United States Patent: 7208530

We earlier made report of what we believe to have been the Patent Application which matured into the United States Patent we include and disclose herein.

As can be seen our full dispatch, as accessible via:

California Hydrogasifies, and Recycles, Even More Carbon | Research & Development; which concerns: "United States Patent Application 0050256212 - Production of Synthetic Transportation Fuels; Date: November, 2006; Inventors: Jospeh Norbeck, et. al., CA and MA";

we documented that a small group of collaborating scientists, most in the employ of the University of California, had developed 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 fuel in a substantially self-sustaining process"; a technology whereby virtually any Carbon-containing material could be gasified with Steam and converted into a synthesis gas of variable composition, which composition could be controlled to target the final production of specific, and various, liquid hydrocarbons.

Description of the process as "self-sustaining" is critical; it confirms that the hydro-gasification of Coal, and of Carbon-recycling organic wastes, can be entirely self-sufficient in both it's supply of energy to drive the process, and, in the generation of the elemental Hydrogen needed to hydrogenate the Carbon content of the Coal and the waste carbonaceous materials, to form thereby a Hydrogen-rich synthesis gas, a syngas suitable for catalytic condensation into a range of liquid hydrocarbon fuels and chemicals.

That Patent Application was, again, as seen herein, successful; and, we regret that our varied insufficiencies caused us to miss that important fact at the time of our prior report.

At least, we believe that to be so. In point of fact, the University of California, in an effort seemingly led by their Professor Joseph Norbeck, has developed an array of Coal, and other Carbon, conversion and conversion-supporting technologies which, like the Carbon Dioxide recycling technologies being developed at Penn State University, truly deserve closer, more competent, study and public reportage than we, with our varied disabilities and limitations, are, sadly, able to provide.

Further, we must note, that these politically-correct, and environmentally sensitive scientists, from the more highly-evolved states of California, and Massachusetts as you will see, bandy the word "Carbon" around incessantly, but, mention our one most abundant and accessible source of Carbon, i.e., Coal, only twice, once near the end of the full Disclosure, very near the end of their final Summary, wherein the true intent is distilled, as in their statement that this is a broad-based technology, a:

"system that can accept arbitrary combinations of coal, urban and agricultural biomass, and municipal solid waste for hydro-gasification".

Comment follows excerpts, with that statement repeated, from the initial link to:

"US Patent 7,208,530 - Production of Synthetic Transportation Fuels (via) Self-Sustained Hydro-Gasification

Date: April, 2007

Inventors: Joseph Norbeck, et. al., CA and MA

(Bourns College of Engineering: Joseph M. Norbeck; "Joseph M. Norbeck; Professor of Chemical and Environmental Engineering; Director: Environmental Research Institute; University of California, Riverside.)

Assignee: The Regents of the University of California.

Abstract: 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 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-gasification reactor under conditions whereby methane rich producer gases are generated and fed into a steam pyrolytic reformer under conditions whereby synthesis gas comprising hydrogen and carbon monoxide are generated. A portion of the hydrogen generated by the steam pyrolytic reformer is fed through a hydrogen purification filter 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 or similar reactor under conditions whereby a liquid fuel is produced.

Claims: A process for producing a synthesis gas for use as a gaseous fuel or as feed into Fischer-Tropsch reactor to produce a liquid fuel, the improvement comprising: forming a liquid suspension 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 super-atmospheric 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 end carbon monoxide are generated; feeding a portion of the hydrogen generated by the steam pyrolytic reformer into the hydro-gasification reactor as said 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 type reactor under conditions whereby a liquid fuel is produced.

The process ... wherein said portion of the hydrogen generated by the steam pyrolytic reformer is obtained through a hydrogen purification filter (and) wherein said conditions and the relative amounts of said carbonaceous material, hydrogen and water in the hydro-gasification reactor are such that said methane rich producer gases are produced exothermally.

(We must note that, in the above, as is explained in the full Disclosure but which might not be clear from our necessarily-abbreviated excerpts, the "hydrogen" with which the raw material is, in part, gasified, is generated within the system itself, after an initial startup. No hydrogen needs to be imported, at additional expense, from an outside source. Further, as in other of our reports documenting related and similar technologies, the gasification, which can produce both methane and synthesis gas, is accomplished in a way that is exothermic, that is, the initial gasification generates heat energy which can be captured and utilized for other purposes, such as generating needed "steam", which can be used as a reactant or to generate electricity for use in the process.)  

The process ... in which said liquid slurry of carbonaceous material is formed by grinding said carbonaceous material in water.

(The above claim itself refers to a proprietary technology developed by the University of California for the preparation of a combined Coal-Biomass/Waste Carbon feed intended to be utilized in this process. We will make report of that technology separately, in a future dispatch.)

The process ... 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.

(Again, the "superheated steam" can be generated with, for the most part, heat energy collected from the exothermic reactions.)

The process ... 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. 

The process ... 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 (and) 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 exothermally.

(As we've previously documented in earlier reports, the almost-generic "Fischer-Tropsch" reaction can itself be exothermic and also generate more heat energy that can be collected and utilized. The overall system, even with the need for energy to generate Hydrogen internally, can be entirely self-sufficient, as is emphasized in the following claims.)

The process ... comprising transferring exothermic 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 (and, the) process ... in which molten salt loops are used to transfer said exothermic heat.

The process ... in which said carbonaceous material comprises biomass (and) in which said biomass comprises municipal solid waste.

(Again, further on, it is clarified that this is a: "system that can accept arbitrary combinations of coal, urban and agricultural biomass, and municipal solid waste for hydro-gasification". The "arbitrary" meaning that we can mix them together in any proportions we might have available; or, use just one of any of them, although it seems to us that the fuel value of at least some Coal would be required in the initial gasification to provide some of the heat energy needed to force the reactions of more "diluted", for want of a better term, "biomass", especially "municipal solid waste".)

A substantially self-sustaining process for producing a liquid fuel from carbonaceous feed, comprising: grinding said carbonaceous material in water to form a suspension slurry of carbonaceous particles; heating the slurry with superheated steam from a steam generator; feeding hydrogen from an internal source, the suspension slurry, and the superheated steam into a hydro-gasification reactor under conditions of a pressure of about 20 to 50 atmospheres without a reaction 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 steam 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 the 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.

(The "self-sustaining", no externally-supplied energy needed, nature of this process is emphasized throughout the full Disclosure.)

This invention was made with support from the City of Riverside. The City of Riverside has certain tights to this invention.

(Are the state governments of West Virginia, Pennsylvania, Ohio and Kentucky as far-sighted and proactive as the city government of Riverside, California? If not, why not?)

Background and Field: The field of the invention is the synthesis of transportation fuel from carbonaceous feed stocks. 

There is a need to identify new sources of chemical energy and methods for its conversion into alternative transportation fuels, driven by many concerns including environmental, health, safety issues, and the inevitable future scarcity of petroleum-based fuel supplies.

Since the resources for the production of petroleum-based fuels are being depleted, dependency on petroleum will become a major problem unless non-petroleum alternative fuels, in particular clean-burning synthetic diesel fuels, are developed. Moreover, normal combustion of petroleum-based fuels in conventional engines can cause 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 waste, 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 can be a safety concern in the case of leaks or sudden rupture. 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.

(Note that, in the above, the inane concept of fueling whole fleets of vehicles with either of the low-energy candidates, Hydrogen or compressed Natural Gas, is summarily dealt with.)

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 exhaust 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 are poisoned quickly by any sulfur present, as is the case in ordinary stocks of petroleum derived diesel fuel, reducing the catalyst efficiency. . 

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 waste water (sewage) treatment are also candidate feed stocks for conversion processes.

The carbonaceous components of this waste material have chemical energy that could be used to reduce 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. 

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.

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: 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 propulsion fuels can also be made, using a Fischer-Tropsch paraffin fuel synthesis reactor.

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.

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 paraffinic fuel, recycled water and sensible heat, in a substantially self-sustaining process.

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 paraffinic fuel, 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 fed 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 reformer is either used as fuel for a gaseous fueled engine or gas turbine 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 (for 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 (and) a Fischer-Tropsch (synthesis gas-to-liquid) fuel synthesizer ... to convert the synthesis gas ... into a sulfur-free clean-burning liquid transportation fuel."

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First, we want to clarify some processes referred to and terminologies used by Norbeck, et. al., herein.

Again, all of the needed Hydrogen is generated within the process itself; and, although it isn't clearly spelled out how, it is alluded to in the passages and references that mention "the steam generator and the steam pyrolytic reformer".

The "steam pyroltic reformer" is an integral process to which any Methane, generated during the initial Coal and Biomass gasification, is directed, and, wherein, as seen in our report of:

West Virginia Coal Association | California Coal, Biomass and Waste Plastic to Hydrocarbons | Research & Development; concerning: "US Patent 7,897,649 - Steam Methane Reformer (utilizing) Gas from Steam Hydro-Gasification; 2011; Inventors: Joseph Norbeck and Chan Seung Park, CA; Assignee: The Regents of the University of California; Abstract: An improved, economical alternative method to supply steam and methane to a steam methane reformer (SMR) is accomplished by a combination of procedures, wherein product gas from a steam hydro-gasification reactor (SHR) is used as the feedstock for the SMR by removing impurities from the product stream from the SHR with a gas cleanup unit that operates substantially at process pressures and at a temperature above the boiling point of water at the process pressure, is located between the SHR and SMR.Claims: A process for converting carbonaceous material to synthesis gas, comprising: heating a slurry, comprising water and carbonaceous material, with hydrogen in a steam hydrogasifier reactor, at a sufficient temperature and pressure to generate a stream of methane, carbon monoxide, and steam rich product gas; wherein the steam in the hydrogasifier is generated as the result of superheating the slurry water; removing sulfur impurities from the producer gas stream; and subjecting the resultant product gas to steam methane reforming, conditions; whereby synthesis gas comprising hydrogen and carbon monoxide is generated at a ratio of between 2:1 and 6:1. The process ... wherein the carbonaceous material comprises municipal waste, biomass, wood, coal, or a natural or synthetic polymer";

that Methane is converted, in the integral "Steam Methane Reformer", into even more synthesis gas, which syngas can have a "hydrogen and carbon monoxide ... ratio of ... 6:1"; and, such high-Hydrogen syngas can then be blended with lower-Hydrogen syngas so as to adjust, as necessary, the ratios of the Hydrogen and the Carbon Monoxide in the final synthesis gas product, to thereby make the finished syngas suitable for Fischer-Tropsch, or other, catalytic chemical condensation into a range of hydrocarbons. 

Our final excerpted passage from "United States Patent 7,208,530 - Production of Synthetic Transportation Fuels (via) Self-Sustained Hydro-Gasification" sums it all up nicely, and we'll forego additional comment. However, if you are new to our reports, and the concept embodied in that final excerpted passage concerning the combined usage of "coal, urban and agricultural biomass, and municipal solid wastes" to synthesize liquid hydrocarbons seems alien or unlikely to you, we refer you to another of our reports, as accessible via:

West Virginia Coal Association | Exxon Co-Gasifies Coal and Carbon-Recycling Biomass | Research & Development; concerning: "US Patent Application 20100083575 - Co-gasification Process for Hydrocarbon Solids and Biomass; 2010; Assignee: ExxonMobil Research and Engineering Company; Abstract: A process for the co-gasification of carbonaceous solids (coal) and biomass ... wherein the solid carbonaceous particles comprise coal (and) wherein the biomass comprises biological matter selected from wood, plant matter, municipal waste, green waste, byproducts of farming or food processing waste, sewage sludge, black liquor from wood pulp, and algae";

wherein no less a hydrocarbon fuel authority than ExxonMobil themselves confirm that Coal and all sorts of renewable and sustainable, and Carbon-recycling, materials and wastes can be converted, together, into a synthesis gas blend of Carbon Monoxide and Hydrogen that, as the University of California herein specifically states and confirms, can be sent to and processed in a "Fischer-Tropsch... fuel synthesizer" and be therein converted "into a sulfur-free clean-burning liquid transportation fuel", that is, "clean and valuable synthetic gasoline and diesel fuels" that "will benefit both the transportation sector and the health of society".


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