United States Patent: 8674152

Our United States Department of energy has recently improved a process that enables the direct conversion of Coal, in combination with an extremely wide variety of renewable, Carbon-recycling, waste and otherwise non-food Biomass, what the USDOE labels as "plant products that are normally considered waste materials",  "into a useful liquid fuel", that is, into a "fuel product"; a synthetic petroleum, as we take it, a "pumpable liquid" that, as the USDOE herein specifies: "can be processed at conventional petroleum refineries".

As a bonus, yes, a bonus, the USDOE's Coal and Biomass liquefaction process co-generates "a high purity CO2 product", from the blended Coal and waste Biomass, along with the "liquid fuel" which "can be processed at conventional petroleum refineries".

 

Deep in the full Disclosure, the DOE suggests that the process, thus, makes the Carbon Dioxide available for "recycling".

Those passages, as will be repeated in our more extended excerpts, stand in contrast to most blind, or commercially prejudiced, critiques of Coal liquefaction processes available in the popular literature, which suspect critiques emphasize that Coal conversion technologies produce CO2 as a waste product.

Some Coal-to-Liquid technologies, perhaps most, especially those indirect processes which rely on an initial Coal gasification to produce hydrocarbon synthesis gas, do co-produce at least some Carbon Dioxide in admixture with the synthesis gas and, unless purified Oxygen is used to support the partial combustion process which is the heart of gasification, the product gas will contain other gaseous contaminants, as well, especially Nitrogen and Nitrogen Oxides.

With apologies for the digression, however, we'll note, that, as seen in:

New Jersey Converts CO2 and Nitrogen Oxides into Fertilizer | Research & Development | News; concerning: "United States Patent 8,524,066 - Electrochemical Production of Urea from NOx and Carbon Dioxide; 2013; Assignee: Liquid Light Inc., NJ; Abstract: Methods and systems for electrochemical production of urea are disclosed. A method may include, but is not limited to, steps (A) to (B). Step (A) may introduce carbon dioxide and NOx to a solution of an electrolyte and a heterocyclic catalyst in an electrochemical cell. The divided electrochemical cell may include an anode in a first cell compartment and a cathode in a second cell compartment. The cathode may reduce the carbon dioxide and the NOx into a first sub-product and a second sub-product, respectively. Step (B) may combine the first sub-product and the second sub-product to produce urea";

such mixtures of Carbon Dioxide and Nitrogen Oxides can be utilized to synthesize the chemical "Urea", which has utility both as a fertilizer and in the synthesis of certain high-performance plastics and polymers.

However, the US Department of Energy's Coal-to-petroleum process herein is capable of producing a relatively pure stream of byproduct Carbon Dioxide, and, we remind you that the USDOE itself, as seen for only one example in our report of:

USDOE 1976 Atmospheric CO2 to Methanol | Research & Development | News; concerning: "United States Patent 3,959,094 - Electrolytic Synthesis of Methanol from CO2; Date: May, 1976; Inventor: Meyer Steinberg, NY; Assignee: The USA as represented by the USDOE; Abstract: A method and system for synthesizing methanol from the CO2 in air using electric power. The CO2 is absorbed by a solution of KOH to form K2CO3 which is electrolyzed to produce methanol, a liquid hydrocarbon fuel. Summary: In accordance with a preferred embodiment of this invention, a solution of KOH is employed to absorb CO2 from air forming an aqueous solution of K2CO3, the solution is then electrolyzed to produce CH3OH (i.e., Methanol) and reform KOH in solution, the CH3OH is then removed, and make-up water is then added prior to repeating the aforementioned steps. Other products ... are also formed which can be separated and recovered as valuable products";

has known for very nearly four decades how to make "valuable products", such as fuel alcohol "methanol", out of Carbon Dioxide recovered from any convenient source. 

That said, we see herein that the USDOE quite recently developed a method for efficiently converting Coal, along with some amount of renewable, Carbon-recycling Biomass, directly into synthetic crude petroleum.

Comment follows and is inserted within excerpts from the initial link in this dispatch to:

"United States Patent 8,674,152 - Coal Liquefaction by Base-Catalyzed Hydrolysis with CO2 Capture

Patent US8674152 - Coal liquefaction by base-catalyzed hydrolysis with CO2 capture - Google Patents

Coal liquefaction by base-catalyzed hydrolysis with CO2 capture - Savannah River Nuclear Solutions, LLC

Date: March 18, 2014

Inventor: Xin Xiao, Georgia

Assignee: Savannah River Nuclear Solutions, LLC, South Carolina

(The above "Savannah River Nuclear Solutions, LLC" are a consortium of companies who operate the Savannah River National Laboratory for the United States Department of Energy. See:

http://srnl.doe.gov/; and: Savannah River National Laboratory Homepage - JtM)

Abstract: The one-step hydrolysis of diverse biomaterials including coal, cellulose materials such as lumber and forestry waste, non-food crop waste, lignin, vegetable oils, animal fats and other source materials used for biofuels under mild processing conditions which results in the formation of a liquid fuel product along with the recovery of a high purity CO2 product is provided.

(At this point in full United States patent disclosures, prior patented art is cited. And, among the technologies upon which the technology disclosed herein by the USDOE is founded is that discussed in our prior report of:

Utah Converts Coal and Wood into Gasoline | Research & Development | News; concerning: "United States Patent 4,728,418 - Process for the Low-temperature Depolymerization of Coal and its Conversion to a Hydrocarbon Oil; 1988; Inventors: Joseph Shabtai, UT, and Ikuo Saito, Japan; Assignee: The University of Utah, Salt Lake City; Abstract: A novel process for the low-temperature depolymerization and liquefaction of coal wherein the coal is subjected to sequential processing steps for the cleavage of different types of intercluster linkages during each processing step. A metal chloride catalyst is intercalated in finely crushed coal and the coal is partially depolymerized under mild hydrotreating conditions during the first processing step. In the second processing step the product from the first step is subjected to base-catalyzed depolymerization with an alcoholic solution of an alkali hydroxide, yielding an almost fully depolymerized coal, which is then hydroprocessed with a sulfided cobalt molybdenum catalyst in a third processing step to obtain a hydrocarbon oil as the final product".

In that report, we included a number of reference links to more information concerning, and explaining, the process of "base-catalyzed depolymerization", or "hydrolysis", of organic materials, which is the foundation of the USDOE's process herein for converting "coal, cellulose materials", and etc., into "liquid fuel product".

Keep in mind, as you read our excerpts and should you elect to access the full Disclosure and read it, that, as in some other expositions of Coal conversion technology, Coal is considered and discussed as just another form of "biomass" or "bio-material". It is fossilized biomass, but biomass nonetheless.)

Government Interests: This invention was made with Government support under Contract No. DE-AC09-08SR22470 awarded by the United States Department of Energy. The Government has certain rights in the invention.

Claims: The process of converting a biomaterial to a fuel product comprising the steps of: providing a biomaterial selected from the group consisting of coal, cellulosic products, animal parts, animal fat, vegetable oil, food grains and mixtures thereof; hydrolyzing said biomaterial using a base or alkalized catalyst comprising hydrides of groups IA, IIA or IIIA metals, oxides or hydrides of groups IA or IIA metals, or groups of organometallic compounds containing groups IA, IIA, or IIIA and at a temperature of about 319 C to yield a reaction product, wherein a hydrocarbon fuel product in the reaction product has a hydrogen to carbon ratio of 1.6; acidifying said reaction product to form CO2 and a liquid hydrocarbon fuel product. 

The process ... wherein said step of acidifying said reaction product further comprises adding HCl to the reaction product and thereby forming a KCl reaction product (and) wherein following said acidifying step, an electrolysis of the KCl reaction product solution is performed within a fuel cell to form a caustic, the fuel cell providing a source of heat. 

The process ... wherein electrolysis products are combined in the fuel cell to form an acid to be used in the acidifying process, the fuel cell reaction further providing an electrical energy source. 

The process ... wherein acidifying step to form CO2 removes carbon and oxygen from available reactants, thereby preventing undesired side reactions that would lower a yield of desired reaction products. 

The process ... wherein said CO2 from the acidifying step may be recovered at an at least about 95% purity level.

(Yet again, as seen for only one example in our report of:

US Air Force April 3, 2014, CO2 to Synthetic Fuels | Research & Development | News; concerning: "United States Patent Application 20140093799 - Devices and Processes for Carbon Dioxide Conversion into Useful Fuels and Chemicals; 2014; Inventors: Richard Masel, IL, Brian Rosen, DE, Wei Zhu, IL; Applicant (and presumed eventual Assignee of rights): Dioxide Materials, Inc., Champaign, IL; Abstract: Electrochemical devices for converting carbon dioxide to useful reaction products include a solid or a liquid with a specific pH and/or water content. Chemical processes using the devices are also disclosed, including processes to produce CO, ... CH3OH (Methanol), CH4 (Methane), ... acrylic acid, diphenyl carbonate, other carbonates, other organic acids and synthetic fuels. ... Government Interests: This invention was made, at least in part, with U.S. government support under U.S. Air Force contract No. FA8650-12-M-2249. The government has certain rights in the invention";

once we have the Carbon Dioxide, especially in such pure form, there are some very productive things we can do with it.)

The process ... wherein said liquid hydrocarbon fuel product is a distillable product that can be processed by a petroleum refinery. 

The process ... wherein said step of hydrolyzing said biomaterial further includes maintaining the biomaterial under pressure conditions greater than 1 atmosphere (and) wherein said cellulose products are selected from the group consisting of peat, forest waste, energy crops, agricultural produce, and yard waste. 

The process ... wherein said hydrolyzing step is conducted in the presence of a solvent selected from at least one of methanol, ethanol, water, isopropyl alcohol, acetone, organic solvents having between 1 to 10 carbon atoms, and liquid products produced from the process.

(If, as above, stuff like "methanol" is needed as a reagent in this process, keep in mind, that, as seen for yet another example in our report of:

Chicago Recycles CO2 to Methanol | Research & Development | News; "United States Patent 4,609,441 - Electrochemical Reduction of Aqueous Carbon Dioxide to Methanol; 1986; Assignee: Gas Research Institute, Chicago; Abstract: A method of producing methanol from carbon dioxide is set forth. A solution of carbon dioxide in an aqueous solvent having electrolyte dissolved therein is electrolyzed utilizing a molybdenum cathode. Faradaic efficiency is generally quite high and without detectable corrosion. Claims: A method of producing methanol from carbon dioxide (which comprises) electrolyzing a solution of carbon dioxide in an aqueous solvent having an electrolyte therein and utilizing a cathode which comprises molybdenum to produce methanol. The invention relates to the electrochemical reduction of aqueous carbon dioxide to form methanol";

we can make any "methanol" we might need out of some of the byproduct Carbon Dioxide.)

The process ... wherein said liquid hydrocarbon fuel product is recovered by one of a distillation process, decantation, or by acidification of the reaction product. 

The process of converting a biomaterial to a fuel product consisting of the following sequential steps of:

- providing a biomaterial selected from the group consisting of coal, cellulosic products, and mixtures thereof;

- hydrolyzing said biomaterial using a base or alkalized catalyst comprising oxides or hydroxides of groups IA or IIA metals, hydrides of groups IA, IIA, or IIIA metals, or groups of organometallic compounds containing groups IA, IIA, or IIIA metals and at a pressure greater than 1 atmosphere and at a temperature of about 319 C to yield a reaction product, the reaction product having a hydrogen to carbon ratio of 1.6

- acidifying said reaction product to form CO2 and a liquid hydrocarbon fuel product. 

The process ... wherein said step of acidifying said reaction product further consists of adding HCl to the reaction product (and) wherein following said acidifying step, electrolysis of the reaction product formed during the acidifying step is conducted within a fuel cell, the fuel cell providing a source of electricity and heat, the heat recovered by the fuel cell being used in said step of hydrolyzing the biomaterial.

Background and Field: This invention relates to a one-step hydrolysis of diverse biomaterials including cellulose materials such as lumber and forestry waste, non-food crop waste, lignin, vegetable oils, animal fats and other source materials used for biofuels, as well as coal under mild processing conditions which results in the formation of a liquid fuel product along with the recovery of a high purity CO2 product. 

Numerous technologies have been known and proposed for converting a variety of biomass into a useful fuel. For instance, food grade biomaterials such as sugar, starch, vegetable oil and animal fats can be converted into a fuel product but competes with food production resources. Efforts to utilize non-food crops such as cellulosic materials can be converted into a biofuel though achieving a cost-effective process has been elusive. 

Currently, only a small percentage of biomass can be converted into a biofuel. For instance, a food product such as corn kernels can be converted into ethanol but the stalks, husks, and similar cellulosic materials are unable to be converted. The availability of vegetable oil and animal fat making biodiesel is also limited and to the extent food resources are turned into a fuel, the cost of the starting material increases putting pressure on food supplies and making the source material more expensive for biofuel production. 

While technologies exist to convert starch, sugars, vegetable oils and animal fats into either an ethanol fuel or a biodiesel, there remains a need within the art to utilize majority biomaterials such as non-food cellulosic materials, and cellulosic and lignin scrap material from other industries such as forestry waste and to utilize rapidly growing biomaterials such as grasses that can be converted into a suitable transportation fuel. 

On the other hand, coal is a "dead" and "aged" biomass with enormous quantity, and has undergone numerous studies which yielded distinct commercial processes directed to direct or indirect liquefaction of coal, in which both need costly hydrogen production. 

To eliminate costly hydrogen production, hydrolysis of coal with alkali was investigated previously with limited success. Only low yields of alkali-soluble products were reported. One of the exception, set forth in U.S. Pat. No. 4,728,418, entitled "Process For The Low-Temperature Depolymerization Coal Its Conversion A Hydrocarbon Oil" (University of Utah), and which is incorporated herein by reference, describes a three step process using the steps of a metal chloride catalyst with partial depolymerization followed by a base-catalyzed depolymerization in an alcohol solution of an alkali hydroxide which is then further processed with an additional catalyst to obtain a hydrocarbon oil as a final product.

(The above is as in our introductory comment concerning our prior report of "U.S. Pat. No. 4,728,418".)

Coal shares a lot of similarities with biomass ... but is much more difficult to convert than biomass. The chemistry to break down coal clusters would convert hard-to-convert biomass, i.e., lignin and cellulose, as well as easy ones (starch, sugar, vegetable oil, animal fat).

Summary: It is an aspect of at least one embodiment of the present invention to provide a base-catalyzed biomass conversion process using a single step hydrolysis or alcoholysis process which results in a liquid hydrocarbon fuel. 

It is yet another aspect of at least one embodiment of the present invention to provide a hydrocarbon fuel product from biomaterials using a caustic solution which results in the release of a high purity carbon dioxide gas from the biomaterials. 

It is a further aspect of at least one embodiment of the present invention to provide for a liquefaction process using a feedstock of coal, brown coal, lignin, cellulose, vegetable oil or animal fats and mixtures thereof using a one-step base-catalyzed reaction which releases a capturable high purity CO2 product. 

It is a further aspect of at least one embodiment of the present invention to provide for a process of producing a liquid petroleum fuel using a base-catalyzed conversion process that provides for a high purity CO2 product gas as a byproduct. 

It is a further aspect of at least one embodiment of the present invention to provide for a method of converting any biomass, coal, or mixtures of such, with a solvent into liquid hydrocarbons catalyzed by a base or alkali, the method comprising:

a) providing a reaction zone containing feedstock, a solvent, and a base or alkali catalyst which operating said reaction zone under conditions effective for the conversion of the feedstock into liquid hydrocarbons;

b) the above feedstock comprising biomass, peat, coal, or mixtures thereof;

c) the above biomass optionally comprising energy crops, agriculture produces, forest wastes, yard wastes, animal parts, or one or more ingredients of such that containing carbon and produced from nature, for example, sugar, starch, lignin, cellulose, animal fat, vegetable oil, restaurant grease, etc. d) supplying the feedstock to the reaction zone and recovering reaction effluent from said reaction zone; e) recovering carbon dioxide byproduct from the effluent of said reaction zone further recovering a liquid carbon fuel from the effluent stream. 

The biomass does not need special pre-treatment except for optional particle size reduction and drying. The solvent may comprise methanol, ethanol, water, isopropyl alcohol, acetone, liquid product from the process, or other organic solvents with 1-10 carbons. 

The base or alkali catalyst comprises oxides or hydroxides of groups IA or IIA metals in the periodic table, or hydrides of groups IA, IIA, or IIIA metals, or organometallic compounds containing groups IA, IIA, or IIIA metals such as sodium methoxide or aluminum isopropoxide. 

The resulting liquid product may be recovered by distillation, decantation or acidifying the reaction effluent. 

The carbon dioxide byproduct is recovered by acidifying the reaction effluent and the liquid hydrocarbon product or liquefied biomass/coal is THF soluble. The carbon dioxide recovered byproduct is (more than) 95% pure. 

The method allows the feedstock to be replaced by coal, peat, brown coal, lignin, cellulose, other biomass, or mixtures thereof."

--------------------------

As you might surmise, based on our excerpts, the USDOE emphasizes multiple times that any grade of Coal and any and all sorts of renewable and Carbon-recycling Biomass, whether vegetable or animal, whether purpose-grown or waste, can be together directly converted into a "liquid hydrocarbon fuel product ... that can be processed by a petroleum refinery".

As a bonus, we get "a capturable high purity CO2 product" which, to be repetitive for emphasis, as taught by no less an authority than the US Navy, as in, for just one out of many examples now, our report of:

US Navy 2008 CO2 to Synfuel | Research & Development | News; concerning: "US Patent 7,420,004 - Producing Synthetic Liquid Hydrocarbon Fuels; 2008; Assignee: The USA, as represented by the Secretary of the Navy; Abstract: A process for producing synthetic hydrocarbons that reacts carbon dioxide, obtained from seawater or air, and hydrogen obtained from water, with a catalyst in a chemical process such as reverse water gas shift combined with Fischer Tropsch synthesis. The hydrogen is produced by ... any other source that is fossil fuel-free, such as wind or wave energy. The process can be either land based or sea based";

we can then use and consume, in processes which can be powered by freely-available "wind or wave" environmental "energy", in the synthesis of even more "synthetic hydrocarbons".

Note: As too often happens, the link to the official US Patent and Trademark Office electronic file of "United States Patent 7,420,004 - Producing Synthetic Liquid Hydrocarbon Fuels", as it is posted in our report, no longer functions properly. That has been a problem with USPTO electronic links. Here's a perhaps more reliable backup:

Patent US7420004 - Process and System for producing synthetic liquid hydrocarbon fuels - Google Patents.

In any case, as per our subject herein: "United States Patent 8,674,152 - Coal Liquefaction by Base-Catalyzed Hydrolysis with CO2 Capture"; technical experts in our United States Government Patent and Trademark Office recently confirmed that our United States Department of Energy and/or it's contractors have developed a process that will enable the direct conversion of any and all ranks of Coal, along with virtually any and all forms of renewable and Carbon-recycling Biomass, whether waste or purpose-grown, into, again, "liquid hydrocarbon fuel product ... that can be processed by a petroleum refinery". 

Keep in mind, that: "This invention was made with Government support under Contract No. DE-AC09-08SR22470 awarded by the United States Department of Energy. The Government has certain rights in the invention".

And, since We the People are the "Government" of the United States of America, We the People own "certain rights in the invention".

If those "certain rights" include being informed about this valuable technology for converting our abundant domestic resources into the "liquid hydrocarbon fuel"s we now squander our national treasure and endanger our national security to continue purchasing from the often-inimical foreign, alien powers of OPEC, then it's far past time we were informed.

If those "certain rights" include putting this technology - - and along with it many more of our Coal Miners and Farmers, and factory workers - - to work, and to thereby secure our, and our grandchildren's, and their grandchildren's, economic and military security in a United States of America completely self-sufficient in it's supply of "liquid hydrocarbon fuel"s, then it's time we were enabled to do so.

We can, as taught and confirmed by our United States Government herein, convert our abundant domestic Coal and the products and wastes of our fields and our forests directly into, essentially, liquid crude petroleum. And, along with the synthetic crude petroleum, we get a virtually pure stream of Carbon Dioxide, which we can,  using technologies also established by our United States Government, also convert into synthetic petroleum and/or synthetic fuels conventionally derived from petroleum.

Seriously: What else do we need to know?


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