Massachusetts Sunlight Converts CO2 to Carbon-Based Products

United States Patent: 7794969

As we've previously stated, we prefer, in the course of our reportage on the very real potentials for the productive utilization of our vast and renewable Carbon Dioxide natural resource, to focus on the numerous technologies that are becoming available for the direct, chemical conversion of CO2 to synthesize a wide variety of valuable products, as seen, for one example, in:

West Virginia Coal Association | Princeton University November 20, 2012 CO2 to Ethanol | Research & Development; concerning: "United States Patent 8,313,634 - Conversion of Carbon Dioxide to Organic Products; 2012; Inventors: Andrew Bocarsly and Emily Barton Cole; Assignee: Princeton University, NJ;

Abstract: The invention relates to various embodiments of an environmentally beneficial method for reducing carbon dioxide. The methods in accordance with the invention include electrochemically or photoelectrochemically reducing the carbon dioxide in a divided electrochemical cell that includes an anode, e.g., an inert metal counterelectrode, in one cell compartment and a metal or p-type semiconductor cathode electrode in another cell compartment that also contains an aqueous solution of an electrolyte and a catalyst of one or more substituted or unsubstituted aromatic amines to produce therein a reduced organic product.

Government Interests: This invention was made with United States government support from National Science Foundation Grant No. CHE-0616475. The United States Government has certain rights in this invention. Claims: A method of converting carbon dioxide to provide at least one product selected from the group consisting of glyoxal, isopropanol, ethanol".

However, there is, as we've also to a certain extent reported, a significant body of technology being developed for the use of biological intermediaries to effect such chemical processing of CO2, ranging from the almost self-evident use of photosynthetic Algae, as seen, for one example, in our report of:

West Virginia Coal Association | California Algae Make Oil from Coal Power Plant Exhaust | Research & Development; concerning: "US Patent Application 20080086938 - Photosynthetic CO2 Sequestration and Pollution Abatement; 2008; (Presumed Assignee: General Atomics, CA); Abstract: A system and method for producing biofuel from pollutant-fed algae are disclosed";

to the less-obvious, not nearly as well known use of other microorganisms, "methanogenic" bacteria, or, more generically, "archeobacteria", some few of which at least are able, in a related way, to utilize and leverage relatively small amounts of electric current to effect similar chemical transformations of Carbon Dioxide. As seen, again for just one example, in:

West Virginia Coal Association | US Gov Hires Penn State Bugs to Convert CO2 to Methane | Research & Development; concerning: "US Patent Application 20090317882 - Electromethanogenic Reactor and Process for Methane Production; 2009; Assignee: The Penn State Research Foundation; Abstract: Biological processes for producing methane gas and capturing carbon from carbon dioxide are provided according to embodiments of the present invention which include providing an electromethanogenic reactor having an anode, a cathode and a plurality of methanogenic microorganisms disposed on the cathode. Electrons and carbon dioxide are provided to the plurality of methanogenic microorganisms disposed on the cathode. The methanogenic microorganisms reduce the carbon dioxide to produce methane gas, even in the absence of hydrogen and/or organic carbon sources".

Other archeobacteria, "thermophiles", who live in hot springs and near volcanic vents, are able to utilize heat energy in a similar way, while still others, such as "iron-reducing" bacteria, manipulate inorganic chemical reactions to fuel their metabolisms.

And, there is yet another class of ancient bacteria who are believed to have first evolved the process of photosynthesis and, then, passed it along to Algae; and, subsequently, through the evolution of Algae, to the rest of the green plants we all depend upon both to feed us and to replenish the Oxygen in our atmosphere.

Cyanobacteria, better, but somewhat inaccurately, known as "Blue-Green Algae", are believed to have been the first organisms to develop the process of photosynthesis, and, since they appeared on the ancient Earth at about the same time as the "methanogens" and "thermophiles", are able to withstand, and even thrive in, some pretty harsh conditions. See:

Cyanobacteria - Wikipedia, the free encyclopedia; which, interestingly enough, contains some information indirectly related to the subject of our discourse herein.

Further, everyone by now is at least superficially aware of the potentials for the genetic modification of various organisms, especially simple organisms like bacteria and algae, to sort of get them to do what we want them to do, in terms of growth, chemical synthesis, etc. The term "recombinant DNA" likely resonates with most of us, even if we don't know exactly, or even vaguely, what it really means.

In essence, as we've been given to understand it, and, our understanding and reporting could well be imprecise, we are now technically capable of identifying what "pieces" of genetic material in an organism's complete set of chromosomes and DNA is responsible for specific metabolic processes. And, in some cases, specific bits of genetic material, and, consequently, the metabolic processes those bits of genetic material control and enable, can be transferred from one organism to another.

Such technology is at the root of the processes, and the company, we begin to make report of in this dispatch.

As we've previously reported, in, for example:

West Virginia Coal Association | USDOE Hires Boston Bugs to Convert CO2 into Carbon Raw Material | Research & Development; concerning: "US Patent 8,349,587 - Methods and Systems for Chemoautotrophic Production of Organic Compounds; 2013; Assignee: Ginkgo BioWorks, Inc., Boston; Abstract: The present disclosure identifies pathways, mechanisms, systems and methods to confer chemoautotrophic production of carbon-based products of interest, such as sugars, alcohols, chemicals, amino acids, polymers, fatty acids and their derivatives, hydrocarbons, isoprenoids, and intermediates thereof, in organisms such that these organisms efficiently convert inorganic carbon to organic carbon-based products of interest using inorganic energy, such as formate, and in particular the use of organisms for the commercial production of various carbon-based products of interest. ... In various embodiments, the inorganic carbon is ... carbon dioxide. Government Interests: This invention was made with government support under contract number DE-AR0000091 awarded by U.S. Department of Energy, Office of ARPA-E. The government has certain rights in the invention. Claims: An engineered cell for producing a carbon-based product, comprising: an at least partially engineered energy conversion pathway ... "; and:
West Virginia Coal Association | USDOE Hires Massachusetts Bugs to Convert CO2 to Alcohol | Research & Development; concerning: "US Patent Application 20120288898 - Microbial Production of Multi-Carbon Chemicals and Fuels from Water and Carbon Dioxide Using Electric Current; 2012; (Presumed Assignee: University of Massachusetts - Amherst; Abstract: The invention provides systems and methods for generating organic compounds using carbon dioxide as a source of carbon and electrical current as an energy source (and,) a bacterium that can accept electrons and that can convert carbon dioxide to a carbon-bearing compound (including) ethanol",

a number of technologies have been developed for the creation and use of such genetically "engineered" microorganisms, in varied Carbon Dioxide recycling scenarios, by companies that have sprung up and are centered around, and draw on science developed by, colleges and universities in the vicinity of Boston, Massachusetts; which, like Silicon Valley in California and the development of semiconductor technology, seems to be one of our national geographic epicenters for the development of biotechnology.

"Joule Unlimited" is one such newer company, more about which can be learned via:

Joule Unlimited - Wikipedia, the free encyclopedia.

That general reference piece confirms a number of news articles concerning Joule Unlimited and their rather concrete accomplishments relative to Carbon Dioxide recycling, not only in terms of technology, but of very real business.

For instance, as can be learned via:

Audi Places Its Biofuel Bets On Joule - Forbes; "'Audi Places It's Biofuel Bets On Joule'; 'Joule’s bioreactors grow microorganisms fed water, pumped-in carbon dioxide, sunlight, and nutrients'. Boston-area biofuel startup Joule and Audi today announced a partnership, where the automaker will test and validate Joule’s fuels for the auto industry. Last week, Joule commissioned a demonstration plant in Hobbs, New Mexico for its radical approach of directly making ethanol from sunlight and CO2 on a fraction of the land used with traditional approaches. ... 'Joule and the fuels it is developing can ultimately enable sustainable mobility, as its highly-efficient process consumes waste CO2 emissions, avoids depletion of natural resources and doesn’t require agricultural feedstock or arable land,' says Reiner Manglod, the head of environmental products at Audi in a statement";

they have won the approval and assistance of at least one very credible corporate patron.

And, they have embarked on a program to establish the biological technology needed to convert - - on an industrial, commercial basis, using environmental energy to drive the chemical processes - - Carbon Dioxide into a wide range of valuable organic products, including liquid fuels.

As seen in excerpts, with additional links and excerpts following, from the initial link in this dispatch to:

"US Patent 7,794,969 - Methods and Compositions for the Recombinant Biosynthesis of n-Alkanes

Methods and compositions for the recombinant biosynthesis of n-alkanes - Joule Unlimited, Inc.

Date: September 14, 2010

Inventors: Nikos Reppas and Christian Ridley, MA

(We won't insert more links, but web-based references indicate that Reppas was, at one time, with the Harvard University Medical School's Department of Genetics. Ridley seems to have once been with the Departments of Chemistry, Chemical Engineering, and Biochemistry at Stanford University.)

Assignee: Joule Unlimited, Inc., Cambridge

Abstract: The present disclosure identifies methods and compositions for modifying photoautotrophic organisms as hosts, such that the organisms efficiently convert carbon dioxide and light into n-alkanes, and in particular the use of such organisms for the commercial production of n-alkanes and related molecules.

(As can be learned via:

photoautotrophic - definition of photoautotrophic by the Free Online Dictionary, Thesaurus and Encyclopedia.; "photoautotrophic organisms" are able to synthesize their "food from inorganic substances using light as an energy source. Green plants and photosynthetic bacteria are photoautotrophs".)

Claims: A method for producing hydrocarbons, comprising:

(i) culturing an engineered cyanobacterium in a culture medium, wherein said engineered cyanobacterium comprises a recombinant acyl ACP reductase (AAR) enzyme and a recombinant alkanal decarboxylative monooxygenase (ADM) enzyme; and:

(ii) exposing said engineered cyanobacterium to light and carbon dioxide, wherein said exposure results in the conversion of said carbon dioxide by said engineered cynanobacterium into n-alkanes, wherein at least one of said n-alkanes is selected from the group consisting of n-tridecane, n-tetradecane, n-pentadecane, n-hexadecane, and n-heptadecane, and wherein the amount of said n-alkanes produced is between 0.1% and 5% dry cell weight and at least two times the amount produced by an otherwise identical cyanobacterium, cultured under identical conditions, but lacking said recombinant AAR and ADM enzymes. 

The method ... wherein said engineered cyanobacterium further produces at least one n-alkene or n-alkanol. 

The method ... further comprising isolating at least one n-alkane, n-alkene or n-alkanol from said engineered cyanobacterium or said culture medium. 

The method ...  wherein said enzymes are encoded by recombinant genes incorporated into the genome of said engineered cyanobacterium.

Background and Summary: The present disclosure relates to methods for conferring alkane-producing properties to a heterotrophic or photoautotrophic host, such that the modified host can be used in the commercial production of bioalkanes. 

Many existing photoautotrophic organisms (i.e., plants, algae, and photosynthetic bacteria) are poorly suited for industrial bioprocessing and have therefore not demonstrated commercial viability. Such organisms typically have slow doubling times (3-72 hrs) compared to industrialized heterotrophic organisms such as Escherichia coli (20 minutes), reflective of low total productivities. While a desire for the efficient biosynthetic production of fuels has led to the development of photosynthetic microorganisms which produce alkyl esters of fatty acids, a need still exists for methods of producing hydrocarbons, e.g., alkanes, using photosynthetic organisms. 

The present invention provides, in certain embodiments, isolated polynucleotides comprising or consisting of nucleic acid sequences selected from the group consisting of the coding sequences for AAR and ADM enzymes, nucleic acid sequences that are codon-optimized variants of these sequences, and related nucleic acid sequences and fragments."

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Much of the above, of course, like "coding sequences for AAR and ADM enzymes" and "codon-optimized variants" is far, far beyond our understanding. But, obviously, some folks do understand it, and understand it all well enough to propose using the knowledge on an industrial basis to convert Carbon Dioxide into stuff like "n-alkanes", which, in addition to the obtuse compounds specified by Joule, could, according to other web-based references, perhaps include such things as Methane, Ethane and Butane.

With "n-alkene or n-alkanol", they're trending into liquid hydrocarbons which could be combined into more interesting, and more familiar, hydrocarbon products.

However, Joule  has continued their CO2-utilization efforts, and have begun to emphasize that a full range of Carbon-based products can be synthesized using variations of their core CO2-recycling technologies.

As evidenced by the more recent:

"United States Patent: 7968321 - Ethanol Production by Microorganisms

Ethanol production by microorganisms - Joule Unlimited, Inc.

Date: June, 2011

Inventors: Brian Green, Nikos Reppas and Dan Robertson, MA

(The above Dan Robertson, by the way, has something of a local, Coal Country connection:

About the management team | Joule Unlimited | Bedford, MA; "Dan Robertson ... has led the bioscience efforts at Joule since its inception in 2007. In addition to his 14 years of industrial experience, Dr. Robertson also has a 14-year academic background focused on the energetics of membrane transport and photosynthesis. He received his PhD degree in Biochemistry from the University of Pittsburgh.")

Assignee: Joule Unlimited, Cambridge

Abstract: The present disclosure relates to methods and compositions for engineering photoautotrophic organisms to convert carbon dioxide and light into fatty acid esters and other molecules, including biofuels. The molecules are then secreted by the organism into a growth medium.

Claims: A method for the biogenic production of ethanol, comprising: culturing an engineered cyanobacterium in a culture medium in the presence of light and CO2, wherein said cyanobacterium comprises a recombinant pyruvate decarboxylase gene and at least one recombinant alcohol dehydrogenase gene, wherein said recombinant pyruvate decarboxylase gene and at least one recombinant alcohol dehydrogenase gene belong to distinct operons wherein the expression of said recombinant alcohol dehydrogenase gene is increased relative to the expression of said recombinant pyruvate decarboxylase gene, and wherein the amount of ethanol released into said culture medium by said engineered organism is equal to or greater than 10 mg/L/hr.

(The production rate of "10 mg/L/hr" isn't great, by the way, or doesn't seem so to us. We won't attempt to do the math; but, you would need a pretty big reactor, we think, to make this meaningful. The method isn't perfect, but, what would you prefer, Cap & Trade taxes? Mandated Geologic Sequestration of CO2 at the expense of customers of Coal-based electricity? Ongoing economic enslavement for the supply of liquid fuels to OPEC?)

The method ...  wherein said cyanobacterium is a thermophilic cyanobacterium.

Background and Summary: The present disclosure relates to methods and compositions for engineering photoautotrophic organisms to convert carbon dioxide and light into fatty acid esters and other molecules which are then secreted by the organism into a growth medium. 

Existing photoautotrophic organisms (i.e., plants, algae, and photosynthetic bacteria) are poorly suited for industrial bioprocessing and have therefore not demonstrated commercial viability for this purpose. Such organisms have slow doubling time (3-72 hrs) compared to industrialized heterotrophic organisms such as Escherichia coli (20 minutes), reflective of low total productivities.

The invention described herein identifies pathways and mechanisms to confer direct carbon-based products producing capacity to photoautotrophic organisms.The resultant engineered carbon-based products-producing photoautotrophs uniquely enable the efficient production of carbon-based products directly from carbon dioxide and light, eliminating the time-consuming and expensive processing steps currently required to generate biofuels and biochemicals from biomass sources including corn, sugar cane, miscanthus, cellulose, and others. Accordingly, the novel microorganisms of the invention are capable of synthesizing carbon-based products of interest derived from various biosynthetic pathways by fixing CO2 and are also capable of releasing such products. 

Such products range from alcohols such as ethanol, propanol, isopropanol, butanol, fatty alcohols, fatty acid esters, wax esters; hydrocarbons and alkanes such as propane, octane, diesel, JP8; polymers such as terephthalate, 1,3-propanediol, 1,4-butanediol, polyols, PHA, PHB, acrylate, adipic acid, .epsilon.-caprolactone, isoprene, caprolactam, rubber; commodity chemicals such as lactate, DHA, 3-hydroxypropionate, .gamma.-valerolactone, lysine, serine, aspartate, aspartic acid, sorbitol, ascorbate, ascorbic acid, isopentenol, lanosterol, omega-3 DHA, lycopene, itaconate, 1,3-butadiene, ethylene, propylene, succinate, citrate, citric acid, glutamate, malate, HPA, lactic acid, THF, gamma butyrolactone, pyrrolidones, hydroxybutyrate, glutamic acid, levulinic acid, acrylic acid, malonic acid; specialty chemicals such as carotenoids, isoprenoids, itaconic acid; pharmaceuticals and pharmaceutical intermediates such as 7-ADCA/cephalosporin, erythromycin, polyketides, statins, paclitaxel, docetaxel, terpenes, peptides, steroids, omega fatty acids and other such suitable products of interest. Such products are useful in the context of fuels, biofuels, industrial and specialty chemicals, additives, as intermediates used to make additional products, such as nutritional supplements, neutraceuticals, polymers, paraffin replacements, personal care products and pharmaceuticals. These compounds can also be used as feedstock for subsequent reactions for example transesterification, hydrogenation, catalytic cracking via either hydrogenation, pyrolisis, or both or epoxidations reactions to make other products. 

A method of selecting and using various organisms to directly convert sunlight and carbon dioxide into carbon-based products is also disclosed."

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And, note, again, in the immediately above, it's not just the "various organisms" that are of import, but, the broad variety of "carbon-based products" that can be made "directly" herein from little more than "sunlight and carbon dioxide".

We'll have more to report on developments at Joule Unlimited in the near future. They've been busy.

Like the documents we've enclosed herein, it all goes to further emphasize a fact we've many times stated:

Carbon Dioxide, as it arises in only a small way, relative to natural sources of emission, such as Earth's inexorable processes of planetary volcanism, from our essential use of Coal in the generation of affordable and abundant electric power, is a valuable raw material resource.

As demonstrated herein by the company, Joule Unlimited, and as affirmed, as it is embodied in the United States Patent and Trademark Office, by our own US Government, we can collect CO2 from whatever convenient source, and, then, using environmentally-derived energy to drive the biologically-facilitated processes, we can convert that CO2 into a wide range of "carbon-based products" such as liquid and gaseous fuels, including "ethanol (and) propane", and "polymers such as ... acrylate (and) rubber".