• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    METHOD FOR PRODUCING 2,3-BUTANEDIOL By subjecting a 2,3-butanediol culture liquid produced by microbial fermentation to a nanofiltration membrane treatment and ion exchange treatment (Step A) and then adding an alkaline substance and by performing distillation (Step B), 2,3-butanediol which has a high purity and remarkably low pigmentation degree can be obtained.
    公开号:BR112014008195B1
    申请号:R112014008195-6
    申请日:2012-10-12
    公开日:2021-04-20
    发明作者:Kenji Kawamura；Izumi MORITA；Katsushige Yamada；Kyohei Isobe；Masateru Ito；Satoshi Sakami
    申请人:Toray Industries, Inc；
    IPC主号:
    专利说明:

    FIELD OF TECHNIQUE
    [001] The present invention relates to a method to obtain highly pure 2,3-butanediol which shows no pigmentation from a 2,3-butanediol fermentation liquid by a simple method. PRIOR TECHNIQUE
    [002] 2,3-Butanediol (BDO) is a useful compound that has 3 types of optical isomers and is used as an intermediate material for pharmaceuticals and cosmetics; and as a material for dyeing, perfumes, liquid crystals, insecticides, softening agents, explosives, plasticizers and the like. Industrially, it is produced through a method in which 2-butene oxide is hydrolyzed in an aqueous solution of perchloric acid. On the other hand, in recent years, in order to solve the problems of depletion of oil sources and global warming, it is necessary to achieve a recycling-oriented and sustainable society. Furthermore, in the chemical industry, the exchange of petroleum materials for materials derived from biomass is being intensively studied. In particular, the microbial fermentation of 2,3-butanediol is attracting attention. It has been reported that 2,3-butanediol is converted to methyl ethyl ketone, which is a general purpose solvent, by chemical conversion (Non-Patent Document 1) and that 2,3-butanediol is converted to 1,3-butadiene by acetylation followed by elimination of acetic acid (Non-Patent Document 2). In particular, the production techniques for 1,3-butadiene are very important as 1,3-butadiene is a starting substance that enables the synthesis of many types of compounds, such as hexamethylenediamine, adipic acid and 1,4-butanediol and the establishment of these techniques can replace existing petroleum-derived synthetic resins with biomass-derived resins.
    [003] Examples of generally known microorganisms that produce 2,3-butanediol include Klebsiella Pneumoniae, Klebsiella axytoca and Paenibacillus polymyxa and 2,3-butanediol is produced by fermentation by these microorganisms. However, fermentation liquids contain not only 2,3-butanediol but also various impurities such as residual medium components and metabolic by-products of microorganisms. Particularly sugars as nutrient sources for microorganisms; organic acids and proteins as their metabolic products; and the like; are reported to generate color impurities by heat (Non-Patent Document 3). Therefore, application of the fermentation liquid to the uses described above requires high-level purification of 2,3-butanediol.
    [004] As a method to purify 2,3-butanediol, Patent Document 1 discloses a purification method in which a diol, such as 2,3-butanediol, is purified by combining nanofiltration membrane treatment and distillation . As another method for purifying a diol, Patent Document 2 discloses a method in which the pH of a 1,3-propanediol fermentation liquid is adjusted to not less than 7 and the resulting fermentation liquid is then subjected to a separation step , to reduce 1,3-propanediol staining. As a method to produce a highly pure diol, Patent Document 3 discloses a method to produce 1,3-propanediol by microfiltration, ultrafiltration, nanofiltration, ion exchange; distillation and then hydrogenation reduction treatment. PRIOR ART DOCUMENTS [Patent Documents] [Patent Document 1] JP 2010-150248 A [Patent Document 2] US 6,361,983 B [Patent Document 3] Patent Application Open to Public Inspection Translated n° JP 2007- 502325 [Non-Patent Document 1] AN Bourns, The Catalytic Action of Aluminum Silicates, Canadian J. Res. (1947) [Non-Patent Document 2] Nathan Shlechter, Pyrolysis of 2;3-Butylene Glycol Diacetate to Butadiene, Indu. Chem Eng. 905 (1945) [Non-Patent Document 3] Yoshiyuki Matsuo, Mode of Overdecomposition of Glucose by Acid: Journal of fermentation technology 39, 5, 256 to 262 (1961) BRIEF DESCRIPTION OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION
    [005] In the method described above to purify 2,3-butanediol, ie; in the purification of a 2,3-butanediol fermentation liquid by treatment with nanofiltration membrane followed by distillation, highly pure 2,3-butanediol can be obtained, but a problem still remains that the distillation step causes remarkable coloration of the 2 ,3-butanediol. In view of this, the present invention aims to provide a method for purifying a 2,3-butanediol fermentation liquid by distillation, wherein 2,3-butanediol is separated/recovered while 2,3-butanediol coloration is prevented. MEANS TO SOLVE PROBLEMS
    [006] As a result of an intensive study to solve the above problem, the present inventors revealed that by subjecting a 2,3-butanediol fermentation liquid to treatment with nanofiltration membrane and ion exchange treatment and then adding an alkaline substance. and by carrying out distillation, 2,3-butanediol which has a high purity and remarkably low degree of pigmentation can be obtained, thus completing the present invention.
    [007] That is, the present invention consists of (1) to (6) below. (1) A method for producing 2,3-butanediol, wherein the method comprises the steps of submitting a 2,3-butanediol culture liquid produced by microbial fermentation to nanofiltration membrane treatment and ion exchange treatment ( Step A) and then adding an alkaline substance and performing distillation (Step B). (2) The method for producing 2,3-butanediol, according to (1), wherein the amount of said alkaline substance added is not greater than 10% by mol in relation to the amount (number of moles) of 2.3 -butanediol. (3) The method for producing 2,3-butanediol according to (1) or (2), wherein said alkaline substance is at least one selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides , alkali metal carbonates, alkali metal hydrogen carbonates and alkaline earth metal carbonates. (4) The method for producing 2,3-butanediol according to any one of (1) to (3), wherein the alkaline substance is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate and calcium carbonate. (5) The method for producing 2,3-butanediol according to any one of (1) to (4), which further comprises concentrating, prior to said Step B, the 2,3-butanediol solution obtained in the said Step A (Step C). (6) The method for producing 2,3-butanediol according to (5), wherein Step C is a step of filtering a 2,3-butanediol solution through a reverse osmosis membrane. EFFECT OF THE INVENTION
    [008] Through the present invention, in a method to produce 2,3-butanediol by microbial fermentation, highly pure and colorless 2,3-butanediol can be obtained by a much simpler method than in the prior art. BRIEF DESCRIPTION OF THE DRAWINGS
    [009] Figure 1 is a schematic diagram illustrating an embodiment of the membrane separation apparatus used in the present invention. BEST MODE FOR CARRYING OUT THE INVENTION (2,3-Butanediol Culture Liquid)
    [010] The present invention is characterized by the fact that the 2,3-butanediol is produced by microbial fermentation. In terms of microorganisms that use sugars as carbon sources for fermentation, Klebsiella pneumoniae, Klebsiella oxymora and Paenibacillus polymyxa are present in the natural environment and are capable of producing (2R,3R)-threo and (2S;3R)-meso isomers. isomers. Furthermore, the genus Ochribactrium as shown in WO2007/094178 is known to selectively produce (2S,3S)-threo isomers. Furthermore, as a microorganism that is capable of fermentation using carbon monoxide as a carbon source, Clostridium autoethanogenum is known as described in WO2009/151342; and 2,3-butanediol produced from a microorganism may be a subject of the present invention.
    [011] Alternatively, the method may be the method using a microorganism that has been given a 2,3-butanediol production capability by genetic recombination; and specific examples of such a method include the method described in Applied Microbiolgy and Biotechnology, Volume 87; Number 6, 2001 to 2009 (2010).
    [012] As described above, 2,3-butanediol produced by microbial fermentation has 3 types of optical isomers. The object of production by the present invention can be any one of the isomers or it can be a mixture of a plurality of the isomers. As each isomer can produce a by-product depending on its use and use, the 2,3-butanediol preferably has a high optical cavity. 2,3-Butanediol that has a high optical cavity can be obtained by using, as described above, a microorganism that produces 2,3-butanediol that has a high optical cavity.
    [013] The culture liquid in the present invention means a liquid obtained as a result of the proliferation of a micro-organism or cells cultivated in a fermentation raw material. The composition of the fermentation feedstock added to the culture liquid can be appropriately altered from the composition of the fermentation feedstock used at the beginning of the culture, so that the productivity of the 2,3-butanediol of interest increases.
    [014] Examples of the carbon source in the fermentation feedstock include sugars such as glucose, fructose, sucrose, xylose, arabinose, galactose, mannose and starch. Furthermore, sugars can be commercially available purified products; degraded products from recycled sources or biomass; or degraded products of cellulose, hemicellulose or lignin materials, prepared by chemical or biological treatment. In such cases, impurities which inhibit fermentative production by microorganisms are preferably reduced by purification. Furthermore, in the cases of Clostridium autoethanogenum described above, carbon monoxide is used as a carbon source. Carbon monoxide can be obtained from incomplete combustion of coal, oil or a source of biomass; it can be recovered from gas generated in a coke oven or simulated in a steel mill; or it can be produced by gasification from a biomass source.
    [015] Preferred examples of the nitrogen source in the fermentation feedstock include ammonia gas, aqueous ammonia, ammonium salts, urea and nitrates, which are low cost inorganic nitrogen sources; and oil tarts, soybean hydrolysates, casein digestion, meat extracts, yeast extracts, peptone, amino acids and vitamins, which are sources of organic nitrogen.
    [016] Examples of inorganic salts can be added as appropriate to the fermentation feedstock include phosphates, magnesium salts, calcium salts, iron salts and manganese salts. In cases where the microorganism used in the present invention requires a specific nutrient (eg, amino acid) for its proliferation, the nutrient itself, or a natural product containing the same, may be added. An anti-formation agent can also be used as required.
    [017] The culture conditions for production of 2,3-butanediol can be selected so that the conditions are ideal for the microorganism used. For example, in terms of the aeration condition during cropping, the crop can be either aerobic crop or anaerobic crop. In view of the increased productivity of 2,3-bitanediol, microaerobic culture is preferred. The pH during cultivation is preferably within the range of 4 to 8. The pH of the culture liquid is adjusted to a predetermined value within the range described above with the use of an alkaline substance and an acidic substance. Preferable examples of the basic substance used include calcium hydroxide, calcium carbonate, sodium hydroxide, potassium hydroxide, ammonia gas and aqueous ammonia. Preferable examples of the acidic substance used include sulfuric acid, hydrochloric acid, acetic acid, carbon dioxide and soda water. The culture temperature is preferably within the range of 20 to 40°C.
    [018] The method for cultivating a microorganism is not limited as long as it is a method known to those skilled in the art and may be either batch culture or continuous culture. In view of productivity, continuous culture is preferred as it is performed while fresh cells capable of producing fermentation proliferate. For example, in terms of the continuous culture method, batch culture or fed-batch culture can be performed in the initial stage of the culture to increase the microbial concentration, followed by continuous culture start (removal) or the cells can be inoculated to a high concentration and continuous culture can be performed from the beginning of the culture. It is possible to start supplying the raw material medium and removing the culture at appropriate timings. The timing to start supplying the raw material medium and the timing to start removing the culture are not necessarily the same. The supply of the raw material medium and the removal of the culture can be carried out either continuously or intermittently. The above-described nutrients required for cell proliferation can be added to the raw material medium to allow for continued cell proliferation. The concentration of the microorganism or cells cultured in the culture liquid is preferably kept within a range that does not cause the death of the microorganism or cells cultured at a high rate due to the inappropriate environment of the culture medium for the proliferation of the organism or cultured cells in order to achieve efficient production. For example, keeping the concentration at not less than 5 g/l in terms of dry weight, good production efficiency can be obtained. The continuous culture operation is usually preferably carried out in a single fermenter in view of culture control. However, the number of fermenters is not restricted as long as continuous culture is performed to produce the product while allowing cell proliferation. A plurality of fermenters can be used due, for example, to a small capacity of each fermenter. In that case, a high productivity of the fermentation product can be obtained by continuous culture with the use of the plurality of fermenters connected in parallel or in series through tubes.
    [019] The composition of the 2,3-butanediol culture liquid subjected to the last treatment with nanofiltration membrane and ion exchange treatment (Step A) is not limited and inorganic sugar(s) and/or salt(s)( s) used for the fermentation feedstock may be contained therein. Furthermore, even in cases where the culture liquid contains fermentation by-products such as organic acids, amino acids and/or furan compounds including furfural, high level purification is possible by the purification method of the present invention, so that the culture liquid can preferably be used. (Stage of Nanofiltration Membrane Treatment and Ion Exchange Treatment (Step A))
    [020] The present invention is characterized by the fact that the last described step of the distillation of 2,3-butanediol (Step B) is preceded by treatment with nanofiltration membrane and ion exchange treatment of the culture liquid of 2, 3-butanediol (Step A). This is due to the fact that, in cases where the 2,3-butanediol culture liquid is subjected to distillation without performing Step A, a large amount of still residue is produced to cause a noticeable decrease in the distillation yield.
    [021] As disclosed in JP 2010 150248 A, filtration of a solution containing 2,3-butanediol through a nanofiltration membrane allows efficient separation of the solution containing 2,3-butanediol through a nanofiltration membrane. efficient separation of 2,3-butanediol on permeate side and inorganic salts. Sugars and colored components on the feeding side. That is, nanofiltration membrane treatment means passing a solution containing 2,3-butanediol through a nanofiltration membrane and recovering the 2,3-butanediol from the permeate side.
    [022] Examples of nanofiltration membrane material include polymeric materials such as piperazine polyamide, polyamide, cellulose acetate, polyvinyl alcohol, polyimide and polyester and inorganic materials such as ceramic. A nanofiltration membrane is generally used as a spirally wound membrane element or a flat membrane or hollow fiber membrane. The nanofiltration membrane used in the present invention is preferably a spirally wound membrane element.
    [023] Specific examples of the preferred nanofiltration membrane element used in the present invention include "GEsepa", which is a cellulose acetate nanofiltration membrane manufactured by GE Osmonics; NF99 and NF99HF, which are nanofiltration membranes that have a functional layer composed of a polyamide, manufactured by Alfa-Laval; NF-45, NF-90, NF-200 and NF-400, which are nanofiltration membranes that have a functional layer composed of a cross-linked polyamide piperazine, manufactured by Filmtec Corporation; and SU-210, SU-220, SU-600, and SU-610, which are nanofiltration membrane elements manufactured by Toray Industries, Inc., containing UTC60 manufactured by the same manufacturer. Among these, the nanofiltration membrane element is most preferably NF99 or NF99HF, which are nanofiltration membranes that have a functional layer composed of a polyamide, manufactured by Alfa-Laval; NF-45, NF-90, NF-200 or NF-400, which are nanofiltration membranes that have a functional layer comprised of a cross-linked polyamide piperazine, manufactured by Filmtec Corporation; or SU-210, SU-220, SU-600, or SU-610, which are nanofiltration membrane modules manufactured by Toray Industries, Inc., containing UTC60 manufactured by the same manufacturer. The nanofiltration membrane element is preferably even larger SU-210, SU-220, SU-600 or SU-610, which are nanofiltration membrane elements manufactured by Toray Industries, Inc., containing UTC60 manufactured by the same manufacturer, which main component is a cross-linked polyamide piperazine.
    [024] Filtration through a nanofiltration membrane can be performed under pressure and the filtration pressure is preferably within the range of 0.1 MPa to 8 MPa. In cases where the filtration pressure is less than 0.1 MPa, the membrane permeation rate may be low, while in cases where the filtration pressure is greater than 8 MPa, the membrane may be damaged. In cases where the membrane is used at a filtration pressure of 0.5 MPa to 7 MPa, the membrane permeation flux is high, so the 2,3-butanediol fermentation liquid can be efficiently permeated and the possibility of damaging the membrane is small, which is more preferable. The membrane is especially preferably used at a filtration pressure of 1 MPa to 6 MPa.
    [025] The concentration of 2,3-butanediol that must be filtered through the nanofiltration membrane is not limited and the concentration is preferably high as a high concentration of 2,3-butanediol in the permeate allows for the reduction of energy needed for concentration and cost can then be reduced.
    [026] Ion exchange treatment is a method to remove ionic components from the 2,3-butanediol solution with the use of an ion exchanger. Examples of the ion exchanger include ion exchange resin, ion exchange membranes, ion exchange fibers, ion exchange papers, gel ion exchangers, liquid ion exchangers, zeolite, carbonaceous ion exchangers, and montmorillonite . In the present invention, treatment using an ion exchange resin is also preferably employed.
    [027] Ion exchange resins are classified depending on their functional groups into strong anion exchange resins, weak anion exchange resins, strong cation exchange resins, weak cation exchange resins, chelate exchange resins and the like. Examples of strong anion exchange resins include “Amberlite” IRA410J, IRA411 and IRA910CT, manufactured by Organo Corporation; and "DIAION" SA10A, SA12A, SA11A, NSA100, SA20A, SA21A, UBK510L, UBK530, UBK550, UBK535 and UBK555, manufactured by Mitsubishi Chemical Corporation. Examples of weak anion exchange resins include "Amberlite" ORA478RF. IRA67, IRA96SB, IRA98 and XE583, manufactured by Organo Corporation; and “DIAION” WA10, WA20, WA21J and WA30, manufactured by Mitsubishi Chemical Corporation. Examples of strong cation exchange resins include "Amberlite" IR120B, IR124, 200CT and 252, manufactured by Organo Corporation; and "DIAION" SK104, SK1B, SK110, SK112, PK208, PK212, PK216, PK218, PK220 and PK228, manufactured by Mitsubishi Chemical Corporation. Examples of weak cation exchange resins include "Amberlite" FPC3500 and IRC76, manufactured by Organo Corporation; and "DIAION" WK10, WK11, WK100 and WK40L, manufactured by Mitsubishi Chemical Corporation.
    [028] In the present invention, the method is preferably desalination with the use of both anion exchange resin(s) and cation exchange resin(s) more preferably desalination with the use of: exchange resin(s) of strong anion(s) and strong cation exchange resin(s) in view of removal of various ions. The anion exchange resin is regenerated with a dilute aqueous alkaline solution of sodium hydroxide or the like and used as the OH type. The cation exchange resin is preferably regenerated with an acidic aqueous hydrochloric acid solution or the like and used as the H type. The desalination method with ion exchange resin(s) can be a batch method or column method and it is not limited as long as efficient desalination is possible with it. The column method is preferably employed as it allows for repeated use. The flow rate through the ion exchange resin is usually controlled on the basis of the SV (space velocity) and the SV is preferably 2 to 50. SV is most preferably 2 to 19 in order to achieve higher purity. The ion exchange resin can be in the form of a type such as a porous type, highly porous type, MR type or the like, which are commercially available and an ion exchange resin having an ideal shape can be selected depending on the quality of the solution.
    [029] The order of treatment with nanofiltration membrane and ion exchange treatment in Step A is not limited. Preferably, the 2,3-butanediol culture liquid is subjected to treatment with a nanofiltration membrane and the 2,3-butanediol solution containing reduced inorganic salts obtained from the permeate side is then subjected to the ion exchange treatment. Therefore, inorganic salts and organic acids that partially pass through the nanofiltration membrane can be removed by the ion exchange resin to increase the rate of removal of inorganic salts. (Distillation: Step (Step B))
    [030] The present invention is characterized by the fact that Step A is followed by the addition of an alkaline substance and distillation (Step B). By Step B, highly pure/colorless 2,3-butanediol can be obtained.
    [031] Preferred examples of the alkaline substance include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and cesium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide; calcium hydroxide and barium hydroxide; alkali metal carbonates and alkali hydrogen carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate; potassium hydrogen carbonate and cesium carbonate, alkaline earth metal carbonates such as basic magnesium carbonate and calcium carbonate; and alkali metal carboxylates such as sodium acetate and potassium acetate. Among these, alkali metal hydroxides, carbonates and hydrogen carbonates; and alkaline earth metal hydroxides and carbonates; and alkaline earth metal hydroxides and carbonates are preferred and sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, calcium hydroxide and calcium carbonate are especially preferred in view of cost and effectiveness of the treatment. Each of these alkaline substances can be added as such, as a solid or can be added as an aqueous solution with which the amount of the added substance can be easily controlled. Each of these alkaline substances can be used alone or a plurality of these can be used.
    [032] The amount of alkaline substance added is not limited. As, in cases where the amount of alkaline substance added is very mild, the distillation yield in the distillation may decrease, the amount is preferably not greater than 10% by mol, more preferably not greater than 5% by mol. mol, preferably even greater, not greater than 3% by mol relative to the amount (number of moles) of 2,3-butanediol. In cases of batch distillation, the amount of alkaline substance added can be determined by calculating the number of moles of 2,3-butanediol based on its concentration. The lower limit of the amount of alkaline substance added is not limited as long as the effect of the present invention is exercised and the amount is preferably not less than 0.001% by mol, more preferably not less than 0.01% by mol , preferably even greater, not less than 0.1 mol%.
    [033] In cases of continuous distillation, the alkaline substance can be added after calculating the flux of the alkali metal to be added [mol/h] based on the flux of 2,3-butanediol per unit time [mol/h]. Although the alkaline substance can be continuously fed to the 2,3-butanediol channel, a feed/mix tank is preferably provided in view of the uniform addition of the substance. US 6,361,983 B and JP 2004-352713 A disclose techniques in which an alkaline substance is added so that the pH of a 1,3-butanediol solution does not fall below 7 to suppress coloration. However, in the present invention, it has been revealed that pH does not contribute to color suppression and even a pH not greater than 7 can produce the effect.
    [034] Upon addition of the alkaline substance, the 2,3-butanediol solution is preferably stirred enough. Although the action of the alkaline substance is still unknown, it is preferable to stir the 2,3-butanediol solution to allow the reaction to proceed long enough as the 2,3-butanediol solution is highly viscous. In this process, the solution can be heated as heating has a viscosity-lowering and reaction-promoting effect. The temperature is preferably not higher than 150 °C in order to prevent the generation of impurities at a high temperature.
    [035] In cases where the alkaline substance is added, it is preferable to concentrate the 2,3-butanediol solution in advance in order to increase the effect (Step C). The concentration of the concentrated 2,3-butanediol is not limited and preferably not less than 50% by weight due to the distillation load. As a small amount of water is preferably contained for better solubility of the alkaline substance; the concentration is preferably less than 99% by weight.
    [036] The method for concentrating the 2,3-butanediol solution can be a general method known to those skilled in the art and examples of the method preferably applied include method using a reverse osmosis membrane, concentration under heat with use of an evaporator and distillation. A method using a reverse osmosis membrane is preferably applied.
    [037] In the method using a reverse osmosis membrane, a 2,3-butanediol solution is filtered through a reverse osmosis membrane to allow water to permeate on the permeate side while the 2,3-butanediol is retained and concentrated on the feed side. Examples of the reverse osmosis membrane preferably used in the present invention include composite membranes which have cellulose acetate polymer as a functional layer (hereinafter referred to as cellulose acetate reverse osmosis membranes) and composite membranes which have a polyamide functional layer (hereinafter referred to as polyamide reverse osmosis membranes). Here, examples of the cellulose acetate polymer include polymers prepared with organic acid esters of cellulose, such as cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose propionate and cellulose butyrate. Each of these can be used alone or two or more of these can be used as a blend or a blended ester. Examples of the polyamide include linear polymers and crosslinked polymers comprised of aliphatic and/or aromatic diamine monomers. Examples of the shape of the membrane that can be used as appropriate include a flat membrane, spiral wound membrane and hollow fiber membrane.
    [038] Specific examples of the reverse osmosis membrane used in the present invention include polyamide reverse osmosis membrane modules manufactured by Toray Industries, Inc., such as low pressure type modules SU-710, SU-720, SU- 720F, SU-710L, SU-720L, SU-720LF, SU-720R, SU-710P and SU,720P, as well as SU-810, SU-820, SU-820L and SU-820FA high pressure type modules; cellulose acetate reverse osmosis membranes manufactured by the same manufacturer, SC-L100R, SC-L200g, SC-1100, SC-1200, SC-2100, SC-2200, SC-3100, SC-3200, SC-8100 and SC -8200; NTR-759HR, NTR-729HF, NTR-70SWC, ES10-D, ES20-D, ES20-U, ES15-D, ES15-U and LF10-D, manufactured by Nitto Denko Corporation; RO98pHt, RO99, HR98PP and CE4040C-30SD, manufactured by Alfa-Laval; "GE Sepa"' manufactured by GE; and BW30-4040, TW30-4040, XLE-4040, LP-4040, LE-4040, SW30-4040 and SW30HRLE-4040, manufactured by FilmTee Corporation.
    [039] In the present invention, the concentration with a reverse osmosis membrane is performed under pressure. The filtration pressure is preferably within the range of 1 MPa to 8 MPa since, in cases where the filtration pressure is less than 1 MPa, the membrane permeation rate can be low, while in cases where filtration pressure is greater than 8 MPa, membrane can be damaged. In cases where the filtration pressure is within the range of 1 MPa to 7 MPa, the membrane permeation flux is high, so that the 2,3-butanediol solution can be efficiently concentrated. The filtration pressure is preferably maximum within the range of 2 MPa to 6 MPa due to the reduction in the possibility of damage to the membrane. In cases of a solution of 2,3-butanediol at a low concentration, a method that uses a reverse osmosis membrane is preferred due to cost.
    [040] The distillation method is not limited and can be simple distillation, precision distillation, atmospheric distillation or reduced pressure distillation which is generally applied. A thin-film distillation apparatus, tray distillation apparatus, compact distillation apparatus or the like can be used. Either a batch method or a continuous method can be applied to the present invention. Distillation under reduced pressure is especially preferred as it can lower the boiling point and therefore can suppress the generation of impurities. More specifically, the heating temperature is preferably 60°C to 150°C. In cases where the heating temperature is less than 60 °C, an extremely low degree of pressure is required, so maintenance of the device is very difficult on an industrial level. On the other hand, in cases where the heating temperature is greater than 150 °C, the decomposition of sugars and the like remaining in the 2,3-butanediol solution in small amounts occurs, causing underproduction of colored substances, which is not preferable . Therefore, the degree of pressure reduction is preferably controlled so that 2,3-butanediol is distilled within the heating temperature range described above.
    [041] Furthermore, in order to reduce the load on the apparatus, crude distillation can be performed before adding the alkaline substance. Crude distillation is carried out before the main distillation described above. The crude distillation method is not limited and simple distillation is generally preferred due to cost. Through the main, the charge in this distillation apparatus can be reduced and the purity of 2,3-butanediol can be increased. Therefore, crude distillation can be carried out before adding the alkaline substance and carrying out the main distillation above.
    [042] The purity of the 2,3-butanediol produced by the present invention is evaluated based on several indices. Examples of indices for the staining degree of 2,3-butanediol include Hazen color number (APHA) which enables highly sensitive evaluation of unknown substances causing staining. In cases where APHA is not greater than 10, staining can hardly be found by visual inspection and in cases where APHA is not greater than 5,2,3-butanediol it is even purer and heat staining has less likely to occur. APHA can be measured by a commercially available method defined by JIS K0071-1, or with a commercially available measurement device. In the present invention, colorless 2,3-butanediol with an APHA not greater than 5 can be obtained.
    [043] Examples of methods for measuring impurities other than colored substances include combinations of gas chromatography (GC) purity measurement, UV detection purity measurement using high performance liquid chromatography (HPLC) and/or the like. As these are based on the evaluation of the ratio of the area of 2,3-butanediol to the total area of detected peaks, a higher ratio means a higher purity of 2,3-butanediol. In purity measurement by measuring electrical conductivity, a lower electrical conductivity means a higher purity of 2,3-butanediol as pure 2,3-butanediol has no electrical conductivity. EXAMPLES
    [044] The present invention is described below in more detail by way of Examples, but the present invention is not limited to the Examples below. (Examples 1 to 3 and Comparative Example 1: Nanofiltration Membrane Treatment and Ion Exchange Treatment Followed by Alkali Addition and Distillation) <Preparation of 2,3-Butanediol Fermentation Liquid>
    [045] As the 2,3-butanediol fermentation microorganism, Paenibacillus palymyxa ATCC12321 was used. The microorganism was inoculated into 5 ml of the medium shown in Table 1 and cultured with shaking at 30 °C for 24 hours. The resultant was similarly inoculated into 50 ml of the medium shown in Table 1 and the preculture was carried out under the same conditions. The resulting preculture was inoculated into 4l of the medium shown in Table 2 and the main culture was carried out. The culture was carried out at a temperature of 30°C, aeration rate of 0.5 vvm and agitation rate of 200 rpm, and neutralization was carried out with sodium hydroxide and sulfuric acid so that the pH becomes 6.5.


    [046] Fermentation progress was judged based on changes in 2,3-butanediol concentration and glucose concentration. Each concentration was measured under the following HPLC conditions. (2,3-Butanediol Concentration Measurement) Column: Shodex Sugar SH1011 (manufactured by Showa Danko KK) Column temperature: 65 °C Mobile phase: 0.05M aqueous sulfuric acid solution, 0.6 ml/min . Detection: RI (Glucose Concentration Measurement) Column: Asahipak NH2P50 4E (manufactured by Showa Denko K.K.) Column temperature: 30 °C Mobile phase: water:acetonitrile = 1:3, 0.6 ml/min. Detection: IR
    [047] In this study, the fermentation of 2,3-butanediol reached saturation on Day 3 after the start of culture. The 2,3-butanediol concentration at that time was 16 g/l and the glucose concentration was 0.9 g/l. The obtained 2,3-butanediol culture liquid was filtered through a microfiltration membrane (manufactured by Toray Industries, Inc.) to remove bacterial cells. This fermentation was repeated 4 times to obtain 16 l of a 2,3-butanediol culture liquid (256 g of 2,3-butanediol). <Purification of 2,3-Butanediol Culture Liquid with Nanofiltration Membrane>
    [048] The culture liquid obtained by the fermentation described above was purified using the membrane separation apparatus shown in Figure 1. As the nanofiltration membrane, a spiral wound membrane element SU-610 (manufactured by Toray Industries, Inc.) was used. The 2,3-butanediol fermentation liquid described above was fed to a supply tank and purification by the nanofiltration membrane was carried out by operation at a supply flow rate of 25 l/min., supply liquid pressure of 3 MPa and supply liquid temperature of 20 °C. The permeate obtained was a clear solution of 2,3-butanediol free of colored components and most of the inorganic salt components could be removed, although some components, such as potassium ions, could not be removed completely. Conditions for measuring ion concentrations by ion chromatography are shown below. The results of this analysis are shown in Table 3. (Anion Concentration Measurement) Column: AS4A-SC (manufactured by DIONEX) Column temperature: 35 °C Eluent: 1.8 mM sodium carbonate/a1 sodium hydrogen carbonate 7 mM Detection: electrical conductivity (Cation Concentration Measurement) Column: CS12A (manufactured by DIONEX) Column temperature: 35 °C Eluent: 20 mM methanesulfonic acid. Detection: electrical conductivity TABLE 3
    <2,3-Butanediol Fermentation Liquid Ion Exchange Purification>
    [049] The permeate obtained by treatment with nanofiltration membrane was subjected to removal of residual ions by ion exchange treatment. An IRA120J strong anion exchange resin (manufactured by Organo Corporation) and an IR410 strong cation exchange resin (manufactured by Organo Corporation) that were regenerated with 1M sodium hydroxide or 1M hydrochloric acid in OH type or type H, respectively, were used. The amount of resin was calculated so that the total amount of inorganic salts and organic acids was the same as the exchange capacity of the ion exchange resin. The columns were filled with the ion exchange resins and the permeate above was passed through the anion exchange resin and then through the cation exchange resin at a SV flow rate of 5. <Purification with Substance Addition Distillation Alkaline>
    [050] The 2,3-butanediol solution after the ion exchange treatment was subjected to dewatering with an MF-10 film evaporator (manufactured by Tokyo Rikakikai). At that time, the water was allowed to evaporate at a degree of pressure reduction of 30 hPa and a heating temperature of 60°C. To 50 g of the resulting concentrated 2,3-butanediol solution, 0.3 g (1.5% by mol relative to the amount (number of moles) of 2,3-butanediol; Example 1), 0.7 g ( 3% by mol with respect to the amount (number of moles) of 2,3-butanediol; Example 2), 2.2 g (10% by mol with respect to the amount (number of moles) of 2,3-butanediol; Example 3) or 4.4 g (20 mol% with respect to the amount (number of moles) of 2,3-butanediol; Example 4) of sodium hydroxide were used and the resulting mixture was sufficiently stirred to the sodium hydroxide be dissolved. Each resulting solution was distilled under reduced pressure (0.67 kPa (5 mmHg)) to obtain purified 2,3-butanediol. The degree of color (APHA), GC purity, distillation yield and electrical conductivity of 2,3-butanediol after distillation were determined by the following measurement methods. (Degree of Coloration (APHA))
    [051] The 2,3-butanediol after distillation was diluted 6 times to prepare 16.67% by weight aqueous solution and the color number of APHA unit was analyzed using a colorimeter (manufactured by Nippon Denshoku Industries Co. ., Ltd.). (GC Purity)
    [052] The 2,3-butanediol after distillation was analyzed by gas chromatography (GC; manufactured by Shimadzu Corporation) and the GC purity was calculated according to Equation I from the peak area ratio of 2,3- butanediol in the total detected peak area. GC purity (%) = 100 x (2,3-BDO peak area) / (total detected peak area) ...Equation 1)
    [053] The analysis conditions for gas chromatography were as follows: Column: RT-BDEXM (0.25 mm x 30 m, manufactured by Restek) Column temperature: 75 °C Vaporization chamber, detector temperature: 230 °C Carrier Gas: He Linear Velocity: 35 cm/s Detection: Flame Ionization Detector (FID) (Distillation Yield)
    [054] The distillation yield was calculated according to Equation 2 from the concentration of 2,3-butanediol as measured by the HPLC Analysis above, the amount of 2,3-butanediol fed before the distillation as calculated from the amount of fed liquid, the amount of distillate after distillation and the recovery of 2,3-butanediol as calculated from the GC purity described above.
    [055] Distillation yield (%) = 100 x {(amount of distillate after distillation), x (GC purity)} / {(concentration of 2,3-BDO before distillation) x (amount of liquid fed before distillation distillation)} ... (Example 2). (Electric conductivity)
    [056] In a multi-function water quality meter (MM-60R, manufactured by DKK-TOA Corporation) equipped with an electrical conductivity cell for low electrical conductivity (CT-57101C, manufactured by DKK-TOA Corporation), 16 .67% by weight of aqueous 2,3-butanediol composition solution was immersed at 23°C and electrical conductivity was measured. The detected measured value was multiplied by 6 to determine the electrical conductivity of 2,3-butanediol.
    [057] The results are shown in Table 4. The results obtained by distillation without addition of sodium hydroxide are also shown as Comparative Example 1. TABLE 4

    [057] As shown in Table 4, it was revealed that when the nanofiltration membrane treatment and the ion exchange treatment were performed, the addition of the alkaline substance allowed the removal of colored impurities. Furthermore, as can be seen from the improved GC purities and lower electrical conductivities, these treatments were also shown to be effective in removing other impurities. (Comparative Example 2: Nanofiltration Membrane Treatment Followed by Alkali Addition and Distillation)
    [058] Similar to Example 1, a 2,3-butanediol culture liquid was prepared by the method described above. Bacterial cells were removed by microfiltration in the same manner and the nanofiltration membrane treatment with the SU-610 nanofiltration membrane (Toray Industries, Inc.) was performed using the membrane purification apparatus shown in Figure 1. The resultant was subjected to a thin film concentration by the method described in Example 1, and 0.7 g of sodium hydroxide, which corresponded to 3% by mol, was added to 50 g of 2,3-butanediol, followed by stirring the mixture. and then performing the distillation under reduced pressure (0.67 kPa (5 mmHg)) to obtain purified 2,3-butanediol. The results of the analysis of this purified 2,3-butanediol are shown in Table 5. (Comparative Example 3: Ion Exchange Treatment Followed by Alkali Addition and Distillation)
    [059] Similar to Example 1, a 2,3-butanediol culture liquid was prepared by the method described above. Bacterial cells were removed by microtitration in the same way and ion exchange was performed by the method described above. At this stage, the amount of the ion exchange resin was 10 times greater than that in Example 1, so this process appeared to be costly. The resultant was subjected to a thin film concentration by the method described in Example 1, and 0.7 g of sodium hydroxide, which corresponded to 3% by mol, was added to 50 g of 2,3-butanediol, followed by stirring of the resulting mixture and then performing distillation under reduced pressure (0.67 kPa (5 mmHg)) to obtain purified 2,3-butanediol. The results of the analysis of this purified 2,3-butanediol are shown in Table 5. TABLE 5

    [060] In view of the results shown in Table 5, it was shown that impurities, such as colored components, cannot be removed by treatment with nanofiltration membrane or ion exchange treatment only even if an alkaline substance was added for distillation and that the distillation yield is low in such a case. (Examples 5 and 6: Effect of Distillation by Addition of Calcium Hydroxide and Calcium Carbonate)
    [061] Similar to Example 1, a 2,3-butanediol culture liquid was prepared and microfiltration membrane treatment and nanofiltration membrane treatment were performed followed by ion exchange treatment and thin film concentration to obtain a solution of purified 2,3-butanediol. Calcium hydroxide or calcium carbonate was added to 50 g of this 3% mol% 2,3-butanediol and the resulting mixture was stirred sufficiently. At that time, undissolved calcium hydroxide or calcium carbonate powder was found due to its low solubility in water, but the mixture was subjected to distillation as such. The distillation was carried out in the same manner as in Example 1. The results on the obtained purified 2,3-butanediol are shown in Table 6. TABLE 6

    [062] From these results, it has been shown that any one of sodium hydroxide, calcium hydroxide and calcium carbonate produces a similar result as the alkaline substance. (Reference Examples 1 to 4: Purification of 2,3-Butanediol and 1,3-Propanediol Model Fermentation Liquids) <Preparation of 2,3-Butanediol and 1,3-Propanediol Model Fermentation Liquid>
    [063] Model fermentation liquids were prepared by adding 2,3-butanediol or 1,3-propanediol to the ethanol fermentation liquid described below. As an ethanol fermentation microorganism, the KO11 strain of Escherichia coli (purchased from ATCC (American Type Culture Collection) was used. The microorganism was inoculated into 5 ml of the medium shown in Table 7 and cultured with stirring at 30 °C for 24 hours. The resultant was similarly inoculated into 50 ml of the medium shown in Table 7 and the preculture was performed under the same conditions. The resulting preculture was inoculated into 4 l of the medium shown in Table 8 and the main culture was carried out. The culture was carried out at a temperature of 30 °C, aeration rate of 0.01 vvm and agitation rate of 400 rpm and the neutralization was carried out with potassium hydroxide and sulfuric acid so that the pH becomes 6.

    [064] Fermentation progress was judged based on changes in ethanol concentration and glucose concentration. Ethanol concentration was measured under the following HPLC conditions. Glucose concentration was measured under the same conditions as in Example 1. (Ethanol Concentration Measurement) Column: Shodex Sugar SH1011 (manufactured by Showa Denko.KK) Column temperature: 65°C Mobile phase: aqueous sulfuric acid solution at 0.05 M, 0.6 ml/min Detection: RI
    [065] In this study, ethanol fermentation reached saturation on Day 3 after the start of culture. The ethanol concentration at that time was 16 g/l and the glucose concentration was 0.9 g/l. The obtained ethanol culture liquid was filtered through a microfiltration membrane (manufactured by Toray Industries, Inc.) to remove bacterial cells. This fermentation was repeated 8 times to obtain 32 l of an ethanol culture liquid. The ethanol culture liquid was divided into 16 L and 480 g aliquots of 2,3-butanediol or 480 g of 1,3-propanediol was added to each aliquot to prepare a 2,3-butanediol model fermentation liquid and a 1,3-propanediol model fermentation liquid. <Nanofiltration Membrane Treatment and Ion Exchange Treatment of Model Fermentation Liquids and Purification with Alkaline Substance Addition Distillation>
    [066] The 2,3-butanediol model fermentation liquid and the 1,3-propanediol model fermentation liquid (1,3-PDO) were subjected to treatment with nanofiltration membrane and ion exchange treatment, followed by thin-film concentration by the same operations as in Example 1. To 50 g of concentrated 2,3-butanediol solution, 0.7 g (3% by mol relative to the amount (number of moles) of 2,3- butanediol; Reference Example 2) of sodium hydroxide was added and, to 50 g of the concentrated 1,3-propanediol solution, 0.5 g (3% by mol relative to the amount (number of moles) of 1.3 -propanediol; Reference Example 4) of sodium hydroxide was added, followed by sufficient stirring of the resulting mixtures until the sodium hydroxide was dissolved. Each resulting solution was distilled under reduced pressure (0.67 kPa (5 mmHg)), to obtain 2,3-butanediol and 1,3-propanediol. The degrees of coloring (APHA) of 2,3-butanediol and 1,3-propanediol after distillation were measured by the same procedure as in Example 1. The results are shown in Table 9. The results obtained by distillation without addition of hydroxide sodium are also shown for the 2,3-butanediol solution (Reference Example 1) and the 1,3-propanediol solution (Reference Example 3). TABLE 9

    [067] As shown in Table 9, it was revealed, based on the comparison between Reference Example 1 and Reference Example 2, that the degree of coloration of 2,3-butanediol subjected to treatment with nanofiltration membrane and treatment of Ion exchange is vastly improved by addition of the alkaline substance and distillation. On the other hand, based on the comparison between Reference Example 3 and Reference Example 4, the increase in the degree of coloration of 1,3-propanediol subjected to nanofiltration membrane and ion exchange treatment caused by distillation without addition of an alkaline substance was less than that observed for 2,3-butanediol and no color enhancing effect was revealed even in the case where the alkaline substance was added for the distillation. These results showed that, as the coloring mechanism in the distillation step is different between 1,3-propanediol and 2,3-butanediol, a suitable purification method for each substance needs to be studied to improve the degree of coloration and that improvement the degree of coloration by adding an alkaline substance through distillation is a specific effect for 2,3-butanediol. INDUSTRIAL APPLICABILITY
    [068] The 2,3-Butanediol obtained by the present invention can be used similarly to that derived from petroleum, as an intermediate material for pharmaceuticals and cosmetics; as a material for paints, perfumes, liquid crystals, insecticides, softening agents, explosives, plasticizers and the like; and as a material for synthetic resins. DESCRIPTION OF SYMBOLS 1. Supply tank 2. Nanofiltration membrane element 3. High pressure pump 4. Nanofiltration membrane permeate flow 5. Flow of a non-permeate nanofiltration membrane 6. Supply liquid flow to nanofiltration membrane
    权利要求:
    Claims (6)
    [0001]
    1. METHOD TO PRODUCE 2,3-BUTANEDIOL, characterized by comprising the steps of: subjecting a 2,3-butanediol culture liquid, produced by microbial fermentation, to treatment with a nanofiltration membrane and ion exchange treatment (Step A ) and then adding an alkaline substance and performing a distillation (Step B).
    [0002]
    2. METHOD, according to claim 1, characterized in that the amount of said alkaline substance added is equal to or less than 10% in mol in relation to the amount (number of moles) of 2,3-butanediol.
    [0003]
    3. METHOD according to any one of claims 1 to 2, characterized in that said alkaline substance is at least one selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, carbonates of alkali metal hydrogen and alkaline earth metal carbonates.
    [0004]
    4. METHOD according to any one of claims 1 to 3, characterized in that said alkaline substance is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, carbonate sodium and calcium carbonate.
    [0005]
    5. METHOD, according to any one of claims 1 to 4, characterized in that it further comprises concentrating, before said Step B, the 2,3-butanediol solution obtained in said Step A (Step C).
    [0006]
    6. METHOD, according to claim 5, characterized in that said Step C is a step of filtering a solution of 2,3-butanediol through a reverse osmosis membrane.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112014008195B1|2021-04-20|method to produce 2,3-butanediol
    JP6800908B2|2020-12-16|How to separate the components of fermented broth
    KR20100107480A|2010-10-05|Recovery of higher alcohols from dilute aqueous solutions
    ES2718679T3|2019-07-03|Production process of 1,4-butanediol
    BRPI0919388B1|2019-02-19|METHOD FOR PRODUCING BIOMASS RESOURCE-derived SUCCINIC ACID
    BR112014019575B1|2019-12-17|method for producing a sugar solution
    Li et al.2021|Recent advances in the separation and purification of lactic acid from fermentation broth
    JP2012012322A|2012-01-19|Lactic acid and method for producing lactic acid
    KR101294336B1|2013-08-08|Methods for Purifying Lactic Acid
    Ezeji et al.2010|Advanced product recovery technologies
    JP6861202B2|2021-04-21|Improved production of vanillin by fermentation
    BR112016011487A2|2020-06-30|2,3-BUTANODIOL PRODUCTION METHOD
    KR101975187B1|2019-05-07|Method of preparaing diol
    KR101540520B1|2015-07-30|Method for succinic acid purification using reverse osmosis membrane
    NZ624973B2|2015-05-28|Process for producing 2,3-butanediol
    JP2010130908A|2010-06-17|Method for producing glycerate
    JP6485009B2|2019-03-20|Method for producing 2,3-butanediol
    Kalisa et al.2018|Current trends in efficient production of 1, 3‐propanediol
    Qureshi2014|Integrated Bioprocessing and simultaneous product recovery for butanol production
    Fernandez2019|Purification of Biomass Hydrolyzates for the Promotion of Xylose Diester Formation
    JP2010126512A|2010-06-10|Method for producing hydroxycarboxylic acid
    KR101376159B1|2014-03-20|Method for recoverying diols from fermentation broth
    同族专利:
    公开号 | 公开日
    CN103987852A|2014-08-13|
    JPWO2013054874A1|2015-03-30|
    CA2851817A1|2013-04-18|
    IN2014CN03491A|2015-07-03|
    CN103987852B|2017-02-15|
    JP6032012B2|2016-11-24|
    EP2767589A4|2015-07-01|
    EP2767589B1|2017-12-20|
    WO2013054874A1|2013-04-18|
    EP2767589A1|2014-08-20|
    BR112014008195A2|2017-06-13|
    US20140238841A1|2014-08-28|
    US10584084B2|2020-03-10|
    MY170936A|2019-09-19|
    NZ624973A|2015-02-27|
    RU2014119257A|2015-11-20|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4479021A|1983-08-30|1984-10-23|Ciba-Geigy Corporation|Continuous process for producing 1,2-alkanediols|
    DE19506280A1|1995-02-23|1996-08-29|Hoechst Ag|Process for the distillation of alcohols|
    US6361983B1|1999-09-30|2002-03-26|E. I. Du Pont De Nemours And Company|Process for the isolation of 1,3-propanediol from fermentation broth|
    JP4530461B2|2000-02-04|2010-08-25|ダイセル化学工業株式会社|Method for purifying 1,3-butylene glycol|
    AR041460A1|2002-10-03|2005-05-18|Shell Int Research|REDUCTION OF THE VISCOSITY OF HIGH MOLECULAR SECONDARY PRODUCTS IN THE PRODUCTION OF 1,3- PROPANODIOL|
    JP4240290B2|2003-04-01|2009-03-18|東洋紡績株式会社|Actinic ray curable resin composition, ink, and laminate coated with the same|
    EP1625224B1|2003-05-06|2010-07-28|E.I. Du Pont De Nemours And Company|Purification of biologically-produced 1,3-propanediol|
    JP2004352713A|2003-05-08|2004-12-16|Mitsubishi Chemicals Corp|Method for producing 1,3-propanediol|
    WO2007094178A1|2006-02-14|2007-08-23|Kaneka Corporation|Novel -butanediol dehydrogenase, gene for the same, and use of the same|
    BRPI0915017B1|2008-06-09|2018-12-26|Lanzatech New Zealand Ltd|a method for producing 2,3-butanediol by microbial fermentation of a gaseous substrate comprising co|
    ES2401155T3|2008-10-03|2013-04-17|Metabolic Explorer|Procedure for the purification of an alcohol from a fermentation broth that uses a falling film evaporator, renewed film, thin film or short path evaporator|
    JP5625334B2|2008-11-28|2014-11-19|東レ株式会社|Method for producing diol or triol|
    PL2438036T3|2009-06-04|2017-09-29|Genomatica, Inc.|Process of separating components of a fermentation broth|
    CN101586126A|2009-06-22|2009-11-25|大连工业大学|Solid-state fermentation of straw resources ferment 2, the 3-butyleneglycol is produced the method for clean fuel|
    CN101580855B|2009-06-22|2012-05-23|大连工业大学|Clean technology for producing 2,3-butanediol by maize straw resource|
    US9018424B2|2011-03-30|2015-04-28|Toray Industries, Inc.|Method of producing diol or triol|
    EP2937328B1|2012-12-19|2018-08-15|Toray Industries, Inc.|Alcohol production method|
    ES2718679T3|2013-04-12|2019-07-03|Toray Industries|Production process of 1,4-butanediol|
    BR112016011487A2|2013-11-22|2020-06-30|Toray Industries, Inc.|2,3-BUTANODIOL PRODUCTION METHOD|JPS6232410A|1985-08-05|1987-02-12|Minolta Camera Co Ltd|Focus detector|
    US4939357A|1987-11-20|1990-07-03|Asahi Kogaku Kogyo K.K.|Optical system for a focal point detecting device|
    JP2586089B2|1988-03-04|1997-02-26|株式会社ニコン|Focus detection optical system|
    US5321461A|1991-08-22|1994-06-14|Olympus Optical Co., Ltd.|Focus detecting device|
    US5424528A|1992-10-30|1995-06-13|Olympus Optical Co., Ltd.|Focus detecting device having at least three reimaging lenses|
    KR20140052189A|2012-10-22|2014-05-07|씨제이제일제당 |Refining method of organic amine, organic amine refined by the method, and polyamide prepared therefrom|
    JP2015017087A|2013-06-13|2015-01-29|三菱化学株式会社|Method for producing diol|
    JP6175319B2|2013-09-10|2017-08-02|東レ株式会社|Process for producing 1,3-butadiene and / or 3-buten-2-ol|
    WO2015037580A1|2013-09-12|2015-03-19|東レ株式会社|Method for producing butadiene|
    JP6485009B2|2013-11-22|2019-03-20|東レ株式会社|Method for producing 2,3-butanediol|
    BR112016011487A2|2013-11-22|2020-06-30|Toray Industries, Inc.|2,3-BUTANODIOL PRODUCTION METHOD|
    DE102013224909A1|2013-12-04|2015-06-11|Wacker Chemie Ag|Process for the isolation of 2,3-butanediol from fermentation mixtures|
    JP6486020B2|2014-05-30|2019-03-20|三菱ケミカル株式会社|Method for producing 2,3-butanediol|
    US10711215B1|2014-08-28|2020-07-14|The Government Of The United States Of America As Represented By The Secretary Of The Navy|Renewable dioxolane-based gasoline-range fuels and diesel additives|
    KR101975187B1|2017-04-28|2019-05-07|지에스칼텍스 주식회사|Method of preparaing diol|
    KR101969530B1|2017-08-02|2019-04-16|지에스칼텍스 주식회사|Method of decolorization and deordorization of polyhydric alcohol|
    KR20210068049A|2018-09-21|2021-06-08|베르살리스 에스.피.에이.|Purification process of bio-1,3-butanediol from fermentation broth|
    US11220645B1|2018-11-07|2022-01-11|The United States Of America As Represented By The Secretary Of The Navy|Renewable high cetane dioxolane fuels|
    法律状态:
    2019-08-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-03-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-04-20| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/10/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2011-226391|2011-10-14|
    JP2011226391|2011-10-14|
    PCT/JP2012/076421|WO2013054874A1|2011-10-14|2012-10-12|Process for producing 2,3-butanediol|
    [返回顶部]