Title of Invention	PRODUCTION OF SYNTHETIC TRANSPORTATION FUELS FROM CARBONACEOUS MATERIALS USING SELF-SUSTAINED HYDRO-GASIFICATION .
Abstract	A process and apparatus lor producing a synthesis gas for use as a gaseous fuel or as feed into a rischer-Tropsch reactor to produce a liquid fuel in a substantially self-sustaining process. A slurry of particles of carbonaceous material in water, and hydrogen from an internal source, are fed into a hydro-gasilication reactor under conditions whereby methane rich producer gases are generated and fed into a steam pyrolytic reformer jnder conditions whereby synthesis gas comprising hydrogen and carbon monoxide arc generated. A portion of the hydrogen gene rated by the steam pyrolytic reformer is fed through a hydrogen purification filler into the hydro-gasification reactor, the hydrogen therefrom constituting the hydrogen from an internal source. The remaining synthesis gas generated by the steam pyrolytic reformer is either used as fuel for a gaseous fueled engine to produce electricity and/or process heat or is fed into a Fischer-Tropsch reactor und;r conditions whereby a liquid fuel is produced. Molten salt loops are used to transfer heat from the hydro-gasification reactor, and F ischer-Tropisch reactor if liquid fuel is produced, to the steam generator and the steam pyrolytic reformer.

Title of Invention

PRODUCTION OF SYNTHETIC TRANSPORTATION FUELS FROM CARBONACEOUS MATERIALS USING SELF-SUSTAINED HYDRO-GASIFICATION .

Abstract

A process and apparatus lor producing a synthesis gas for use as a gaseous fuel or as feed into a rischer-Tropsch reactor to produce a liquid fuel in a substantially self-sustaining process. A slurry of particles of carbonaceous material in water, and hydrogen from an internal source, are fed into a hydro-gasilication reactor under conditions whereby methane rich producer gases are generated and fed into a steam pyrolytic reformer jnder conditions whereby synthesis gas comprising hydrogen and carbon monoxide arc generated. A portion of the hydrogen gene rated by the steam pyrolytic reformer is fed through a hydrogen purification filler into the hydro-gasification reactor, the hydrogen therefrom constituting the hydrogen from an internal source. The remaining synthesis gas generated by the steam pyrolytic reformer is either used as fuel for a gaseous fueled engine to produce electricity and/or process heat or is fed into a Fischer-Tropsch reactor und;r conditions whereby a liquid fuel is produced. Molten salt loops are used to transfer heat from the hydro-gasification reactor, and F ischer-Tropisch reactor if liquid fuel is produced, to the steam generator and the steam pyrolytic reformer.

Full Text	serious environmental pollution unless strict methods of exhaust emission control are used. A clean burning synthetic diesel fuel can help reduce the emissions from diesel engines. The production of clean-burning transportation fuels requires either the reformulation of existing petroleum-based fuels or the discovery of new methods for power production or fuel synthesis from unused materials. There are many sources available, derived from either renewable organic or waste carbonaceous materials. Utilizing carbonaceous waste to produce synthetic fuels is an economically viable method since the input feed stock is already considered of little value, discarded as wastte, and disposal is often polluting. Liquid transportation fuels have inherent advantages over gaseous fuels, having higher energy densities than gaseous fuels at the same pressure and temperature. Liquid fuels can be stored at atmospheric or low pressures whereas to achieve liquid fuel energy densities, a gaseous fuel would have to be stored in a tank on a vehicle at high pressures that canbe a safety concern in the case of leaks or sudden rupiture. The distribution of liquid fuels is much easier than gaseous fuels, using simple pumps and pipelines. The liquid fueling infrastructure of the existing transportation sector ensures easy integration into the existing market of any production of clean-burning synthetic liquid transportation fuels. The availability of clean-burning liquid transportation fuels is a national priority. Producing synthesis gases cleanly and efficiently from carbonaceous sources, that can be subjected to a Fischer-Tropsch process to produce clean and valuable synthetic gasoline and diesel fuels, will benefit both the transportation sector and the health of society. Such a process allows for the application of current state-of-art engine esxhaust after-treatment methods for NOx reduction, removal of toxic particulates present in diesel engine exhaust, and the reduction of normal combustion product pollutants, currently accomplished by catalysts that sire poisoned quickly by any sulfur present, as is the case in ordinary stocks of petroleum derived diesel fuel, reducing the catalyst efficiency. Typically, Fischer-Tropsch liquid fuels, produced from biomass derived synthesis gases, ere sulfur-free, aromatic free, and in the case of synthetic diesel fuel have an ultrahigh cetane value. Biomass material is the most commonly processed carbonaceous waste feed stock used to produce renewable fuels. Waste plastic, rubber, manure, crop residues, forestry, tree and grass cuttings and biosolids from waster water (sewage) treatment are also candidate feed stocks for conversion processes. Biomass feted stocks can be converted to produce electricity, heat, valuable chemicals or fuels. California tops the nation in the use and development of several bomass utilization technologies. Each year in California, more than 45 million tons of municipal solid waste is discarded for treatment by waste management facilities. Approximately half this waste ends up in landfills. . For example, in just the Riverside County , California area, it is estimated that about 4000 tons of waste wood are disposed of per day. According to other estimates; over 100,000 tons of biomass per day are dumped into landfills in the Riverside County collection area. This municipal waste comprises about 30% waste paper or cardboard, 40/o organic (green and food) waste, and 30% combinations of wood, paper, plastic and metal waste. The carbonaceous components of this waste material have chemical energy that could be used to red uce the need for other energy sources if it can be converted into a clean-burning fuel. These waste sources of carbonaceous material are not the only sources available. While many existing carbonaceous waste materials, such as paper, can be sorted, reused and recycled, for other materials, the waste producer would not need to pay a tipping fee, if the waste were to be delivered directly to a conversion facility. A tipping fee, presently at $30-$35 per ton, is usually charged by the waste management agency to offset disposal costs. Consequently not only can disposal costs be reduced by transporting the waste to a waste-to-synthetic fuels processing plant, but additional waste would be made available because of the lowered cost of disposal. The burning of wood in a wood stove is an example of using biomass to produce heat energy. Unfortunately, the open burning the biomass waste to obtain energy and heat is not a clean and efficient method to utilize the calorific value. Today, many new ways of utilizing carbonaceous waste are being discovered. For example, one way is to produce synthetic liquid transportation fuels, and another way is to produce energetic gases for conversion into electricity. Using fuels from renewable biomass sources can actually decrease the net accumulation of greenhouse gases, such as carbon dioxide, while providing clean, efficient energy for transportation. One of the principal benefits of co-production of synthetic liquid fuels from biomass sources is that it can provide a storable transportation fuel while reducing the effects of greenhouse gases contributing to global warming. In the future, these co-production processes could provide clean-burning fuels for a renewable fuel economy that could be sustained continuously. A number of processes exist to convert coal and other carbonaceous materials to clean-burning transportation fuels, but they tend to be too expensive to compete on the market with petroleum-based fuels, or they produce volatile fuels, such as methanol and ethanol that have vapor pressure values too high for use in high pollution areas, such as the Southern California air-basin, without legislative exemption from clean air regulations. An example of the latter process s the Hynol Methanol Process, which uses hydro-gasification and steam reformer reactors to synthesize methanol using a co-feed of solid carbonaceous materials and natural gas, and which has a demonstrated carbon conversion efficiency of >85% in bench-scale demonstrations. The need to identify new resources and methods for the production of transportation fuels requires not only investigating improvements in ways to produce current petroleum-based fuels but also research into new methods for the synthesis of functionally equivalent alternative fuels obtained using resources and methods that are not in use today. The production of synthetic liquid fuels from carbonaceous materials such as waste organic materials is one way to solve these problems. The utilization of carbonaceous waste materials to produce synthetic fuels can be considered a feasible method of obtaining new resources for fuel production since the material feed stock is already considered a waste, without value and often it's disposal creates additional sources of environmental pollution. SUMMARY OF THE INVENTION The present invention makes use of steam pyrolysis, hydro-gasification and steam reformer reactors to produce a synthesis gas that can be converted into a synthetic paraffinic fuel, preferably a diesel fuel, although synthetic gasolines and jet propuision fuels can also be made, using a Fischer-Tropsch paraffin fuel synthesis reactor. Alternatively, the synthesis r gas may be used in a co-generated power conversion and process heat system. The present invention provides comprehensive equilibrium thermo- chemical analyses for a general class of co-production processes for the synthesis of clean-burning liquid transportation fuels, thermal process energy and electric power generation from feeds of coal, or other carbonaceous materials, and liquid water. It enables a unique design, efficiency of operation and comprehensive analysis of coal, or any other carbonaceous feed materials to co-produced fuel, power and heat systems. The invention provides a process and apparatus for producing a synthesis gas for use as a gaseous fuel or as feed into a Fischer-Tropsch reactor to produce a liquid parajffinicjuel, recycled water and sensible heat, in a substantially self-sustaining process. A slurry of particles of carbonaceous material suspended in liquid water, and hydrogen from an internal source, are fed into a steam generator for pyrolysis and hydro-gasification reactor under conditions whereby super-heated steam, methane, carbon dioxide and carbon monoxide are generated and :ed into a steam reformer under conditions whereby synthesis gas comprising primarily of hydrogen and carbon monoxide are generated. Using a hydrogen separation filter for purification, a portion of the hydrogen generated by the steam reformer is fed into the hydro- gasification reactor as the hydrogen from an internal source. The remaining synthesis gas generated by the steam refonmer is either used as fuel for a gaseous fueled engine or gas turbir e to produce electricity and process heat, or is fed into a Fischer-Tropsch fuel synthesis reactor under conditions to produce a liquid fuel, and recycled water. The correct stoichiometric ratio of hydrogen to carbon monoxide molecules fed into the Fischer-Tropsch fuel synthesis reactor, is controlled by the water to carbon ratio in the feed stocks. Molten salt loops are used to transfer heat from the exothermic hydro- gasification reactor (and from the exothermic Fischer-Tropsch reactor if liquid fuel is produced) to the endothermic steam generator for pyrolysis and the steam reformer reactor vessels. In particular, the present invention provides the following features. 1) A general purpose solid carbonaceous material feed system that can accept arbitrary combinations of coal, urban and agricultural biomass, and municipal solid waste for hydro-gasification. 2) A first stage, steam generator for pyrolysis and hydro- gasification unit. 3) A steam reformer as a second stage reactor to produce hydrogen rich synthesis gas from the output of the first stage steam generator for pyrolysis and hydro-gasification unit. The molal steam to carbon ratio is maintained as necessary to bring the chemical reactions close to equilibrium; 4) Either (a) a Fischer-Tropsch (synthesis gas-to-liquid) fuel synthesizer as a third and final stage reactor to conyert the synthesis gas from the steajj reformer into a sulfur-free clean-burning liquid transportation fuel, and recycled water or (b) use of uenerated synthesis gas as fuel for process heat and/or in a fuel engine or g£,3.turbine that,can generate electricity; 5) Three thermo-chemical process reactors are operated to produce nearly pure paraffinic hydrocarbon liquids (similar to petroleum derived diesel fuels) and wax-like compounds (similar to petroleum derived USP paraffinic jellies, which can be further refined into more diesel-like fuels using conventional methods) from carbonaceous feed stocks (such as waste wood) in a continuous self-sustainable fashion without the need for additional fuels or external energy sources. The reactor configurations can also be optimized for the production of other synthetic fuels, such as dimethyl ether (a fuel similar to propane, that can be used as; a transportation fuel in diesel engines and gas turbines) and gaseous fuel grade hydrogen (a fuel that can be used in engines and turbines, and if purified to remove carbon monoxide, as an electrochemical fuel in a fuel cell), as well as energetic synthesis gases for combined cycle power conversion and electric power production. The fundamental advantages of this invention, over what was achievable with the prior art, are (a) energy efficient (>85%) methane production from the available carbon in the carbonaceous feed stock using steam pyrolysis to activate the carbon and hydrogen gas as the sole initiating reactant, in contradistinction to partial oxidative gasification usually requiring an additional energy intensive air separation system to provide the necessary oxygen; (b) chemically self-sustained operation of the first stage hydro- gasification reactor by feeding-back surplus hydrogen gas produced in the second stage methane steam reformer reactor; (c) energy efficient synthesis of clean-burning transportation fuels using the effluent gases from the steam reformer, such as: (i) paraffinic compounds using a third stage Fischer- Tropsch fuel synthesis reactor, (ii) dimethyl ether synthesis using a third stage synthesis reactor, and (iii) hydrogen production using a hydrogen separation and/or purification filter without the need for a third stage fuel synthesis reactor; (d) thermally self-sustained operation of all reactors by effective management of thermal and chemical energy using combinations of molten salt or water/steam heat transfer fluids, combustion of product energetic gases to start and maintain process temperatures, recovered process heat for the generation of electric power, without the need for additional fuels and external energy sources; (e) significantly reduced airborne emissions from all enclosed processes reactors and/or synthesis gas combustors when compared to direct naturally aspirated combustion (usually known as open incineration) of the carbonaceous 1eed materials; and f) the ability to capture all gaseous carbon dioxide effluen t from process reactors or intra-process synthesis gas combustors for sequestration and/or chemical conversion into condensed phase compounds using conventional technologies. These novel configurations of the process reactors have the capability to improve the overall efficiency cf energy utilization for carbonaceous material conversion in a co-prodiction plant for synthetic fuels, chemicals and energy. ACCOMPANYING BRIEF DESCRIPTION OF THEpRAWlNGS Figure 1 is a flow diagram showing the overall modeling of the present invention; Figure 2 is a graph showing a plot of carbon conversion vs. H2 /C and H20/C ratios at 800°C and 30 atm. in HPR; Figure 3 is a graph showing a plot of CH4/C feed ratio vs. H2/C andH20/C ratios at 800°C and 30 atm. in HPR; Figure 4 is a graph showing a plot of C02/C feed ratio vs. H2/C andH20/C ratio sat 800°C and 30 atm. in HPR; Figure 5 is a graph showing a plot of CO/ C feed ratio vs. H2/Cand H20/C ratios at 800°C and 30 atm. in HPR; Figure 6 is a graph showing the effects of Temperature and Pressure conditions on C02/H ration the hydro-gasifier reactor (HGR) at fixed feed of 2.629 moles of H2 and 0.0657 moles of H20 per mole of C; Figure 7 is a graph showing the effect of Temperature and Pressure conditions on CH4/H ratio in the HGR at fixed feed of 2.629 moles of H2 and 0.0657 moles of H20 per mole of C; Figure 8 is a graph showing the effect of Temperature and Pressure conditions on H2/C ratio in the HG R at fixed feed of 2.629 moles of H2 and 0.0657 moles of H20 per mole of C; Figure 9 is a graph showin 3 the effect of Temperature and Pressure conditions on CO/H in the HGR at fixed feed of 2.629 moles of H2 and 0.0657moles of H20 per mole of C; Figure 10 is a graph show ng the effect of input H20/C ratio on steam reformer (SPR) performance measure by l:he net H2/CO ratio after H2 recycling for the HGR at 1000°C and 30 atm; Figure 11 is a graph showing the effect of changing the input H20/C ratio on SPR products, CO, C02 and CH4 in the SPR at 1000°C and 30 atm; Figure 12 is a graph showing the effect of Temperature and Pressure conditions on H2/CO ratio in the SPR (2.76 moles of H20/mole of C added to the SPR); Figure 13 is a graph showing the effect of Temperature and Pressure conditions on CHJC ratio in the SPR (2.76 moles of H20/mole of C added to the SPR); Figure 14 is a diagram showing the Mass Flow Schematic of Biomass Hydro-gasification for production of Fischer-Tropsch paraffin fuels; Figure 15 is a diagram showing the Molal Flow Schematic of Biomass Hydro-gasification for production of Fischer-Tropsch paraffin fuels; Figure 16 is a diagram showing the Thermal Energy Management Schematic of Biomass Hydro-gasification for production of Fischer-Tropsch paraffin fuels; Figure 17 is a diagram showing the Water/Steam Flow Schematic of Biomass Hydro-gasification for production of Fischer-Tropsch paraffin fuels; Figure 18 is a diagram showing Molten Salt Flow Schematic of Biomass Hydro-gasification for production of Fischer-Tropsch paraffin fuels; Figure 19 is a diagram showing Mass Flow Schematic of Biomass Hydro-gasification for production of dimethyl ether; Figure 20 is a diagram show ng Mole Flow Schematic of Biomass Hydro-gasification for production of dimethyl ether; Figure 21 is a diagram showing Thermal Energy Management Schematic of Biomass Hydro-gasification for production of dimethyl ether; Figure 22 is a diagram showing Water/Steam Flow Schematic of Biomass Hydro-gasification for production of dimethyl ether; Figure 23 is a diagram showing Molten Salt Flow Schematic of Biomass Hydro-gasification for production of dimethyl ether; Figure 24 is a diagram showing Mass Flow Schematic of Biomass Hydro-gasification for production of gaseous hydrogen fuel; Figure 25 is a diagram showing Mole Flow Schematic of Biomass Hydro-gasification for production of gaseous hydrogen fuel; Figure 26 is a diagram showing Thermal Energy Management Schematic of Biomass Hydro-gasification for production of gaseous hydrogen fuel; Figure 27 is a diagram showing Water/Steam Flow Schematic of Biomass Hydro-gasification for production of gaseous hydrogen fuel; Figure 28 is a diagram showing Molten Salt Flow Schematic of Biomass Hydro-gasification for production of gaseous hydrogen fuel; Figure 29 is a diagram showing Mass Flow Schematic of Biomass Hydro-gasification for production ot electricity; Figure 30 is a diagram showing Mole Flow Schematic of Biomass Hydro-gasification for production ot electricity; Figure 31 is a diagram showing Thermal energy Management Schematic of Biomass Hydro-gasification for production of electricity; Figure 32 is a diagram showing Water/Steam Flow Schematic of Biomass Hydro-gasification for production of electricity; Figure 33 is a diagram showing Molten Salt Flow Schematic of Biomass Hydro-gasification for production of electricity; Figure 34 is a mass flow schematic of biomass hydro-gasification for Fischer-Tropsch paraffin fuel production using an adiabatic HGR and a 9:1 water feed; Figure 35 is a molal flow schematic of biomass hydro-gasification for Fischer-Tropsch paraffin fuel production using an adiabatic HGR and a 9:1 water feed; Figure 36 is a thermal energy management schematic of biomass hydro-gasification for Fischer-Tropsch paraffin fuel production using an adiabatic HGR and a 9:1 water feed; Figure 37 is a water/steam flow schematic of biomass hydro- gasification for Fischer-Tropsch paraffin fuel production using an adiabatic HGR and a 9:1 water feed; Figure 38 is a molten salt flow schematic of biomass hydro-gasification for Fischer-Tropsch paraffin fuel production using an adiabatic HGR and a 9:1 water feed. DETAILED DESCRIPTION OF THE INVENTION A steam generator for pyro ysis, hydro-gasification reactor (HGR) and steam pyrolytic reformer (SPR) (a so called a steam pyrolytic reactor, steam reformer or steam reactor) such as used in a Hynol process, may be utilized to produce the synthesis gas (syn gas) through steam pyrolysis of the feed stock, hydro-gasification and steam reforming reactions. The reactions start in the HGR to convert carbon in the carbonaceous matter into a methane rich producer gas and continue through the SPR to produce synthesis gas with the correct hydrogen and carbon monoxide stiochiometry for efficient operation of the Rscher-Tropsch process. With the Fischer-Tropsch process as the final step in processing, products such as synthetic gasoline, synthetic diesel fuel and recycled water can be produced. The feedstock requirement is highly flexible. Many feeds that consist of different carbonaceous materials can be wet milled to form a water slurry that can be fed at high pressure into a steam pyroiyzer, hydro-gasifier and steam reformer reactors for synthesis gas production. The feed to water mass ratio can even vary during tie running of the process, with a knowledge of the chemical content of the feed, to maintain the carbon-hydrogen stiochiometry required for an opt mized fuel synthesis process. Appropriate carbonaceous materials include biomass, natural gas, oil, petroleum coke, coal, petrochemical and refinery by-products and wastes, plastics, tires, sewage sludge and other organic wastes. For example, wood is an example of waste biomass material that it; readily available in Riverside County, California. This particular waste stream could be augmented with other carbonaceous materials, such as green waste and biosolids from water treatment that are available in Riverside County, and would otherwise go to landfill. When used to make a transportation fuel, such as diesel fuel, the process is designed so that the feedstock makes the maximum amount of Fischer-Tropsch paraffinic prod act required. The desired output consists of a liquid hydrocarbon, such as cetane, C16H34, within the carbon number range, 12 to 20, suitable as a diesel fuel. Excess synthesis gas output from the SPR, i.e., "leftover" chemical energy from the Fischer Tropsch synthetic fuel producing process, can be used as an energetic fuel to run a gas turbine for electricity production. The synthesis gas output after recycling enough hydrogen to sustain the hydro-gasifier, may be used for this purpose also, depending on the needs of the user. The following provides a method for maximizing the economic potential from the present invention in the conversion of carbonaceous materials to a usable transportation fuels and inclusive of the possibility for direct electric power production through a gas turbine combined cycle. 1) Find approximate data on available carbonaceous wastes, their chemical composition and perform further analysis on the practical need for the process. 2) Model the important reactions within the process consisting of the steam generator for pyrolysis, lydro-gasifier, steam reformer, and the Fischer-Tropsch (or other fuel synthesis) reactor on a continuous flow-through basis. This may be done by optimizing the Fischer-Tropsch (or other fuel synthesizer) feedstock for the optimum stoichiometric hydrogen to carbon monoxide mole ratio for fuel to be synthesized. 3) Perform an economic analysis on the costs to obtain and prepare the input material required, capital costs, operating and maintenance, and product yield and costs. Specific implementations are given below in conjunction with flow charts provided in the Figures, demonstrating the conversion of waste wood, as the candidate carbonaceous material, to a liquid diesel transportation fuel, recycled water and an alternative power source, via a Fischer-Tropsch process linked to a gas turbine combined cycle. The thermo-chemical conversion of carbonaceous materials occurs by two main processes: hydro-gasification and steam reformation, with steam pyrolysis of the feedstock occurring within the steam generator to pre-treat feedstock and activate the carbon contained therein. The hydro-gasifier requires an input of the pyrolyzed carbonaceous waste, hydrogen, steam, reacting in a vessel at high temperature and pressure, which in a specific implementation is approximately 30 atmospheres and 1000 degrees Celsius. Steam reforming of the methane rich effluent gas from the HGR also requires an approximate pressure of 30 atmospheres and 1000 degrees Celsius. More generally, each process can be conducted over a temperature range of about 700 to 1200 degrees Celsius and a pressure of about 20 to 50 atmospheres. Lower temperatures and pressures can produce useful reaction rates with the use of appropriate reaction catalysts. Referring to Figure 1, which is an overall flow diagram, the order of general processes that carry out these main reaction processes is shown (specific amounts for a particular embodiment are in the flow diagrams shown in Figures 14 through 38). Piping is used to convey the materials through the process. The feed 11 is chopped milled or ground in a grinder 10 into small particles, mixed with the recycled water 12 and placed in a receptacle or tank 14 as a liquid, suspension slurry 16 that is transportable as a compressed fluid by a pump 18 to a steam generator 20 where the slurry 16 is superheated and pyrolyzed, followed by either separation of the steam in a steam separator 22 so that stearr goes through piping 24 that is separate from piping that delivers the pumped, dense slurry paste 26, or a direct steam pyrolysis feed through piping 27. The dense slurry paste feed 26, or the direct steam pyrolysis feed 27, enters the HGR 28. Hydrogen from an internal source (from the steam reformer via a hydrogen separation filter described below) and a fraction of the previously produced steam flow into the HGR 28 for the desired output. The output gases consists largely of methane, hydrogen, carbon monoxide, and super-heated steam. The gases produced by the HGR 28 leaves the chamber and is pumped over to tie SPR 30. The un-reacted residue (or ash) from the HGR, is periodically removed from the bottom of the reactor vessel using a double buffered lock-hopper arrangement, that is commonly used in comparable high pressure gasific ation systems. The ash is expected to be comprised of sand, Si02, and alumina, Al203, with trace amounts of metals. The input to the SPR 30 is delivered from either the steam separator 22 by piping 32 through a heater 34 anc further piping 36, or via the HGR 28 output piping, to provide greater-than-theoretical steam to carbon ratio into the SPR 30, to mitigate coking in the reactor. The output is a higher amount of hydrogen, and CO, with the appropriate stiochiometry for the desired hydrocarbon fuel synthesis process described below. The output of the SPR 30 is directed via piping 38 through heat exchangers 40 and 42. Condensed water 44 is separated and removed from the SPR output, via a heat exchanger and liquid water expander 47. The non- condensable gaseous output of SPR 30 is then conveyed to a hydrogen separation filter 46. A portion of tie hydrogen from the SPR output, about one-half in this embodiment, is carried from the filter 46, passed through the heat exchanger 40 with a resultar t rise in its temperature (in the embodiment from 220 degrees centigrade to 970 degrees Centigrade) and delivered to the HGR 28 as its hydrogen input. The hot effluent from the SPR output is cooled by passing through heat exchangers 40 and 42, used to heat the recycled hydrogen, and make steam respectively. The condensed water 44 leaving the heat exchanger 47 is recycled back to make the water supply 12 for the slurry feed. By such means, a self-sustaining process is obtained. The fuel synthesis gas is then used for one of two options. Based on the calorific value, the synthesis gas may go through a gas turbine combined cycle for direct energy production or through a fuel synthesis reactor (in this embodiment, a Fischer-Tropsch process to produce a clean diesel fuel and recycled water). In accordance with a specific embodiment of the invention, the synthesis gas is directed through an expansion turbine 48, to recover mechanical energy by lowering the pressure of the gaseous feed into the Fischer-Tropsch reactor 50. The mechanical power produced by the liquid state turbine, the Brayton and Rankine cycle turbines can be used to provide power for internal slurry, water feed pumps, iair compressor, with the surplus exported via electricity generation, see Tables 1 through 7. Efficiency may be maximized by adjusting input and process parameters. The biomass/ coal vaiying-mixture feed is synthesized into a slurry by adding water whereby after steam separation the carbon to hydrogen ratio will be appropriate for the process. A slurry feed needs enough water to run the hydro-gas fier, the steam reformer, and to keep the feed in a viable slurry after steam separation. Prior art attempts at biomass conversion using solid dry feed had many mechanical problems of feeding a solid into the high pressure, and high temperature HGR reaction chamber. This method of slurry feed has already been demonstrated and studied, according to the results for the "Hydrothermal Treatment of Municipal Solid Waste to Form High Solids Slurries in a Pilot Scale System", by C. B. Thorsness et al., UCRL-ID 119686, published by Lawrence Livermore Nation Laboratory, Livermore, CA in 1995. In addition, there is related art published on the making and operating of coal water slurry feeds. For example, see Z. Aktas et al., Fuel Processing Technology 62 2000 1-15.The principle reactions of the two main processes, hydro-gasification and steam reforming, are shown here. The HGR independent reactions can be expressed as: Reactions 2 and 3 are enc othermic. Reaction 1 is sufficiently exothermic to provide the heat of reaction for reactions 2 and 3. Some preheating of the HGR will be needed to tiring the reactor up to its operating temperature. Thus, the HGR is intended to be self-sustaining once the reactions have started and achieve steady state. The main purpose of the HGR process is to maximize the carbon conversion from the feed stock into the energetic gases CH4 and CO. After this process, hydrogen is produced by reacting superheated steam with CH4 and CO within the SPR. In the SPR, half the hydrogen is obtained from the superheated steam and the remainder from the CH4. The principle reactions in the SPR are considered to be: The steam reforming reactior s (4 and 5) are often run with steam concentrations higher than required for the stiochiometry shown above. This is done to avoid coke formation and to improve conversion efficiency. The required steam concentration is usually specified in the form of the steam-to-carbon mole ratio (S:C), the ratio of water steam molecules per carbon atom in the HGR feed. The preferred (S:C) ratio for the SPR operation is greater than 3. This steam rich condition favors the water-gas shift reaction. This reaction is only slightly exothermic (AH°= -41 kJ/mole CO); however, it produces additional hydrogen gas and converts carbon monoxide into carbon dioxide. Unfortunately, an additional unwanted secondary reaction can occur, the methanation reaction, which consumes hydrogen: The resulting effluent after the two main reactors is a synthesis of gases rich in hydrogen, carbon monoxide, and steam. Approximately half the hydrogen produced in the SPR is recycled back to the HGR. Consequently, no outside source of hydrogen is needed to maintain steady state operation. The HGR and SPR processes, therefore, may be considered to be chemically self-sustaining. The remaining syntnesis gas is then available for the production of fuels and process heat. The present invention using the Fischer-Tropsch process can produce a zero-sulfur, ultrahigh cetane value diesel-like fuel and valuable paraffin wax products. The absence of sulfur enables low pollutant and particle emitting diesel fuels to be realized. The present invention also provides a source of by-products. One useful by-product is purified water, which can be re-cycled to create the slurry feed into the process. In a report by Rentech titled "Fischer-Tropsch technology" dated 1998 see Rentech web publications at http://www.rentechinc.com. Rentech states that the Fischer-Tropsch process with an iron catalyst makes about 7/1 Oths of a barrel of water per barrel of Fischer-Tropsch products. A cobalt catalyzed Fischer-Tropsch process makes about 1.1 to 1.3 barrels of water for each barrel of Fischer-Tropsch products, a greater amount than iron. Part of the water may be recycled to make steam in the steam reformer unit and for cooling in both the synthesis gas and Fischer-Tropsch step of the overall process. The Fischer-Tropsch reactions also produce tail gas that contains hydrogen, CO, CO2, and some light hydrocarbon gases. Hydrogen can be stripped out of the tail gas and recycled either to the HGR or the Fischer- Tropsch reactor. Any small amounts of other gases such as CO and C02 may be flared off. Two main products of Fischer-Tropsch may be characterized as synthetic oil and petroleum wax. According to Rentech, in the above report for their particular implementation of the Fischer-Tropsch process, the mix of solid wax to liquid ratio is about 50/50. Fischer-Tropsch products are totally free of sulfur, nitrogen, nickel, vanadium, asphaltenes, and aromatics that are typically found in crude oil. The products are almost exclusively paraffins and olefins with very few, or no, complex cyclic hydrocarbons or oxygenates that would otherwise require further separation and/or processing in order to be usable end-products. The absence of sulfur, nitrogen, and aromatics substantially reduces harmful emissions. California's Air Resources Board (CARB) specifications for diesel fuel require a minimum cetane value of 48 and reduced sulfur content. The above Rentech study with Shell diesel fue produced from a Fischer-Tropsch process has a cetane value of 76. The CARB standard for sulfur in diesel fuel placed in the vehicle tank is 500 ppm by weight, and Shell's Fischer-Tropsch process diesel fuel has no detectable amount in the ppm range. The CARB standard for aromatic content is no more than 10% by volume (20% for small refineries). The Shell Fischer-Tropsch process diesel fuel had no detectable aromatics. Rentech further affirmed through studies that the diesel fuel may need no further processing because of the purity and olefin products that may even be advantageous over crude oil diesel. The Fischer-Tropsch diesel process is clean and the product is cleaner, has a higher cetane value, and most likely does not need further processing, when compared to a crude oil diesel. A gas turbine combined cycle for electric power production is an option. If the Fischer-Tropsch product is unexpectedly too costly, the use of the synthesis gas heating value can be a viable option, based on an overall efficiency of 65% of the synthesis gas energy converting to electric energy. This number is reasonable since the synthesis gas starts at a high temperature as opposed to taking natural gas in from a pipeline. Process modeling can be used to reasonably produce a synthesis gas maximized for a yield high in CO and stoichiometric hydrogen. First, the unit operation reactions of the hydro-gasifier, steam reformer, and Fischer-Tropsch reactors are modeled. This may be accomplished by using Stanjan, a DOS-based computer program that uses equilibrium modeling. By varying the parameters of temperature, pressure, original feedstock and gas flows, a parameterization study was carried out based on costs and output benefit. The hydro-gasifier variables were modified for the maximum practical carbon conversion efficiency. The steam reformer variables were modified for maximum practical CO output, er ough hydrogen for recycling output, and minimum CO2 production. The study looked at the various parameters whereby two different values varied for one constant, resulting in 3-D parameterization studies. The following discusses the results from the computer modeling of the main reactions using Stanjan programming. Referring to Figure 2, the effect of varying the water or steam and hydrogen ratios on the conversion efficiency of carbon in feedstock in the HGR is shown at 800°C and 30 atm. As the hydrogen and water input to the HGR increases, the conversion efficiency of carbon in feedstock increases until it reaches 100%. The condition that fails in the area of 100% conversion efficiency achieves one of the modeling objectives, and these conditions were used. In order to avoid the cost of recycling of H2, the minimum amount of H2 recycled to the HGR must be chosen. Figure 3 shows the effect of H2 and H20 on CH4 in the HGR at 800°C and 30 atm. Figure 4 shows the effect of H2 and H20 on C02 in the HGR at 800°C and 30 atm. At a high amount of H2 and low amount of H2O input, the amount of CO2 is low. Although the objective is to minimize the amount of C02 in the synthesis gas, it is not necessary to minimize C02 in the HGR because C02 is gauged in the SPR reactions through the water-gas-shift reaction to obtain a proper ratio of H2 and CO for a maximum Fischer-Tropsch diesel fraction. Figure 5 shows the effect of H2 and H20 on CO in the HGR at 800°C and 30 atm. Figures 6,7,8 and 9 show the effects of varying temperature and pressure on the chemical composition of the effluent gases from the HGR at feed of 2.76 mol H2 and 0.066 mol H20 per mole C in the feed stock. At these conditions of H2 and H20 input to the HGR, the carbon conversion efficiency is estimated to close to 100% in a temperature range of 800 to 1000°C and a pressure range of 30 atm. to 50 atm, for equilibrium chemistry. Figure 10 shows the ratio of H2 and CO available for feed into the Fischer-Tropsch fuel synthesis reactor, against the steam content added to the SPR at 800°C and 30atm. This ratio increases with the increasing amount of steam added to the SPR and reaches 2.1 at about 3.94 mol steam (or water) added per mol C in feedstock. With this amount of steam added, the system will achieve chemical and thermal self-sustainability and provide a proper ratio of H2 and CO for Fischer-Tropsch synthesis of cetane. Figure 11 shows the effect of H20 added to the SPR at 800°C and 30atm. Figures 12 and 13 show the effect of temperature and pressure on the H2 and CO ratio and the conversion of CH4 in the SPR. At higher temperature and lower pressure, this ratio is higher. In a smilar trend with the H2 and CO ratio, the conversion of CH4 increases with increasing temperature and with decreasing pressure. It is thus high temperature and low pressure favored in the SPR. The products of Fischer-Tropsch paraffinic liquid fuels are in a wide range of carbon number. According to the above Rentech report, about half of the products are diesel fuel. Also about half of the products come in the form of wax, with minor amounts of gases such as un-reacted reactants and hydrocarbon gases (methane, ethane, propane and so forth). To exemplify the present invention, cetane, whici is in middle position of diesel range (Cn to C2o ), was chosen as diesel fuel. The results of thermo-chemical and thermodynamic modeling of the hydro-gasified conversion of waste wood (biomass), as a prototypical carbonaceous feed material, were used to examine the details and illustrate the features of this invention. These simulations of the novel sequence of process reactors were undertaken to discover the thermo-chemical conditions needed to achieve the production of synthetic fuels. For example, in the production of synthetic diesel fuel, the objectives were to attain self-sustained operation of the first stage hydro-gasifier. In a particular embodiment, this is accomplished at an equilibrium temperature! of 1000°C (738°Cwhen adiabatic) and 30 atmospheres pressure with a total hydrogen to carbon feed mole ratio of at least 3.48:1 (1.67: when adiabatic), and water to carbon feed ratio of at least 0.07:1 (0.43 when adiabatic), a water steam to carbon feed mole ratio of at least 3.91:1 (1.67:1 when adiabatic) into the second stage steam reforming reactor also operating at an equilibrium temperature of 1000°C (900°C when adiabatic) and 30 atmospheres pressure, to obtain conditions for simultaneous optimal quantities of product hydrogen for self- sustained operation of the first stage hydro-gasification reactor and an adequate hydrogen to carbon mole ratio of at least 2.1:1 in the residual synthesis gas stream to feed the third stage Fischer-Tropsch reactor, operating at 200°C and 10 atmospheres pressure, and adiabatic self- sustained operation of a special HGR and SPR combination reactor, followed by a conventionally operated SPR and Fischer-Tropsch reactors, with full thermal and chemical potential energy management. Tables 1 through 5 show the overall energy transfer rates into and out from each heat exchanger and power conversion component for each operating mode of the conversion process. The mass flow, molal flow, thermal energy management, water/steam and molten salt schematic diagrams for each of the five operating modes of the conversion process are also shown as Figs14-18,19-23, 24-28, 29-33 and 34-38 respectively. Tables 6 and 7 summarize the results of the performance studies and process configuration parameters for each of the five operating modes of the conversion process. The carbonaceous material feed process initially described above uses a water slurry suspension feed technology, originally developed by Texaco for use in its partial-oxidation gasifiers, that can accept a wide variety of carbonaceous materials, and can be metered by controlled pumping into the first stage hydrogen gasification reactor (HGR) to produce a methane rich gas with high conversion efficiency (measured to have at least 85% carbon feed chemical utilization efficiency). Enough heat is available to be able to generate super-heated steam from the biomass-water slurry feed to supply and operate the second stage steam-methane reformer. The reformer product gas is fed into a hydrogen membrane filter that allows almost pure hydrogen to pass back into the first stage reactor to sustain the hydro-gasification of the biomass. The remaining second stage product gas, not passing through the hydrogen filter, is cooled to condense and re-cycle any water vapor present back into the slurry carbonaceous feed sys;tem. The unfiltered gas is fed into the fuel synthesis reactors, which comprise a Fischer-Tropsch paraffin hydro- carbon synthesis reactor, which operates at 200°C and 10 atmospheres pressure. Process modeling reveals that the hydrogen/carbon molecular feed ratio must be at least 2.1:1 to optimize production of chemically pure and clean-burning [sulfur-free] diesel-like liquid fuels and high value chemically pure paraffin-like waxes, without additional fuel or energy. (Figs. 14-18 and Tables 1, 6 and 7 or Figs. 34-38 and Tables 5, 6 and 7 for adiabatic first stage reactor operation), or a dimethyl ether synthesis reactor, which operates at 200C and 70 atmospheres pressure. This reactor produces approximately 92.4% DME and 7.1% methanol. The methanol is combusted to co-generate about 30 MW of electricity and 20fv1W of process heat for exchange with the molten salt and water/steam heat transfer loops (see Figs. 19-23 and Tables 2, 6 and 7), hydrogen gaseous fuel synthesis (see Figs. 24-28 and Tables 3, 6 and 7), and all electric power production without fuel synthesis (see Figs. 29- 33 and Table 4, 6 and 7). Net export of electric power is possible in all five modes of operation of the simulated biomass hydro-gasification process plant. The results of these simulations are summarized in Table 6 and 7. The overall energy utilization goes from 50.7% (71.2% when adi abatic) for Fischer-Tropsch synthesis to 67.2% for hydrogen production. Optimized electric power production utilizes about 38.2% of the chemical potential energy in the biomass feed stock for clean-burning power conversion. In general the process modes could be switched using an appropriate proportional valve to distribute the synthesis gas production after separation of enough pure hydrogen gas for the first stage hydro-gasification reactor. The results of the overall modeling shown in Figure 1 are summarized as follows. 1. Optimum conditions of the HGR: Operating at 1000°C and 30atm; 2.76 mol H2 per mol C in feedstock to maintain self-sustainability; 0.066 mol H20 per mol C in feedstock. 2. Optimum conditions of the SPiR: Operating at 1000°C and 30atm; 4.022 mol H20 per mol C in feedstock. 3. Fischer-Tropsch products: 0.199 ton wax per ton of feedstock; 68.3 gallons of cetane (C16H34) diesel per ton of feedstock. Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process and apparatus described in the specification. As one of ordinary skill in the art will readily appreciate from the disclosure of the present invention, processes and apparatuses, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized according 1:o the present invention. Accordingly, the appended claims are intended to include within their scope such processes and apparatuses. Table 1 Biomass conversion optimized for production of Fischer-Tropsch Paraffins Energy rate in (MW) Energy rate out (MW) Component PCE Heat Work PCE Heat Work Heat Exchangers HX 1 53.4 53.4 HX2 Portion 1 78.8 Portion 2 212.9 HX3 Portion 1 2.2 2.2 Portion 2 112.0 HX 4 (HGR) 50.2 HX 5 (SPR) 93.3 HX6 Portion 1 46.6 Portion 2 8.7 HX 7 216.3 HX 8 43.3 Portion 1 of HX 2 78.8 HX 9 (FTR) 45.9 HX10 11.8 HXG1 165.0 HXG2 21.8 HX G3 68.4 Hydraulic Power Slurry Pump 0.3 Liquid State Water Turbine 0.2 Brayton Cycle Turbine 1 7.9 Turbine 2 75.0 Turbine 3 0.0 Air Compressor 43.4 Rankine Cycle Heat 290.0 Mechanical Power 0.5 103.5 Waste Heat From Steam Cycle 186.9 Chemical Conversion Process synthetic paraffins produced 137 synthetic diesel fuel produced* 116 Input into Conversion Process Biomass (waste wood) input PCE 473.0 Overall Energy Balances Total Energy 473.0 827.3 44.1 137 1014.2 186.6 Net Waste Heat Rejected 186.9 Net Input Energy Required 0.0 Power Conversion Process Net Electricity Production 123.8 Total Electricity Available for Export 123.8 Dverall Thermodynamic Conversion Efficiency 50.7% notes * synthetic paraffins produced are considered to be 50% cetane and 50% wax wax can be conventionally processed to produce cetane with 70% efficiency Table 2 Biomass conversion optimized for production ol dimethyl ether (DME) En srgy rate in (MW) Energy rate out (MW) Component PCE Heat Work PCE Heat Work Heat Exchangers HX1 53.4 53.4 HX2 Portion 1 54.5 Portion 2 160.0 HX 3 3.8 HX 4 (HGR) 50.2 HX5(SPR) 91.3 HX 6 36.6 HX7 152.8 HX 8 29.9 Portion 1 of HX 2 54.5 HX 9 (DME-R) 32.3 HX 10 0.7 HX11 1.6 HX12 3.2 HXG1 150.2 HXG2 21.3 HX G3 66.8 HXG4 Portion 1 (to HX 7) 49.4 Portion 2 (to HX 2) 64.5 Hydraulic Power Slurry Pump 0.2 Liquid State Water Turbine 0.1 Brayton Cycles Turbine 2 3.4 Turbine 3 4.0 Turbine 4 70.7 Compressor 5.2 Air Compressor 39.8 Rankine Cycle Heat (HX 3, 9,10,11,12 & G4) 266.1 Mechanical Power 0.4 95.0 Waste Heat From Steam Cycle 171.5 Chemical Conversion Process dimethyl ether (DME) production 160.6 Input into Conversion Process Biomass (waste wood) input PCE 47 3.0 Overall Energy Balances Total Energy 473.0 698.2 45.6 160.6 869.8 173.2 Net Waste Heat Rejected 171.5 Net Input Energy Required 0.0 Power Conversion Process Net Electricity Production 110.3 Electricity Available for Export 110.3 Overall Thermodynamic Conversion Efficiency 57.3% Table 3 Biomass conversion optimized for production of gaseous hydrogen fuel Energy irate in (MW) Energy rate out (MW) Component PCE Heat Work PCE Heat Work Heat Exchangers HX 1 53.4 53.4 HX2 Portion 1 54.5 Portion 2 160.0 HX3 105.4 HX 4 (HGR) 50.2 HX 5 (SPR) 91.3 HX 6 36.6 HX7 152.8 HX 8 29.9 Portion 1 of HX 2 54.5 HXG1 151.0 HX G2 20.5 HXG3 Portion 1 (to HX 7) 10.7 Portion 2 (to HX 2) 53.6 Hydraulic Power Slurry Pump 0.2 Liquid State Water Turbine 0.1 Brayton Cycle Turbine 1 6.7 Turbine 2 57.3 Air Compressor 29.4 Rankine Cycle Heat 213.6 Mechanical Power 0.4 76.3 Waste Heat From Steam Cycle 137.7 Chemical Conversion Process Gaseous H2 fuel production 221.4 Input into Conversion Process Biomass (waste wood) input PCE 473.0 Overall Energy Balances Total Energy 47"3.0 645.8 29.9 221.4 783.5 140.4 Net Waste Heat Rejected 137.7 Net Input Energy Required 0.0 Power Conversion Process Net Electricity Production 96.4 Total Electricity Available for Export 96.4 Overall Thermodynamic Conversion Efficiency 67.2% Table 4 Biomass conversion optimised for production of electric power Energy rate in (MW) Energy rate out (MW) Component PCE Heat Work PCE Heat Work Heat Exchangers HX 1 53.4 53.4 HX2 Portioi 1 78.8 Portion 2 212.9 HX 4 (HGR) 50.2 HX 5 (SPR) 93.3 HX 6 55.2 HX7 216.3 HX 8 43.3 Portion 1 of HX 2 78.8 HX G1 243.2 HXG2 Portion 1 73.0 Portion 2 (for Steam Turbine 2) 70.3 HXG3 Portion 1 (to HX 2) 77.1 Portion 2 (to HX 7) 88.0 HX G4 (from cold side of HX C 1) 56.4 56.4 Hydraulic Power Liquid Pump 0.3 Liquid State Turbine 0.2 Rankine Cycle #1 HX 2 (portion 2) 212.9 HXG3 77.1 Mechanical Power 0.5 103.5 Waste Heat From Steam Cy :le 186.9 CPE of syntheisis gas f lei 596.8 Brayton Cycle #1 Turbinii 1 7.9 Air Compressor 64.6 Combined Cycles Gas Cycle Turbine 2 109.3 Steam Cycle 2 HXG2 70.3 HX G4 56.4 Mechanical Power 0.2 45.3 Waste Heat From Steam Cy:le 81.7 Input into Conversion Process Biomass (waste wood) input P 2E 473.0 Overall Energy Balances Total Energy 473.0 1008.3 65.5 596.8 1276.9 266.2 Net Waste Heat Rejec ed 268.6 Net Input Energy Requi ed 0.0 Power Conversion Process Net Electricity Product on 180.6 Total Electricity Available for Export 180-o6 Overall Thermodynamic Conversion Efficiency 38.2% Table 5 Biomass conversion optimized for production of Fischer-Tropsch Paraffins with increased input watenbic mass ratio =9:1 and adiabatic HGR (AHGR) Energy rate in (MW) Ene'rgy rate out (MW) Component PCE Heat Work PCE Heat Work Heat Exchangers HX 1 22.8 22.8 HX 2 Portion 1 49.0 Portion 2 1511 HX 3 Portion 1 56.4 Portion 2 24.8 HX 4 23.6 23.6 HX 5 (SPR) 129.8 HX 6 32.8 32.8 HX 7 603.4 481.8 HX 8 15.9 Portion 1 of HX 2 49.0 HX9(FTR) 37.4 37.3 HX 10 17.3 HXG1 122.0 HX G2 23.7 HX G3 Portion 1 18.8 18.8 Portion 2 8.0 Hydraulic Power Liquid Pump 0.6 Turbine 1 7.3 Turbine 2 54.9 Turbine 3 0.0 Brayton Cycle Turbine 4 20.5 20.5 Turbine 5 103.5 103.5 Turbine 6 1.0 1.0 Compressor 2.8 Air Compressor 31.2 Condenser Heat 85.8 Turbine 7& 8 0.1 23.6 Waste Heat From Steam Cycle 62.2 Chemical Conversion Process synthetic paraffins produced 214.9 synthetic diesel fuel produced* Input into Conversion Process Biomass (waste wood) input PCE 473.0 Overall Energy Balances Total Energy 473.0 1106.9 34.7 214.9 1169.2 210.8 Net Waste Heat Rejected 62.2 Net Input Energy Required 0.0 Power Conversion Process Net Electricity Production 155.1 Total Electricity Available for Export erall Thermodynamic Conversion Efficiency notes * synthetic paraffins produced are considered to be 50% cetane and 50% wax wax can be conventionally processed to produce cetane with 70% efficiency revision 10/12/01 Jtes No additional energy or energetic feedstock is requierd for all conversion options All rejected waste heat is at a temperature below 40C aid is not considered recoverable # DME stored as a compressed liquid at 20C, 5.1 atm. pressure, density 668 g/L and LHV 28.4 MJ/kg revision 10/9/200 tes No additional energy or energetic feedstock is req Jierd for all conversion options All rejected waste heat is at a temperature below 20C and is not considered recoverable # DME stored as a compressed liquid at 20C, 5.1 aim. pressure, density 668 g/L and LHV 28.4 MJ/kg 1 bbl of compressed liquid DME has a mass of 106.2 kg and LHV CPE of 3.02 G J + Cubic meters of liquified hydrogen (at 20 deg K) per day at 1 atm. pressure Approximately 3.7 MJ/kg is needed to cool and liqjjfy hydrogen having an HHV of 144 MJ/kg * All therm ochemical and thermodynamic simulation data as of 10/1/2001 WE CLATM: 1. A process for producing a synthesis gas for use as a gaseous fuel or as feed into Fischer-Tropsch reactor to produc e a liquid fuel, the improvement comprising: forming a liquid suspens on slurry of particles of carbonaceous material in water; feeding said suspension slurry and hydrogen from an internal source into a hydro-gasification reactor under conditions of at least 20 atmospheres of pressure without a reaction catalyst and at a temperature under said pressure whereby methane rich producer gases are generated; feeding the methane rich producer gases from the hydro-gasification reactor into a steam pyrolytic reformer under conditions whereby synthesis gas comprising hydrogen and carbon monoxide are ge lerated; feeding a portion of the h ydrogen generated by the steam pyrolytic reformer into the hydro-gasification reactor as s lid hydrogen from an internal source; and either utilizing said synthesis gas generated by the steam pyrolytic reformer for process heat or as fuel for an engine to produce electricity, or feeding said synthesis gas into the Fischer-Tropsch reactor under conditions whereby a liquid fuel is produced. 2. The process as claimed in claim 1, wherein said portion of the hydrogen generated by the steam pyrolytic reformer is obtai ned through a hydrogen purification filter, 3. The process as claimed in claim 1, wherein said conditions and the relative amounts of said carbonaceous materia , hydrogen and water in the hydro-gasification reactor are such that said methane rich producer gases are produced exothermally. 4. The process as claimed it claim 1, in which said liquid slurry of carbonaceous material is formed by gr nding said carbonaceous material in water. 5. The process as claimed ir claim 1, in which said liquid slurry of carbonaceous material is heated with superheated steam from a steam generator prior to being fed into the hydro-gasification reactor. 6. The process as claimed in claim 5. in which the superheated steam is separated from the slurry, prior to feeding the slurry into the hydro-gasification reactor, and is fed into the steam pyrolytic reformer to react with the methane rich producer gases from the hydro-gasification reactor. 7. The process as claimed in claim 5, in which the slurry, together with the superheated steam, is fed into the hydro-gasification reactor. 8. The process as claimed in claim 7, in which synthesis gas generated by the steam pyrolytic reformer is fed into a Fischer-Tropsch reactor under conditions whereby a liquid fuel is produced. 9. The process as claimed in claim 8, wherein said conditions and the relative amounts of hydrogen and carbon monoxide in the Fischer-Tropsch reactor are such that said liquid fuel is produced exotherma lly 10. The process as claimed in claim 9, comprising transferring exothermic heat from one or both of the hydro-gasifica ion reactor and Fischer-Tropsch reactor to one or both of the steam generator and the steam pyrolytic reformer. 11. The process as claimed in claim 9, comprising transferring exothermic heat from the hydro-gasification reactor-and Fischer-Tropsch reactor to the steam generator and the steam pyrolytic reformer. 12. The process as claimed in claim 11, in which molten salt loops are used to transfer said exothermic heat. 13. The process as claimed in claim 1, in which said carbonaceous material comprises biomass. 14. The process as claimed iit claim 13, in which said biomass comprises municipal solid waste. 15. The process as claimed n claim 8, in which the relative amounts of hydrogen and carbon monoxide in tht synthesis gas fed into the Fischer-Tropsch reactor are such that said liquid fuel is substantially cetane. \ 16 A substantially self-sustaining process for producing a liquid fuel from carbonaceous feed, comprising: grinding said carbonacec us material in water to form a suspension slurry of carbonaceous particles; heating the slurry with superheated steam from a steam generator; feeding hydrogen from a i internal source, the suspension slurry, and the superheated steam into a hydro-gasific ation reactor under conditions of a pressure of about 20 to 50 atmospheres without a -eaction catalyst and at a temperature in the range of about 700 to 1200 degrees Celsius, and in amounts whereby methane rich producer gases are generated exothermally; feeding the methane rich producer gases from the hydro-gasification reactor and said superheated steam into a steai n pyrolytic reformer under conditions whereby synthesis gas comprising hydrogen and carbon monoxide are generated; feeding a portion of the hydrogen generated by the steam pyrolytic reformer, obtained through a hydrogen purification filter, into the hydro-gasification reactor, the hydrogen therefrom constituting said hydrogen from an internal source; feeding the remainder of he synthesis gas generated by the steam pyrolytic reformer into the Fischer-Tropsch reactor under conditions whereby a liquid fuel is produced exothermally; and ^ transferring exothermic heat from the hydro-gasification reactor and Fischer-Tropsch reactor to the steam generator and the steam pyrolytic reformer, whereby said process is substantially self-sustaining. 17. The process as claimed ir claim 16 in which molten salt loops are used to transfer said exothermic heat. 18. The process as claimed ir claim 16, in which said carbonaceous material comprises biomass. 19. The process as claimed iti claim 16, in which said biomass comprises municipal solid waste. 20. Apparatus for producing a synthesis gas for use as a gaseous fuel or as feed into Fiscier-Tropsch reactor to produce a liquid fuel, comprising: a source of carbonaceous; material and water; a hydro-gasification reactor; and a steam pyrolytic reformer; piping connecting said source of carbonaceous material and water to the hydro-gasification reactor for feeding carbonaceous material and water thereto to generate methane and carbon monoxide; piping connecting the hydro-gasification reactor to the steam pyrolytic reformer for feeding methane rich producer gases generated in the hydro-gasification reactor to the steam pyrolytic reformer to generate synthesis gas comprising hydrogen and carbon monoxide; and piping connecting the steam pyrolytic reformer to the hydro- gasification reactor for feeding a portion of the hydrogen generated by the steam pyrolytic reformer into the hydro-gasification reactor. 21. The apparatus as claimed in claim 20, having a hydrogen purification filter through which said portion of hydrogen generated by the steam pyrolytic reformer is obtained. 22. The apparatus as claimed in claim 20, having a grinder forming particles of the carbonaceous material, a receptacle for the particles and water to form a slurry of the carbonaceous particles, and piping connecting the receptacle to the hydro-gasification reactor for feeding the slurry thereto. 23. The apparatus as claimec in claim 22, having a steam generator to heat the slurry of carbonaceous material with superheated steam, a steam separator for separating the superheated steam from the slurry prior to the slurry being fed into the hydro-gasification reactor, and piping for feeding the separated steam into the steam pyrolytic reformer to react with the methane rich p-oducer cases from the hydro-gasification reactor. The apparatus as claimed in claim 2:2, having a steam generator to heat the slurry of carbonaceous material with superheated steam whereby the slurry and superheated steam can be fed into the hydro-gasification reactor. The apparatus as claimed in claim 24, having a Fischer-Tropsch reactor and piping connecting the s:eam pyrolytic reformer to the Fischer- Tropsch reactor for feeding the remainder of the synthesis gas generated by the steam pyrolytic reformer into the Fischer-Tropsch reactor to produce a liquid fuel. The apparatus as claimed in claim 25, having molten salt loops to transfer heat from one or both of the hydro-gasification reactor and Fischer- Tropsch reactor to one or both of the; steam generator and the steam pyrolytic reformer. The apparatus as claimed in claim 26, having molten salt loops to transfer heat from the hydro-gasification reactor and Fischer-Tropsch reactor to the steam generator and the steam pyrolytic reformer. 28. Apparatus for producing a liquid fuel in a substantially self- sustaining process, comprising: a source of carbonaceous material and water; a hydro-gasification reactor; a steam pyrolytic reformer; a hydrogen purificat on filter; r a Fischer-Tropsch reactor; a grinder forming particles of the carbonaceous material; a receptacle for the particles and water to form a slurry of the carbonaceous particles; a steam generator to heat the slurry and activate the carbon by pyrolysis with superheatec steam; piping connecting the steam separator to the hydro-gasification reactor for feeding the slurry and superheated steam thereto to generate methane and carbon monoxide; piping connecting the hydro-gasification reactor to the steam pyrolytic reformer for feeding methane rich producer gases generated in the hydro-gasification reactor to the steam pyrolytic reformer to form a synthesis gas comprising hydrogen and carbon monoxide; piping connecting the steam pyrolytic reformer to the hydro- gasification reactor through the hydrogen purification filter for feeding a portion of hydrogen generated by the steam pyrolytic reformer into the hydro-gasification reactor; and piping connecting the steam pyrolytic reformer to the Fischer- Tropsch reactor for feeding the remainder of the synthesis gas generated by the steam pyrolytic reformer into the Fischer-Tropsch reactor to produce a liquid fuel. The apparatus as claimed in claim 28, having molten salt loops to transfer heat from one or both of ihe hydro-gasification reactor and Fischer- Tropsch reactor to one 01 both of the steam generator and the steam pyrolytic reformer. The apparatus as claimed h claim 28, having molten salt loops to transfer heat from the hydro-gasification reactor and Fischer-Tropsch reactor to the steam generator and the steam pyrolytic reformer. A process and apparatus lor producing a synthesis gas for use as a gaseous fuel or as feed into a rischer-Tropsch reactor to produce a liquid fuel in a substantially self-sustaining process. A slurry of particles of carbonaceous material in water, and hydrogen from an internal source, are fed into a hydro-gasilication reactor under conditions whereby methane rich producer gases are generated and fed into a steam pyrolytic reformer jnder conditions whereby synthesis gas comprising hydrogen and carbon monoxide arc generated. A portion of the hydrogen gene rated by the steam pyrolytic reformer is fed through a hydrogen purification filler into the hydro-gasification reactor, the hydrogen therefrom constituting the hydrogen from an internal source. The remaining synthesis gas generated by the steam pyrolytic reformer is either used as fuel for a gaseous fueled engine to produce electricity and/or process heat or is fed into a Fischer-Tropsch reactor und;r conditions whereby a liquid fuel is produced. Molten salt loops are used to transfer heat from the hydro-gasification reactor, and F ischer-Tropisch reactor if liquid fuel is produced, to the steam generator and the steam pyrolytic reformer.

Full Text

serious environmental pollution unless strict methods of exhaust emission
control are used. A clean burning synthetic diesel fuel can help reduce the
emissions from diesel engines.

The production of clean-burning transportation fuels requires either the
reformulation of existing petroleum-based fuels or the discovery of new
methods for power production or fuel synthesis from unused materials. There
are many sources available, derived from either renewable organic or waste
carbonaceous materials. Utilizing carbonaceous waste to produce synthetic
fuels is an economically viable method since the input feed stock is already
considered of little value, discarded as wastte, and disposal is often polluting.

Liquid transportation fuels have inherent advantages over gaseous
fuels, having higher energy densities than gaseous fuels at the same pressure
and temperature. Liquid fuels can be stored at atmospheric or low pressures
whereas to achieve liquid fuel energy densities, a gaseous fuel would have to
be stored in a tank on a vehicle at high pressures that canbe a safety
concern in the case of leaks or sudden rupiture. The distribution of liquid fuels
is much easier than gaseous fuels, using simple pumps and pipelines. The
liquid fueling infrastructure of the existing transportation sector ensures easy
integration into the existing market of any production of clean-burning
synthetic liquid transportation fuels.

The availability of clean-burning liquid transportation fuels is a national
priority. Producing synthesis gases cleanly and efficiently from carbonaceous
sources, that can be subjected to a Fischer-Tropsch process to produce clean
and valuable synthetic gasoline and diesel fuels, will benefit both the
transportation sector and the health of society. Such a process allows for the
application of current state-of-art engine esxhaust after-treatment methods for
NOx reduction, removal of toxic particulates present in diesel engine
exhaust, and the reduction of normal combustion product pollutants, currently
accomplished by catalysts that sire poisoned quickly by any sulfur present, as
is the case in ordinary stocks of petroleum derived diesel fuel, reducing the

catalyst efficiency. Typically, Fischer-Tropsch liquid fuels, produced from
biomass derived synthesis gases, ere sulfur-free, aromatic free, and in the
case of synthetic diesel fuel have an ultrahigh cetane value.

Biomass material is the most commonly processed carbonaceous
waste feed stock used to produce renewable fuels. Waste plastic, rubber,
manure, crop residues, forestry, tree and grass cuttings and biosolids from
waster water (sewage) treatment are also candidate feed stocks for
conversion processes. Biomass feted stocks can be converted to produce
electricity, heat, valuable chemicals or fuels. California tops the nation in the
use and development of several bomass utilization technologies. Each year
in California, more than 45 million tons of municipal solid waste is discarded
for treatment by waste management facilities. Approximately half this waste
ends up in landfills. . For example, in just the Riverside County , California
area, it is estimated that about 4000 tons of waste wood are disposed of per
day. According to other estimates; over 100,000 tons of biomass per day are
dumped into landfills in the Riverside County collection area. This municipal
waste comprises about 30% waste paper or cardboard, 40/o organic (green
and food) waste, and 30% combinations of wood, paper, plastic and metal
waste. The carbonaceous components of this waste material have chemical
energy that could be used to red uce the need for other energy sources if it
can be converted into a clean-burning fuel. These waste sources of
carbonaceous material are not the only sources available. While many
existing carbonaceous waste materials, such as paper, can be sorted, reused
and recycled, for other materials, the waste producer would not need to pay a
tipping fee, if the waste were to be delivered directly to a conversion facility. A
tipping fee, presently at $30-$35 per ton, is usually charged by the waste
management agency to offset disposal costs. Consequently not only can
disposal costs be reduced by transporting the waste to a waste-to-synthetic
fuels processing plant, but additional waste would be made available because
of the lowered cost of disposal.

The burning of wood in a wood stove is an example of using biomass
to produce heat energy. Unfortunately, the open burning the biomass waste
to obtain energy and heat is not a clean and efficient method to utilize the
calorific value. Today, many new ways of utilizing carbonaceous waste are
being discovered. For example, one way is to produce synthetic liquid
transportation fuels, and another way is to produce energetic gases for
conversion into electricity.

Using fuels from renewable biomass sources can actually decrease the
net accumulation of greenhouse gases, such as carbon dioxide, while
providing clean, efficient energy for transportation. One of the principal
benefits of co-production of synthetic liquid fuels from biomass sources is that
it can provide a storable transportation fuel while reducing the effects of
greenhouse gases contributing to global warming. In the future, these
co-production processes could provide clean-burning fuels for a renewable
fuel economy that could be sustained continuously.

A number of processes exist to convert coal and other carbonaceous
materials to clean-burning transportation fuels, but they tend to be too
expensive to compete on the market with petroleum-based fuels, or they
produce volatile fuels, such as methanol and ethanol that have vapor
pressure values too high for use in high pollution areas, such as the Southern
California air-basin, without legislative exemption from clean air regulations.
An example of the latter process s the Hynol Methanol Process, which uses
hydro-gasification and steam reformer reactors to synthesize methanol using
a co-feed of solid carbonaceous materials and natural gas, and which has a
demonstrated carbon conversion efficiency of >85% in bench-scale
demonstrations.

The need to identify new resources and methods for the production of
transportation fuels requires not only investigating improvements in ways to
produce current petroleum-based fuels but also research into new methods
for the synthesis of functionally equivalent alternative fuels obtained using

resources and methods that are not in use today. The production of synthetic
liquid fuels from carbonaceous materials such as waste organic materials is
one way to solve these problems. The utilization of carbonaceous waste
materials to produce synthetic fuels can be considered a feasible method of
obtaining new resources for fuel production since the material feed stock is
already considered a waste, without value and often it's disposal creates
additional sources of environmental pollution.

SUMMARY OF THE INVENTION

The present invention makes use of steam pyrolysis, hydro-gasification
and steam reformer reactors to produce a synthesis gas that can be
converted into a synthetic paraffinic fuel, preferably a diesel fuel, although
synthetic gasolines and jet propuision fuels can also be made, using a
Fischer-Tropsch paraffin fuel synthesis reactor. Alternatively, the synthesis

r

gas may be used in a co-generated power conversion and process heat
system. The present invention provides comprehensive equilibrium thermo-
chemical analyses for a general class of co-production processes for the
synthesis of clean-burning liquid transportation fuels, thermal process energy
and electric power generation from feeds of coal, or other carbonaceous
materials, and liquid water. It enables a unique design, efficiency of operation
and comprehensive analysis of coal, or any other carbonaceous feed
materials to co-produced fuel, power and heat systems.

The invention provides a process and apparatus for producing a
synthesis gas for use as a gaseous fuel or as feed into a Fischer-Tropsch
reactor to produce a liquid parajffinicjuel, recycled water and sensible heat, in
a substantially self-sustaining process. A slurry of particles of carbonaceous
material suspended in liquid water, and hydrogen from an internal source, are
fed into a steam generator for pyrolysis and hydro-gasification reactor under
conditions whereby super-heated steam, methane, carbon dioxide and carbon
monoxide are generated and :ed into a steam reformer under conditions
whereby synthesis gas comprising primarily of hydrogen and carbon

monoxide are generated. Using a hydrogen separation filter for purification, a
portion of the hydrogen generated by the steam reformer is fed into the hydro-
gasification reactor as the hydrogen from an internal source. The remaining
synthesis gas generated by the steam refonmer is either used as fuel for a
gaseous fueled engine or gas turbir e to produce electricity and process heat,
or is fed into a Fischer-Tropsch fuel synthesis reactor under conditions to
produce a liquid fuel, and recycled water. The correct stoichiometric ratio of
hydrogen to carbon monoxide molecules fed into the Fischer-Tropsch fuel
synthesis reactor, is controlled by the water to carbon ratio in the feed stocks.
Molten salt loops are used to transfer heat from the exothermic hydro-
gasification reactor (and from the exothermic Fischer-Tropsch reactor if liquid
fuel is produced) to the endothermic steam generator for pyrolysis and the
steam reformer reactor vessels.

In particular, the present invention provides the following features.

1) A general purpose solid carbonaceous material feed system that
can accept arbitrary combinations of coal, urban and agricultural biomass,
and municipal solid waste for hydro-gasification.

2) A first stage, steam generator for pyrolysis and hydro-
gasification unit.

3) A steam reformer as a second stage reactor to produce
hydrogen rich synthesis gas from the output of the first stage steam generator
for pyrolysis and hydro-gasification unit. The molal steam to carbon ratio is
maintained as necessary to bring the chemical reactions close to equilibrium;

4) Either (a) a Fischer-Tropsch (synthesis gas-to-liquid) fuel
synthesizer as a third and final stage reactor to conyert the synthesis gas from
the steajj reformer into a sulfur-free clean-burning liquid transportation fuel,
and recycled water or (b) use of uenerated synthesis gas as fuel for process
heat and/or in a fuel engine or g£,3.turbine that,can generate electricity;

5) Three thermo-chemical process reactors are operated to
produce nearly pure paraffinic hydrocarbon liquids (similar to petroleum
derived diesel fuels) and wax-like compounds (similar to petroleum derived
USP paraffinic jellies, which can be further refined into more diesel-like fuels
using conventional methods) from carbonaceous feed stocks (such as waste
wood) in a continuous self-sustainable fashion without the need for additional
fuels or external energy sources. The reactor configurations can also be
optimized for the production of other synthetic fuels, such as dimethyl ether (a
fuel similar to propane, that can be used as; a transportation fuel in diesel
engines and gas turbines) and gaseous fuel grade hydrogen (a fuel that can
be used in engines and turbines, and if purified to remove carbon monoxide,
as an electrochemical fuel in a fuel cell), as well as energetic synthesis gases
for combined cycle power conversion and electric power production.

The fundamental advantages of this invention, over what was
achievable with the prior art, are (a) energy efficient (>85%) methane
production from the available carbon in the carbonaceous feed stock using
steam pyrolysis to activate the carbon and hydrogen gas as the sole initiating
reactant, in contradistinction to partial oxidative gasification usually requiring
an additional energy intensive air separation system to provide the necessary
oxygen; (b) chemically self-sustained operation of the first stage hydro-
gasification reactor by feeding-back surplus hydrogen gas produced in the
second stage methane steam reformer reactor; (c) energy efficient synthesis
of clean-burning transportation fuels using the effluent gases from the steam
reformer, such as: (i) paraffinic compounds using a third stage Fischer-
Tropsch fuel synthesis reactor, (ii) dimethyl ether synthesis using a third stage
synthesis reactor, and (iii) hydrogen production using a hydrogen separation
and/or purification filter without the need for a third stage fuel synthesis
reactor; (d) thermally self-sustained operation of all reactors by effective
management of thermal and chemical energy using combinations of molten
salt or water/steam heat transfer fluids, combustion of product energetic
gases to start and maintain process temperatures, recovered process heat for

the generation of electric power, without the need for additional fuels and
external energy sources; (e) significantly reduced airborne emissions from all
enclosed processes reactors and/or synthesis gas combustors when
compared to direct naturally aspirated combustion (usually known as open
incineration) of the carbonaceous 1eed materials; and f) the ability to capture
all gaseous carbon dioxide effluen t from process reactors or intra-process
synthesis gas combustors for sequestration and/or chemical conversion into
condensed phase compounds using conventional technologies.

These novel configurations of the process reactors have the capability
to improve the overall efficiency cf energy utilization for carbonaceous
material conversion in a co-prodiction plant for synthetic fuels, chemicals and
energy.

ACCOMPANYING
BRIEF DESCRIPTION OF THEpRAWlNGS

Figure 1 is a flow diagram showing the overall modeling of the present
invention;

Figure 2 is a graph showing a plot of carbon conversion vs. H2 /C and
H20/C ratios at 800°C and 30 atm. in HPR;

Figure 3 is a graph showing a plot of CH4/C feed ratio vs. H2/C
andH20/C ratios at 800°C and 30 atm. in HPR;

Figure 4 is a graph showing a plot of C02/C feed ratio vs. H2/C
andH20/C ratio sat 800°C and 30 atm. in HPR;

Figure 5 is a graph showing a plot of CO/ C feed ratio vs. H2/Cand
H20/C ratios at 800°C and 30 atm. in HPR;

Figure 6 is a graph showing the effects of Temperature and Pressure
conditions on C02/H ration the hydro-gasifier reactor (HGR) at fixed feed of
2.629 moles of H2 and 0.0657 moles of H20 per mole of C;

Figure 7 is a graph showing the effect of Temperature and Pressure
conditions on CH4/H ratio in the HGR at fixed feed of 2.629 moles of H2 and
0.0657 moles of H20 per mole of C;

Figure 8 is a graph showing the effect of Temperature and Pressure
conditions on H2/C ratio in the HG R at fixed feed of 2.629 moles of H2 and
0.0657 moles of H20 per mole of C;

Figure 9 is a graph showin 3 the effect of Temperature and Pressure
conditions on CO/H in the HGR at fixed feed of 2.629 moles of H2 and
0.0657moles of H20 per mole of C;

Figure 10 is a graph show ng the effect of input H20/C ratio on steam
reformer (SPR) performance measure by l:he net H2/CO ratio after H2
recycling for the HGR at 1000°C and 30 atm;

Figure 11 is a graph showing the effect of changing the input H20/C
ratio on SPR products, CO, C02 and CH4 in the SPR at 1000°C and 30 atm;

Figure 12 is a graph showing the effect of Temperature and Pressure
conditions on H2/CO ratio in the SPR (2.76 moles of H20/mole of C added to
the SPR);

Figure 13 is a graph showing the effect of Temperature and Pressure
conditions on CHJC ratio in the SPR (2.76 moles of H20/mole of C added to
the SPR);

Figure 14 is a diagram showing the Mass Flow Schematic of Biomass
Hydro-gasification for production of Fischer-Tropsch paraffin fuels;

Figure 15 is a diagram showing the Molal Flow Schematic of Biomass
Hydro-gasification for production of Fischer-Tropsch paraffin fuels;

Figure 16 is a diagram showing the Thermal Energy Management
Schematic of Biomass Hydro-gasification for production of Fischer-Tropsch
paraffin fuels;

Figure 17 is a diagram showing the Water/Steam Flow Schematic of
Biomass Hydro-gasification for production of Fischer-Tropsch paraffin fuels;

Figure 18 is a diagram showing Molten Salt Flow Schematic of
Biomass Hydro-gasification for production of Fischer-Tropsch paraffin fuels;

Figure 19 is a diagram showing Mass Flow Schematic of Biomass
Hydro-gasification for production of dimethyl ether;

Figure 20 is a diagram show ng Mole Flow Schematic of Biomass
Hydro-gasification for production of dimethyl ether;

Figure 21 is a diagram showing Thermal Energy Management
Schematic of Biomass Hydro-gasification for production of dimethyl ether;

Figure 22 is a diagram showing Water/Steam Flow Schematic of
Biomass Hydro-gasification for production of dimethyl ether;

Figure 23 is a diagram showing Molten Salt Flow Schematic of
Biomass Hydro-gasification for production of dimethyl ether;

Figure 24 is a diagram showing Mass Flow Schematic of Biomass
Hydro-gasification for production of gaseous hydrogen fuel;

Figure 25 is a diagram showing Mole Flow Schematic of Biomass
Hydro-gasification for production of gaseous hydrogen fuel;

Figure 26 is a diagram showing Thermal Energy Management
Schematic of Biomass Hydro-gasification for production of gaseous hydrogen
fuel;

Figure 27 is a diagram showing Water/Steam Flow Schematic of
Biomass Hydro-gasification for production of gaseous hydrogen fuel;

Figure 28 is a diagram showing Molten Salt Flow Schematic of
Biomass Hydro-gasification for production of gaseous hydrogen fuel;

Figure 29 is a diagram showing Mass Flow Schematic of Biomass
Hydro-gasification for production ot electricity;

Figure 30 is a diagram showing Mole Flow Schematic of Biomass
Hydro-gasification for production ot electricity;

Figure 31 is a diagram showing Thermal energy Management
Schematic of Biomass Hydro-gasification for production of electricity;

Figure 32 is a diagram showing Water/Steam Flow Schematic of
Biomass Hydro-gasification for production of electricity;

Figure 33 is a diagram showing Molten Salt Flow Schematic of
Biomass Hydro-gasification for production of electricity;

Figure 34 is a mass flow schematic of biomass hydro-gasification for
Fischer-Tropsch paraffin fuel production using an adiabatic HGR and a 9:1
water feed;

Figure 35 is a molal flow schematic of biomass hydro-gasification for
Fischer-Tropsch paraffin fuel production using an adiabatic HGR and a 9:1
water feed;

Figure 36 is a thermal energy management schematic of biomass
hydro-gasification for Fischer-Tropsch paraffin fuel production using an
adiabatic HGR and a 9:1 water feed;

Figure 37 is a water/steam flow schematic of biomass hydro-
gasification for Fischer-Tropsch paraffin fuel production using an adiabatic
HGR and a 9:1 water feed;

Figure 38 is a molten salt flow schematic of biomass hydro-gasification
for Fischer-Tropsch paraffin fuel production using an adiabatic HGR and a 9:1
water feed.

DETAILED DESCRIPTION OF THE INVENTION

A steam generator for pyro ysis, hydro-gasification reactor (HGR) and
steam pyrolytic reformer (SPR) (a so called a steam pyrolytic reactor, steam
reformer or steam reactor) such as used in a Hynol process, may be utilized
to produce the synthesis gas (syn gas) through steam pyrolysis of the feed
stock, hydro-gasification and steam reforming reactions. The reactions start
in the HGR to convert carbon in the carbonaceous matter into a methane rich
producer gas and continue through the SPR to produce synthesis gas with the
correct hydrogen and carbon monoxide stiochiometry for efficient operation of
the Rscher-Tropsch process. With the Fischer-Tropsch process as the final
step in processing, products such as synthetic gasoline, synthetic diesel fuel
and recycled water can be produced.

The feedstock requirement is highly flexible. Many feeds that consist
of different carbonaceous materials can be wet milled to form a water slurry
that can be fed at high pressure into a steam pyroiyzer, hydro-gasifier and
steam reformer reactors for synthesis gas production. The feed to water
mass ratio can even vary during tie running of the process, with a knowledge
of the chemical content of the feed, to maintain the carbon-hydrogen
stiochiometry required for an opt mized fuel synthesis process. Appropriate
carbonaceous materials include biomass, natural gas, oil, petroleum coke,
coal, petrochemical and refinery by-products and wastes, plastics, tires,
sewage sludge and other organic wastes. For example, wood is an example
of waste biomass material that it; readily available in Riverside County,
California. This particular waste stream could be augmented with other
carbonaceous materials, such as green waste and biosolids from water
treatment that are available in Riverside County, and would otherwise go to
landfill.

When used to make a transportation fuel, such as diesel fuel, the
process is designed so that the feedstock makes the maximum amount of
Fischer-Tropsch paraffinic prod act required. The desired output consists of a

liquid hydrocarbon, such as cetane, C16H34, within the carbon number range,
12 to 20, suitable as a diesel fuel. Excess synthesis gas output from the SPR,
i.e., "leftover" chemical energy from the Fischer Tropsch synthetic fuel
producing process, can be used as an energetic fuel to run a gas turbine for
electricity production. The synthesis gas output after recycling enough
hydrogen to sustain the hydro-gasifier, may be used for this purpose also,
depending on the needs of the user. The following provides a method for
maximizing the economic potential from the present invention in the
conversion of carbonaceous materials to a usable transportation fuels and
inclusive of the possibility for direct electric power production through a gas
turbine combined cycle.

1) Find approximate data on available carbonaceous wastes, their
chemical composition and perform further analysis on the practical need for
the process.

2) Model the important reactions within the process consisting of
the steam generator for pyrolysis, lydro-gasifier, steam reformer, and the
Fischer-Tropsch (or other fuel synthesis) reactor on a continuous flow-through
basis. This may be done by optimizing the Fischer-Tropsch (or other fuel
synthesizer) feedstock for the optimum stoichiometric hydrogen to carbon
monoxide mole ratio for fuel to be synthesized.

3) Perform an economic analysis on the costs to obtain and
prepare the input material required, capital costs, operating and maintenance,
and product yield and costs.

Specific implementations are given below in conjunction with flow
charts provided in the Figures, demonstrating the conversion of waste wood,
as the candidate carbonaceous material, to a liquid diesel transportation fuel,
recycled water and an alternative power source, via a Fischer-Tropsch
process linked to a gas turbine combined cycle.

The thermo-chemical conversion of carbonaceous materials occurs by
two main processes: hydro-gasification and steam reformation, with steam
pyrolysis of the feedstock occurring within the steam generator to pre-treat
feedstock and activate the carbon contained therein. The hydro-gasifier
requires an input of the pyrolyzed carbonaceous waste, hydrogen, steam,
reacting in a vessel at high temperature and pressure, which in a specific
implementation is approximately 30 atmospheres and 1000 degrees Celsius.
Steam reforming of the methane rich effluent gas from the HGR also requires
an approximate pressure of 30 atmospheres and 1000 degrees Celsius.
More generally, each process can be conducted over a temperature range of
about 700 to 1200 degrees Celsius and a pressure of about 20 to 50
atmospheres. Lower temperatures and pressures can produce useful reaction
rates with the use of appropriate reaction catalysts.

Referring to Figure 1, which is an overall flow diagram, the order of
general processes that carry out these main reaction processes is shown
(specific amounts for a particular embodiment are in the flow diagrams shown
in Figures 14 through 38). Piping is used to convey the materials through the
process. The feed 11 is chopped milled or ground in a grinder 10 into small
particles, mixed with the recycled water 12 and placed in a receptacle or tank
14 as a liquid, suspension slurry 16 that is transportable as a compressed
fluid by a pump 18 to a steam generator 20 where the slurry 16 is
superheated and pyrolyzed, followed by either separation of the steam in a
steam separator 22 so that stearr goes through piping 24 that is separate
from piping that delivers the pumped, dense slurry paste 26, or a direct steam
pyrolysis feed through piping 27.

The dense slurry paste feed 26, or the direct steam pyrolysis feed 27,
enters the HGR 28. Hydrogen from an internal source (from the steam
reformer via a hydrogen separation filter described below) and a fraction of
the previously produced steam flow into the HGR 28 for the desired output.
The output gases consists largely of methane, hydrogen, carbon monoxide,
and super-heated steam. The gases produced by the HGR 28 leaves the

chamber and is pumped over to tie SPR 30. The un-reacted residue (or ash)
from the HGR, is periodically removed from the bottom of the reactor vessel
using a double buffered lock-hopper arrangement, that is commonly used in
comparable high pressure gasific ation systems. The ash is expected to be
comprised of sand, Si02, and alumina, Al203, with trace amounts of metals.
The input to the SPR 30 is delivered from either the steam separator 22 by
piping 32 through a heater 34 anc further piping 36, or via the HGR 28 output
piping, to provide greater-than-theoretical steam to carbon ratio into the SPR
30, to mitigate coking in the reactor. The output is a higher amount of
hydrogen, and CO, with the appropriate stiochiometry for the desired
hydrocarbon fuel synthesis process described below.

The output of the SPR 30 is directed via piping 38 through heat
exchangers 40 and 42. Condensed water 44 is separated and removed from
the SPR output, via a heat exchanger and liquid water expander 47. The non-
condensable gaseous output of SPR 30 is then conveyed to a hydrogen
separation filter 46. A portion of tie hydrogen from the SPR output, about
one-half in this embodiment, is carried from the filter 46, passed through the
heat exchanger 40 with a resultar t rise in its temperature (in the embodiment
from 220 degrees centigrade to 970 degrees Centigrade) and delivered to the
HGR 28 as its hydrogen input. The hot effluent from the SPR output is cooled
by passing through heat exchangers 40 and 42, used to heat the recycled
hydrogen, and make steam respectively. The condensed water 44 leaving the
heat exchanger 47 is recycled back to make the water supply 12 for the slurry
feed. By such means, a self-sustaining process is obtained.

The fuel synthesis gas is then used for one of two options. Based on
the calorific value, the synthesis gas may go through a gas turbine combined
cycle for direct energy production or through a fuel synthesis reactor (in this
embodiment, a Fischer-Tropsch process to produce a clean diesel fuel and
recycled water). In accordance with a specific embodiment of the invention,
the synthesis gas is directed through an expansion turbine 48, to recover
mechanical energy by lowering the pressure of the gaseous feed into the

Fischer-Tropsch reactor 50. The mechanical power produced by the liquid
state turbine, the Brayton and Rankine cycle turbines can be used to provide
power for internal slurry, water feed pumps, iair compressor, with the surplus
exported via electricity generation, see Tables 1 through 7.

Efficiency may be maximized by adjusting input and process
parameters. The biomass/ coal vaiying-mixture feed is synthesized into a
slurry by adding water whereby after steam separation the carbon to
hydrogen ratio will be appropriate for the process. A slurry feed needs
enough water to run the hydro-gas fier, the steam reformer, and to keep the
feed in a viable slurry after steam separation. Prior art attempts at biomass
conversion using solid dry feed had many mechanical problems of feeding a
solid into the high pressure, and high temperature HGR reaction chamber.
This method of slurry feed has already been demonstrated and studied,
according to the results for the "Hydrothermal Treatment of Municipal Solid
Waste to Form High Solids Slurries in a Pilot Scale System", by C. B.
Thorsness et al., UCRL-ID 119686, published by Lawrence Livermore Nation
Laboratory, Livermore, CA in 1995. In addition, there is related art published
on the making and operating of coal water slurry feeds. For example, see Z.
Aktas et al., Fuel Processing Technology 62 2000 1-15.The principle
reactions of the two main processes, hydro-gasification and steam reforming,
are shown here. The HGR independent reactions can be expressed as:

Reactions 2 and 3 are enc othermic. Reaction 1 is sufficiently
exothermic to provide the heat of reaction for reactions 2 and 3. Some
preheating of the HGR will be needed to tiring the reactor up to its operating
temperature. Thus, the HGR is intended to be self-sustaining once the
reactions have started and achieve steady state.

The main purpose of the HGR process is to maximize the carbon
conversion from the feed stock into the energetic gases CH4 and CO. After
this process, hydrogen is produced by reacting superheated steam with CH4
and CO within the SPR. In the SPR, half the hydrogen is obtained from the
superheated steam and the remainder from the CH4. The principle reactions
in the SPR are considered to be:

The steam reforming reactior s (4 and 5) are often run with steam
concentrations higher than required for the stiochiometry shown above. This
is done to avoid coke formation and to improve conversion efficiency. The
required steam concentration is usually specified in the form of the
steam-to-carbon mole ratio (S:C), the ratio of water steam molecules per
carbon atom in the HGR feed. The preferred (S:C) ratio for the SPR
operation is greater than 3. This steam rich condition favors the water-gas
shift reaction. This reaction is only slightly exothermic (AH°= -41 kJ/mole
CO); however, it produces additional hydrogen gas and converts carbon
monoxide into carbon dioxide. Unfortunately, an additional unwanted
secondary reaction can occur, the methanation reaction, which consumes
hydrogen:

The resulting effluent after the two main reactors is a synthesis of
gases rich in hydrogen, carbon monoxide, and steam. Approximately half the
hydrogen produced in the SPR is recycled back to the HGR. Consequently,
no outside source of hydrogen is needed to maintain steady state operation.
The HGR and SPR processes, therefore, may be considered to be chemically
self-sustaining. The remaining syntnesis gas is then available for the
production of fuels and process heat.

The present invention using the Fischer-Tropsch process can produce
a zero-sulfur, ultrahigh cetane value diesel-like fuel and valuable paraffin wax
products. The absence of sulfur enables low pollutant and particle emitting
diesel fuels to be realized.

The present invention also provides a source of by-products. One
useful by-product is purified water, which can be re-cycled to create the slurry
feed into the process. In a report by Rentech titled "Fischer-Tropsch
technology" dated 1998 see Rentech web publications at
http://www.rentechinc.com. Rentech states that the Fischer-Tropsch process
with an iron catalyst makes about 7/1 Oths of a barrel of water per barrel of
Fischer-Tropsch products. A cobalt catalyzed Fischer-Tropsch process
makes about 1.1 to 1.3 barrels of water for each barrel of Fischer-Tropsch
products, a greater amount than iron. Part of the water may be recycled to
make steam in the steam reformer unit and for cooling in both the synthesis
gas and Fischer-Tropsch step of the overall process.

The Fischer-Tropsch reactions also produce tail gas that contains
hydrogen, CO, CO2, and some light hydrocarbon gases. Hydrogen can be
stripped out of the tail gas and recycled either to the HGR or the Fischer-
Tropsch reactor. Any small amounts of other gases such as CO and C02
may be flared off.

Two main products of Fischer-Tropsch may be characterized as
synthetic oil and petroleum wax. According to Rentech, in the above report
for their particular implementation of the Fischer-Tropsch process, the mix of
solid wax to liquid ratio is about 50/50. Fischer-Tropsch products are totally
free of sulfur, nitrogen, nickel, vanadium, asphaltenes, and aromatics that are
typically found in crude oil. The products are almost exclusively paraffins and
olefins with very few, or no, complex cyclic hydrocarbons or oxygenates that
would otherwise require further separation and/or processing in order to be
usable end-products. The absence of sulfur, nitrogen, and aromatics
substantially reduces harmful emissions.

California's Air Resources Board (CARB) specifications for diesel fuel
require a minimum cetane value of 48 and reduced sulfur content. The above
Rentech study with Shell diesel fue produced from a Fischer-Tropsch process
has a cetane value of 76. The CARB standard for sulfur in diesel fuel placed
in the vehicle tank is 500 ppm by weight, and Shell's Fischer-Tropsch process
diesel fuel has no detectable amount in the ppm range. The CARB standard
for aromatic content is no more than 10% by volume (20% for small
refineries). The Shell Fischer-Tropsch process diesel fuel had no detectable
aromatics.

Rentech further affirmed through studies that the diesel fuel may need
no further processing because of the purity and olefin products that may even
be advantageous over crude oil diesel. The Fischer-Tropsch diesel process is
clean and the product is cleaner, has a higher cetane value, and most likely
does not need further processing, when compared to a crude oil diesel.

A gas turbine combined cycle for electric power production is an option.
If the Fischer-Tropsch product is unexpectedly too costly, the use of the
synthesis gas heating value can be a viable option, based on an overall
efficiency of 65% of the synthesis gas energy converting to electric energy.
This number is reasonable since the synthesis gas starts at a high
temperature as opposed to taking natural gas in from a pipeline.

Process modeling can be used to reasonably produce a synthesis gas
maximized for a yield high in CO and stoichiometric hydrogen. First, the unit
operation reactions of the hydro-gasifier, steam reformer, and
Fischer-Tropsch reactors are modeled. This may be accomplished by using
Stanjan, a DOS-based computer program that uses equilibrium modeling. By
varying the parameters of temperature, pressure, original feedstock and gas
flows, a parameterization study was carried out based on costs and output
benefit. The hydro-gasifier variables were modified for the maximum practical
carbon conversion efficiency. The steam reformer variables were modified for
maximum practical CO output, er ough hydrogen for recycling output, and

minimum CO2 production. The study looked at the various parameters
whereby two different values varied for one constant, resulting in 3-D
parameterization studies. The following discusses the results from the
computer modeling of the main reactions using Stanjan programming.

Referring to Figure 2, the effect of varying the water or steam and
hydrogen ratios on the conversion efficiency of carbon in feedstock in the
HGR is shown at 800°C and 30 atm. As the hydrogen and water input to the
HGR increases, the conversion efficiency of carbon in feedstock increases
until it reaches 100%. The condition that fails in the area of 100% conversion
efficiency achieves one of the modeling objectives, and these conditions were
used. In order to avoid the cost of recycling of H2, the minimum amount of H2
recycled to the HGR must be chosen. Figure 3 shows the effect of H2 and
H20 on CH4 in the HGR at 800°C and 30 atm. Figure 4 shows the effect of H2
and H20 on C02 in the HGR at 800°C and 30 atm. At a high amount of H2
and low amount of H2O input, the amount of CO2 is low. Although the
objective is to minimize the amount of C02 in the synthesis gas, it is not
necessary to minimize C02 in the HGR because C02 is gauged in the SPR
reactions through the water-gas-shift reaction to obtain a proper ratio of H2
and CO for a maximum Fischer-Tropsch diesel fraction. Figure 5 shows the
effect of H2 and H20 on CO in the HGR at 800°C and 30 atm.

Figures 6,7,8 and 9 show the effects of varying temperature and
pressure on the chemical composition of the effluent gases from the HGR at
feed of 2.76 mol H2 and 0.066 mol H20 per mole C in the feed stock. At these
conditions of H2 and H20 input to the HGR, the carbon conversion efficiency
is estimated to close to 100% in a temperature range of 800 to 1000°C and a
pressure range of 30 atm. to 50 atm, for equilibrium chemistry.

Figure 10 shows the ratio of H2 and CO available for feed into the
Fischer-Tropsch fuel synthesis reactor, against the steam content added to
the SPR at 800°C and 30atm. This ratio increases with the increasing amount
of steam added to the SPR and reaches 2.1 at about 3.94 mol steam (or

water) added per mol C in feedstock. With this amount of steam added, the
system will achieve chemical and thermal self-sustainability and provide a
proper ratio of H2 and CO for Fischer-Tropsch synthesis of cetane. Figure 11
shows the effect of H20 added to the SPR at 800°C and 30atm. Figures 12
and 13 show the effect of temperature and pressure on the H2 and CO ratio
and the conversion of CH4 in the SPR. At higher temperature and lower
pressure, this ratio is higher. In a smilar trend with the H2 and CO ratio, the
conversion of CH4 increases with increasing temperature and with decreasing
pressure. It is thus high temperature and low pressure favored in the SPR.

The products of Fischer-Tropsch paraffinic liquid fuels are in a wide
range of carbon number. According to the above Rentech report, about half
of the products are diesel fuel. Also about half of the products come in the
form of wax, with minor amounts of gases such as un-reacted reactants and
hydrocarbon gases (methane, ethane, propane and so forth). To exemplify
the present invention, cetane, whici is in middle position of diesel range (Cn
to C2o ), was chosen as diesel fuel.

The results of thermo-chemical and thermodynamic modeling of the
hydro-gasified conversion of waste wood (biomass), as a prototypical
carbonaceous feed material, were used to examine the details and illustrate
the features of this invention. These simulations of the novel sequence of
process reactors were undertaken to discover the thermo-chemical conditions
needed to achieve the production of synthetic fuels. For example, in the
production of synthetic diesel fuel, the objectives were to attain self-sustained
operation of the first stage hydro-gasifier. In a particular embodiment, this is
accomplished at an equilibrium temperature! of 1000°C (738°Cwhen
adiabatic) and 30 atmospheres pressure with a total hydrogen to carbon feed
mole ratio of at least 3.48:1 (1.67: when adiabatic), and water to carbon feed
ratio of at least 0.07:1 (0.43 when adiabatic), a water steam to carbon feed
mole ratio of at least 3.91:1 (1.67:1 when adiabatic) into the second stage
steam reforming reactor also operating at an equilibrium temperature of
1000°C (900°C when adiabatic) and 30 atmospheres pressure, to obtain

conditions for simultaneous optimal quantities of product hydrogen for self-
sustained operation of the first stage hydro-gasification reactor and an
adequate hydrogen to carbon mole ratio of at least 2.1:1 in the residual
synthesis gas stream to feed the third stage Fischer-Tropsch reactor,
operating at 200°C and 10 atmospheres pressure, and adiabatic self-
sustained operation of a special HGR and SPR combination reactor, followed
by a conventionally operated SPR and Fischer-Tropsch reactors, with full
thermal and chemical potential energy management.

Tables 1 through 5 show the overall energy transfer rates into and out
from each heat exchanger and power conversion component for each
operating mode of the conversion process. The mass flow, molal flow, thermal
energy management, water/steam and molten salt schematic diagrams for
each of the five operating modes of the conversion process are also shown as
Figs14-18,19-23, 24-28, 29-33 and 34-38 respectively. Tables 6 and 7
summarize the results of the performance studies and process configuration
parameters for each of the five operating modes of the conversion process.

The carbonaceous material feed process initially described above uses
a water slurry suspension feed technology, originally developed by Texaco for
use in its partial-oxidation gasifiers, that can accept a wide variety of
carbonaceous materials, and can be metered by controlled pumping into the
first stage hydrogen gasification reactor (HGR) to produce a methane rich
gas with high conversion efficiency (measured to have at least 85% carbon
feed chemical utilization efficiency). Enough heat is available to be able to
generate super-heated steam from the biomass-water slurry feed to supply
and operate the second stage steam-methane reformer. The reformer product
gas is fed into a hydrogen membrane filter that allows almost pure hydrogen
to pass back into the first stage reactor to sustain the hydro-gasification of the
biomass. The remaining second stage product gas, not passing through the
hydrogen filter, is cooled to condense and re-cycle any water vapor present
back into the slurry carbonaceous feed sys;tem. The unfiltered gas is fed into
the fuel synthesis reactors, which comprise a Fischer-Tropsch paraffin hydro-

carbon synthesis reactor, which operates at 200°C and 10 atmospheres
pressure. Process modeling reveals that the hydrogen/carbon molecular feed
ratio must be at least 2.1:1 to optimize production of chemically pure and
clean-burning [sulfur-free] diesel-like liquid fuels and high value chemically
pure paraffin-like waxes, without additional fuel or energy. (Figs. 14-18 and
Tables 1, 6 and 7 or Figs. 34-38 and Tables 5, 6 and 7 for adiabatic first stage
reactor operation), or a dimethyl ether synthesis reactor, which operates at
200C and 70 atmospheres pressure. This reactor produces approximately
92.4% DME and 7.1% methanol. The methanol is combusted to co-generate
about 30 MW of electricity and 20fv1W of process heat for exchange with the
molten salt and water/steam heat transfer loops (see Figs. 19-23 and Tables
2, 6 and 7), hydrogen gaseous fuel synthesis (see Figs. 24-28 and Tables 3, 6
and 7), and all electric power production without fuel synthesis (see Figs. 29-
33 and Table 4, 6 and 7).

Net export of electric power is possible in all five modes of operation of
the simulated biomass hydro-gasification process plant. The results of these
simulations are summarized in Table 6 and 7. The overall energy utilization
goes from 50.7% (71.2% when adi abatic) for Fischer-Tropsch synthesis to
67.2% for hydrogen production. Optimized electric power production utilizes
about 38.2% of the chemical potential energy in the biomass feed stock for
clean-burning power conversion. In general the process modes could be
switched using an appropriate proportional valve to distribute the synthesis
gas production after separation of enough pure hydrogen gas for the first
stage hydro-gasification reactor.

The results of the overall modeling shown in Figure 1 are summarized
as follows.

1. Optimum conditions of the HGR: Operating at 1000°C and
30atm; 2.76 mol H2 per mol C in feedstock to maintain self-sustainability;
0.066 mol H20 per mol C in feedstock.

2. Optimum conditions of the SPiR: Operating at 1000°C and
30atm; 4.022 mol H20 per mol C in feedstock.

3. Fischer-Tropsch products: 0.199 ton wax per ton of feedstock;
68.3 gallons of cetane (C16H34) diesel per ton of feedstock.

Although the present invention and its advantages have been
described in detail, it should be understood that various changes,
substitutions and alterations can be made herein without departing from the
spirit and scope of the invention as defined by the appended claims.
Moreover, the scope of the present application is not intended to be limited to
the particular embodiments of the process and apparatus described in the
specification. As one of ordinary skill in the art will readily appreciate from the
disclosure of the present invention, processes and apparatuses, presently
existing or later to be developed that perform substantially the same function
or achieve substantially the same result as the corresponding embodiments
described herein may be utilized according 1:o the present invention.
Accordingly, the appended claims are intended to include within their scope
such processes and apparatuses.

Table 1 Biomass conversion optimized for production of Fischer-Tropsch Paraffins

Energy rate in (MW) Energy rate out (MW)

Component PCE Heat Work PCE Heat Work

Heat Exchangers

HX 1 53.4 53.4

HX2

Portion 1 78.8

Portion 2 212.9

HX3

Portion 1 2.2 2.2

Portion 2 112.0

HX 4 (HGR) 50.2

HX 5 (SPR) 93.3

HX6

Portion 1 46.6

Portion 2 8.7

HX 7 216.3

HX 8 43.3

Portion 1 of HX 2 78.8

HX 9 (FTR) 45.9

HX10 11.8

HXG1 165.0

HXG2 21.8

HX G3 68.4

Hydraulic Power

Slurry Pump 0.3

Liquid State Water Turbine 0.2

Brayton Cycle

Turbine 1 7.9

Turbine 2 75.0

Turbine 3 0.0

Air Compressor 43.4

Rankine Cycle

Heat 290.0

Mechanical Power 0.5 103.5

Waste Heat From Steam Cycle 186.9

Chemical Conversion Process

synthetic paraffins produced 137

synthetic diesel fuel produced* 116

Input into Conversion Process

Biomass (waste wood) input PCE 473.0
Overall Energy Balances

Total Energy 473.0 827.3 44.1 137 1014.2 186.6

Net Waste Heat Rejected 186.9

Net Input Energy Required 0.0

Power Conversion Process

Net Electricity Production 123.8

Total Electricity Available for Export 123.8

Dverall Thermodynamic Conversion Efficiency 50.7%

notes

* synthetic paraffins produced are considered to be 50% cetane and 50% wax
wax can be conventionally processed to produce cetane with 70% efficiency

Table 2 Biomass conversion optimized for production ol dimethyl ether (DME)

En srgy rate in (MW) Energy rate out (MW)
Component PCE Heat Work PCE Heat Work

Heat Exchangers

HX1 53.4 53.4

HX2

Portion 1 54.5

Portion 2 160.0

HX 3 3.8

HX 4 (HGR) 50.2

HX5(SPR) 91.3

HX 6 36.6

HX7 152.8

HX 8 29.9

Portion 1 of HX 2 54.5

HX 9 (DME-R) 32.3

HX 10 0.7

HX11 1.6

HX12 3.2

HXG1 150.2

HXG2 21.3

HX G3 66.8

HXG4
Portion 1 (to HX 7) 49.4

Portion 2 (to HX 2) 64.5

Hydraulic Power

Slurry Pump 0.2

Liquid State Water Turbine 0.1

Brayton Cycles

Turbine 2 3.4

Turbine 3 4.0

Turbine 4 70.7

Compressor 5.2

Air Compressor 39.8

Rankine Cycle
Heat (HX 3, 9,10,11,12 & G4) 266.1

Mechanical Power 0.4 95.0

Waste Heat From Steam Cycle 171.5

Chemical Conversion Process

dimethyl ether (DME) production 160.6

Input into Conversion Process

Biomass (waste wood) input PCE 47 3.0
Overall Energy Balances

Total Energy 473.0 698.2 45.6 160.6 869.8 173.2
Net Waste Heat Rejected 171.5

Net Input Energy Required 0.0

Power Conversion Process

Net Electricity Production 110.3

Electricity Available for Export 110.3

Overall Thermodynamic Conversion Efficiency 57.3%

Table 3 Biomass conversion optimized for production of gaseous hydrogen fuel

Energy irate in (MW) Energy rate out (MW)

Component PCE Heat Work PCE Heat Work

Heat Exchangers

HX 1 53.4 53.4

HX2

Portion 1 54.5

Portion 2 160.0

HX3 105.4

HX 4 (HGR) 50.2

HX 5 (SPR) 91.3

HX 6 36.6

HX7 152.8

HX 8 29.9

Portion 1 of HX 2 54.5

HXG1 151.0

HX G2 20.5

HXG3
Portion 1 (to HX 7) 10.7

Portion 2 (to HX 2) 53.6

Hydraulic Power

Slurry Pump 0.2

Liquid State Water Turbine 0.1

Brayton Cycle

Turbine 1 6.7

Turbine 2 57.3

Air Compressor 29.4

Rankine Cycle

Heat 213.6

Mechanical Power 0.4 76.3

Waste Heat From Steam Cycle 137.7

Chemical Conversion Process

Gaseous H2 fuel production 221.4

Input into Conversion Process

Biomass (waste wood) input PCE 473.0
Overall Energy Balances

Total Energy 47"3.0 645.8 29.9 221.4 783.5 140.4
Net Waste Heat Rejected 137.7

Net Input Energy Required 0.0

Power Conversion Process

Net Electricity Production 96.4

Total Electricity Available for Export 96.4

Overall Thermodynamic Conversion Efficiency 67.2%

Table 4 Biomass conversion optimised for production of electric power

Energy rate in (MW) Energy rate out (MW)

Component PCE Heat Work PCE Heat Work

Heat Exchangers

HX 1 53.4 53.4

HX2

Portioi 1 78.8

Portion 2 212.9

HX 4 (HGR) 50.2

HX 5 (SPR) 93.3

HX 6 55.2

HX7 216.3

HX 8 43.3

Portion 1 of HX 2 78.8

HX G1 243.2

HXG2

Portion 1 73.0

Portion 2 (for Steam Turbine 2) 70.3

HXG3

Portion 1 (to HX 2) 77.1

Portion 2 (to HX 7) 88.0

HX G4 (from cold side of HX C 1) 56.4 56.4

Hydraulic Power

Liquid Pump 0.3

Liquid State Turbine 0.2

Rankine Cycle #1

HX 2 (portion 2) 212.9

HXG3 77.1

Mechanical Power 0.5 103.5

Waste Heat From Steam Cy :le 186.9

CPE of syntheisis gas f lei 596.8

Brayton Cycle #1

Turbinii 1 7.9

Air Compressor 64.6

Combined Cycles

Gas Cycle

Turbine 2 109.3

Steam Cycle 2

HXG2 70.3

HX G4 56.4

Mechanical Power 0.2 45.3

Waste Heat From Steam Cy:le 81.7

Input into Conversion Process

Biomass (waste wood) input P 2E 473.0
Overall Energy Balances

Total Energy 473.0 1008.3 65.5 596.8 1276.9 266.2
Net Waste Heat Rejec ed 268.6

Net Input Energy Requi ed 0.0

Power Conversion Process

Net Electricity Product on 180.6

Total Electricity Available for Export 180-o6

Overall Thermodynamic Conversion Efficiency 38.2%

Table 5 Biomass conversion optimized for production of Fischer-Tropsch Paraffins
with increased input watenbic mass ratio =9:1 and adiabatic HGR (AHGR)

Energy rate in (MW) Ene'rgy rate out (MW)

Component PCE Heat Work PCE Heat Work

Heat Exchangers

HX 1 22.8 22.8

HX 2

Portion 1 49.0

Portion 2 1511

HX 3

Portion 1 56.4

Portion 2 24.8

HX 4 23.6 23.6

HX 5 (SPR) 129.8

HX 6 32.8 32.8

HX 7 603.4 481.8

HX 8 15.9

Portion 1 of HX 2 49.0

HX9(FTR) 37.4

37.3
HX 10 17.3

HXG1 122.0

HX G2 23.7

HX G3

Portion 1 18.8 18.8

Portion 2 8.0

Hydraulic Power

Liquid Pump 0.6

Turbine 1 7.3

Turbine 2 54.9

Turbine 3 0.0
Brayton Cycle

Turbine 4 20.5 20.5

Turbine 5 103.5 103.5

Turbine 6 1.0 1.0

Compressor 2.8

Air Compressor 31.2

Condenser

Heat 85.8

Turbine 7& 8 0.1 23.6

Waste Heat From Steam Cycle 62.2

Chemical Conversion Process

synthetic paraffins produced 214.9

synthetic diesel fuel produced*
Input into Conversion Process

Biomass (waste wood) input PCE 473.0
Overall Energy Balances

Total Energy 473.0 1106.9 34.7 214.9 1169.2 210.8

Net Waste Heat Rejected 62.2

Net Input Energy Required 0.0

Power Conversion Process

Net Electricity Production 155.1

Total Electricity Available for Export
erall Thermodynamic Conversion Efficiency

notes

* synthetic paraffins produced are considered to be 50% cetane and 50% wax
wax can be conventionally processed to produce cetane with 70% efficiency

revision 10/12/01

Jtes

No additional energy or energetic feedstock is requierd for all conversion options
All rejected waste heat is at a temperature below 40C aid is not considered recoverable
# DME stored as a compressed liquid at 20C, 5.1 atm. pressure, density 668 g/L and LHV 28.4 MJ/kg

revision 10/9/200

tes

No additional energy or energetic feedstock is req Jierd for all conversion options

All rejected waste heat is at a temperature below 20C and is not considered recoverable

# DME stored as a compressed liquid at 20C, 5.1 aim. pressure, density 668 g/L and LHV 28.4 MJ/kg
1 bbl of compressed liquid DME has a mass of 106.2 kg and LHV CPE of 3.02 G J

+ Cubic meters of liquified hydrogen (at 20 deg K) per day at 1 atm. pressure

Approximately 3.7 MJ/kg is needed to cool and liqjjfy hydrogen having an HHV of 144 MJ/kg

* All therm ochemical and thermodynamic simulation data as of 10/1/2001

WE CLATM:

1. A process for producing a synthesis gas for use as a gaseous fuel or as feed
into Fischer-Tropsch reactor to produc e a liquid fuel, the improvement comprising:

forming a liquid suspens on slurry of particles of carbonaceous material in
water;

feeding said suspension slurry and hydrogen from an internal source into a
hydro-gasification reactor under conditions of at least 20 atmospheres of pressure without
a reaction catalyst and at a temperature under said pressure whereby methane rich
producer gases are generated;

feeding the methane rich producer gases from the hydro-gasification reactor
into a steam pyrolytic reformer under conditions whereby synthesis gas comprising
hydrogen and carbon monoxide are ge lerated;

feeding a portion of the h ydrogen generated by the steam pyrolytic reformer
into the hydro-gasification reactor as s lid hydrogen from an internal source; and

either utilizing said synthesis gas generated by the steam pyrolytic reformer
for process heat or as fuel for an engine to produce electricity, or feeding said synthesis
gas into the Fischer-Tropsch reactor under conditions whereby a liquid fuel is produced.

2. The process as claimed in claim 1, wherein said portion of the hydrogen
generated by the steam pyrolytic reformer is obtai ned through a hydrogen purification
filter,

3. The process as claimed in claim 1, wherein said conditions and the relative
amounts of said carbonaceous materia , hydrogen and water in the hydro-gasification
reactor are such that said methane rich producer gases are produced exothermally.

4. The process as claimed it claim 1, in which said liquid slurry of
carbonaceous material is formed by gr nding said carbonaceous material in water.

5. The process as claimed ir claim 1, in which said liquid slurry of
carbonaceous material is heated with superheated steam from a steam generator prior to
being fed into the hydro-gasification reactor.

6. The process as claimed in claim 5. in which the superheated steam is
separated from the slurry, prior to feeding the slurry into the hydro-gasification reactor,
and is fed into the steam pyrolytic reformer to react with the methane rich producer gases
from the hydro-gasification reactor.

7. The process as claimed in claim 5, in which the slurry, together with the
superheated steam, is fed into the hydro-gasification reactor.

8. The process as claimed in claim 7, in which synthesis gas generated by the
steam pyrolytic reformer is fed into a Fischer-Tropsch reactor under conditions whereby a
liquid fuel is produced.

9. The process as claimed in claim 8, wherein said conditions and the relative
amounts of hydrogen and carbon monoxide in the Fischer-Tropsch reactor are such that
said liquid fuel is produced exotherma lly

10. The process as claimed in claim 9, comprising transferring exothermic heat
from one or both of the hydro-gasifica ion reactor and Fischer-Tropsch reactor to one or
both of the steam generator and the steam pyrolytic reformer.

11. The process as claimed in claim 9, comprising transferring exothermic heat
from the hydro-gasification reactor-and Fischer-Tropsch reactor to the steam generator
and the steam pyrolytic reformer.

12. The process as claimed in claim 11, in which molten salt loops are used to
transfer said exothermic heat.

13. The process as claimed in claim 1, in which said carbonaceous material
comprises biomass.

14. The process as claimed iit claim 13, in which said biomass comprises
municipal solid waste.

15. The process as claimed n claim 8, in which the relative amounts of

hydrogen and carbon monoxide in tht synthesis gas fed into the Fischer-Tropsch reactor
are such that said liquid fuel is substantially cetane.

\ 16 A substantially self-sustaining process for producing a liquid fuel from

carbonaceous feed, comprising:

grinding said carbonacec us material in water to form a suspension slurry of
carbonaceous particles;

heating the slurry with superheated steam from a steam generator;

feeding hydrogen from a i internal source, the suspension slurry, and the
superheated steam into a hydro-gasific ation reactor under conditions of a pressure of
about 20 to 50 atmospheres without a -eaction catalyst and at a temperature in the range
of about 700 to 1200 degrees Celsius, and in amounts whereby methane rich producer
gases are generated exothermally;

feeding the methane rich producer gases from the hydro-gasification reactor
and said superheated steam into a steai n pyrolytic reformer under conditions whereby
synthesis gas comprising hydrogen and carbon monoxide are generated;

feeding a portion of the hydrogen generated by the steam pyrolytic reformer,
obtained through a hydrogen purification filter, into the hydro-gasification reactor, the
hydrogen therefrom constituting said hydrogen from an internal source;

feeding the remainder of he synthesis gas generated by the steam pyrolytic
reformer into the Fischer-Tropsch reactor under conditions whereby a liquid fuel is
produced exothermally; and
^ transferring exothermic heat from the hydro-gasification reactor and

Fischer-Tropsch reactor to the steam generator and the steam pyrolytic reformer, whereby
said process is substantially self-sustaining.

17. The process as claimed ir claim 16 in which molten salt loops are used to
transfer said exothermic heat.

18. The process as claimed ir claim 16, in which said carbonaceous material
comprises biomass.

19. The process as claimed iti claim 16, in which said biomass comprises
municipal solid waste.

20. Apparatus for producing a synthesis gas for use as a gaseous
fuel or as feed into Fiscier-Tropsch reactor to produce a liquid fuel,
comprising:

a source of carbonaceous; material and water;
a hydro-gasification reactor; and
a steam pyrolytic reformer;

piping connecting said source of carbonaceous material and
water to the hydro-gasification reactor for feeding carbonaceous
material and water thereto to generate methane and carbon monoxide;

piping connecting the hydro-gasification reactor to the steam
pyrolytic reformer for feeding methane rich producer gases generated
in the hydro-gasification reactor to the steam pyrolytic reformer to
generate synthesis gas comprising hydrogen and carbon monoxide;
and

piping connecting the steam pyrolytic reformer to the hydro-
gasification reactor for feeding a portion of the hydrogen generated by
the steam pyrolytic reformer into the hydro-gasification reactor.

21. The apparatus as claimed in claim 20, having a hydrogen purification filter
through which said portion of hydrogen generated by the steam
pyrolytic reformer is obtained.

22. The apparatus as claimed in claim 20, having a grinder forming particles
of the carbonaceous material, a receptacle for the particles and water
to form a slurry of the carbonaceous particles, and piping connecting
the receptacle to the hydro-gasification reactor for feeding the slurry
thereto.

23. The apparatus as claimec in claim 22, having a steam generator to heat
the slurry of carbonaceous material with superheated steam, a steam
separator for separating the superheated steam from the slurry prior to
the slurry being fed into the hydro-gasification reactor, and piping for
feeding the separated steam into the steam pyrolytic reformer to react
with the methane rich p-oducer cases from the hydro-gasification
reactor.

The apparatus as claimed in claim 2:2, having a steam generator to heat
the slurry of carbonaceous material with superheated steam whereby
the slurry and superheated steam can be fed into the hydro-gasification
reactor.

The apparatus as claimed in claim 24, having a Fischer-Tropsch reactor
and piping connecting the s:eam pyrolytic reformer to the Fischer-
Tropsch reactor for feeding the remainder of the synthesis gas
generated by the steam pyrolytic reformer into the Fischer-Tropsch
reactor to produce a liquid fuel.

The apparatus as claimed in claim 25, having molten salt loops to transfer
heat from one or both of the hydro-gasification reactor and Fischer-
Tropsch reactor to one or both of the; steam generator and the steam
pyrolytic reformer.

The apparatus as claimed in claim 26, having molten salt loops to transfer
heat from the hydro-gasification reactor and Fischer-Tropsch reactor to
the steam generator and the steam pyrolytic reformer.

28. Apparatus for producing a liquid fuel in a substantially self-
sustaining process, comprising:

a source of carbonaceous material and water;
a hydro-gasification reactor;
a steam pyrolytic reformer;
a hydrogen purificat on filter; r
a Fischer-Tropsch reactor;
a grinder forming particles of the carbonaceous material;
a receptacle for the particles and water to form a slurry of the
carbonaceous particles;

a steam generator to heat the slurry and activate the carbon by
pyrolysis with superheatec steam;

piping connecting the steam separator to the hydro-gasification
reactor for feeding the slurry and superheated steam thereto to
generate methane and carbon monoxide;

piping connecting the hydro-gasification reactor to the steam
pyrolytic reformer for feeding methane rich producer gases generated
in the hydro-gasification reactor to the steam pyrolytic reformer to form
a synthesis gas comprising hydrogen and carbon monoxide;

piping connecting the steam pyrolytic reformer to the hydro-
gasification reactor through the hydrogen purification filter for feeding a
portion of hydrogen generated by the steam pyrolytic reformer into the
hydro-gasification reactor; and

piping connecting the steam pyrolytic reformer to the Fischer-
Tropsch reactor for feeding the remainder of the synthesis gas
generated by the steam pyrolytic reformer into the Fischer-Tropsch
reactor to produce a liquid fuel.

The apparatus as claimed in claim 28, having molten salt loops to transfer
heat from one or both of ihe hydro-gasification reactor and Fischer-
Tropsch reactor to one 01 both of the steam generator and the steam
pyrolytic reformer.

The apparatus as claimed h claim 28, having molten salt loops to transfer
heat from the hydro-gasification reactor and Fischer-Tropsch reactor to
the steam generator and the steam pyrolytic reformer.

A process and apparatus lor producing a synthesis gas for use as a gaseous fuel or as feed into a rischer-Tropsch reactor to produce a liquid fuel in a substantially self-sustaining process. A slurry of particles of carbonaceous material in water, and hydrogen from an internal source, are fed into a hydro-gasilication reactor under conditions whereby methane rich producer gases are generated and fed into a steam pyrolytic reformer jnder conditions whereby synthesis gas comprising hydrogen and carbon monoxide arc generated. A portion of the hydrogen gene rated by the steam pyrolytic reformer is fed through a hydrogen purification filler into the hydro-gasification reactor, the hydrogen therefrom constituting the hydrogen from an internal source. The remaining synthesis gas generated by the steam pyrolytic reformer is either used as fuel for a gaseous fueled engine to produce electricity and/or process heat or is fed into a Fischer-Tropsch reactor und;r conditions whereby a liquid fuel is produced. Molten salt loops are used to transfer heat from the hydro-gasification reactor, and F ischer-Tropisch reactor if liquid fuel is produced, to the steam generator and the steam pyrolytic reformer.

Documents:

1161-KOLNP-2004-CORRESPONDENCE.pdf

1161-KOLNP-2004-FOR ALTERATION OF ENTRY.pdf

1161-KOLNP-2004-FORM 27.pdf

1161-kolnp-2004-granted-abstract.pdf

1161-kolnp-2004-granted-claims.pdf

1161-kolnp-2004-granted-correspondence.pdf

1161-kolnp-2004-granted-description (complete).pdf

1161-kolnp-2004-granted-drawings.pdf

1161-kolnp-2004-granted-examination report.pdf

1161-kolnp-2004-granted-form 1.pdf

1161-kolnp-2004-granted-form 18.pdf

1161-kolnp-2004-granted-form 3.pdf

1161-kolnp-2004-granted-form 5.pdf

1161-kolnp-2004-granted-gpa.pdf

1161-kolnp-2004-granted-reply to examination report.pdf

1161-kolnp-2004-granted-specification.pdf

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Patent Number

228808

Indian Patent Application Number

1161/KOLNP/2004

PG Journal Number

07/2009

Publication Date

13-Feb-2009

Grant Date

11-Feb-2009

Date of Filing

12-Aug-2004

Name of Patentee

THE REGENTS OF THE UNIVERSITY OF CALIFORNIA

Applicant Address

1111 FRANKLIN STREET, 5TH FLOOR, OAKLAND, CA

Inventors:

#	Inventor's Name	Inventor's Address
1	NORBECK JOSEPH N	600 WEST CENTRAL #240, RIVERSIDE, CA 92507
2	HACKETT COLIN E	8414 DAISY LANE, RIVESIDE, CA 92508
3	HEUMANN JAMES EDWARD	222 OLD NEWPORT BLVD., NEWPORT BEACH, CA 92663
4	NGO UY QUOC	380 N. MOLLISON AVE., #135, EL CAJON, CA 92021
5	TRAN NGUVNE THE	7862 14TH STREET, APT. A, WESTMINSTER, CA 92683
6	YILMAZ BILGE	8 BEACON TERRACE, APT. #2, SOMERVILLE, MA 02143-3568

PCT International Classification Number

C01B 3/24

PCT International Application Number

PCT/US03/03489

PCT International Filing date

2003-02-04

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	60/355,405	2002-02-05	U.S.A.