WO2009067771A1 - Production of ethanol from algae - Google Patents

Production of ethanol from algae Download PDF

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Publication number
WO2009067771A1
WO2009067771A1 PCT/BR2008/000357 BR2008000357W WO2009067771A1 WO 2009067771 A1 WO2009067771 A1 WO 2009067771A1 BR 2008000357 W BR2008000357 W BR 2008000357W WO 2009067771 A1 WO2009067771 A1 WO 2009067771A1
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WO
WIPO (PCT)
Prior art keywords
algae
process according
alcohol
hydrolysis
fermentation
Prior art date
Application number
PCT/BR2008/000357
Other languages
English (en)
French (fr)
Inventor
Nei Pereira Junior
Elis Cristina ARAÚJO ELEUTHERIO
Marcos Dias Pereira
Dárlio Inácio ALVES TEIXEIRA
Maria Isabel Madeira Liberto
Allen Norton Hagler
Julio DE MENDONÇA LOUZADA
Gustavo DE MENDONÇA VALLADARES
Original Assignee
Universidade Federal Do Rio De Janeiro
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Universidade Federal Do Rio De Janeiro filed Critical Universidade Federal Do Rio De Janeiro
Priority to BRPI0819746A priority Critical patent/BRPI0819746A8/pt
Publication of WO2009067771A1 publication Critical patent/WO2009067771A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00Preparation of oxygen-containing organic compounds
    • C12P7/02Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/06Ethanol, i.e. non-beverage
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel

Definitions

  • algae are cultivated with the aid of buoys, in areas where the wind and the current are not strong.
  • most common species are Kappaphycus, Gelidium, Gigardina, Gracilaria, Encheuma, Hypmea and Pterocladia.
  • the algae selectively assimilate many of the minerals contained in water. They photosynthesize and synthesize the carbohydrate polymer that constitutes the structural framework of the alga body, which may be agar-agar, carrageen or others polymers.
  • the most known substances extracted from macro-algae are of three types: alginates, extracted from chestnut algae; agar-agar and carrageens, extracted from varies species of red algae.
  • the agar-agar is a mucilage (vegetable gelatin) constituted of agarose and agaropectin polymers.
  • the alginates, agar-agar and carrageens are used, in the form of polymers, as thickening or gelling agents in the industrial manufacture of food products, cosmetics and pharmaceuticals, by virtue of the texture it gives them.
  • the industrially-discarded algae residue constitutes an excellent raw material for transformation into ethanol according to the methodology that constitutes the object of this international patent registration.
  • agar-agar and carrageen polymer For many centuries on the menu of oriental peoples, it is commonplace to use the agar-agar and carrageen polymer as a gelling and thickening product, respectively.
  • the recipe for agar-agar was subsequently incorporated, serendipitously, to microbiology to solidify culture means designed for the growth of microbes.
  • agar-agar and carrageen are used in various industrial and biotechnological sectors where these polymers are necessary (Renn, D. W., 1990. Seaweeds and biotechnology — inseparable companions. Hydrobiologia, 204-205 (1): 7-13; Marinho-Soriano, E. (2001) Agar polysaccharides from Gracilaria species
  • patent application PI7701845 describes a process of obtaining ethanol from amide produced by green amilogenic microalgae.
  • the production of alcohol using amide as a raw material is a process that was already known at the time.
  • Patent US7135308 protects a process for the production of ethanol from algae cultures of the Zygnemataceae, Cladophoraceae and Oedogoniales species, or a combination thereof, which after harvesting and drying are submitted to an anaerobic aqueous environment for fermenting in the presence of yeast typically used in the beer-making industry.
  • Patent application CA2005426 describes a process of producing ethanol in vivo, carried out by genetically-modified photosynthesizing bacteria with genes isolated from Saccharomyces cerevisiae or Zymomonas mobilis.
  • Patent document EP645456 describes a process and a system for the production of ethanol from saccharogenic microalgae.
  • Patent JP52082785 describes a process of producing alcohol from the fermenting of amide accumulated in algae of the Chlamydomonas and Scenedesmus species cultivated in a liquid environment containing a source of carbon, a source of nitrogen and inorganic elements.
  • Patent JP7031485 also claims a process of producing alcohol from saccharogenic algae using the step of adding a solution containing 80% of an organic solvent capable of denaturing the inner cellular membrane of the algae.
  • Patent application US2008155890 discloses a system of cultivating algae of the Synechococcus and Chlorella species in addition to cyanobacteria, for the production of biodiesel.
  • Patent application CN 1699516 describes a process for preparing biodiesel using oil extracted from microalgae.
  • the present invention refers to a process of producing alcohol from fermenting of hydrolyzed sugars of gelling and/or thickening polysaccharides obtained from algae cultivated in natural or artificial aquatic environments, eutrophized or not.
  • the main steps of this process are: collection, cleaning and treatment of algae to remove toxic elements and/or microbial inhibitors; fragmentation; drying; hydrolysis of the total sugars produced by the algae; fermentation of the sugars resulting from hydrolysis of the algae polysaccharides, with the use of yeast capable of promoting fermentation of galactosides; and alcohol distillation.
  • Drawings Figure 1 Organization chart containing the steps of the process of producing alcohol from algae.
  • the process of producing alcohol from biomass of galactan-producing marine, red and/or dark macroalgae of this invention occurs by the hydrolysis of gelling and/or thickening polysaccharides which are obtained from algae cultivated in natural or artificial aquatic environments; eutrophized or not.
  • Carbohydrate polymers are understood to be those containing galactosides and/or glycosides, produced naturally and stored by the cells of the macroalgae.
  • Gelling and thickening polysaccharides are those formed by galactosides in their D and L forms, whereas the content of the glycoside polymers is represented by the algae cellulose.
  • Artificial environments are understood to be man-made environments for aquiculture, principally for pisciculture, carciniculture, malacoculture, herpetoculture, and other economically feasible cultures.
  • the algae that can be used in this process are macroscopic, preferably those belonging to the Gelidium, Gigardina, Gracilaria, Encheuma and Pterocladia species.
  • the first step of this process comprises the collection of algae which are then cleaned and fragmented for submission to a partial or total drying process. This step is essential to control the carbohydrate content (Brix Degree) to be used in the fermentation phase.
  • fragmentation of the alga body can be performed by any mechanical procedure known in the state of the art. Preferably, fragmentation should be carried out by cutting into very small pieces.
  • Partial drying of the algae can be by processes known in the state of the art, such as: filter pressing, open-air drying; gas drying; solar collector; incident artificial light; chemical drying; and others.
  • the algae may be completely or partially dried, and algae having a maximum humidity content of
  • the third step of this process comprises the initial hydrolysis of the carbohydrate polymers.
  • the hydrolysis of said carbohydrate polymers can be carried out both by traditional physio-chemical processes and by enzymatic processes or by both processes in conjunction.
  • the physio-chemical hydrolysis used by this process is acid hydrolysis, and should be carried out in an aqueous environment containing an acid, at a temperature of between 60 and 120 0 C under pressure of between 1 and 3atm.
  • hydrolysis occurs at a pressure of between 1 and 2atm.
  • the physio-chemical process to be used in acid hydrolysis comprises the use of a solution containing on average the equivalent of: a. 20% fermentable substrate previously defined in the correspondent in dried algae; b. 5% acid in a concentration destined for each polymer type; c. 75 % water.
  • the acid used in this step can be hydrochloric acid or others that do not alter the chemical structure of the resulting monomers.
  • the application of heat by microwaves, under pressure, may also be used.
  • the efficiency of the heating by microwave allows a reduction of the reaction times of days and hours to minutes and seconds. This is the main but not the sole advantage of this mode of operation. It is evermore common to apply hydrolysis reactions assisted' by microwaves to produce monosaccharides from cellulose, amide and other natural polymers.
  • the acid is substituted for an enzymatic preparation, containing an agarolitic and/or carragenolitic enzyme duly buffered or a mixture of agarolitic and/or carragenolitic enzymes duly buffered; the temperature and pressure conditions are identical to those used in physio-chemical hydrolysis.
  • mixed hydrolysis will be used, involving physio-chemical and enzymatic processes.
  • the fourth step in the process of producing alcohol according to this invention comprises the separation of total sugars obtained after the hydrolysis described in the prior step.
  • Total fermentable sugars are understood to be those carbohydrates, in the form of monomers, dimers or trimers, resulting from the hydrolysis of galactan polymers of the macroalgae, fermentable by yeast of previously defined species.
  • the succus of fermentable sugars can be separated from the partially hydrolyzed mixture by filtering.
  • the concentration of fermentable carbohydrates should be diluted so as to comply with the aforementioned Brix degree range.
  • the yeast to be added to the vat, to initiate the fermentation process should be previously cultivated to propagate in culture environments containing growth factors, in addition to the macro and micro nutrients required for the development of cellular biomass.
  • the sixth step begins by allocating said must to suitable equipment for fermenting such as, for example, open or sealed vats. This step will occur by adding the must to said vats that may or may not contain yeast capable of fermenting the galactosidic and glucosidic monomers.
  • the yeasts used are those capable of fermenting galactosides and glycosides, having high alcoholic tolerance and resistance to the microbial inhibitors present in the algae extracts.
  • the yeasts that can be used for fermenting the algae products are those related to the following species or anamorphs thereof: Candida sp; Clavispora sp; Debaryomyces sp; Geotrichum sp; Kloeckera sp; Kluyveromyces sp; Metschnikowia sp; Pachysolen sp; Pichia sp; Kazachstania spp; Rhodotorula sp; Saccharomyces sp; Torulaspora sp; sp; Zygosaccharomyces sp.
  • the yeasts used in the process of producing alcohol according to this invention are of the thermo-tolerant kind, capable of carrying out the fermentative process at high temperatures.
  • the fermentation step occurs by adding a fermentatively efficient quantity of yeast to said must.
  • fermentation occurs anaerobically, at a temperature between 25 and 45°C; pressure between 0.5 and 3atms and slightly acidic pH (3.5 to 5.5).
  • a fermentatively efficient quantity of yeast is understood to be such content that is capable of promoting fermentation of the must at an ideal velocity, that enables the yeast to develop at a low stress level, generating a higher ethanol yield and a lower production of secondary products of the fermentative process such as, for example, glycerol, acetic acid and succinic acid.
  • the yeast cells should remain mostly isolated, in view of the risks of aggregating together with others forming clusters. Additionally, antibiotics and bactericides should be added to the culture, capable of keeping the culture free of contaminations by exogenic bacteria during the fermentation process, so as to optimize the efficiency of the process described herein.
  • the efficiency of the fermentation can be evaluated by standard procedures used in the traditional sugar/alcohol industry, verifying the maximum conversion of galactosides, at which point the fermentation process should be interrupted.
  • the efficiency of the fermentation can preferably be evaluated by using the following formula:
  • Theoretical volume of alcohol that could be produced Interrupting the fermentation can be carried out by separating the yeast from the unrefined alcohol.
  • unrefined alcohol is understood to be the product resulting from the fermented must that contains alcohol and impurities deriving from the fermentation process.
  • Separating the yeast can be achieved by methods known in the state of the art, such as centrifugation and induced flocculation.
  • the yeast separated from the unrefined alcohol can be treated with antibiotics and diluted, to be used in a new fermentation, which may be subsequent or not.
  • the unrefined alcohol obtained can then be distilled to obtain more concentrated ethanol, in the form of hydrated alcohol, which can then be used in the production of anhydrate ethyl alcohol.
  • the whole process should be carried out in an environment free of potential contaminants, principally those bacteria capable of interacting with the yeast causing undesirable flocculation, which will reduce the efficiency of the conversion of sugars into alcohol, thus impairing the productivity of the process.
  • Decontamination of the yeast culture can be obtained by the final concentration of ethanol itself or by adding bactericides and antibiotics to said culture.

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biotechnology (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
PCT/BR2008/000357 2007-11-26 2008-11-26 Production of ethanol from algae WO2009067771A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
BRPI0819746A BRPI0819746A8 (pt) 2007-11-26 2008-11-26 processo para obtenção de etanol a partir de algas

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BRPI0704200-0A BRPI0704200A2 (pt) 2007-11-26 2007-11-26 processo para obtenção de etanol a partir de algas
BRPI0704200-0 2007-11-26

Publications (1)

Publication Number Publication Date
WO2009067771A1 true WO2009067771A1 (en) 2009-06-04

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BR (2) BRPI0704200A2 (pt)
WO (1) WO2009067771A1 (pt)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011027360A1 (en) * 2009-09-07 2011-03-10 Council Of Scientific & Industrial Research (An Indian Registered Body Incorporated Under The Registration Of Societies Act (Act Xxxi Of 1860) A process for integrated production of ethanol and seaweed sap from kappaphycus alvarezii
WO2012085689A1 (es) * 2010-12-23 2012-06-28 Ecopetrol S.A. Proceso mejorado de obtencion de azucares fermentables a partir de microalgas y macroalgas
WO2013121365A1 (en) * 2012-02-14 2013-08-22 Seambio Fuel Limited Methods and systems for cultivation of microalgae
WO2016085545A1 (en) * 2014-11-26 2016-06-02 River Road Research, Inc. Method for converting food waste and other biological waste into invertebrate feed
US9528656B1 (en) * 2013-10-14 2016-12-27 Arrowhead Center, Inc. Elastomeric, hydrogen-resistant biopolymer and its use in oil and gas refining, and in the storage and transport of hydrogen gas
CN107130002A (zh) * 2017-05-22 2017-09-05 中国水产科学研究院南海水产研究所 一种电场和微波耦合强化海藻厌氧发酵制取甲烷的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB119030A (en) * 1919-05-14 1920-05-14 Erik Christian Bayer A Process for the Production of Alcohol and Yeast from Sea-weed.
GB171479A (en) * 1920-08-16 1921-11-16 William Richard Walkey Improvements in or relating to the preparation of alcohol
WO2008105618A1 (en) * 2007-02-26 2008-09-04 Korea Institute Of Industrial Technology Method of producing biofuel using sea algae

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB119030A (en) * 1919-05-14 1920-05-14 Erik Christian Bayer A Process for the Production of Alcohol and Yeast from Sea-weed.
GB171479A (en) * 1920-08-16 1921-11-16 William Richard Walkey Improvements in or relating to the preparation of alcohol
WO2008105618A1 (en) * 2007-02-26 2008-09-04 Korea Institute Of Industrial Technology Method of producing biofuel using sea algae

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8969056B2 (en) 2009-09-07 2015-03-03 Council Of Scientific And Industrial Research Process for integrated production of ethanol and seaweed sap from Kappaphycus alverezii
CN102597251A (zh) * 2009-09-07 2012-07-18 科学与工业研究委员会 用于由长心卡帕藻集成生产乙醇和海藻液的方法
JP2013503650A (ja) * 2009-09-07 2013-02-04 カウンスィル オブ サイエンティフィック アンド インダストリアル リサーチ Kappaphycusalvarezii(カラギナン原藻)から抽出したエタノール及び海藻樹液の統合生産プロセス
CN102597251B (zh) * 2009-09-07 2014-01-29 科学与工业研究委员会 用于由长心卡帕藻集成生产乙醇和海藻液的方法
WO2011027360A1 (en) * 2009-09-07 2011-03-10 Council Of Scientific & Industrial Research (An Indian Registered Body Incorporated Under The Registration Of Societies Act (Act Xxxi Of 1860) A process for integrated production of ethanol and seaweed sap from kappaphycus alvarezii
WO2012085689A1 (es) * 2010-12-23 2012-06-28 Ecopetrol S.A. Proceso mejorado de obtencion de azucares fermentables a partir de microalgas y macroalgas
WO2013121365A1 (en) * 2012-02-14 2013-08-22 Seambio Fuel Limited Methods and systems for cultivation of microalgae
US9528656B1 (en) * 2013-10-14 2016-12-27 Arrowhead Center, Inc. Elastomeric, hydrogen-resistant biopolymer and its use in oil and gas refining, and in the storage and transport of hydrogen gas
US9914787B2 (en) 2013-10-14 2018-03-13 Arrowhead Center, Inc. Elastomeric, hydrogen-resistant biopolymer and its use in oil and gas and hydrogen gas piping and transportation
WO2016085545A1 (en) * 2014-11-26 2016-06-02 River Road Research, Inc. Method for converting food waste and other biological waste into invertebrate feed
US10588331B2 (en) 2014-11-26 2020-03-17 River Road Research, Inc. Method for converting food waste and other biological waste into invertebrate feed
CN107130002A (zh) * 2017-05-22 2017-09-05 中国水产科学研究院南海水产研究所 一种电场和微波耦合强化海藻厌氧发酵制取甲烷的方法
CN107130002B (zh) * 2017-05-22 2021-05-25 中国水产科学研究院南海水产研究所 一种电场和微波耦合强化海藻厌氧发酵制取甲烷的方法

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Publication number Publication date
BRPI0819746A2 (pt) 2014-11-04
BRPI0819746A8 (pt) 2019-01-02
BRPI0704200A2 (pt) 2010-08-03

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