We've made earlier report on the work underway at the University of California - Riverside, UCR, wherein both Coal and renewable, Carbon-recycling wastes are being together converted into liquid hydrocarbon fuels.
Two of our dispatches concerning their efforts are accessible on the West Virginia Coal Association's web site, via the links:
California Hydrogasifies, and Recycles, Even More Carbon | Research & Development; concerning: "United States Patent Application 20050256212 - Production of Synthetic Transportation Fuels; November, 2006; Inventors: Jospeh Norbeck, et. al., CA and MA; 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"; and, the very closely-related:
California Hydrogasifies Coal & Carbon-Recycling Wastes | Research & Development; concerning: "United States Patent 7,500,997 - Steam Pyrolysis ... to Enhance the Hydro-Gasification of Carbonaceous Materials; 2009; Inventors: Joseph Norbeck and Collin Hackett, CA; 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. In one embodiment, a slurry of carbonaceous material in water, and hydrogen from an internal source, are fed into a hydro-gasification reactor to generate methane rich producer gases which are fed into a steam pyrolytic reformer to generate synthesis gas comprising hydrogen and carbon monoxide. A portion of the hydrogen is used as the internal hydrogen source. The remaining synthesis gas is either used as fuel to produce electricity and/or process heat or is fed into a Fischer-Tropsch reactor to produce liquid fuel. (And) wherein the carbonaceous material comprises municipal waste, biomass, wood, coal, or a natural or synthetic polymer".
Norbeck and his colleagues at UCR have, in fact, developed an extensive body of Carbon conversion technology; a body of technology so extensive that it is beyond our sadly limited capacities to organize and condense all of it for you in a comprehensible way. So, we will continue to hack our way through the thicket and get the information to you in at least a piecemeal way.
Before getting to the core of our presentation herein, though, some revealing background might be useful.
The University of California - Riverside's own web site, via the link:
About UCR: Joseph Norbeck; tells us that:
"A revolutionary process developed at UCR may one day turn sewage sludge, municipal solid waste, agricultural waste and other carbon-containing-material, such as coal, into synthetic, cleaner-burning diesel fuel.
Research by Professor Joe Norbeck and colleagues is being actively commercialized for large national and international markets for sulfur-free, lower-cost diesel fuel.
A Riverside-based energy company, Viresco LLC, has licensed commercial rights to the process from UCR and is working to develop it for large-scale production. Viresco has begun demonstrating the technology in pilot scale and has received grants from the Department of Energy to build a pilot plant. There have been 12 patents awarded or submitted on this technology.
For Norbeck, the head of the UCR Environmental Research Institute and former director of CE-CERT, the reasons for pursuing the project are simple. 'It comes down to two things. Can we reduce our dependence on foreign oil and can we transition to lower cost clean alternative fuels as seamlessly as possible? This technology looks ideal to meet these goals.'"
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In other words, we can "reduce our dependence on foreign oil" by converting our own domestic Carbon resources into liquid hydrocarbon fuels. And, even in California, where they mine no Coal, they recognize, that, due to current economies of scale, any successful attempt to commercialize such technologies must be founded on our largest domestic Carbon resource, Coal.
And, with that fact in mind, Norbeck and his UCR colleagues have continued their development of an extensive and thorough Carbon conversion technology, as witness excerpts from the initial link herein, to:
"US Patent 7,897,649 - Steam Methane Reformer (utilizing) Gas from Steam Hydro-Gasification
Date: March, 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.
(Hang in there, it becomes clearer.)
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.
(Note: Again, as in other of our reports concerning similar developments, the potential exists to, in a system based on the steam-gasification of Carbon, generate a "synthesis gas" of variable composition, wherein the Hydrogen and Carbon Monoxide are present in specifiable relative amounts, so as to be suitable for catalytic condensation into desired ranges of hydrocarbons.)
The process ... wherein steam methane reforming is conducted under conditions whereby the composition of synthesis gas exiting the SMR has a H.sub.2:CO mole ratio range of 2:1 to 6:1.
The process ... wherein the carbonaceous material comprises municipal waste, biomass, wood, coal, or a natural or synthetic polymer.
The process ... in which synthesis gas generated by the steam methane reforming is fed into a Fischer-Tropsch reactor under conditions whereby a liquid fuel is produced.
A process for converting municipal waste, biomass, wood, coal, or a natural or synthetic polymer to synthesis gas, comprising: simultaneously heating carbonaceous material, in a steam hydrogasifier reactor, in the presence of both hydrogen and water, at about 700C to about 900C and pressure about 132 psi to 560 psi; to generate steam, methane and carbon monoxide rich producer gas; wherein the steam generated in the hydrogasifier is the result of superheating the slurry water; removing sulfur impurities from the producer gas stream substantially at said pressure and at a temperature above the boiling point of water; subjecting the resultant product gas to steam methane reforming conditions whereby to generate synthesis gas comprising hydrogen and carbon monoxide at a ratio of between 2:1 and 6:1.
(Note: To be certain that it's clear, the initial Carbon resource is gasified with Steam in a process that generates both a "synthesis gas", that is, a blend of Carbon Monoxide and Hydrogen, and Methane. The gasification of Coal, or any Carbon source, with Steam, to produce Methane is well-established art, as seen, for just one example, in our report of:
GE Converts Coal to Methane and Recycles Carbon for USDOE | Research & Development; concerning: "United States Patent 4,558,027 - Catalysts for Carbon and Coal Gasification; 1985; Inventors: Douglas McKee, et. al., NY (All employees of General Electric Company); Assignee: The United States of America; The invention relates to improved catalysts for carbon and coal gasification and improved processes for catalytic, coal gasification. Abstract: Catalyst for the production of methane from carbon and/or coal by means of catalytic gasification".
The intent of UCR, in the process of our subject herein, "US Patent 7,897,649", is to break all of the products of Coal gasification, including the Methane, down into a blend of Carbon Monoxide and Hydrogen in proportions suitable for the further catalytic condensation of liquid hydrocarbons.)
The process ... comprising transferring exothermic heat from the Fischer-Tropsch reaction to the hydro-gasification reaction and/or steam methane reforming reaction.
(Note: As we've earlier documented, and as we will further document in reports to follow, that catalytic chemical condensation of synthesis gas into hydrocarbons, generically "the Fischer-Tropsch reaction", is exothermic, and generates heat energy which can be reclaimed and recycled within the total system, and, used to economically drive other chemical reactions that are essential to the overall process. - JtM)
The process ... wherein the steam methane reforming conducted is using steam only generated from said simultaneous heating step.
The process ... wherein the sulfur impurities is H2S.
(Note: Any Sulfur in the initial raw material is converted to Hydrogen Sulfide, "H2S", during the steam gasification, and which is then extracted from the synthesis gas. And, we remind you, that, as seen for just one example in:
Florida Hydrogen and Sulfur from H2S | Research & Development; concerning: "United States Patent 6,572,829 - Photocatalytic Process for Decomposing Hydrogen Sulfide; 2003; Assignee: University of Central Florida; Abstract: System for separating hydrogen and sulfur from hydrogen sulfide (H2S) gas";
such H2S can be treated as a valuable by-product of the process, rather than as a waste.)
The process ... wherein removing impurities from the producer gas stream is at a temperature above the boiling point of water at the process pressure.
The process ... wherein steam is also generated from the simultaneously heating of the slurry of carbonaceous material in the presence of both hydrogen and water.
(Note: As is clear in the full Disclosure, nearly all, if not all, of the Hydrogen required by the process is generated within the process itself. If more is needed, it could, somewhat obviously, be obtained by the University of Central Florida's process of "United States Patent 6,572,829", as cited above, from the
"H2S" generated from the "sulfur impurities", via the steam gasification, in the initial raw materials.)
The process ... wherein the steam generated is sufficient to supply the steam methane reforming reactor whereby synthesis gas comprising hydrogen and carbon monoxide is generated.
The process ... wherein the simultaneously heating of said slurry of carbonaceous material and hydrogen is performed without a reaction catalyst.
A process for converting carbonaceous material to synthesis gas, comprising: simultaneously heating the carbonaceous material in the presence of hydrogen and water, at a sufficient temperature and pressure, to generate steam, methane and carbon monoxide rich producer gas; wherein the steam generated within the hydrogasifier is the result of superheating the slurry water; removing sulfur impurities from the producer gas stream, wherein removing impurities from the producer gas stream is at a temperature above the boiling point of water at about 132 psi to 560 psi; and subjecting the resultant producer gas to steam methane reforming, under conditions whereby synthesis gas comprising hydrogen and carbon monoxide at a ratio of between 2:1 and 6:1 is generated.
(Note: By way of summary, the initial steam gasification of the Coal and other Carbon feedstock results in the production of both the Hydrogen-Carbon Monoxide syngas blend and some Methane. The Methane is then "reformed", or reacted, with Steam, and both are broken down into more, but high Hydrogen content, syngas, which Hydrogen-rich syngas is blended with the original syngas made from Coal and other Carbon sources, to make a final synthesis gas suitable in composition for catalytic condensation into a full range of liquid, and perhaps gaseous, hydrocarbons.)
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.
(Note: As we've documented in previous reports, and as we will further document in other reports soon to follow, synthetic liquid fuels derived at least from the indirect liquefaction of Coal burn much "cleaner" than their petroleum-based counterparts. Diesel fuels based on Coal, in particular, seem to be much more environmentally-benign than conventional Diesel fuels made from petroleum.)
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.
Alternatively, one can (convert) coal ... to a value added convenient clean liquid fuel, such as high quality, environment friendly synthetic diesel or other hydrocarbon fuels.
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 gas (a mixture of hydrogen and carbon monoxide, also referred to as synthesis gas) cleanly and efficiently from carbonaceous sources, that can be subjected to a Fischer-Tropsch type process to produce clean and valuable synthetic gasoline and diesel fuels, will benefit both the transportation sector and the health of society.
A Fischer-Tropsch type process or reactor, which is defined herein to include respectively a Fischer-Tropsch process or reactor, is any process or reactor that uses synthesis gas to produce a liquid fuel.
(Note: Thus, as we have indicated and documented in many reports, although their are many variants of catalytic processes which can convert Coal-derived synthesis gas into hydrocarbons, they are all acceptably labeled, generically, as "Fischer-Tropsch type" reactions.)
A Fischer-Tropsch type 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.
Typically, Fischer-Tropsch type liquid fuels, produced from synthesis gas, are sulfur-free, aromatic free, and in the case of synthetic diesel fuel have an ultrahigh cetane value.
(Note: Again, it is documented that synthetic liquid fuels, made indirectly via the gasification of Coal, are, simply, cleaner and better than those made conventionally from petroleum.)
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.
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.
(Note: Again, the above would be in "the future". Now, at this time, only Coal can offer the Carbon production volumes necessary to make the development of all of the rest of it possible. If we start, now, with Coal as the foundation, we can begin to build what would be the needed, very large "farming" industry which could supply more and more of the raw materials, as, over the next century, we begin to deplete our still-vast reserves of Coal. We can, thus, build a sustainable, Carbon-recycling future with an industry now made economically feasible by Coal.)
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 ... .
(Note: Methanol and Ethanol, as confirmed above, and by numerous of our other previous reports, can be made from Coal, and other Carbon resources, including, even, Carbon Dioxide, by known and established processes. And, there is nothing at all wrong with making them. They are nearly precious, since they can, again as we've documented, be converted through now-commercial technologies into Gasoline; and just about any other organic chemical product we might want. Our take on Norbeck's seeming disparagement of them, as above, is that it is a deliberate swipe at the competition to the University of California's process herein of making, essentially, Diesel fuel out of our various Carbon resources. Nuts to that. Let's get busy and make 'em all; and, tell OPEC and Big Oil to take a hike.)
More recently, a process was developed in our laboratories to produce synthesis gas in which a slurry of particles of carbonaceous material in water, and hydrogen from an internal source, are fed into a hydro-gasification reactor under conditions to generate rich producer gas. This is fed along with steam into a steam pyrolytic reformer under conditions to generate synthesis gas. This process is described in detail in Norbeck et al. U.S. patent application Ser. No. 10/503,435 (published as US 2005/0256212), entitled: "Production Of Synthetic Transportation Fuels From Carbonaceous Material Using Self-Sustained Hydro-Gasification."
(Note: That is the United States Patent "application", as in our introductory comments, about which we earlier reported.)
In a further version of the process, using a steam hydro-gasification reactor (SHR) the carbonaceous material is heated simultaneously in the presence of both hydrogen and steam to undergo steam pyrolysis and hydro-gasification in a single step. This process is described in detail in Norbeck et al. U.S. patent application Ser. No. 10/911,348 (published as US 2005/0032920), entitled: "Steam Pyrolysis As A Process to Enhance The Hydro-Gasification of Carbonaceous Material."
(Note: That "application, we believe, matured, again as in our introductory comments, into "United States Patent 7,500,997", again about which we earlier reported.)
(Both) disclosures ... are incorporated herein by reference.
Producing synthesis gas via gasification and producing a liquid fuel from synthesis gas are totally different processes. Of particular interest to the present invention is the production of synthesis gas using a steam methane reformer (SMR), a reactor that is widely used to produce synthesis gas for the production of liquid fuels and other chemicals.
Carbon monoxide and hydrogen are produced in the SMR by using steam and methane as the feed. Heating process water in a steam generator produces the required steam. The methane (can be) supplied in the form of compressed ... light molecular weight off-gas stream from a chemical or refinery process.
(Note: In this case, the Methane is a co-product, with Hydrogen and Carbon Monoxide synthesis gas, from the Steam-gasification of Coal and other Carbon resources.)
More particularly, a process is provided for converting carbonaceous material to synthesis gas, comprising simultaneously heating carbonaceous material in the presence of both hydrogen and steam, at a temperature and pressure sufficient to generate a stream of methane and carbon monoxide rich gas product, which can be called a producer gas.
Impurities are removed from the producer gas stream substantially at the process temperature and pressure, and the resultant producer gas is subjected to steam methane reforming under conditions whereby synthesis gas comprising hydrogen and carbon monoxide is generated.
In a specific process, for converting municipal waste, biomass, wood, coal, or a natural or synthetic polymer to synthesis gas, the carbonaceous material is simultaneously heated in the presence of both hydrogen and steam, at a temperature of about 700C to about 900C and pressure about 132 psi to 560 psi whereby to generate a stream of methane and carbon monoxide rich producer gas.
Impurities are removed from the producer gas stream substantially at the process temperature and pressure, following which the resultant producer gas is subjected to steam methane reforming under conditions whereby to generate synthesis gas comprising hydrogen and carbon monoxide at a H2:CO mole ratio range of about 3 to 1.
The required H2:CO mole ratio of a Fischer-Tropsche reactor with a cobalt based catalyst is 2:1.
Accordingly, there is an excess of hydrogen, which can be separated and fed into the SHR (i.e., the steam hydro-gasification reactor wherein the Coal and other Carbon resources are initially processed) to make a self-sustainable process, i.e., without requiring an external hydrogen feed. The synthesis gas generated by the steam methane reforming can be fed into a Fischer-Tropsch reactor under conditions whereby a liquid fuel is produced. Exothermic heat from the Fischer-Tropsch reaction can be transferred to the steam hydro-gasification reaction and/or steam methane reforming reaction."
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And, there you have it:
In a complete and integrated process based on Coal, a complete and self-contained process that requires no outside supply of either energy or Hydrogen, we can convert Coal and any naturally CO2-recycling and renewable organic materials, such as any "municipal waste, biomass, wood" and plastic we might have lying around, into liquid "clean-burning transportation fuels".
Really:
Is there anything about any of it that anyone, outside of OPEC and, possibly, Big Oil, wouldn't like?
We say "possibly" with respect to Big Oil since, as we previously reported, for one example, in:
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";