We have known, in the United States of America, for a very long time that Coal can be combined with Carbon-recycling, renewable wastes, or deliberately-cultivated botanical materials, and then "gasified" through a process of partial oxidation, i.e., partial combustion, with the products of such gasification including, typically, a blend of Carbon Monoxide and Hydrogen - - called "synthesis gas", or "syngas", which can be catalytically condensed via one of several long-known processes into liquid and/or gaseous hydrocarbons - - and, in some cases, depending upon what, if any, gasification catalyst is utilized, a lesser or greater volume of Methane.
As an example of such technology, from more than a quarter of a century ago, we refer you to our report of:
West Virginia Coal Association | Texaco Makes Methane from Coal & "Stuff" | Research & Development; concerning: "United States Patent 3,888,043 - Production of Methane; 1975; Texaco Incorporated; Abstract: Continuous process for the production of a gaseous stream comprising at least 90 mole % of methane (dry basis) from a sulfur containing hydrocarbonaceous fuel without polluting the environment ... . The product gas ... may be used as a substitute for natural gas or as a feedstock for organic chemical synthesis. The process ... wherein said hydrocarbonaceous fuel is a pump-able slurry of solid carbonaceous fuels selected from the group consisting of coal, particulate carbon, petroleum cokes, concentrated sewer sludge in a vaporizable carrier such as water, liquid hydrocarbon fuel and mixtures thereof".
The development and refinement of such technology has continued, conducted largely by members of the Big Oil community and unbeknownst to the vast majority of the common citizens in US Coal Country, or the United States of America as a whole, for that matter, as seen, again for just one example, in our report of:
West Virginia Coal Association | Exxon Co-Gasifies Coal and Carbon-Recycling Biomass | Research & Development; concerning the relatively recent: "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 in which the biomass material is pyrolyzed to provide a biomass pyrolysis oil and biomass char or coke which are then mixed with the carbonaceous solid to form a slurry. This slurry is then heated if necessary to achieve a viscosity which can be processed conveniently in the gasifier. The heat required for pyrolyzing the biomass can conveniently be obtained from the heat exchanger used to cool the hot synthesis gas product emerging from the gasifier. The process ... wherein the solid carbonaceous particles comprise coal. The process ... 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. A process ... wherein steam is co-fed into the gasifier reactor with the ... slurry".
One current, prolific developer of such Coal-Biomass co-gasification technologies is, perhaps surprisingly, the University of California, primarily in the person of one of their professors, Joseph Norbeck, often in collaboration with one or another of his colleagues, as seen, for example, in our reports of:
West Virginia Coal Association | California Synfuels from Coal and Carbon-Recycling Wastes | Research & Development; concerning: "US Patent 7,208,530 - Production of Synthetic Transportation Fuels (via) Self-Sustained Hydro-Gasification; 2007; Inventors: Joseph Norbeck, et. al.; 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 (i.e.,) a synthesis gas for use as a ... 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 ... . The process ... in which said liquid slurry of carbonaceous material is formed by grinding said carbonaceous material in water. The process ... in which said carbonaceous material comprises biomass (and) in which said biomass comprises municipal solid waste. (The) system that can accept arbitrary combinations of coal, urban and agricultural biomass, and municipal solid waste for hydro-gasification. A substantially self-sustaining process for producing a liquid fuel from carbonaceous feed"; and:West Virginia Coal Association | California 2012 Coal and Carbon-Recycling Waste to Syngas | Research & Development; concerning: "United States Patent 8,143,319 - Steam Hydro-Gasification with Increased Conversion Times; 2012; Inventors: Chan Seung Park and Joseph Norbeck; Assignee: The Regents of the University of California; Abstract: A method and apparatus for converting carbonaceous material to a stream of carbon rich gas, comprising heating a slurry feed containing the carbonaceous material in a hydrogasification process using hydrogen and steam, at a temperature and pressure sufficient to generate a methane and carbon monoxide rich stream ... . In particular embodiments, the slurry feed containing the carbonaceous material is fed, along with hydrogen, to a kiln type reactor before being fed to the fluidized bed reactor. ... Optionally, a grinder can be provided in the kiln type reactor. The process ... wherein the carbonaceous material is solid. The process ... including the step of subjecting the stream of methane and carbon monoxide rich gas to steam methane reforming under conditions whereby synthesis gas comprising hydrogen and carbon monoxide is generated. The process ... in which synthesis gas generated by the steam methane reforming is fed into a Fischer-Tropsch-type reactor under conditions whereby a liquid fuel is produced. Background and Field: The field of the invention is the synthesis of transportation fuel from carbonaceous feed stocks".
The significance and importance of such processes, for "the synthesis of transportation fuel", via an intermediate "hydro-gasification" of a "slurry" of "coal, urban and agricultural biomass, and municipal solid waste", to form both a carbon monoxide-rich synthesis gas and methane, which methane is then "reformed" with steam to form more, but hydrogen-enriched, synthesis gas, which can then be passed into "a Fischer-Tropsch-type reactor" to effect "the synthesis of transportation fuel", should, we would think, with their implications for a sustainable, carbon-recycling US liquid hydrocarbon fuel self-sufficiency, be obvious.Note, though, in all of the above examples, that the Coal and the Biomass are, prior to being fed into the gasifier, to be mixed together, blended, in a "carrier" liquid, which is typically just "water", but, as in ExxonMobil's "US Patent Application 20100083575" can be a "biomass pyrolysis oil", or another "vaporizable carrier"; as, perhaps, as in Texaco's "United States Patent 3,888,043", even a "liquid hydrocarbon fuel".
Water, we would think, would be preferable; at least in terms of economy and simplicity, and, perhaps, in terms of the additional Hydrogen which might be made available through dissociation of the H2O.
And, Water is, in fact what Joe Norbeck and his colleagues at the University of California have settled on as their preferred carrier fluid, as they explain to us herein just how such a "slurry" - - of Coal and Biomass in Water, well-suited for gasification processes to form hydrocarbon synthesis gas blends of Carbon Monoxide and Hydrogen, and, perhaps, Methane - - can be made.
Further, we wanted to point out so that it isn't missed, Norbeck suggests an additional route for the more direct recycling of Carbon Dioxide in this process, in addition to the indirect utilization of CO2 via the inclusion of Biomass.
As seen in excerpts from the initial link in this dispatch to:
"United States Patent 8,118,894 - Commingled Coal and Biomass Slurries
Patent US8118894 - Commingled coal and biomass slurries - Google Patents
Commingled coal and biomass slurries - The Regents of the University of California
(Note: Review of a sample of our past reports has confirmed that, strangely, links to United States Patent and Trademark Office patent and patent application electronic files are unreliable, unstable; and, often reconnect with unrelated documents. Thus, we always try to include links to secondary site files of the US patents and patent applications about which we report.)
Date: February, 2012
Inventors: Joseph Norbeck, et. al., CA
Assignee: The Regents of the University of California, Oakland
Abstract: An energy efficient process for converting biomass into a higher carbon content, high energy density slurry. Water and biomass are mixed at a temperature and under a pressure that are much lower than in prior processes, but under a non-oxidative gas, which enables a stable slurry to be obtained containing up to 60% solids by weight, 20-40% carbon by weight, in the slurry. The temperature is nominally about 200 C under non-oxidative gas pressure of about 150 psi, conditions that are substantially less stringent than those required by the prior art. In another embodiment, the biomass water slurry can be mixed with a coal water slurry to further optimize the carbon content and pumpability of the biomass slurry.
A process for converting biomass into a higher carbon content, high energy density slurry, comprising: providing ground coal and a pretreated biomass slurry; and forming from the ground coal and the pretreated biomass slurry a coal-biomass slurry having a viscosity (as specified) and having a solid loading of at least 40 weight percent; and wherein the pretreated biomass slurry is formed from a biomass slurry by heating the biomass slurry under a non-oxidative gas such that the heating allows use of at least 35% treated biomass in the coal-biomass slurry while maintaining the viscosity.
(Note that, although the focus seems to be on "biomass", it might comprise only "35%" of the solids in the slurry. The remaining 65% would be Coal, although the ratios can vary over a broad range.)The process ... wherein the biomass slurry is formed from wood or plant material and water (and) wherein the coal-biomass slurry has a water:carbon ratio of approximately 2:1 (and) adjusting the water:carbon ratio in the coal-biomass slurry to approximately 3:1 (and) in which the step of heating is performed at to a temperature of about 200 C under a non-oxidative gas pressure of about 150 psi.
The process ... in which the non-oxidative gas is selected from the group consisting of argon, helium, nitrogen, hydrogen, carbon dioxide, or gaseous hydrocarbons, or mixtures thereof.
A process for converting biomass into a higher carbon content, high energy density slurry, comprising providing a mixture of biomass and water containing 50% solids, and heating the mixture to a temperature of about 200 C under a non-oxidative gas ... to obtain a stable slurry ...that allows formation of a commingled coal-biomass slurry having a viscosity (as specified).
In a process of hydrogasification of a biomass slurry ... the improvement comprising: converting the biomass slurry into a higher carbon content, high energy density slurry by pre-treating the biomass slurry to form a pretreated biomass slurry, and by combining the pretreated biomass slurry with, an amount of a coal slurry to thereby form a coal-biomass slurry ... .
The process ... wherein the biomass slurry is formed from wood or plant material and water (and) wherein the coal-biomass slurry has a water: carbon ratio of approximately 2:1.
In a process in which a biomass slurry is fed into a hydro-gasification reactor, the improvement comprising a step of converting the biomass into a higher carbon content, high energy density slurry by combining an amount of coal slurry with a mixture of biomass and water containing 50% solids, wherein the mixture is (further treated as specified).
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.
(The above three facts should be kept in mind by all who, in perhaps short-sighted euphoria, jump on the current shale gas-fueled vehicle bandwagon.)
The availability of clean-burning liquid transportation fuels is a national priority. Producing synthesis gas (which is a mixture of hydrogen and carbon monoxide) 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. Similarly, a Fischer-Tropsch type liquid fuel is a fuel produced by such a process or reactor. 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 biomass derived synthesis gas, are sulfur-free, aromatic free, and in the case of synthetic diesel fuel have an ultrahigh cetane value.
(All of the above is true of "Fischer-Tropsch type liquid fuels" derived only from Coal, as well, as we have confirmed in a number of prior reports, including, as one example:
West Virginia Coal Association | US EPA Recommends Coal Liquefaction as a Clean Alternative | Research & Development; concerning: "Clean Alternative Fuels: Fischer-Tropsch; United States Environmental Protection Agency; 2002; A Success Story (!) For the past 50 years, Fischer-Tropsch fuels have powered all of South Africa’s vehicles, from buses to trucks to taxicabs. The fuel is primarily supplied by Sasol, a world leader in Fischer-Tropsch technologies. Sasol’s South African facility produces more than 150,000 barrels of high quality fuel from domestic low-grade coal daily. Fischer-Tropsch technology converts coal ... into a high-value, clean-burning fuel (that) is colorless, odorless, and low in toxicity. In addition, it is virtually interchangeable with conventional diesel fuels and can be blended with diesel at any ratio with little to no modification. Fischer-Tropsch fuels offer important emissions benefits compared with diesel, reducing nitrogen oxide, carbon monoxide, and particulate matter".)
Biomass material is the most commonly processed carbonaceous waste feed stock used to produce renewable fuels.
(The above might be true now; but, remember that technologies like that seen in our report of:
West Virginia Coal Association | USDOE Converts CO2 to Gasoline | Research & Development; concerning: "United States Patent 4,197,421 - Synthetic Carbonaceous Fuels and Feedstocks; 1980; Assignee: The United States of America; Abstract: This invention relates to the use of a three compartment electrolytic cell in the production of synthetic carbonaceous fuels and chemical feedstocks such as gasoline, methane and methanol by electrolyzing an aqueous sodium carbonate/bicarbonate solution, obtained from scrubbing atmospheric carbon dioxide with an aqueous sodium hydroxide solution, whereby the hydrogen generated at the cathode and the carbon dioxide liberated in the center compartment are combined thermocatalytically into methanol and gasoline blends";
demonstrate "Biomass material" isn't the only "carbonaceous waste feed stock" that can be "used to produce renewable fuels".)
The carbonaceous components of ... 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 gas 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 ... . Of particular interest to the present invention are processes developed more recently in which a slurry of carbonaceous material is fed into a hydro-gasifier reactor. One such 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."
(The US patent application noted above is now, we believe, "US Patent 7,208,530 - Production of Synthetic Transportation Fuels (via) Self-Sustained Hydro-Gasification", as in our previous report cited in our opening comments.)
All of these processes require the formation of a slurry of biomass that can be fed to the hydro-gasification reactor. To enhance the efficiency of the chemical conversions taking place in these processes, it is desirable to have a low water to carbon ratio, therefore a high energy density, slurry, which also makes the slurry more pumpable. High solids content coal/water slurries have successfully been used in coal gasifiers in the feeding systems of pressurized reactors. A significant difference between coal/water slurries and biomass/water slurries is that coal slurries contain up to 70% solids by weight compared to about 20% solids by weight in biomass slurries. Comparing carbon content, coal slurries contain up to about 50% carbon by weight compared to about 8-10% carbon by weight in biomass slurries. The polymeric structure if cell walls of the biomass mainly consists of cellulose, hemicellulose and lignin. All of these components contain hydroxyl groups. These hydroxyl groups play a key role in the interaction between water and biomass, in which the water molecules are absorbed to form a hydrogen bond. This high hyrgroscopicity of biomass is generally why biomass slurries are not readily produced with a high carbon content.
Our previous work ... disclosed novel methods that enabled the production of a stable biomass slurry containing up to 60% solids by weight, so as to provide 20-40% carbon by weight in the slurry. However, it was not appreciated at that time the optimal conditions required for using such biomass slurries in hydrogasfication processes, such as the optimum viscosity of the slurry to be delivered/pumped.
Summary: Provided is a steam hydrogasification process efficient for gasification of both coal and biomass feedstocks, either alone or commingled. The process can utilize water to provide an internal source of hydrogen and to control the synthesis gas ratio over a wide range. This requires the formation of a slurry with a high carbon to water ratio, but with a viscosity to allow ease of handling during preparation, storage and transfer to the reactor.
The present invention provides an energy efficient process for converting biomass into a higher carbon content, high energy density slurry.
In particular, a coal water slurry is combined with a mixture of water and biomass ... ."
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And, again, such "a coal water slurry ... combined with a mixture of water and" renewable, Carbon-recycling "biomass" would be directed into a process like that disclosed in another US Patent awarded to Norbeck and colleagues, 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; Assignee: The Regents of the University of California; 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 ... . (And) wherein the carbonaceous material comprises municipal waste, biomass, wood, coal, or a natural or synthetic polymer (and) 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".
And, the end result is the production - - from Coal, from Carbon-recycling and renewable Biomass, and even from completely unwanted "Waste" - - of "liquid fuel".
But, make no mistake:
At our current level of agricultural and forestry production of "Biomass" materials, and at our current level of sophistication in the collection and sorting of "municipal waste", for the direction of those materials into a process like that disclosed by and related to our subject herein, "US Patent 8,118,894 - Commingled Coal and Biomass Slurries", for, ultimately, via processes like that disclosed in the above-cited "US Patent 8,143,319 - Steam Hydro-Gasification with Increased Conversion Times; A method and apparatus for converting carbonaceous material to a stream of carbon rich gas (for) the synthesis of transportation fuel from carbonaceous feed stocks";
there is only one "carbonaceous feed stock" we have and can produce enough of in the near term to make any of this US jobs-creating, OPEC-beating scenario possible on a practical, or meaningful, basis:
Coal.