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At least 595 records · Page 33
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Process assessment of small scale low temperature methanol synthesis

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

09 BIOMASS FUELS↗
DOE OSTI2016

Integrated bioprocess for conversion of gaseous substrates to liquids

In the quest for inexpensive feedstocks for the cost-effective production of liquid fuels, we have examined gaseous substrates that could be made available at low cost and sufficiently large scale for industrial fuel production. In this work, we introduce a new bioconversion scheme that effectively converts syngas, generated from gasification of coal, natural gas, or biomass, into lipids that can be used for biodiesel production. We present an integrated conversion method comprising a two-stage system. In the first stage, an anaerobic bioreactor converts mixtures of gases of CO 2 and CO or H 2 to acetic acid, using the anaerobic acetogen Moorella thermoacetica . The acetic acid product is fed as a substrate to a second bioreactor, where it is converted aerobically into lipids by an engineered oleaginous yeast, Yarrowia lipolytica . We first describe the process carried out in each reactor and then present an integrated system that produces microbial oil, using synthesis gas as input. The integrated continuous bench-scale reactor system produced 18 g/L of C16-C18 triacylglycerides directly from synthesis gas, with an overall productivity of 0.19 g•L -1 •h -1 and a lipid content of 36%. Although suboptimal relative to the performance of the individual reactor components, the presented integrated system demonstrates the feasibility of substantial net fixation of carbon dioxide and conversion of gaseous feedstocks to lipids for biodiesel production. The system can be further optimized to approach the performance of its individual units so that it can be used for the economical conversion of waste gases from steel mills to valuable liquid fuels for transportation.

09 BIOMASS FUELS↗
DOE OSTI2023

Sorption-enhanced steam reforming of toluene using multifunctional perovskite phase transition sorbents in a chemical looping scheme

Abstract Sorption-enhanced steam reforming (SESR) of toluene (SESRT) using catalytic CO 2 sorbents is a promising route to convert the aromatic tar byproducts formed in lignocellulosic biomass gasification into hydrogen (H 2 ) or H 2 -rich syngas. Commonly used sorbents such as CaO are effective in capturing CO 2 initially but are prone to lose their sorption capacity over repeated cycles due to sintering at high temperatures. Herein, we present a demonstration of SESRT using A- and B-site doped Sr 1− x A’ x Fe 1− y B’ y O 3− δ (A’ = Ba, Ca; B’ = Co) perovskites in a chemical looping scheme. We found that surface impregnation of 5–10 mol% Ni on the perovskite was effective in improving toluene conversion. However, upon cycling, the impregnated Ni tends to migrate into the bulk and lose activity. This prompted the adoption of a dual bed configuration using a pre-bed of NiO/ γ –Al 2 O 3 catalyst upstream of the sorbent. A comparison is made between isothermal operation and a more traditional temperature-swing mode, where for the latter, an average sorption capacity of ∼38% was witnessed over five SESR cycles with H 2 -rich product syngas evidenced by a ratio of H 2 : CO x > 4.0. XRD analysis of fresh and cycled samples of Sr 0.25 Ba 0.75 Fe 0.375 Co 0.625 O 3- δ reveal that this material is an effective phase transition sorbent—capable of cyclically capturing and releasing CO 2 without irreversible phase changes occurring.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

What Is the Best Use of Biomass? A Harmonized LCA-TEA Framework Quantifying Economic and Environmental Metrics for Bioenergy Pathways

Bioresource utilization is expected to play a pivotal role in complementing existing energy pathways and enhancing energy resilience. This study develops a harmonized life cycle assessment (LCA) and techno-economic analysis (TEA) framework to evaluate the greenhouse gas (GHG) reduction potential, minimum fuel selling price (MFSP), and marginal abatement cost (MAC) of bioenergy pathways. We analyze 19 pathways, including liquid biofuels (via catalytic fast pyrolysis, Fischer–Tropsch synthesis, and gasification), bioelectricity, and biomass-to-hydrogen, with and without carbon capture and storage (CCS). The GHG impacts are assessed using the GREET 2022 model, while U.S. Billion-Ton 2016 biomass availability projections are used to estimate scale-up potential. Additionally, we evaluate the influence of a low-carbon electricity grid on pathway performance. Our results show that CCS implementation reduces carbon intensities (CI) to net-negative values for several pathways, with MAC ranging from $\$$32 to $\$$600 per metric ton (MT) CO2e avoided. Bioelectricity pathways with CCS achieve the lowest MAC ($\$$32–$\$$68/tCO2e), while liquid biofuels and hydrogen pathways remain critical for hard-to-abate sectors like aviation and heavy industry. Pathways with net-positive electricity demand benefit from a low-carbon grid, whereas those co-producing electricity experience increased MAC under lower electricity grid CI scenarios. This open-source framework provides a robust tool for harmonized evaluation of bioenergy pathways, enabling policymakers and stakeholders to identify cost-effective strategies for biomass utilization and carbon abatement at scale. The findings underscore the importance of CCS, co-product credits, and feedstock availability in optimizing bioenergy deployment for a low-carbon economy.

09 BIOMASS FUELS↗
DOE OSTI2023

Development of a 300 MWe Utility Scale Oxy-Fuel sCO2 Turbine

A 300 MWe direct-fired supercritical carbon dioxide (sCO2) oxy-fuel turbine is being developed that will burn natural gas-fired, coal syngas and even hydrogen mixtures capable of 1,150ºC turbine inlet temperature at 300 bar. This design will significantly improve the state-of-the-art for thermal efficiency and results in a high-pressure stream of CO2 with 98%+ carbon capture, making the power plant near emission-free and more efficient than Natural Gas Combined Cycle (NGCC) plants with carbon capture. This power plant will be capable of burning coal through gasification and cleanup of the synthesis gas (syngas). sCO2 power cycles are a transformational technology for the energy industry, providing higher efficiency heat source energy conversion for conventional and alternative energy sources. This novel cycle significantly reduces capital costs because of smaller equipment footprints, design modularity, and allows for rapid cyclic load and source following to balance solar and wind energy power swings. Oxy-fuel sCO2 cycles take these advantages even further, utilizing higher firing temperatures, improved efficiency, and simpler carbon capture strategies. This turbine will require cooled turbine nozzles and blades as well as advanced thermal management systems to accommodate these high temperatures. The cooled blade heat transfer correlations required new test programs at higher Reynolds number than air-breathing gas turbines for impingement, serpentine, and pin-fin regions. Novel blade optimization was performed to maximize aerodynamic efficiency, while minimizing cooling flows. A turbine layout was generated utilizing individual combustor cans with cooled liners feeding into a 6-stage axial flow turbine with cooled stator nozzles and turbine blades. The case design and thermal management preliminary design will be described.

Moore, Jeffrey↗
DOE OSTI2019

Screening Compounds for Fast Pyrolysis and Catalytic Biofuel Upgrading Using Artificial Neural Networks

Abstract There is significant interest among researchers in finding economically sustainable alternatives to fossil-derived drop-in fuels and fuel additives. Fast pyrolysis, a method for converting biomass into liquid hydrocarbons with the potential for use as fuels or fuel additives, is a promising technology that can be two to three times less expensive at scale when compared to alternative approaches such as gasification and fermentation. However, many bio-oils directly derived from fast pyrolysis have a high oxygen content and high acidity, indicating poor performance in diesel engines when used as fuels or fuel additives. Thus, a combination of selective fast pyrolysis and chemical catalysis could produce tuned bioblendstocks that perform optimally in diesel engines. The variance in performance for derived compounds introduces a feedback loop in researching acceptable fuels and fuel additives, as various combustion properties for these compounds must be determined after pyrolysis and catalytic upgrading occurs. The present work aims to reduce this feedback loop by utilizing artificial neural networks trained with quantitative structure-property relationship values to preemptively screen pure component compounds that will be produced from fast pyrolysis and catalytic upgrading. The quantitative structure-property relationship values selected as inputs for models are discussed, the cetane number and sooting propensity of compounds derived from the catalytic upgrading of phenol are predicted, and the viability of these compounds as fuels and fuel additives is analyzed. The model constructed to predict cetane number has a test set prediction root-mean-squared error of 9.874 cetane units, and the model constructed to predict yield sooting index has a test set prediction root-mean-squared error of 13.478 yield sooting index units (on the unified scale).

09 BIOMASS FUELS↗
DOE OSTI2020

Predicting the Cetane Number, Yield Sooting Index, Kinematic Viscosity, and Cloud Point for Catalytically Upgraded Pyrolysis Oil Using Artificial Neural Networks

Abstract The conversion of biomass using fast pyrolysis has the potential to be significantly less expensive at scale compared to alternative methods such as fermentation and gasification. Selective upgrading of the products of fast pyrolysis through chemical catalysis produces compounds with lower oxygen content and lower acidity; however, identifying the specific catalytic pathways for producing viable fuels and fuel additives often requires a trial-and-error approach. Specifically, key properties of the compounds must be experimentally tested to evaluate the viability of the resultant compounds. The present work proposes predictive models constructed with artificial neural networks (ANNs) for cetane number (CN), yield sooting index (YSI), kinematic viscosity (KV), and cloud point (CP), with blind test set median absolute errors of 5.14 cetane units, 3.36 yield sooting index units, 0.07 millimeters squared per second, and 4.89 degrees Celsius, respectively. Furthermore, the cetane number, yield sooting index, kinematic viscosity, and cloud point were predicted for over three hundred expected products from the catalytic upgrading of pyrolysis oil. It was discovered that 130 of these compounds have predicted cetane numbers greater than 40, with four of these compounds possessing predicted yield sooting index values significantly less than that of diesel fuel and predicted viscosities and cloud points comparable to that of diesel fuel.

09 BIOMASS FUELS↗
DOE OSTI2018

Optoacoustic Effects in Pentaerythritol Tetranitrate with Ultrafine Aluminum-Particle Inclusions under Pulsed-Laser Action

Results of studying optoacoustic characteristics of pentaerythritol tetranitrate (PETN) specimens with inclusions of ultrafine aluminum particles (100 nm) are presented. Regularities of the increase of extinction coefficient k{sub ef} and signal amplitude U on a piezodetector by increasing laser-pulse fluence H have been established. Estimates have been made, and it has been concluded that, during a laser pulse, heating of aluminum inclusions and a shell surrounding it occurs up to a gasification temperature and appear craters on a specimen’s surface appear at H > 0.1 J/cm{sup 2}.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Performance and Emissions Control of Commercial-Scale Biochar Production Unit

Abstract. Two commercial biochar production machines – a single-auger unit and a larger dual-auger version – were operated to evaluate feedstock specifications, biochar quality, throughput rates, and emissions profiles. Biochar was produced from woody biomass feedstocks of various species, contamination levels, comminution methods, and moisture contents. Feedstocks with ash content exceeding 15% dry basis or moisture content exceeding 25% wet basis were observed to decrease fixed carbon content of biochar and to increase the labor effort required to operate the machine. The dual-auger version of the machine was able to process 380 kg h -1 of biomass feedstock (dry basis) to produce 63 kg h -1 of biochar with a mean electricity demand of 4.5 kW. Average CO, propane, NO x , and SO 2 emission rates from the flare of this machine were measured to be 160, 120, 51, and 43 g h -1 , respectively, with total particulate matter (PM), PM 10 , and PM 2.5 emission rates of 380, 40, and 4.5 g h -1 , respectively. Results from these experiments indicate that high-quality biochar can be produced from a variety of feedstocks, including forest residuals, as long as the ash and moisture content are within the specifications. Future research and development should focus on increasing the throughput of the machine, implementing an automated control system to reduce the operational effort, and improving safety and product consistency. Keywords: Biochar, Biomass, Biomass conversion technology, Carbon sequestration, Forest residuals, Gasification, Pyrolysis.

Agriculture↗
DOE OSTI2018

Utilization of Wet Forest Biomass as both the Feedstock and Electricity Source for an Integrated Biochar Production System

Abstract. A belt dryer and gasifier generator set were integrated into a biochar production plant to use process heat to dry biomass feedstock from forest residuals and to provide electric power to the plant using a side stream of dried biomass. Experiments were conducted to characterize the dryer throughput and drying capacity using process heat from a stack heat exchanger attached to the biochar machine flare. A matrix of tests was conducted at high and low flow rates for both the heat exchanger air flow rate (which varied the temperature and heat input to the dryer) and the residence time of feedstock in the belt dryer. Mean feedstock input moisture during dryer characterization was 45% and the mean moisture after exiting the dryer was 27%. The optimal test condition, providing the greatest water removal rate, was determined to have high air flow rate through the heat exchanger and short dryer residence time. This condition was used to demonstrate the integrated system for an 8-h production day. The integrated system dried incoming feedstock from 36% to 22% with a dryer throughput rate of 495 kg h -1 w.b. and an evaporation rate of 88.8 kg h -1 , providing the necessary dry feedstock for the 20-kW gasifier generator set and the biochar machine, which produced 75 kg h -1 of biochar. This system required the operational effort of 0.92 labor hours per production hour. Results from this demonstration indicate that the integrated system provides key benefits in a biochar production operation including greater control of feedstock drying and the ability to operate without an external (non-biomass) source of fuel for electricity generation. Keywords: Biochar, Biomass, Biomass drying, Forest residuals, Gasification, Pyrolysis.

Agriculture↗
DOE OSTI2018

Performance Analysis of a Biomass Gasifier Genset at Varying Operating Conditions

Abstract. An All Power Labs PP20 gasifier generation set (Berkeley, Calif.) was tested to evaluate its suitability for powering biomass conversion technologies (BCT) at remote forest operations sites. Feedstock of the species tanoak (), coast redwood (), and Douglas fir () were tested at moisture contents of 15% and 25% (wet basis). The PP20 was connected to a load bank with five different load profiles designed to simulate possible BCT loads. Two parameters of power quality, voltage variability, and frequency deviation, were determined to be within acceptable limits. The unit also successfully powered a remote biochar operation in Branscomb, California. Emissions of the PP20, when compared to diesel generator regulations, would meet non-methane hydrocarbons (NMHC) and NO X requirements but exceed the CO emissions limits by a factor of ten. The CO emissions could be reduced by adding a catalytic converter. The results indicate that it is possible to use a PP20 unit to provide electric power for the highly variable loads of a BCT system. Keywords: Bioenergy, Biomass conversion technology, Gasification, Renewable energy.

Agriculture↗
DOE OSTI2018

Strategies for Reducing Moisture Content in Forest Residues at the Harvest Site

Abstract. The moisture content (MC) of biomass derived from forest residues can pose a challenge to biomass utilization. It plays a significant role in determining the cost of transportation and subsequent market price. Additionally, emerging biomass conversion technologies, such as gasification, torrefaction, and briquetting, have very narrow specifications for the MC (e.g., <15%) in their feedstocks. The goal of this study was to develop strategies for reducing moisture content by evaluating different arrangement patterns of forest residues and its effect on MC reduction at the harvest site. The study compared four different arrangement patterns including criss-cross, teepees, traditional piling (processor piled), and scattered residues in three different timber harvest units in northern California. Two of the arrangement patterns (criss-cross and processor piled) were also covered with a plastic cover. Samples were collected from each treatment using a transect method and were recorded for 12 months. There was an overall drop of MC from 52% (freshly cut) to 12% between all arrangements over the study period. The cost of construction per pile, averaged $37, $41, and $48 for teepees, criss-cross, and processor piles, respectively. Even though, there was no significant difference in MC reduction between piles (except scattered), each pile arrangement of forest residues directly affected biomass feedstock operations, logistics, and costs. Keywords: Feedstock quality, Logging slash, Transect sampling method, Woody biomass energy.

Agriculture↗
DOE OSTI2014

The Mesaba Energy Project: Clean Coal Power Initiative, Round 2

The Mesaba Energy Project is a nominal 600 MW integrated gasification combine cycle power project located in Northeastern Minnesota. It was selected to receive financial assistance pursuant to code of federal regulations ("CFR") 10 CFR 600 through a competitive solicitation under Round 2 of the Department of Energy's Clean Coal Power Initiative, which had two stated goals: (1) to demonstrate advanced coal-based technologies that can be commercialized at electric utility scale, and (2) to accelerate the likelihood of deploying demonstrated technologies for widespread commercial use in the electric power sector.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2014

Long Term Environment and Economic Impacts of Coal Liquefaction in China

The project currently is composed of six specific tasks – three research tasks, two outreach and training tasks, and one project management and communications task. Task 1 addresses project management and communication. Research activities focused on Task 2 (Describe and Quantify the Economic Impacts and Implications of the Development and Deployment of Coal-to-Liquid Facilities in China), Task 3 (Development of Alternative Coal Gasification Database), and Task 4 (Geologic Carbon Management Options). There also were significant activities related to Task 5 (US-China Communication, Collaboration, and Training on Clean Coal Technologies) as well as planning activity performed in support of Task 6 (Training Programs).

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2014

Computational Design and Experimental Validation of New Thermal Barrier Systems

This project (10/01/2010-9/30/2014), “Computational Design and Experimental Validation of New Thermal Barrier Systems”, originates from Louisiana State University (LSU) Mechanical Engineering Department and Southern University (SU) Department of Computer Science. This project will directly support the technical goals specified in DE-FOA-0000248, Topic Area 3: Turbine Materials, by addressing key technologies needed to enable the development of advanced turbines and turbine-based systems that will operate safely and efficiently using coal-derived synthesis gases. In this project, the focus is to develop and implement novel molecular dynamics method to improve the efficiency of simulation on novel TBC materials; perform high performance computing (HPC) on complex TBC structures to screen the most promising TBC compositions; perform material characterizations and oxidation/corrosion tests; and demonstrate our new thermal barrier coating (TBC) systems experimentally under integrated gasification combined cycle (IGCC) environments.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Task 3.3: Warm Syngas Cleanup and Catalytic Processes for Syngas Conversion to Fuels Subtask 3: Advanced Syngas Conversion to Fuels

This collaborative joint research project is in the area of advanced gasification and conversion, within the Chinese Academy of Sciences (CAS)-National Energy Technology Laboratory (NETL)-Pacific Northwest National Laboratory (PNNL) Memorandum of Understanding. The goal for this subtask is the development of advanced syngas conversion technologies.

Lebarbier Dagel, Vanessa M.↗
DOE OSTI2014

Bio-inspired MOF-based Catalysts for Lignin Valorization.

Lignin is a potentially plentiful source of renewable organics, with %7E50Mtons/yr produced by the pulp/paper industry and 200-300 Mtons/yr projected production by a US biofuels industry. This industry must process approximately 1 billion tons of biomass to meet the US Renewable Fuel goals. However, there are currently no efficient processes for converting lignin to value-added chemicals and drop-in fuels. Lignin is therefore an opportunity for production of valuable renewable chemicals, but presents staggering technical and economic challenges due to the quantities of material involved and the strong chemical bonds comprising this polymer. Aggressive chemistries and high temperatures are required to degrade lignin without catalysts. Moreover, chemical non-uniformity among lignins leads to complex product mixtures that tend to repolymerize. Conventional petrochemical approaches (pyrolysis, catalytic cracking, gasification) are energy intensive (400-800 degC), require complicated separations, and remove valuable chemical functionality. Low-temperature (25-200 degC) alternatives are clearly desirable, but enzymes are thermally fragile and incompatible with liquid organic compounds, making them impractical for large-scale biorefining. Alternatively, homogeneous catalysts, such as recently developed vanadium complexes, must be separated from product mixtures, while many heterogenous catalysts involve costly noble metals. The objective of this project is to demonstrate proof of concept that an entirely new class of biomimetic, efficient, and industrially robust synthetic catalysts based on nanoporous Metal- Organic Frameworks (MOFs) can be developed. Although catalytic MOFs are known, catalysis of bond cleavage reactions needed for lignin degradation is completely unexplored. Thus, fundamental research is required that industry and most sponsoring agencies are currently unwilling to undertake. We introduce MOFs infiltrated with titanium and nickel species as catalysts for the C-O bond hydrogenolysis in model compounds, which mimic the b-O-4, a-O-4, and 4-O-5 linkages of natural lignin. The versatile IRMOF-74(n) series is proposed as a platform for creating efficient hydrogenolysis catalysts as it not only displays tunable pore sizes, but also has the required thermal and chemical stability. The catalytic C-O bond cleavage occurs at 10 bar hydrogen pressure and temperatures as low as 120 degC. The conversion efficiency of the aromatic ether substrates into the corresponding hydrocarbons and phenols varies as PhCH 2 CH 2 OPh > PhCH 2 OPh > PhOPh (Ph = phenyl), while the catalytic activity generally follows the following trend Ni@IRMOF-74>Ti@IRMOF-74>IRMOF-74. Conversions as high as 80%, coupled with good selectivity for hydrogenolysis vs. hydrogenation, highlight the potential of MOF-based catalysts for the selective cleavage of recalcitrant aryl-ether bonds found in lignin and other biopolymers. This project supports the DOE Integrated Biorefinery Program goals, the objective of which is to convert biomass to fuels and high-value chemicals, by addressing an important technology gap: the lack of low-temperature catalysts suitable for industrial lignin degradation. Biomass, which is %7E30 wt% lignin, constitutes a potentially major source of platform chemicals that could improve overall profitability and productivity of all energy-related products, thereby benefiting consumers and reducing national dependence on imported oil. Additionally, DoD has a strong interest in low-cost drop-in fuels (Navy Biofuel Initiative) and has signed a Memorandum of Understanding with DOE and USDA to develop a sustainable biofuels industry.

Allendorf, Mark D.↗
DOE OSTI2014

Coal-Derived Warm Syngas Purification and CO 2 Capture-Assisted Methane Production

Gasifier-derived syngas from coal has many applications in the area of catalytic transformation to fuels and chemicals. Raw syngas must be treated to remove a number of impurities that would otherwise poison the synthesis catalysts. Inorganic impurities include alkali salts, chloride, sulfur compounds, heavy metals, ammonia, and various P, As, Sb, and Se- containing compounds. Systems comprising multiple sorbent and catalytic beds have been developed for the removal of impurities from gasified coal using a warm cleanup approach. This approach has the potential to be more economic than the currently available acid gas removal (AGR) approaches and improves upon currently available processes that do not provide the level of impurity removal that is required for catalytic synthesis application. Gasification also lends itself much more readily to the capture of CO 2 , important in the regulation and control of greenhouse gas emissions. CO 2 capture material was developed and in this study was demonstrated to assist in methane production from the purified syngas. Simultaneous CO 2 sorption enhances the CO methanation reaction through relaxation of thermodynamic constraint, thus providing economic benefit rather than simply consisting of an add-on cost for carbon capture and release. Molten and pre-molten LiNaKCO 3 can promote MgO and MgO-based double salts to capture CO 2 with high cycling capacity. A stable cycling CO 2 capacity up to 13 mmol/g was demonstrated. This capture material was specifically developed in this study to operate in the same temperature range and therefore integrate effectively with warm gas cleanup and methane synthesis. By combining syngas methanation, water-gas-shift, and CO 2 sorption in a single reactor, single pass yield to methane of 99% was demonstrated at 10 bar and 330°C when using a 20 wt% Ni/MgAl 2 O 4 catalyst and a molten-phase promoted MgO-based sorbent. Under model feed conditions both the sorbent and catalyst exhibited favorable stability after multiple test cycles. The cleanup for warm gas cleanup of inorganics was broken down into three major steps: chloride removal, sulfur removal, and the removal for a multitude of trace metal contaminants. Na 2 CO 3 was found to optimally remove chlorides at an operating temperature of 450ºC. For sulfur removal two regenerable ZnO beds are used for bulk H 2 S removal at 450ºC (<5 ppm S) and a non-regenerable ZnO bed for H 2 S polishing at 300ºC (<40 ppb S). It was also found that sulfur from COS could be adsorbed (to levels below our detection limit of 40 ppb) in the presence of water that leads to no detectable slip of H 2 S. Finally, a sorbent material comprising of Cu and Ni was found to be effective in removing trace metal impurities such as AsH 3 and PH 3 when operating at 300ºC. Proof-of-concept of the integrated cleanup process was demonstrated with gasifier-generated syngas produced at the Western Research Institute using Wyoming Decker Coal. When operating with a ~1 SLPM feed, multiple inorganic contaminant removal sorbents and a tar-reforming bed was able to remove the vast majority of contaminants from the raw syngas. A tar-reforming catalyst was employed due to the production of tars generated from the gasifier used in this particular study. It is envisioned that in a real application a commercial scale gasifier operating at a higher temperature would produce lesser amount of tar. Continuous operation of a poison-sensitive copper-based WGS catalyst located downstream from the cleanup steps resulted in successful demonstration.

54 ENVIRONMENTAL SCIENCES↗