United States Patent Application: 0110287503
We've presented many reports documenting the potentials for utilizing certain, well-known varieties of Algae, grown and cultivated in various types of enclosures, to capture and recycle, and to convert into hydrocarbon oils, industrial effluent Carbon Dioxide.
A succinct summary of how it all could work is seen in our report of:
USDOE Algae Recycle CO2 into Liquid Fuels | Research & Development; concerning: "Liquid Fuels from Microalgae; 1987; USDOE Contract Number: AC36-99-GO10337; National Renewable Energy Laboratory (NREL), Golden, CO; USDOE; Abstract: The goal of the DOE/SERI Aquatic Species Program is to develop the technology to produce gasoline and diesel fuels from microalgae. A technical and economic analysis, "Fuels from Microalgae," demonstrates that liquid fuels can be produced from mass-cultured microalgae at prices that will be competitive with those of conventional fuels by the year 2010."
The above report, as with others, similar, we've brought to your attention, focuses mainly on the extraction, from the Algae, after they have been fed a diet enriched with Carbon Dioxide collected from whatever handy source, of biological "lipids", essentially botanical oils and fats, which can then be rather directly refined into conventional liquid hydrocarbon fuels, including, as the USDOE specifies in the above-cited "Liquid Fuels from Microalgae", "diesel fuels and ... gasoline".
In that report, the USDOE, in confirmation of other, similar documents we have brought to your attention, notes that some residual cellular debris will remain from the Algae, after the "lipids" have been extracted for refining into liquid hydrocarbon fuels. And, the USDOE, as have others, suggest that such debris can be gasified, and made through such gasification to produce such seemingly-useful things as "methane".
Coal, of course, and it seems almost gratuitous now to make note of the fact, can as well be gasified and made to yield Methane, and/or, a hydrocarbon synthesis gas, composed primarily of Hydrogen and Carbon Monoxide, which can be catalytically condensed, as via the now-generic Fischer-Tropsch synthesis, into various types of liquid hydrocarbons.
The processes for such gasification of Coal and of residual Algae biomass are so similar, in fact, that the two raw materials can actually be combined in a gasification process, as seen in our report of:
Exxon Co-Gasifies Coal and Carbon-Recycling Biomass | Research & Development; concerning: "United States Patent Application 20100083575 - Co-gasification Process for Hydrocarbon Solids and Biomass; 2010; ExxonMobil Research and Engineering Company; A process for the co-gasification of carbonaceous solids (coal) and biomass ... 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."
Traditional processes for the gasification of Coal and/or biomass typically call for the addition of Water, H2O, usually in the form of Steam, to the mix of reactants with which the carbonaceous raw material is gasified, so that additional Hydrogen becomes available in the resulting hydrocarbon synthesis gas.
Water, though, brings with it additional Oxygen, which can result in the formation of excess Carbon Dioxide.
And, although Carbon Dioxide, too, can be reacted with Hydrogen in a hydrocarbon synthesis process, such reactions, as can be learned in:
Pittsburgh 1931 CO2 to Methanol | Research & Development; concerning: "US Patent 1,831,179 - Producing Reduction Products of Carbon Dioxide; 1931; The Selden Company, Pittsburgh; The invention relates to the process of preparing reduction products of carbon dioxide. More particularly, this invention relates to the catalytic reduction of carbon dioxide in the presence of hydrogen or hydrogen containing gases and catalysts";
typically result in the synthesis of what are sometimes call "oxygenated hydrocarbons", i.e., alcohols, such as Methanol and Ethanol.
As we have also documented, however, as for one instance in:
California Rocket Scientists Liquefy Coal | Research & Development; concerning: "United States Patent 4,243,509 - Coal Hydrogenation; 1981; Rockwell International Corporation; Disclosure is made of a method and apparatus for reacting carbonaceous material such as pulverized coal with heated hydrogen to form hydrocarbon gases and liquids suitable for conversion to fuels";
it is also possible, even desirable, since such processes result in a "cleaner" product slate consisting mostly of basic, non-oxygenated and more-easily refined, hydrocarbons, to gasify Coal, and presumably other solid or semi-solid carbon sources, in the first place with elemental, molecular Hydrogen as the primary agent of gasification.
And, that is confirmed by the United States Patent Application we present in this dispatch, wherein Carbon Dioxide-recycling Algal biomass, after extraction of the lipids which can be more easily refined into hydrocarbons, and/or perhaps even with those lipids, is reacted with elemental Hydrogen, and made thereby to produce hydrocarbon products and hydrocarbon precursors carrying a reduced burden of Oxygen and oxidized compounds.
Comment follows and is inserted within excerpts from the initial link in this dispatch to:
"United States Patent Application 20110287503 - Producing Hydrocarbon Products from Algal Biomass
Date: November, 2011
Inventors: Francis Lupton and Thomas Traynor, Illinois
Assignee: UOP LLC, Illinois
(The above assignee, UOP, once known as Universal Oil Products, is, we believe, unless it has been very recently divested, a division or subsidiary of Honeywell, as indicated in our previous report of:
Honeywell Recycles CO2 with Algae | Research & Development; concerning: "Honeywell's UOP Awarded Funding for Carbon Dioxide Reuse Through Algae Biofuel Production; Mar. 2, 2010 – UOP, a Honeywell (NYSE: HON) company, announced today that it has been awarded a $1.5 million cooperative agreement from the U.S. Department of Energy for a project to demonstrate technology to capture carbon dioxide and produce algae for use in biofuel and energy production. The funding will be used for the design of a demonstration system that will capture carbon dioxide from exhaust stacks at Honeywell’s manufacturing facility in Hopewell, Va., and deliver the captured CO2 to a cultivation system for algae."
And, UOP has been active for many years in the field of hydrocarbon conversion, as seen, for example, in:
West Virginia Coal Association | Chicago 1945 Coal to High-Octane Gasoline | Research & Development; concerning: "United States Patent 2,377,728 - Hydrogenation of Hydrocarbonaceous Materials; 1945; Assignee: Universal Oil Products, Chicago; Abstract: This invention relates to the production of valuable liquid products including high antiknock motor fuel from coal.")
Abstract: Methods for producing hydrocarbon oils from algal biomass are provided. The algal biomass is hydrogenolysed under reaction conditions sufficient to produce a partially deoxygenated lipid-based oil. The algal biomass may be whole algal biomass, residual algal biomass, or both. The algal biomass is hydrogenolysed by liquefying the algal biomass in the presence of a hydrogenolytic catalyst in a hydrogen atmosphere at an elevated temperature and pressure to produce an organic phase containing the partially deoxygenated lipid-based oil, an aqueous phase, and a solid phase. The aqueous and solid phases may be removed from the partially deoxygenated lipid-based oil. The partially deoxygenated lipid-based oil is then substantially deoxygenated using a hydroprocessing catalyst to produce the hydrocarbon oil.
(This process, thus, will work on either the "lipids" as extracted from CO2-recycling Algae, as in the USDOE report, "Liquid Fuels from Microalgae", cited above, and/or on the "residual algal biomass" left behind after the more premium cellular lipids have been extracted. The entire Algal biomass can, if preferable to a separate and preliminary lipid extraction, can thus be utilized; a fact which has other implications relative to the use of Algae for Carbon Dioxide recycling and Coal conversion purposes, as well, as we point out further on.)
Claims: A method for producing a hydrocarbon oil from algal biomass comprising the steps of: hydrogenolysing the algal biomass under reaction conditions sufficient to produce a partially deoxygenated lipid-based oil; and substantially deoxygenating the partially deoxygenated lipid-based oil
(There appear in the full Disclosure a number of technical terms that might, will even likely, be unfamiliar to many of our readers. The above "hydrogenolysing the algal biomass", for instance, means, in the simplest terms, that they are breaking the complex Algae-produced organic compounds down into more basic hydrocarbons, composed of smaller molecules, by forcibly reacting the biomass with Hydrogen.)
The method ... wherein the step of hydrogenolysing comprises hydrogenolysing in the presence of a hydrogenolytic catalyst in a quantity comprising from about 0.5 grams catalyst to about 2.5 grams catalyst per 100 grams of algal biomass.
The method ... wherein the step of hydrogenolysing comprises hydrogenolysing with hydrogen gas under the following reaction conditions: an elevated pressure comprising from about 100 psi ... about 300 psi; an elevated temperature from about 200C to about 400C; and a reaction time from about 60 minutes to about 200 minutes.
(Neither the reaction temperatures or pressures are inordinately high; they are easily achieved and maintained in industrially-sized conventional chemical processing installations.)
The method ... wherein the step of hydrogenolysing comprises hydrogenlysing whole algal biomass, residual algal biomass, or both.
(Note, that, as we indicated above, we can use this process to treat the residual Algal biomass after the premium lipids have been extracted, or, the entire, raw Algal biomass. That is an important point to be made, since some types of CO2-recycling Algae, which don't produce an abundance of easily-processed lipids, are still worth cultivating, such as, for instance, those described in our report of:
USDOE Algae Make Hydrogen for Coal and CO2 Hydrogenation | Research & Development; concerning: "United States Patent 4,442,211 - Method for Producing Hydrogen and Oxygen by Use of Algae; 1984: Assignee: The United States of America; Abstract: Efficiency of process for producing H2 by subjecting algae in an aqueous phase to light irradiation is increased by culturing algae which has been bleached during a first period of irradiation in a culture medium in an aerobic atmosphere until it has regained color and then subjecting this algae to a second period of irradiation wherein hydrogen is produced at an enhanced rate. Claims: A method of producing H2 and O2 by use of algae and light";
wherein certain strains of CO2-consuming Algae that can cyclically produce and excrete elemental Hydrogen during the course of their daily metabolism can be grown, which Hydrogen could then be directed to the hydrogenation of Coal, as in our above cited report of "United States Patent 4,243,509 - Coal Hydrogenation", or, used in the process of our subject, "US Patent Application 20110287503 - Producing Hydrocarbon Products from Algal Biomass", to convert excess biomass into "hydrocarbon oil".
Such synergies would no doubt increase productivity; but, there would, based on some simple laws concerning materials and energy balances, inevitably be some excess Algal biomass generated, over and above what could be consumed in the production of "hydrocarbon oil" with the Algae-produced Hydrogen; especially so if some of the Hydrogen were directed to and consumed in processes like that of "United States Patent 4,243,509 - Coal Hydrogenation". Excess Algae biomass could, then, simply be directed into a process like that in the above-cited ExxonMobil "US Patent Application 20100083575 - Co-gasification Process for Hydrocarbon Solids and Biomass".)
The method ... further comprising the step of extracting neutral lipids from the algal biomass prior to the hydrogenolysing step to produce a neutral oil extract and the residual algal biomass.
The method ... wherein the step of hydrogenolysing comprises hydrogenolysing in a neutral solvent producing the partially deoxygenated lipid-based oil in the neutral solvent.
The method ... wherein the ... neutral solvent selected from the group consisting of hexadecane, water, hexane, and a combination thereof.
A method for producing a hydrocarbon oil from algal biomass, the method comprising the steps of: liquefying the algal biomass in the presence of a hydrogenolytic catalyst and hydrogen gas to produce a partially deoxygenated lipid-based oil; and substantially deoxygenating the partially deoxygenated lipid-based oil using a hydroprocessing catalyst to produce the hydrocarbon oil.
(Note: Such "hydroprocessing (aka: hydrotreating) catalyst"s are well-known and broadly utilized in the petroleum refining industry. UOP, in fact, as seen via:
Hydrotreating | Honeywell UOP; "UOP and Albemarle formed the Hydroprocessing Alliance in 2006 to support the production of clean transportation fuels worldwide. UOP is a leading developer of hydrocracking catalysts, and hydrotreating and hydrocracking process technology. Albemarle is a leading developer and supplier of innovative hydrotreating catalysts and technologies for refineries";
markets a broad line of such materials and technologies to the petroleum refining industry.)
The method ... wherein the step of liquefying comprises liquefying to convert neutral lipids, polar lipids, and glycolipids from whole algal biomass, to convert polar lipids and glycolipids from residual algal biomass, or both, into paraffins in the hydrocarbon oil.
Description and Background: The present invention generally relates to biofuels, and more particularly relates to methods for producing hydrocarbon products from algal biomass.
Alternative sources for petroleum fuel are being sought as natural oil supplies are being depleted, petroleum costs are increasing, concerns about pollution, and political pressure to decrease dependence on foreign fuel stock. Biofuels are derived from biomass and are intended to provide an alternative to petroleum fuels. Biofuels can be burned directly as fuel for certain boiler and furnace applications, and can also serve as a potential feedstock in processes for the production of transportation fuels in petroleum refineries. Biomass can also be used to make other useful organic chemical products. Algae are one type of biomass that is of particular interest because they are one of the fastest growing plants on the planet therefore offering one of the highest yields per unit area. Algae also do not need arable land, and can be grown with impaired water.
Algae have been used as a feedstock to produce biofuel using various methods.
Algae contain neutral lipids ... (and, the) neutral lipids (hereinafter "TAG lipids") in algae have been converted to FAME (fatty acid methyl esters) biodiesel using conventional lipid extraction with a solvent such as hexane and base-catalyzed transesterification methods.
FAME biodiesel has flow properties and ignition properties (cetane values) compatible with most diesel engines. This conventional production of biofuel from algae uses only a fraction (the neutral lipids) of the total available lipid material in the algae leaving a large percentage of "residual algal biomass" remaining after the TAG lipids have been extracted to form a neutral oil extract. This and other conventional methods are incapable of converting the glycolipids and other polar lipids in the algae into biofuel. These lipids cannot be extracted from algal biomass by conventional methods, and thus, cannot be transesterified. Therefore, conventional methods produce only a small fraction of the energy that can potentially be obtained from the algae.
The conventional methods also require the use of strong alkali catalysts which pose significant material handing and waste disposal problems and also do not directly produce a product that is a useable biofuel due to its high oxygen content. A separate deoxygenation process is typically required to convert the neutral oil extract obtained from conventional methods into a useable biofuel.
Accordingly, it is desirable to provide methods for producing biofuels from algae. It is also desired to convert more of the lipids available in the algae into a hydrocarbon product that can be processed into biofuels thus increasing the useful oil yield compared to conventional methods. It is also desired to produce a substantially deoxygenated hydrocarbon product in one step without the use of caustic chemicals.
Various exemplary embodiments of the present invention are directed to methods for producing biofuel from algal biomass. The algal biomass is hydrogenolysed in the presence of a hydrogenolytic catalyst to liquefy the algal biomass into a partially deoxygenated lipid-based oil and the partially deoxygenated lipid-based oil is substantially deoxygenated using a hydroprocessing catalyst to produce a hydrocarbon oil. The hydrocarbon oil can then be used as biofuels and/or processed by known methods into biofuels.
"Residual algal biomass" refers to the dried bagasse remaining after the neutral lipids, e.g., triacelycerols (TAGs) are recovered as "TAG oil" by the solvent extraction. The residual algal biomass comprises the polar lipids and the glycolipids, residual protein and carbohydrates, and algal cell debris. The total mass of the bagasse after the solvent extraction of TAG oil is at least 70% of the total algal biomass.
Algal biomass may be provided by harvesting algae from a source (which) may be a bioreactor ... .
(We've made note of such "bioreactor"s previously, as in our report of:
West Virginia Coal Association | USDOE Algae Recycle More CO2 and Produce Hydrogen | Research & Development; concerning: "United States Patent 7,642,405 - Designer Algae for Photo-biological Hydrogen Production; 2010; Abstract: A switchable photosystem-II designer algae for photo-biological hydrogen production. The designer transgenic algae includes at least two transgenes for enhanced photo-biological H2 production. In one embodiment, a photo-bioreactor and gas-product separation and utilization system produce photo-biological H2 from the switchable ... designer alga";
and, will have more to report on them in the future, concerning their direct applicability to point source emitters of Carbon Dioxide. )
To form the residual algal biomass, the whole algal biomass from (a specified) concentrator ... is dried in a dryer ... by evaporation or the like to provide dried concentrated algal paste ... . The neutral triacelycerols (TAGs) are then extracted from the dried concentrated algal paste in a neutral lipid extractor ... by known lipid extraction methods using an organic solvent such as hexane or the like to produce a "neutral oil extract" (also referred to herein as "TAG oil").
The TAG oil produced ... may be withdrawn from the neutral lipid extractor and conventionally processed to produce FAME biodiesel as noted above.
A mixture of the organic solvent and residual dried concentrated algal paste is provided at (the) output and to an input of (the) evaporator. The organic solvent is evaporated in evaporator ... leaving the residual algal biomass which is provided to (the) reactor ... .
The algal biomass is hydrogenolysed in the presence of a hydrogenolytic catalyst in a hydrogen gas atmosphere at selected reaction conditions as (described and specified).
As noted previously, paraffinic hydrocarbons are the principal chemical compounds in the hydrocarbon oil produced in the reactor from hydrogenolysis (e.g., liquefaction) and deoxygenation of algal biomass in accordance with exemplary embodiments of the present invention (i.e.) as a result of hydrogenolysing (liquefying) and deoxygenating the residual algal biomass.
While the production of the paraffinic hydrocarbons (is) described, the present invention is not so limited. Other paraffinic hydrocarbons including normal paraffins having between eight and fourteen carbons may also be obtained by hydrogenolysing and deoxygenating algal biomass. In addition, other valuable chemical compounds are also produced in the hydrocarbon oil. Hydrocarbon oil produced in accordance with exemplary embodiments described herein can be used directly as biofuel, and/or as a feedstock for further processing into a transportation biofuel such as biodiesel, biojet fuel, and biogasoline.
The hydrocarbon oil produced in accordance with exemplary embodiments as described herein may be used as a feedstock to produce chemicals as well as biofuels.
Accordingly, methods for producing biofuels from algal biomass have been provided. From the foregoing, it is to be appreciated that ... (more) of the lipid material available in the algae is converted to a hydrocarbon product that can be used and/or processed into biofuel thus increasing the useful oil yield as compared to conventional lipid extraction methods."
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Although we lapsed into a, perhaps, overly-long and overly-technical exposition of the details, this is, in essence, a process for converting virtually the entire organic mass of Algae, fed and grown on industrial effluent Carbon Dioxide, into "biodiesel, biojet fuel, and biogasoline".
It relies in large part on prior art for the initial "conventional lipid extraction", which lipids are then quite compatible with conventional petroleum refinery techniques; and, we will have more on that prior art, including technologies for "bioreactors" attached to and contiguous with the exhaust emission components of various CO2-emitting industrial facilities, in the future.
But, it also relies on a somewhat secondary "hydrogenolysis" of the "residual algal biomass", which results in virtually all of the CO2-based biomass being converted into hydrocarbons, in a process, that, as seen in the above-cited "United States Patent 4,243,509 - Coal Hydrogenation", and in others similar about which we have reported, is so much like those other technologies that can be applied to Coal, that they could be combined in a fully integrated process - - like that in ExxonMobil's above-cited "US Patent Application 20100083575 - Co-gasification Process for Hydrocarbon Solids and Biomass", although Exxon isn't using elemental Hydrogen and the product slate is somewhat different - - which could productively consume and utilize what is, essentially, reclaimed and reprocessed Carbon Dioxide, in a hydrocarbon fuel synthesis system based on, due to economies of scale, and utilizing as a primary raw material, Coal.
Finally, and again, the Carbon Dioxide-recycling process of our subject herein, "United States Patent Application 20110287503 - Producing Hydrocarbon Products from Algal Biomass", does rely on and require a supply of elemental, molecular Hydrogen.
And, as seen and explained, among others similar and related, in:
West Virginia Coal Association | Germany & Pennsylvania Hydrogen from Hydropower | Research & Development; concerning, in part: "United States Patent 6,864,596 - Hydrogen Production from Hydro Power; 2005; Assignees: Voith Siemens Hydropower Generation GmbH and Incorporated, Germany and York, PA";
we have plenty of options for using almost freely-available environmental energy to generate all of the elemental Hydrogen we might need right in heart of United States Coal Country.