WO2006128381A1 - Procede permettant de preparer le propanediol-1,3 en se servant de la glycerine en tant que sous-produit du carburant diesel biologique - Google Patents

Procede permettant de preparer le propanediol-1,3 en se servant de la glycerine en tant que sous-produit du carburant diesel biologique Download PDF

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Publication number
WO2006128381A1
WO2006128381A1 PCT/CN2006/001181 CN2006001181W WO2006128381A1 WO 2006128381 A1 WO2006128381 A1 WO 2006128381A1 CN 2006001181 W CN2006001181 W CN 2006001181W WO 2006128381 A1 WO2006128381 A1 WO 2006128381A1
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Prior art keywords
biodiesel
product
propanediol
fermentation
glycerol
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PCT/CN2006/001181
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English (en)
French (fr)
Inventor
Dehua Liu
Hongjuan Liu
Rihui Lin
Jian Hao
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Tsinghua University
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Application filed by Tsinghua University filed Critical Tsinghua University
Priority to CA2610777A priority Critical patent/CA2610777C/en
Priority to KR1020087000176A priority patent/KR101281847B1/ko
Priority to JP2008513903A priority patent/JP5067888B2/ja
Priority to EP06742068.7A priority patent/EP1892300B1/en
Priority to US11/916,180 priority patent/US8486673B2/en
Priority to AU2006254616A priority patent/AU2006254616B2/en
Priority to BRPI0613543A priority patent/BRPI0613543B8/pt
Publication of WO2006128381A1 publication Critical patent/WO2006128381A1/zh
Priority to NO20080001A priority patent/NO338330B1/no
Priority to HK08104152.8A priority patent/HK1109915A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/18—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic polyhydric
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/32—Processes using, or culture media containing, lower alkanols, i.e. C1 to C6
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the invention belongs to the field of biochemical technology, and particularly provides a method for directly producing 1,3-propanediol by using crude glycerin as a by-product in the production process of biodiesel. Background technique
  • Biodiesel is a renewable energy source made from oil-containing plants, animal fats and waste cooking oil.
  • the reaction formula is shown in Figure 1.
  • biodiesel As a renewable and clean energy source, biodiesel has been used in many countries such as the United States, the European Union and Japan. At present, China has not yet realized the industrialization of biodiesel.
  • the main methods of producing biodiesel are:
  • Chemical method At present, industrial preparation of biodiesel is mainly carried out by chemical method, that is, using animal and vegetable oils and lower alcohols such as methanol or ethanol to carry out transesterification under acidic or basic catalyst to form corresponding fatty acid methyl esters or Ethyl ester (Ma F, Hanna M A. Biodiesel production: a review. Bioresource Technology, 1999, 70: 1-15).
  • 1,3-propanediol is an important chemical raw material that can be used as an organic solvent. Used in inks, printing and dyeing, coatings, lubricants, antifreeze and other industries.
  • the most important use of 1,3-propanediol is as a monomer for the synthesis of polyester and polyurethane, especially polybutylene terephthalate (PTT) formed by polymerization with terephthalic acid, showing a ratio of 1,2- Propylene glycol, butanediol, and ethylene glycol are superior properties of polymers synthesized from monomers.
  • PTT polybutylene terephthalate
  • PTT polyethylene terephthalate
  • PTT fiber has the advantages of abrasion resistance, low water absorption, low static electricity, etc., and can compete with nylon in the carpet field. It can also be used for non-woven fabrics, engineering plastics, clothing, home decoration, linings, fabrics, etc. with excellent properties.
  • PTT was named one of the six major petrochemical products in the United States in 1998 and is considered to be an upgraded product of PET.
  • Glycerol is disproportionated to 1,3-propanediol under intestinal anaerobic conditions (USP 5254467, EP0373230 A1).
  • Anaerobic bacteria such as Klebsiella are fermentatively produced under anaerobic conditions to produce 1, 3-propanediol (Ruch et al. Regulation of glycerol catabolism in Klebsiella aerogenes.
  • the raw materials in the above methods are all derived from the reagent glycerin or glycerol fermentation broth, and there has been no report on the direct fermentation of crude glycerol by biodiesel by-product to produce 1,3-propanediol.
  • Xiu Zhilong et al. Xiu Zhilong et al., a method for coupling biodiesel and 1,3-propanediol.
  • the invention provides a method for directly producing 1,3-propanediol by using crude glycerin as a by-product of biodiesel, which saves the cost of separation and purification of glycerin and effectively reduces the production cost. This method can be practically applied to the coupled production of biodiesel and 1,3-propanediol.
  • the invention provides a method for directly producing 1,3-propanediol by using biodiesel by-product crude glycerin, which utilizes the glycerin as a by-product in the production process of biodiesel and further converts it into high value-added 1,3-propanediol.
  • the cost of separating and purifying glycerin is saved, and the production cost is effectively reduced.
  • the method can also be used for the coupled production of biodiesel and 1,3-propanediol, and the use of inexpensive raw materials to obtain high value-added biodiesel and 1,3-propanediol can effectively improve the utilization of raw materials and by-product glycerin and reduce production costs.
  • the present invention provides a process for the direct production of 1,3-propanediol from crude glycerol, a by-product of biodiesel.
  • biodiesel by-product crude glycerin can be used to produce 1,3-propanediol without further treatment, and biodiesel by-product crude glycerin is derived from chemical, biological or supercritical production organisms.
  • Deputy in the diesel process The crude product was glycerol and no further treatment was required.
  • the present invention provides a method for producing 1, 3-propanediol by fermentation, characterized by using biodiesel by-product crude glycerin as a substrate, the method comprising (a) 1, 3-propanediol Producing the strain into a seed medium containing crude glycerin as a by-product of biodiesel; (b) adding the seed liquid to a fermentation medium containing crude glycerin of biodiesel by-product, fermenting; and (c) separating and purifying to obtain 1,3 - Propylene glycol.
  • FIG. 1 is a schematic diagram of the preparation of biodiesel by transesterification of animal and vegetable oils. Detailed description of the invention
  • the present invention provides a process for the direct production of 1,3-propanediol from crude glycerin, a by-product of biodiesel.
  • biodiesel by-product crude glycerin can be used to produce 1,3-propanediol without further treatment, and biodiesel by-product crude glycerin is derived from chemical, biological or supercritical production organisms. Crude glycerin, a by-product of the diesel process, requires no further processing.
  • the present invention provides a method for producing 1,3-propanediol by a fermentation process, characterized by using a biodiesel by-product crude glycerin as a substrate, the method comprising (a) 1, 3-propanediol Producing the strain into a seed medium containing crude glycerin as a by-product of biodiesel; (b) adding the seed liquid to a fermentation medium containing crude glycerin of biodiesel by-product, fermenting; and (c) separating and purifying to obtain 1, 3 - Propylene glycol.
  • the biodiesel by-product crude glycerol is a by-product crude glycerin in the biodiesel production process.
  • the 1,3-propanediol producing strain may be Klebsiella pneumoniae, Clostridium butyricum or Clostridium pasteurianum.
  • the crude glycerin, a by-product of the biodiesel production process can be used as a feed substrate for the fed-batch process without further processing.
  • the 1,3-propanediol producing strain is cultured by culturing at 30 ° C to 37 ° C for 16 h to 20 h.
  • the glycerol contained in the fermentation medium is 10 to 30 g/L biodiesel by-product crude glycerin.
  • the pH is controlled in the step (b) during the fermentation to a pH of from 6.8 to 8.0, and the pH is preferably controlled using a 3-4 M alkali solution or aqueous ammonia.
  • the fermentation in step (b) is an anaerobic or aerobic fermentation at 30 ° C to 37 ° C.
  • the biodiesel by-product crude glycerin or the mixed solution of glycerin and glucose is simultaneously added in step (b) to control the concentration of glycerin in the fermentation broth to 10 to 40 g/L, preferably glucose in the mixed solution.
  • the ratio of concentration to glycerol is 5 to 10:1.
  • the 1,3-propanediol is obtained by separation, purification by desalting, distillation, vacuum distillation steps.
  • the byproducts 2,3-butanediol, lactic acid, acetic acid, ethanol, succinic acid are simultaneously produced.
  • the crude glycerin can be directly used as a substrate for the production of 1,3-propanediol by fermentation without further treatment, and can also be used as a substrate for the fed-batch fermentation process, including the following steps:
  • the 1,3-propanediol is separated and purified by steps such as desalting, distillation, vacuum distillation, etc. to prepare the product 1,3-propanediol, and the by-product 2,3-butanediol can also be prepared. Lactic acid, acetic acid, ethanol, succinic acid.
  • the substrate for the production of 1,3-propanediol by the above fermentation method is derived from chemical method, biological method and super Crude glycerin, a by-product of the critical process for the production of biodiesel.
  • the crude glycerin, a by-product in the biodiesel production process does not need to be further processed, and a part is used as a fermentation substrate, and a part is used for the addition.
  • the process of the invention is suitable for the co-production of biodiesel and 1,3-propanediol.
  • the advantage and beneficial effect of the method of the invention is that the crude glycerin, which is a by-product in the biodiesel production process, is efficiently converted into high value-added 1,3-propanediol, and the by-products in the fermentation process are 2,3-butanediol, lactic acid and acetic acid. Ethanol and succinic acid are also widely used chemical products and can also be separated as products.
  • the method of the invention saves the cost of separating and purifying glycerol, and effectively reduces the production cost. For example, the coupled production of biodiesel and 1,3-propanediol can greatly improve raw material utilization and production efficiency, and reduce production costs.
  • biodiesel refers to renewable energy sources made from oil-containing plants, animal fats and waste cooking oils.
  • by-product crude glycerin refers to the unpurified by-product glycerol obtained during the production of biodiesel.
  • the glycerin used in the following examples is the by-product glycerin obtained in the biodiesel production process.
  • the yeast powder was purchased from Wenzhou Jinqi Condiment Co., Ltd.
  • K 2 HP04 was purchased from Changsha Yutai Industrial Co., Ltd.
  • KH 2 P04 was purchased from Changsha Gaosheng Technology.
  • Chemical company MgS0 4 was purchased from Tianjin Changhe Chemical
  • (NH 4 ) 2 S0 4 was purchased from Sinopec Baling Branch
  • defoaming agent was purchased from Zhejiang University Chemical Plant
  • glucose was purchased from Shijiazhuang Huaying United Glucose Factory
  • other reagents were purchased. Since Weiss Laboratory Supplies Co., Ltd.
  • Example 1 Example 1:
  • the glycerin, a by-product obtained in the biodiesel production process, is used as a fermentation substrate and the other part is used to feed the substrate.
  • Seed culture Add Klebsiella to seed medium containing 20g/L biodiesel by-product glycerin (500ml flask, liquid volume 100ml), culture temperature 30 ° C, shaker speed 150 rpm, Oxygen culture for 20 h.
  • Fermentation culture The fermentation culture was carried out using a 5 L fermenter (Biostat B, Germany), a liquid volume of 4 L, a culture temperature of 37 ° C, and a pH of 6.8 with potassium hydroxide.
  • the seed liquid was connected to the initial fermentation medium containing 30 g/L of biodiesel by-product glycerin.
  • the biodiesel by-product crude glycerin was added during the fermentation, and glucose was added at the same time.
  • the ratio of glycerol to glucose was 8:1 to control the flow rate.
  • the glycerol concentration in the fermentation broth was maintained at 30 g/L.
  • the fermentation process was carried out using anaerobic gas with 0.2 vvm of nitrogen.
  • the glycerin, a by-product obtained in the biodiesel production process, is used as a fermentation substrate and the other part is used to feed the substrate.
  • Seed culture Klebsiella is added to seed medium containing 20g/L biodiesel by-product glycerin (500ml flask, liquid volume 100ml), culture temperature 37°C, shaker speed 150rpm, good Oxygen culture for 16 h.
  • Fermentation culture The fermentation culture uses a 5L fermenter with a liquid volume of 4L, a culture temperature of 37 V, and a pH of 8.0 with potassium hydroxide.
  • the seed liquid was connected to the initial fermentation medium containing 30 g/L biodiesel by-product crude glycerin.
  • biodiesel by-product glycerin was added, and glucose was added at the same time.
  • the ratio of glycerin to glucose was 10:1 to control the flow rate.
  • the glycerol concentration in the fermentation broth was maintained at 30 g/L. 32h before the fermentation process, anaerobic gas was introduced, 0.2vvm nitrogen gas was introduced, and after 32h, aerobic gas was used, and 0.2vvm air was introduced.
  • the crude glycerin, a by-product obtained in the biodiesel production process, is used as a fermentation substrate and the other part is used to feed the substrate.
  • A. Seed culture Klebsiella is added to a seed medium containing 20 g/L biodiesel by-product crude glycerin (500 ml flask, liquid volume 100 ml), culture temperature 30 ° C, shaker speed 150 rpm, Aerobic culture for 16h.
  • Fermentation culture The fermentation culture was carried out using a 50 L fermenter (Biostat B, Germany), a liquid volume of 40 L, a culture temperature of 37 ° C, and a pH of 7.0 with potassium hydroxide.
  • the seed liquid was connected to the initial fermentation medium containing 10 g/L biodiesel by-product crude glycerin.
  • the biodiesel by-product crude glycerin was added during the fermentation, and glucose was added at the same time.
  • the ratio of glycerol to glucose was 10:1 to control the flow rate. Maintain the glycerol concentration in the fermentation broth for 10-16h at 10g/L, 16h After maintaining at 30g / l. 5vvm ⁇ The fermentation process into the 0. 5vvm air.
  • the crude glycerin, a by-product obtained in the biodiesel production process, is used as a fermentation substrate and the other part is used to feed the substrate.
  • Seed culture Add Klebsiella to seed medium containing 20g/L biodiesel by-product glycerin (500ml flask, liquid volume 100ml), culture temperature 30 ° C, shaker speed 150 rpm, Oxygen culture for 16 h.
  • Fermentation culture The fermentation culture uses a 500L fermenter with a liquid volume of 350L, a culture temperature of 37 °C, and a pH of 7.0 with potassium hydroxide.
  • the seed liquid was connected to the initial fermentation medium containing 20 g/L biodiesel by-product crude glycerin.
  • the biodiesel by-product crude glycerin was added during the fermentation, and glucose was added at the same time.
  • the ratio of glycerol to glucose was 10:1 to control the flow rate.
  • the glycerin concentration in the fermentation broth was maintained at 10 g/L for 10-16 h and maintained at 30 g/l after 16 h.
  • the fermentation process was carried out with 0.5 vvm of air.
  • the concentration of 1,3-propanediol in the fermentation broth was 63.2 g/l
  • the molar yield of 1,3-propanediol was 0.60
  • the production intensity was l.lg/(lh).

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Description

利用生物柴油爵 j产物甘油生产 1,3-丙二醇的方法 技术领域
本发明属于生物化工技术领域， 特别提供了一种直接利用生物柴油 生产过程中的副产物粗品甘油生产 1,3-丙二醇的方法。 背景技术
生物柴油是以含油植物、 动物油脂以及废食用油为原料制成的可再 生能源， 反应式见图 1。
生物柴油作为可再生的清洁能源， 已在美国、 欧盟及日本等多个国 家推行使用， 目前中国还未实现生物柴油的产业化。 生物柴油的生产方 法主要有：
( 1 ) 化学法： 目前工业上制备生物柴油主要是使用化学法， 即用动植 物油脂和甲醇或乙醇等低碳醇在酸性或者碱性催化剂下进行转酯反应， 生成相应的脂肪酸甲酯或乙酯 （Ma F, Hanna M A. Biodiesel production: a review. Bioresource Technology, 1999, 70: 1〜15 ) 。
(2) 生物法： 是指用生物酶或生物细胞来催化转酯反应， 生成相应的 脂肪酸甲酉旨或乙酉旨 （Ma F， Hanna M A. Biodiesel production: a review. Bioresource Technology, 1999, 70: 1〜15 )。
( 3 ) 超临界法： 在不使用任何催化剂的情况下， 在超临界溶剂体系中 进行转酉^化转化。 (Saka S, Kusdiana D. Biodiesel fuel from rapeseed oil as prepared in supercritical methanol. Fuel, 2001, 80 (2): 225〜231 ; Kusdiana D Saka S. Kinetics of transesterification in rapeseed oil to biodiesel fuel as treated in supercritical methanol. Fuel, 2001,80 (5): 693〜698; 缪晓玲， 吴 庆余. 微藻生物质可再生能源的开发利用. 可再生能源， 2003， 3： 13〜 16)
上述方法生产生物柴油的过程中， 均可得到副产物甘油。 目前随着 生物柴油产量的不断增大， 副产物甘油的产量也迅速增加， 如何有效利 用生物柴油副产物甘油已成为生物柴油生产企业的一大难题。
1，3-丙二醇 （PDO ) 是一种重要的化工原料， 可作为有机溶剂应 用于油墨、 印染、 涂料、 润滑剂、 抗冻剂等行业。 1,3-丙二醇最主要 的用途是作为聚酯和聚氨酯合成的单体， 特别是与对苯二甲酸聚合 生成的聚对苯二甲酸丙二酯 （PTT)， 显示了比以 1 ,2-丙二醇、 丁二 醇、 乙二醇为单体合成的聚合物更优良的性能。 目前全球每年消费 数千万吨聚对苯二甲酸乙二酯 （PET) , 而 PTT的化学稳定性、 生物 可降解性等与 PET相当， 但耐污染性、 韧性和回弹性及抗紫外性能 等更优越。 此外 PTT纤维还具有耐磨、 吸水性低、 低静电等优点， 可在地毯领域与尼龙竞争。 它还可用于具有优良性能的无纺布、 工 程塑料、 服装、 家庭装饰、 垫衬料、 织物等方面。 PTT 被评为美国 98年六大石化新产品之一， 被认为将是 PET的升级产品。
PTT的优越性能及市场潜力早在 50年前就被人们所认识，只因 原料 1， 3-丙二醇生产技术难度大、 成本高而导致 PTT很难大规模 工业化生产， 迄今为止， 只有 Dupont和 Shell两家跨国公司采用传 统的化学合成路线， 以环氧乙垸或丙烯为原料生产仅供它们合成 PTT自用的 1,3-丙二醇。 化学合成法的缺点是副产物多， 选择性差， 操作条件需高温高压， 设备投资巨大， 原料为不可再生资源， 且环 氧乙烷和另一路线的中间产物丙烯醛分别是易燃易爆或剧毒的危险 品。 由于发酵法生产 1 ,3-丙二醇选择性高， 操作条件温和， 因此近 年来受到特别的重视。 目前， 由甘油发酵生产 1 ,3-丙二醇主要有以 下几条途径：
1 ) 采用肠道细菌厌氧条件下将甘油歧化为 1，3-丙二醇 ( USP5254467, EP0373230 A1 )。
2 ) 克雷伯氏杆菌等厌氧菌在厌氧条件下发酵生产 1 ,3-丙二醇 ( Ruch et al. Regulation of glycerol catabolism in Klebsiella aerogenes.
J Bacteriol. 1974,119(1):50〜56; Streekstra et al. Overflow metabolism during anaeric growth of Klebsiella pneumoniae NCTC418 on glycerol and dihydroxyacetone in c emostat culture. Arch Microbiol. 1987, 147:268 〜 275;Zeng et al. Pathway analysis of glycerol fermentation by Klebsiella pneumoniae: Regulation of reducing equivalent balance and product formation. Enzyme Microbiol Technol. 1993，15:770〜779. )。
3 )采用克雷伯氏杆菌在微氧条件下发酵生产 1,3-丙二醇 (王剑锋 等， 克雷伯氏菌微氧发酵生产 1,3-丙二 的研究， 现代化工， 2001， 21 ( 5 )： 28— 31。 修志龙等， 一种微生物微氧发酵生产 1,3-丙二醇的 方法， 中国专利公开号： CN1348007)
4) 采用克雷伯氏杆菌在厌氧条件下发酵产 1，3-丙二醇和 2,3-丁 二醇 ( Biebl et al. Fermentation of glycerol to 1,3-propanediol and 2,3-butanediol. Appl Microbiol Biotechnol,1998,50:24-29 ) o
上述方法中的原料均来源于试剂甘油或甘油发酵液， 目前还未 有利用生物柴油副产物甘油粗品直接发酵生产 1,3-丙二醇的报道。修 志龙等 （修志龙等， 一种偶联生产生物柴油和 1,3-丙二醇的方法 中 国专利公开号： CN1648207A) 曾提出通过膜过滤将生物柴油副产物 甘油进行分离并同时进行 1,3-丙二醇的发酵生产，但实际上由于膜过 滤成本很高， 膜的清洗和再生也十分困难， 尤其是将两个过程同时 进行， 对实际操作， 特别是大规模生产难以实现。 发明概述
本发明提供了一种直接利用生物柴油副产物粗品甘油生产 1,3-丙 二醇的方法， 节省了甘油分离提纯的费用， 有效降低了生产成本。 该 方法可实际应用于生物柴油和 1，3-丙二醇的耦合生产。
本发明提供了一种直接利用生物柴油副产物粗品甘油生产 1,3-丙 二醇的方法， 是将生物柴油生产过程中的副产物甘油合理利用， 进一 步转化为高附加值的 1 ,3-丙二醇， 节省了甘油分离提纯的费用， 有效 降低了生产成本。 该方法还可用于生物柴油和 1,3-丙二醇的耦合生 产， 利用廉价原料得到高附加值的生物柴油和 1,3-丙二醇， 可有效提 高原料及副产物甘油的利用率， 降低生产成本。
本发明提供了一种直接利用生物柴油副产物粗品甘油生产 1,3-丙 二醇的方法。 利用本发明的方法， 可以使用生物柴油副产物粗品甘油而 无需进行进一步处理就可以用于生产 1,3-丙二醇， 生物柴油副产物粗品 甘油是来源于化学法、 生物法或超临界法生产生物柴油过程中的副 产物粗品甘油， 无需进一步处理。
在一个实施方案中，本发明提供了一种发酵法生产 1 ,3-丙二醇的方 法， 其特征在于利用生物柴油副产物粗品甘油作为底物， 所述方法 包括 （a) 将 1 ,3-丙二醇生产菌种接入含生物柴油副产物粗品甘油的 种子培养基中； （b ) 将种子液加入含生物柴油副产物粗品甘油的发 酵培养基， 发酵； 以及 （c) 分离、 提纯获得 1，3-丙二醇。 附图说明
图 1为 动植物油脂经过转酯反应制备生物柴油示意图。 发明详述
本发明提供了一种直接利用生物柴油副产物粗品甘油生产 1,3-丙 二醇的方法。 利用本发明的方法， 可以使用生物柴油副产物粗品甘油而 无需进行进一步处理就可以用于生产 1,3-丙二醇， 生物柴油副产物粗品 甘油是来源于化学法、 生物法或超临界法生产生物柴油过程中的副 产物粗品甘油， 无需进一步处理。
在一个实施方案中，本发明提供了一种发酵法生产 1，3-丙二醇的方 法， 其特征在于利用生物柴油副产物粗品甘油作为底物， 所述方法 包括 （a) 将 1 ,3-丙二醇生产菌种接入含生物柴油副产物粗品甘油的 种子培养基中； （b ) 将种子液加入含生物柴油副产物粗品甘油的发 酵培养基， 发酵； 以及 （c ) 分离、 提纯获得 1 ,3-丙二醇。
在一个实施方案中，所述生物柴油副产物粗品甘油是生物柴油生 产过程中的副产物粗品甘油。
在一个实施方案中，所述 1 ,3-丙二醇生产菌种可以是常规使用的 克雷伯氏杆菌 ( Klebsiella pneumoniae )、 丁酸梭菌 ( Clostridium butyricum ) 或巴斯德梭菌 ( Clostridium pasteurianum )。
在一个实施方案中，生物柴油生产过程中的副产物粗品甘油无需 进一步处理即可作为流加发酵过程中所需的流加底物。
在一个实施方案中， 在 30 °C〜37°C培养 16h〜20h培养所述 1 ,3- 丙二醇生产菌种。 在一个实施方案中， 发酵培养基中所含甘油为 10〜30g/L生物柴 油副产物粗品甘油。
在一个实施方案中，步骤（b)中在发酵时控制 pH值为 6.8〜8.0， 并优选利用 3— 4M碱溶液或氨水控制 pH值。
在一个实施方案中， 步骤 （b) 中所述发酵是在 30°C〜37°C进行 的厌氧或有氧发酵。
在一个实施方案中， 在步骤 （b ) 中同时流加生物柴油副产物粗 品甘油或该甘油和葡萄糖的混合溶液使发酵液中甘油浓度控制在 10〜40g/L, 优选所述混合溶液中葡萄糖与甘油浓度比为 5〜10:1。
在一个实施方案中， 经脱盐、 蒸馏、 真空精馏步骤分离、 提纯获 得 1,3-丙二醇。
在一个实施方案中， 同时产生副产物 2,3-丁二醇、 乳酸、 乙酸、 乙醇、 丁二酸。
在本发明的一个优选的实施方案中， 提供了一种采用发酵法直 接利用生物柴油生产过程中的副产物粗品甘油直接生产 1,3-丙二醇 的方法， 包括将生物柴油生产过程中的副产物粗品甘油无需进一步 处理即可直接作为发酵法生产 1,3-丙二醇的底物，还可作为流加发酵 过程中所需的流加底物， 包括如下步骤：
( a) 将克雷伯氏杆菌， 丁酸梭菌， 巴斯德梭菌等可产生 1,3-丙 二醇的菌种接入含生物柴油副产物粗品甘油的种子培养基中进行培 养， 优选所述培养条件为 30°C〜37°C培养 161！〜 20h;
(b) 将种子液加入含生物柴油副产物粗品甘油的初始发酵培养 基， 发酵， 优选在 30°C〜37°C条件下进行厌氧或有氧发酵； 同时流 加生物柴油副产物粗品甘油或该甘油和葡萄糖的混合溶液 （甘油与 葡萄糖浓度比为 5〜10: 1 ) 使发酵液中甘油浓度控制在 10〜40g/L; 并控制 pH值为 6.8〜8.0， 优选釆用 3— 4M碱溶液或氨水；
( c) 发酵结束时经例如脱盐、 蒸馏、 真空精馏等步骤将 1,3-丙 二醇分离、 提纯， 制备产品 1,3-丙二醇，同时还可制备其副产物 2,3- 丁二醇、 乳酸、 乙酸、 乙醇、 丁二酸。
上述发酵法生产 1,3-丙二醇的底物是来源于化学法、生物法及超 临界法生产生物柴油过程中的副产物粗品甘油。
在本发明中， 生物柴油生产过程中的副产物粗品甘油无需进一 步处理， 一部分作为发酵底物， 一部分用于流加。
本发明的方法适用于生物柴油和 1，3-丙二醇联产。
本发明方法的优点和有益效果在于有效利用生物柴油生产过程 中的副产物粗品甘油转化为高附加值的 1,3-丙二醇，发酵过程中的副 产物 2,3-丁二醇、 乳酸、 乙酸、 乙醇、 丁二酸也是用途很广的化工产 品， 也可作为产物分离。 本发明方法节省了甘油分离提纯的费用， 有效降低了生产成本。如用于生物柴油和 1,3-丙二醇的耦合生产则可 大大提高原料利用率和生产效率， 降低生产成本。
术语定义
术语 "生物柴油" 是指以含油植物、 动物油脂以及废食用油为原 料制成的可再生能源。
术语 "副产物粗品甘油"是指在生产生物柴油过程中所获得的未经 提纯的副产物甘油。 具体实施方式
下面再举具体实施例对本发明予以进一步说明：
下列实施例中所用甘油为生物柴油生产过程中获得的副产物甘油， 酵母粉购自温州金驹调味品公司， K2HP04购自长沙誉泰实业有限公司， KH2P04 购自长沙高胜科技化工公司， MgS04购自天津长河化工， (NH4)2S04购自中石化巴陵分公司， 消泡剂购自浙江大学化工厂，葡萄糖 购自石家庄华营联合葡萄糖厂，其他试剂均购自韦斯实验用品有限公司。 实施例 1 :
( 1 ) 生物柴油生产过程中获得的副产物甘油， 将一部分作为发酵底物， 另一部分用于流加底物。
( 2) 菌种： 克雷伯氏杆菌 ( /ebwW/a pweM o ' e， ACCC10082), 购 自中国科学院微生物研究所。
( 3 ) 培养基： 培养基组分 种子培养 发酵培养 微量元素溶液
基 基 (mg/1)
( / 1) ( / 1)
甘油 20g 10-30g ZnCl2 70
Κ2ΗΡ04·3Η20 4.45g 2.225g MnCl2-4H20 100
(NH4)2S04 2.0g 2.0g H3BO3 60
KH2PO4 1.3g 0.65g CoCl2-6H20 200
MgS04-7H20 0.2g 0.2g NiCl2'6H20 25 酵母粉 l.Og l-5g NiCl2-H20 27.64 微量元素溶 2ml 2ml Na2Mo04-2H20 35 fix.
CaC03 2.0g CuCl2-H20 20 消泡剂 0.1ml CuS04-5H20 29.28 浓盐酸 (37%) 0.9ml
( 3 ) 培养方式:
A. 种子培养： 将克雷伯氏杆菌接入含有 20g/L生物柴油副产物甘 油的种子培养基中 （500ml三角瓶， 装液量 100ml)， 培养温度 30°C， 摇 床转速 150rpm， 有氧培养 20h。
B. 发酵培养： 发酵培养采用 5L发酵罐 （Biostat B, Germany), 装 液量 4L， 培养温度 37°C， 用氢氧化钾控制 pH值 6.8。 将种子液接入含 30g/L 生物柴油副产物甘油的初始发酵培养基中， 发酵过程中流加生 物柴油副产物粗品甘油， 同时流加葡萄糖， 甘油与葡萄糖浓度比为 8: 1 控制其流速使发酵液中甘油浓度维持在 30g/L。 发酵过程采用厌 氧， 通入 0.2vvm氮气。
( 4) 发酵结果如下：
发酵结束时发酵液中 1,3-丙二醇浓度 44g/l， 1,3—丙二醇摩尔得率 0.45， 生产强度 0.8g/(lh) (发酵产物测定参考： 赵红英等， 1,3-丙二醇 发酵过程中底物抑制及其对策的研究， 现代化工， 2002 (7)： 34-38)。 实施例 2: 06 001181
( 1 ) 生物柴油生产过程中获得的副产物甘油， 将一部分作为发酵底物， 另一部分用于流加底物。
( 2) 菌种培养基均同实施例 1
( 3 ) 培养方式：
A. 种子培养： 将克雷伯氏杆菌接入含有 20g/L生物柴油副产物甘 油的种子培养基中 （500ml三角瓶， 装液量 100ml), 培养温度 37°C， 摇 床转速 150rpm， 好氧培养 16h。
B. 发酵培养： 发酵培养采用 5L发酵罐， 装液量 4L， 培养温度 37 V , 用氢氧化钾控制 pH值 8.0。 将种子液接入含 30g/L生物柴油副产物 粗品甘油的初始发酵培养基中， 发酵过程中流加生物柴油副产物甘 油， 同时流加葡萄糖， 甘油与葡萄糖浓度比为 10:1控制其流速使发 酵液中甘油浓度维持在 30g/L。发酵过程前 32h采用厌氧，通入 0.2vvm 氮气， 32h后采用有氧， 通入 0.2vvm空气。
(4 ) 发酵结果如下：
发酵结束时发酵液中 1,3-丙二醇浓度 64g/l。 1,3—丙二醇摩尔得率 0.51， 生产强度 0.95g/(lh)。 实施例 3 :
( 1 ) 生物柴油生产过程中获得的副产物粗品甘油，将一部分作为发酵底 物， 另一部分用于流加底物。
( 2 ) 菌种培养基均同实施例 1
( 3 ) 培养方式：
A. 种子培养： 将克雷伯氏杆菌接入含有 20g/L生物柴油副产物粗 品甘油的种子培养基中（500ml三角瓶，装液量 100ml),培养温度 30°C， 摇床转速 150rpm， 好氧培养 16h。
B. 发酵培养： 发酵培养采用 50L发酵罐（Biostat B, Germany), 装 液量 40L， 培养温度 37°C， 用氢氧化钾控制 pH值 7.0。 将种子液接入含 10g/L 生物柴油副产物粗品甘油的初始发酵培养基中， 发酵过程中流 加生物柴油副产物粗品甘油， 同时流加葡萄糖， 甘油与葡萄糖浓度 比为 10:1控制其流速使发酵液中甘油浓度 10— 16h维持在 10g/L，16h 后维持在 30g/l。 发酵过程通入 0. 5vvm空气。
( 4) 发酵结果如下：
发酵结束时发酵液中 1,3-丙二醇浓度 67g/l。 1,3—丙二醇摩尔得率 0.59， 生产强度 lg/(lh)。 . 实施例 4:
( 1 ) 生物柴油生产过程中获得的副产物粗品甘油，将一部分作为发酵底 物， 另一部分用于流加底物。
( 2) 菌种培养基均同实施例 1
( 3 ) 培养方式：
A. 种子培养： 将克雷伯氏杆菌接入含有 20g/L生物柴油副产物甘 油的种子培养基中 （500ml三角瓶， 装液量 100ml)， 培养温度 30°C， 摇 床转速 150rpm， 有氧培养 16h。
B. 发酵培养： 发酵培养采用 500L发酵罐， 装液量 350L, 培养温 度 37°C， 用氢氧化钾控制 pH值 7.0。 将种子液接入含 20g/L生物柴油副 产物粗品甘油的初始发酵培养基中，发酵过程中流加生物柴油副产物 粗品甘油， 同时流加葡萄糖， 甘油与葡萄糖浓度比为 10: 1控制其流 速使发酵液中甘油浓度 10— 16h维持在 10g/L， 16h后维持在 30g/l。 发酵过程通入 0.5vvm空气。
( 4) 发酵结果如下：
发酵结束时发酵液中 1,3-丙二醇浓度 63.2g/l， 1,3—丙二醇摩尔得 率 0.60， 生产强度 l .lg/(lh)。

Claims

权 利 要 求
1、 一种发酵法生产 1,3-丙二醇的方法， 其特征在于利用生物柴 油副产物粗品甘油作为底物， 所述方法包括如下步骤：
( a) 将 1,3-丙二醇生产菌种接入含生物柴油副产物粗品甘油的 种子培养基中；
(b) 将种子液加入含生物柴油副产物粗品甘油的发酵培养基， 发酵；
( c) 分离、 提纯获得 1,3-丙二醇。
2、 按照权利要求 1的方法， 其特征在于所述生物柴油副产物粗 品甘油是生物柴油生产过程中的副产物粗品甘油。
3、 按照权利要求 1 的方法， 其特征在于步骤 （a) 中所述 1,3- 丙二醇生产菌种是克雷伯氏杆菌、 丁酸梭菌或巴斯德梭菌。
4、 按照权利要求 3的方法， 其特征在于步骤（a) 中所述菌种在 30°C〜37°C培养 161！〜 20h。
5、 按照权利要求 1 的方法， 其特征在于步骤 （b) 所述发酵培 养基中含有 10〜30g/L生物柴油副产物粗品甘油。
6、 按照权利要求 1 的方法， 其特征在于步骤 （b ) 中在发酵时 控制 pH值为 6.8〜8.0。
7、按照权利要求 6的方法，其特征在于用 3— 4M碱溶液或氨水 控制 pH值。
8、 按照权利要求 1 的方法， 其特征在于步骤 （b ) 中所述发酵 是在 30°C〜37°C进行的厌氧或有氧发酵。
9、 按照权利要求 1 的方法， 其特征在于在步骤 （b) 中同时流 加生物柴油副产物粗品甘油或该甘油和葡萄糖的混合溶液使发酵液 中甘油浓度控制在 10〜40g/L。
10、 按照权利要求 9 的方法， 其特征在于所述混合溶液中葡萄 糖与甘油浓度比为 5〜10: 1。
11、 按照权利要求 1一 10 任一项的方法， 其特征在于经脱盐、 蒸馏、 真空精馏步骤分离、 提纯获得 1，3-丙二醇。
12、 按照权利要求 ·1一 10 任一项的方法， 其特征在于同时产生 副产物 2，3-丁二醇、 乳酸、 乙酸、 乙醇、 丁二酸。
13、 按照权利要求 1一 10 任一项所述的方法， 其特征在于： 生 物柴油生产过程中无需进一步处理的副产物粗品甘油作为流加发酵 过程中所需的流加底物。
14、 按照权利要求 1一 10 任一项所述的方法， 其特征在于： 发 酵法生产 1,3-丙二醇的底物生物柴油副产物粗品甘油是来源于化学 法、 生物法或超临界法生产生物柴油过程中的副产物粗品甘油， 无 需进一步处理。
15、 按照权利要求 1一 10 任一项所述的方法， 其特征在于： 将 生物柴油生产过程中的副产物粗品甘油作为发酵法生产 1，3-丙二醇 的底物， 包括步骤：
( a) 将菌种克雷伯氏杆菌或丁酸梭菌、 巴斯德梭菌接入含生物 柴油副产物粗品甘油的种子培养基中， 30° (：〜 37Ό培养 161！〜 20h;
( b ) 将种子液加入含生物柴油副产物粗品甘油的初始发酵培养 基， 30°C〜37°C条件下进行厌氧或有氧发酵， 同时流加生物柴油副 产物粗品甘油或该甘油和葡萄糖的混合溶液， 使发酵液中甘油浓度 控制在 10〜40g/L， 其中所述的混合溶液中葡萄糖与甘油浓度比为 5〜10: 1， 并采用 3— 4M碱溶液或氨水控制 pH值为 6.8〜8.0；
( c ) 发酵结束时经脱盐、 蒸馏、 真空精馏步骤将 1,3-丙二醇分 离、 提纯， 获得 1 ,3-丙二醇，同时产生其副产物 2,3-丁二醇、 乳酸、 乙 酸、 乙醇、 丁二酸。
16、 按照权利要求 15 所述的方法， 其特征在于： 生物柴油生产 过程中的副产物粗品甘油作为流加发酵过程中所需的流加底物。
17、按照权利要求 15所述的方法，其特征在于：发酵法生产 1,3- 丙二醇的底物是来源于化学法、 生物法或超临界法生产生物柴油过 程中的副产物粗品甘油。
PCT/CN2006/001181 2005-06-03 2006-06-01 Procede permettant de preparer le propanediol-1,3 en se servant de la glycerine en tant que sous-produit du carburant diesel biologique WO2006128381A1 (fr)

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CA2610777A CA2610777C (en) 2005-06-03 2006-06-01 Method for producing 1,3-propanediol using crude glycerol, a by-product from biodiesel production
KR1020087000176A KR101281847B1 (ko) 2005-06-03 2006-06-01 바이오디젤 생산의 부산물인 조 글리세롤을 이용한 1,3-프로판디올 제조방법
JP2008513903A JP5067888B2 (ja) 2005-06-03 2006-06-01 バイオディーゼル生産からの副産物である粗製グリセロールを用いた１，３−プロパンジオールの産生方法
EP06742068.7A EP1892300B1 (en) 2005-06-03 2006-06-01 Method for producing 1,3-propanediol using crude glycerol, a by-product from biodiesel production
US11/916,180 US8486673B2 (en) 2005-06-03 2006-06-01 Method for producing 1,3-propanediol using crude glycerol, a by-product from biodiesel production
AU2006254616A AU2006254616B2 (en) 2005-06-03 2006-06-01 Method for preparing 1,3-propanediol by using glycerine as the by-product of the biological diesel oil
BRPI0613543A BRPI0613543B8 (pt) 2005-06-03 2006-06-01 Método para produção de 1,3-propanodiol usando glicerol bruto, um subproduto da produção de biodiesel
NO20080001A NO338330B1 (no) 2005-06-03 2008-01-02 Fremgangsmåte til fremstilling av av 1,3-propandiol fra glycerol, et biprodukt fra fremstilling av biodiesel
HK08104152.8A HK1109915A1 (zh) 2005-06-03 2008-04-14 利用生物柴油副產物甘油生產 -丙二醇的方法

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CNB2005100118678A CN1327001C (zh) 2005-06-03 2005-06-03 利用生物柴油副产物甘油生产1,3－丙二醇的方法
CN200510011867.8 2005-06-03

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US8236994B2 (en) 2006-10-31 2012-08-07 Metabolic Explorer Process for the biological production of 1,3-propanediol from glycerol with high yield
EP2248904A1 (en) 2009-05-05 2010-11-10 Metabolic Explorer Continuous culture for 1,3-propanediol production using high glycerine concentration
US20120058531A1 (en) * 2009-05-05 2012-03-08 Metabolic Explorer Continuous culture for 1,3-propanediol production using high glycerine concentration
WO2011042434A1 (en) 2009-10-05 2011-04-14 Metabolic Explorer 1,3-propanediol production with immobilised cells reactors
WO2012062832A1 (en) 2010-11-10 2012-05-18 Metabolic Explorer Microorganisms for 1,3-propanediol production using high glycerine concentration
EP3012325A1 (en) 2010-11-10 2016-04-27 Metabolic Explorer Microorganisms for 1,3-propanediol production using high glycerine concentration
WO2018150023A1 (en) 2017-02-20 2018-08-23 Metabolic Explorer Microbial consortium comprising clostridia for 1,3-propanediol production from glycerol
US10982237B2 (en) 2017-02-20 2021-04-20 Metabolic Explorer Microbial consortium for 1,3-propanediol production using high glycerol concentration
EP3438270A1 (en) 2017-08-04 2019-02-06 Metabolic Explorer Microorganism and method for improved 1,3-propanediol production by fermentation on a culture medium with high glycerine content
WO2019025580A1 (en) 2017-08-04 2019-02-07 Metabolic Explorer MICROORGANISM AND PROCESS FOR THE ENHANCED PRODUCTION OF 1,3-PROPANEDIOL BY FERMENTATION ON A GLYCERIN HIGH CULTURE MEDIUM
US11655486B2 (en) 2017-08-04 2023-05-23 Metabolic Explorer Microorganism and method for improved 1,3-propanediol production by fermentation on a culture medium with high glycerine content
WO2020030775A1 (en) 2018-08-10 2020-02-13 Metabolic Explorer Microorganisms with improved 1,3-propanediol and butyric acid production
US11814663B2 (en) 2018-08-10 2023-11-14 Metabolic Explorer Microorganisms with improved 1,3-propanediol and butyric acid production

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HK1109915A1 (zh) 2008-06-27
NO338330B1 (no) 2016-08-08
EP1892300A1 (en) 2008-02-27
CA2610777C (en) 2016-07-19
RU2404248C2 (ru) 2010-11-20
JP5067888B2 (ja) 2012-11-07
KR101281847B1 (ko) 2013-07-03
BRPI0613543B1 (pt) 2017-05-09
RU2007143867A (ru) 2009-06-10
JP2008541738A (ja) 2008-11-27
BRPI0613543A2 (pt) 2011-01-18
CN1696297A (zh) 2005-11-16
NO20080001L (no) 2008-03-03
CN1327001C (zh) 2007-07-18
AU2006254616B2 (en) 2011-08-11
US8486673B2 (en) 2013-07-16
KR20080018936A (ko) 2008-02-28
BRPI0613543B8 (pt) 2022-07-12
AU2006254616A1 (en) 2006-12-07
EP1892300A4 (en) 2010-12-15
EP1892300B1 (en) 2015-08-26
CA2610777A1 (en) 2006-12-07

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