fluids. Supercritical fluids will be used both to perform reactions of biomass to chemicals and products as well as to perform extractions/separations of bio-based chemicals from non-homogeneous mixtures. This work supports the Biomass Program’s Thermochemical Platform Goals. Supercritical fluids are a thermochemical approach to processing biomass that, while aligned with the Biomass Program’s interests in gasification and pyrolysis, offer the potential for more precise and controllable reactions. Indeed, the literature with respect tomore » the use of water as a supercritical fluid frequently refers to “supercritical water gasification” or “supercritical water pyrolysis.”« less

Computational aerothermodynamics

NASA Technical Reports Server (NTRS)

Deiwert, George S.

1989-01-01

Computational aerothermodynamics concerns the coupling of real gas effects with equations of motion to include thermochemical rate processes for chemical and energy exchange phenomena. These processes concern the creation and destruction of gas species by chemical reactions and the transfer of energy between the various species and between the various energy modes (e.g., translation, rotation, vibration, ionization, dissociation/recombination, etc.) of the species. To gain some insight into when such phenomena occur for current and future aerospace flight vehicles the author shows the flight regimes of some typical vehicles (e.g., Concord, aerospace plane, Space Shuttle, associated space transfer vehicles, Apollo entry vehicle, etc.) in terms of flight altitude and flight speed. Also indicated are regimes where chemical reactions such as dissociation and ionization are important and where nonequilibrium thermochemical phenomena are important.

Hydrothermal carbonization of animal manures: Processes and energetics

USDA-ARS?s Scientific Manuscript database

Hydrothermal carbonization (HTC) is an emerging technology for thermochemically converting biomass and waste materials into value-added carbonaceous char called hydrochar. HTC is well suited to manage wet feedstocks streams because pre-drying prior to processing is not required as with gasification...

Techno-economic comparison of biojet fuel production from lignocellulose, vegetable oil and sugar cane juice.

PubMed

Diederichs, Gabriel Wilhelm; Ali Mandegari, Mohsen; Farzad, Somayeh; Görgens, Johann F

2016-09-01

In this study, a techno-economic comparison was performed considering three processes (thermochemical, biochemical and hybrid) for production of jet fuel from lignocellulosic biomass (2G) versus two processes from first generation (1G) feedstocks, including vegetable oil and sugar cane juice. Mass and energy balances were constructed for energy self-sufficient versions of these processes, not utilising any fossil energy sources, using ASPEN Plus® simulations. All of the investigated processes obtained base minimum jet selling prices (MJSP) that is substantially higher than the market jet fuel price (2-4 fold). The 1G process which converts vegetable oil, obtained the lowest MJSPs of $2.22/kg jet fuel while the two most promising 2G processes- the thermochemical (gasification and Fischer-Tropsch synthesis) and hybrid (gasification and biochemical upgrading) processes- reached MJSPs of $2.44/kg and $2.50/kg jet fuel, respectively. According to the economic sensitivity analysis, the feedstock cost and fixed capital investment have the most influence on the MJSP. Copyright © 2016 Elsevier Ltd. All rights reserved.

a Protocol for High-Accuracy Theoretical Thermochemistry

NASA Astrophysics Data System (ADS)

Welch, Bradley; Dawes, Richard

2017-06-01

Theoretical studies of spectroscopy and reaction dynamics including the necessary development of potential energy surfaces rely on accurate thermochemical information. The Active Thermochemical Tables (ATcT) approach by Ruscic^{1} incorporates data for a large number of chemical species from a variety of sources (both experimental and theoretical) and derives a self-consistent network capable of making extremely accurate estimates of quantities such as temperature dependent enthalpies of formation. The network provides rigorous uncertainties, and since the values don't rely on a single measurement or calculation, the provenance of each quantity is also obtained. To expand and improve the network it is desirable to have a reliable protocol such as the HEAT approach^{2} for calculating accurate theoretical data. Here we present and benchmark an approach based on explicitly-correlated coupled-cluster theory and vibrational perturbation theory (VPT2). Methyldioxy and Methyl Hydroperoxide are important and well-characterized species in combustion processes and begin the family of (ethyl-, propyl-based, etc) similar compounds (much less is known about the larger members). Accurate anharmonic frequencies are essential to accurately describe even the 0 K enthalpies of formation, but are especially important for finite temperature studies. Here we benchmark the spectroscopic and thermochemical accuracy of the approach, comparing with available data for the smallest systems, and comment on the outlook for larger systems that are less well-known and characterized. ^{1}B. Ruscic, Active Thermochemical Tables (ATcT) values based on ver. 1.118 of the Thermochemical Network (2015); available at ATcT.anl.gov ^{2}A. Tajti, P. G. Szalay, A. G. Császár, M. Kállay, J. Gauss, E. F. Valeev, B. A. Flowers, J. Vázquez, and J. F. Stanton. JCP 121, (2004): 11599.

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

Engineering of Corynebacterium glutamicum for growth and succinate production from levoglucosan, a pyrolytic sugar substrate.

PubMed

Kim, Eun-Mi; Um, Youngsoon; Bott, Michael; Woo, Han Min

2015-10-01

Thermochemical processing provides continuous production of bio-oils from lignocellulosic biomass. Levoglucosan, a pyrolytic sugar substrate C6H10O5 in a bio-oil, has been used for ethanol production using engineered Escherichia coli. Here we provide the first example for succinate production from levoglucosan with Corynebacterium glutamicum, a well-known industrial amino acid producer. Heterologous expression of a gene encoding a sugar kinase from Lipomyces starkeyi, Gibberella zeae or Pseudomonas aeruginosa was employed for levoglucosan conversion in C. glutamicum because the wild type was unable to utilize levoglucosan as sole carbon source. As result, expression of a levoglucosan kinase (LGK) of L. starkeyi only enabled growth with levoglucosan as sole carbon source in CgXII minimal medium by catalyzing conversion of levoglucosan to glucose-6-phosphate. Subsequently, the lgk gene was expressed in an aerobic succinate producer of C. glutamicum, strain BL-1. The recombinant strain showed a higher succinate yield (0.25 g g(-1)) from 2% (w/v) levoglucosan than the reference strain BL-1 from 2% (w/v) glucose (0.19 g g(-1)), confirming that levoglucosan is an attractive carbon substrate for C. glutamicum producer strains. In summary, we demonstrated that a pyrolytic sugar could be a potential carbon source for microbial cell factories. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Thermochemical process for the production of hydrogen using chromium and barium compound

DOEpatents

Bamberger, Carlos E.; Richardson, Donald M.

1977-01-25

Hydrogen is produced by a closed cyclic process involving the reduction and oxidation of chromium compounds by barium hydroxide and the hydrolytic disproportionation of Ba.sub.2 CrO.sub.4 and Ba.sub.3 (CrO.sub.4).sub.2.

Thermochemical reactor systems and methods

DOEpatents

Lipinski, Wojciech; Davidson, Jane Holloway; Chase, Thomas Richard

2016-11-29

Thermochemical reactor systems that may be used to produce a fuel, and methods of using the thermochemical reactor systems, utilizing a reactive cylindrical element, an optional energy transfer cylindrical element, an inlet gas management system, and an outlet gas management system.

Process for the thermochemical production of hydrogen

DOEpatents

Norman, John H.; Russell, Jr., John L.; Porter, II, John T.; McCorkle, Kenneth H.; Roemer, Thomas S.; Sharp, Robert

1978-01-01

Hydrogen is thermochemically produced from water in a cycle wherein a first reaction produces hydrogen iodide and H.sub.2 SO.sub.4 by the reaction of iodine, sulfur dioxide and water under conditions which cause two distinct aqueous phases to be formed, i.e., a lighter sulfuric acid-bearing phase and a heavier hydrogen iodide-bearing phase. After separation of the two phases, the heavier phase containing most of the hydrogen iodide is treated, e.g., at a high temperature, to decompose the hydrogen iodide and recover hydrogen and iodine. The H.sub.2 SO.sub.4 is pyrolyzed to recover sulfur dioxide and produce oxygen.

Thermochemical generation of hydrogen and oxygen from water

DOEpatents

Robinson, Paul R.; Bamberger, Carlos E.

1981-01-01

A thermochemical cyclic process for the production of hydrogen exploits the reaction between sodium manganate (NaMnO.sub.2) and titanium dioxide (TiO.sub.2) to form sodium titanate (Na.sub.2 TiO.sub.3), manganese (II) titanate (MnTiO.sub.3) and oxygen. The titanate mixture is treated with sodium hydroxide, in the presence of steam, to form sodium titanate, sodium manganate (III), water and hydrogen. The sodium titanate-manganate (III) mixture is treated with water to form sodium manganate (III), titanium dioxide and sodium hydroxide. Sodium manganate (III) and titanium dioxide are recycled following dissolution of sodium hydroxide in water.

Thermochemical generation of hydrogen and oxygen from water

DOEpatents

Robinson, Paul R.; Bamberger, Carlos E.

1982-01-01

A thermochemical cyclic process for the production of hydrogen exploits the reaction between sodium manganate (NaMnO.sub.2) and titanium dioxide (TiO.sub.2) to form sodium titanate (Na.sub.2 TiO.sub.3), manganese (II) titanate (MnTiO.sub.3) and oxygen. The titanate mixture is treated with sodium hydroxide, in the presence of steam, to form sodium titanate, sodium manganate (III), water and hydrogen. The sodium titanate-manganate (III) mixture is treated with water to form sodium manganate (III), titanium dioxide and sodium hydroxide. Sodium manganate (III) and titanium dioxide are recycled following dissolution of sodium hydroxide in water.

Methods and systems for producing syngas

DOEpatents

Hawkes, Grant L; O& #x27; Brien, James E; Stoots, Carl M; Herring, J. Stephen; McKellar, Michael G; Wood, Richard A; Carrington, Robert A; Boardman, Richard D

2013-02-05

Methods and systems are provided for producing syngas utilizing heat from thermochemical conversion of a carbonaceous fuel to support decomposition of at least one of water and carbon dioxide using one or more solid-oxide electrolysis cells. Simultaneous decomposition of carbon dioxide and water or steam by one or more solid-oxide electrolysis cells may be employed to produce hydrogen and carbon monoxide. A portion of oxygen produced from at least one of water and carbon dioxide using one or more solid-oxide electrolysis cells is fed at a controlled flow rate in a gasifier or combustor to oxidize the carbonaceous fuel to control the carbon dioxide to carbon monoxide ratio produced.

Compatibility of Space Nuclear Power Plant Materials in an Inert He/Xe Working Gas Containing Reactive Impurities

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

MM Hall

2006-01-31

A major materials selection and qualification issue identified in the Space Materials Plan is the potential for creating materials compatibility problems by combining dissimilar reactor core, Brayton Unit and other power conversion plant materials in a recirculating, inert He/Xe gas loop containing reactive impurity gases. Reported here are results of equilibrium thermochemical analyses that address the compatibility of space nuclear power plant (SNPP) materials in high temperature impure He gas environments. These studies provide early information regarding the constraints that exist for SNPP materials selection and provide guidance for establishing test objectives and environments for SNPP materials qualification testing.

Catalytic cartridge SO.sub.3 decomposer

DOEpatents

Galloway, Terry R.

1982-01-01

A catalytic cartridge internally heated is utilized as a SO.sub.3 decomposer for thermochemical hydrogen production. The cartridge has two embodiments, a cross-flow cartridge and an axial flow cartridge. In the cross-flow cartridge, SO.sub.3 gas is flowed through a chamber and incident normally to a catalyst coated tube extending through the chamber, the catalyst coated tube being internally heated. In the axial-flow cartridge, SO.sub.3 gas is flowed through the annular space between concentric inner and outer cylindrical walls, the inner cylindrical wall being coated by a catalyst and being internally heated. The modular cartridge decomposer provides high thermal efficiency, high conversion efficiency, and increased safety.

Reassessment of the OHZ process for the thermochemical decomposition of water. Final report

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

Findl, E.; Kulesa, F.; Strickland, G.

1983-08-01

A two-step thermochemical process to sequentially produce hydrogen and oxygen from water by the use of a cation-exchanged zeolite, cycled over a temperature range of 25/sup 0/ to 600/sup 0/C, was reassessed at Brookhaven National Laboratory (BNL). Based on the work of Kasai and Bishop (Union Carbide Corp., 1976), C.C.S. Associates (CCSA) performed a preliminary plant-design study for the OHZ (oxygen-hydrogen-zeolite) process, and was responsible for a few laboratory tests of the zeolite. The results of the BNL's more detailed studies showed that although the thermochemical phenomenon is valid, it is neither practical nor a cost-effective method of producing hydrogenmore » from water. Experimental findings were based on tests of indium-exchanged mordenite zeolite (10 grams, as powder) without carrier gas. The cost reassessment, which was made without using any of BNL's experimental data, showed that the hydrogen costs projected by CCSA were low by a factor of about six (2-h cycle time). The corrected costs, $46 to 50/10/sup 6/ Btu H/sub 2/, are about twice those predicted for electrolytic hydrogen ($24/10/sup 6/ Btu). Corrected costs for a cycle time of 4 hours were $54 to 58/10/sup 6/ Btu. This reassessment, which is based on a realistic review of CCSA's preliminary process design, has shown that the corrected costs projected for OHZ hydrogen are so high that no further consideration should be given to development of the concept. 6 references, 14 figures, 6 tables.« less

Process Design and Economics for the Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels: Thermochemical Research Pathways with In Situ and Ex Situ Upgrading of Fast Pyrolysis Vapors

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

Dutta, Abhijit; Sahir, A. H.; Tan, Eric

This report was developed as part of the U.S. Department of Energy’s Bioenergy Technologies Office’s efforts to enable the development of technologies for the production of infrastructure-compatible, cost-competitive liquid hydrocarbon fuels from biomass. Specifically, this report details two conceptual designs based on projected product yields and quality improvements via catalyst development and process integration. It is expected that these research improvements will be made within the 2022 timeframe. The two conversion pathways detailed are (1) in situ and (2) ex situ upgrading of vapors produced from the fast pyrolysis of biomass. While the base case conceptual designs and underlying assumptionsmore » outline performance metrics for feasibility, it should be noted that these are only two of many other possibilities in this area of research. Other promising process design options emerging from the research will be considered for future techno-economic analysis. Both the in situ and ex situ conceptual designs, using the underlying assumptions, project MFSPs of approximately $3.5/gallon gasoline equivalent (GGE). The performance assumptions for the ex situ process were more aggressive with higher distillate (diesel-range) products. This was based on an assumption that more favorable reaction chemistry (such as coupling) can be made possible in a separate reactor where, unlike in an in situ upgrading reactor, one does not have to deal with catalyst mixing with biomass char and ash, which pose challenges to catalyst performance and maintenance. Natural gas was used for hydrogen production, but only when off gases from the process was not sufficient to meet the needs; natural gas consumption is insignificant in both the in situ and ex situ base cases. Heat produced from the burning of char, coke, and off-gases allows for the production of surplus electricity which is sold to the grid allowing a reduction of approximately 5¢/GGE in the MFSP.« less

Should biochar be used in container substrates?

USDA-ARS?s Scientific Manuscript database

Biochar is charred organic matter that remains after a process called pyrolysis. Pyrolysis is a thermochemical decomposition of organic matter. In this process, organic matter is subjected to extremely high temperatures (200 to 800 °C) in the absence of oxygen. The history of biochar use begins i...

Thermochemical cycle analysis using linked CECS72 and HYDRGN computer programs

NASA Technical Reports Server (NTRS)

Donovan, L. F.

1977-01-01

A combined thermochemical cycle analysis computer program was designed. Input to the combined program is the same as input to the thermochemical cycle analysis program except that the extent of the reactions need not be specified. The combined program is designed to be run interactively from a computer time-sharing terminal. This mode of operation allows correction or modification of the cycle to take place during cycle analysis. A group of 13 thermochemical cycles was used to test the combined program.

Process for thermochemically producing hydrogen

DOEpatents

Bamberger, Carlos E.; Richardson, Donald M.

1976-01-01

Hydrogen is produced by the reaction of water with chromium sesquioxide and strontium oxide. The hydrogen producing reaction is combined with other reactions to produce a closed chemical cycle for the thermal decomposition of water.

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

Kim, J.; Moon, T.J.; Howell, J.R.

This paper presents an analysis of the heat transfer occurring during an in-situ curing process for which infrared energy is provided on the surface of polymer composite during winding. The material system is Hercules prepreg AS4/3501-6. Thermoset composites have an exothermic chemical reaction during the curing process. An Eulerian thermochemical model is developed for the heat transfer analysis of helical winding. The model incorporates heat generation due to the chemical reaction. Several assumptions are made leading to a two-dimensional, thermochemical model. For simplicity, 360{degree} heating around the mandrel is considered. In order to generate the appropriate process windows, the developedmore » heat transfer model is combined with a simple winding time model. The process windows allow for a proper selection of process variables such as infrared energy input and winding velocity to give a desired end-product state. Steady-state temperatures are found for each combination of the process variables. A regression analysis is carried out to relate the process variables to the resulting steady-state temperatures. Using regression equations, process windows for a wide range of cylinder diameters are found. A general procedure to find process windows for Hercules AS4/3501-6 prepreg tape is coded in a FORTRAN program.« less

Using Pyrolysis and its Bioproducts to Help Close the Loop in Sustainable Life Support Systems

NASA Technical Reports Server (NTRS)

McCoy, LaShelle E.

2012-01-01

The next step in human exploration of space is beyond low Earth orbit and possibly to sites such as the Moon and Mars. Resupply of critical life support components for missions such as these are difficult or impossible. Life support processes for closing the loop of water, oxygen and carbon have to be identified .. Currently, there are many technologies proposed for terrestrial missions for waste, water, air processing and the creation of consumables. There are a variety of different approaches, but few address all of these issues simultaneously. One candidate is pyrolysis; a method where waste streams can be heated in the absence of oxygen to undergo a thermochemical conversion producing a series of bioproducts. Bioproducts like biochar made from non-edible biomass and human solid waste can possibly provide valuable benefits such as waste reduction, regolith fertilization for increased food production, and become a consumable for water processing and air revitalization systems. Syngas containing hydrogen, carbon monoxide and cbon dioxide, can be converted to methane and dimethyl ether to create propellants. Bio-oils can be utilized as a heating fuel or fed to bioreactors that utilize oil-eating microbes. Issues such as carbon sequestration and subsequent carbon balance of the closed system and identifying ideal process methods to achieve the highest quality products, whilst being energy friendly, will also be addressed.

Coal Technology Program progress report, March 1976

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

Not Available

Shakedown tests of the bench-scale hydrocarbonization system were successfully completed. Wyodak coal was fed to the reactor at a rate of 9.9 lb/hr where it was hydrocarbonized at 1050/sup 0/F under 20-atm hydrogen pressure. Laboratory results including settling tests, bench-scale settling tests, and sample ageing tests were continued. Two of ten compounds tested with the laboratory-scale apparatus were effective in increasing settling rates of solids in Solvent Refined Coal unfiltered oil, but bench-scale tests failed to show any improvements in the settling rate over the untreated SRC-UFO. Analytical chemistry efforts involved the removal and concentration of organic components in by-productmore » waters from fossil fuel conversion processes. A sephadex gel is being used to achieve hydrophilic-lipophilic separations in organic mixtures as a step in the analysis of fossil fuel related materials. Engineering Evaluations of the Synthiol and Hydrocarbonization Processes continued with the Synthiol process flow diagrams, heat and material balances, and utilities requirements being completed. Inspection techniques were developed for wear- and process-resistant coatings. Orders were placed for the Incoloy 800 tubing and a smaller quantity of Inconel 600 tubing for the tube matrix in the coal-fueled MIUS fluidized bed. An engineering feasibility review of General Atomic's proposal to ERDA for a bench-scale test program on thermochemical water splitting for hydrogen production was completed. (auth)« less

Steam gasification of a thermally pretreated high lignin corn stover simultaneous saccharification and fermentation digester residue

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

Howe, Daniel T.; Taasevigen, Danny; Garcia-Perez, Manuel

Efficient conversion of all components in lignocellulosic biomass is essential to realizing economic feasibility of biorefineries. However, when utilizing biochemical pathways, lignin cannot be fermented. Furthermore, the high lignin and high ash residue resulting from simultaneous saccharification and fermentation (SSF) reactors is difficult to thermochemically process due to feed line plugging and bed agglomeration. In this study a corn stover SSF digester residue was thermally pretreated at 300°C for 22.5 minutes (min) and then gasified in a bubbling fluidized bed gasifier to study the effect of thermal pretreatment on its processing behavior. Untreated, pelletized SSF residue was gasified at themore » same conditions to establish the baseline processing behavior. Results indicate that the thermal pretreatment process removes a substantial portion of the polar and non-polar extractives, with a resultant increase in the concentration of lignin, cellulose, and ash. Feed line plugging was not observed, although bed agglomeration was occurring at similar rates for both feedstocks, suggesting that overall ash content is the most important factor affecting bed agglomeration. Benzene, phenol, and polyaromatic hydrocarbons in the tar were present at higher concentrations in the treated material, with higher tar loading in the product gas. Total product gas generation is lower for the treated material, although the overall gas composition does not change.« less

Integrated solar thermochemical reaction system for steam methane reforming

DOE PAGES

Zheng, Feng; Diver, Rich; Caldwell, Dustin D.; ...

2015-06-05

Solar-aided upgrade of the energy content of fossil fuels, such as natural gas, can provide a near-term transition path towards a future solar-fuel economy and reduce carbon dioxide emission from fossil fuel consumption. Both steam and dry reforming a methane-containing fuel stream have been studied with concentrated solar power as the energy input to drive the highly endothermic reactions but the concept has not been demonstrated at a commercial scale. Under a current project with the U.S. Department of Energy, PNNL is developing an integrated solar thermochemical reaction system that combines solar concentrators with micro- and meso-channel reactors and heatmore » exchangers to accomplish more than 20% solar augment of methane higher heating value. The objective of our three-year project is to develop and prepare for commercialization such solar reforming system with a high enough efficiency to serve as the frontend of a conventional natural gas (or biogas) combined cycle power plant, producing power with a levelized cost of electricity less than 6¢/kWh, without subsidies, by the year 2020. In this paper, we present results from the first year of our project that demonstrated a solar-to-chemical energy conversion efficiency as high as 69% with a prototype reaction system.« less

Characterisation of two-stage ignition in diesel engine-relevant thermochemical conditions using direct numerical simulation

DOE PAGES

Krisman, Alex; Hawkes, Evatt R.; Talei, Mohsen; ...

2016-08-30

With the goal of providing a more detailed fundamental understanding of ignition processes in diesel engines, this study reports analysis of a direct numerical simulation (DNS) database. In the DNS, a pseudo turbulent mixing layer of dimethyl ether (DME) at 400 K and air at 900 K is simulated at a pressure of 40 atmospheres. At these conditions, DME exhibits a two-stage ignition and resides within the negative temperature coefficient (NTC) regime of ignition delay times, similar to diesel fuel. The analysis reveals a complex ignition process with several novel features. Autoignition occurs as a distributed, two-stage event. The high-temperaturemore » stage of ignition establishes edge flames that have a hybrid premixed/autoignition flame structure similar to that previously observed for lifted laminar flames at similar thermochemical conditions. In conclusion, a combustion mode analysis based on key radical species illustrates the multi-stage and multi-mode nature of the ignition process and highlights the substantial modelling challenge presented by diesel combustion.« less

Perennial grass (Arundo donax L.) as a feedstock for thermo-chemical conversion to energy and materials.

PubMed

Saikia, Ruprekha; Chutia, Rahul Singh; Kataki, Rupam; Pant, Kamal K

2015-01-01

In the present study, perennial grass species Arundo donax L. was pyrolysed in a fixed-bed reactor and characterization was performed for the liquid and the solid products. The effect of process parameters such as temperature (350-650 °C), heating rate (10 °C and 40 °C min(-1)) and sweeping gas flow rate (50-250 ml min(-1)) was also investigated. Maximum bio-oil yield of ∼ 26% was observed at 500 °C for the heating rate of 40 °C min(-1). Chemical composition of the bio-oil was analysed through NMR, FTIR and GC-MS. The biochar was characterized by Scanning Electron Microscopy (SEM), Fourier Transform Infrared (FTIR) spectroscopy along with elemental analysis (CHN). The biochar produced as a co-product of A. donax pyrolysis can be a potential soil amendment with multiple benefits including increased soil fertility and C-sequestration. Current investigation suggests suitability of A. donax as a potential feedstock for exploitation of energy and biomaterials through pyrolytic route. Copyright © 2015 Elsevier Ltd. All rights reserved.

Solid-liquid extraction of alkali metals and organic compounds by leaching of food industry residues.

PubMed

Yu, Chaowei; Zheng, Yi; Cheng, Yu-Shen; Jenkins, Bryan M; Zhang, Ruihong; VanderGheynst, Jean S

2010-06-01

Leaching was studied for its application in extracting inorganic and organic constituents from fresh fermented grape pomace, air-dried fermented grape pomace and air-dried sugar beet pulp. Samples of each feedstock were leached in water at ambient temperature for 30 or 120 min at dry solid-to-liquid ratios of 1/20 and 1/50 kg/L. Leaching removed 82% of sodium, 86% of potassium, and 76% of chlorine from sugar beet pulp, and reduced total ash concentration in air-dry fermented grape pomace from 8.2% to 2.9% of dry matter, 8.2% to 4.4% in fresh fermented grape pomace, and 12.5% to 5.4% in sugar beet pulp. Glycerol (7-11 mg/dry g), ethanol (131-158 mg/dry g), and acetic acid (24-31 mg/dry g) were also extracted from fermented grape pomace. These results indicate that leaching is a beneficial pretreatment step for improving the quality of food processing residues for thermochemical and biochemical conversion. (c) 2010 Elsevier Ltd. All rights reserved.

Modelling the combustion of charcoal in a model blast furnace

NASA Astrophysics Data System (ADS)

Shen, Yansong; Shiozawa, Tomo; Yu, Aibing; Austin, Peter

2013-07-01

The pulverized charcoal (PCH) combustion in ironmaking blast furnaces is abstracting remarkable attention due to various benefits such as lowering CO2 emission. In this study, a three-dimensional CFD model is used to simulate the flow and thermo-chemical behaviours in this process. The model is validated against the experimental results from a pilot-scale combustion test rig for a range of conditions. The typical flow and thermo-chemical phenomena is simulated. The effect of charcoal type, i.e. VM content is examined, showing that the burnout increases with VM content in a linear relationship. This model provides an effective way for designing and optimizing PCH operation in blast furnace practice.

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

Nexant, Inc., San Francisco, California

The first section (Task 1) of this report by Nexant includes a survey and screening of various acid gas removal processes in order to evaluate their capability to meet the specific design requirements for thermochemical ethanol synthesis in NREL's thermochemical ethanol design report (Phillips et al. 2007, NREL/TP-510-41168). MDEA and selexol were short-listed as the most promising acid-gas removal agents based on work described in Task 1. The second report section (Task 2) describes a detailed design of an MDEA (methyl diethanol amine) based acid gas removal system for removing CO2 and H2S from biomass-derived syngas. Only MDEA was chosenmore » for detailed study because of the available resources.« less

A theoretical study of the structure and thermochemical properties of alkali metal fluoroplumbates MPbF3.

PubMed

Boltalin, A I; Korenev, Yu M; Sipachev, V A

2007-07-19

Molecular constants of MPbF3 (M=Li, Na, K, Rb, and Cs) were calculated theoretically at the MP2(full) and B3LYP levels with the SDD (Pb, K, Rb, and Cs) and cc-aug-pVQZ (F, Li, and Na) basis sets to determine the thermochemical characteristics of the substances. Satisfactory agreement with experiment was obtained, including the unexpected nonmonotonic dependence of substance dissociation energies on the alkali metal atomic number. The bond lengths of the theoretical CsPbF3 model were substantially elongated compared with experimental estimates, likely because of errors in both theoretical calculations and electron diffraction data processing.

Thermochemical generation of hydrogen and oxygen from water. [NaMnO/sub 2/ and TiO/sub 2/

DOEpatents

Robinson, P.R.; Bamberger, C.E.

1980-02-08

A thermochemical cyclic process for the production of hydrogen exploits the reaction between sodium manganate (NaMnO/sub 2/) and titanium dioxide (TiO/sub 2/) to form sodium titanate (Na/sub 2/TiO/sub 3/), manganese (II) titanate (MnTiO/sub 3/) and oxygen. The titanate mixture is treated with sodium hydroxide, in the presence of steam, to form sodium titanate, sodium manganate (III), water and hydrogen. The sodium titanate-manganate (III) mixture is treated with water to form sodium manganate (III), titanium dioxide and sodium hydroxide. Sodium manganate (III) and titanium dioxide are recycled following dissolution of sodium hydroxide in water.

Biomass in a petrochemical world

PubMed Central

Roddy, Dermot J.

2013-01-01

The world's increasingly voracious appetite for fossil fuels is driven by fast-growing populations and ever-rising aspirations for the lifestyles and standard of living exemplified in the developed world. Forecasts for higher electricity consumption, more comfortable living environments (via heating or cooling) and greater demand for transport fuels are well known. Similar growth in demand is projected for petrochemical-based products in the form of man-made fibres for clothing, ubiquitous plastic artefacts, cosmetics, etc. All drawing upon the same finite oil, gas and coal feedstocks. Biomass can, in principle, substitute for all of these feedstocks. Although ultimately finite, biomass resources can be expanded and renewed if this is a societal priority. This paper examines the projected growth of an energy-intensive international petrochemicals industry, considers its demand for both utilities and feedstocks, and considers the extent to which biomass can substitute for fossil fuels. The scope of this study includes biomass component extraction, direct chemical conversion, thermochemical conversion and biochemical conversion. Noting that the petrochemicals industry consumes around 10 per cent of the world's fossil fuels as feedstocks and almost as much again in utilities, various strategies for addressing future demand are considered. The need for long-term infrastructure and logistics planning is highlighted. PMID:24427511

Multi-scale visualization and characterization of lignocellulosic plant cell wall deconstruction during thermochemical pretreatment

Treesearch

Shishir P. S. Chundawat; Bryon S. Donohoe; Leonardo da Costa Sousa; Thomas Elder; Umesh P. Agarwal; Fachuang Lu; John Ralph; Michael E. Himmel; Venkatesh Balan; Bruce E. Dale

2011-01-01

Deconstruction of lignocellulosic plant cell walls to fermentable sugars by thermochemical and/or biological means is impeded by several poorly understood ultrastructural and chemical barriers. A promising thermochemical pretreatment called ammonia fiber expansion (AFEX) overcomes the native recalcitrance of cell walls through subtle morphological and physicochemical...

Cesium Neonide: Molecule or Thermochemical Exercise?

ERIC Educational Resources Information Center

Blake, P. G.; Clack, D. W.

1982-01-01

Thermochemical cycles are used to decide which hypothetical compounds might exist and, if not, what is the factor that condemns them to non-existence. Hypothetical compounds of rare gases provide examples of the approach with added historical interest that thermochemical considerations led to prediction and demonstration that XePtF-6 was stable.…

Kristin Smith | NREL

Science.gov Websites

Smith Photo of Kristin Smith Kristin Smith Thermochemical Process Design Engineer Kristin.Smith @nrel.gov | 303-384-7877 Orcid ID http://orcid.org/0000-0001-6397-031X Research Interests Kristin Smith is a

Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

DOEpatents

Bamberger, C.E.; Robinson, P.R.

A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cyclic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

DOEpatents

Bamberger, Carlos E.; Robinson, Paul R.

1980-01-01

A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cylic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

Regeneration of glass nanofluidic chips through a multiple-step sequential thermochemical decomposition process at high temperatures.

PubMed

Xu, Yan; Wu, Qian; Shimatani, Yuji; Yamaguchi, Koji

2015-10-07

Due to the lack of regeneration methods, the reusability of nanofluidic chips is a significant technical challenge impeding the efficient and economic promotion of both fundamental research and practical applications on nanofluidics. Herein, a simple method for the total regeneration of glass nanofluidic chips was described. The method consists of sequential thermal treatment with six well-designed steps, which correspond to four sequential thermal and thermochemical decomposition processes, namely, dehydration, high-temperature redox chemical reaction, high-temperature gasification, and cooling. The method enabled the total regeneration of typical 'dead' glass nanofluidic chips by eliminating physically clogged nanoparticles in the nanochannels, removing chemically reacted organic matter on the glass surface and regenerating permanent functional surfaces of dissimilar materials localized in the nanochannels. The method provides a technical solution to significantly improve the reusability of glass nanofluidic chips and will be useful for the promotion and acceleration of research and applications on nanofluidics.

Equilibrium model analysis of waste plastics gasification using CO2 and steam.

PubMed

Kannan, P; Lakshmanan, G; Al Shoaibi, A; Srinivasakannan, C

2017-12-01

Utilization of carbon dioxide (CO 2 ) in thermochemical treatment of waste plastics may significantly help to improve CO 2 recycling, thus simultaneously curtailing dioxins/furans and CO 2 emissions. Although CO 2 is not such an effective gasifying agent as steam, a few investigations have explored the utilization of CO 2 in conjunction with steam to achieve somewhat higher carbon conversion. This work presents a comparative evaluation study of CO 2 and steam gasification of a typical post-consumer waste plastics mixture using an Aspen Plus equilibrium model. The effect of flow rate of gasifying medium (CO 2 and/or steam) and gasification temperature on product gas composition, carbon conversion, and cold gas efficiency has been analyzed. Simulation results demonstrate that CO 2 can serve as a potential gasifying agent for waste plastics gasification. The resulting product gas was rich in CO whereas CO 2 -steam blends yield a wider H 2 /CO ratio, thus extending the applications of the product gas.

Modeling of a CeO2 thermochemistry reduction process for hydrogen production by solar concentrated energy

NASA Astrophysics Data System (ADS)

Valle-Hernández, Julio; Romero-Paredes, Hernando; Arancibia-Bulnes, Camilo A.; Villafan-Vidales, Heidi I.; Espinosa-Paredes, Gilberto

2016-05-01

In this paper the simulation of the thermal reduction for hydrogen production through the decomposition of cerium oxide is presented. The thermochemical cycle for hydrogen production consists of the endothermic reduction of CeO2 at high temperature, where concentrated solar energy is used as a source of heat; and of the subsequent steam hydrolysis of the resulting cerium oxide to produce hydrogen. For the thermochemical process, a solar reactor prototype is proposed; consisting of a cubic receptacle made of graphite fiber thermally insulated. Inside the reactor a pyramidal arrangement with nine tungsten pipes is housed. The pyramidal arrangement is made respect to the focal point where the reflected energy is concentrated. The solar energy is concentrated through the solar furnace of high radiative flux. The endothermic step is the reduction of the cerium oxide to lower-valence cerium oxide, at very high temperature. The exothermic step is the hydrolysis of the cerium oxide (III) to form H2 and the corresponding initial cerium oxide made at lower temperature inside the solar reactor. For the modeling, three sections of the pipe where the reaction occurs were considered; the carrier gas inlet, the porous medium and the reaction products outlet. The mathematical model describes the fluid mechanics; mass and energy transfer occurring therein inside the tungsten pipe. Thermochemical process model was simulated in CFD. The results show a temperature distribution in the solar reaction pipe and allow obtaining the fluid dynamics and the heat transfer within the pipe. This work is part of the project "Solar Fuels and Industrial Processes" from the Mexican Center for Innovation in Solar Energy (CEMIE-Sol).

Solar fuels production as a sustainable alternative for substituting fossil fuels: COSOLπ project

NASA Astrophysics Data System (ADS)

Hernando Romero-Paredes, R.; Alvarado-Gil, Juan José; Arancibia-Bulnes, Camilo Alberto; Ramos-Sánchez, Víctor Hugo; Villafán-Vidales, Heidi Isabel; Espinosa-Paredes, Gilberto; Abanades, Stéphane

2017-06-01

This article presents, in summary form, the characteristics of COSOLπ development project and some of the results obtained to date. The benefits of the work of this project will include the generation of a not polluting transportable energy feedstock from a free, abundant and available primary energy source, in an efficient method with no greenhouse gas emission. This will help to ensure energy surety to a future transportation/energy infrastructure, without any fuel import. Further technological development of thermochemical production of clean fuels, together with solar reactors and also with the possibility of determining the optical and thermal properties of the materials involved a milestone in the search for new processes for industrialization. With the above in mind, important national academic institutions: UAM, UNAM, CINVESTAV, UACH, UNISON among others, have been promoting research in solar energy technologies. The Goals and objectives are to conduct research and technological development driving high-temperature thermochemical processes using concentrated solar radiation as thermal energy source for the future sustainable development of industrial processes. It focuses on the production of clean fuels such as H2, syngas, biofuels, without excluding the re-value of materials used in the industry. This project conducts theoretical and experimental studies for the identification, characterization, and optimization of the most promising thermochemical cycles, and for the thorough investigation of the reactive chemical systems. It applies material science and nano-engineering to improve chemicals properties and stability upon cycling. The characterization of materials will serve to measure the chemical composition and purity (MOX fraction-1) of each of the samples. The characterizations also focus on the solid particle morphology (shape, size, state of aggregation, homogeneity, specific surface) images obtained from SEM / TEM and BET measurements. Likewise will the thermal and optical characterization of the influence that these parameters represent in the solar reactor. The experimental and theoretical results obtained for each redox system will be compared and analyzed to determine the cycle with the highest potential. Advances on simulation, design, construction and experimentation on solar reactors to conduct thermochemical splitting water reactions are presented.

Proctor and gamble technology process assessment for bioenergy production

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

Hu, Hongqiang; Boardman, Richard Doin; Wright, Christopher Todd

P&G intends to replace as much as their current heat and power by renewable energy sources. For 2014, P&G’s total energy including electricity, natural gas and steam is approximately 1,540,000 MMBTU annually (Table 2). The biomass and wastes around P&G facility can be grouped into six categories (Figure 6): (1) Agriculture residue and grass, (2) Refuse (inorganic) solid material, (3) Food waste, (4) Organic waste stream, (5) livestock manure, (6) wastewater and sludge. The six feedstock sources can provide a total energy of 3,520,000 MMBTU per year (Table 10), among which the agriculture residue is the biggest fraction, about 67%,more » followed by livestock manures 27%. Therefore, the available energy sources around P&G facility are enough to meet their energy needs. These energy feedstocks would be treated by two processes: anaerobic digestion for biogas subsequently for heat and power and thermochemical process (combustion, pyrolysis and gasification) for heat and power (Figure 8 and 9). For AD, a one-stage complete mixing digester is preferable; and fluidized bed reactors are favorable for thermochemical process.« less

Fungal production of single cell oil using untreated copra cake and evaluation of its fuel properties for biodiesel.

PubMed

Khot, Mahesh; Gupta, Rohini; Barve, Kadambari; Zinjarde, Smita; Govindwar, Sanjay; Kumar, Ameeta Ravi

2015-04-01

This study evaluated the microbial conversion of coconut oil waste, a major agro-residue in tropical countries, into single cell oil (SCO) feedstock for biodiesel production. Copra cake was used as a low-cost renewable substrate without any prior chemical or enzymatic pretreatment for submerged growth of an oleaginous tropical mangrove fungus, Aspergillus terreus IBB M1. The SCO extracted from fermented biomass was converted into fatty acid methyl esters (FAMEs) by transesterification and evaluated on the basis of fatty acid profiles and key fuel properties for biodiesel. The fungus produced a biomass (8.2 g/l) yielding 257 mg/g copra cake SCO with ~98% FAMEs. The FAMEs were mainly composed of saturated methyl esters (61.2%) of medium-chain fatty acids (C12-C18) with methyl oleate (C18:1; 16.57%) and methyl linoleate (C18:2; 19.97%) making up the unsaturated content. A higher content of both saturated FAMEs and methyl oleate along with the absence of polyunsaturated FAMEs with ≥4 double bonds is expected to impart good fuel quality. This was evident from the predicted and experimentally determined key fuel properties of FAMEs (density, kinematic viscosity, iodine value, acid number, cetane number), which were in accordance with the international (ASTM D6751, EN 14214) and national (IS 15607) biodiesel standards, suggesting their suitability as a biodiesel fuel. The low cost, renewable nature, and easy availability of copra cake, its conversion into SCO without any thermochemical pretreatment, and pelleted fungal growth facilitating easier downstream processing by simple filtration make this process cost effective and environmentally favorable.

Comparative study on the pyrolysis behaviour and kinetics of two macroalgae biomass (Gracilaria changii and Gelidium pusillum) by thermogravimetric analysis

NASA Astrophysics Data System (ADS)

Roslee, A. N.; Munajat, N. F.

2017-10-01

Macroalgae are often referred as seaweed and could be significant biomass resource for the production of numerous energy carriers including biofuels. In this study, the chemical composition of Gracilaria changii (G. changii) and Gelidium pusillum (G. pusillum) were determined through proximate and ultimate analysis and the thermal degradation behaviour of G. changii and G. pusillum were investigated via thermogravimetric analysis (TGA) in determining the important main composition to be considered as biomass fuels. It has found the pyrolysis of G. changii and G. pusillum consists of three stages and stage II is the main decomposition stage with major mass loss of around 52.16% and 44.42%, respectively. The TGA data were then used for determination of kinetic parameters of the pyrolysis process using three model-free methods: Kissinger, Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO). The apparent activation energy calculated by using Kissinger method for G. changii was lower than G. Pusillum, i.e.173.12 kJ/mol and 193.22 kJ/mol, respectively. The activation energies calculated from KAS and FWO methods were increased with increasing the pyrolysis conversion with average activation energies of 172.32 kJ/mol and 181.19 kJ/mol for G. changii while for G. pusillum (177.42 kJ/mol and 187.4 kJ/mol). G. pusillum has lower and wider distribution of activation energy and revealed that the pyrolysis process for G. changii was easier than G. pusillum. These data provide information for further application for designing and modelling in thermochemical conversion system of macroalgae biomass.

Search for New Highly Energetic Phases under Compression and Shear

DTIC Science & Technology

2015-05-01

bar barn British thermal unit (thermochemical) calorie (thermochemical) cal (thermochemical/cm ) curie degree (angle) degree Fahrenheit...corresponding finite element algorithms and subroutines are developed. (c) Problems on compression and shear of a sample in rotational diamond anvil...element algorithms and subroutines are developed. Model problems on martensitic microstructure evolution are solved. (f) Experimental approaches to study

Thermochemical Processes | Bioenergy | NREL

Science.gov Websites

model catalysts appear on a montage of images of wood chips, liquid gasoline, a gas tanker truck, and a , pipes, and hoses, pouring a liquid from a large hose into a bucket. Integration, Scale-Up, and Piloting

Study of the formation of thermochemical laser-induced periodic surface structures on Cr, Ti, Ni and NiCr films under femtosecond irradiation

NASA Astrophysics Data System (ADS)

Dostovalov, A. V.; Korolkov, V. P.; Terentyev, V. S.; Okotrub, K. A.; Dultsev, F. N.; Babin, S. A.

2017-07-01

The formation of femtosecond laser-induced periodic surface structures (LIPSS's) on Cr, Ti, Ni and NiCr films (with different Cr contents) is investigated. It is established that thermochemical LIPSS's with periods of 950, 930 and 980 nm are formed, respectively, on the surfaces of titanium, chromium, and nichrome (with a chromium content of 20%); however, thermochemical LIPSS's are not formed on the surfaces of nickel and nichrome with a low chromium content, although Raman data indicate that oxidation occurs in all cases. A weakly ordered ablated structure with a period of 250-300 nm is found to be formed on oxidised areas of thermochemical LIPSS's in the case of chromium and nichrome (80/20). Experimental data on selective etching of thermochemical LIPSS's on titanium and chromium films are presented.

Evaluation of chemical, thermobaric and thermochemical pre-treatment on anaerobic digestion of high-fat cattle slaughterhouse waste.

PubMed

Harris, Peter W; Schmidt, Thomas; McCabe, Bernadette K

2017-11-01

This work aimed to enhance the anaerobic digestion of fat-rich dissolved air flotation (DAF) sludge through chemical, thermobaric, and thermochemical pre-treatment methods. Soluble chemical oxygen demand was enhanced from 16.3% in the control to 20.84% (thermobaric), 40.82% (chemical), and 50.7% (thermochemical). Pre-treatment altered volatile fatty acid concentration by -64% (thermobaric), 127% (chemical) and 228% (thermochemical). Early inhibition was reduced by 20% in the thermochemical group, and 100% in the thermobaric group. Specific methane production was enhanced by 3.28% (chemical), 8.32% (thermobaric), and 8.49% (thermochemical) as a result of pre-treatment. Under batch digestion, thermobaric pre-treatment demonstrated the greatest improvement in methane yield with respect to degree of pre-treatment applied. Thermobaric pre-treatment was also the most viable for implementation at slaughterhouses, with potential for heat-exchange to reduce pre-treatment cost. Further investigation into long-term impact of pre-treatments in semi-continuous digestion experiments will provide additional evaluation of appropriate pre-treatment options for high-fat slaughterhouse wastewater. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

Char from sugarcane bagasse

USDA-ARS?s Scientific Manuscript database

Unused sugarcane bagasse represents an underutilized resource in sugarcane growing regions of the world. This is a renewable resource that can be used in a thermochemical process to create chars, which could be incorporated back into agricultural activities. The practice is likely to improve soil ...

Production cost comparisons of hydrogen from fossil and nuclear fuel and water decomposition

NASA Technical Reports Server (NTRS)

Ekman, K. R.

1981-01-01

The comparative costs entailed in producing hydrogen by major technologies that rely on petroleum, natural gas, coal, thermochemical cycles, and electrolysis are examined. Techniques were developed for comparing these processes by formulating the process data and economic assessments on a uniform and consistent basis. These data were normalized to permit a meaningful comparative analysis of product costs of these processes.

Silicon materials task of the low-cost solar array project. Phase 4: Effects of impurities and processing on silicon solar cells

NASA Technical Reports Server (NTRS)

Hopkins, R. H.; Hanes, M. H.; Davis, J. R.; Rohatgi, A.; Rai-Choudhury, P.; Mollenkopf, H. C.

1981-01-01

The effects of impurities, various thermochemical processes, and any impurity-process interactions upon the performance of terrestrial solar cells are defined. The results form a basis for silicon producers, wafer manufacturers, and cell fabricators to develop appropriate cost benefit relationships for the use of less pure, less costly solar grade silicon.

Compositional and stable carbon isotopic fractionation during non-autocatalytic thermochemical sulfate reduction by gaseous hydrocarbons

USGS Publications Warehouse

Xia, Xinyu; Ellis, Geoffrey S.; Ma, Qisheng; Tang, Yongchun

2014-01-01

The possibility of autocatalysis during thermochemical sulfate reduction (TSR) by gaseous hydrocarbons was investigated by examination of previously reported laboratory and field data. This reaction was found to be a kinetically controlled non-autocatalytic process, and the apparent lack of autocatalysis is thought to be due to the absence of the required intermediate species. Kinetic parameters for chemical and carbon isotopic fractionations of gaseous hydrocarbons affected by TSR were calculated and found to be consistent with experimentally derived values for TSR involving long-chain hydrocarbons. Model predictions based on these kinetic values indicate that TSR by gaseous hydrocarbon requires high-temperature conditions. The oxidation of C2–5 hydrocarbons by sulfate reduction is accompanied by carbon isotopic fractionation with the residual C2–5 hydrocarbons becoming more enriched in 13C. Kinetic parameters were calculated for the stable carbon isotopic fractionation of gaseous hydrocarbons that have experienced TSR. Model predictions based on these kinetics indicate that it may be difficult to distinguish the effects of TSR from those of thermal maturation at lower levels of hydrocarbon oxidation; however, unusually heavy δ13C2+ values (>−10‰) can be diagnostic of high levels of conversion (>50%). Stoichiometric and stable carbon isotopic data show that methane is stable under the investigated reaction conditions and is likely a product of TSR by other gaseous hydrocarbons rather than a significant reactant. These results indicate that the overall TSR reaction mechanism for oxidation of organic substrates containing long-chain hydrocarbons involves three distinct phases as follows: (1) an initial slow and non-autocatalytic stage characterized by the reduction of reactive sulfate by long-chain saturated hydrocarbons; (2) a second autocatalytic reaction phase dominated by reactions involving reduced sulfur species and partially oxidized hydrocarbons; (3) and a final, or late-stage, TSR reaction in which hydrocarbon oxidation continues at a slower rate via the non-autocatalytic reduction of sulfate by gaseous hydrocarbons.

Process Simulation and Cost Analysis for Removing Inorganics from Wood Chips using Combined Mechanical and Chemical Preprocessing

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

Hu, Hongqiang; Westover, Tyler L.; Cherry, Robert

Naturally occurring and introduced inorganic species (ash) in biomass feedstocks negatively impact thermochemical energy conversion processes such as pyrolysis, hydrothermal liquefaction, gasification and combustion to biopower. As such, it is desirable to better understand the cost:benefit ratios of various ash reduction processes. Here, a novel process simulation model was developed using AspenPlus to reduce the ash content of Loblolly logging residues using both air classification and a dilute-acid leaching process. For costing purposes, a throughput of 25 tons/hour was selected. At this scale, the process cost for a standalone air classification process was $3 per ton for a biomass feedstock.more » Ash reduction via dilute –acid leaching was simulated based on experimentally determined kinetics of ion diffusion at an acid concentration of 0.5% H2SO4 and temperature of 75°F. The total estimated processing cost for leaching at these conditions was approximately $14/ton of dry biomass. Sensitivity analysis of three parameters on mineral reduction in the leaching process revealed that increasing leaching temperature was not economically feasible, while it was viable to apply a longer retention time in leaching for higher ash removal or achieve a lower water content in final products with reasonable extra costs. In addition, scenarios combining air classification with leaching were examined. A whole process cost of approximately $16/ton of biomass at a biomass feedstock rate of 25 ton/hour considering a 9% of biomass classified as light fraction to be leached. The leaching operating costs constituted 75% of this amount, of which the heating costs of dryer was 44%. This suggests that the process costs would be substantially reduced if more efficient drying methods are applied in future.« less

Hydrothermal carbonization: modeling, final properties design and applications: a review

USDA-ARS?s Scientific Manuscript database

Active research on biomass hydrothermal carbonization (HTC) continues to demonstrate its advantages over other thermochemical processes, in particular the interesting benefits associated with carbonaceous solid products called hydrochar (HC). The areas of applications of HC range from biofuel to dop...

Modelling of heat transfer during torrefaction of large lignocellulosic biomass

NASA Astrophysics Data System (ADS)

Regmi, Bharat; Arku, Precious; Tasnim, Syeda Humaira; Mahmud, Shohel; Dutta, Animesh

2018-02-01

Preparation of feedstock is a major energy intensive process for the thermochemical conversion of biomass into fuel. By eliminating the need to grind biomass prior to the torrefaction process, there would be a potential gain in the energy requirements as the entire step would be eliminated. In regards to a commercialization of torrefaction technology, this study has examined heat transfer inside large cylindrical biomass both numerically and experimentally during torrefaction. A numerical axis-symmetrical 2-D model for heat transfer during torrefaction at 270°C for 1 h was created in COMSOL Multiphysics 5.1 considering heat generation evaluated from the experiment. The model analyzed the temperature distribution within the core and on the surface of biomass during torrefaction for various sizes. The model results showed similarities with experimental results. The effect of L/D ratio on temperature distribution within biomass was observed by varying length and diameter and compared with experiments in literature to find out an optimal range of cylindrical biomass size suitable for torrefaction. The research demonstrated that a cylindrical biomass sample of 50 mm length with L/D ratio of 2 can be torrefied with a core-surface temperature difference of less than 30 °C. The research also demonstrated that sample length has a negligible effect on core-surface temperature difference during torrefaction when the diameter is fixed at 25 mm. This information will help to design a torrefaction processing system and develop a value chain for biomass supply without using an energy-intensive grinding process.

Modelling of heat transfer during torrefaction of large lignocellulosic biomass

NASA Astrophysics Data System (ADS)

Regmi, Bharat; Arku, Precious; Tasnim, Syeda Humaira; Mahmud, Shohel; Dutta, Animesh

2018-07-01

Preparation of feedstock is a major energy intensive process for the thermochemical conversion of biomass into fuel. By eliminating the need to grind biomass prior to the torrefaction process, there would be a potential gain in the energy requirements as the entire step would be eliminated. In regards to a commercialization of torrefaction technology, this study has examined heat transfer inside large cylindrical biomass both numerically and experimentally during torrefaction. A numerical axis-symmetrical 2-D model for heat transfer during torrefaction at 270°C for 1 h was created in COMSOL Multiphysics 5.1 considering heat generation evaluated from the experiment. The model analyzed the temperature distribution within the core and on the surface of biomass during torrefaction for various sizes. The model results showed similarities with experimental results. The effect of L/D ratio on temperature distribution within biomass was observed by varying length and diameter and compared with experiments in literature to find out an optimal range of cylindrical biomass size suitable for torrefaction. The research demonstrated that a cylindrical biomass sample of 50 mm length with L/D ratio of 2 can be torrefied with a core-surface temperature difference of less than 30 °C. The research also demonstrated that sample length has a negligible effect on core-surface temperature difference during torrefaction when the diameter is fixed at 25 mm. This information will help to design a torrefaction processing system and develop a value chain for biomass supply without using an energy-intensive grinding process.

Life cycle assessment of hydrogen production from S-I thermochemical process coupled to a high temperature gas reactor

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

Giraldi, M. R.; Francois, J. L.; Castro-Uriegas, D.

The purpose of this paper is to quantify the greenhouse gas (GHG) emissions associated to the hydrogen produced by the sulfur-iodine thermochemical process, coupled to a high temperature nuclear reactor, and to compare the results with other life cycle analysis (LCA) studies on hydrogen production technologies, both conventional and emerging. The LCA tool was used to quantify the impacts associated with climate change. The product system was defined by the following steps: (i) extraction and manufacturing of raw materials (upstream flows), (U) external energy supplied to the system, (iii) nuclear power plant, and (iv) hydrogen production plant. Particular attention wasmore » focused to those processes where there was limited information from literature about inventory data, as the TRISO fuel manufacture, and the production of iodine. The results show that the electric power, supplied to the hydrogen plant, is a sensitive parameter for GHG emissions. When the nuclear power plant supplied the electrical power, low GHG emissions were obtained. These results improve those reported by conventional hydrogen production methods, such as steam reforming. (authors)« less

Modeling and comparative assessment of municipal solid waste gasification for energy production

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

Arafat, Hassan A., E-mail: harafat@masdar.ac.ae; Jijakli, Kenan

Highlights: • Study developed a methodology for the evaluation of gasification for MSW treatment. • Study was conducted comparatively for USA, UAE, and Thailand. • Study applies a thermodynamic model (Gibbs free energy minimization) using the Gasify software. • The energy efficiency of the process and the compatibility with different waste streams was studied. - Abstract: Gasification is the thermochemical conversion of organic feedstocks mainly into combustible syngas (CO and H{sub 2}) along with other constituents. It has been widely used to convert coal into gaseous energy carriers but only has been recently looked at as a process for producingmore » energy from biomass. This study explores the potential of gasification for energy production and treatment of municipal solid waste (MSW). It relies on adapting the theory governing the chemistry and kinetics of the gasification process to the use of MSW as a feedstock to the process. It also relies on an equilibrium kinetics and thermodynamics solver tool (Gasify®) in the process of modeling gasification of MSW. The effect of process temperature variation on gasifying MSW was explored and the results were compared to incineration as an alternative to gasification of MSW. Also, the assessment was performed comparatively for gasification of MSW in the United Arab Emirates, USA, and Thailand, presenting a spectrum of socioeconomic settings with varying MSW compositions in order to explore the effect of MSW composition variance on the products of gasification. All in all, this study provides an insight into the potential of gasification for the treatment of MSW and as a waste to energy alternative to incineration.« less

Cellulose-Hemicellulose Interactions at Elevated Temperatures Increase Cellulose Recalcitrance to Biological Conversion

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

Mittal, Ashutosh; Himmel, Michael E; Kumar, Rajeev

It has been previously shown that cellulose-lignin droplets' strong interactions, resulting from lignin coalescence and redisposition on cellulose surface during thermochemical pretreatments, increase cellulose recalcitrance to biological conversion, especially at commercially viable low enzyme loadings. However, information on the impact of cellulose-hemicellulose interactions on cellulose recalcitrance following relevant pretreatment conditions are scarce. Here, to investigate the effects of plausible hemicellulose precipitation and re-association with cellulose on cellulose conversion, different pretreatments were applied to pure Avicel(R) PH101 cellulose alone and Avicel mixed with model hemicellulose compounds followed by enzymatic hydrolysis of resulting solids at both low and high enzyme loadings. Solidsmore » produced by pretreatment of Avicel mixed with hemicelluloses (AMH) were found to contain about 2 to 14.6% of exogenous, precipitated hemicelluloses and showed a remarkably much lower digestibility (up to 60%) than their respective controls. However, the exogenous hemicellulosic residues that associated with Avicel following high temperature pretreatments resulted in greater losses in cellulose conversion than those formed at low temperatures, suggesting that temperature plays a strong role in the strength of cellulose-hemicellulose association. Molecular dynamics simulations of hemicellulosic xylan and cellulose were found to further support this temperature effect as the xylan-cellulose interactions were found to substantially increase at elevated temperatures. Furthermore, exogenous, precipitated hemicelluloses in pretreated AMH solids resulted in a larger drop in cellulose conversion than the delignified lignocellulosic biomass containing comparably much higher natural hemicellulose amounts. Increased cellulase loadings or supplementation of cellulase with xylanases enhanced cellulose conversion for most pretreated AMH solids; however, this approach was less effective for solids containing mannan polysaccharides, suggesting stronger association of cellulose with (hetero) mannans or lack of enzymes in the mixture required to hydrolyze such polysaccharides.« less

Thermochemically recuperated and steam cooled gas turbine system

DOEpatents

Viscovich, Paul W.; Bannister, Ronald L.

1995-01-01

A gas turbine system in which the expanded gas from the turbine section is used to generate the steam in a heat recovery steam generator and to heat a mixture of gaseous hydrocarbon fuel and the steam in a reformer. The reformer converts the hydrocarbon gas to hydrogen and carbon monoxide for combustion in a combustor. A portion of the steam from the heat recovery steam generator is used to cool components, such as the stationary vanes, in the turbine section, thereby superheating the steam. The superheated steam is mixed into the hydrocarbon gas upstream of the reformer, thereby eliminating the need to raise the temperature of the expanded gas discharged from the turbine section in order to achieve effective conversion of the hydrocarbon gas.

Catalytic cartridge SO.sub.3 decomposer

DOEpatents

Galloway, Terry R.

1982-01-01

A catalytic cartridge surrounding a heat pipe driven by a heat source is utilized as a SO.sub.3 decomposer for thermochemical hydrogen production. The cartridge has two embodiments, a cross-flow cartridge and an axial flow cartridge. In the cross-flow cartridge, SO.sub.3 gas is flowed through a chamber and incident normally to a catalyst coated tube extending through the chamber, the catalyst coated tube surrounding the heat pipe. In the axial-flow cartridge, SO.sub.3 gas is flowed through the annular space between concentric inner and outer cylindrical walls, the inner cylindrical wall being coated by a catalyst and surrounding the heat pipe. The modular cartridge decomposer provides high thermal efficiency, high conversion efficiency, and increased safety.

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

Maiti, Debtanu; Daza, Yolanda A.; Yung, Matthew M.

Density functional theory (DFT) based investigation of two parameters of prime interest -- oxygen vacancy and surface terminations along (100) and (110) planes -- has been conducted for La (1-x)Sr xFe(1-y)Co yO (3-more » $$\\delta$$) perovskite oxides in view of their application towards thermochemical carbon dioxide conversion reactions. The bulk oxygen vacancy formation energies for these mixed perovskite oxides are found to increase with increasing lanthanum and iron contents in the 'A' site and 'B' site, respectively. Surface terminations along (100) and (110) crystal planes are studied to probe their stability and their capabilities to accommodate surface oxygen vacancies. Amongst the various terminations, the oxygen-rich (110) surface and strontium-rich (100) surface are the most stable, while transition metal-rich terminations along (100) revealed preference towards the production of oxygen vacancies. The carbon dioxide adsorption strength, a key descriptor for CO 2 conversion reactions, is found to increase on oxygen vacant surfaces thus establishing the importance of oxygen vacancies in CO 2 conversion reactions. Amongst all the surface terminations, the lanthanum-oxygen terminated surface exhibited the strongest CO 2 adsorption strength. Finally, the theoretical prediction of the oxygen vacancy trends and the stability of the samples were corroborated by the temperature-programmed reduction and oxidation reactions and in situ XRD crystallography.« less

Dielectric properties of biomass and biochar mixtures for bioenergy applications

USDA-ARS?s Scientific Manuscript database

Biomass is an abundant and renewable energy resource, which may be converted into energy-dense products through thermochemical processes such as pyrolysis and gasification. Since microwave heating depends on the dielectric properties of the biomass material, these properties were measured at freque...

Effect of carbon dioxide on the thermal degradation of lignocellulosic biomass.

PubMed

Kwon, Eilhann E; Jeon, Eui-Chan; Castaldi, Marco J; Jeon, Young Jae

2013-09-17

Using biomass as a renewable energy source via currently available thermochemical processes (i.e., pyrolysis and gasification) is environmentally advantageous owing to its intrinsic carbon neutrality. Developing methodologies to enhance the thermal efficiency of these proven technologies is therefore imperative. This study aimed to investigate the use of CO2 as a reaction medium to increase not only thermal efficiency but also environmental benefit. The influence of CO2 on thermochemical processes at a fundamental level was experimentally validated with the main constituents of biomass (i.e., cellulose and xylan) to avoid complexities arising from the heterogeneous matrix of biomass. For instance, gaseous products including H2, CH4, and CO were substantially enhanced in the presence of CO2 because CO2 expedited thermal cracking behavior (i.e., 200-1000%). This behavior was then universally observed in our case study with real biomass (i.e., corn stover) during pyrolysis and steam gasification. However, further study is urgently needed to optimize these experimental findings.

Yannick J. Bomble, Ph.D. | NREL

Science.gov Websites

Yannick.Bomble@nrel.gov | 303-384-7729 Research Interests Development of thermophilic bacteria for improved Quantum chemical calculations for the study of thermochemical properties and processes Affiliated Research ©matiques Superieures, Lycée Faidherbe, Lille, France, 1998 Professional Experience Senior Research

The Thermit Reaction: A Dazzling Thermochemical Demonstration.

ERIC Educational Resources Information Center

Kauffman, George B.

1997-01-01

Describes an outdoor scientific demonstration of metal reduction, a reaction known as the thermit process. Heat from an ignition mixture is required to initiate the reaction, which then becomes self-sustaining. The demonstration provides a dazzling introduction to such fundamental general chemistry topics as oxidation-reduction, metallurgy,…

Hydrogen fuel - Universal energy

NASA Astrophysics Data System (ADS)

Prince, A. G.; Burg, J. A.

The technology for the production, storage, transmission, and consumption of hydrogen as a fuel is surveyed, with the physical and chemical properties of hydrogen examined as they affect its use as a fuel. Sources of hydrogen production are described including synthesis from coal or natural gas, biomass conversion, thermochemical decomposition of water, and electrolysis of water, of these only electrolysis is considered economicially and technologically feasible in the near future. Methods of production of the large quantities of electricity required for the electrolysis of sea water are explored: fossil fuels, hydroelectric plants, nuclear fission, solar energy, wind power, geothermal energy, tidal power, wave motion, electrochemical concentration cells, and finally ocean thermal energy conversion (OTEC). The wind power and OTEC are considered in detail as the most feasible approaches. Techniques for transmission (by railcar or pipeline), storage (as liquid in underwater or underground tanks, as granular metal hydride, or as cryogenic liquid), and consumption (in fuel cells in conventional power plants, for home usage, for industrial furnaces, and for cars and aircraft) are analyzed. The safety problems of hydrogen as a universal fuel are discussed, noting that they are no greater than those for conventional fuels.

Coal technology program progress report, February 1976

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

None

Final testing of the 20-atm bench-scale system is underway in preparation for experiments with hydrogen. Laboratory-scale testing of a number of inexpensive pure compounds to improve the settling rate of solids in Solvent Refined Coal (SRC) unfiltered oil (UFO), bench-scale testing of the effect of the Tretolite additive on settling, and characterization tests on a new sample of UFO from the PAMCO-SRC process are reported. Experimental engineering support of an in situ gasification process include low-temperature pyrolyses at exceptionally low heating rates (0.3/sup 0/C/min). Highly pyrophoric chars were consistently produced. Aqueous by-products from coal conversion technologies and oil shale retortingmore » have been analyzed directly to determine major organic components. A report is being prepared discussing various aspects of the engineering evaluations of nuclear process heat for coal. A bench-scale test program on thermochemical water splitting for hydrogen production is under consideration. In the coal-fueled MIUS program, preparations for procurement of tubing for the matrix in the fluidized-bed furnace and for fabrication of the furnace continued. Analyses of the AiResearch gas turbine and recuperator under coal-fueled MIUS operating conditions are near completion. Process flow diagrams and heat and material balances were completed for most of the units in the synthoil process. Overall utilities requirements were calculated and the coal preparation flowsheets were finalized. For hydrocarbonization, the flowsheet was revised to include additional coal data. Flowsheets were finalized for the acid gas separation and recycle, and the oil-solids separation. (LTN)« less

Oxygen vacancy formation characteristics in the bulk and across different surface terminations of La (1₋x)Sr xFe (1₋y)Co yO (3₋δ) perovskite oxides for CO 2 conversion

DOE PAGES

Maiti, Debtanu; Daza, Yolanda A.; Yung, Matthew M.; ...

2016-03-07

Density functional theory (DFT) based investigation of two parameters of prime interest -- oxygen vacancy and surface terminations along (100) and (110) planes -- has been conducted for La (1-x)Sr xFe(1-y)Co yO (3-more » $$\\delta$$) perovskite oxides in view of their application towards thermochemical carbon dioxide conversion reactions. The bulk oxygen vacancy formation energies for these mixed perovskite oxides are found to increase with increasing lanthanum and iron contents in the 'A' site and 'B' site, respectively. Surface terminations along (100) and (110) crystal planes are studied to probe their stability and their capabilities to accommodate surface oxygen vacancies. Amongst the various terminations, the oxygen-rich (110) surface and strontium-rich (100) surface are the most stable, while transition metal-rich terminations along (100) revealed preference towards the production of oxygen vacancies. The carbon dioxide adsorption strength, a key descriptor for CO 2 conversion reactions, is found to increase on oxygen vacant surfaces thus establishing the importance of oxygen vacancies in CO 2 conversion reactions. Amongst all the surface terminations, the lanthanum-oxygen terminated surface exhibited the strongest CO 2 adsorption strength. Finally, the theoretical prediction of the oxygen vacancy trends and the stability of the samples were corroborated by the temperature-programmed reduction and oxidation reactions and in situ XRD crystallography.« less

Hydrogenation of CO 2 to methanol: Importance of metal–oxide and metal–carbide interfaces in the activation of CO 2

DOE PAGES

Rodriguez, José A.; Liu, Ping; Stacchiola, Dario J.; ...

2015-09-30

In this study, the high thermochemical stability of CO 2 makes it very difficult to achieve the catalytic conversion of the molecule into alcohols or other hydrocarbon compounds, which can be used as fuels or the starting point for the generation of fine chemicals. Pure metals and bimetallic systems used for the CO 2 → CH 3OH conversion usually bind CO 2 too weakly and, thus, show low catalytic activity. Here, we discuss a series of recent studies that illustrate the advantages of metal–oxide and metal–carbide interfaces when aiming at the conversion of CO2 into methanol. CeO x/Cu(111), Cu/CeO x/TiOmore » 2(110), and Au/CeO x/TiO 2(110) exhibit an activity for the CO 2 → CH 3OH conversion that is 2–3 orders of magnitude higher than that of a benchmark Cu(111) catalyst. In the Cu–ceria and Au–ceria interfaces, the multifunctional combination of metal and oxide centers leads to complementary chemical properties that open active reaction pathways for methanol synthesis. Efficient catalysts are also generated after depositing Cu and Au on TiC(001). In these cases, strong metal–support interactions modify the electronic properties of the admetals and make them active for the binding of CO 2 and its subsequent transformation into CH 3OH at the metal–carbide interfaces.« less

Integration of pyrolysis and anaerobic digestion--use of aqueous liquor from digestate pyrolysis for biogas production.

PubMed

Hübner, Tobias; Mumme, Jan

2015-05-01

Anaerobic digestion of aqueous pyrolysis liquor derived from pyrolysis of solid digestate was tested in batch mode using an un-adapted inoculum. Three pyrolysis liquors produced at 330°C, 430°C and 530°C in four COD-based concentrations of 3, 6, 12 and 30 g L(-1) were investigated. The three lower concentrations showed considerable biogas production, whereas the 30 g L(-1) dosage caused process inhibition. The highest methane yield of 199.1±18.5 mL g(COD)(-1) (COD removal: 56.9±5.3%) was observed for the 330°C pyrolysis liquor, followed by the 430°C sample with only slightly lower values. The 530°C sample dropped to a yield of 129.3±19.7 mL g(COD)(-1) (COD removal: 36.9±5.6%). Most VOCs contained in the pyrolysis liquor (i.e. furfural, phenol, catechol, guaiacol, and levoglucosan) were reduced below detection limit (cresol by 10-60%). Consequently, integrated pyrolysis and anaerobic digestion in addition to thermochemical conversion of digestate also promises bioconversion of pyrolysis liquors. Copyright © 2015 Elsevier Ltd. All rights reserved.

Effect of sodium carbonate catalyst weight on production of bio-oil via thermochemical liquefaction of corncobs in ethanol-water solution

NASA Astrophysics Data System (ADS)

Sembodo, Bregas Siswahjono Tatag; Sulistyo, Hary; Sediawan, Wahyudi Budi; Fahrurrozi, Mohammad

2018-02-01

Lignocellulosic biomass has recently received serious attention as an energy source that can replace fossil fuels. Corncob is one of lignocellulosic biomass wastes, which can be further processed into bio-oil through thermochemical liquefaction process. Bio-oil is expected to be further processed into fuel oil. In this research the effect of Na2CO3 catalyst weight on the yield of bio-oil was investigated. The composition of bio-oil produced in this process was analyzed by GC-MS. Bio-oil formation rate were analyzed through mathematical model development. First model aasumed as an isothermal process, while second model was not. It is found that both models were able to provide a good approach to experimental data. The average reaction rate constants was obtained from isothermal model, while the activation energy level and collision factors were obtained from non-isothermal model. The reaction rate will increase by addition of Na2CO3 (0 - 0.5 g) as catalyst to 250 mL system solution, then the activation energy will decrease from 1964.265 joules/mole to 1029.994 joules/mole. The GC-MS analysis results showed that the bio-oil were contained of ester compounds, phenolic compounds, cyclic compunds, heterocyclic compounds, and poly-alcohols compounds.

Researching the Possibility of Creating Highly Effective Catalysts for the Thermochemical Heat Regeneration and Hydrocarbon Reforming

DTIC Science & Technology

2006-11-01

PHYSICAL PROPERTIES OF THE PLASMA SPRAYING PROCESS The sprayed -on material is formed by gradual deposition of separate discretely solidifying with great... deposition processes and their ecological purity. Essentially, the method of ion-plasma spraying is evaporation of a metal (or alloy ) atoms from the...29 5.1 PHYSICAL PROPERTIES OF THE PLASMA SPRAYING PROCESS ...................34 6. CATALYST SUPPORTERS FOR THE 1ST STAGE OF

Computer-Aided Process Model For Carbon/Phenolic Materials

NASA Technical Reports Server (NTRS)

Letson, Mischell A.; Bunker, Robert C.

1996-01-01

Computer program implements thermochemical model of processing of carbon-fiber/phenolic-matrix composite materials into molded parts of various sizes and shapes. Directed toward improving fabrication of rocket-engine-nozzle parts, also used to optimize fabrication of other structural components, and material-property parameters changed to apply to other materials. Reduces costs by reducing amount of laboratory trial and error needed to optimize curing processes and to predict properties of cured parts.

Determination of Geochemical Bio-Signatures in Mars-Like Basaltic Environments

PubMed Central

Olsson-Francis, Karen; Pearson, Victoria K.; Steer, Elisabeth D.; Schwenzer, Susanne P.

2017-01-01

Bio-signatures play a central role in determining whether life existed on early Mars. Using a terrestrial basalt as a compositional analog for the martian surface, we applied a combination of experimental microbiology and thermochemical modeling techniques to identify potential geochemical bio-signatures for life on early Mars. Laboratory experiments were used to determine the short-term effects of biota on the dissolution of terrestrial basalt, and the formation of secondary alteration minerals. The chemoorganoheterotrophic bacterium, Burkholderia sp. strain B_33, was grown in a minimal growth medium with and without terrestrial basalt as the sole nutrient source. No growth was detected in the absence of the basalt. In the presence of basalt, during exponential growth, the pH decreased rapidly from pH 7.0 to 3.6 and then gradually increased to a steady-state of equilibrium of between 6.8 and 7.1. Microbial growth coincided with an increase in key elements in the growth medium (Si, K, Ca, Mg, and Fe). Experimental results were compared with theoretical thermochemical modeling to predict growth of secondary alteration minerals, which can be used as bio-signatures, over a geological timescale. We thermochemically modeled the dissolution of the basalt (in the absence of biota) in very dilute brine at 25°C, 1 bar; the pH was buffered by the mineral dissolution and precipitation reactions. Preliminary results suggested that at the water to rock ratio of 1 × 107, zeolite, hematite, chlorite, kaolinite, and apatite formed abiotically. The biotic weathering processes were modeled by varying the pH conditions within the model to adjust for biologic influence. The results suggested that, for a basaltic system, the microbially-mediated dissolution of basalt would result in “simpler” secondary alteration, consisting of Fe-hydroxide and kaolinite, under conditions where the abiotic system would also form chlorite. The results from this study demonstrate that, by using laboratory-based experiments and thermochemical modeling, it is possible to identify secondary alteration minerals that could potentially be used to distinguish between abiotic and biotic weathering processes on early Mars. This work will contribute to the interpretation of data from past, present, and future life detection missions to Mars. PMID:28943863

Determination of Geochemical Bio-Signatures in Mars-Like Basaltic Environments.

PubMed

Olsson-Francis, Karen; Pearson, Victoria K; Steer, Elisabeth D; Schwenzer, Susanne P

2017-01-01

Bio-signatures play a central role in determining whether life existed on early Mars. Using a terrestrial basalt as a compositional analog for the martian surface, we applied a combination of experimental microbiology and thermochemical modeling techniques to identify potential geochemical bio-signatures for life on early Mars. Laboratory experiments were used to determine the short-term effects of biota on the dissolution of terrestrial basalt, and the formation of secondary alteration minerals. The chemoorganoheterotrophic bacterium, Burkholderia sp. strain B_33, was grown in a minimal growth medium with and without terrestrial basalt as the sole nutrient source. No growth was detected in the absence of the basalt. In the presence of basalt, during exponential growth, the pH decreased rapidly from pH 7.0 to 3.6 and then gradually increased to a steady-state of equilibrium of between 6.8 and 7.1. Microbial growth coincided with an increase in key elements in the growth medium (Si, K, Ca, Mg, and Fe). Experimental results were compared with theoretical thermochemical modeling to predict growth of secondary alteration minerals, which can be used as bio-signatures, over a geological timescale. We thermochemically modeled the dissolution of the basalt (in the absence of biota) in very dilute brine at 25°C, 1 bar; the pH was buffered by the mineral dissolution and precipitation reactions. Preliminary results suggested that at the water to rock ratio of 1 × 10 7 , zeolite, hematite, chlorite, kaolinite, and apatite formed abiotically. The biotic weathering processes were modeled by varying the pH conditions within the model to adjust for biologic influence. The results suggested that, for a basaltic system, the microbially-mediated dissolution of basalt would result in "simpler" secondary alteration, consisting of Fe-hydroxide and kaolinite, under conditions where the abiotic system would also form chlorite. The results from this study demonstrate that, by using laboratory-based experiments and thermochemical modeling, it is possible to identify secondary alteration minerals that could potentially be used to distinguish between abiotic and biotic weathering processes on early Mars. This work will contribute to the interpretation of data from past, present, and future life detection missions to Mars.

Investigation of Thermochemistry Associated with the Carbon–Carbon Coupling Reactions of Furan and Furfural Using ab Initio Methods

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

Liu, Cong; Assary, Rajeev S.; Curtiss, Larry A.

2014-06-26

Upgrading of furan and small oxygenates obtained from the decomposition of cellulosic materials via formation of carbon-carbon bonds is critical to effective conversion of biomass to liquid transportation fuels. Simulation-driven molecular level understanding of carbon-carbon bond formation is required to design efficient catalysts and processes. Accurate quantum chemical methods are utilized here to predict the reaction energetics for conversion of furan (C4H4O) to C5-C8 ethers and the transformation of furfural (C5H6O2) to C13-C26 alkanes. Furan, can be coupled with various C1 to C4 lower molecular weight carbohydrates obtained from the pyrolysis via Diels-Alder type reactions in the gas phase tomore » produce C5-C8 cyclic ethers. The computed reaction barriers for these reactions (~25 kcal/mol) are lower than the cellulose activation or decomposition reactions (~50 kcal/mol). Cycloaddition of C5-C8 cyclo-ethers with furans can also occur in the gas phase, and the computed activation energy is similar to that of the first Diels-Alder reaction. Furfural, obtained from biomass, can be coupled with aldehydes or ketones with α-hydrogen atoms to form longer chain aldol products and these aldol products can undergo vapor phase hydrocycloaddition (activation barrier of ~20 kcal/mol) to form the precursors of C26 cyclic hydrocarbons. These thermochemical studies provide the basis for further vapor phase catalytic studies required for upgrading of furans/furfurals to longer chain hydrocarbons.« less

Controlling cation segregation in perovskite-based electrodes for high electro-catalytic activity and durability.

PubMed

Li, Yifeng; Zhang, Wenqiang; Zheng, Yun; Chen, Jing; Yu, Bo; Chen, Yan; Liu, Meilin

2017-10-16

Solid oxide cell (SOC) based energy conversion systems have the potential to become the cleanest and most efficient systems for reversible conversion between electricity and chemical fuels due to their high efficiency, low emission, and excellent fuel flexibility. Broad implementation of this technology is however hindered by the lack of high-performance electrode materials. While many perovskite-based materials have shown remarkable promise as electrodes for SOCs, cation enrichment or segregation near the surface or interfaces is often observed, which greatly impacts not only electrode kinetics but also their durability and operational lifespan. Since the chemical and structural variations associated with surface enrichment or segregation are typically confined to the nanoscale, advanced experimental and computational tools are required to probe the detailed composition, structure, and nanostructure of these near-surface regions in real time with high spatial and temporal resolutions. In this review article, an overview of the recent progress made in this area is presented, highlighting the thermodynamic driving forces, kinetics, and various configurations of surface enrichment and segregation in several widely studied perovskite-based material systems. A profound understanding of the correlation between the surface nanostructure and the electro-catalytic activity and stability of the electrodes is then emphasized, which is vital to achieving the rational design of more efficient SOC electrode materials with excellent durability. Furthermore, the methodology and mechanistic understanding of the surface processes are applicable to other materials systems in a wide range of applications, including thermo-chemical photo-assisted splitting of H 2 O/CO 2 and metal-air batteries.

Improving Catalyst Efficiency in Bio-Based Hydrocarbon Fuels; NREL (National Renewable Energy Laboratory)

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

None

This article investigates upgrading biomass pyrolysis vapors to form hydrocarbon fuels and chemicals using catalysts with different concentrations of acid sites. It shows that greater separation of acid sites makes catalysts more efficient at producing hydrocarbon fuels and chemicals. The conversion of biomass into liquid transportation fuels has attracted significant attention because of depleting fossil fuel reserves and environmental concerns resulting from the use of fossil fuels. Biomass is a renewable resource, which is abundant worldwide and can potentially be exploited to produce transportation fuels that are less damaging to the environment. This renewable resource consists of cellulose (40–50%), hemicellulosemore » (25–35%), and lignin (16–33%) biopolymers in addition to smaller quantities of inorganic materials such as silica and alkali and alkaline earth metals (calcium and potassium). Fast pyrolysis is an attractive thermochemical technology for converting biomass into precursors for hydrocarbon fuels because it produces up to 75 wt% bio-oil,1 which can be upgraded to feedstocks and/or blendstocks for further refining to finished fuels. Bio-oil that has not been upgraded has limited applications because of the presence of oxygen-containing functional groups, derived from cellulose, hemicellulose and lignin, which gives rise to high acidity, high viscosity, low heating value, immiscibility with hydrocarbons and aging during storage. Ex situ catalytic vapor phase upgrading is a promising approach for improving the properties of bio-oil. The goal of this process is to reject oxygen and produce a bio-oil with improved properties for subsequent downstream conversion to hydrocarbons.« less

Development and application of computational aerothermodynamics flowfield computer codes

NASA Technical Reports Server (NTRS)

Venkatapathy, Ethiraj

1994-01-01

Research was performed in the area of computational modeling and application of hypersonic, high-enthalpy, thermo-chemical nonequilibrium flow (Aerothermodynamics) problems. A number of computational fluid dynamic (CFD) codes were developed and applied to simulate high altitude rocket-plume, the Aeroassist Flight Experiment (AFE), hypersonic base flow for planetary probes, the single expansion ramp model (SERN) connected with the National Aerospace Plane, hypersonic drag devices, hypersonic ramp flows, ballistic range models, shock tunnel facility nozzles, transient and steady flows in the shock tunnel facility, arc-jet flows, thermochemical nonequilibrium flows around simple and complex bodies, axisymmetric ionized flows of interest to re-entry, unsteady shock induced combustion phenomena, high enthalpy pulsed facility simulations, and unsteady shock boundary layer interactions in shock tunnels. Computational modeling involved developing appropriate numerical schemes for the flows on interest and developing, applying, and validating appropriate thermochemical processes. As part of improving the accuracy of the numerical predictions, adaptive grid algorithms were explored, and a user-friendly, self-adaptive code (SAGE) was developed. Aerothermodynamic flows of interest included energy transfer due to strong radiation, and a significant level of effort was spent in developing computational codes for calculating radiation and radiation modeling. In addition, computational tools were developed and applied to predict the radiative heat flux and spectra that reach the model surface.

Stabilization of lead and copper by biochar amendments in arms range soils: Influence of biochar characteristics, soil property, and equilibrium conditions

USDA-ARS?s Scientific Manuscript database

Soil amendment of char products (biochar) from thermochemical processing (slow/fast pyrolysis and gasification) of biomass for biofuel production has received considerable interests for contaminant sorption, soil fertilization, and carbon sequestration. Of potential sites for biochar application, h...

Chemical characterization of chars developed from thermochemical treatment of Kentucky bluegrass seed screenings

USDA-ARS?s Scientific Manuscript database

Char produced from the gasification of post-seed harvest Kentucky bluegrass residues could be recycled to a cropping system as a soil amendment if chemical characterization determined that the gasification process had not produced or concentrated deleterious chemical or physical factors that might h...

Study of Oxygen Diffusion in Reduced LiNbO3 Crystals

NASA Astrophysics Data System (ADS)

Yatsenko, A. V.; Pritulenko, A. S.; Yagupov, S. V.; Sugak, D. Yu.; Sol'skii, I. M.

2018-03-01

Using the method of impedance spectroscopy and optical density measurements, the diffusion of oxygen in single crystals of lithium niobate of the congruent composition after the reductive thermochemical processing is studied. The parameters describing the diffusion of oxygen in the temperature range 493-693 K are established.

Thermochemical Production of Hydrogen from Water.

ERIC Educational Resources Information Center

Bamberger, C. E.; And Others

1978-01-01

Discusses the possible advantages of decomposing water by means of thermochemical cycles. Explains that, if energy consumption can be minimized, this method is capable of producing hydrogen more efficiently than electrolysis. (GA)

Trade Study of Five In-Situ Propellant Production System for a Mars Sample Return Mission

NASA Technical Reports Server (NTRS)

Green, S. T.; Deffenbaugh, D. M.; Miller, M. A.

1999-01-01

One of the goals of NASA''s HEDS enterprise is to establish a long-term human presence on Mars at a fraction of the cost of employing today''s technology. The most direct method of reducing mission cost is to reduce the launch mass of the spacecraft. If the propellants for the return phase of the mission are produced on Mars, the total spacecraft mass could be reduced significantly. An interim goal is a Mars Sample Return (MSR) mission, which is proposed to demonstrate the feasibility of in-situ propellant production (ISPP). Five candidate ISPP systems for producing two fuels and oxygen from the Martian atmosphere are considered in this design trade-off study:(1) Zirconia cell with methanol synthesis, (2) Reverse water gas shift (RWGS) with water electrolysis and methanol synthesis, (3) Sabatier process for methane production with water electrolysis, (4) Sabatier process with water electrolysis and partial methane pyrolysis, and (5) Sabatier/RWGS combination with water electrolysis. These systems have been the subject of numerous previous analytical studies and laboratory demonstrations. In this investigation, the systems are objectively compared on the basis of thermochemical performance models using a commonly used chemical plant analysis software package. The realistic effects of incomplete chemical conversion and gas phase separator performance are included in these models. This study focuses on the chemical processing and product separation subsystems. The CO2 compression upstream of the chemical plane and the liquefaction/storage components are not included here.

Corrosion Considerations for Thermochemical Biomass Liquefaction Process Systems in Biofuel Production

NASA Astrophysics Data System (ADS)

Brady, M. P.; Keiser, J. R.; Leonard, D. N.; Whitmer, L.; Thomson, J. K.

2014-12-01

Thermochemical liquefaction processing of biomass to produce bio-derived fuels (e.g., gasoline, jet fuel, diesel, home heating oil, etc.) is of great recent interest as a renewable energy source. Approaches under investigation include direct liquefaction, hydrothermal liquefaction, hydropyrolysis, fast pyrolysis, etc., to produce energy dense liquids that can be utilized as produced or further processed to provide products of higher value. An issue with bio-oils is that they tend to contain significant concentrations of organic oxygenates, including acids, which make the bio-oil a potential source of corrosion issues in transport, storage, and use. Efforts devoted to modified/further processing of bio-oils to make them less corrosive are currently being widely pursued. Another issue that must also be addressed in bio-oil liquefaction is potential corrosion issues in the process equipment. Depending on the specific process, bio-oil liquefaction production temperatures are typically in the 300-600°C range, and the process environment can contain aggressive sulfur and halide species from both the biomass used and/or process additives. Detailed knowledge of the corrosion resistance of candidate process equipment alloys in these bio-oil production environments is currently lacking. This paper summarizes recent, ongoing efforts to assess the extent of corrosion of bio-oil process equipment, with the ultimate goal of providing a basis for the selection of the lowest cost alloy grades capable of providing the long-term corrosion resistance needed for future bio-oil production plants.

Removal of introduced inorganic content from chipped forest residues via air classification

DOE PAGES

Lacey, Jeffrey A.; Aston, John E.; Westover, Tyler L.; ...

2015-08-04

Inorganic content in biomass decreases the efficiency of conversion processes, especially thermochemical conversions. The combined concentrations of specific ash forming elements are the primary attributes that cause pine residues to be considered a degraded energy conversion feedstock, as compared to clean pine. Air classification is a potentially effective and economical tool to isolate high inorganic content biomass fractions away from primary feedstock sources to reduce their ash content. In this work, loblolly pine forest residues were air classified into 10 fractions whose ash content and composition were measured. Ash concentrations were highest in the lightest fractions (5.8–8.5 wt%), and inmore » a heavy fraction of the fines (8.9–15.1 wt%). The removal of fractions with high inorganic content resulted in a substantial reduction in the ash content of the remaining biomass in forest thinnings (1.69–1.07 wt%) and logging residues (1.09–0.68 wt%). These high inorganic content fractions from both forest residue types represented less than 7.0 wt% of the total biomass, yet they contained greater than 40% of the ash content by mass. Elemental analysis of the air classified fractions revealed the lightest fractions were comprised of high concentrations of soil elements (silicon, aluminum, iron, sodium, and titanium). However, the elements of biological origin including calcium, potassium, magnesium, sulfur, manganese, and phosphorous were evenly distributed throughout all air classified fractions, making them more difficult to isolate into fractions with high mineral concentrations. Under the conditions reported in this study, an economic analysis revealed air classification could be used for ash removal for as little as $2.23 per ton of product biomass. As a result, this study suggests air classification is a potentially attractive technology for the removal of introduced soil minerals from pine forest residues.« less

Experimental and numerical study of steam gasification of a single charcoal particle

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

Mermoud, F.; Van de Steene, L.; Golfier, F.

2006-04-15

The present work deals with a study coupling experiments and modeling of charcoal gasification by steam at large particle scale. A reliable set of experiments was first established using a specially developed 'macro-TG' apparatus where a particle was suspended and continuously weighed during its gasification. The main control parameters of a fixed-bed process were modified separately: steam gasification of beech charcoal spheres of different diameters (10 to 30 mm) was studied at different temperatures (830 to 1030{sup o}C), different steam partial pressures (0.1 to 0.4 atm H{sub 2}O), and different gas velocities around the particle (0.09 to 0.30 m/s). Simulationsmore » with the particle model were performed for each case. Confrontations with experimental data indicate that the model predictions are both qualitatively and quantitatively satisfactory, with an accuracy of 7%, until 60% of conversion, despite the fact that the phenomena of reactive surface evolution and particle fracturing are not well understood. Anisotropy and peripheral fragmentation make the end of the process difficult to simulate. Finally, an analysis of the thermochemical situation is proposed: it is demonstrated that the usual homogeneous or shrinking core particle models are not satisfying and that only the assumption of thermal equilibrium between the particle and the surrounding gas is valid for a model at bed scale. (author)« less

Conceptual energy and water recovery system for self-sustained nano membrane toilet.

PubMed

Hanak, Dawid P; Kolios, Athanasios J; Onabanjo, Tosin; Wagland, Stuart T; Patchigolla, Kumar; Fidalgo, Beatriz; Manovic, Vasilije; McAdam, Ewan; Parker, Alison; Williams, Leon; Tyrrel, Sean; Cartmell, Elise

2016-10-15

With about 2.4 billion people worldwide without access to improved sanitation facilities, there is a strong incentive for development of novel sanitation systems to improve the quality of life and reduce mortality. The Nano Membrane Toilet is expected to provide a unique household-scale system that would produce electricity and recover water from human excrement and urine. This study was undertaken to evaluate the performance of the conceptual energy and water recovery system for the Nano Membrane Toilet designed for a household of ten people and to assess its self-sustainability. A process model of the entire system, including the thermochemical conversion island, a Stirling engine and a water recovery system was developed in Aspen Plus®. The energy and water recovery system for the Nano Membrane Toilet was characterised with the specific net power output of 23.1 Wh/kg settledsolids and water recovery rate of 13.4 dm 3 /day in the nominal operating mode. Additionally, if no supernatant was processed, the specific net power output was increased to 69.2 Wh/kg settledsolids . Such household-scale system would deliver the net power output (1.9-5.8 W). This was found to be enough to charge mobile phones or power clock radios, or provide light for the household using low-voltage LED bulbs.

Optimization and economic evaluation of industrial gas production and combined heat and power generation from gasification of corn stover and distillers grains.

PubMed

Kumar, Ajay; Demirel, Yasar; Jones, David D; Hanna, Milford A

2010-05-01

Thermochemical gasification is one of the most promising technologies for converting biomass into power, fuels and chemicals. The objectives of this study were to maximize the net energy efficiency for biomass gasification, and to estimate the cost of producing industrial gas and combined heat and power (CHP) at a feedrate of 2000kg/h. Aspen Plus-based model for gasification was combined with a CHP generation model, and optimized using corn stover and dried distillers grains with solubles (DDGS) as the biomass feedstocks. The cold gas efficiencies for gas production were 57% and 52%, respectively, for corn stover and DDGS. The selling price of gas was estimated to be $11.49 and $13.08/GJ, respectively, for corn stover and DDGS. For CHP generation, the electrical and net efficiencies were as high as 37% and 88%, respectively, for corn stover and 34% and 78%, respectively, for DDGS. The selling price of electricity was estimated to be $0.1351 and $0.1287/kWh for corn stover and DDGS, respectively. Overall, high net energy efficiencies for gas and CHP production from biomass gasification can be achieved with optimized processing conditions. However, the economical feasibility of these conversion processes will depend on the relative local prices of fossil fuels. Copyright 2009 Elsevier Ltd. All rights reserved.

Kinetic calculations of explosives with slow-burning constituents

NASA Astrophysics Data System (ADS)

Howard, W. Michael; Souers, P. Clark; Fried, Laurence E.

1998-07-01

The equilibrium thermochemical code CHEETAH V1.40 has been modified to detonate part of the explosive and binder. An Einstein thermal description of the unreacted constituents is used, and the Einstein temperature may be increased to reduce heat absorption. We study the effect of the reactivity and thermal transport on the detonation velocity. Hydroxy-terminated-polybutadiene binders have low energy and density and would degrade the detonation velocity if they burned. Runs with unburned binder are closer to the measured values. Aluminum and ammonium perchlorate are also largely unburned within the sonic reaction zone that determines the detonation velocity. All three materials appear not to fully absorb heat as well. The normal assumption of total reaction in a thermochemical code is clearly not true for these special cases, where the detonation velocities have widely different values for different combinations of processes.

Innovative pretreatment strategies for biogas production.

PubMed

Patinvoh, Regina J; Osadolor, Osagie A; Chandolias, Konstantinos; Sárvári Horváth, Ilona; Taherzadeh, Mohammad J

2017-01-01

Biogas or biomethane is traditionally produced via anaerobic digestion, or recently by thermochemical or a combination of thermochemical and biological processes via syngas (CO and H 2 ) fermentation. However, many of the feedstocks have recalcitrant structure and are difficult to digest (e.g., lignocelluloses or keratins), or they have toxic compounds (such as fruit flavors or high ammonia content), or not digestible at all (e.g., plastics). To overcome these challenges, innovative strategies for enhanced and economically favorable biogas production were proposed in this review. The strategies considered are commonly known physical pretreatment, rapid decompression, autohydrolysis, acid- or alkali pretreatments, solvents (e.g. for lignin or cellulose) pretreatments or leaching, supercritical, oxidative or biological pretreatments, as well as combined gasification and fermentation, integrated biogas production and pretreatment, innovative biogas digester design, co-digestion, and bio-augmentation. Copyright © 2016 Elsevier Ltd. All rights reserved.

Additive erosion reduction influences in the turbulent boundary layer

NASA Astrophysics Data System (ADS)

Buckingham, A. C.

1981-05-01

Results of a sequence of flow, heat and mass transfer calculations are presented which theoretically characterize the erosive environment at the wall surface of refractory metal coated and uncoated gun barrels. The theoretical results include analysis of the wall surface temperature, heat flux, and shear stress time histories on thin (10 mil.) Cr, Mo, Nb, and Ta plated steel barrel walls as uncoated steel walls. The calculations combine effects of a number of separate processes which were previously (and purposely) studied individually. These include solid particle additive concentrations, gas wall thermochemical influences, and transient turbulent wall boundary layer flow with multicomponent molecular diffusion and reactions from interaction of propellant combustion and the eroding surface. The boundary layer model includes particulate additive concentrations as well as propellant combustion products, considered for the present to be in the local thermochemical equilibrium.

Process modeling for carbon-phenolic nozzle materials

NASA Technical Reports Server (NTRS)

Letson, Mischell A.; Bunker, Robert C.; Remus, Walter M., III; Clinton, R. G.

1989-01-01

A thermochemical model based on the SINDA heat transfer program is developed for carbon-phenolic nozzle material processes. The model can be used to optimize cure cycles and to predict material properties based on the types of materials and the process by which these materials are used to make nozzle components. Chemical kinetic constants for Fiberite MX4926 were determined so that optimization of cure cycles for the current Space Shuttle Solid Rocket Motor nozzle rings can be determined.

Advances in surfaces and osseointegration in implantology. Biomimetic surfaces

PubMed Central

Albertini, Matteo; Fernandez-Yague, Marc; Lázaro, Pedro; Herrero-Climent, Mariano; Bullon, Pedro; Gil, Francisco-Javier

2015-01-01

The present work is a revision of the processes occurring in osseointegration of titanium dental implants according to different types of surfaces -namely, polished surfaces, rough surfaces obtained from subtraction methods, as well as the new hydroxyapatite biomimetic surfaces obtained from thermochemical processes. Hydroxyapatite’s high plasma-projection temperatures have proven to prevent the formation of crystalline apatite on the titanium dental implant, but lead to the formation of amorphous calcium phosphate (i.e., with no crystal structure) instead. This layer produce some osseointegration yet the calcium phosphate layer will eventually dissolve and leave a gap between the bone and the dental implant, thus leading to osseointegration failure due to bacterial colonization. A new surface -recently obtained by thermochemical processes- produces, by crystallization, a layer of apatite with the same mineral content as human bone that is chemically bonded to the titanium surface. Osseointegration speed was tested by means of minipigs, showing bone formation after 3 to 4 weeks, with the security that a dental implant can be loaded. This surface can be an excellent candidate for immediate or early loading procedures. Key words:Dental implants, implants surfaces, osseointegration, biomimetics surfaces. PMID:25662555

Formation of Polychlorinated Biphenyls on Secondary Copper Production Fly Ash: Mechanistic Aspects and Correlation to Other Persistent Organic Pollutants

NASA Astrophysics Data System (ADS)

Jiang, Xiaoxu; Liu, Guorui; Wang, Mei; Zheng, Minghui

2015-09-01

Emission of unintentionally formed polychlorinated biphenyls (PCBs) from industrial thermal processes is a global issue. Because the production and use of technical PCB mixtures has been banned, industrial thermal processes have become increasingly important sources of PCBs. Among these processes, secondary copper smelting is an important PCB source in China. In the present study, the potential for fly ash-mediated formation of PCBs in the secondary copper industry, and the mechanisms involved, were studied in laboratory thermochemical experiments. The total PCB concentrations were 37-70 times higher than the initial concentrations. Thermochemical reactions on the fly ash amplified the potential toxic equivalents of PCBs. The formation of PCBs over time and the effect of temperature were investigated. Based on analyses of PCB homologue profiles with different reaction conditions, a chlorination mechanism was proposed for forming PCBs in addition to a de novo synthesis mechanism. The chlorination pathway was supported by close correlations between each pair of adjacent homologue groups. Formation of PCBs and multiple persistent organic pollutants, including polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and polychlorinated naphthalenes, occurred during the tests, indicating that these compounds may share similar formation mechanisms.

Corrosion considerations for thermochemical biomass liquefaction process systems in biofuel production

DOE PAGES

Brady, Michael P.; Keiser, James R.; Leonard, Donovan N.; ...

2014-11-11

Thermochemical liquifaction processing of biomass to produce bio-derived fuels (e.g. gasoline, jet fuel, diesel, home heating oil, etc.) is of great recent interest as a renewable energy source. Approaches under investigation include direct liquefaction, hydrothermal liquefaction, hydropyrolysis, fast pyrolysis, etc. to produce energy dense liquids that can be utilized as produced or further processed to provide products of higher value. An issue with bio-oils is that they tend to contain significant concentrations of organic compounds, which make the bio-oil acidic and a potential source of corrosion issues in in transport, storage, and use. Efforts devoted to modified/further processing of bio-oilsmore » to make them less corrosive are currently being widely pursued. Another aspect that must also be addressed is potential corrosion issues in the bio-oil liquefaction process equipment itself. Depending on the specific process, bio-oil liquefaction production temperatures can reach up to 400-600 °C, and involve the presence of aggressive sulfur, and halide species from both the biomass used and/or process additives. Detailed knowledge of the corrosion resistance of candidate process equipment alloys in these bio-oil production environments is currently lacking. Lastly, this paper summarizes our recent, ongoing efforts to assess the extent to which corrosion of bio-oil process equipment may be an issue, with the ultimate goal of providing the basis to select the lowest cost alloy grades capable of providing the long-term corrosion resistance needed for future bio-oil production plants.« less

Thermochemically recuperated and steam cooled gas turbine system

DOEpatents

Viscovich, P.W.; Bannister, R.L.

1995-07-11

A gas turbine system is described in which the expanded gas from the turbine section is used to generate the steam in a heat recovery steam generator and to heat a mixture of gaseous hydrocarbon fuel and the steam in a reformer. The reformer converts the hydrocarbon gas to hydrogen and carbon monoxide for combustion in a combustor. A portion of the steam from the heat recovery steam generator is used to cool components, such as the stationary vanes, in the turbine section, thereby superheating the steam. The superheated steam is mixed into the hydrocarbon gas upstream of the reformer, thereby eliminating the need to raise the temperature of the expanded gas discharged from the turbine section in order to achieve effective conversion of the hydrocarbon gas. 4 figs.

Cellulosic ethanol: status and innovation

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

Lynd, Lee R.; Liang, Xiaoyu; Biddy, Mary J.

Although the purchase price of cellulosic feedstocks is competitive with petroleum on an energy basis, the cost of lignocellulose conversion to ethanol using today's technology is high. Cost reductions can be pursued via either in-paradigm or new-paradigm innovation. Here, as an example of new-paradigm innovation, consolidated bioprocessing using thermophilic bacteria combined with milling during fermentation (cotreatment) is analyzed. Acknowledging the nascent state of this approach, our analysis indicates potential for radically improved cost competitiveness and feasibility at smaller scale compared to current technology, arising from (a) R&D-driven advances (consolidated bioprocessing with cotreatment in lieu of thermochemical pretreatment and added fungalmore » cellulase), and (b) configurational changes (fuel pellet coproduction instead of electricity, gas boiler(s) in lieu of a solid fuel boiler).« less

Cellulosic ethanol: status and innovation

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

Lynd, Lee R.; Liang, Xiaoyu; Biddy, Mary J.

Although the purchase price of cellulosic feedstocks is competitive with petroleum on an energy basis, the cost of lignocellulose conversion to ethanol using today’s technology is high. Cost reductions can be pursued via either in-paradigm or new-paradigm innovation. As an example of new-paradigm innovation, consolidated bioprocessing using thermophilic bacteria combined with milling during fermentation (cotreatment) is analyzed. Acknowledging the nascent state of this approach, our analysis indicates potential for radically improved cost competitiveness and feasibility at smaller scale compared to current technology, arising from (a) R&D-driven advances (consolidated bioprocessing with cotreatment in lieu of thermochemical pretreatment and added fungal cellulase),more » and (b) configurational changes (fuel pellet coproduction instead of electricity, gas boiler(s) in lieu of a solid fuel boiler).« less

Cellulosic ethanol: status and innovation

DOE PAGES

Lynd, Lee R.; Liang, Xiaoyu; Biddy, Mary J.; ...

2017-05-18

Although the purchase price of cellulosic feedstocks is competitive with petroleum on an energy basis, the cost of lignocellulose conversion to ethanol using today's technology is high. Cost reductions can be pursued via either in-paradigm or new-paradigm innovation. Here, as an example of new-paradigm innovation, consolidated bioprocessing using thermophilic bacteria combined with milling during fermentation (cotreatment) is analyzed. Acknowledging the nascent state of this approach, our analysis indicates potential for radically improved cost competitiveness and feasibility at smaller scale compared to current technology, arising from (a) R&D-driven advances (consolidated bioprocessing with cotreatment in lieu of thermochemical pretreatment and added fungalmore » cellulase), and (b) configurational changes (fuel pellet coproduction instead of electricity, gas boiler(s) in lieu of a solid fuel boiler).« less

Catalytic cartridge SO/sub 3/ decomposer

DOEpatents

Galloway, T.R.

1980-11-18

A catalytic cartridge surrounding a heat pipe driven by a heat source is utilized as a SO/sub 3/ decomposer for thermochemical hydrogen production. The cartridge has two embodiments, a cross-flow cartridge and an axial flow cartridge. In the cross-flow cartridge, SO/sub 3/ gas is flowed through a chamber and incident normally to a catalyst coated tube extending through the chamber, the catalyst coated tube surrounding the heat pipe. In the axial-flow cartridge, SO/sub 3/ gas is flowed through the annular space between concentric inner and outer cylindrical walls, the inner cylindrical wall being coated by a catalyst and surrounding the heat pipe. The modular cartridge decomposer provides high thermal efficiency, high conversion efficiency, and increased safety. A fusion reactor may be used as the heat source.

Constraints on core-mantle boundary topography from models of thermal and thermochemical convection

NASA Astrophysics Data System (ADS)

Deschamps, Frédéric; Rogister, Yves; Tackley, Paul J.

2018-01-01

Mantle flow induces dynamic topography at the core-mantle boundary (CMB), with distribution and amplitude that depend on details of the flow. To assess whether observations of CMB topography can give constraints on deep mantle structure, we determine CMB dynamic topography associated with different models of mantle convection, including thermochemical and purely thermal models. We investigate the influence of key controlling parameters, specifically the thermal viscosity ratio (ΔηT) and, for thermochemical models, the density contrast (ΔρC) and viscosity ratio (ΔηC) between primordial and regular materials. In purely thermal models, plume clusters induce positive topography with an amplitude that decreases with increasing ΔηT. In thermochemical models with moderate density contrasts, around 100-200 kg m-3, reservoirs of dense material induce depressions in CMB topography, surrounded by a ridge of positive topography. The average depression depth and ridge height increase with increasing ΔρC and ΔηC, but decrease with increasing ΔηT. We find that for purely thermal models or thermochemical models with ΔρC ˜ 90 kg m-3 and less, the long-wavelength (spherical harmonic degrees up to l = 4) dynamic topography and shear wave velocity anomalies predicted by thermochemical distributions anticorrelate. By contrast, for models with ΔρC ≥ 100 kg m-3 and ΔηC > 1, long-wavelength dynamic topography and shear wave velocity anomalies correlate well. This potentially provides a test to infer the nature, that is, either purely or mostly thermal (ΔρC ≤ 100 kg m-3 m-3) or strongly thermochemical (ΔρC ≥ 100 kg m-3), of the low shear wave velocity provinces observed by global tomographic images. The presence of post-perovskite, provided that its viscosity is similar to that of bridgmanite, does not alter these conclusions.

Status of the DOE /STOR/-sponsored national program on hydrogen production from water via thermochemical cycles

NASA Technical Reports Server (NTRS)

Baker, C. E.

1977-01-01

A pure thermochemical cycle is a system of linked regenerative chemical reactions which accepts only water and heat and produces hydrogen. Thermochemical cycles are potentially a more efficient and cheaper means of producing hydrogen from water than is the generation of electricity followed by electrolysis. The Energy Storage Systems Division of the Department of Energy is currently funding a national program on thermochemical hydrogen production. The National Aeronautics and Space Administration is responsible for the technical management of this program. The goal is to develop a cycle which can potentially operate with an efficiency greater than 40% using a heat source providing a maximum available temperature of 1150 K. A closed bench-scale demonstration of such a cycle would follow. This cycle would be labeled a 'reference cycle' and would serve as a baseline against which future cycles would be compared.

Combination of biochar and poultry litter impact on soil properties and corn yield

USDA-ARS?s Scientific Manuscript database

Biochar, a by-product of a thermochemical process called pyrolysis, which involves burning of any agricultural and animal waste (biomass) under high temperature and absence of oxygen. It is assumed that since biochar is very high in aromatic carbon, which persists in soil environment for very long ...

Biochar as soil amendment to improve soil quality, crop yield, and carbon sequestration

USDA-ARS?s Scientific Manuscript database

Biochar, a by-product of a thermochemical process called pyrolysis, which involves burning of any agricultural and animal waste (biomass) under high temperature and absence of oxygen. It is assumed that since biochar is very high in aromatic carbon, which persists in soil environment for very long ...

High-temperature Y267 EPDM elastomer: field and laboratory experiences, August 1981

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

Hirasuna, A.R.; Friese, G.J.; Stephens, C.A.

1982-03-01

Experiences which indicate the superiority of Y267 EPDM elastomer for high-temperature brines and other environments uses are summarized. Its good processing qualities, extremely good thermochemical stability, extremely good mechanical properties, its low-cost constituents, and its good performance in hydrocarbons are described in some case histories. (MCW)

An MPI-CUDA approach for hypersonic flows with detailed state-to-state air kinetics using a GPU cluster

NASA Astrophysics Data System (ADS)

Bonelli, Francesco; Tuttafesta, Michele; Colonna, Gianpiero; Cutrone, Luigi; Pascazio, Giuseppe

2017-10-01

This paper describes the most advanced results obtained in the context of fluid dynamic simulations of high-enthalpy flows using detailed state-to-state air kinetics. Thermochemical non-equilibrium, typical of supersonic and hypersonic flows, was modeled by using both the accurate state-to-state approach and the multi-temperature model proposed by Park. The accuracy of the two thermochemical non-equilibrium models was assessed by comparing the results with experimental findings, showing better predictions provided by the state-to-state approach. To overcome the huge computational cost of the state-to-state model, a multiple-nodes GPU implementation, based on an MPI-CUDA approach, was employed and a comprehensive code performance analysis is presented. Both the pure MPI-CPU and the MPI-CUDA implementations exhibit excellent scalability performance. GPUs outperform CPUs computing especially when the state-to-state approach is employed, showing speed-ups, of the single GPU with respect to the single-core CPU, larger than 100 in both the case of one MPI process and multiple MPI process.

Overview of current biological and thermo-chemical treatment technologies for sustainable sludge management.

PubMed

Zhang, Linghong; Xu, Chunbao Charles; Champagne, Pascale; Mabee, Warren

2014-07-01

Sludge is a semi-solid residue produced from wastewater treatment processes. It contains biodegradable and recalcitrant organic compounds, as well as pathogens, heavy metals, and other inorganic constituents. Sludge can also be considered a source of nutrients and energy, which could be recovered using economically viable approaches. In the present paper, several commonly used sludge treatment processes including land application, composting, landfilling, anaerobic digestion, and combustion are reviewed, along with their potentials for energy and product recovery. In addition, some innovative thermo-chemical techniques in pyrolysis, gasification, liquefaction, and wet oxidation are briefly introduced. Finally, a brief summary of selected published works on the life cycle assessment of a variety of sludge treatment and end-use scenarios is presented in order to better understand the overall energy balance and environmental burdens associated with each sludge treatment pathway. In all scenarios investigated, the reuse of bioenergy and by-products has been shown to be of crucial importance in enhancing the overall energy efficiency and reducing the carbon footprint. © The Author(s) 2014.

Stochastic effects in a thermochemical system with Newtonian heat exchange.

PubMed

Nowakowski, B; Lemarchand, A

2001-12-01

We develop a mesoscopic description of stochastic effects in the Newtonian heat exchange between a diluted gas system and a thermostat. We explicitly study the homogeneous Semenov model involving a thermochemical reaction and neglecting consumption of reactants. The master equation includes a transition rate for the thermal transfer process, which is derived on the basis of the statistics for inelastic collisions between gas particles and walls of the thermostat. The main assumption is that the perturbation of the Maxwellian particle velocity distribution can be neglected. The transition function for the thermal process admits a continuous spectrum of temperature changes, and consequently, the master equation has a complicated integro-differential form. We perform Monte Carlo simulations based on this equation to study the stochastic effects in the Semenov system in the explosive regime. The dispersion of ignition times is calculated as a function of system size. For sufficiently small systems, the probability distribution of temperature displays transient bimodality during the ignition period. The results of the stochastic description are successfully compared with those of direct simulations of microscopic particle dynamics.

Studies of the use of heat from high temperature nuclear sources for hydrogen production processes

NASA Technical Reports Server (NTRS)

Farbman, G. H.

1976-01-01

Future uses of hydrogen and hydrogen production processes that can meet the demand for hydrogen in the coming decades were considered. To do this, a projection was made of the market for hydrogen through the year 2000. Four hydrogen production processes were selected, from among water electrolysis, fossil based and thermochemical water decomposition systems, and evaluated, using a consistent set of ground rules, in terms of relative performance, economics, resource requirements, and technology status.

Characterization of Products from Fast Micropyrolysis of Municipal Solid Waste Biomass

DOE PAGES

Klemetsrud, Bethany; Ukaew, Suchada; Thompson, Vicki S.; ...

2016-09-05

Biomass feedstock costs remain one of the largest impediments to biofuel production economics. Municipal solid waste (MSW) represents an attractive feedstock with year-round availability, an established collection infrastructure paid for by waste generators, low cost and the potential to be blended with higher cost feedstocks to reduce overall feedstock costs. Paper waste, yard waste and construction and demolition waste (C&D) were examined for their applicability in the pyrolysis conversion pathway. Paper waste consisted of non-recyclable paper such as mixed low grade paper, food and beverage packaging, kitchen paper wastes and coated paper; yard waste consisted of grass clippings and C&Dmore » wastes consisted of engineered wood products obtained from a construction waste landfill. We tested the waste materials for thermochemical conversion potential using a bench scale fast micro-pyrolysis process. Bio-oil yields were the highest for the C&D materials and lowest for the paper waste. The C&D wastes had the highest level of lignin derived compounds (phenolic and cyclics) while the paper waste had higher levels of carbohydrate derived compounds (aldehydes, organic acids, ketones, alcohols and sugar derived). But, the paper material had higher amounts of lignin derived compounds than expected based upon lignin content that is likely due to the presence of polyphenolic resins used in paper processing. The paper and yard wastes had significantly higher levels of ash content than the C&D wastes (14-15% versus 0.5-1.3%), which further correlated to higher levels of alkali and alkaline earth metals, which are known to reduce pyrolysis bio-oil yields. There appeared to be an inverse correlation of both calcium and potassium content with the amount of chromatographic product peaks, indicative of cracking reactions occurring during product formation. Furthermore the effect of acid washing was evaluated for grass clipping and waste paper and the bio-oil yield was increased from 58% to 73% and 67% to 73%, respectively.« less

Characterization of Products from Fast Micropyrolysis of Municipal Solid Waste Biomass

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

Klemetsrud, Bethany; Ukaew, Suchada; Thompson, Vicki S.

Biomass feedstock costs remain one of the largest impediments to biofuel production economics. Municipal solid waste (MSW) represents an attractive feedstock with year-round availability, an established collection infrastructure paid for by waste generators, low cost and the potential to be blended with higher cost feedstocks to reduce overall feedstock costs. Paper waste, yard waste and construction and demolition waste (C&D) were examined for their applicability in the pyrolysis conversion pathway. Paper waste consisted of non-recyclable paper such as mixed low grade paper, food and beverage packaging, kitchen paper wastes and coated paper; yard waste consisted of grass clippings and C&Dmore » wastes consisted of engineered wood products obtained from a construction waste landfill. We tested the waste materials for thermochemical conversion potential using a bench scale fast micro-pyrolysis process. Bio-oil yields were the highest for the C&D materials and lowest for the paper waste. The C&D wastes had the highest level of lignin derived compounds (phenolic and cyclics) while the paper waste had higher levels of carbohydrate derived compounds (aldehydes, organic acids, ketones, alcohols and sugar derived). But, the paper material had higher amounts of lignin derived compounds than expected based upon lignin content that is likely due to the presence of polyphenolic resins used in paper processing. The paper and yard wastes had significantly higher levels of ash content than the C&D wastes (14-15% versus 0.5-1.3%), which further correlated to higher levels of alkali and alkaline earth metals, which are known to reduce pyrolysis bio-oil yields. There appeared to be an inverse correlation of both calcium and potassium content with the amount of chromatographic product peaks, indicative of cracking reactions occurring during product formation. Furthermore the effect of acid washing was evaluated for grass clipping and waste paper and the bio-oil yield was increased from 58% to 73% and 67% to 73%, respectively.« less

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

Rao, C.N.R., E-mail: cnrrao@jncasr.ac.in; Dey, Sunita

Generation of H{sub 2} and CO by splitting H{sub 2}O and CO{sub 2} respectively constitutes an important aspect of the present-day concerns with energy and environment. The solar thermochemical route making use of metal oxides is a viable means of accomplishing these reduction reactions. The method essentially involves reducing a metal oxide by heating and passing H{sub 2}O or CO{sub 2} over the nonstoichiometric oxide to cause reverse oxidation by abstracting oxygen from H{sub 2}O or CO{sub 2}. While ceria, perovskites and other oxides have been investigated for this purpose, recent studies have demonstrated the superior performance of perovskites ofmore » the type Ln{sub 1−x}A{sub x}Mn{sub 1−y}M{sub y}O{sub 3} (Ln=rare earth, A=alkaline earth, M=various +2 and +3 metal ions), in the thermochemical generation of H{sub 2} and CO. We present the important results obtained hitherto to point out how the alkaine earth and the Ln ions, specially the radius of the latter, determine the performance of the perovskites. The encouraging results obtained are exemplefied by Y{sub 0.5}Sr{sub 0.5}MnO{sub 3} which releases 483 µmol/g of O{sub 2} at 1673 K and produces 757 µmol/g of CO from CO{sub 2} at 1173 K. The production of H{sub 2} from H{sub 2}O is also quite appreciable. Modification of the B site ion of the perovskite also affects the performance. In addition to perovskites, we present the generation of H{sub 2} based on the Mn{sub 3}O{sub 4}/NaMnO{sub 2} cycle briefly. - Graphical abstract: Ln{sub 0.5}A{sub 0.5}Mn{sub 1−x}M{sub x}O{sub 3} (Ln=lanthanide; A=Ca, Sr; M=Al, Ga, Sc, Mg, Cr, Fe, Co) perovskites are employed for the two step thermochemical splitting of CO{sub 2} and H{sub 2}O for the generation of CO and H{sub 2}. - Highlights: • Perovskite oxides based on Mn are ideal for the two-step thermochemical splitting of CO{sub 2} and H{sub 2}O. • In Ln{sub 1−x}A{sub x}MnO{sub 3} perovskite (Ln=rare earth, A=alkaline earth) both Ln and A ions play major roles in the thermochemical process. • H{sub 2}O splitting is also achieved by the use of the Mn{sub 3}O{sub 4}-sodium carbonate system. • Thermochemical splitting of CO{sub 2} and H{sub 2}O using perovskite oxides is explained. • Mn based perovskites.« less

Thermochemical factors affecting the dehalogenation of aromatics.

PubMed

Sadowsky, Daniel; McNeill, Kristopher; Cramer, Christopher J

2013-12-17

Halogenated aromatics are one of the largest chemical classes of environmental contaminants, and dehalogenation remains one of the most important processes by which these compounds are degraded and detoxified. The thermodynamic constraints of aromatic dehalogenation reactions are thus important for understanding the feasibility of such reactions and the redox conditions necessary for promoting them. Accordingly, the thermochemical properties of the (poly)fluoro-, (poly)chloro-, and (poly)bromobenzenes, including standard enthalpies of formation, bond dissociation enthalpies, free energies of reaction, and the redox potentials of Ar-X/Ar-H couples, were investigated using a validated density functional protocol combined with continuum solvation calculations when appropriate. The results highlight the fact that fluorinated aromatics stand distinct from their chloro- and bromo- counterparts in terms of both their relative thermodynamic stability toward dehalogenation and how different substitution patterns give rise to relevant properties, such as bond strengths and reduction potentials.

Review of the Two-Step H2O/CO2-Splitting Solar Thermochemical Cycle Based on Zn/ZnO Redox Reactions

PubMed Central

Loutzenhiser, Peter G.; Meier, Anton; Steinfeld, Aldo

2010-01-01

This article provides a comprehensive overview of the work to date on the two‑step solar H2O and/or CO2 splitting thermochemical cycles with Zn/ZnO redox reactions to produce H2 and/or CO, i.e., synthesis gas—the precursor to renewable liquid hydrocarbon fuels. The two-step cycle encompasses: (1) The endothermic dissociation of ZnO to Zn and O2 using concentrated solar energy as the source for high-temperature process heat; and (2) the non-solar exothermic oxidation of Zn with H2O/CO2 to generate H2/CO, respectively; the resulting ZnO is then recycled to the first step. An outline of the underlying science and the technological advances in solar reactor engineering is provided along with life cycle and economic analyses. PMID:28883361

Assessment of relative flammability and thermochemical properties of some thermoplastic materials

NASA Technical Reports Server (NTRS)

Kourtides, D. A.; Parker, J. A.

1978-01-01

The thermochemical and flammability characteristics of some typical thermoplastic materials currently in use and others being considered for use in aircraft interiors are described. The properties studied included (1) thermal mechanical properties such as glass transition and melt temperature, (2) changes in polymer enthalpy by differential scanning calorimetry, (3) thermogravimetric analysis in an anaerobic and oxidative environment, (4) oxygen index, (5) smoke evolution, (6) relative toxicity of the volatile products of pyrolysis, and (7) selected physical properties. The generic polymers which were evaluated included: acrylonitrile-butadiene-styrene, bisphenol A polycarbonate, bisphenol fluorenone carbonatedimethylsiloxane block polymer, phenolphthalein-bisphenol A polycarbonate, phenolphthalein polycarbonate, polyether sulfone, polyphenylene oxide, polyphenylene sulfide, polyaryl sulfone, chlorinated polyvinyl chloride homopolymer, polyvinyl fluoride, and polyvinylidene fluoride. Processing parameters including molding characteristics of some of the advanced polymers are described. Test results and relative rankings of some of the flammability, smoke and toxicity properties are presented.

Multi-step approach for comparing the local air pollution contributions of conventional and innovative MSW thermo-chemical treatments.

PubMed

Ragazzi, M; Rada, E C

2012-10-01

In the sector of municipal solid waste management the debate on the performances of conventional and novel thermo-chemical technologies is still relevant. When a plant must be constructed, decision makers often select a technology prior to analyzing the local environmental impact of the available options, as this type of study is generally developed when the design of the plant has been carried out. Additionally, in the literature there is a lack of comparative analyses of the contributions to local air pollution from different technologies. The present study offers a multi-step approach, based on pollutant emission factors and atmospheric dilution coefficients, for a local comparative analysis. With this approach it is possible to check if some assumptions related to the advantages of the novel thermochemical technologies, in terms of local direct impact on air quality, can be applied to municipal solid waste treatment. The selected processes concern combustion, gasification and pyrolysis, alone or in combination. The pollutants considered are both carcinogenic and non-carcinogenic. A case study is presented concerning the location of a plant in an alpine region and its contribution to the local air pollution. Results show that differences among technologies are less than expected. Performances of each technology are discussed in details. Copyright © 2012 Elsevier Ltd. All rights reserved.

Perspectives of advanced thermal management in solar thermochemical syngas production using a counter-flow solid-solid heat exchanger

NASA Astrophysics Data System (ADS)

Falter, Christoph; Sizmann, Andreas; Pitz-Paal, Robert

2017-06-01

A modular reactor model is presented for the description of solar thermochemical syngas production involving counter-flow heat exchangers that recuperate heat from the solid phase. The development of the model is described including heat diffusion within the reactive material as it travels through the heat exchanger, which was previously identified to be a possibly limiting factor in heat exchanger design. Heat transfer within the reactive medium is described by conduction and radiation, where the former is modeled with the three-resistor model and the latter with the Rosseland diffusion approximation. The applicability of the model is shown by the analysis of heat exchanger efficiency for different material thicknesses and porosities in a system with 8 chambers and oxidation and reduction temperatures of 1000 K and 1800 K, respectively. Heat exchanger efficiency is found to rise strongly for a reduction of material thickness, as the element mass is reduced and a larger part of the elements takes part in the heat exchange process. An increase of porosity enhances radiation heat exchange but deteriorates conduction. The overall heat exchange in the material is improved for high temperatures in the heat exchanger, as radiation dominates the energy transfer. The model is shown to be a valuable tool for the development and analysis of solar thermochemical reactor concepts involving heat exchange from the solid phase.

Biological Hydrogen Production: Simultaneous Saccharification and Fermentation With Nitrogen and Phosphorus Removal from Wastewater Effluent

DTIC Science & Technology

2010-01-01

requiring thermochemical pretreatment , aswould typically be required with lignocellulosic feedstocks. Therefore it offers a readily-processed and...Standards and Technology. The pH of the reactors was controlled throughout all fermentations by the automatic addition of 0.1 N NaOH . Total organic...nutrients. The optimized conditions developed with paper as a substrate may also convey to the use of a similar process with lignocellulosic biomass

Application of thermochemical modeling to aircraft interior polymeric materials

DOT National Transportation Integrated Search

1982-06-01

This report summarizes the results from a twelve-month study of the feasibility of applying certain basic concepts in the thermochemical modeling to aircraft cabin fire safety. The concepts developed earlier on a NASA-sponsored program were applied t...

Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles

NASA Astrophysics Data System (ADS)

Lany, Stephan

2018-02-01

The ideal material for solar thermochemical water splitting, which has yet to be discovered, must satisfy stringent conditions for the free energy of reduction, including, in particular, a sufficiently large positive contribution from the solid-state entropy. By inverting the commonly used relationship between defect formation energy and defect concentration, it is shown here that charged defect formation causes a large electronic entropy contribution manifesting itself as the temperature dependence of the Fermi level. This result is a general feature of charged defect formation and motivates new materials design principles for solar thermochemical hydrogen production.

Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles

DOE PAGES

Lany, Stephan

2018-02-21

The ideal material for solar thermochemical water splitting, which has yet to be discovered, must satisfy stringent conditions for the free energy of reduction, including, in particular, a sufficiently large positive contribution from the solid-state entropy. By inverting the commonly used relationship between defect formation energy and defect concentration, it is shown here that charged defect formation causes a large electronic entropy contribution manifesting itself as the temperature dependence of the Fermi level. This result is a general feature of charged defect formation and motivates new materials design principles for solar thermochemical hydrogen production.

Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles

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

Lany, Stephan

The ideal material for solar thermochemical water splitting, which has yet to be discovered, must satisfy stringent conditions for the free energy of reduction, including, in particular, a sufficiently large positive contribution from the solid-state entropy. By inverting the commonly used relationship between defect formation energy and defect concentration, it is shown here that charged defect formation causes a large electronic entropy contribution manifesting itself as the temperature dependence of the Fermi level. This result is a general feature of charged defect formation and motivates new materials design principles for solar thermochemical hydrogen production.

Experimental validation of thermo-chemical algorithm for a simulation of pultrusion processes

NASA Astrophysics Data System (ADS)

Barkanov, E.; Akishin, P.; Miazza, N. L.; Galvez, S.; Pantelelis, N.

2018-04-01

To provide better understanding of the pultrusion processes without or with temperature control and to support the pultrusion tooling design, an algorithm based on the mixed time integration scheme and nodal control volumes method has been developed. At present study its experimental validation is carried out by the developed cure sensors measuring the electrical resistivity and temperature on the profile surface. By this verification process the set of initial data used for a simulation of the pultrusion process with rod profile has been successfully corrected and finally defined.

Carbonate thermochemical cycle for the production of hydrogen

DOEpatents

Collins, Jack L [Knoxville, TN; Dole, Leslie R [Knoxville, TN; Ferrada, Juan J [Knoxville, TN; Forsberg, Charles W [Oak Ridge, TN; Haire, Marvin J [Oak Ridge, TN; Hunt, Rodney D [Oak Ridge, TN; Lewis, Jr, Benjamin E [Knoxville, TN; Wymer, Raymond G [Oak Ridge, TN

2010-02-23

The present invention is directed to a thermochemical method for the production of hydrogen from water. The method includes reacting a multi-valent metal oxide, water and a carbonate to produce an alkali metal-multi-valent metal oxide compound, carbon dioxide, and hydrogen.

Strengths, challenges, and opportunities for hydrothermal pretreatment in lignocellulosic biorefineries

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

Yang, Bin; Tao, Ling; Wyman, Charles E.

Pretreatment prior to or during biological conversion is required to achieve high sugar yields essential to economic production of fuels and chemicals from low cost, abundant lignocellulosic biomass. Aqueous thermochemical pretreatments achieve this performance objective from pretreatment coupled with subsequent enzymatic hydrolysis, but chemical pretreatment can also suffer from additional costs for exotic materials of construction, the need to recover or neutralize the chemicals, introduction of compounds that inhibit downstream operations, and waste disposal, as well as for the chemicals themselves. The simplicity of hydrothermal pretreatment with just hot water offers the potential to greatly improve the cost of themore » entire conversion process if sugar degradation during pretreatment, production of un-fermentable oligomers, and the amount of expensive enzymes needed to obtain satisfactory yields from hydrothermally pretreated solids can be reduced. Biorefinery economics would also benefit if value could be generated from lignin and other components that are currently fated to be burned for power. However, achieving these goals will no doubt require development of advanced hydrothermal pretreatment configurations. For example, passing water through a stationary bed of lignocellulosic biomass in a flowthrough configuration achieves very high yields of hemicellulose sugars, removes more than 75% of the lignin for potential valorization, and improves sugar release from the pretreated solids with lower enzyme loadings. Unfortunately, the large quantities of water needed to achieve this performance result in very dilute sugars, high energy costs for pretreatment and product recover, and large amounts of oligomers. Furthermore, improving our understanding of hydrothermal pretreatment fundamentals is needed to gain insights into R&D opportunities to improve performance, and help identify novel configurations that lower capital and operating costs and achieve higher yields.« less

Strengths, challenges, and opportunities for hydrothermal pretreatment in lignocellulosic biorefineries

DOE PAGES

Yang, Bin; Tao, Ling; Wyman, Charles E.

2017-10-11

Pretreatment prior to or during biological conversion is required to achieve high sugar yields essential to economic production of fuels and chemicals from low cost, abundant lignocellulosic biomass. Aqueous thermochemical pretreatments achieve this performance objective from pretreatment coupled with subsequent enzymatic hydrolysis, but chemical pretreatment can also suffer from additional costs for exotic materials of construction, the need to recover or neutralize the chemicals, introduction of compounds that inhibit downstream operations, and waste disposal, as well as for the chemicals themselves. The simplicity of hydrothermal pretreatment with just hot water offers the potential to greatly improve the cost of themore » entire conversion process if sugar degradation during pretreatment, production of un-fermentable oligomers, and the amount of expensive enzymes needed to obtain satisfactory yields from hydrothermally pretreated solids can be reduced. Biorefinery economics would also benefit if value could be generated from lignin and other components that are currently fated to be burned for power. However, achieving these goals will no doubt require development of advanced hydrothermal pretreatment configurations. For example, passing water through a stationary bed of lignocellulosic biomass in a flowthrough configuration achieves very high yields of hemicellulose sugars, removes more than 75% of the lignin for potential valorization, and improves sugar release from the pretreated solids with lower enzyme loadings. Unfortunately, the large quantities of water needed to achieve this performance result in very dilute sugars, high energy costs for pretreatment and product recover, and large amounts of oligomers. Furthermore, improving our understanding of hydrothermal pretreatment fundamentals is needed to gain insights into R&D opportunities to improve performance, and help identify novel configurations that lower capital and operating costs and achieve higher yields.« less

Third millenium ideal gas and condensed phase thermochemical database for combustion (with update from active thermochemical tables).

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

Burcat, A.; Ruscic, B.; Chemistry

2005-07-29

The thermochemical database of species involved in combustion processes is and has been available for free use for over 25 years. It was first published in print in 1984, approximately 8 years after it was first assembled, and contained 215 species at the time. This is the 7th printed edition and most likely will be the last one in print in the present format, which involves substantial manual labor. The database currently contains more than 1300 species, specifically organic molecules and radicals, but also inorganic species connected to combustion and air pollution. Since 1991 this database is freely available onmore » the internet, at the Technion-IIT ftp server, and it is continuously expanded and corrected. The database is mirrored daily at an official mirror site, and at random at about a dozen unofficial mirror and 'finger' sites. The present edition contains numerous corrections and many recalculations of data of provisory type by the G3//B3LYP method, a high-accuracy composite ab initio calculation. About 300 species are newly calculated and are not yet published elsewhere. In anticipation of the full coupling, which is under development, the database started incorporating the available (as yet unpublished) values from Active Thermochemical Tables. The electronic version now also contains an XML file of the main database to allow transfer to other formats and ease finding specific information of interest. The database is used by scientists, educators, engineers and students at all levels, dealing primarily with combustion and air pollution, jet engines, rocket propulsion, fireworks, but also by researchers involved in upper atmosphere kinetics, astrophysics, abrasion metallurgy, etc. This introductory article contains explanations of the database and the means to use it, its sources, ways of calculation, and assessments of the accuracy of data.« less

Thermochemical Process Integration, Scale-Up, and Piloting Publications |

Science.gov Websites

-Economic Assessment of Ex Situ Catalytic Fast Pyrolysis of Biomass: A Fixed Bed Reactor Implementation Scenario for Future Feasibility, Topics in Catalysis Image of a schematic of hot gas filter and ex situ Research Pathways with In Situ and Ex Situ Upgrading of Fast Pyrolysis Vapors, NREL Technical Report Image

Method for Biochar Passivation Using Low Percent Oxygen

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

Smith, Kristin; Dupuis, Dan; Wilcox, Esther

2016-06-06

The thermochemical process development unit may be configured for pyrolysis or gasification. The pyrolysis unit operations include: feed transport system; entrained flow reactor; solids removal and collection; and liquid scrubbing, collection, and filtration. Char accumulates in the collection drums at a rate of ~1.5 kg/hr and must be passivated before it is stored or transported.

Physical Vapor Transport of Lead Telluride

NASA Technical Reports Server (NTRS)

Palosz, W.

1997-01-01

Mass transport properties of physical vapor transport of PbTe are investigated. Thermochemical analysis of the system and its implications for the growth conditions are discussed. The effect of the material preparation and pre-processing on the stoichiometry and residual gas pressure and composition, and on related mass flux is shown. A procedure leading to high mass transport rates is presented.

Thermochemical Process Integration, Scale-Up, and Piloting | Bioenergy |

Science.gov Websites

; represented by spheres of hydrogen and carbon monoxide, then to "Gas Cleanup, Solids Removal, Reforming ; represented by a gasoline dispenser nozzle. A green arrow of "Fast Pyrolysis" and blue arrows for Distillation," and finally to "Fuels," represented by a gasoline dispenser nozzle Variety of

Intro to NREL's Thermochemical Pilot Plant

ScienceCinema

Magrini, Kim

2018-02-13

NREL's Thermochemical Pilot Plant converts biomass into higher hydrocarbon fuels and chemicals.NREL is researching biomass pyrolysis. The lab is examining how to upgrade bio-oils via stabilization. Along with this, NREL is developing the engineering system requirements for producing these fuels and chemicals at larger scales.

Solar photothermochemical alkane reverse combustion

PubMed Central

Chanmanee, Wilaiwan; Islam, Mohammad Fakrul; Dennis, Brian H.; MacDonnell, Frederick M.

2016-01-01

A one-step, gas-phase photothermocatalytic process for the synthesis of hydrocarbons, including liquid alkanes, aromatics, and oxygenates, with carbon numbers (Cn) up to C13, from CO2 and water is demonstrated in a flow photoreactor operating at elevated temperatures (180–200 °C) and pressures (1–6 bar) using a 5% cobalt on TiO2 catalyst and under UV irradiation. A parametric study of temperature, pressure, and partial pressure ratio revealed that temperatures in excess of 160 °C are needed to obtain the higher Cn products in quantity and that the product distribution shifts toward higher Cn products with increasing pressure. In the best run so far, over 13% by mass of the products were C5+ hydrocarbons and some of these, i.e., octane, are drop-in replacements for existing liquid hydrocarbons fuels. Dioxygen was detected in yields ranging between 64% and 150%. In principle, this tandem photochemical–thermochemical process, fitted with a photocatalyst better matched to the solar spectrum, could provide a cheap and direct method to produce liquid hydrocarbons from CO2 and water via a solar process which uses concentrated sunlight for both photochemical excitation to generate high-energy intermediates and heat to drive important thermochemical carbon-chain-forming reactions. PMID:26903631

Modeling of the steam hydrolysis in a two-step process for hydrogen production by solar concentrated energy

NASA Astrophysics Data System (ADS)

Valle-Hernández, Julio; Romero-Paredes, Hernando; Pacheco-Reyes, Alejandro

2017-06-01

In this paper the simulation of the steam hydrolysis for hydrogen production through the decomposition of cerium oxide is presented. The thermochemical cycle for hydrogen production consists of the endothermic reduction of CeO2 to lower-valence cerium oxide, at high temperature, where concentrated solar energy is used as a source of heat; and of the subsequent steam hydrolysis of the resulting cerium oxide to produce hydrogen. The modeling of endothermic reduction step was presented at the Solar Paces 2015. This work shows the modeling of the exothermic step; the hydrolysis of the cerium oxide (III) to form H2 and the corresponding initial cerium oxide made at lower temperature inside the solar reactor. For this model, three sections of the pipe where the reaction occurs were considered; the steam water inlet, the porous medium and the hydrogen outlet produced. The mathematical model describes the fluid mechanics; mass and energy transfer occurring therein inside the tungsten pipe. Thermochemical process model was simulated in CFD. The results show a temperature distribution in the solar reaction pipe and allow obtaining the fluid dynamics and the heat transfer within the pipe. This work is part of the project "Solar Fuels and Industrial Processes" from the Mexican Center for Innovation in Solar Energy (CEMIE-Sol).

Direct reduction processes for titanium oxide in molten salt

NASA Astrophysics Data System (ADS)

Suzuki, Ryosuke O.

2007-02-01

Molten salt electrolysis using CaCl2 is employed to produce pure titanium and its alloys directly from TiO2 and a mixture of elemental oxides, respectively, as an alternate to the Kroll process. This is because CaO, which is a reduction by-product, is highly soluble in CaCl2. Good-quality titanium containing only a small amount of residual oxygen has been successfully produced and scaled to industrial levels. Thermochemical and electrochemical bases are reviewed to optimize the process conditions. Several processes using molten salt are being examined for future progress in titanium processing.

Environmental, Economic, and Scalability Considerations and Trends of Selected Fuel Economy-Enhancing Biomass-Derived Blendstocks

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

Dunn, Jennifer B.; Biddy, Mary; Jones, Susanne

Twenty-four biomass-derived compounds and mixtures, identified based on their physical properties, which could be blended into fuels to improve spark ignition engine fuel economy, were assessed for their economic, technology readiness, and environmental viability. These bio-blendstocks were modeled to be produced biochemically, thermochemically, or through hybrid processes. To carry out the assessment, 17 metrics were developed for which each bio-blendstock was determined to be favorable, neutral, or unfavorable. Cellulosic ethanol was included as a reference case. Overall economic and, to some extent, environmental viability is driven by projected yields for each of these processes. The metrics used in this analysismore » methodology highlight the near-term potential to achieve these targeted yield estimates when considering data quality and current technical readiness for these conversion strategies. Key knowledge gaps included the degree of purity needed for use as a bio-blendstock. Less stringent purification requirements for fuels could cut processing costs and environmental impacts. Additionally, more information is needed on the blending behavior of many of these bio-blendstocks with gasoline to support the technology readiness evaluation. Altogether, the technology to produce many of these blendstocks from biomass is emerging, and as it matures, these assessments must be revisited. Importantly, considering economic, environmental, and technology readiness factors, in addition to physical properties of blendstocks that could be used to boost engine efficiency and fuel economy, in the early stages of project research and development can help spotlight those most likely to be viable in the near term.« less

Environmental, Economic, and Scalability Considerations and Trends of Selected Fuel Economy-Enhancing Biomass-Derived Blendstocks

DOE PAGES

Dunn, Jennifer B.; Biddy, Mary; Jones, Susanne; ...

2017-10-30

Twenty-four biomass-derived compounds and mixtures, identified based on their physical properties, which could be blended into fuels to improve spark ignition engine fuel economy, were assessed for their economic, technology readiness, and environmental viability. These bio-blendstocks were modeled to be produced biochemically, thermochemically, or through hybrid processes. To carry out the assessment, 17 metrics were developed for which each bio-blendstock was determined to be favorable, neutral, or unfavorable. Cellulosic ethanol was included as a reference case. Overall economic and, to some extent, environmental viability is driven by projected yields for each of these processes. The metrics used in this analysismore » methodology highlight the near-term potential to achieve these targeted yield estimates when considering data quality and current technical readiness for these conversion strategies. Key knowledge gaps included the degree of purity needed for use as a bio-blendstock. Less stringent purification requirements for fuels could cut processing costs and environmental impacts. Additionally, more information is needed on the blending behavior of many of these bio-blendstocks with gasoline to support the technology readiness evaluation. Altogether, the technology to produce many of these blendstocks from biomass is emerging, and as it matures, these assessments must be revisited. Importantly, considering economic, environmental, and technology readiness factors, in addition to physical properties of blendstocks that could be used to boost engine efficiency and fuel economy, in the early stages of project research and development can help spotlight those most likely to be viable in the near term.« less

Environmental, Economic, and Scalability Considerations and Trends of Selected Fuel Economy-Enhancing Biomass-Derived Blendstocks

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

Dunn, Jennifer B.; Biddy, Mary; Jones, Susanne

24 biomass-derived compounds and mixtures, identified based on their physical properties, that could be blended into fuels to improve spark ignition engine fuel economy were assessed for their economic, technology readiness, and environmental viability. These bio-blendstocks were modeled to be produced biochemically, thermochemically, or through hybrid processes. To carry out the assessment, 17 metrics were developed for which each bio-blendstock was determined to be favorable, neutral, or unfavorable. Cellulosic ethanol was included as a reference case. Overall, bio-blendstock yields in biochemical processes were lower than in thermochemical processes, in which all biomass, including lignin, is converted to a product. Bio-blendstockmore » yields were a key determinant in overall viability. Key knowledge gaps included the degree of purity needed for use as a bio-blendstock as compared to a chemical. Less stringent purification requirements for fuels could cut processing costs and environmental impacts. Additionally, more information is needed on the blendability of many of these bio-blendstocks with gasoline to support the technology readiness evaluation. Overall, the technology to produce many of these blendstocks from biomass is emerging and as it matures, these assessments must be revisited. Importantly, considering economic, environmental, and technology readiness factors in addition to physical properties of blendstocks that could be used to boost fuel economy can help spotlight those most likely to be viable in the near term.« less

Approximate thermochemical tables for some C-H and C-H-O species

NASA Technical Reports Server (NTRS)

Bahn, G. S.

1973-01-01

Approximate thermochemical tables are presented for some C-H and C-H-O species and for some ionized species, supplementing the JANAF Thermochemical Tables for application to finite-chemical-kinetics calculations. The approximate tables were prepared by interpolation and extrapolation of limited available data, especially by interpolations over chemical families of species. Original estimations have been smoothed by use of a modification for the CDC-6600 computer of the Lewis Research Center PACl Program which was originally prepared for the IBM-7094 computer Summary graphs for various families show reasonably consistent curvefit values, anchored by properties of existing species in the JANAF tables.

Analysis of thermo-chemical nonequilibrium models for carbon dioxide flows

NASA Technical Reports Server (NTRS)

Rock, Stacey G.; Candler, Graham V.; Hornung, Hans G.

1992-01-01

The aerothermodynamics of thermochemical nonequilibrium carbon dioxide flows is studied. The chemical kinetics models of McKenzie and Park are implemented in separate three-dimensional computational fluid dynamics codes. The codes incorporate a five-species gas model characterized by a translational-rotational and a vibrational temperature. Solutions are obtained for flow over finite length elliptical and circular cylinders. The computed flowfields are then employed to calculate Mach-Zehnder interferograms for comparison with experimental data. The accuracy of the chemical kinetics models is determined through this comparison. Also, the methodology of the three-dimensional thermochemical nonequilibrium code is verified by the reproduction of the experiments.

An Overview of Natural Gas Conversion Technologies for Co-Production of Hydrogen and Value-Added Solid Carbon Products

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

Dagle, Robert A.; Dagle, Vanessa; Bearden, Mark D.

This report was prepared in response to the U.S. Department of Energy Fuel Cell Technologies Office Congressional Appropriation language to support research on carbon-free production of hydrogen using new chemical processes that utilize natural gas to produce solid carbon and hydrogen. The U.S. produces 9-10 million tons of hydrogen annually with more than 95% of the hydrogen produced by steam-methane reforming (SMR) of natural gas. SMR is attractive because of its high hydrogen yield; but it also converts the carbon to carbon dioxide. Non-oxidative thermal decomposition of methane to carbon and hydrogen is an alternative to SMR and produces COmore » 2-free hydrogen. The produced carbon can be sold as a co-product, thus providing economic credit that reduces the delivered net cost of hydrogen. The combination of producing hydrogen with potentially valuable carbon byproducts has market value in that this allows greater flexibility to match the market prices of hydrogen and carbon. That is, the higher value product can subsidize the other in pricing decisions. In this report we highlight the relevant technologies reported in the literature—primarily thermochemical and plasma conversion processes—and recent research progress and commercial activities. Longstanding technical challenges include the high energetic requirements (e.g., high temperatures and/or electricity requirements) necessary for methane activation and, for some catalytic processes, the separation of solid carbon product from the spent catalyst. We assess current and new carbon product markets that could be served given technological advances, and we discuss technical barriers and potential areas of research to address these needs. We provide preliminary economic analysis for these processes and compare to other emerging (e.g., electrolysis) and conventional (e.g., SMR) processes for hydrogen production. The overarching conclusion of this study is that the cost of hydrogen can be potentially reduced to target levels of $2/kg with the co-production and sale of a sufficiently high-value carbon product. Technological advances are required to understand the reaction conditions and design reactor systems that can achieve high yields of the select carbon products and segregate or separate the high-value carbon products, and optimize the production process for both hydrogen and carbon.« less

Thermochemical CO2 splitting via redox cycling of ceria reticulated foam structures with dual-scale porosities.

PubMed

Furler, Philipp; Scheffe, Jonathan; Marxer, Daniel; Gorbar, Michal; Bonk, Alexander; Vogt, Ulrich; Steinfeld, Aldo

2014-06-14

Efficient heat transfer of concentrated solar energy and rapid chemical kinetics are desired characteristics of solar thermochemical redox cycles for splitting CO2. We have fabricated reticulated porous ceramic (foam-type) structures made of ceria with dual-scale porosity in the millimeter and micrometer ranges. The larger void size range, with dmean = 2.5 mm and porosity = 0.76-0.82, enables volumetric absorption of concentrated solar radiation for efficient heat transfer to the reaction site during endothermic reduction, while the smaller void size range within the struts, with dmean = 10 μm and strut porosity = 0-0.44, increases the specific surface area for enhanced reaction kinetics during exothermic oxidation with CO2. Characterization is performed via mercury intrusion porosimetry, scanning electron microscopy, and thermogravimetric analysis (TGA). Samples are thermally reduced at 1773 K and subsequently oxidized with CO2 at temperatures in the range 873-1273 K. On average, CO production rates are ten times higher for samples with 0.44 strut porosity than for samples with non-porous struts. The oxidation rate scales with specific surface area and the apparent activation energy ranges from 90 to 135.7 kJ mol(-1). Twenty consecutive redox cycles exhibited stable CO production yield per cycle. Testing of the dual-scale RPC in a solar cavity-receiver exposed to high-flux thermal radiation (3.8 kW radiative power at 3015 suns) corroborated the superior performance observed in the TGA, yielding a shorter cycle time and a mean solar-to-fuel energy conversion efficiency of 1.72%.

On the thermo-chemical origin of the stratified region at the top of the Earth's core

NASA Astrophysics Data System (ADS)

Nakagawa, Takashi

2018-03-01

I developed a combined model of the thermal and chemical evolution of the Earth's core and investigated its influence on a thermochemically stable region beneath the core-mantle boundary (CMB). The chemical effects of the growing stable region are caused by the equilibrium chemical reaction between silicate and the metallic core. The thermal effects can be characterized by the growth of the sub-isentropic shell, which may have a rapid growth rate compared to that of the chemically stable region. When the present-day CMB heat flow was varied, the origin of the stable region changed from chemical to thermochemical to purely thermal because the rapid growth of the sub-isentropic shell can replace the chemically stable region. Physically reasonable values of the present-day CMB heat flow that can maintain the geodynamo action over 4 billion years should be between 8 and 11 TW. To constrain the thickness of the thermochemically stable region beneath the CMB, the chemical diffusivity is important and should be ∼O(10-8) m2/s to obtain a thickness of the thermochemically stable region beneath the CMB consistent with that inferred from geomagnetic secular variations (140 km). However, the strength of the stable region found in this study is too high to be consistent with the constraint on the stability of the stable region inferred from geomagnetic secular variations.

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

Udengaard, Niels; Knight, Richard; Wendt, Jesper

This final report presents the results of a four-year technology demonstration project carried out by a consortium of companies sponsored in part by a $25 million funding by the Department of Energy (DOE) under the American Recovery and Reinvestment Act (ARRA). The purpose of the project was to demonstrate a new, economical technology for the thermochemical conversion of woody biomass into gasoline and to demonstrate that the gasoline produced in this way is suitable for direct inclusion in the already existing gasoline pool. The process that was demonstrated uses the Andritz-Carbona fluidized-bed steam-oxygen gasification technology and advanced tar reforming catalyticmore » systems to produce a clean syngas from waste wood, integrated conventional gas cleanup steps, and finally utilizes Haldor Topsoe’s (Topsoe) innovative Topsoe Improved Gasoline Synthesis (TIGASTM) syngas-to-gasoline process. Gas Technology Institute (GTI) carried out the bulk of the testing work at their Flex Fuel development facility in Des Plaines, Illinois; UPM in Minnesota supplied and prepared the feedstocks, and characterization of liquid products was conducted in Phillips 66 labs in Oklahoma. The produced gasoline was used for a single-engine emission test at Southwest Research Institute (SwRI®) in San Antonio, TX, as well as in a fleet test at Transportation Research Center, Inc. (TRC Inc.) in East Liberty, Ohio. The project benefited from the use of existing pilot plant equipment at GTI, including a 21.6 bone dry short ton/day gasifier, tar reformer, Morphysorb® acid gas removal, associated syngas cleanup and gasifier feeding and oxygen systems.« less

A steady state model of agricultural waste pyrolysis: A mini review.

PubMed

Trninić, M; Jovović, A; Stojiljković, D

2016-09-01

Agricultural waste is one of the main renewable energy resources available, especially in an agricultural country such as Serbia. Pyrolysis has already been considered as an attractive alternative for disposal of agricultural waste, since the technique can convert this special biomass resource into granular charcoal, non-condensable gases and pyrolysis oils, which could furnish profitable energy and chemical products owing to their high calorific value. In this regard, the development of thermochemical processes requires a good understanding of pyrolysis mechanisms. Experimental and some literature data on the pyrolysis characteristics of corn cob and several other agricultural residues under inert atmosphere were structured and analysed in order to obtain conversion behaviour patterns of agricultural residues during pyrolysis within the temperature range from 300 °C to 1000 °C. Based on experimental and literature data analysis, empirical relationships were derived, including relations between the temperature of the process and yields of charcoal, tar and gas (CO2, CO, H2 and CH4). An analytical semi-empirical model was then used as a tool to analyse the general trends of biomass pyrolysis. Although this semi-empirical model needs further refinement before application to all types of biomass, its prediction capability was in good agreement with results obtained by the literature review. The compact representation could be used in other applications, to conveniently extrapolate and interpolate these results to other temperatures and biomass types. © The Author(s) 2016.

Waste-to-energy: Dehalogenation of plastic-containing wastes.

PubMed

Shen, Yafei; Zhao, Rong; Wang, Junfeng; Chen, Xingming; Ge, Xinlei; Chen, Mindong

2016-03-01

The dehalogenation measurements could be carried out with the decomposition of plastic wastes simultaneously or successively. This paper reviewed the progresses in dehalogenation followed by thermochemical conversion of plastic-containing wastes for clean energy production. The pre-treatment method of MCT or HTT can eliminate the halogen in plastic wastes. The additives such as alkali-based metal oxides (e.g., CaO, NaOH), iron powders and minerals (e.g., quartz) can work as reaction mediums and accelerators with the objective of enhancing the mechanochemical reaction. The dehalogenation of waste plastics could be achieved by co-grinding with sustainable additives such as bio-wastes (e.g., rice husk), recyclable minerals (e.g., red mud) via MCT for solid fuels production. Interestingly, the solid fuel properties (e.g., particle size) could be significantly improved by HTT in addition with lignocellulosic biomass. Furthermore, the halogenated compounds in downstream thermal process could be eliminated by using catalysts and adsorbents. Most dehalogenation of plastic wastes primarily focuses on the transformation of organic halogen into inorganic halogen in terms of halogen hydrides or salts. The integrated process of MCT or HTT with the catalytic thermal decomposition is a promising way for clean energy production. The low-cost additives (e.g., red mud) used in the pre-treatment by MCT or HTT lead to a considerable synergistic effects including catalytic effect contributing to the follow-up thermal decomposition. Copyright © 2015 Elsevier Ltd. All rights reserved.

The use of poly-cation oxides to lower the temperature of two-step thermochemical water splitting

DOE PAGES

Zhai, Shang; Rojas, Jimmy; Ahlborg, Nadia; ...

2018-01-01

We report the discovery of a new class of oxides – poly-cation oxides (PCOs) – that consist of multiple cations and can thermochemically split water in a two-step cycle to produce hydrogen (H 2 ) and oxygen (O 2 ).

Energetic and environmental assessment of thermochemical and biochemical ways for producing energy from agricultural solid residues: Coffee Cut-Stems case.

PubMed

García, Carlos A; Peña, Álvaro; Betancourt, Ramiro; Cardona, Carlos A

2018-06-15

Forest residues are an important source of biomass. Among these, Coffee Cut-Stems (CCS) are an abundant wood waste in Colombia obtained from coffee crops renovation. However, only low quantities of these residues are used directly in combustion processes for heating and cooking in coffee farms where their energy efficiency is very low. In the present work, an energy and environmental assessment of two bioenergy production processes (ethanol fermentation and gasification) using CCS as raw material was performed. Biomass gasification seems to be the most promising thermochemical method for bioenergy production whereas, ethanol fermentation is a widely studied biochemical method to produce biofuels. Experimental runs of the CCS gasification were carried out and the synthesis gas composition was monitored. Prior to the fermentation process, a treatment of the CCS is required from which sugar content was determined and then, in the fermentation process, the ethanol yield was calculated. Both processes were simulated in order to obtain the mass and energy balance that are used to assess the energy efficiency and the potential environmental impact (PEI). Moderate high energy efficiency and low environmental impacts were obtained from the CCS gasification. In contrast, high environmental impacts in different categories and low energy efficiencies were calculated from the ethanolic fermentation. Biomass gasification seems to be the most promising technology for the use of Coffee Cut-Stems with high energy yields and low environmental issues. Copyright © 2017 Elsevier Ltd. All rights reserved.

Agro-industrial waste to solid biofuel through hydrothermal carbonization.

PubMed

Basso, Daniele; Patuzzi, Francesco; Castello, Daniele; Baratieri, Marco; Rada, Elena Cristina; Weiss-Hortala, Elsa; Fiori, Luca

2016-01-01

In this paper, the use of grape marc for energy purposes was investigated. Grape marc is a residual lignocellulosic by-product from the winery industry, which is present in every world region where vine-making is addressed. Among the others, hydrothermal carbonization was chosen as a promising alternative thermochemical process, suitable for the treatment of this high moisture substrate. Through a 50 mL experimental apparatus, hydrothermal carbonization tests were performed at several temperatures (namely: 180, 220 and 250 °C) and residence times (1, 3, 8 h). Analyses on both the solid and the gaseous phases obtained downstream of the process were performed. In particular, solid and gas yields versus the process operational conditions were studied and the obtained hydrochar was evaluated in terms of calorific value, elemental analysis, and thermal stability. Data testify that hydrochar form grape marc presents interesting values of HHV (in the range 19.8-24.1 MJ/kg) and physical-chemical characteristics which make hydrochar exploitable as a solid biofuel. In the meanwhile, the amount of gases produced is very small, if compared to other thermochemical processes. This represents an interesting result when considering environmental issues. Statistical analysis of data allows to affirm that, in the chosen range of operational conditions, the process is influenced more by temperature than residence time. These preliminary results support the option of upgrading grape marc toward its energetic valorisation through hydrothermal carbonization. Copyright © 2015 Elsevier Ltd. All rights reserved.

Biological Hydrogen Production: Simultaneous Saccharification and Fermentation with Nitrogen and Phosphorus Removal from Wastewater Effluent

DTIC Science & Technology

2010-07-29

bedirectly catalyzed tomonosaccharidesby cellulaseswithout requiring thermochemical pretreatment , aswould typically be required with lignocellulosic ...of a similar process with lignocellulosic biomass, although such biomass would likely require ther- mochemical pretreatment prior to enzymatic...by the automatic addition of 0.1 N NaOH . Total organic carbon (TOC), ammonia nitrogen, nitrate nitrogen, nitrite nitrogen and phosphorus analyses

Water circulation and global mantle dynamics: Insight from numerical modeling

NASA Astrophysics Data System (ADS)

Nakagawa, Takashi; Nakakuki, Tomoeki; Iwamori, Hikaru

2015-05-01

We investigate water circulation and its dynamical effects on global-scale mantle dynamics in numerical thermochemical mantle convection simulations. Both dehydration-hydration processes and dehydration melting are included. We also assume the rheological properties of hydrous minerals and density reduction caused by hydrous minerals. Heat transfer due to mantle convection seems to be enhanced more effectively than water cycling in the mantle convection system when reasonable water dependence of viscosity is assumed, due to effective slab dehydration at shallow depths. Water still affects significantly the global dynamics by weakening the near-surface oceanic crust and lithosphere, enhancing the activity of surface plate motion compared to dry mantle case. As a result, including hydrous minerals, the more viscous mantle is expected with several orders of magnitude compared to the dry mantle. The average water content in the whole mantle is regulated by the dehydration-hydration process. The large-scale thermochemical anomalies, as is observed in the deep mantle, is found when a large density contrast between basaltic material and ambient mantle is assumed (4-5%), comparable to mineral physics measurements. Through this study, the effects of hydrous minerals in mantle dynamics are very important for interpreting the observational constraints on mantle convection.

Effects of Dopant Metal Variation and Material Synthesis Method on the Material Properties of Mixed Metal Ferrites in Yttria Stabilized Zirconia for Solar Thermochemical Fuel Production

DOE PAGES

Leonard, Jeffrey; Reyes, Nichole; Allen, Kyle M.; ...

2015-01-01

Mixed metal ferrites have shown much promise in two-step solar-thermochemical fuel production. Previous work has typically focused on evaluating a particular metal ferrite produced by a particular synthesis process, which makes comparisons between studies performed by independent researchers difficult. A comparative study was undertaken to explore the effects different synthesis methods have on the performance of a particular material during redox cycling using thermogravimetry. This study revealed that materials made via wet chemistry methods and extended periods of high temperature calcination yield better redox performance. Differences in redox performance between materials made via wet chemistry methods were minimal and thesemore » demonstrated much better performance than those synthesized via the solid state method. Subsequently, various metal ferrite samples (NiFe 2 O 4 , MgFe 2 O 4 , CoFe 2 O 4 , and MnFe 2 O 4 ) in yttria stabilized zirconia (8YSZ) were synthesized via coprecipitation and tested to determine the most promising metal ferrite combination. It was determined that 10 wt.% CoFe 2 O 4 in 8YSZ produced the highest and most consistent yields of O 2 and CO. By testing the effects of synthesis methods and dopants in a consistent fashion, those aspects of ferrite preparation which are most significant can be revealed. More importantly, these insights can guide future efforts in developing the next generation of thermochemical fuel production materials.« less

Process of producing liquid hydrocarbon fuels from biomass

DOEpatents

Kuester, James L.

1987-07-07

A continuous thermochemical indirect liquefaction process to convert various biomass materials into diesel-type transportation fuels which fuels are compatible with current engine designs and distribution systems comprising feeding said biomass into a circulating solid fluidized bed gasification system to produce a synthesis gas containing olefins, hydrogen and carbon monoxide and thereafter introducing the synthesis gas into a catalytic liquefaction system to convert the synthesis gas into liquid hydrocarbon fuel consisting essentially of C.sub.7 -C.sub.17 paraffinic hydrocarbons having cetane indices of 50+.

Method for increasing steam decomposition in a coal gasification process

DOEpatents

Wilson, Marvin W.

1988-01-01

The gasification of coal in the presence of steam and oxygen is significantly enhanced by introducing a thermochemical water-splitting agent such as sulfuric acid, into the gasifier for decomposing the steam to provide additional oxygen and hydrogen usable in the gasification process for the combustion of the coal and enrichment of the gaseous gasification products. The addition of the water-splitting agent into the gasifier also allows for the operation of the reactor at a lower temperature.

Method for increasing steam decomposition in a coal gasification process

DOEpatents

Wilson, M.W.

1987-03-23

The gasification of coal in the presence of steam and oxygen is significantly enhanced by introducing a thermochemical water- splitting agent such as sulfuric acid, into the gasifier for decomposing the steam to provide additional oxygen and hydrogen usable in the gasification process for the combustion of the coal and enrichment of the gaseous gasification products. The addition of the water-splitting agent into the gasifier also allows for the operation of the reactor at a lower temperature.

Thermochemical energy storage with ammonia: Aiming for the sunshot cost target

NASA Astrophysics Data System (ADS)

Lavine, Adrienne S.; Lovegrove, Keith M.; Jordan, Joshua; Anleu, Gabriela Bran; Chen, Chen; Aryafar, Hamarz; Sepulveda, Abdon

2016-05-01

Thermochemical energy storage has the potential to reduce the cost of concentrating solar thermal power. This paper presents recent advances in ammonia-based thermochemical energy storage (TCES), supported by an award from the U.S. Dept. of Energy SunShot program. Advances have been made in three areas: identification of promising approaches for underground containment of the gaseous products of the dissociation reaction, demonstration that ammonia synthesis can be used to generate steam for a supercritical-steam Rankine cycle, and a preliminary design for integration of the endothermic reactors within a tower receiver. Based on these advances, ammonia-based TCES shows promise to meet the 15/kWht SunShot cost target.

Chemsheet as a Simulation Platform for Pyrometallurgical Processes

NASA Astrophysics Data System (ADS)

Penttilä, Karri; Salminen, Justin; Tripathi, Nagendra; Koukkari, Pertti

ChemSheet is a thermodynamic multi-phase multi-component simulation software, which is used as an Add-in in Microsoft Excel. In ChemSheet, the unique Constrained Gibbs free energy method can be used to include dynamic constraints and reaction rates of kinetically slow reactions, yet retaining full consistency of the multiphase thermodynamic model. With appropriate data, ChemSheet models can be used to simulate reactors and processes in all fields of thermochemistry. The presentation will cover off-line modeling of Cu-flash smelters and advanced thermochemical simulation coupled with on-line process control of Cu-Ni smelting. The presentation will describe an off-line model of Cu-smelter based on critically assessed properties of the Al-Ca-Cu-Fe-O-S-Si -system (slag, matte and liquid metal) by using the quasichemical model. A four-stage reactor model (shaft, settler, uptake and bath) is used for optimizing process parameters and feed particle distribution. As a second example, an advanced thermochemical model of a Ni-Cu sulphide smelting plant will be given. The on-line model covers the operation of treating Ni-Cu-S concentrate via roasters, electric furnace and converters, producing a high grade Bessemer matte product for further refining. The model integrates the thermochemistry of the roasters and electric furnace, and predicts important process parameters such as degree of sulphur elimination in the fluid-bed roasters, matte grade, iron metallization, slag losses and the iron to silica ratio in the electric furnace slag. Both models can be used to assist process engineers and operators in calculating the addition rates of coke, flux and air for different feed scenarios.

A general model for techno-economic analysis of CSP plants with thermochemical energy storage systems

NASA Astrophysics Data System (ADS)

Peng, Xinyue; Maravelias, Christos T.; Root, Thatcher W.

2017-06-01

Thermochemical energy storage (TCES), with high energy density and wide operating temperature range, presents a potential solution for CSP plant energy storage. We develop a general optimization based process model for CSP plants employing a wide range of TCES systems which allows us to assess the plant economic feasibility and energy efficiency. The proposed model is applied to a 100 MW CSP plant employing ammonia or methane TCES systems. The methane TCES system with underground gas storage appears to be the most promising option, achieving a 14% LCOE reduction over the current two-tank molten-salt CSP plants. For general TCES systems, gas storage is identified as the main cost driver, while the main energy driver is the compressor electricity consumption. The impacts of separation and different reaction parameters are also analyzed. This study demonstrates that the realization of TCES systems for CSP plants is contingent upon low storage cost and a reversible reaction with proper reaction properties.

Thermochemical characterization of some thermoplastic materials. [flammability and toxicity properties for aircraft interiors

NASA Technical Reports Server (NTRS)

Kourtides, D. A.; Parker, J. A.; Hilado, C. J.

1977-01-01

The thermochemical and flammability characteristics of some typical thermoplastic materials currently in use or being considered for use in aircraft interiors are described. The properties studied included thermomechanical properties such as glass-transition and melt temperature, changes in polymer enthalpy, thermogravimetric analysis in anerobic and oxidative environments, oxygen index, smoke evolution, relative toxicity of the volatile products of pyrolysis, and selected physical properties. The generic polymers evaluated included acrylonitrile butadiene styrene, bisphenol A polycarbonate, 9,9 bis (4-hydroxyphenyl) fluorene polycarbonate-poly (dimethylsiloxane) block polymer, phenolphthalein-bisphenol A polycarbonate, phenolphthalein polycarbonate, polyether sulfone, polyphenylene oxide, polyphenylene sulfide, polyaryl sulfone, chlorinated polyvinyl chloride homopolymer, polyvinyl fluoride, and polyvinylidene fluoride. Processing parameters, including molding characteristics of some of the advanced polymers, are described. Test results and relative rankings of some of the flammability, smoke, and toxicity properties are presented. Under these test conditions, some of the advanced polymers evaluated were significantly less flammable and toxic than or equivalent to polymers in current use.

A solar-hydrogen economy for U.S.A.

NASA Astrophysics Data System (ADS)

Bockris, J. Om.; Veziroglu, T. N.

The benefits, safety, production, distribution, storage, and uses, as well as the economics of a solar and hydrogen based U.S. energy system are described. Tropical and subtropical locations for the generation plants would provide power from photovoltaics, heliostat arrays, OTEC plants, or genetically engineered algae to produce hydrogen by electrolysis, direct thermal conversion, thermochemical reactions, photolysis, or hybrid systems. Either pipelines for gas transport or supertankers for liquefied hydrogen would distribute the fuel, with storage in underground reservoirs, aquifers, and pressurized bladders at sea. The fuel would be distributed to factories, houses, gas stations, and airports. It can be used in combustion engines, gas turbines, and jet engines, and produces water vapor as an exhaust gas. The necessary research effort to define and initiate construction of technically and economically viable solar-hydrogen plants is projected to be 3 yr, while the technical definition of fusion power plants, the other nondepletable energy system, is expected to take 25 yr.

Feedstock and Conversion Supply System Design and Analysis

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

Jacobson, J.; Mohammad, R.; Cafferty, K.

The success of the earlier logistic pathway designs (Biochemical and Thermochemical) from a feedstock perspective was that it demonstrated that through proper equipment selection and best management practices, conventional supply systems (referred to in this report as “conventional designs,” or specifically the 2012 Conventional Design) can be successfully implemented to address dry matter loss, quality issues, and enable feedstock cost reductions that help to reduce feedstock risk of variable supply and quality and enable industry to commercialize biomass feedstock supply chains. The caveat of this success is that conventional designs depend on high density, low-cost biomass with no disruption frommore » incremental weather. In this respect, the success of conventional designs is tied to specific, highly productive regions such as the southeastern U.S. which has traditionally supported numerous pulp and paper industries or the Midwest U.S for corn stover.« less

Bio-oil production from fast pyrolysis of waste furniture sawdust in a fluidized bed.

PubMed

Heo, Hyeon Su; Park, Hyun Ju; Park, Young-Kwon; Ryu, Changkook; Suh, Dong Jin; Suh, Young-Woong; Yim, Jin-Heong; Kim, Seung-Soo

2010-01-01

The amount of waste furniture generated in Korea was over 2.4 million tons in the past 3 years, which can be used for renewable energy or fuel feedstock production. Fast pyrolysis is available for thermo-chemical conversion of the waste wood mostly into bio-oil. In this work, fast pyrolysis of waste furniture sawdust was investigated under various reaction conditions (pyrolysis temperature, particle size, feed rate and flow rate of fluidizing medium) in a fluidized-bed reactor. The optimal pyrolysis temperature for increased yields of bio-oil was 450 degrees C. Excessively smaller or larger feed size negatively affected the production of bio-oil. Higher flow and feeding rates were more effective for the production of bio-oil, but did not greatly affect the bio-oil yields within the tested ranges. The use of product gas as the fluidizing medium had a potential for increased bio-oil yields.

Thermochemical Processes in Plasma Aerodynamics

DTIC Science & Technology

2006-06-01

hydrocarbon fuel possesses not only much lower induction time but also more effective potential in thermodynamic combustion cycle (more complete exergy ... Internal Plasma- Assisted Combustion, AIAA Paper 2004-1014. Proc. 42 "d AIAA Aerospace Sciences Meeting & Exhibit, 4-8 January 2004, Reno, NV, P. 10 2...Vystavkin N, Sukovatkin N, Serov Yu, Savischenko N, Yuriev A., External and Internal Plasma- Assisted Combustion AIAA Paper 2003-6240. Proc. 41st

Neutralization and Acid Dissociation of Hydrogen Carbonate Ion: A Thermochemical Approach

ERIC Educational Resources Information Center

Koga, Nobuyoshi; Shigedomi, Kana; Kimura, Tomoyasu; Tatsuoka, Tomoyuki; Mishima, Saki

2013-01-01

A laboratory inquiry into the thermochemical relationships in the reaction between aqueous solutions of NaHCO[subscript 3] and NaOH is described. The enthalpy change for this reaction, delta[subscript r]H, and that for neutralization of strong acid and NaOH(aq), delta[subscript n]H, are determined calorimetrically; the explanation for the…

Thermochemical properties of flame gases from fine wildland fuels

Treesearch

Frank A. Albini

1979-01-01

Describes a theoretical model for calculating thermochemical properties of the gaseous fuel that burns in the free flame at the edge of a spreading fire in fine forest fuels. Predicted properties are the heat of combustion, stoichiometric air/fuel mass ratio, mass-averaged temperature, and mass fraction of unburned fuel in the gas mixture emitted from the flame-...

Development and application of computational aerothermodynamics flowfield computer codes

NASA Technical Reports Server (NTRS)

Venkatapathy, Ethiraj

1992-01-01

Presented is a collection of papers on research activities carried out during the funding period of October 1991 to March 1992. Topics covered include: blunt body flows in thermochemical equilibrium; thermochemical relaxation in high enthalpy nozzle flow; single expansion ramp nozzle simulations; lunar return aerobraking; line boundary problem for three dimensional grids; and unsteady shock induced combustion.

Thermochemical pretreatments of organic fraction of municipal solid waste from a mechanical-biological treatment plant.

PubMed

Álvarez-Gallego, Carlos José; Fdez-Güelfo, Luis Alberto; de los Ángeles Romero Aguilar, María; Romero García, Luis Isidoro

2015-02-09

The organic fraction of municipal solid waste (OFMSW) usually contains high lignocellulosic and fatty fractions. These fractions are well-known to be a hard biodegradable substrate for biological treatments and its presence involves limitations on the performance of anaerobic processes. To avoid this, thermochemical pretreatments have been applied on the OFMSW coming from a full-scale mechanical-biological treatment (MBT) plant, in order to pre-hydrolyze the waste and improve the organic matter solubilisation. To study the solubilisation yield, the increments of soluble organic matter have been measured in terms of dissolved organic carbon (DOC), soluble chemical oxygen demand (sCOD), total volatile fatty acids (TVFA) and acidogenic substrate as carbon (ASC). The process variables analyzed were temperature, pressure and NaOH dosage. The levels of work for each variable were three: 160-180-200 °C, 3.5-5.0-6.5 bar and 2-3-4 g NaOH/L. In addition, the pretreatment time was also modified among 15 and 120 min. The best conditions for organic matter solubilisation were 160 °C, 3 g NaOH/L, 6.5 bar and 30 min, with yields in terms of DOC, sCOD, TVFA and ASC of 176%, 123%, 119% and 178% respectively. Thus, predictably the application of this pretreatment in these optimum conditions could improve the H2 production during the subsequent Dark Fermentation process.

Thermodynamic properties of minerals

USGS Publications Warehouse

Robie, Richard A.

1962-01-01

In the ten years since the publication of the national Bureau of Standards comprehensive tables of thermochemical properties, by Rossini and other (1952), a very large body of modern calorimetric and equilibrium data has become available. Because of the complex interrelations among many thermochemical data and the necessity for internal consistency among these values, a complete revision of this standard reference is required. This is also true of the summaries of thermochemical data for the sulfides (Richardson and Jeffes 1952) and for the oxides (Coughlin 1954). The following tables present critically selected values for the heat and free energy of formation, the logarithm of the equilibrium constant of formation Log Kf, the entropy and the molar volume, at 298.15°K (25.0°C) and one atmosphere for minerals.

Potential of phosphorus recovery from sewage sludge and manure ash by thermochemical treatment.

PubMed

Havukainen, Jouni; Nguyen, Mai Thanh; Hermann, Ludwig; Horttanainen, Mika; Mikkilä, Mirja; Deviatkin, Ivan; Linnanen, Lassi

2016-03-01

All life forms require phosphorus (P), which has no substitute in food production. The risk of phosphorus loss from soil and limited P rock reserves has led to the development of recycling P from industrial residues. This study investigates the potential of phosphorus recovery from sewage sludge and manure ash by thermochemical treatment (ASH DEC) in Finland. An ASH DEC plant could receive 46-76 kt/a of sewage sludge ash to produce 51-85 kt/a of a P-rich product with a P2O5 content of 13-18%, while 320-750 kt/a of manure ash could be supplied to produce 350-830 kt/a of a P-rich product with a P content of 4-5%. The P2O5 potential in the total P-rich product from the ASH DEC process using sewage sludge and manure ash is estimated to be 25-47 kt/a, which is significantly more than the P fertilizer demand in Finland's agricultural industries. The energy efficiency of integrated incineration and the ASH DEC process is more dependent on the total solid content and the subsequent need for mechanical dewatering and thermal drying than on the energy required by the ASH DEC process. According to the results of this study, the treated sewage sludge and manure ash using the ASH DEC process represent significant potential phosphorus sources for P fertilizer production. Copyright © 2016 Elsevier Ltd. All rights reserved.

Multiple sulfur isotopes monitor fluid evolution of an Archean orogenic gold deposit

NASA Astrophysics Data System (ADS)

LaFlamme, Crystal; Sugiono, Dennis; Thébaud, Nicolas; Caruso, Stefano; Fiorentini, Marco; Selvaraja, Vikraman; Jeon, Heejin; Voute, François; Martin, Laure

2018-02-01

The evolution of a gold-bearing hydrothermal fluid from its source to the locus of gold deposition is complex as it experiences rapid changes in thermochemical conditions during ascent through the crust. Although it is well established that orogenic gold deposits are generated during time periods of abundant crustal growth and/or reworking, the source of fluid and the thermochemical processes that control gold precipitation remain poorly understood. In situ analyses of multiple sulfur isotopes offer a new window into the relationship between source reservoirs of Au-bearing fluids and the thermochemical processes that occur along their pathway to the final site of mineralisation. Whereas δ34S is able to track changes in the evolution of the thermodynamic conditions of ore-forming fluids, Δ33S is virtually indelible and can uniquely fingerprint an Archean sedimentary reservoir that has undergone mass independent fractionation of sulfur (MIF-S). We combine these two tracers (δ34S and Δ33S) to characterise a gold-bearing laminated quartz breccia ore zone and its sulfide-bearing alteration halo in the (+6 Moz Au) structurally-controlled Archean Waroonga deposit located in the Eastern Goldfields Superterrane of the Yilgarn Craton, Western Australia. Over 250 analyses of gold-associated sulfides yield a δ34S shift from what is interpreted as an early pre-mineralisation phase, with chalcopyrite-pyrrhotite (δ34S = +0.7‰ to +2.9‰) and arsenopyrite cores (δ34S = ∼-0.5‰), to a syn-mineralisation stage, reflected in Au-bearing arsenopyrite rims (δ34S = -7.6‰ to +1.5‰). This shift coincides with an unchanging Δ33S value (Δ33S = +0.3‰), both temporally throughout the Au-hosting hydrothermal sulfide paragenesis and spatially across the Au ore zone. These results indicate that sulfur is at least partially recycled from MIF-S-bearing Archean sediments. Further, the invariant nature of the observed MIF-S signature demonstrates that sulfur is derived from a homogeneous MIF-S-bearing fluid reservoir at depth, rather than being locally sourced at the site of Au precipitation. Finally, by constraining the MIF-S-bearing sulfur source to a fixed reservoir, we are able to display the thermochemical evolution of the ore fluid in δ34S space and capture the abrupt change in oxidation state that causes Au precipitation. Our results highlight the importance of constraining multiple sulfur isotopes in space and time in order to elucidate the source and evolution of any given Au-bearing fluid.

Engineering Design Elements of a Two-Phase Thermosyphon to Trannsfer NGNP Nuclear Thermal Energy to a Hydrogen Plant

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

Piyush Sabharwal

2009-07-01

Two hydrogen production processes, both powered by a Next Generation Nuclear Plant (NGNP), are currently under investigation at Idaho National Laboratory. The first is high-temperature steam electrolysis, which uses both heat and electricity; the second is thermo-chemical production through the sulfur iodine process primarily using heat. Both processes require a high temperature (>850°C) for enhanced efficiency; temperatures indicative of the NGNP. Safety and licensing mandates prudently dictate that the NGNP and the hydrogen production facility be physically isolated, perhaps requiring separation of over 100 m.

Chemical kinetics on extrasolar planets.

PubMed

Moses, Julianne I

2014-04-28

Chemical kinetics plays an important role in controlling the atmospheric composition of all planetary atmospheres, including those of extrasolar planets. For the hottest exoplanets, the composition can closely follow thermochemical-equilibrium predictions, at least in the visible and infrared photosphere at dayside (eclipse) conditions. However, for atmospheric temperatures approximately <2000K, and in the uppermost atmosphere at any temperature, chemical kinetics matters. The two key mechanisms by which kinetic processes drive an exoplanet atmosphere out of equilibrium are photochemistry and transport-induced quenching. I review these disequilibrium processes in detail, discuss observational consequences and examine some of the current evidence for kinetic processes on extrasolar planets.

Pyrolysis characteristics and kinetics of acid tar waste from crude benzol refining: A thermogravimetry-mass spectrometry analysis.

PubMed

Chihobo, Chido H; Chowdhury, Arindrajit; Kuipa, Pardon K; Simbi, David J

2016-12-01

Pyrolysis is an attractive thermochemical conversion technology that may be utilised as a safe disposal option for acid tar waste. The kinetics of acid tar pyrolysis were investigated using thermogravimetry coupled with mass spectrometry under a nitrogen atmosphere at different heating rates of 10, 15 and 20 K min -1 The thermogravimetric analysis shows three major reaction peaks centred around 178 °C, 258 °C, and 336 °C corresponding to the successive degradation of water soluble lower molecular mass sulphonic acids, sulphonated high molecular mass hydrocarbons, and high molecular mass hydrocarbons. The kinetic parameters were evaluated using the iso-conversional Kissinger-Akahira-Sunose method. A variation in the activation energy with conversion revealed that the pyrolysis of the acid tar waste progresses through complex multi-step kinetics. Mass spectrometry results revealed a predominance of gases such as hydrogen, methane and carbon monoxide, implying that the pyrolysis of acid tar waste is potentially an energy source. Thus the pyrolysis of acid tar waste may present a viable option for its environmental treatment. There are however, some limitations imposed by the co-evolution of corrosive gaseous components for which appropriate considerations must be provided in both pyrolysis reactor design and selection of construction materials. © The Author(s) 2016.

Elemental and thermo-chemical analysis of oil palm fronds for biomass energy conversion

NASA Astrophysics Data System (ADS)

Guangul, Fiseha Mekonnen; Sulaiman, Shaharin Anwar; Raghavan, Vijay R.

2012-06-01

Oil palm frond is the most abundant yet untapped biomass waste in Malaysia. This paper investigates the characteristics of raw oil palm fronds and its ash to evaluate its potential utilization as a biomass fuel for gasification process using single throat downdraft gasifier. The morphological nature, elemental content, proximate and ultimate analysis and calorific value were studied. Field emission scanning electron microscopy and x-ray fluorescence were used to investigate the surface morphology, elemental and mineralogical nature of oil palm frond and its ash. The results were compared with other agricultural and forestry biomass wastes. From proximate analysis volatile matter, fixed carbon and ash were found to be 83.5%, 15.2% and 1.3%, respectively on dry basis. From ultimate analysis result values of 44.58%, 4.53%, 0.71% and 0.07% for carbon, hydrogen, nitrogen and sulfur were found respectively on dry basis. Oxygen was determined by difference and found to be 48.81%. The proximate and ultimate analysis results indicate that oil palm frond is better than agricultural wastes and less than most forestry wastes to use as a feedstock in the gasification process in order to get a better quality of syngas. The amount of ash content in OPF was found to be much less than in agricultural wastes and higher than most forestry wastes. From x-ray fluorescence analysis CaO and K2O were found as the major oxides in oil palm fronds and rice husk ash with the amount of 28.46% and 15.71% respectively. The overall results of oil palm fronds were found to be satisfactory to use as a feedstock for the process of gasification.

Production of Hydrogen by Superadiabatic Decomposition of Hydrogen Sulfide - Final Technical Report for the Period June 1, 1999 - September 30, 2000

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

Rachid B. Slimane; Francis S. Lau; Javad Abbasian

2000-10-01

The objective of this program is to develop an economical process for hydrogen production, with no additional carbon dioxide emission, through the thermal decomposition of hydrogen sulfide (H{sub 2}S) in H{sub 2}S-rich waste streams to high-purity hydrogen and elemental sulfur. The novel feature of the process being developed is the superadiabatic combustion (SAC) of part of the H{sub 2}S in the waste stream to provide the thermal energy required for the decomposition reaction such that no additional energy is required. The program is divided into two phases. In Phase 1, detailed thermochemical and kinetic modeling of the SAC reactor withmore » H{sub 2}S-rich fuel gas and air/enriched air feeds is undertaken to evaluate the effects of operating conditions on exit gas products and conversion efficiency, and to identify key process parameters. Preliminary modeling results are used as a basis to conduct a thorough evaluation of SAC process design options, including reactor configuration, operating conditions, and productivity-product separation schemes, with respect to potential product yields, thermal efficiency, capital and operating costs, and reliability, ultimately leading to the preparation of a design package and cost estimate for a bench-scale reactor testing system to be assembled and tested in Phase 2 of the program. A detailed parametric testing plan was also developed for process design optimization and model verification in Phase 2. During Phase 2 of this program, IGT, UIC, and industry advisors UOP and BP Amoco will validate the SAC concept through construction of the bench-scale unit and parametric testing. The computer model developed in Phase 1 will be updated with the experimental data and used in future scale-up efforts. The process design will be refined and the cost estimate updated. Market survey and assessment will continue so that a commercial demonstration project can be identified.« less

Improving Students' Chemical Literacy Levels on Thermochemical and Thermodynamics Concepts through a Context-Based Approach

ERIC Educational Resources Information Center

Cigdemoglu, Ceyhan; Geban, Omer

2015-01-01

The aim of this study was to delve into the effect of context-based approach (CBA) over traditional instruction (TI) on students' chemical literacy level related to thermochemical and thermodynamics concepts. Four eleventh-grade classes with 118 students in total taught by two teachers from a public high school in 2012 fall semester were enrolled…

Cascading pressure reactor and method for solar-thermochemical reactions

DOEpatents

Ermanoski, Ivan

2017-11-14

Reactors and methods for solar thermochemical reactions are disclosed. The reactors and methods include a cascade of reduction chambers at successively lower pressures that leads to over an order of magnitude pressure decrease compared to a single-chambered design. The resulting efficiency gains are substantial, and represent an important step toward practical and efficient solar fuel production on a large scale.

Using a Laboratory Inquiry with High School Students to Determine the Reaction Stoichiometry of Neutralization by a Thermochemical Approach

ERIC Educational Resources Information Center

Journal of Chemical Education, 2015

2015-01-01

This paper presents the design and practical application of a laboratory inquiry at high school chemistry level for systematic chemistry learning, as exemplified by a thermochemical approach to the reaction stoichiometry of neutralization using Job's method of continuous variation. In the laboratory inquiry, students are requested to propose the…

Experimental and thermodynamic study of Co-Fe and Mn-Fe based mixed metal oxides for thermochemical energy storage application

NASA Astrophysics Data System (ADS)

André, Laurie; Abanades, Stéphane; Cassayre, Laurent

2017-06-01

Metal oxides are potential materials for thermochemical heat storage, and among them, cobalt oxide and manganese oxide are attracting attention. Furthermore, studies on mixed oxides are ongoing, as the synthesis of mixed oxides could be a way to answer the drawbacks of pure metal oxides, such as slow reaction kinetics, loss-in-capacity over cycles or sintering, selected for thermochemical heat storage application. The addition of iron oxide is under investigation and the obtained results are presented. This work proposes a comparison of thermodynamic modelling with experimental data in order to identify the impact of iron oxide addition to cobalt oxide and manganese oxide. Fe addition decreased the redox activity and energy storage capacity of Co3O4, whereas the cycling stability of Mn2O3 was significantly improved with added Fe amounts above 20 mol% while the energy storage capacity was unchanged. The thermodynamic modelling method to predict the behavior of the Mn-Fe-O and Co-Fe-O systems was validated, and the possibility to identify other mixed oxides becomes conceivable, by enabling the selection of transition metals additives for metal oxides destined for thermochemical energy storage applications.

Optimized structure and thermochemical properties of flavonoids determined by the CHIH(medium) DFT model chemistry versus experimental techniques

NASA Astrophysics Data System (ADS)

Mendoza-Wilson, Ana María.; Lardizabal-Gutiérrez, Daniel; Torres-Moye, Enrique; Fuentes-Cobas, Luis; Balandrán-Quintana, René R.; Camacho-Dávila, Alejandro; Quintero-Ramos, Armando; Glossman-Mitnik, Daniel

2007-12-01

The purpose of this work was to evaluate the accuracy of the CHIH(medium)-DFT model chemistry (PBEg/CBSB2 ∗∗//PBEg/CBSB4) in the determination of the optimized structure and thermochemical properties of heterocyclic systems of medium size such as flavonoids, wherefore were selected three of the most abundant flavonoids in vegetable tissues, and which posses the higher antioxidant activity: quercetin, (+)-catechin and cyanidin. As reference systems were employed three cyclic compounds: phenol, catechol and resorcinol. The thermochemical properties evaluated were enthalpy of formation, bond dissociation enthalpy (BDE) and ionization potential (IP), following the scheme of isodesmic reactions. The theoretical results were compared with experimental data generated by X-ray diffraction and calorimetric techniques realized in part by us, whereas other data were taken from the literature. The results obtained in this work reveal that the CHIH(medium)-DFT model chemistry represents an accurate computational tool to calculate structural and thermochemical properties in the studied flavonoid and reference compounds. The average absolute deviation of enthalpy of formation for reference compounds was 3.0 kcal/mol, 2.64 kcal/mol for BDE, and 2.97 kcal/mol for IP.

Evaluation of the performance of MP4-based procedures for a wide range of thermochemical and kinetic properties

NASA Astrophysics Data System (ADS)

Yu, Li-Juan; Wan, Wenchao; Karton, Amir

2016-11-01

We evaluate the performance of standard and modified MPn procedures for a wide set of thermochemical and kinetic properties, including atomization energies, structural isomerization energies, conformational energies, and reaction barrier heights. The reference data are obtained at the CCSD(T)/CBS level by means of the Wn thermochemical protocols. We find that none of the MPn-based procedures show acceptable performance for the challenging W4-11 and BH76 databases. For the other thermochemical/kinetic databases, the MP2.5 and MP3.5 procedures provide the most attractive accuracy-to-computational cost ratios. The MP2.5 procedure results in a weighted-total-root-mean-square deviation (WTRMSD) of 3.4 kJ/mol, whilst the computationally more expensive MP3.5 procedure results in a WTRMSD of 1.9 kJ/mol (the same WTRMSD obtained for the CCSD(T) method in conjunction with a triple-zeta basis set). We also assess the performance of the computationally economical CCSD(T)/CBS(MP2) method, which provides the best overall performance for all the considered databases, including W4-11 and BH76.

Production of synthetic fuels using syngas from a steam hydrogasification and reforming process

NASA Astrophysics Data System (ADS)

Raju, Arun Satheesh Kumar

This thesis is aimed at the research, optimization and development of a thermo-chemical process aimed at the production of synthesis gas (mixture of H2 and CO) with a flexible H2 to CO ratio using coupled steam hydrogasification and steam reforming processes. The steam hydrogasification step generates a product gas containing significant amounts of methane by gasifying a carbonaceous feed material with steam and internally generated H2. This product gas is converted to synthesis gas with an excess H2 to CO using the steam reformer. Research involving experimental and simulation work has been conducted on steam hydrogasification, steam reforming and the Fischer-Tropsch reaction. The Aspen Plus simulation tool has been used to develop a process model that can perform heat and mass balance calculations of the whole process using built-in reactor modules and an empirical FT model available in the literature. This model has been used to estimate optimum feed ratios and process conditions for specific feedstocks and products. Steam hydrogasification of coal and wood mixtures of varying coal to wood ratios has been performed in a stirred batch reactor. The carbon conversion of the feedstocks to gaseous products is around 60% at 700°C and 80% at 800°C. The coal to wood ratio of the feedstock does not exert a significant influence on the carbon conversion. The rates of formation of CO, CO 2 and CH4 during gasification have been calculated based on the experimental results using a simple kinetic model. Experimental research on steam reforming has been performed. It has been shown that temperature and the feed CO2/CH4 ratio play a dominant role in determining the product gas H2/CO ratio. Reforming of typical steam hydrogasification product-gas stream has been investigated over a commercial steam reforming catalyst. The results demonstrate that the combined use of steam hydrogasification process with a reformer can generate a synthesis gas with a predetermined H2/CO ratio from carbonaceous feedstocks. Experimental work on the Fischer-Tropsch synthesis has also been performed. A life cycle analysis has been performed with the objective of comparing the life cycle energy consumption and emissions of synthetic diesel fuel produced through the CE-CERT process with other fuel/vehicle combinations. The experimental and simulation results presented here demonstrate that the CE-CERT process is versatile and can potentially handle a number of different feedstocks. CE-CERT process appears to be suitable for commercialization in very large scales with a coal feedstock and also in a distributed network of smaller scale reactors utilizing localized renewable feedstocks.

Numeric Databases in Chemical Thermodynamics at the National Institute of Standards and Technology

PubMed Central

Chase, Malcolm W.

1989-01-01

During the past year the activities of the Chemical Thermodynamics Data Center and the JANAF Thermochemical Tables project have been combined to obtain an extensive collection of thermodynamic information for many chemical species, including the elements. Currently available are extensive bibliographic collections and data files of heat capacity, enthalpy, vapor pressure, phase transitions, etc. Future plans related to materials science are to improve the metallic oxide temperature dependent tabulations, upgrade the recommended values periodically, and maintain the bibliographic citations and the thermochemical data current. The recommended thermochemical information is maintained on-line, and tied to the calculational routines within the data center. Recent thermodynamic evaluations on the elements and oxides will be discussed, as well as studies in related activities at NIST. PMID:28053395

Estimates of thermochemical relaxation lengths behind normal shock waves relevant to manned lunar and Mars return missions, the aeroassist flight experiment, and Mars entry

NASA Technical Reports Server (NTRS)

Howe, John T.

1991-01-01

Thermochemical relaxation distances behind the strong normal shock waves associated with vehicles that enter the Earth atmosphere upon returning from a manned lunar or Mars mission are estimated. The relaxation distances for a Mars entry are estimated as well, in order to highlight the extent of the relaxation phenomena early in currently envisioned space exploration studies. The thermochemical relaxation length for the Aeroassist Flight Experiment is also considered. These estimates provide an indication as to whether finite relaxation needs to be considered in subsequent detailed analyses. For the Mars entry, relaxation phenomena that are fully coupled to the flow field equations are used. The relaxation-distance estimates can be scaled to flight conditions other than those discussed.

Thermo-Chemical Phenomena Simulation for Ablation

DTIC Science & Technology

2011-02-21

DATES COVERED (1/01/08-30/11/10) 4. TITLE AND SUBTITLE Thermo- Chemical Phenomena Simulation for Ablation 5a. CONTRACT NUMBER...First, a physic based chemical kinetic model for high-temperature gas is developed and verified by comparing with data from the RAM-C-II probe and the...found to be negligible and the energy exchange is dominated by the chemical process for conductive-convective heat transfer. A simplified and more

Conditional Moment Closure of Mixing and Reaction in Turbulent Nonpremixed Combustion

NASA Technical Reports Server (NTRS)

Smith, Nigel S. A.

1996-01-01

Nonpremixed combustion is the process whereby fuel and oxidizer species, which are each nonflammable in isolation, concurrently mix to burn a flammable mixture, and chemically react in the flammable mixture. In cases of practical industrial interest, the bulk of nonpremixed combustion occurs in a turbulent mixing regime where enhanced mass transfer rates flow the maximum power density to be achieved in any given thermochemical device.

Process of producing liquid hydrocarbon fuels from biomass

DOEpatents

Kuester, J.L.

1987-07-07

A continuous thermochemical indirect liquefaction process is described to convert various biomass materials into diesel-type transportation fuels which fuels are compatible with current engine designs and distribution systems comprising feeding said biomass into a circulating solid fluidized bed gasification system to produce a synthesis gas containing olefins, hydrogen and carbon monoxide and thereafter introducing the synthesis gas into a catalytic liquefaction system to convert the synthesis gas into liquid hydrocarbon fuel consisting essentially of C[sub 7]-C[sub 17] paraffinic hydrocarbons having cetane indices of 50+. 1 fig.

Rational design of metal nitride redox materials for solar-driven ammonia synthesis.

PubMed

Michalsky, Ronald; Pfromm, Peter H; Steinfeld, Aldo

2015-06-06

Fixed nitrogen is an essential chemical building block for plant and animal protein, which makes ammonia (NH3) a central component of synthetic fertilizer for the global production of food and biofuels. A global project on artificial photosynthesis may foster the development of production technologies for renewable NH3 fertilizer, hydrogen carrier and combustion fuel. This article presents an alternative path for the production of NH3 from nitrogen, water and solar energy. The process is based on a thermochemical redox cycle driven by concentrated solar process heat at 700-1200°C that yields NH3 via the oxidation of a metal nitride with water. The metal nitride is recycled via solar-driven reduction of the oxidized redox material with nitrogen at atmospheric pressure. We employ electronic structure theory for the rational high-throughput design of novel metal nitride redox materials and to show how transition-metal doping controls the formation and consumption of nitrogen vacancies in metal nitrides. We confirm experimentally that iron doping of manganese nitride increases the concentration of nitrogen vacancies compared with no doping. The experiments are rationalized through the average energy of the dopant d-states, a descriptor for the theory-based design of advanced metal nitride redox materials to produce sustainable solar thermochemical ammonia.

Rational design of metal nitride redox materials for solar-driven ammonia synthesis

PubMed Central

Michalsky, Ronald; Pfromm, Peter H.; Steinfeld, Aldo

2015-01-01

Fixed nitrogen is an essential chemical building block for plant and animal protein, which makes ammonia (NH3) a central component of synthetic fertilizer for the global production of food and biofuels. A global project on artificial photosynthesis may foster the development of production technologies for renewable NH3 fertilizer, hydrogen carrier and combustion fuel. This article presents an alternative path for the production of NH3 from nitrogen, water and solar energy. The process is based on a thermochemical redox cycle driven by concentrated solar process heat at 700–1200°C that yields NH3 via the oxidation of a metal nitride with water. The metal nitride is recycled via solar-driven reduction of the oxidized redox material with nitrogen at atmospheric pressure. We employ electronic structure theory for the rational high-throughput design of novel metal nitride redox materials and to show how transition-metal doping controls the formation and consumption of nitrogen vacancies in metal nitrides. We confirm experimentally that iron doping of manganese nitride increases the concentration of nitrogen vacancies compared with no doping. The experiments are rationalized through the average energy of the dopant d-states, a descriptor for the theory-based design of advanced metal nitride redox materials to produce sustainable solar thermochemical ammonia. PMID:26052421

Disequilibrium in planetary atmospheres and the search for habitability

NASA Astrophysics Data System (ADS)

Simoncini, E.

It has long been observed that Earth's atmosphere is uniquely far from its thermochemical equilibrium state in terms of its chemical composition. Studying this state of disequilibrium is important for its potential role in the detection of life on other suitable planets \\citep{Lovelock_1965,Kleidon_2010,Simoncini_2015}. We developed a methodology to calculate the extent of atmospheric chemical disequilibrium\\citep{Simoncini_2015,Kondepudi_1996}. This tool allows us to understand, on a thermodynamic basis, how life affected - and still affects - geochemical processes on Earth, and if other planetary atmospheres are habitable or have a disequilibrium similar to the Earth's one. A new computational framework called KROME has been applied to atmospheric models in order to give a correct computation of reactions´ kinetics \\citep{Grassi_2015}. In this work we present a first computation of the extent of disequilibrium for the present Earth atmosphere, considering the specific contribution of the different atmospheric processes, such as thermochemical reactions, eddy diffusion, photochemistry, deposition, and the effect of the biosphere. We then assess the effect of life on atmospheric disequilibrium of the Earth and provide a useful discussion about how the study of atmospheric disequilibrium can help in finding habitable (exo)planets. We finally compare the chemical disequilibrium of Earth and Mars atmospheres, for present and early conditions.

A perspective on renewable bioenergy from photosynthetic algae as feedstock for biofuels and bioproducts

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

Laurens, Lieve M. L.; Chen-Glasser, Melodie; McMillan, James D.

There has been substantial technical progress in developing algae-based bioenergy in recent years and a large part of industry and academic research and deployment projects have pivoted away from a pure biofuels strategy. This letter summarizes the findings of a recently completed, comprehensive report, that represents a collaborative effort of at least 20 co-authors, where we analyzed the prospects for using microalgae and macroalgae as feedstocks for biofuels and bioenergy production. The scope of this report includes a discussion of international activities advancing bioenergy and non-energy bioproducts from algae, progress on the use of macroalgae (both cast and cultivated seaweeds)more » for biogas applications, distinct biochemical and thermochemical conversion pathways, multi-product biorefining opportunities, as well as a thorough review of process economics and sustainability considerations. It is envisioned that a higher value algal biomass-based bioproducts industry will provide the additional revenue needed to reduce the net cost of producing algae-based biofuels. As such, a biorefinery approach that generates multiple high-value products from algae will be essential to fully valorize algal biomass and enable economically viable coproduction of bioenergy. Furthermore, to accelerate the implementation of algae-based production, minimizing energy, water, nutrients and land use footprints of integrated algae-based operations needs to be a primary objective of larger scale demonstrations and future research and development.« less

Comprehensive kinetic model for the low-temperature oxidation of hydrocarbons

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

Gaffuri, P.; Faravelli, T.; Ranzi, E.

1997-05-01

The oxidation chemistry in the low- and intermediate-temperature regimes (600--900 K) is important and plays a significant role in the overall combustion process. Autoignition in diesel engines as well as end-gas autoignition and knock phenomena in s.i. engines are initiated at these low temperatures. The low-temperature oxidation chemistry of linear and branched alkanes is discussed with the aim of unifying their complex behavior in various experimental systems using a single detailed kinetic model. New experimental data, obtained in a pressurized flow reactor, as well as in batch- and jet-stirred reactors, are useful for a better definition of the region ofmore » cool flames and negative temperature coefficient (NTC) for pure hydrocarbons from propane up to isooctane. Thermochemical oscillations and the NTC region of the reaction rate of the low-temperature oxidation of n-heptane and isooctane in a jet-stirred flow reactor are reproduced quite well by the model, not only in a qualitative way but in terms of the experimental frequencies and intensities of cool flames. Very good agreement is also observed for fuel conversion and intermediate-species formation. Irrespective of the experimental system, the same critical reaction steps always control these phenomena. The results contribute to the definition of a limited set of fundamental kinetic parameters that should be easily extended to model heavier alkanes.« less

Assessment of anaerobic biodegradability of five different solid organic wastes

NASA Astrophysics Data System (ADS)

Kristanto, Gabriel Andari; Asaloei, Huinny

2017-03-01

The concept of waste to energy emerges as an alternative solution to increasing waste generation and energy crisis. In the waste to energy concept, waste will be used to produce renewable energy through thermochemical, biochemical, and physiochemical processes. In an anaerobic digester, organic matter brake-down due to anaerobic bacteria produces methane gas as energy source. The organic waste break-down is affected by various characteristics of waste components, such as organic matter content (C, N, O, H, P), solid contents (TS and VS), nutrients ratio (C/N), and pH. This research aims to analyze biodegradability and potential methane production (CH4) from organic waste largely available in Indonesia. Five solid wastes comprised of fecal sludge, cow rumen, goat farm waste, traditional market waste, and tofu dregs were analyzed which showed tofu dregs as waste with the highest rate of biodegradability compared to others since the tofu dregs do not contain any inhibitor which is lignin, have 2.7%VS, 14 C/N ratios and 97.3% organic matter. The highest cumulative methane production known as Biochemical Methane Potential was achieved by tofu dregs with volume of 77 ml during 30-day experiment which then followed by cow rumen, goat farm waste, and traditional market waste. Subsequently, methane productions were calculated through percentage of COD reduction, which showed the efficiency of 99.1% that indicates complete conversion of the high organic matter into methane.

A perspective on renewable bioenergy from photosynthetic algae as feedstock for biofuels and bioproducts

DOE PAGES

Laurens, Lieve M. L.; Chen-Glasser, Melodie; McMillan, James D.

2017-04-15

There has been substantial technical progress in developing algae-based bioenergy in recent years and a large part of industry and academic research and deployment projects have pivoted away from a pure biofuels strategy. This letter summarizes the findings of a recently completed, comprehensive report, that represents a collaborative effort of at least 20 co-authors, where we analyzed the prospects for using microalgae and macroalgae as feedstocks for biofuels and bioenergy production. The scope of this report includes a discussion of international activities advancing bioenergy and non-energy bioproducts from algae, progress on the use of macroalgae (both cast and cultivated seaweeds)more » for biogas applications, distinct biochemical and thermochemical conversion pathways, multi-product biorefining opportunities, as well as a thorough review of process economics and sustainability considerations. It is envisioned that a higher value algal biomass-based bioproducts industry will provide the additional revenue needed to reduce the net cost of producing algae-based biofuels. As such, a biorefinery approach that generates multiple high-value products from algae will be essential to fully valorize algal biomass and enable economically viable coproduction of bioenergy. Furthermore, to accelerate the implementation of algae-based production, minimizing energy, water, nutrients and land use footprints of integrated algae-based operations needs to be a primary objective of larger scale demonstrations and future research and development.« less

Development and Optimization of a Flocculation Procedure for Improved Solid-Liquid Separation of Digested Biomass

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

Patton, Caroline; Lischeske, James J.; Sievers, David A.

2015-11-03

One viable treatment method for conversion of lignocellulosic biomass to biofuels begins with saccharification (thermochemical pretreatment and enzymatic hydrolysis), followed by fermentation or catalytic upgrading to fuels such as ethanol, butanol, or other hydrocarbons. The post-hydrolysis slurry is typically 4-8 percent insoluble solids, predominantly consisting of lignin. Suspended solids are known to inhibit fermentation as well as poison catalysts and obstruct flow in catalyst beds. Thus a solid-liquid separation following enzymatic hydrolysis would be highly favorable for process economics, however the material is not easily separated by filtration or gravimetric methods. Use of a polyacrylamide flocculant to bind the suspendedmore » particles in a corn stover hydrolyzate slurry into larger flocs (1-2mm diameter) has been found to be extremely helpful in improving separation. Recent and ongoing research on novel pretreatment methods yields hydrolyzate material with diverse characteristics. Therefore, we need a thorough understanding of rapid and successful flocculation design in order to quickly achieve process design goals. In this study potential indicators of flocculation performance were investigated in order to develop a rapid analysis method for flocculation procedure in the context of a novel hydrolyzate material. Flocculation conditions were optimized on flocculant type and loading, pH, and mixing time. Filtration flux of the hydrolyzate slurry was improved 170-fold using a cationic polyacrylamide flocculant with a dosing of approximately 22 mg flocculant/g insoluble solids at an approximate pH of 3. With cake washing, sugar recovery exceeded 90 percent with asymptotic yield at 15 L wash water/kg insoluble solids.« less

Effect of dry torrefaction on kinetics of catalytic pyrolysis of sugarcane bagasse

NASA Astrophysics Data System (ADS)

Daniyanto, Sutijan, Deendarlianto, Budiman, Arief

2015-12-01

Decreasing world reserve of fossil resources (i.e. petroleum oil, coal and natural gas) encourage discovery of renewable resources as subtitute for fossil resources. Biomass is one of the main natural renewable resources which is promising resource as alternate resources to meet the world's energy needs and raw material to produce chemical platform. Conversion of biomass, as source of energy, fuel and biochemical, is conducted using thermochemical process such as pyrolysis-gasification process. Pyrolysis step is an important step in the mechanism of pyrolysis - gasification of biomass. The objective of this study is to obtain the kinetic reaction of catalytic pyrolysis of dry torrified sugarcane bagasse which used Ca and Mg as catalysts. The model of kinetic reaction is interpreted using model n-order of single reaction equation of biomass. Rate of catalytic pyrolysis reaction depends on the weight of converted biomass into char and volatile matters. Based on TG/DTA analysis, rate of pyrolysis reaction is influenced by the composition of biomass (i.e. hemicellulose, cellulose and lignin) and inorganic component especially alkali and alkaline earth metallic (AAEM). From this study, it has found two equations rate of reaction of catalytic pyrolysis in sugarcane bagasse using catalysts Ca and Mg. First equation is equation of pyrolysis reaction in rapid zone of decomposition and the second equation is slow zone of decomposition. Value of order reaction for rapid decomposition is n > 1 and for slow decomposition is n<1. Constant and order of reactions for catalytic pyrolysis of dry-torrified sugarcane bagasse with presence of Ca tend to higher than that's of presence of Mg.

Pyrolysis and gasification of landfilled plastic wastes with Ni-Mg-La/Al2O3 catalyst.

PubMed

Kaewpengkrow, Prangtip; Atong, Duangduen; Sricharoenchaikul, Viboon

2012-12-01

Pyrolysis and gasification processes were utilized to study the feasibility of producing fuels from landfilled plastic wastes. These wastes were converted in a gasifier at 700-900 degrees C. The equivalence ratio (ER) was varied from 0.4-0.6 with or without addition ofa Ni-Mg-La/Al2O3 catalyst. The pyrolysis and gasification of plastic wastes without catalyst resulted in relatively low H2, CO and other fuel gas products with methane as the major gaseous species. The highest lower heating value (LHV) was obtained at 800 degrees C and for an ER of 0.4, while the maximum cold gas efficiency occurred at 700 degrees C and for an ER of 0.4. The presence of the Ni-Mg-La/Al2O3 catalyst significantly enhanced H2 and CO production as well as increasing the gas energy content to 15.76-19.26 MJ/m3, which is suitable for further usage as quality fuel gas. A higher temperature resulted in more H2 and CO and other product gas yields, while char and liquid (tars) decreased. The maximum gas yield, gas calorific value and cold gas efficiency were achieved when the Ni-Mg-La/Al2O3 catalyst was used at 900 degrees C. In general, addition of prepared catalyst resulted in greater H2, CO and other light hydrocarbon yields from superior conversion of wastes to these gases. Thus, thermochemical treatment of these problematic wastes using pyrolysis and gasification processes is a very attractive alternative for sustainable waste management.

Comparison of ethanol production from corn cobs and switchgrass following a pyrolysis-based biorefinery approach.

PubMed

Luque, Luis; Oudenhoven, Stijn; Westerhof, Roel; van Rossum, Guus; Berruti, Franco; Kersten, Sascha; Rehmann, Lars

2016-01-01

One of the main obstacles in lignocellulosic ethanol production is the necessity of pretreatment and fractionation of the biomass feedstocks to produce sufficiently pure fermentable carbohydrates. In addition, the by-products (hemicellulose and lignin fraction) are of low value, when compared to dried distillers grains (DDG), the main by-product of corn ethanol. Fast pyrolysis is an alternative thermal conversion technology for processing biomass. It has recently been optimized to produce a stream rich in levoglucosan, a fermentable glucose precursor for biofuel production. Additional product streams might be of value to the petrochemical industry. However, biomass heterogeneity is known to impact the composition of pyrolytic product streams, as a complex mixture of aromatic compounds is recovered with the sugars, interfering with subsequent fermentation. The present study investigates the feasibility of fast pyrolysis to produce fermentable pyrolytic glucose from two abundant lignocellulosic biomass sources in Ontario, switchgrass (potential energy crop) and corn cobs (by-product of corn industry). Demineralization of biomass removes catalytic centers and increases the levoglucosan yield during pyrolysis. The ash content of biomass was significantly decreased by 82-90% in corn cobs when demineralized with acetic or nitric acid, respectively. In switchgrass, a reduction of only 50% for both acids could be achieved. Conversely, levoglucosan production increased 9- and 14-fold in corn cobs when rinsed with acetic and nitric acid, respectively, and increased 11-fold in switchgrass regardless of the acid used. After pyrolysis, different configurations for upgrading the pyrolytic sugars were assessed and the presence of potentially inhibitory compounds was approximated at each step as double integral of the UV spectrum signal of an HPLC assay. The results showed that water extraction followed by acid hydrolysis and solvent extraction was the best upgrading strategy. Ethanol yields achieved based on initial cellulose fraction were 27.8% in switchgrass and 27.0% in corn cobs. This study demonstrates that ethanol production from switchgrass and corn cobs is possible following a combined thermochemical and fermentative biorefinery approach, with ethanol yields comparable to results in conventional pretreatments and fermentation processes. The feedstock-independent fermentation ability can easily be assessed with a simple assay.

Plasma gasification of refuse derived fuel in a single-stage system using different gasifying agents.

PubMed

Agon, N; Hrabovský, M; Chumak, O; Hlína, M; Kopecký, V; Masláni, A; Bosmans, A; Helsen, L; Skoblja, S; Van Oost, G; Vierendeels, J

2016-01-01

The renewable evolution in the energy industry and the depletion of natural resources are putting pressure on the waste industry to shift towards flexible treatment technologies with efficient materials and/or energy recovery. In this context, a thermochemical conversion method of recent interest is plasma gasification, which is capable of producing syngas from a wide variety of waste streams. The produced syngas can be valorized for both energetic (heat and/or electricity) and chemical (ammonia, hydrogen or liquid hydrocarbons) end-purposes. This paper evaluates the performance of experiments on a single-stage plasma gasification system for the treatment of refuse-derived fuel (RDF) from excavated waste. A comparative analysis of the syngas characteristics and process yields was done for seven cases with different types of gasifying agents (CO2+O2, H2O, CO2+H2O and O2+H2O). The syngas compositions were compared to the thermodynamic equilibrium compositions and the performance of the single-stage plasma gasification of RDF was compared to that of similar experiments with biomass and to the performance of a two-stage plasma gasification process with RDF. The temperature range of the experiment was from 1400 to 1600 K and for all cases, a medium calorific value syngas was produced with lower heating values up to 10.9 MJ/Nm(3), low levels of tar, high levels of CO and H2 and which composition was in good agreement to the equilibrium composition. The carbon conversion efficiency ranged from 80% to 100% and maximum cold gas efficiency and mechanical gasification efficiency of respectively 56% and 95%, were registered. Overall, the treatment of RDF proved to be less performant than that of biomass in the same system. Compared to a two-stage plasma gasification system, the produced syngas from the single-stage reactor showed more favourable characteristics, while the recovery of the solid residue as a vitrified slag is an advantage of the two-stage set-up. Copyright © 2015 Elsevier Ltd. All rights reserved.

Aqueous stream characterization from biomass fast pyrolysis and catalytic fast pyrolysis

DOE PAGES

Black, Brenna A.; Michener, William E.; Ramirez, Kelsey J.; ...

2016-09-05

Here, biomass pyrolysis offers a promising means to rapidly depolymerize lignocellulosic biomass for subsequent catalytic upgrading to renewable fuels. Substantial efforts are currently ongoing to optimize pyrolysis processes including various fast pyrolysis and catalytic fast pyrolysis schemes. In all cases, complex aqueous streams are generated containing solubilized organic compounds that are not converted to target fuels or chemicals and are often slated for wastewater treatment, in turn creating an economic burden on the biorefinery. Valorization of the species in these aqueous streams, however, offers significant potential for substantially improving the economics and sustainability of thermochemical biorefineries. To that end, heremore » we provide a thorough characterization of the aqueous streams from four pilot-scale pyrolysis processes: namely, from fast pyrolysis, fast pyrolysis with downstream fractionation, in situ catalytic fast pyrolysis, and ex situ catalytic fast pyrolysis. These configurations and processes represent characteristic pyrolysis processes undergoing intense development currently. Using a comprehensive suite of aqueous-compatible analytical techniques, we quantitatively characterize between 12 g kg -1 of organic carbon of a highly aqueous catalytic fast pyrolysis stream and up to 315 g kg -1 of organic carbon present in the fast pyrolysis aqueous streams. In all cases, the analysis ranges between 75 and 100% of mass closure. The composition and stream properties closely match the nature of pyrolysis processes, with high contents of carbohydrate-derived compounds in the fast pyrolysis aqueous phase, high acid content in nearly all streams, and mostly recalcitrant phenolics in the heavily deoxygenated ex situ catalytic fast pyrolysis stream. Overall, this work provides a detailed compositional analysis of aqueous streams from leading thermochemical processes -- analyses that are critical for subsequent development of selective valorization strategies for these waste streams.« less

Aqueous stream characterization from biomass fast pyrolysis and catalytic fast pyrolysis

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

Black, Brenna A.; Michener, William E.; Ramirez, Kelsey J.

Here, biomass pyrolysis offers a promising means to rapidly depolymerize lignocellulosic biomass for subsequent catalytic upgrading to renewable fuels. Substantial efforts are currently ongoing to optimize pyrolysis processes including various fast pyrolysis and catalytic fast pyrolysis schemes. In all cases, complex aqueous streams are generated containing solubilized organic compounds that are not converted to target fuels or chemicals and are often slated for wastewater treatment, in turn creating an economic burden on the biorefinery. Valorization of the species in these aqueous streams, however, offers significant potential for substantially improving the economics and sustainability of thermochemical biorefineries. To that end, heremore » we provide a thorough characterization of the aqueous streams from four pilot-scale pyrolysis processes: namely, from fast pyrolysis, fast pyrolysis with downstream fractionation, in situ catalytic fast pyrolysis, and ex situ catalytic fast pyrolysis. These configurations and processes represent characteristic pyrolysis processes undergoing intense development currently. Using a comprehensive suite of aqueous-compatible analytical techniques, we quantitatively characterize between 12 g kg -1 of organic carbon of a highly aqueous catalytic fast pyrolysis stream and up to 315 g kg -1 of organic carbon present in the fast pyrolysis aqueous streams. In all cases, the analysis ranges between 75 and 100% of mass closure. The composition and stream properties closely match the nature of pyrolysis processes, with high contents of carbohydrate-derived compounds in the fast pyrolysis aqueous phase, high acid content in nearly all streams, and mostly recalcitrant phenolics in the heavily deoxygenated ex situ catalytic fast pyrolysis stream. Overall, this work provides a detailed compositional analysis of aqueous streams from leading thermochemical processes -- analyses that are critical for subsequent development of selective valorization strategies for these waste streams.« less

Thermochemical hydrogen production via a cycle using barium and sulfur - Reaction between barium sulfide and water

NASA Technical Reports Server (NTRS)

Ota, K.; Conger, W. L.

1977-01-01

The reaction between barium sulfide and water, a reaction found in several sulfur based thermochemical cycles, was investigated kinetically at 653-866 C. Gaseous products were hydrogen and hydrogen sulfide. The rate determining step for hydrogen formation was a surface reaction between barium sulfide and water. An expression was derived for the rate of hydrogen formation.

Status of the DOE (STOR)-sponsored national program on hydrogen production from water via thermochemical cycles

NASA Technical Reports Server (NTRS)

Baker, C. E.

1977-01-01

The program structure is presented. The activities of the thermochemical cycles program are grouped according to the following categories: (1) specific cycle development, (2) support research and technology, (3) cycle evaluation. Specific objectives and status of on-going activities are discussed. Chemical reaction series for the production of hydrogen are presented. Efficiency and economic evaluations are also discussed.

The African and Pacific Superplumes and Thermochemical Piles and Their Relationship to Supercontinent Pangea

NASA Astrophysics Data System (ADS)

Zhong, S.; Leng, W.; Zhang, N.; McNamara, A. K.

2008-12-01

The long-wavelength structure for the present-day Earth's mantle is characterized by circum-Pacific subduction and the antipodal African and Pacific superplumes. The African and Pacific superplumes are anchored on two major thermochemical piles that extend from the core-mantle boundary (CMB) to possibly >500 km above CMB. These two superplumes are where most of large igneous provinces (LIPs) and plume-related volcanism are originated in the last 250 Ma. The thermochemical piles may provide distinct geochemical signatures observed in oceanic island basalts, although it remains controversial whether the piles consist of primordial mantle materials or recycled crust and lithosphere. Geodynamic modeling has demonstrated that the main structural features of the mantle including the circum-Pacific subduction, African and Pacific superplumes, and the thermochemical piles, are closely related to mantle convection associated with plate motion history for the last 120 Ma. However, outstanding questions remain. When did the African and Pacific superplumes and thermochemical piles start to take the current forms? How stable and stationary have they been in the mantle? How are they related to the observations of tectonics and volcanism priori to 120 Ma ago? Our recent studies on long-wavelength mantle convection and supercontinent cycles suggest that the African and Pacific superplumes and thermochemical piles are dynamic features and that they may move laterally in response to mantle flow associated with surface plate motion, such as past subduction and convergence between Laurentia and Gondwana. In particular, our studies suggest that the African superplume and pile did not form until Laurentia and Gondwana collided to form Pangea, while the Pacific anomaly may have been there for a longer time. Our results also suggest that, after lengthy convergence between Laurentia and Gondwana that pushed away the pile materials away from the African hemisphere, later subduction surrounding Pangea may not bring enough chemically dense mantle materials to form the African pile, if the pile consists of the primordial mantle, thus suggesting an origin of the recycled crust and lithosphere for the pile. While focusing on the African anomaly, we will also discuss potential ways to constrain the evolution of the Pacific superplume and pile.

SUNgas: Thermochemical Approaches to Solar Fuels

NASA Astrophysics Data System (ADS)

Davidson, Jane

2013-04-01

Solar energy offers an intelligent solution to reduce anthropogenic emissions of greenhouse gases and to meet an expanding global demand for energy. A transformative change from fossil to solar energy requires collection, storage, and transport of the earth's most abundant but diffuse and intermittent source of energy. One intriguing approach for harvest and storage of solar energy is production of clean fuels via high temperature thermochemical processes. Concentrated solar energy is the heat source and biomass or water and carbon dioxide are the feedstocks. Two routes to produce fuels using concentrated solar energy and a renewable feed stock will be discussed: gasification of biomass or other carbonaceous materials and metal oxide cycles to produce synthesis gas. The first and most near term route to solar fuels is to gasify biomass. With conventional gasification, air or oxygen is supplied at fuel-rich levels to combust some of the feedstock and in this manner generate the energy required for conversion to H2 and CO. The partial-combustion consumes up to 40% of the energetic value of the feedstock. With air combustion, the product gas is diluted by high levels of CO2 and N2. Using oxygen reduces the product dilution, but at the expense of adding an oxygen plant. Supplying the required heat with concentrated solar radiation eliminates the need for partial combustion of the biomass feedstock. As a result, the product gas has an energetic value greater than that of the feedstock and it is not contaminated by the byproducts of combustion. The second promising route to solar fuels splits water and carbon dioxide. Two-step metal-oxide redox cycles hold out great potential because they the temperature required to achieve a reasonable degree of dissociation is lower than direct thermal dissociation and O2 and the fuel are produced in separate steps. The 1^st step is the endothermic thermal dissociation of the metal oxide to the metal or lower-valence metal oxide. The 2^nd exothermic step is the hydrolysis of the reduced metal to form H2 and the corresponding metal oxide. Two promising options for 2-step cycles, the Zn/ZnO and non-stoichiometric ceria redox cycles, will be compared with a focus on efficiency and state of the art achievements.

Definitive Ideal-Gas Thermochemical Functions of the H216O Molecule

NASA Astrophysics Data System (ADS)

Furtenbacher, Tibor; Szidarovszky, Tamás; Hrubý, Jan; Kyuberis, Aleksandra A.; Zobov, Nikolai F.; Polyansky, Oleg L.; Tennyson, Jonathan; Császár, Attila G.

2016-12-01

A much improved temperature-dependent ideal-gas internal partition function, Qint(T), of the H216O molecule is reported for temperatures between 0 and 6000 K. Determination of Qint(T) is principally based on the direct summation technique involving all accurate experimental energy levels known for H216O (almost 20 000 rovibrational energies including an almost complete list up to a relative energy of 7500 cm-1), augmented with a less accurate but complete list of first-principles computed rovibrational energy levels up to the first dissociation limit, about 41 000 cm-1 (the latter list includes close to one million bound rovibrational energy levels up to J = 69, where J is the rotational quantum number). Partition functions are developed for ortho- and para-H216O as well as for their equilibrium mixture. Unbound rovibrational states of H216O above the first dissociation limit are considered using an approximate model treatment. The effect of the excited electronic states on the thermochemical functions is neglected, as their contribution to the thermochemical functions is negligible even at the highest temperatures considered. Based on the high-accuracy Qint(T) and its first two moments, definitive results, in 1 K increments, are obtained for the following thermochemical functions: Gibbs energy, enthalpy, entropy, and isobaric heat capacity. Reliable uncertainties (approximately two standard deviations) are estimated as a function of temperature for each quantity determined. These uncertainties emphasize that the present results are the most accurate ideal-gas thermochemical functions ever produced for H216O. It is recommended that the new value determined for the standard molar enthalpy increment at 298.15 K, 9.904 04 ± 0.000 01 kJ mol-1, should replace the old CODATA datum, 9.905 ± 0.005 kJ mol-1.

In vivo comparison of simultaneous versus sequential injection technique for thermochemical ablation in a porcine model.

PubMed

Cressman, Erik N K; Shenoi, Mithun M; Edelman, Theresa L; Geeslin, Matthew G; Hennings, Leah J; Zhang, Yan; Iaizzo, Paul A; Bischof, John C

2012-01-01

To investigate simultaneous and sequential injection thermochemical ablation in a porcine model, and compare them to sham and acid-only ablation. This IACUC-approved study involved 11 pigs in an acute setting. Ultrasound was used to guide placement of a thermocouple probe and coaxial device designed for thermochemical ablation. Solutions of 10 M acetic acid and NaOH were used in the study. Four injections per pig were performed in identical order at a total rate of 4 mL/min: saline sham, simultaneous, sequential, and acid only. Volume and sphericity of zones of coagulation were measured. Fixed specimens were examined by H&E stain. Average coagulation volumes were 11.2 mL (simultaneous), 19.0 mL (sequential) and 4.4 mL (acid). The highest temperature, 81.3°C, was obtained with simultaneous injection. Average temperatures were 61.1°C (simultaneous), 47.7°C (sequential) and 39.5°C (acid only). Sphericity coefficients (0.83-0.89) had no statistically significant difference among conditions. Thermochemical ablation produced substantial volumes of coagulated tissues relative to the amounts of reagents injected, considerably greater than acid alone in either technique employed. The largest volumes were obtained with sequential injection, yet this came at a price in one case of cardiac arrest. Simultaneous injection yielded the highest recorded temperatures and may be tolerated as well as or better than acid injection alone. Although this pilot study did not show a clear advantage for either sequential or simultaneous methods, the results indicate that thermochemical ablation is attractive for further investigation with regard to both safety and efficacy.

GH51 Arabinofuranosidase and Its Role in the Methylglucuronoarabinoxylan Utilization System in Paenibacillus sp. Strain JDR-2

PubMed Central

Sawhney, Neha

2014-01-01

Methylglucuronoarabinoxylan (MeGAXn) from agricultural residues and energy crops is a significant yet underutilized biomass resource for production of biofuels and chemicals. Mild thermochemical pretreatment of bagasse yields MeGAXn requiring saccharifying enzymes for conversion to fermentable sugars. A xylanolytic bacterium, Paenibacillus sp. strain JDR-2, produces an extracellular cell-associated GH10 endoxylanse (XynA1) which efficiently depolymerizes methylglucuronoxylan (MeGXn) from hardwoods coupled with assimilation of oligosaccharides for further processing by intracellular GH67 α-glucuronidase, GH10 endoxylanase, and GH43 β-xylosidase. This process has been ascribed to genes that comprise a xylan utilization regulon that encodes XynA1 and includes a gene cluster encoding transcriptional regulators, ABC transporters, and intracellular enzymes that convert assimilated oligosaccharides to fermentable sugars. Here we show that Paenibacillus sp. JDR-2 utilized MeGAXn without accumulation of oligosaccharides in the medium. The Paenibacillus sp. JDR-2 growth rate on MeGAXn was 3.1-fold greater than that on oligosaccharides generated from MeGAXn by XynA1. Candidate genes encoding GH51 arabinofuranosidases with potential roles were identified. Following growth on MeGAXn, quantitative reverse transcription-PCR identified a cluster of genes encoding a GH51 arabinofuranosidase (AbfB) and transcriptional regulators which were coordinately expressed along with the genes comprising the xylan utilization regulon. The action of XynA1 on MeGAXn generated arabinoxylobiose, arabinoxylotriose, xylobiose, xylotriose, and methylglucuronoxylotriose. Recombinant AbfB processed arabinoxylooligosaccharides to xylooligosaccharides and arabinose. MeGAXn processing by Paenibacillus sp. JDR-2 may be achieved by extracellular depolymerization by XynA1 coupled to assimilation of oligosaccharides and further processing by intracellular enzymes, including AbfB. Paenibacillus sp. JDR-2 provides a GH10/GH67 system complemented with genes encoding intracellular GH51 arabinofuranosidases for efficient utilization of MeGAXn. PMID:25063665

Development of a brazing process for the production of water- cooled bipolar plates made of chromium-coated metal foils for PEM fuel cells

NASA Astrophysics Data System (ADS)

Mueller, M.; Hoehlich, D.; Scharf, I.; Lampke, T.; Hollaender, U.; Maier, H. J.

2016-03-01

Beside lithium batteries, PEM fuel cells are the most promising strategy as a power source to achieve the targets for introducing and increasing the usage of electric vehicles. Due to limited space and weight problems, water cooled, metallic bipolar plates in a fuel cell metal stack are preferred in motor vehicles. These plates are stamped metal sheets with a complex structure, interconnected media-tight. To meet the multiple tasks and requirements in use, complex and expensive combinations of materials are currently in use (carbon fiber composites, graphite, gold-plated nickel, stainless and acid resistant steel). The production of such plates is expensive as it is connected with considerable effort or the usage of precious metals. As an alternative, metalloid nitrides (CrN, VN, W2N, etc.) show a high chemical resistance, hardness and a good conductivity. So this material category meets the basic requirements of a top layer. However, the standard methods for their production (PVD, CVD) are expensive and have a slow deposition rate and a lower layer thicknesses. Because of these limitations, a full functionality over the life cycle of a bipolar plate is not guaranteed. The contribution shows the development and quantification of an alternative production process for bipolar plates. The expectation is to get significant advantages from the combination of chromium electrodeposition and thermochemical treatment to form chromium nitrides. Both processes are well researched and suitable for series production. The thermochemical treatment of the chromium layer also enables a process-integrated brazing.

Online residence time distribution measurement of thermochemical biomass pretreatment reactors

DOE PAGES

Sievers, David A.; Kuhn, Erik M.; Stickel, Jonathan J.; ...

2015-11-03

Residence time is a critical parameter that strongly affects the product profile and overall yield achieved from thermochemical pretreatment of lignocellulosic biomass during production of liquid transportation fuels. The residence time distribution (RTD) is one important measure of reactor performance and provides a metric to use when evaluating changes in reactor design and operating parameters. An inexpensive and rapid RTD measurement technique was developed to measure the residence time characteristics in biomass pretreatment reactors and similar equipment processing wet-granular slurries. Sodium chloride was pulsed into the feed entering a 600 kg/d pilot-scale reactor operated at various conditions, and aqueous saltmore » concentration was measured in the discharge using specially fabricated electrical conductivity instrumentation. This online conductivity method was superior in both measurement accuracy and resource requirements compared to offline analysis. Experimentally measured mean residence time values were longer than estimated by simple calculation and screw speed and throughput rate were investigated as contributing factors. In conclusion, a semi-empirical model was developed to predict the mean residence time as a function of operating parameters and enabled improved agreement.« less

Thermochemical cyclic system for decomposing H/sub 2/O and/or CO/sub 2/ by means of cerium-titanium-sodium-oxygen compounds

DOEpatents

Bamberger, C.E.

1980-04-24

A thermochemical closed cyclic process for the decomposition of water and/or carbon dioxide to hydrogen and/or carbon monoxide begins with the reaction of ceric oxide (CeO/sub 2/), titanium dioxide (TiO/sub 2/) and sodium titanate (Na/sub 2/TiO/sub 3/) to form sodium cerous titanate (NaCeTi/sub 2/O/sub 6/) and oxygen. Sodium cerous titanate (NaCeTi/sub 2/O/sub 6/) reacted with sodium carbonate (Na/sub 2/CO/sub 3/) in the presence of steam, produces hydrogen. The same reaction, in the absence of steam, produces carbon monoxide. The products, ceric oxide and sodium titanate, obtained in either case, are treated with carbon dioxide and water to produce ceric oxide, titanium dioxide, sodium titanate, and sodium bicarbonate. After dissolving sodium bicarbonate from the mixture in water, the remaining insoluble compounds are used as starting materials for a subsequent cycle. The sodium bicarbonate can be converted to sodium carbonate by heating and returned to the cycle.

State-of-the-art thermochemical and kinetic computations for astrochemical complex organic molecules: formamide formation in cold interstellar clouds as a case study

PubMed Central

Vazart, Fanny; Calderini, Danilo; Puzzarini, Cristina; Skouteris, Dimitrios

2017-01-01

We propose an integrated computational strategy aimed at providing reliable thermochemical and kinetic information on the formation processes of astrochemical complex organic molecules. The approach involves state-of-the-art quantum-mechanical computations, second-order vibrational perturbation theory, and kinetic models based on capture and transition state theory together with the master equation approach. Notably, tunneling, quantum reflection, and leading anharmonic contributions are accounted for in our model. Formamide has been selected as a case study in view of its interest as a precursor in the abiotic amino acid synthesis. After validation of the level of theory chosen for describing the potential energy surface, we have investigated several pathways of the OH+CH2NH and NH2+HCHO reaction channels. Our results indicate that both reaction channels are essentially barrier-less (in the sense that all relevant transition states lie below or only marginally above the reactants) and can, therefore, occur under the low temperature conditions of interstellar objects provided that tunneling is taken into the proper account. PMID:27689448

Improving the Thermochemical Energy Storage Performance of the Mn2 O3 /Mn3 O4 Redox Couple by the Incorporation of Iron.

PubMed

Carrillo, Alfonso J; Serrano, David P; Pizarro, Patricia; Coronado, Juan M

2015-06-08

Redox cycles of manganese oxides (Mn2 O3 /Mn3 O4 ) are a promising alternative for thermochemical heat storage systems coupled to concentrated solar power plants as manganese oxides are abundant and inexpensive materials. Although their cyclability for such a purpose has been proved, sintering processes, related to the high-temperature conditions at which charge-discharge cycles are performed, generally cause a cycle-to-cycle decrease in the oxidation rate of Mn3 O4 . To guarantee proper operation, both reactions should present stable reaction rates. In this study, it has been demonstrated that the incorporation of Fe, which is also an abundant material, into the manganese oxides improves the redox performance of this system by increasing the heat storage density, narrowing the redox thermal hysteresis, and, above all, stabilizing and enhancing the oxidation rate over long-term operation, which counteracts the negative effects caused by sintering, although its presence is not avoided. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-Temperature Thermochemical Storage with Redox-Stable Perovskites for Concentrating Solar Power, CRADA Number: CRD-14-554

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

Ma, Zhiwen

As part of a Federal Opportunity Announcement (FOA) Award, the project will be led by Colorado School of Mines (CSM) to explore and demonstrate the efficacy of highly reducible, redox-stable oxides to provide efficient thermochemical energy storage for heat release at temperatures of 900 degrees Celcius or more. NREL will support the material development for its application in a concentrating solar power (CSP) plant. In the project, NREL will provide its inventive system design, chemical looping for CSP, and use it as a platform to accommodate the chemical processes using a cost effective perovskite materials identified by CSM. NREL willmore » design a 5-10kW particle receiver for perovskite reduction to store solar energy and help the development of a fluidized-bed reoxidation reactor and system integration. NREL will develop the demonstration receiver for on-sun test in the 5-10 kWt range in NREL's high flux solar furnace. NREL will assist in system analysis and provide techno-economic inputs for the overall system configuration.« less

Thermochemical cyclic system for decomposing H.sub.2 O and/or CO.sub.2 by means of cerium-titanium-sodium-oxygen compounds

DOEpatents

Bamberger, Carlos E.

1982-01-01

A thermochemical closed cyclic process for the decomposition of water and/or carbon dioxide to hydrogen and/or carbon monoxide begins with the reaction of ceric oxide (CeO.sub.2), titanium dioxide (TiO.sub.2) and sodium titanate (Na.sub.2 TiO.sub.3) to form sodium cerous titanate (NaCeTi.sub.2 O.sub.6) and oxygen. Sodium cerous titanate (NaCeTi.sub.2 O.sub.6) reacted with sodium carbonate (Na.sub.2 CO.sub.3) in the presence of steam, produces hydrogen. The same reaction, in the absence of steam, produces carbon monoxide. The products, ceric oxide and sodium titanate, obtained in either case, are treated with carbon dioxide and water to produce ceric oxide, titanium dioxide, sodium titanate, and sodium bicarbonate. After dissolving sodium bicarbonate from the mixture in water, the remaining insoluble compounds are used as starting materials for a subsequent cycle. The sodium bicarbonate can be converted to sodium carbonate by heating and returned to the cycle.

Marsilea spp.-A novel source of lignocellulosic biomass: Effect of solubilized lignin on anaerobic biodegradability and cost of energy products.

PubMed

Rajesh Banu, J; Sugitha, S; Kannah, R Yukesh; Kavitha, S; Yeom, Ick Tae

2018-05-01

The present study concerns the liquefying potential of an unusual source of lignocellulosic biomass (Marsilea spp., water clover, an aquatic fern) during combinative pretreatment. The focus was on how the pretreatment affects the biodegradability, methane production, and profitability of thermochemical dispersion disintegration (TCDD) based on liquefaction and soluble lignin. The TCDD process was effective at 12,000 rpm and 11 min under the optimized thermochemical conditions (80 °C and pH 11). The results from biodegradability tests imply that 30% liquefaction was sufficient to achieve enhanced biodegradability of about 0.280 g-COD/g-COD. When biodegradability was >30% inhibition was observed (0.267 and 0.264 g-COD/g-COD at 35-40% liquefaction) due to higher soluble lignin release (4.53-4.95 g/L). Scalable studies revealed that achievement of 30% liquefaction was beneficial in terms of the energy and cost benefit ratios (0.956 and 1.02), when compared to other choices. Copyright © 2018 Elsevier Ltd. All rights reserved.

Crystallization of Nanocomposite Glasses Made by the SSG Process

DTIC Science & Technology

1993-01-12

thermogravimetric analysis (TGA). The role of glass structure and composition in the thermochemical stability will be discussed. 37 II. EXPERIMENTAL PROCEDLRES The...applications in the materials field. tion and r-plot analysis of this porous nanocomposite showed Because of the nanoscale mixing of inorganic and organic a... nanoparticles in There is a need for substrates with very low relative permit- magnetic recording media can lead to smaller storage units tivitv 1ɛ) in %ery

Hydrogen as a Fuel for DOD (Defense Horizons, Number 36, Nov 2003)

DTIC Science & Technology

2003-11-01

could extend this period or expand this use considerably, longer-term options are still needed. The ultimate form of nuclear energy is fusion energy . If... fusion energy is eventually developed, it can be used to produce hydrogen by either electrolysis or thermochemical processes. It is expected that...hydrogen is very low, and removal of tritium from the hydro- gen would be impractical. Serious design studies were performed using fusion energy for

Methodology Report for H2SModel

DTIC Science & Technology

2012-01-01

thermochemical) cal (thermochemical/ cm2) curie degree (angl e ) degree Fahrenheit electron volt erg erg/second foot foot- pound- force gal l... Dosimetry ) model developed by Asgharian ([7, 10]) . First, transport of H2S in the lung is modeled by the area-averaged convective-diffusion equation...performance. Technical Report DNA TR 85 52, Defense Nuclear Agency, Washington, D.C. , 1984. [10] Asgharian, B., et al. Multiple Path Particle Dosimetry

Observations of Circumstellar Thermochemical Equilibrium: The Case of Phosphorus

NASA Technical Reports Server (NTRS)

Milam, Stefanie N.; Charnley, Steven B.

2011-01-01

We will present observations of phosphorus-bearing species in circumstellar envelopes, including carbon- and oxygen-rich shells 1. New models of thermochemical equilibrium chemistry have been developed to interpret, and constrained by these data. These calculations will also be presented and compared to the numerous P-bearing species already observed in evolved stars. Predictions for other viable species will be made for observations with Herschel and ALMA.

Computational Chemistry Comparison and Benchmark Database

National Institute of Standards and Technology Data Gateway

SRD 101 NIST Computational Chemistry Comparison and Benchmark Database (Web, free access)   The NIST Computational Chemistry Comparison and Benchmark Database is a collection of experimental and ab initio thermochemical properties for a selected set of molecules. The goals are to provide a benchmark set of molecules for the evaluation of ab initio computational methods and allow the comparison between different ab initio computational methods for the prediction of thermochemical properties.

Linking lowermost mantle structure, core-mantle boundary heat flux and mantle plume formation

NASA Astrophysics Data System (ADS)

Li, Mingming; Zhong, Shijie; Olson, Peter

2018-04-01

The dynamics of Earth's lowermost mantle exert significant control on the formation of mantle plumes and the core-mantle boundary (CMB) heat flux. However, it is not clear if and how the variation of CMB heat flux and mantle plume activity are related. Here, we perform geodynamic model experiments that show how temporal variations in CMB heat flux and pulses of mantle plumes are related to morphologic changes of the thermochemical piles of large-scale compositional heterogeneities in Earth's lowermost mantle, represented by the large low shear velocity provinces (LLSVPs). We find good correlation between the morphologic changes of the thermochemical piles and the time variation of CMB heat flux. The morphology of the thermochemical piles is significantly altered during the initiation and ascent of strong mantle plumes, and the changes in pile morphology cause variations in the local and the total CMB heat flux. Our modeling results indicate that plume-induced episodic variations of CMB heat flux link geomagnetic superchrons to pulses of surface volcanism, although the relative timing of these two phenomena remains problematic. We also find that the density distribution in thermochemical piles is heterogeneous, and that the piles are denser on average than the surrounding mantle when both thermal and chemical effects are included.

Water Footprint and Land Requirement of Solar Thermochemical Jet-Fuel Production.

PubMed

Falter, Christoph; Pitz-Paal, Robert

2017-11-07

The production of alternative fuels via the solar thermochemical pathway has the potential to provide supply security and to significantly reduce greenhouse gas emissions. H 2 O and CO 2 are converted to liquid hydrocarbon fuels using concentrated solar energy mediated by redox reactions of a metal oxide. Because attractive production locations are in arid regions, the water footprint and the land requirement of this fuel production pathway are analyzed. The water footprint consists of 7.4 liters per liter of jet fuel of direct demand on-site and 42.4 liters per liter of jet fuel of indirect demand, where the dominant contributions are the mining of the rare earth oxide ceria, the manufacturing of the solar concentration infrastructure, and the cleaning of the mirrors. The area-specific productivity is found to be 33 362 liters per hectare per year of jet fuel equivalents, where the land coverage is mainly due to the concentration of solar energy for heat and electricity. The water footprint and the land requirement of the solar thermochemical fuel pathway are larger than the best power-to-liquid pathways but an order of magnitude lower than the best biomass-to-liquid pathways. For the production of solar thermochemical fuels arid regions are best-suited, and for biofuels regions of a moderate and humid climate.

Methane on Titan: Photochemical-Meteorological-Hydrogeochemical Cycle

NASA Astrophysics Data System (ADS)

Atreya, S. K.; Niemann, H. B.; Owen, T. C.; Adams, E. Y.; Demick, J. E.; GCMS Team

2005-08-01

Photochemically driven destruction of methane in Titan's stratosphere leads to irreversible conversion to heavier hydrocarbons (1). The latter would largely condense out of the atmosphere (2). In the absence of recycling, Titan's methane would thus be destroyed in 10-100 million years (1). However, methane is key to the maintenance of Titan's nitrogen atmosphere. Without warming provided by CH4-generated hydrocarbon hazes in the stratosphere and pressure induced opacity in the infrared, particularly by H2-N2 and CH4-N2 collisions in the troposphere, the atmosphere would gradually diminish to tens of millibar pressure (3). Thus, the source-sink cycle of methane is crucial to the evolutionary history of Titan and its atmosphere. The GCMS measurements show that a ``methalogical" cycle with surface evaporation, cloud formation, followed by precipitation (rain) of methane exists. However, this ``closed" cycle does not recycle methane lost to heavy hydrocarbons. A source is required. Unlike the deep, hot, H2-rich interiors of the giant planets, Titan's interior is ill suited for thermochemical conversion of hydrocarbons back to methane. Instead we propose that serpentinization is an effective process for producing methane in Titan's interior (4). Hydration of ultramafic silicates, followed by reaction between the released H2 gas and CO2 or carbon grains can produce large quantities of CH4 at relatively mild (40-90oC) temperatures. Such thermal conditions are believed to exist below the purported water-ammonia ocean (5). Storage of methane produced via serpentinization can occur in form of clathrates. Evidence of outgassing from Titan's interior is provided by GCMS (6) and VIMS (7) data. (1) Wilson, Atreya, JGR 109, E06002, doi:10.1029/2003JE002181, 2004. (2) Wilson, Atreya, PSS 51, 1017, 2003. (3) Lorenz etal. Science 275, 642, 1997. (4) Owen etal. Phys. Uspekhi, in press. (5) Grasset, Pargamin, PSS 53, 371, 2005. (6) Niemann etal., Submitted to Nature, 2005. (7) Sotin etal., Nature 435, 786, 2005.

ThermoFit: A Set of Software Tools, Protocols and Schema for the Organization of Thermodynamic Data and for the Development, Maintenance, and Distribution of Internally Consistent Thermodynamic Data/Model Collections

NASA Astrophysics Data System (ADS)

Ghiorso, M. S.

2013-12-01

Internally consistent thermodynamic databases are critical resources that facilitate the calculation of heterogeneous phase equilibria and thereby support geochemical, petrological, and geodynamical modeling. These 'databases' are actually derived data/model systems that depend on a diverse suite of physical property measurements, calorimetric data, and experimental phase equilibrium brackets. In addition, such databases are calibrated with the adoption of various models for extrapolation of heat capacities and volumetric equations of state to elevated temperature and pressure conditions. Finally, these databases require specification of thermochemical models for the mixing properties of solid, liquid, and fluid solutions, which are often rooted in physical theory and, in turn, depend on additional experimental observations. The process of 'calibrating' a thermochemical database involves considerable effort and an extensive computational infrastructure. Because of these complexities, the community tends to rely on a small number of thermochemical databases, generated by a few researchers; these databases often have limited longevity and are universally difficult to maintain. ThermoFit is a software framework and user interface whose aim is to provide a modeling environment that facilitates creation, maintenance and distribution of thermodynamic data/model collections. Underlying ThermoFit are data archives of fundamental physical property, calorimetric, crystallographic, and phase equilibrium constraints that provide the essential experimental information from which thermodynamic databases are traditionally calibrated. ThermoFit standardizes schema for accessing these data archives and provides web services for data mining these collections. Beyond simple data management and interoperability, ThermoFit provides a collection of visualization and software modeling tools that streamline the model/database generation process. Most notably, ThermoFit facilitates the rapid visualization of predicted model outcomes and permits the user to modify these outcomes using tactile- or mouse-based GUI interaction, permitting real-time updates that reflect users choices, preferences, and priorities involving derived model results. This ability permits some resolution of the problem of correlated model parameters in the common situation where thermodynamic models must be calibrated from inadequate data resources. The ability also allows modeling constraints to be imposed using natural data and observations (i.e. petrologic or geochemical intuition). Once formulated, ThermoFit facilitates deployment of data/model collections by automated creation of web services. Users consume these services via web-, excel-, or desktop-clients. ThermoFit is currently under active development and not yet generally available; a limited capability prototype system has been coded for Macintosh computers and utilized to construct thermochemical models for H2O-CO2 mixed fluid saturation in silicate liquids. The longer term goal is to release ThermoFit as a web portal application client with server-based cloud computations supporting the modeling environment.

Thermochemical pretreatments for enhancing succinic acid production from industrial hemp (Cannabis sativa L.).

PubMed

Gunnarsson, Ingólfur B; Kuglarz, Mariusz; Karakashev, Dimitar; Angelidaki, Irini

2015-04-01

The aim of this study was to develop an efficient thermochemical method for treatment of industrial hemp biomass, in order to increase its bioconversion to succinic acid. Industrial hemp was subjected to various thermochemical pretreatments using 0-3% H2SO4, NaOH or H2O2 at 121-180°C prior to enzymatic hydrolysis. The influence of the different pretreatments on hydrolysis and succinic acid production by Actinobacillus succinogenes 130Z was investigated in batch mode, using anaerobic bottles and bioreactors. Enzymatic hydrolysis and fermentation of hemp material pretreated with 3% H2O2 resulted in the highest overall sugar yield (73.5%), maximum succinic acid titer (21.9 g L(-1)), as well as the highest succinic acid yield (83%). Results obtained clearly demonstrated the impact of different pretreatments on the bioconversion efficiency of industrial hemp into succinic acid. Copyright © 2015. Published by Elsevier Ltd.

Development and application of computational aerothermodynamics flowfield computer codes

NASA Technical Reports Server (NTRS)

Venkatapathy, Ethiraj

1993-01-01

Computations are presented for one-dimensional, strong shock waves that are typical of those that form in front of a reentering spacecraft. The fluid mechanics and thermochemistry are modeled using two different approaches. The first employs traditional continuum techniques in solving the Navier-Stokes equations. The second-approach employs a particle simulation technique (the direct simulation Monte Carlo method, DSMC). The thermochemical models employed in these two techniques are quite different. The present investigation presents an evaluation of thermochemical models for nitrogen under hypersonic flow conditions. Four separate cases are considered. The cases are governed, respectively, by the following: vibrational relaxation; weak dissociation; strong dissociation; and weak ionization. In near-continuum, hypersonic flow, the nonequilibrium thermochemical models employed in continuum and particle simulations produce nearly identical solutions. Further, the two approaches are evaluated successfully against available experimental data for weakly and strongly dissociating flows.

Expanding the biomass resource: sustainable oil production via fast pyrolysis of low input high diversity biomass and the potential integration of thermochemical and biological conversion routes.

PubMed

Corton, J; Donnison, I S; Patel, M; Bühle, L; Hodgson, E; Wachendorf, M; Bridgwater, A; Allison, G; Fraser, M D

2016-09-01

Waste biomass is generated during the conservation management of semi-natural habitats, and represents an unused resource and potential bioenergy feedstock that does not compete with food production. Thermogravimetric analysis was used to characterise a representative range of biomass generated during conservation management in Wales. Of the biomass types assessed, those dominated by rush ( Juncus effuses ) and bracken ( Pteridium aquilinum ) exhibited the highest and lowest volatile compositions respectively and were selected for bench scale conversion via fast pyrolysis. Each biomass type was ensiled and a sub-sample of silage was washed and pressed. Demineralization of conservation biomass through washing and pressing was associated with higher oil yields following fast pyrolysis. The oil yields were within the published range established for the dedicated energy crops miscanthus and willow. In order to examine the potential a multiple output energy system was developed with gross power production estimates following valorisation of the press fluid, char and oil. If used in multi fuel industrial burners the char and oil alone would displace 3.9 × 10 5  tonnes per year of No. 2 light oil using Welsh biomass from conservation management. Bioenergy and product development using these feedstocks could simultaneously support biodiversity management and displace fossil fuels, thereby reducing GHG emissions. Gross power generation predictions show good potential.

Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies: Evaluation Number 18

NASA Technical Reports Server (NTRS)

Burkholder, J. B.; Sander, S. P.; Abbatt, J. P. D.; Barker, J. R.; Huie, R. E.; Kolb, C. E.; Kurylo, M. J.; Orkin, V. L.; Wilmouth, D. M.; Wine, P. H.

2015-01-01

This is the eighteenth in a series of evaluated sets of rate constants, photochemical cross sections, heterogeneous parameters, and thermochemical parameters compiled by the NASA Panel for Data Evaluation. The data are used primarily to model stratospheric and upper tropospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. The evaluation is available in electronic form from the following Internet URL: http://jpldataeval.jpl.nasa.gov/

Removal of Oxygen from Electronic Materials by Vapor-Phase Processes

NASA Technical Reports Server (NTRS)

Palosz, Witold

1997-01-01

Thermochemical analyses of equilibrium partial pressures over oxides with and without the presence of the respective element condensed phase, and hydrogen, chalcogens, hydrogen chalcogenides, and graphite are presented. Theoretical calculations are supplemented with experimental results on the rate of decomposition and/or sublimation/vaporization of the oxides under dynamic vacuum, and on the rate of reaction with hydrogen, graphite, and chalcogens. Procedures of removal of a number of oxides under different conditions are discussed.

Seasonal Solar Thermal Absorption Energy Storage Development.

PubMed

Daguenet-Frick, Xavier; Gantenbein, Paul; Rommel, Mathias; Fumey, Benjamin; Weber, Robert; Gooneseker, Kanishka; Williamson, Tommy

2015-01-01

This article describes a thermochemical seasonal storage with emphasis on the development of a reaction zone for an absorption/desorption unit. The heat and mass exchanges are modelled and the design of a suitable reaction zone is explained. A tube bundle concept is retained for the heat and mass exchangers and the units are manufactured and commissioned. Furthermore, experimental results of both absorption and desorption processes are presented and the exchanged power is compared to the results of the simulations.

A theoretical thermochemical study of solute-solvent dielectric effects in the displacement of codon-anticodon base pairs

NASA Astrophysics Data System (ADS)

Monajjemi, M.; Razavian, M. H.; Mollaamin, F.; Naderi, F.; Honarparvar, B.

2008-12-01

Quantum-chemical solvent effect theories describe the electronic structure of a molecular subsystem embedded in a solvent or other molecular environment. The solvation of biomolecules is important in molecular biology, since numerous processes involve proteins interacting in changing solvent-solute systems. In this theoretical study, we focus on mRNA-tRNA base pairs as a fundamental step in protein synthesis influenced by hydrogen bonding between two antiparallel trinucleotides, namely, the mRNA codon and tRNA anticodon. We use the mean reaction field theories, which describe electrostatic and polarization interactions between solute and solvent in the AAA, UUU, AAG, and UUC triplex sequences optimized in various solvent media such as water, dimethylsulfoxide, methanol, ethanol, and cyclopean using the self-consistent reaction field model. This process depends on either the reaction potential function of the solvent or charge transfer operators that appear in solute-solvent interaction. Because of codon and anticodon biological criteria, we performed nonempirical quantum-mechanical calculations at the BLYP and B3LYP/3-21G, 6-31G, and 6-31G* levels of theory in the gas phase and five solvents at three temperatures. Finally, to obtain more information, we calculated thermochemical parameters to find that the dielectric constant of solvents plays an important role in the displacement of amino acid sequences on codon-anticodon residues in proteins, which can cause some mutations in humans.

Scaling up of renewable chemicals.

PubMed

Sanford, Karl; Chotani, Gopal; Danielson, Nathan; Zahn, James A

2016-04-01

The transition of promising technologies for production of renewable chemicals from a laboratory scale to commercial scale is often difficult and expensive. As a result the timeframe estimated for commercialization is typically underestimated resulting in much slower penetration of these promising new methods and products into the chemical industries. The theme of 'sugar is the next oil' connects biological, chemical, and thermochemical conversions of renewable feedstocks to products that are drop-in replacements for petroleum derived chemicals or are new to market chemicals/materials. The latter typically offer a functionality advantage and can command higher prices that result in less severe scale-up challenges. However, for drop-in replacements, price is of paramount importance and competitive capital and operating expenditures are a prerequisite for success. Hence, scale-up of relevant technologies must be interfaced with effective and efficient management of both cell and steel factories. Details involved in all aspects of manufacturing, such as utilities, sterility, product recovery and purification, regulatory requirements, and emissions must be managed successfully. Copyright © 2016 Elsevier Ltd. All rights reserved.

Allothermal steam gasification of biomass in cyclic multi-compartment bubbling fluidized-bed gasifier/combustor - new reactor concept.

PubMed

Iliuta, Ion; Leclerc, Arnaud; Larachi, Faïçal

2010-05-01

A new reactor concept of allothermal cyclic multi-compartment fluidized bed steam biomass gasification is proposed and analyzed numerically. The concept combines space and time delocalization to approach an ideal allothermal gasifier. Thermochemical conversion of biomass in periodic time and space sequences of steam biomass gasification and char/biomass combustion is simulated in which the exothermic combustion compartments provide heat into an array of interspersed endothermic steam gasification compartments. This should enhance unit heat integration and thermal efficiency and procure N(2)-free biosyngas with recourse neither to oxygen addition in steam gasification nor contact between flue and syngas. The dynamic, one-dimensional, multi-component, non-isothermal model developed for this concept accounts for detailed solid and gas flow dynamics whereupon gasification/combustion reaction kinetics, thermal effects and freeboard-zone reactions were tied. Simulations suggest that allothermal operation could be achieved with switch periods in the range of a minute supporting practical feasibility for portable small-scale gasification units. Copyright 2009 Elsevier Ltd. All rights reserved.

A review of catalytic microwave pyrolysis of lignocellulosic biomass for value-added fuel and chemicals.

PubMed

Morgan, Hervan Marion; Bu, Quan; Liang, Jianghui; Liu, Yujing; Mao, Hanping; Shi, Aiping; Lei, Hanwu; Ruan, Roger

2017-04-01

Lignocellulosic biomass is an abundant renewable resource and can be efficiently converted into bio-energy by a bio-refinery. From the various techniques available for biomass thermo-chemical conversion; microwave assisted pyrolysis (MAP) seems to be the very promising. The principles of microwave technology were reviewed and the parameters for the efficient production of bio-oil using microwave technology were summarized. Microwave technology by itself cannot efficiently produce high quality bio-oil products, catalysts are used to improve the reaction conditions and selectivity for valued products during MAP. The catalysts used to optimize MAP are revised in the development of this article. The origins for bio-oils that are phenol rich or hydrocarbon rich are reviewed and their experimental results were summarized. The kinetics of MAP is discussed briefly in the development of the article. Future prospects and scientific development of MAP are also considered in the development of this article. Copyright © 2017 Elsevier Ltd. All rights reserved.

Experiments Developed to Study Microgravity Smoldering Combustion

NASA Technical Reports Server (NTRS)

Vergilii, Franklin

2001-01-01

The overall objective of the Microgravity Smoldering Combustion (MSC) research program is to understand and predict smoldering combustion under normal and microgravity (near-zero-gravity) conditions to help prevent and control smolder-originated fires, in both environments. Smoldering is defined as a nonflaming, self-sustaining, propagating, exothermic surface reaction. If a material is sufficiently permeable, smoldering is not confined to its outer surface, but can propagate as a reaction wave through the interior of the material. The MSC program will accomplish its goals by conducting smolder experiments on the ground and in a space-based laboratory, and developing theoretical models of the process. Space-based experiments are necessary because smoldering is a very slow process and, consequently, its study in a microgravity environment requires extended periods of time that can only be achieved in space. Smoldering can occur in a variety of processes ranging from the smolder of porous insulating materials to underground coal combustion. Many materials can sustain smoldering, including wood, cloth, foams, tobacco, other dry organic materials, and charcoal. The ignition, propagation, transition to flaming, and extinction of the smolder reaction are controlled by complex, thermochemical mechanisms that are not well understood. As with many forms of combustion, gravity affects the availability of the oxidizer and the transport of heat, and therefore, the rate of combustion. The smoldering combustion of porous materials has been studied both experimentally and theoretically, usually in the context of fire safety. Smoldering encompasses a number of fundamental processes, including heat and mass transfer in a porous media; endothermic pyrolysis of combustible material; ignition, propagation, and extinction of heterogeneous exothermic reactions at the solid-gas pore interface; and the onset of gas phase reactions (flaming) from existing surface reactions. Smoldering presents a serious fire risk because the combustion can propagate slowly in a material's interior and go undetected for long periods of time. It typically yields a substantially higher conversion of fuel to toxic compounds than does flaming (though more slowly), and may undergo a sudden transition to flaming.

Dynamics of Compressible Convection and Thermochemical Mantle Convection

NASA Astrophysics Data System (ADS)

Liu, Xi

The Earth's long-wavelength geoid anomalies have long been used to constrain the dynamics and viscosity structure of the mantle in an isochemical, whole-mantle convection model. However, there is strong evidence that the seismically observed large low shear velocity provinces (LLSVPs) in the lowermost mantle are chemically distinct and denser than the ambient mantle. In this thesis, I investigated how chemically distinct and dense piles influence the geoid. I formulated dynamically self-consistent 3D spherical convection models with realistic mantle viscosity structure which reproduce Earth's dominantly spherical harmonic degree-2 convection. The models revealed a compensation effect of the chemically dense LLSVPs. Next, I formulated instantaneous flow models based on seismic tomography to compute the geoid and constrain mantle viscosity assuming thermochemical convection with the compensation effect. Thermochemical models reconcile the geoid observations. The viscosity structure inverted for thermochemical models is nearly identical to that of whole-mantle models, and both prefer weak transition zone. Our results have implications for mineral physics, seismic tomographic studies, and mantle convection modelling. Another part of this thesis describes analyses of the influence of mantle compressibility on thermal convection in an isoviscous and compressible fluid with infinite Prandtl number. A new formulation of the propagator matrix method is implemented to compute the critical Rayleigh number and the corresponding eigenfunctions for compressible convection. Heat flux and thermal boundary layer properties are quantified in numerical models and scaling laws are developed.

Waste biomass-to-energy supply chain management: a critical synthesis.

PubMed

Iakovou, E; Karagiannidis, A; Vlachos, D; Toka, A; Malamakis, A

2010-10-01

The development of renewable energy sources has clearly emerged as a promising policy towards enhancing the fragile global energy system with its limited fossil fuel resources, as well as for reducing the related environmental problems. In this context, waste biomass utilization has emerged as a viable alternative for energy production, encompassing a wide range of potential thermochemical, physicochemical and bio-chemical processes. Two significant bottlenecks that hinder the increased biomass utilization for energy production are the cost and complexity of its logistics operations. In this manuscript, we present a critical synthesis of the relative state-of-the-art literature as this applies to all stakeholders involved in the design and management of waste biomass supply chains (WBSCs). We begin by presenting the generic system components and then the unique characteristics of WBSCs that differentiate them from traditional supply chains. We proceed by discussing state-of-the-art energy conversion technologies along with the resulting classification of all relevant literature. We then recognize the natural hierarchy of the decision-making process for the design and planning of WBSCs and provide a taxonomy of all research efforts as these are mapped on the relevant strategic, tactical and operational levels of the hierarchy. Our critical synthesis demonstrates that biomass-to-energy production is a rapidly evolving research field focusing mainly on biomass-to-energy production technologies. However, very few studies address the critical supply chain management issues, and the ones that do that, focus mainly on (i) the assessment of the potential biomass and (ii) the allocation of biomass collection sites and energy production facilities. Our analysis further allows for the identification of gaps and overlaps in the existing literature, as well as of critical future research areas. (c) 2010 Elsevier Ltd. All rights reserved.