United States Patent: 8076121
We remind you that we have previously documented the potentials for combining a facility that converts Coal into liquid and/or gaseous hydrocarbon fuels with another, integrated, facility that employs Algae, or other suitable and related photosynthesic microorganism, cultivated in one or another of various types of "bioreactor", to recycle any byproduct Carbon Dioxide arising from the Coal conversion process.
One example of our reportage on such potentials can be accessed via:
West Virginia Coal Association | Coal + Biomass to Liquids, with Algae CO2 Recycling | Research & Development; concerning: "US Patent Application 20120144887 - Integrated Coal to Liquids Process and System with CO2 Mitigation Using Algal Biomass; 2012; Inventors: Rocco A. Fiato, et. al., NJ; Assignee: Accelergy Corporation; Abstract: An ICBTL (Integrated Coal and Biomass To Liquids) system having a low GHG footprint for converting coal or coal and biomass to liquid fuels in which a carbon-based feed is converted to liquids by direct liquefaction and optionally by indirect liquefaction and the liquids are upgraded to produce premium fuels. CO2 produced by the process is used to produce algal biomass and photosynthetic microorganisms in a photobioreactor. Optionally, lipids extracted from the some or all of the algal biomass is hydroprocessed to produce fuel components and biomass residues and the carbon-based feed (are) gasified to produce hydrogen and syngas for the direct and indirect liquefaction processes".
And, as explained in that report, several of the inventors named in "US Patent Application 20120144887", in addition to the accomplished Rocco Fiato, are long-term veterans of ExxonMobil, with solid, verifiable backgrounds in carbon conversion science.
Such integrated technologies would produce not only biological "lipids" from the co-product CO2, which lipids lend themselves to rather direct processing into an alternative Diesel fuel, but, as well, residual biomass left by the lipid extraction, which residual biomass can then be added to the Coal going into the primary gasification process; or, to avoid potential material imbalances, taken from the system and directed into other uses, such as the production of fertilizer, with the consequent nourishment and stimulation of other, terrestrial, CO2-consuming green plants.
An additional economic advantage of such integrated systems lies in a rather complicated and indirect relationship between the photosynthetic metabolism and the Coal gasification.
Without citing any of our prior reports concerning the issue, there are economic tradeoffs to be considered in deciding whether to support the initial Coal, and other, renewable, Carbon gasification with plain Air or with more purified and concentrated Oxygen to support the partial oxidation. The use of Air results in the generation of some unwanted byproduct Nitrogen Oxides, while purifying and concentrating Oxygen for use in the gasification entails additional expense.
But, photosynthetic microorganisms that would recycle the byproduct Carbon Dioxide also generate Oxygen as their own byproduct of photosynthetic metabolism. And, they have a need for Nitrogen compounds in their mix of nutrients. Thus, they could produce Oxygen which could be used to enrich Air consumed in the gasification, thus reducing the percentage of Nitrogen and, consequently, the amount of co-produced Nitrogen Oxides; while any Nitrogen Oxides that were co-produced could be utilized in the production Nitrogen-based fertilizer to support the growth of the Algae.
So effective and productive could such a combined system be, that, as seen in
West Virginia Coal Association | California Algae Eliminate Coal-to-Liquid CO2 Emissions | Research & Development; concerning: "United States Patent Application 20100285576 - Method to Produce Synthesis Gas or Liquid Fuels from Commingled Algae and Coal Feedstock Using a Steam-Hydrogasification Reactor and a Steam Methane Reformer with CO2 Utilization Through an Algae Farm; 2010; Inventors: Joseph M. Norbeck, et. al., CA; (Presumed Assignee: The Regents of the University of California); This invention involves the conversion of coal-algae ... commingled slurry feedstock into a high methane content product gas using a steam hydrogasification process. This gas is then reformed into synthesis gas (H2 and CO). Excess H2 from the synthesis gas is separated and recycled back to the gasifier. The synthesis gas is converted into a liquid fuel such as Fischer-Tropsch diesel. The CO2 emissions from the steam hydrogasification process can be captured and used to grow the algae, which can subsequently be commingled with coal ... to form slurry feedstocks for the hydrogasifier. Thus, this process eliminates CO2 emissions from the conversion plant";
virtually no Carbon Dioxide would be emitted by the total, combined, Coal and Algae conversion process.
Further, we remind you, that, as seen in:
West Virginia Coal Association | California Hydrogasifies Coal & Carbon-Recycling Wastes | Research & Development; concerning: "US Patent 7,500,997 - Steam Pyrolysis ... to Enhance the Hydro-Gasification of Carbonaceous Materials; 2009; Inventors: Joseph Norbeck and Collin Hackett; 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";
the Algae biomass that represents CO2 recycled from the initial Coal gasification can be supplemented with additional organic material, which would contain additional CO2 recycled from outside the system, that is, CO2 biologically extracted and recycled from the environment itself.
Herein, we see that another California entity has even further developed and refined such concepts, bringing them all more less together; as evidenced by excerpts from the initial and one following link in this dispatch, with explanatory links and excerpts inserted:
"US Patent 8,076,121 - Process for Conversion of Hydrocarbonaceous Assets and Photobiofuels Production
(Integrated process for conversion of hydrocarbonaceous assets and photobiofuels production - Chevron U.S.A. Inc. And, yes, Coal is our most abundant, most precious, "hydrocarbonaceous asset". - JtM)
Date: December, 2011
Inventor: Dennis O'Rear, CA
Assignee: Chevron USA Inc., CA
Abstract: The present invention is generally directed to processes that integrate CO2-producing conversions of hydrocarbonaceous assets with biofuels processes that utilize CO2 in photosynthesis. In some embodiments, such processes involve the absorption of CO2 in an absorption liquid. In some such embodiments, such absorption is carried out in an absorption tower. In some other such embodiments, there is a subsequent desorption of the CO2. Generally, at least some of the CO2 captured by the absorption liquid is used to grow microbes or diatom species.
Claims: An integrated process combining hydrocarbonaceous conversion with a photobiofuels process that utilizes CO2 produced from said hydrocarbonaceous conversion to support photosynthesis, the process comprising the steps of:
a) converting at least one hydrocarbonaceous asset (into) a first ... CO2-containing gas, wherein said at least one hydrocarbonaceous asset is selected from the group consisting of ... coal, ... waste plastics, waste tires, municipal waste, and combinations thereof;
b) absorbing at least a portion of the CO2 from the first super-atmospheric pressure CO2-containing gas into an absorption liquid, the absorbing being done at a first temperature;
c) desorbing at least a portion of the absorbed CO2 ... to form a second CO2-containing gas, wherein the second temperature is higher than the first temperature, and the concentration of CO2 in the second ... gas is higher than the concentration of CO2 in the first ... CO2-containing gas;
d) providing at least a portion of the CO2 in the second super-atmospheric pressure CO2-containing gas to support algal and/or diatomaceous photosynthesis in a photobiofuels process, wherein at least a portion of the CO2 is produced at night;
e) storing at least a portion of the second super-atmospheric pressure CO2-containing gas produced at night in containers of a type selected from the group consisting of aboveground gas tanks, underground salt domes, and combinations thereof;
f) recovering, during daylight hours, at least a portion the stored ... CO2-containing gas; and:
g) providing at least a portion of the CO2 in the recovered second ... CO2-containing gas to support photosynthesis in the photobiofuels process.
The process ... further comprising setting a target salinity in the absorption liquid provided in the photobiofuels process, and controlling the salinity to this target by controlled blending of water from the converting of hydrocarbonaceous assets.
The process ... wherein the converting of said hydrocarbonaceous assets comprises converting via a Fischer-Tropsch process.
(Fischer–Tropsch process - Wikipedia, the free encyclopedia; "The Fischer–Tropsch process ... is a collection of chemical reactions that converts a mixture of carbon monoxide and hydrogen into liquid hydrocarbons. The process ... produces a ... synthetic fuel, typically from coal.")
The process ... wherein the photobiofuels process comprises (i) providing microalgae, (ii) regulating the metabolism of the microalgae by modulating a temperature, salinity, and/or pH thereof, and (iii) harvesting said microalgae.
The process ... further comprising a step of producing O2 in the photobiofuels process and diverting at least a portion of the produced O2 to the converting of the at least one hydrocarbonaceous assets.
The process ... further comprising the steps of:
a) removing a reduced nitrogen species from the first super-atmospheric pressure CO2-containing gas obtained from the converting of hydrocarbonaceous assets; and:
b) consuming the reduced nitrogen species in the photobiofuels process.
Background and Field: This invention relates generally to biofuels production, and specifically to methods for harnessing carbon dioxide (CO2) produced during hydrocarbonaceous asset conversion, and using said CO2 to support photosynthesis in a biofuels precursor.
Carbon dioxide (CO2) is a well-known greenhouse gas and attempts to reduce the emissions of this gas into the atmosphere are desirable. CO2 is commonly formed when hydrocarbonaceous assets are converted into hydrocarbonaceous products, e.g., hydrogen or power.
The current high costs associated with capturing and sequestering this CO2 using conventional amine scrubbing technology coupled with sequestration of high pressure CO2 are such that doing so is generally not economically-viable.
Accordingly, it is desirable to reduce both CO2 emissions and the costs associated with their sequestration. Toward this end, it has been proposed that CO2 be captured when electrical power is generated from hydrocarbonaceous assets ... .
Methods to capture and mitigate the entrance of CO2 into the atmosphere have primarily focused on amine scrubbing from flue gas or super-atmospheric gas streams coupled with compression of the CO2 prior to sequestration underground. This presents problems. First, the costs to compress the CO2 can be significant. Second, there are questions as to whether or not the CO2 sequestered in underground reservoirs will in fact, remain there.
One approach to reduce greenhouse gas emissions is to substitute a crop-based biofuel for a petroleum-derived fuel. In preparing the crop-based biofuel, CO2 is consumed during the plant growth cycle. For example, there is interest in ethanol production from corn, and biodiesel from various grains. The problems with this crop-based approach include:
(1) diversion of scarce farmland that is engaged in growing food for manufacture of transportation fuels;
(2) use of scarce fresh water for the production of biofuels (in the United States, the decline of the Ogallala aquifer due to agricultural use could restrict future agriculture); and:
(3) the energy used to create the finished biofuel (i.e., product) reduces the net energy production, wherein associated energy utilization steps include fertilization, planting, harvesting, drying, milling, fermenting, extracting, distilling, transesterification and the like (some studies have indicated that there is no net energy production from ethanol).
An alternative to crop-based biofuels is to use a photobiofuels process which converts the CO2 into liquid hydrocarbonaceous products by use of photosynthetically-responsive microbes ("microbes").
A photobiofuels process, in the context of this invention, is a biological process employing microorganisms such as algae (e.g., microalgae) and/or diatoms (e.g., phytoplankton) to convert carbon dioxide into liquid hydrocarbonaceous products such as triglycerides, alcohols, acids, mono-esters and other oxygenated compounds. In doing this, the photobiofuels process uses sunlight as an energy source to produce lipids (triglycerides) and carbohydrates (e.g., sugars and starches). The photobiofuels process can also produce oxygen as a by-product.
(O'Rear goes into some detail about the various, general types of "photobiofuels process"es. We have addressed some of them in previous reports, and will further detail them in the future. There are multiple options; and, the important thing for our purposes herein isn't in exactly how we do it; but, the plain fact that we can do it; that is, recycle Coal conversion byproduct CO2 into biofuels and into more raw material for the Coal conversion process itself. - JtM)
Description: The present invention is generally directed to processes that integrate CO2-producing conversions of hydrocarbonaceous assets with biofuels processes that utilize CO2 in photosynthesis. In some embodiments, such processes involve the absorption of CO2 in an absorption liquid. In some such embodiments, such absorption is carried out in an absorption tower. In some or other such embodiments, there is a subsequent desorption of the CO2. Generally, at least some of the CO2 captured by the absorption liquid is used to grow microbes or diatom species.
In some alternate embodiments, the present invention is directed to an integrated process for conversion of hydrocarbonaceous assets, the process comprising the steps of:
(1) converting hydrocarbonaceous assets to produces a CO2-containing gas;
(2) absorbing at least a portion of the CO2 of the CO2-containing gas into an absorption liquid in an absorption tower, wherein the absorption liquid flows downward, and wherein the CO2-containing gas flows upward; and:
(3) using at least a portion of the CO2 in the absorption liquid to support photosynthesis in a; photobiofuels process. In some such embodiments, the process may further comprise the steps of:
(i) forming biomass in the absorption liquid used in the photobiofuels process;
(ii) removing the biomass to form a regenerated absorption liquid; and:
(iii) recycling at least a portion of the regenerated absorption liquid to the absorption tower.
In some of the above-described embodiments, the processes can further comprise the production of O2 in the photobiofuels process and use of at least a portion of this O2 to convert the hydrocarbonaceous assets, wherein use of the O2 is typically as a gaseous oxidant for synthesis gas production and/or an oxidant of synthesis gas to produce power, and wherein the photobiofuels process is typically a closed photobiofuels process.
In some of the above-described embodiments, energy is created during the converting of hydrocarbonaceous assets, wherein said energy typically manifests itself in a form such as, but not limited to, electrical power, steam, hot gases, super-atmospheric pressure gases, and combinations thereof; and wherein at least a portion of this energy is typically utilized in the photobiofuels process in a manner such as, but not limited to, stirring and pumping the liquid in the photobiofuels process, sonicating the liquid, processing the liquid in a high shear mixer, separating microalgae contained therein from the liquid, drying microalgae contained therein, grinding microalgae contained therein to tree lipids and other components, separating the components, and the like.
In some of the above-described embodiments, the processes further comprise producing a methylester for use as a biodiesel, the producing comprising the substeps of:
(a) recovering triglycerides from the photobiofuels process;
(b) transesterifying the triglycerides from the photobiofuels process with an alcohol to form an ester and glycerin; and:
(c) purifying the ester; wherein at least a portion of the alcohol used in the transesterification is manufactured, in the process for converting hydrocarbonaceous assets, by synthesis gas conversion processes such as, but not limited to, methanol synthesis, Fisher-Tropsch and the like.
(Thus, one of the Coal conversion products can serve to enable the production of Bio-Diesel from the Carbon Dioxide-recycling Algae.)
In some of the above-described embodiments, the processes further comprise the steps of:
(a) removing a reduced nitrogen species from the CO2-containing gas derived from the converting of hydrocarbonaceous assets; and:
(b) consuming the reduced nitrogen species in the photobiofuels process.
In some of the above-described process embodiments, the step of converting the hydrocarbonaceous assets involves a Fischer-Tropsch process, and wherein said process further comprises the steps of:
(a) recovering triglycerides from the photobiofuels process;
(b) recovering a product from the Fischer-Tropsch process;
(c) processing at least a portion of both the triglyceride and the Fisher-Tropsch product in a hydroprocessing process to form paraffinic liquid hydrocarbonaceous products; and:
(d) recovering at least a portion of the paraffinic liquid hydrocarbonaceous products.
In some of the above-described embodiments, the processes further comprise the steps of:
(a) recovering triglycerides from the photobiofuels process;
(b) converting the triglycerides to fatty acids, at least a portion of which are unsaturated;
(c) oligomerizing the unsaturated fatty acids to form polyacids; and:
(d) esterifying the polyacids with an alcohol to form an unsaturated polyester operable for use as a synthetic lubricant.
(Definitions:) 'Hydrocarbonaceous assets' are materials comprising the elements H and C, and optionally S, N, O, and other elements used to manufacture hydrocarbonaceous products. Examples of such assets include ... coal, ... waste plastics, waste tires, municipal waste, derivatives of these, and their combinations and/or mixtures'".
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Make no mistake: The indirect conversion of Coal, "via a Fischer-Tropsch process", into liquid hydrocarbon fuels, enables the conversion of various waste and renewable Carbon resources, i.e., "waste plastics, waste tires, municipal waste", into those same hydrocarbon fuels, right along with the Coal. And, any Carbon Dioxide that might be co-produced in the hydrocarbon fuel, "Fischer-Tropsch process" can be recycled by Algae, who will produce not only "photobiofuels", i.e., for instance, a substitute Diesel, but, as well, additional "waste" biomass for the initial Coal gasification and Oxygen both to support that initial gasification and prevent co-production of excess Nitrogen Oxides.
Further, issuance of the above US Patent was accompanied by the simultaneous issuance of another patent, to the same inventor, for additional technical innovation integral to the concepts embodied in the Disclosure of that Patent, as seen in:
"United States Patent: 8076122 - Process for Integrating Conversion of Hydrocarbonaceous Assets and Photobiofuels Using and Absorption Tower
(Process for integrating conversion of hydrocarbonaceous assets and photobiofuels production using an absorption tower - Chevro)
Date: December, 2011
Inventor: Dennis O'Rear, CA
Assignee: Chevron USA Inc., CA
Abstract: The present invention is generally directed to processes that integrate CO2-producing conversions of hydrocarbonaceous assets with biofuels processes that utilize CO2 photosynthesis. In some embodiments such processes involve the absorption of CO2 in an absorption liquid. In some such embodiments such absorption is carried out in an absorption tower. In some other such embodiments, there is a subsequent desorption of the CO2. Generally, at least some of the CO2 captured by the absorption liquid is used to grow microbes or diatom species.
This invention relates generally to biofuels production, and specifically to methods for harnessing carbon dioxide (CO2) produced during hydrocarbonaceous asset conversion, and using said CO2 to support photosynthesis in a biofuels precursor.
The present invention is generally directed to processes that integrate CO2-producing conversions of hydrocarbonaceous assets with biofuels processes that utilize CO2 in photosynthesis.
The present invention is generally directed to processes that integrate CO2-producing conversions of hydrocarbonaceous assets with biofuels processes that utilize CO2 in photosynthesis, i.e., photobiofuels processes. In some embodiments, such processes involve the absorption of CO2 in an absorption liquid. In some such embodiments, such absorption is carried out in an absorption tower. In some other such embodiments, there is a subsequent desorption of the CO2. Generally, at least some of the CO2 captured by the absorption liquid is used to grow microbes or diatom species.
Certain terms and phrases are defined throughout this description as they are first used, while certain other terms used in this description are defined below:
"Processes for conversion of hydrocarbonaceous assets" are processes that first convert a hydrocarbonaceous asset to synthesis gas (via a synthesis gas generation process) and then convert the synthesis gas into a fuels process (via a synthesis gas conversion process). The processes for conversion of hydrocarbonaceous assets contain a super-atmospheric pressure CO2-containing gas stream which is more suitable for extraction of CO2 than is an atmospheric gas stream (such as flue gas)."
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The full Disclosure of "United States Patent 8,076,122" is, in fact, too difficult for us, with our limited capacities, to differentiate from the co-issued "United States Patent 8,076,121", so we won't belabor the issue by attempting to do so.
One point that is made by Chevron, and not reflected in our excerpts, is that Methanol is one of the products which can be made from the synthesis gas derived from the Coal and the specified Carbon-recycling wastes, in a fashion similar to that seen in our report of:
Mobil Oil Coal to Methanol to Gasoline | Research & Development; concerning: "United States Patent 4,447,310 - Production of Distillates through Methanol to Gasoline; 1984; Mobil Oil Corporation; A process for producing a wide slate of fuel products from coal is provided by integrating a methanol-to-gasoline conversion process with ... coal gasification (wherein) coal is gasified under oxidation conditions to produce a synthesis gas which is converted to methanol".
And, some of that Methanol can be used to react with some of the crude CO2-recycling Algae lipids, or oils, to produce both the Diesel fuel and, as in: "esterifying the polyacids with an alcohol to form an unsaturated polyester operable for use as a synthetic lubricant"; some other valuable products, as well.
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Thus, the products of Coal conversion can serve to enhance the products of Carbon Dioxide recycling.
In any case, by combining Coal with, as specified, "waste plastics, waste tires, municipal waste, derivatives of these, and their combinations and/or mixtures" and the residual Algae biomass from the processes of our subjects, "United States Patent 8,076,122" and "United States Patent 8,076,121", it would seem more than possible to, as in the process divulged in our above-cited previous report, concerning:
"US Patent Application 20100285576 - Method to Produce Synthesis Gas or Liquid Fuels from Commingled Algae and Coal Feedstock Using a Steam-Hydrogasification Reactor and a Steam Methane Reformer with CO2 Utilization Through an Algae Farm; 2010; (Presumed Assignee: The Regents of the University of California); This invention involves the conversion of coal-algae ... commingled slurry feedstock into a high methane content product gas using a steam hydrogasification process. This gas is then reformed into synthesis gas (H2 and CO). (And) this process eliminates CO2 emissions from the conversion plant";
convert both Coal and Biomass into a hydrocarbon synthesis gas suitable for "methanol synthesis, Fisher-Tropsch and the like", while actually, at the same time, indirectly consuming Carbon Dioxide, as it is represented in various organic "wastes"s, as detailed above.
Not only that, but pernicious semi-synthetic organic wastes, and environmental contaminants, i.e., "waste plastics, waste tires, municipal waste", can be consumed and productively utilized in these processes, which result in the production of "transportation fuels", without the emission of Carbon Dioxide; with all of it made possible by the availability of one, genuinely abundant resource: Coal.
