United States Patent Application: 0130144087
We've earlier reported on the Coal and Carbon conversion technologies being developed by the Celanese Corporation, of Texas, which some old-timers will remember to be a better-known company than they seem nowadays to be.
We haven't given them as much attention over the long course of our reportage as perhaps we should have, especially in light of the fact, that, as seen in:
West Virginia Coal Association | Obama White House Says China Coal-to-Liquids = US Jobs | Research & Development; concerning the official news release from President Obama:
"The White House; Office of the Press Secretary; January 19, 2011
FACT SHEET: U.S.-China Commercial Relations
China is a key market for U.S. exports. Those exports are generating jobs in every corner of the United States and across every major sector. These involve some of our country’s largest companies, but also an increasing number of small and medium-sized enterprises. (The) Chinese government has indicated that its companies signed 70 contracts for $25 billion in U.S. exports from 12 states. These included sectors ranging from auto parts to agriculture, machinery to chemicals. In addition, 11 investment contracts were signed worth $3.24 billion. These cross-border collaborations, both public and private, underpin the expanding U.S.-China commercial partnership, contributing to economic growth and development in both countries. A number of these transactions highlight the increased collaboration in such areas as clean energy and green technologies. Examples of some of the deals associated with this visit include:
we had documented their participation in China's extraordinary, enviable plans to free herself from dependence on foreign suppliers of petroleum through full implementation, and industrialization, of technologies that convert her abundant Coal into a complete range of hydrocarbon products.
As we've also addressed, China, in conjunction with her advancement of Coal conversion, is establishing the technology and the industry to, first, recover Carbon Dioxide via botanical, photosynthetic processes, and, then, to convert those botanical products, with their content of captured Carbon Dioxide, along with Coal, into hydrocarbons; as seen, for example, in:
West Virginia Coal Association | China Coal Conversion Plant Recycle CO2 | Research & Development; concerning the Biodiesel Magazine article: "'China Coal-to-Liquid Plant Will Use Algae-based CO2 Capture'; 2011; A partnership in China that will bring together a Houston-based coal-to-liquids company and a major Chinese coal and construction firm will utilize a CO2 capture system powered by algae. Accelergy Corporation will provide the Yankuang Group with its trademarked TerraSync terrestrial sequestration system to capture carbon from the future facility in Erdos, an area in China’s Inner Mongolia Province. Along with the TerraSync system, Accelergy will also create a hybrid configuration of a microcatalytic coal liquefaction system in conjunction with a Fischer Tropsch system provided by Yankuang. The algae-based carbon system captures the CO2 produced from the CTL process and then passes the carbon to a series of photobioreactors that grow concentrated algae strains sourced from the region"; and:West Virginia Coal Association | China Coal and CO2-Recycling Biomass to Liquid Fuel | Research & Development; concerning: "US Patent Application 20100186291 - Liquid Fuel Production From Cellulosic Biomass and Coal; 2010; Assignee: China Fuel Bioenergy Technology Development Company, Limited, China; Abstract: A liquid fuel production process from Cellulosic biomass and coal comprises providing a mixture of Cellulosic biomass and coal, subjecting the mixture to gasification to obtain synthesis gas and converting the synthesis gas to a liquid fuel under the presence of catalyst. ... Additionally, co-gasification of Cellulosic biomass and coal can reduce the ash fusion temperature of coal".
As we've documented in other reports, such as:
West Virginia Coal Association | Chevron Algae Recycle Coal Conversion CO2 into Bio-Diesel | Research & Development; concerning: "United States Patent 8,076,121 - Process for Conversion of Hydrocarbonaceous Assets and Photobiofuels Production; 2011; Assignee: Chevron USA Inc.; 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";
and, as in our above citation of "China Coal-to-Liquid Plant Will Use Algae-based CO2 Capture":
West Virginia Coal Association | Coal + Biomass to Liquids, with Algae CO2 Recycling | Research & Development; concerning: "United States Patent Application 20120144887 - Integrated Coal to Liquids Process and System with CO2 Mitigation Using Algal Biomass; 2012; Assignee: Accelergy Corporation, Houston; 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";
the potential for capturing Carbon Dioxide from any source with Algae; and, then, combining that Algae, or biomass or waste carbon of any sort, with Coal as a feed into a direct or indirect conversion process to produce hydrocarbons, is a technical concept gaining widespread adoption.
And, herein, we see that the Celanese Corporation, too, as noted by the White House to be one of the United States companies participating in China's Coal-to-hydrocarbon conversion industrial revolution, has developed their own technology for recycling, through the use of Algae and other photosynthetic biomass, Carbon Dioxide in a Coal conversion process.
Comment follows excerpts from the initial link in this dispatch to the very, very recent publication of:
"United States Patent Application 20130144087 - Co-Gasification of Aquatic Biomass and Coal
CO-GASIFICATION OF AQUATIC BIOMASS AND COAL - Celanese International Corporation
June 6, 2013
Inventor: Dinesh Arora, Texas
Assignee: Celanese International Corporation, Irving, Texas
(Celanese Corporation; Celanese - Wikipedia, the free encyclopedia; "Celanese Corporation is a Fortune 500 global technology and specialty materials company with its headquarters in Dallas, Texas. The company is a leading producer of acetyl products, which are intermediate chemicals for nearly all major industries, and is the world's largest producer of vinyl acetate monomer (VAM). Celanese's operations are primarily located in North America, Europe, and Asia. In 2012, Celanese reported net sales of $6.42 billion.")
Abstract: The invention also relates to co-gasification processes for forming syngas from aquatic biomass and a fossil fuel. In one aspect, the invention is to a process for producing syngas, comprising: introducing aquatic biomass, a fossil fuel, water and oxygen to a gasifier and forming syngas comprising hydrogen, carbon monoxide and carbon dioxide; and feeding aquatic biomass with carbon dioxide derived from the syngas. In other aspects, the invention relates to integrated processes for producing industrial chemicals, such as alcohols, carboxylic acids, esters, aldehydes, olefins and polymers from such syngas.
(Note, in the above, the potential for making not just liquid fuels, "alcohols", but a full range of hydrocarbons, including "polymers", from such hydrocarbon "syngas".
Keep in mind that this technology is closely-similar in concept to others, related, such as that seen in:
West Virginia Coal Association | Exxon Co-Gasifies Coal and Carbon-Recycling Biomass | Research & Development; concerning: "US Patent Application 20100083575 - Co-gasification Process for Hydrocarbon Solids and Biomass; 2010; 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. ... 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 (and) wherein the biomass comprises biological matter selected from wood, plant matter, municipal waste, green waste, byproducts of farming or food processing waste, sewage sludge, black liquor from wood pulp, and algae".)
Claims: A process for producing syngas, comprising:
(a) introducing aquatic biomass, a fossil fuel, water and oxygen to a gasifier and forming syngas comprising hydrogen, carbon monoxide and carbon dioxide; and:
(b) feeding aquatic biomass with carbon dioxide derived from the syngas.
The process ... wherein the aquatic biomass that is introduced into the gasifier comprises the aquatic biomass that is fed in step (b).
The process ... wherein the aquatic biomass is selected from the group consisting of microalgae, macroalgae, microplants, duckweed, water hyacinth, cattails, banana tree stem, kelp, and green algae.
The process ... wherein the gasifier is an entrained flow slagging gasifier.
The process ... wherein runoff from the gasifier provides nutrients for the aquatic biomass that is fed with carbon dioxide.
(Note, above, the potential for utilizing/recycling waste water produced by the gasification process. )
The process ... wherein the aquatic biomass and fossil fuel are introduced to the gasifier at a weight ratio from 1:99 to 40:60.
The process ... wherein the aquatic biomass is formed from microalgae (or) macroalgae ... .
The process ... wherein the fossil fuel comprises coal.
A process for producing ethanol from aquatic biomass and a fossil fuel, comprising the steps of:
(a) introducing aquatic biomass, a fossil fuel, water and oxygen to a gasifier and forming syngas comprising hydrogen, carbon monoxide and carbon dioxide;
(b) feeding aquatic biomass with carbon dioxide derived from the syngas.
(c) compressing the syngas to form compressed product gas;
(d) directing a first portion of the compressed product gas to an alcohol synthesis reactor to produce methanol;
(e) directing a second portion of the compressed product gas to a gas separator to produce a hydrogen stream and a carbon monoxide stream;
(f) reacting the carbon monoxide stream with the methanol to produce acetic acid; and:
(g) reacting the hydrogen stream with acetic acid to produce ethanol.
(The above conversion of "carbon monoxide with ... methanol to produce acetic acid" with the subsequent reaction of "hydrogen ... with acetic acid to produce ethanol" is a reaction sequence and process we had intended to report on and to document for you as we went along, via separate dispatches based on other sources, since there are very interesting implications for the employment of "carbon monoxide", "methanol" and, even separately "acetic acid", in the synthesis of "ethanol", insofar as the more direct recycling of Carbon Dioxide, to synthesize hydrocarbons, is concerned. We'll eventually get to it.)
A process for producing syngas, comprising: (a) introducing aquatic biomass, a fossil fuel, water and oxygen to a gasifier and forming a product gas comprising hydrogen and carbon monoxide; (b) increasing the ratio of hydrogen to carbon monoxide using the water gas shift reaction and forming byproduct carbon dioxide; and (c) feeding aquatic biomass with carbon dioxide formed in step (b).
The process ... wherein runoff from the gasifier provides nutrients for the algae.
The process ... wherein the fossil fuel comprises coal.
Background and Field: The present invention relates generally to integrated processes for producing industrial chemicals such as alcohols, carboxylic acids, esters, aldehydes, olefins and polymers from biomass. In particular, the invention relates to improved co-gasification processes for forming syngas from biomass and a fossil fuel, where the syngas is optionally well suited for forming one or more industrial chemicals and, in particular, ethanol.
Biomass gasification is a widely known process for producing synthesis gas, commonly referred to as syngas. Almost all types of biomass may be gasified. Syngas is a gas mixture comprising varying amounts of carbon monoxide (CO) and hydrogen (H2), and optionally carbon dioxide.
Under low oxygen conditions and high temperatures, biomass gasification may generate a fuel known as producer gas. Producer gas is similar to syngas but also contains nitrogen. Though syngas and/or producer gas may have a lower energy density than natural gas, syngas and/or producer gas may suitable for use in a variety of applications.
In commercial applications, syngas and/or producer gas from biomass has a usable chemical energy content and may be used in various applications, such as heat production, combined heat and power (CHP) generation, stand-alone electricity production, and in fuels. Syngas and/or producer gas, for example, may be used as a fuel for gas turbines or internal combustion engines.
There is also an interest in using syngas to produce industrial chemicals. However, there are several challenges in using biomass to produce syngas for integration with the production of industrial chemicals. Unlike many other syngas applications, production of industrial chemical may require a high grade syngas having a low nitrogen, argon and carbon dioxide content. In addition, due to economics, industrial chemicals may require significant capital expenditures to operate a cost-efficient biomass gasification. Because biomass gasifies at relatively low temperatures compared to coal ... , biomass gasification may produce tars and phenolics that can foul and poison downstream catalysts and therefore require removal and costly disposal.
Owing to its increasing use in fuel applications, a particularly desired industrial chemical that may be derived ultimately from syngas is ethanol, which (can be and is) produced from ... coal, or from fermentation processes. Conventional methods for producing ethanol from petrochemical feed stocks, as well as from cellulose materials, include the acid-catalyzed hydration of ethylene, methanol homologation, direct alcohol synthesis, and methanol-to-olefin (MTO) technologies. Instability in petrochemical feed stock prices contributes to fluctuations in the cost of conventionally produced ethanol, making the need for alternative sources of ethanol production all the greater when feed stock prices rise. Starchy materials, as well as cellulose material, are converted to ethanol by fermentation. However, fermentation is typically used for consumer production of ethanol, which is suitable for fuels or human consumption. In addition, the fermentation of starchy materials competes with food sources and places restraints on the production of ethanol.
Current demand for ethanol is expected to increase because ethanol is a clean burning fuel source that may be derived from renewable sources. Although fermentation provides a production pathway from biomass to ethanol, competing uses of fermentation raw materials such as corn effectively limit the total amount of ethanol that can be produced from fermentation. Thus, there is a strong interest in producing ethanol according to renewable fuels standards using a method other than fermentation.
One alternative to direct fermentation to ethanol that is proposed is the biochemical and synthetic conversion of biomass to acetic acid, followed by conversion of acetic acid to ethanol using esterification and hydrogenation ... . Other processes that do not involve fermentation or biochemical conversion have also been proposed (such as) the selective production of ethanol from syngas. Syngas derived from cellulosic biomass (or other sources) can be catalytically converted into methanol, which in turn can be catalytically converted into acetic acid or acetates. The acetic acid or acetates can be reduced to ethanol according to several variations.
In light of the state of the art, the need exists for improved integrated processes for forming syngas from biomass, where the syngas is particularly well suited for forming various industrial chemicals, and in particular ethanol. In addition, the need exists for improved gasification processes that are well suited for adapting to fluctuations in the availability of fossil fuel and biomass feed sources.
In some embodiments, (this) invention is directed to the co-gasification of aquatic biomass and a fossil fuel. For example, in one embodiment, the invention is (directed) to a process for producing syngas, comprising the steps of:
(a) introducing aquatic biomass, a fossil fuel (e.g., coal), water and oxygen to a gasifier and forming syngas comprising hydrogen, carbon monoxide and carbon dioxide; and:(b) feeding aquatic biomass with carbon dioxide derived from the syngas.
In this aspect, the gasifier preferably is an entrained flow slagging gasifier. The aquatic biomass that is introduced into the gasifier preferably comprises the aquatic biomass that is fed in step (b). For co-gasification processes, entrained flow, slagging gasifiers are preferred, which preferably operate at pressures greater than 30 bar, optionally greater than 50 bar. Runoff from the gasifier optionally provides nutrients for the aquatic biomass that is fed with carbon dioxide. The aquatic biomass and fossil fuel may be introduced to the gasifier at a weight ratio from 1:99 to 40:60.
In preferred embodiments, the aquatic biomass comprises microalgae ... .
Optionally, the syngas from the co-gasification process may be used to form various derivative chemicals as described above. For example, The resulting syngas may be compressed, optionally at a compression ratio less than 5:1, e.g., less than 3:1, to form compressed product gas. A first portion of the compressed product gas may be directed to an alcohol synthesis reactor to produce methanol, and a second portion of the compressed product gas may be directed to a gas separator to produce a hydrogen stream and a carbon monoxide stream. The carbon monoxide stream may be reacted with the methanol to produce acetic acid; and the hydrogen stream may be reacted with acetic acid to produce ethanol.
In another embodiment, the invention is to a process for producing syngas, comprising:
(a) introducing aquatic biomass, a fossil fuel, water and oxygen to a gasifier and forming a product gas comprising hydrogen and carbon monoxide;
(b) increasing the ratio of hydrogen to carbon monoxide using the water gas shift reaction and forming byproduct carbon dioxide; and (c) feeding aquatic biomass with carbon dioxide formed in step (b)".
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And, again, a "a product gas comprising hydrogen and carbon monoxide", as made herein from Coal and CO2-recycling "aquatic biomass", would be, as Celanese herein specifies, a "syngas", which, as explained separately via:
Syngas as fuel - What is syngas - Synthesis gas; "Syngas is the direct end-product of the gasification process. Though it can be used as a standalone fuel, the energy density of Syngas is only about 50 percent that of natural gas and is therefore mostly suited for use in producing transportation fuels and other chemical products. As its unabbreviated name implies, Synthesis gas is mainly used as an intermediary building block for the final production (synthesis) of various fuels such as synthetic natural gas, methanol and synthetic petroleum fuel (synthesized gasoline and diesel fuel)";
can be catalytically and chemically condensed into some stuff, like "gasoline and diesel fuel", we seem to be in great need of, as well as, as again specified herein by Celanese, some less-obvious things, like "polymers", i.e., plastic, which we also find ourselves currently overly-beholden to OPEC for our supply of.
As in our above citation of "The White House; Office of the Press Secretary; January 19, 2011; FACT SHEET: U.S.-China Commercial Relations", the Texas-based Celanese is likely making ready to put their technologies, like that disclosed by our subject, "US Patent Application 20130144087 - Co-Gasification of Aquatic Biomass and Coal", to work in China, where, in a more-sustainable, maybe even CO2-negative process, they will be converting Coal, via intermediate production of synthesis gas, into, as Celanese herein suggests, some interesting stuff like "ethanol".
President Obama and his staff seem to know at least a little about these substantial, sustainable potentials for using Coal, supplemented with CO2-recycling "Aquatic Biomass", to synthesize "gasoline and diesel fuel", "polymers" and "ethanol"; and, in their publication of the above-cited "U.S.-China Commercial Relations" fact sheet, have at least done a little to let the US public at large know about those potentials.
Why haven't we common US citizens, living in the heart of US Coal Country, been openly and publicly told anything, at all, about any of them?