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Use of hot gas cleanup is proposed for a later phase of the program. This system appears to have potential for efficient integration with hot gas cleanup in a power generation system. However, because it is air-blown it would not be a good choice for coproduction of clean gaseous or liquid fuels.

In addition to the programs given in Table , there is a program for developing the Wilsonville facility centered around hot gas cleanup. In January the hot gas particulate removal test facility at Wilsonville, Alabama, was expanded to include system development and integration studies for advanced power systems and was renamed the Wilsonville Power Systems Development Facility. The facility could ultimately be reworked for gasifier research. The two gasification research programs suffered a 58 percent reduction in funding in FY , with a further reduction proposed in the FY budget request.

Some additional discussion of advanced research opportunities for gasification can be found in Chapter 9. The raw gaseous products from coal gasification include hydrogen H 2 , carbon monoxide CO , carbon dioxide CO 2 , water H 2 O , ammonia NH 3 , hydrogen sulfide H 2 S , nitrogen N 2 , methane CH 4 , and, for the lower-temperature processes, higher hydrocarbons and tar. For conversion to ''clean" gas suitable for combustion in simple equipment or for further processing to other clean fuels or chemicals, the mixture is scrubbed to consist primarily of H 2 , CO, CH 4 , and N 2.

This type of "synthesis gas" syngas mixture is currently of industrial importance for production of commodity chemicals and, to a growing extent, production of fuels. In this section the following major product categories are discussed: hydrogen, synthetic natural gas, methanol and other oxygenated products from synthesis gas, and products from F-T Fischer-Tropsch synthesis. The costs presented are based on the standard utility financing used by DOE. Major uses for hydrogen include ammonia manufacture for fertilizers and the refining of petroleum liquids with low hydrogen and high sulfur content.

Hydrogen is also required to convert fossil resources into transportation fuels, since the hydrogen-to-carbon ratio for liquid transportation fuels is approximately two, compared to less than one for coal and slightly greater than one for petroleum tars. In addition, a high level of acid gas H 2 S, CO 2 , hydrogen chloride [HCl] removal is needed to maintain catalyst reactivity. Hydrogen can also be separated from synthesis gas by cryogenic distillation. Pressure swing methods for hydrogen separation are advantageous principally for small- and medium-scale applications.

If pure hydrogen could be obtained economically as a coproduct from the coal-derived fuel gas supplied for electric power generation, it might be used for high-efficiency fuel cell operation, hydrogenation of by-product coal pyrolysis. New materials to allow efficient, low-cost separation of hydrogen from coal-derived gas by selective membrane diffusion offer performance enhancements NRC, , as discussed further in Chapter 9. While the stoichiometry of the reaction is.

While the above methane synthesis reaction is highly exothermic, the gasification reactions to form synthesis gas are about equally endothermic, and the balancing of these reactions to minimize thermal losses from heating and cooling is essential for achievement of high-efficiency. A large number of catalysts and systems have been studied with the goal of minimizing cost. The one commercial SNG facility in the United States, the Great Plains plant in North Dakota, was built in the late s by a consortium of natural gas companies in anticipation of constraints on natural gas supply and associated price rises.

Despite the low-cost of coal today and technically satisfactory operation, the plant is only profitable because contractual product prices are higher than the market price and a large portion of the capital costs is borne by the federal government. The Great Plains plant uses 14 Lurgi dry bottom gasifiers followed by cold gas cleanup to reduce sulfur content to less than 1. Goals include improvement in sulfur tolerance by appropriate choice of catalyst and operating conditions, better reactor temperature control, and avoidance of carbon formation favored by low-hydrogen-content fuel gas.

Methane is also produced noncatalytically in low-temperature gasification by thermal equilibration. The Exxon fluidized-bed catalytic gasification process makes use of this reaction with cryo. Substitution of coal-generated low- and medium-Btu gas for natural gas for power generation and industrial use could make additional supplies of natural gas available for domestic and commercial consumers.

Thus, the need for major dedicated SNG manufacture could well be delayed beyond the year However, since the major cost and energy consumption are incurred by the gasification step, opportunities for improvement are similar to those for oxygen-blown advanced IGCC and fuel cell systems.

A program aimed at improving gasification thermal efficiency could be applied to both uses, providing an additional incentive for an integrated gasification program. By careful choice of catalyst and conditions, synthesis gas can be reacted to produce higher hydrocarbons and oxygenates such as methanol. These products are useful for commodity chemicals, are of increasing interest for use as transportation fuels, and have been considered for production of storable supplementary fuel for IGCC electric power plants EPRI, ; Tam et al.

The reaction between carbon monoxide and hydrogen to produce paraffinic oxygenates or hydrocarbons is extremely exothermic Probstein and Hicks, The heat evolved is approximately 20 percent of the heat of combustion of the product and, because of the narrow temperature range over which the catalysts provide satisfactory selectivity to the desired product, control of reaction temperature is a major engineering challenge.

The difference between the several catalytic processes in use or under development is largely related to differences in approach to temperature control and choice of catalyst. Methanol has been a major commodity for many years, with principal uses in the chemical industry and as a solvent.

It can also be used as a motor fuel and, with the requirement for inclusion of oxygenates in gasoline, its use for preparing. Methane can also be produced from coal pyrolysis, and lower-temperature processes can provide up to 20 percent methane by volume in the gasifier product. High-temperature entrained-flow processes produce little methane. Its direct use as a gasoline blending agent is limited by its relatively low solubility in gasoline and its tendency to be extracted by any water present in the gasoline distribution system.

Its use as the primary fuel component offers good performance but is limited by cost in competition with imported petroleum, a potential problem with formaldehyde emissions, and the difficulties of establishing an adequate distribution system and availability of automotive systems designed to use this fuel. Other limitations of methanol are its high toxicity, potential reaction with elastomers used in the automobile fuel system, the fact that it burns with an invisible flame, the potential for ground water pollution, and a limited driving range because of the low energy content per unit volume.

Both coal and natural gas can be used as syngas sources. The current commercial processes use a fixed-bed catalytic reactor in a gas recycle loop. There are a wide range of mechanical designs used to control the heat released from the reaction. Lurgi and Imperial Chemical Industries technologies currently dominate, but other designs are offered by Mitsubishi, Linde, and Toyo corporations.

New developments in methanol technology include use of a liquid-phase slurry reactor for methanol synthesis and fluidized-bed methanol synthesis being developed by Mitsubishi Gas Chemical. Liquid-phase slurry reactors offer improved control of temperature and are of considerable interest for both methanol and F-T hydrocarbon production. A DOE-owned liquid-phase slurry reactor plant at LaPorte, Texas, has been operated with industry cost sharing for a number of years.

In the fluidized-bed design a fine catalyst is fluidized by syngas. Better contact between syngas and catalyst gives a higher methanol concentration exiting the reactor, which reduces the quantity of recycled gas, the recycle compressor size, and the heat exchange area in the synthesis loop. A study on production technologies for liquid transportation fuels NRC, provides some perspective on costs of methanol production using both coal and natural gas as syngas sources.

At present, however, new plants for hydrocarbon fuel production from natural gas use the F-T synthesis, indicating no current major advantages for prior synthesis of methanol. This cost is approximately competitive with methanol production from coal using advanced technology and coproduction with electric power Tam, Even when domestic natural gas prices rise to a level where dedicated production from coal could compete economically, natural gas is expected to remain the lowest-cost syngas source for methanol production due to the large overseas supply of very low-cost natural gas.

Identify the geometry about interior atoms in ch3nh2 drag the items into the appropriate bins

However, as discussed later in the section on coal refineries and coproduct systems, coproduction with gasification combined-cycle power generation might be competitive with imported methanol. Such a process could be more efficient and advantageously integrated with coproduction of electricity. The F-T process reacts and polymerizes synthesis gas to produce a wide range of products: light hydrocarbon gases, paraffinic waxes, and oxygenates.

Further processing of these products is necessary to upgrade the waxy diesel fraction, the low-octane-number gasoline fraction, and the large amount of oxygenates in the product water. A premium diesel fuel can be manufactured from the higher-molecular-weight hydrocarbons and the wax. The gasoline boiling range fraction has low octane number and requires more substantial upgrading to produce useful motor fuel. The distillation of high-molecular-weight products can be adjusted by choice of catalyst and operating conditions; wax produced as an intermediate is hydrocracked to produce a high cetane product.

Greatest current interest is in the production of high-molecular-weight material for diesel and jet fuels, for which the low-sulfur and high hydrogen content compared to petroleum fractions commands a premium price. As with methanol, there is active industrial interest in the use of low-cost overseas natural gas to manufacture F-T synthesis products. Sasol Synthol circulating fluid bed; light olefins and olefinic naphtha from coal feed.

Slurry-phase process using coal feed; percent paraffins, percent olefins; 7 percent oxygenates. Commercialized in after year development program. F-T processes has been conducted by Exxon. Important research areas are in catalyst development and optimization of processing conditions. Highlights of F-T development and commercialization activities are summarized in Table The results of DOE-sponsored design and systems studies on the cost of coal liquids production for stand-alone indirect liquefaction plants and for coproduction of coal liquids with gasification-based power generation are discussed below see Coal Refineries and Coproduct Systems.

Air-to-Fuel Ratio for Combustion With Carbon Monoxide : Chemistry & Biology Concepts

In direct liquefaction, hydrogen is added to coal in a solvent slurry at elevated temperatures and pressures. The first U. Interest revived when the Arab oil embargo of caused high oil prices, resulting in increased federal funding for such research. The DOE provided much of the funding for these successful demonstrations, but none of the processes proved economical when oil prices fell in the early s. Overseas, Veba Oil and others built and operated a large-scale pilot plant at Bottrop, Germany, in the late s and early s.

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The facility is currently being used to hydrogenate chlorinated wastes. This facility was funded primarily by the German government. Demonstration of the liquid solvent extraction process developed by the British Coal Corporation is continuing at the Point of Ayr Plant in Wales with both industrial and government support. Products of direct coal liquefaction can be refined to meet all current specifications for transportation fuels derived from petroleum.

Major products are likely to be gasoline, propane, butane, and diesel fuel. Production of high-quality. Direct liquefaction is generally believed to be 5 to 10 percent higher in efficiency than indirect liquefaction because of lower consumption of gasified coal Stiegel, High octane is achieved by the high aromatic content of the liquids.

At one time, this was considered to be an advantage; however, the CAAAs Clean Air Act amendments of place sharp limits on the aromatic content of motor fuels in the United States. Fortunately, the benzene content of gasoline made from coal is extremely low; the concentration of other aromatics can be reduced by hydrogenation to produce naphthenes at a modest increase in cost. This increases the volume of the products, decreases the octane number, and increases process hydrogen consumption.

The projected cost for direct coal liquefaction has dropped by over 50 percent since the early s Lumpkin, Recent improvements in economics cannot be attributed to any single breakthrough but rather to the accumulation of improvements over several years of operation, notably the following:. This series of modifications led to higher liquid yields, improved conversion of nondistillable liquids, less rejection of energy along with discarded coal minerals, and increased throughput relative to early two-stage systems.

The current U. All of the foreign projects have had the bulk of their financing contributed by government. Small test units capable of continuous operation for sustained periods of time were available at Hydrocarbon Research, Inc. Hydrocarbon Research, Inc. The unit operates approximately half-time, but funding.


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Research at West Virginia University on the production of coal-derived precursors using solvent extraction techniques as carbon product feedstocks has been supported by DOE. However, DOE funding for advanced research in direct liquefaction has decreased in recent years see Chapter 9.

A assessment of research needs conducted by DOE's Office of Program Analysis outlined a comprehensive program aimed at bringing down the cost of direct liquefaction Schindler, Industry participants in the aforementioned study stressed the need for federal funding of a large-scale pilot plant capable of processing tons or more of coal per day, but such a unit was never funded. In addition, funding of intermediate-size flow units of the size of the Hydrocarbon Research, Inc. Smaller pilot plants are needed to evaluate catalysts, explore operating conditions, and provide low-cost testing of new ideas.

This cost reduction results from the incorporation of more recent results from the DOE Wilsonville plant, improved gasification, and from inclusion of 3 percent inflation in the DOE-sponsored estimates. The earlier estimates assumed 10 percent return and did not include inflation.


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  • The assessment Schindler, also recommended a broad range of fundamental and exploratory research, based on the recognition that possible improvements to the current technology may be limited but that advances in conversion chemistry may bring down the cost of liquid fuels produced from coal to be competitive with petroleum products. This study assumed nth plant costs with 3 percent per year price inflation over the plant life, 25 percent owner equity with 15 percent return, and 8 percent interest charges for the 75 percent loan. Integration of direct coal liquefaction with an existing petroleum refinery could take advantage of existing facilities and ease the transition between petroleum and coal feedstock.

    DOE sponsored work on simultaneous processing "coprocessing" of coal with heavy petroleum fractions in an ebullated-bed hydroprocessing reactor. One CCT program submission utilizing this technique was selected for funding but was unable to find the private sector funding needed to proceed. The primary product was a low-volatile smokeless domestic solid fuel, although the value of the liquid products was also soon recognized.

    With the oil embargo and increased oil prices of the early s, interest renewed in coal pyrolysis, but in more recent times interest has again declined along with petroleum prices Khan and Kurata, Pyrolysis kinetics are reasonably well understood and have been modeled extensively Solomon et al. Both yield and liquid fuel properties depend on pyrolysis conditions. However, a significant part of the feed coal remains as char with market value comparable to or somewhat less than that of the feed coal. Coal pyrolysis offers some promise of lower liquid costs if the char can be upgraded to higher-value specialty products, such as form coke, smokeless fuel, activated carbon, or electrode carbon, or if the liquid yield can be significantly increased by using low-cost reactants steam and carbon dioxide or catalysts.

    Pyrolysis liquids have a low hydrogen-to-carbon ratio, generally less than one, in contrast to petroleum tars and bitumens around 1. They also contain substantial amounts of oxygen, compared to tars, and thus require more extensive hydrogen addition to produce specification fuels.

    Their tendency to polymerize on standing can cause operational problems, which also must be addressed. Little heat is required to produce pyrolysis liquids from coal, however, and production as a side stream to coal gasification or fluidized-bed combustion is efficient. Pyrolysis reactors generally operate at modest pressures and temperatures compared to other coal conversion systems and offer high throughput. Both of these features lead to low capital cost. The cost of pyrolysis liquids could thus be low and might be competitive with bitumen or for integration with oil refinery.

    They could also be combined with direct coal liquefaction. When made from low-sulfur coal, pyrolysis liquids have limited potential as a substitute without refining for petroleum fuel oil, and an ongoing CCT program ENCOAL Mild Coal Gasification project is aimed at this market. Pyrolysis liquids have traditionally been a source of coal tar chemicals, and the DOE Mild Gasification program is aimed, in part, at this market see below. These budget decisions reflect a diminished commitment to the use of coal for production of clean liquid fuels by either indirect or direct liquefaction.

    Of particular note is the proposed reduction of 84 percent in FY funding for Advanced Research and Environmental Technology; programs in this area are expected to lead to improvements in efficiency and cost reductions for liquid fuel production see Chapter 9. A coal refinery or coproduct system is defined as ''a system consisting of one or more individual processes integrated in such a way as to allow coal to be processed into two or more products supplying at least two different markets" DOE, The concept resulted from the realization that coal must be processed in nontraditional ways to meet the needs of potential expanded markets.

    A key feature of the coal refinery concept is the production of more than one product form, for example, steam and electricity or fuel gas and electricity. Cogeneration was initially practiced in energy-intensive industrial plants to meet internal needs for steam and electricity. Steam and electricity coproduct systems are now a major commercial activity. With few exceptions cogeneration facilities are designed to use natural gas because of the lower investment compared to a plant that uses coal. As natural gas prices rise to a level that renders the higher investment in coal facilities economically advantageous, advanced cogeneration systems, where the first step is gasification, could also supply coal liquids, fuel gas, and syngas made from coal.

    Currently, there appears to be ample. Steam and electricity would continue to be major products. This time might well arrive before manufacture of synthetic natural gas is required to meet domestic demand. The first major opportunity for coproducts would then arise from the predicted mid-term need for new high-performance coal-based, power generation systems. These high-performance systems will probably involve coal gasification offering the possibility of coproducts from the gasifier syngas, fuel gas, and pyrolysis tar.

    The production of coproducts, in conjunction with SNG manufacture, was of major commercial and DOE 7 interest until the s, when low oil and gas prices and ample supplies eliminated the near-term economic incentive for synthetic fuels processes. The expected growth in coal-based power generation appears to offer a more robust opportunity for fuel and chemical coproducts than the traditional single product or dedicated plant approach. The business environment and regulatory changes that have encouraged cogeneration could provide a framework for extension to the use of coal as a source of energy and a resulting greater variety of coproduct streams.

    Recent industrial concerns regarding efficient production of major products and conservation of capital are resulting in steam and power being supplied by external companies that build and operate facilities for supply of steam and electricity to both local manufacturing plants and utilities. In some cases these companies are subsidiaries of a utility. Such companies might supply fuel gas and syngas to chemical and petrochemical companies.

    Nonetheless, the complexity of the potential business relationships and the need for a flexible approach should not be underestimated. With today's emphasis on increased generation efficiency and the availability of high-performance gas turbines and fuel cells, an incentive for development of high-efficiency gasification systems specifically designed to provide fuel for power generation has been established.

    As discussed earlier, these systems can differ from systems optimized to produce highly purified synthesis gas for conversion to chemicals and clean fuels in that dilution by methane and nitrogen is acceptable; a higher level of impurities can also be tolerated. Prior to the formation of DOE in programs were conducted under the auspices of the Energy Research and Development Administration. The savings for coproduction were attributed to a combination of better heat integration and the economies involved in once-through operation.

    For coproduction, the gasoline boiling range fraction was sent to the turbines, thus reducing total liquid production but also avoiding the costs of upgrading the low-octane-number naphtha produced by this process. While the required selling price was similar to that for the Mitre study, the assumed refined product values were higher, with a larger assumed premium for the diesel fuel.

    This assumption, together with other cost differences, makes comparison of the two studies difficult. The difference results from a combination of the inclusion of inflation in the DOE-sponsored studies, higher product values, improved gasification technology, and use of the slurry reactor. However, it is important to note that the estimated costs from the Mitre and Bechtel studies are for the "nth" plant and are below pioneer plant costs.

    As in the case of advanced power generation technologies, early market entry would likely require some federal cost sharing see Chapter 8. Coproduction of coal liquids and electric power based on IGCC systems offers additional opportunities for cost reduction in the production of hydrogen, which could be used for direct liquefaction. No estimates of the magnitude of possible benefits are available for direct liquefaction; however, they would prob-. See Chapter 2 and the Glossary for discussion of financing options. The U.

    DOE activities related to this directive have included continuation of the program sponsored by DOE's Morgantown Energy Technology Center aimed at commercialization of the mild gasification process, which is based on pyrolysis and is directed toward producing specialty cokes and tars for production of chemicals. No further funding for the program has been requested for FY The two year operational test period began in July , and solid process-derived fuel and coal-derived liquids have been produced.

    A conceptual study of electricity and coal liquids production—as proposed in the FY congressional budget request—could extend the existing preliminary studies. Gasification Product Improvement Facility Status.

    Article outline

    Paper presented at the Contractors Conference, U. Washington, D. Prepared for U. Pittsburgh, Pennsylvania: DOE. FY Congressional Budget Request. Annual Energy Outlook Energy Information Administration, U. Coproduction of Methanol and Electricity.

    Introduction

    Gray, D. Coal Refineries: An Update. Kastens, M. Hirst, and C. Liquid fuels from coal. Industrial and Engineering Chemistry Khan, M. Lumpkin, R. Recent progress in the direct liquefaction of coal. Science Fuels to Drive Our Future. Oil and Gas Journal. Alternate fuels: China's. Oil and Gas Journal Schindler, H.

    Prepared for the U. Solomon, P. Fletcher, and R. Progress in coal pyrolysis. Fuel 72 5 Stiegel, G. Indirect Liquefaction. Tam, S. Pollack, and J. Arlington, Virginia: Council on Alternate Fuels. This volume provides a picture of likely future coal use and associated technology requirements through the year Coal offers an overview of coal-related programs and recent budget trends and explores principal issues in future U.

    Coal will be important to energy policymakers, executives in the power industry and related trade associations, environmental organizations, and researchers. Based on feedback from you, our users, we've made some improvements that make it easier than ever to read thousands of publications on our website. Jump up to the previous page or down to the next one. Also, you can type in a page number and press Enter to go directly to that page in the book.

    Switch between the Original Pages , where you can read the report as it appeared in print, and Text Pages for the web version, where you can highlight and search the text. To search the entire text of this book, type in your search term here and press Enter. Strenuous efforts have been made to elucidate the mechanisms of these methane-converting enzymes, which would enable their catalysis to be replicated in vitro.

    Biodiesel can be made from CO 2 using the microbes Moorella thermoacetica and Yarrowia lipolytica. This process is known as biological gas-to-liquids. Using gas-to-liquids processes, refineries can convert some of their gaseous waste products flare gas into valuable fuel oils , which can be sold as is or blended only with diesel fuel. Gas-to-liquids processes may also be used for the economic extraction of gas deposits in locations where it is not economical to build a pipeline. This process will be increasingly significant as crude oil resources are depleted.

    Royal Dutch Shell produces a diesel from natural gas in a factory in Bintulu , Malaysia. New generation of GTL technology is being pursued for the conversion of unconventional, remote and problem gas into valuable liquid fuels. Other mainly U. Another proposed solution to stranded gas involves use of novel FPSO for offshore conversion of gas to liquids such as methanol , diesel , petrol , synthetic crude , and naphtha. From Wikipedia, the free encyclopedia. Main article: Fischer—Tropsch process. Main article: Syngas to gasoline plus. Philosophical Transactions of the Royal Society A.

    Retrieved Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH.


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