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CN1351650A - Application of Microemulsion in Fermentation Process - Google Patents

Application of Microemulsion in Fermentation Process Download PDF

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CN1351650A
CN1351650A CN00808009A CN00808009A CN1351650A CN 1351650 A CN1351650 A CN 1351650A CN 00808009 A CN00808009 A CN 00808009A CN 00808009 A CN00808009 A CN 00808009A CN 1351650 A CN1351650 A CN 1351650A
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马赛厄斯·韦格纳
让-皮埃尔·莫利托
克里斯琴·德豪特
贝努特·阿布里贝特
本特·罗格
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BASF Personal Care and Nutrition GmbH
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C12N1/00Microorganisms, 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
    • C12N1/26Processes using, or culture media containing, hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K23/00Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/56Glucosides; Mucilage; Saponins

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Abstract

The invention relates to the use of oil/water emulsions in fermentation processes, these emulsions containing at least water, an emulsifier and an oil phase, the oil phase being selected from one or more compounds of the group consisting of a) fatty acid alkyl esters and/or b) triglycerides of vegetable origin, wherein the average droplet size of the emulsion is in the range of 1 to 100 nm.

Description

微乳在发酵过程中的应用Application of Microemulsion in Fermentation Process

本发明涉及微乳在发酵过程中的应用。The invention relates to the application of microemulsion in the fermentation process.

在合成复杂的天然物质或其他有机化合物如抗生素时,人们越来越多地采用微生物学的方法。在微生物或者部分微生物时,特别是有细菌或真菌参与时,就涉及到厌氧或需氧条件下的物质转换。就这些方法而论,各专业领域不同,界限也总是模糊不清,如所用的“生物转化”,“生物转变”或“发酵”。在本申请范围内后者也是这种方法的用语,这时,将微生物主要是细菌用于转变或合成化学化合物的。Microbiological methods are increasingly being used when synthesizing complex natural substances or other organic compounds such as antibiotics. In the case of microorganisms or parts of microorganisms, especially when bacteria or fungi are involved, it involves the transformation of substances under anaerobic or aerobic conditions. As far as these methods are concerned, the fields of expertise differ and the boundaries are always blurred, eg "biotransformation", "biotransformation" or "fermentation" are used. The latter is also termed within the scope of this application for methods in which microorganisms, mainly bacteria, are used for the conversion or synthesis of chemical compounds.

对于发酵过程的开发和优化来说,尤其是,在其中发生微生物转变的反应介质是具有意义的。一般地说,反应介质都是一种水状溶液或水分散体,特别影响到方法的收益和效率。微生物需要碳、氮和某些以结合形式存在的痕量元素如钙、铁、磷或锌作为养料,以便进行新陈代谢,尽量达到所要求的产物。此外还要经常保持一定而多数是窄范围的温度和pH-范围。至于其他详细情节请参阅W.克鲁格尔(Crueger)/A.克鲁格尔的教科书:“生物工艺学-应用微生物学教程”,1984年第2版,R.Oldenbourg出版社出版。该书第五章专门论述了发酵技术的基础。因此这文献也属本申请公开的内容。作为微生物的养料,除能量丰富的糖类及其衍生物外,在许多方法中都添加天然的脂肪和油类,以及这类物质的衍生物,如甘油、甘油酯、脂肪酸或脂肪酯。当然培养基内不宜有任何内含物,它对微生物的新陈代谢有负面影响。For the development and optimization of fermentation processes, in particular, the reaction medium in which the transformation of the microorganisms takes place is of interest. Generally speaking, the reaction medium is an aqueous solution or dispersion, which especially affects the yield and efficiency of the process. Microorganisms need carbon, nitrogen and certain trace elements such as calcium, iron, phosphorus or zinc in combined form as nutrients in order to carry out metabolism and try to achieve the required products. In addition, certain, often narrow, temperature and pH ranges must always be maintained. For other detailed plots, please refer to the textbook of W. Crueger/A. Crueger: "Biotechnology-Applied Microbiology Tutorial", 2nd edition in 1984, published by R.Oldenbourg Press. Chapter 5 of the book is devoted to the basics of fermentation technology. Therefore, this document also belongs to the disclosed content of the present application. As food for the microorganisms, besides energy-rich sugars and their derivatives, natural fats and oils, as well as derivatives of such substances, such as glycerol, glycerides, fatty acids or fatty esters, are added in many ways. Of course, there should be no inclusions in the medium, which have a negative impact on the metabolism of microorganisms.

从德国专利DE3738812A1中已知,例如利用微生物制造α-Ω-二羧酸的方法,该方法使用热带假丝酵母(Candida tropicalis)杆菌将十二烷基酸甲酯转化为所要的二羧酸。转化是在水性介质中,pH值为6.0,温度30℃下产生。除了给微生物供应能量的葡萄糖外,介质还含有作为乳化剂的乙氧基化的脱水山梨糖醇单油酸酯、酵母提取物、玉米浆以及无机的氮源和磷源。然后,给介质定量添加月桂酸甲酯。文献没有提到乳液的类型、它在发酵物中生成或在其中向介质定量加入月桂酸甲酯。由欧洲专利EP0 535 939A1已知,有一种制备Ω-9-多种不饱和脂肪酸的方法,其中,在水性培养基中,适宜的微生物在有糖类存在作为能量供应者以及有无机或有机的氮源,和有脂肪酸甲酯存在下生产所要求的多种不饱和脂肪酸。From German patent DE 3738812 A1, for example, a method for the production of α-omega-dicarboxylic acids by microorganisms is known, which converts methyl dodecanoate into the desired dicarboxylic acid using the bacterium Candida tropicalis. The transformation takes place in an aqueous medium at a pH of 6.0 at a temperature of 30°C. In addition to glucose, which supplies energy to the microorganisms, the medium contains ethoxylated sorbitan monooleate as emulsifier, yeast extract, corn steep liquor, and inorganic sources of nitrogen and phosphorus. Then, methyl laurate was dosed to the medium. The literature does not mention the type of emulsion, its formation in the ferment or in which methyl laurate is dosed to the medium. Known from European patent EP0 535 939A1, there is a process for the preparation of omega-9-polyunsaturated fatty acids, wherein, in an aqueous medium, suitable microorganisms are present in the presence of carbohydrates as energy suppliers and with inorganic or organic Nitrogen source, and the presence of fatty acid methyl esters to produce the required polyunsaturated fatty acids.

而且还有一些方法,其中只利用上述现有技术的脂肪物质作为能量供应者。这是特别具有经济效益的,因为这种脂肪物质通常比糖、淀粉和类似的化合物其价更低廉。帕克(Park)等人(帕克等人,“发酵与生物工程杂志”,第82卷,第2期,第183~186页,1996)曾描述过一种发酵过程以制造太乐菌素(Tylosin),其中是在水性介质中使用弗氏链霉菌株(Streptomyces fradiae)的微生物,作为唯一碳源的菜籽油的原始用量大约含60克/公升。Also there are methods in which only the above-mentioned prior art fatty substances are used as energy suppliers. This is particularly economical since such fatty substances are generally less expensive than sugars, starches and similar compounds. (Park et al., "Journal of Fermentation and Bioengineering", Vol. 82, No. 2, Pages 183-186, 1996) have described a fermentation process to produce Tylosin (Tylosin ), in which microorganisms of the strain Streptomyces fradiae were used in an aqueous medium, the original amount of rapeseed oil as the sole carbon source contained approximately 60 g/liter.

此外,在发酵过程中,介质或发酵汁内的含氧量起着决定性的作用。因此,氧在需氧过程中具有基质的作用。对各种方法是否能使富含的氧由气相过渡到含有微生物的液相是关键。一个重要参数表明特异的交换表面,一般来说交换表面是间接地由氧的过渡系数kLa来确定的(请参阅克鲁格尔的文献,第5章,第71页)。通常通过搅拌发酵汁可调节氧的供入至最佳,其中氧或空气和液体混合,使界面产生气体交换。通过强烈的搅动,有明显的机械能的供入,如帕克等人所实施的,但也能破坏部分培养基,而使此法的收率减少。除此以外,坏死的微生物本身继续裂解,通过所形成的裂解产物可以导致培养基的毒化,于是不可能经济地生产。在戈玛(Goma)和洛尔斯(Rols)的工作(G.戈玛,J.L.洛尔斯,“生物工艺通讯”,第13卷,第1期,第7~12页,1991)中知道,发酵过程中使用豆油制造抗生素时,可改进氧的过渡系数kLa,在投入相同能量(搅动)的情况下,能提高总过程的产率。In addition, the oxygen content in the medium or in the fermented juice plays a decisive role in the fermentation process. Therefore, oxygen has the role of a substrate in aerobic processes. Whether various methods can make the rich oxygen transition from the gas phase to the liquid phase containing microorganisms is the key. An important parameter indicates the specific exchange surface, which is generally determined indirectly by the oxygen transition coefficient kLa (see Kruger's literature, Chapter 5, p. 71). Oxygen supply is usually adjusted to an optimum by agitation of the fermented juice, where oxygen or air is mixed with the liquid to allow gas exchange at the interface. By vigorous agitation, there is a significant input of mechanical energy, as performed by Parker et al., but it can also destroy part of the medium and reduce the yield of this method. In addition, the necrotic microorganisms themselves continue to lyse, and the resulting lysates can lead to poisoning of the culture medium, so that economical production is not possible. Known from the work of Goma and Rols (G. Goma, J.L. Rols, Bioprocess Letters, Vol. 13, No. 1, pp. 7-12, 1991) , When soybean oil is used to produce antibiotics in the fermentation process, the transition coefficient kLa of oxygen can be improved, and the yield of the overall process can be increased under the same energy input (stirring).

本发明的任务是改进发酵过程,一方面使用廉价的碳源,另一方面要保证给微生物以充分供氧,而不通过搅拌以使微生物有高的机械负担。必须寻找一个方法,使发酵过程中的机械能量减少到最低程度,从而不致于降低收率。主要是即使减少能量投入,也能提高收率。The object of the present invention is to improve the fermentation process, on the one hand using an inexpensive carbon source, and on the other hand ensuring a sufficient supply of oxygen to the microorganisms without a high mechanical burden on the microorganisms by means of agitation. It is necessary to find a way to minimize the mechanical energy in the fermentation process so as not to reduce the yield. The main reason is that the yield can be increased even if the energy input is reduced.

已发现,使用特定的、小细粒的油悬浮于水(油/水)的乳液即可解决上述任务。It has been found that the use of specific, finely divided emulsions of oil suspended in water (oil/water) solves the above-mentioned tasks.

在最初实施方案中,在发酵过程中使用油/水的乳液时,要求其中的乳液至少含有水、乳化剂及油相,而油相含有一种或多种选自下列的化合物:In the first embodiment, when an oil/water emulsion is used in the fermentation process, it is required that the emulsion contains at least water, an emulsifier and an oil phase, and the oil phase contains one or more compounds selected from the group consisting of:

a)脂肪酸烷基酯和/或a) fatty acid alkyl esters and/or

b)植物源的甘油三酯,而且乳液的液滴大小为1至100纳米。b) triglycerides of vegetable origin, and the droplet size of the emulsion is from 1 to 100 nanometers.

按照本发明制成的乳液其细度特小。因而涉及所谓的微乳液,其定义是宏观上是均匀的、光学上是透明、经常是低粘度、在热力学上是稳定的混合物,它是由两种互不相混的液体组成的,而且至少有一种非离子的或离子性表面活性剂,尤其是含有两个疏水基。微乳的形成的条件是,油-水-界面张力几乎近于零。一般地说,必需至少添加一种非离子表面活性剂,进而添加一种助表面活性剂,以达到这种特定的乳液形式。对此请参阅文献“胶体和表面化学导论,D.J.Shaw,Butferworth,1992,第269和270页”。按照本发明所用的乳液液滴的大小为1~100纳米。优选是在10~80纳米的范围内,特别是在10~30纳米的范围。油滴的细度使油相和水相之间形成一个很大的表面,这样就使含有微生物的水相和含有养分的油相之间能很快接触。通过大的表面还能简化气体的交换,尤其是氧和CO2的交换。乳液粘度也额外减小,以致波及全部发酵介质。所以,接着就能明显地减少发酵介质的搅拌速度,因而可望提高发酵过程的收率。The emulsions produced according to the invention have an exceptionally small fineness. It thus concerns so-called microemulsions, which are defined as macroscopically homogeneous, optically transparent, often low-viscosity, thermodynamically stable mixtures consisting of two immiscible liquids and at least There is a nonionic or ionic surfactant, especially containing two hydrophobic groups. The condition for the formation of microemulsion is that the oil-water-interfacial tension is almost zero. Generally speaking, at least one nonionic surfactant and then one cosurfactant must be added to achieve this particular emulsion form. Please refer to the literature "Introduction to Colloid and Surface Chemistry, DJ Shaw, Butferworth, 1992, pages 269 and 270". The emulsion droplets used according to the invention have a size of 1 to 100 nanometers. It is preferably in the range of 10-80 nm, especially in the range of 10-30 nm. The fineness of the oil droplets creates a large surface area between the oil and water phases, allowing for quick contact between the water phase containing microorganisms and the oil phase containing nutrients. The exchange of gases, especially oxygen and CO 2 , is also simplified by the large surface. The viscosity of the emulsion is also additionally reduced so that the entire fermentation medium is affected. Therefore, it is then possible to significantly reduce the stirring speed of the fermentation medium, thereby expecting to increase the yield of the fermentation process.

按照本发明,微乳是水性发酵介质,它含有微生物,以及必要时的其他助剂和添加剂。这方法的细节,特别是定量加入乳液的速度和量,是由微生物的种类和所择的发酵方法决定,专业人员是能够适应具体情况的。According to the invention, microemulsions are aqueous fermentation media which contain microorganisms and, if necessary, other auxiliaries and additives. The details of this method, especially the speed and amount of dosing into the emulsion, are determined by the type of microorganism and the fermentation method chosen, and professionals are able to adapt to the specific situation.

除水、油相之外,微乳还含有:a)由脂肪酸烷基酯类的化合物或b)天然植物油及其衍生物。这涉及到a)和b)类的疏水的、不溶于水或者仅微溶于水的化合物,它们既可在发酵过程中用作所用细菌的养份也可作为能量供应者,它也可作为原料(基质)以通过生物转化而制出所要求的产物。In addition to the water and oil phases, the microemulsion also contains: a) compounds composed of fatty acid alkyl esters or b) natural vegetable oils and their derivatives. This concerns hydrophobic, water-insoluble or only slightly water-soluble compounds of the classes a) and b), which are used both as nutrients and as energy suppliers for the bacteria used in the fermentation process, which also serve as Raw materials (substrates) are biotransformed to produce the desired product.

适宜的a)类的甲基酯,特别是从总量为7至23个碳原子的饱和的、不饱和的、直链的或支链的脂肪酸衍生的甲酯。这由式(I)代表的化合物:Suitable methyl esters of type a) are especially methyl esters derived from saturated, unsaturated, straight-chain or branched-chain fatty acids with a total of 7 to 23 carbon atoms. This is represented by the compound of formula (I):

R1-COO-R2  (I)其中R1代表有6-22个碳原子的烷基,R2代表有1-4个碳原子的烷基,优先的是,甲基和乙基。特别优先的是使用甲酯作为a)的成份。式(I)的酯类或甲酯是用通常方法获得的,例如通过甘油三酯和甲醇的酯化反应和接着的蒸馏。适宜的脂肪酸有:己酸、庚酸、辛酸、壬酸、癸酸、十一烷基酸、月桂酸、十三烷基酸、肉豆蔻酸、十五烷基酸、棕榈酸、十七烷基酸、硬脂酸、十九烷基酸、花生酸和山萮酸。不饱和酸的代表有,例如,月桂烯酸、肉豆蔻烯酸、棕榈炔酸、岩芹烯酸、油酸、反油酸、蓖麻油酸、亚油酸、反亚油酸、亚麻酸、顺(式)-9-二十碳烯酸、花生四烯酸和芥酸。还有,这些酸的甲酯的混合物也是适宜的。使用含有油酸甲酯、棕榈酸甲酯、硬脂酸甲酯和/或壬酸甲酯类的甲酯的微乳是特别优先。基于天然脂肪酸混合物,例如由亚麻子油、椰子油、棕榈油、棕榈仁油、橄榄油、蓖麻油、菜籽油、芝麻油、豆油或葵花油(菜籽油和葵花油有时有新和旧法栽培的品种)中获得的甲酯也可以使用。R 1 -COO-R 2 (I) wherein R 1 represents an alkyl group having 6-22 carbon atoms, R 2 represents an alkyl group having 1-4 carbon atoms, preferably methyl and ethyl. Particular preference is given to using methyl esters as constituents of a). Esters or methyl esters of formula (I) are obtained by usual methods, for example by esterification of triglycerides with methanol and subsequent distillation. Suitable fatty acids are: caproic acid, heptanoic acid, caprylic acid, nonanoic acid, capric acid, undecyl acid, lauric acid, tridecyl acid, myristic acid, pentadecyl acid, palmitic acid, heptadecane fatty acid, stearic acid, nonadecanoic acid, arachidic acid and behenic acid. Representative of unsaturated acids are, for example, lauric acid, myristoleic acid, palmitoleic acid, petracenoic acid, oleic acid, elaidic acid, ricinoleic acid, linoleic acid, elaidic acid, linolenic acid, cis-9-eicosenoic acid, arachidonic acid and erucic acid. Also, mixtures of the methyl esters of these acids are also suitable. The use of microemulsions containing methyl esters of methyl oleate, methyl palmitate, methyl stearate and/or methyl nonanoate is particularly preferred. Based on natural fatty acid mixtures, for example from linseed oil, coconut oil, palm oil, palm kernel oil, olive oil, castor oil, rapeseed oil, sesame oil, soybean oil or sunflower oil (rapeseed oil and sunflower oil sometimes have new and old cultivated The methyl ester obtained in the species) can also be used.

b)类适宜的化合物是植物源的天然油类。因此主要涉及甘油三酯的混合物,其中甘油有时和长链脂肪酸可完全酯化。特别适宜的植物油则选自:花生油、椰子油、亚麻子油、棕榈油、橄榄油、棕榈仁油、蓖麻油、菜籽油、芝麻油、豆油和葵花油。Suitable compounds of class b) are natural oils of vegetable origin. It is therefore primarily concerned with mixtures of triglycerides in which glycerol is sometimes fully esterified with long-chain fatty acids. Particularly suitable vegetable oils are selected from the group consisting of peanut oil, coconut oil, linseed oil, palm oil, olive oil, palm kernel oil, castor oil, rapeseed oil, sesame oil, soybean oil and sunflower oil.

花生油(基于脂肪酸)平均含有54(重量)%的油酸、24(重量)%的亚油酸、1(重量)%的亚麻酸、1(重量)%花生酸、10(重量)%的棕榈酸以及4(重量)%的硬脂酸。熔点为2~3℃。Peanut oil (based on fatty acids) contains on average 54% by weight oleic acid, 24% by weight linoleic acid, 1% by weight linolenic acid, 1% by weight arachidic acid, 10% by weight palmitic acid acid and 4 (weight) % stearic acid. The melting point is 2-3°C.

亚麻子油一般含有5(重量)%的棕榈酸、4(重量)%的硬脂酸、22(重量)%的油酸、17(重量)%的亚油酸和52(重量)%的亚麻酸。碘值位于155~205的范围内。皂化值为188~196,熔点约为-20℃。Linseed oil generally contains 5% by weight of palmitic acid, 4% by weight of stearic acid, 22% by weight of oleic acid, 17% by weight of linoleic acid and 52% by weight of flax acid. The iodine value is in the range of 155-205. The saponification value is 188-196, and the melting point is about -20°C.

椰子油在脂肪酸中含有约0.2~1(重量)%的己酸、5~8(重量)%的辛酸、6~9(重量)%的癸酸、45~51(重量)%的月桂酸、16~19(重量)%的肉豆蔻酸、9~11(重量)%的棕榈酸、2~3(重量)%的硬脂酸、少于0.5(重量)%的山萮酸、8~10(重量)%的油酸以及至多1(重量)%的亚油酸。碘值位于7.5~9.5的范围内,皂化值为0.88~0.90。熔点20~23℃。Coconut oil contains about 0.2 to 1 (weight)% caproic acid, 5 to 8 (weight)% caprylic acid, 6 to 9 (weight)% capric acid, 45 to 51 (weight)% lauric acid, 16~19(weight)% of myristic acid, 9~11(weight)% of palmitic acid, 2~3(weight)% of stearic acid, less than 0.5(weight)% of behenic acid, 8~10 % by weight of oleic acid and up to 1 % by weight of linoleic acid. The iodine value is in the range of 7.5-9.5, and the saponification value is 0.88-0.90. The melting point is 20-23°C.

橄榄油主要含油酸(请参阅Lebensmittelchem.Gerichtl.Chem.,39,112~114,1985)。棕榈油作为脂肪酸成份含有约2(重量)%的肉豆蔻酸、42(重量)%的棕榈酸、5(重量)%的硬脂酸、41(重量)%的油酸、10(重量)%的亚油酸。棕榈仁油,就脂肪酸光谱而言通常有下列成份:9(重量)%的己酸/辛酸/癸酸,50(重量)%的月桂酸、15(重量)%的肉豆蔻酸、7(重量)%的棕榈酸、2(重量)%的硬脂酸、15(重量)%的油酸和1(重量)%的亚油酸。Olive oil mainly contains oleic acid (see Lebensmittelchem. Gerichtl. Chem., 39, 112-114, 1985). Palm oil contains about 2 (weight)% of myristic acid, 42 (weight)% of palmitic acid, 5 (weight)% of stearic acid, 41 (weight)% of oleic acid, 10 (weight)% of linoleic acid. Palm kernel oil, in terms of fatty acid spectrum, generally has the following composition: 9 (weight) % caproic/caprylic/capric acid, 50 (weight) % lauric acid, 15 (weight) % myristic acid, 7 (weight) % ) % of palmitic acid, 2 (weight) % of stearic acid, 15 (weight) % of oleic acid and 1 (weight) % of linoleic acid.

菜籽油作为脂肪酸成份通常含有约48(重量)%的芥酸、15(重量)%的油酸、14(重量)%的亚油酸、8(重量)%的亚麻酸、5(重量)%的二十烯酸、3(重量)%的棕榈酸、2(重量)%的十六烯酸和1(重量)%的二十二烷二烯酸。用新法栽培的菜籽油是富含不饱和成份。通常脂肪酸的组份是芥酸0.5(重量)%、油酸63(重量)%、亚油酸20(重量)%、亚麻酸9(重量)%、二十烯酸1(重量)%、棕榈酸4(重量)%、十六烯酸2(重量)%和二十二烷二烯酸1(重量)%。Rapeseed oil generally contains about 48% by weight of erucic acid, 15% by weight of oleic acid, 14% by weight of linoleic acid, 8% by weight of linolenic acid, 5% by weight % eicosenoic acid, 3% by weight palmitic acid, 2% by weight hexadecenoic acid and 1% by weight docosadienoic acid. The rapeseed oil cultivated by the new method is rich in unsaturated components. Usually the components of fatty acid are 0.5 (weight)% of erucic acid, 63 (weight)% of oleic acid, 20 (weight)% of linoleic acid, 9 (weight)% of linolenic acid, 1 (weight)% of eicosenoic acid, palm Acid 4% by weight, hexadecenoic acid 2% by weight and docosadienoic acid 1% by weight.

蓖麻油含有80~85(重量)%的蓖麻酸的甘油酯,此外还含有约7(重量)%的油酸的甘油酯、3(重量)%的亚油酸的甘油酯以及大约2(重量)%的棕榈酸和硬脂酸的甘油酯。Castor oil contains 80~85 (weight) % glycerides of ricinoleic acid, in addition also contains about 7 (weight) % glycerides of oleic acid, 3 (weight) % glycerides of linoleic acid and about 2 ( weight) % glycerides of palmitic and stearic acids.

豆油含有总脂肪酸的55~65(重量)%的多种不饱和酸,特别是亚油酸和亚麻酸。葵花油有类似的情况,基于总脂肪酸,通常的脂肪酸光谱为:约1(重量)%的肉豆蔻酸、3~10(重量)%的棕榈酸、14~65(重量)%的油酸和20~75(重量)%的亚油酸。Soybean oil contains 55-65% by weight of the total fatty acids of various unsaturated acids, especially linoleic acid and linolenic acid. Sunflower oil has a similar situation, based on total fatty acids, the usual fatty acid spectrum is: about 1 (weight)% myristic acid, 3-10 (weight)% palmitic acid, 14-65 (weight)% oleic acid and 20-75% (weight) of linoleic acid.

有关上述甘油三酯中脂肪酸成份的所有数据都是已知的,它依赖于原料的质量,因此数字上可能有偏差。特别优先的是含有选自椰子油、葵花油和/或菜籽油的b)类养料的微乳。All data on the fatty acid composition of the above triglycerides are known, it depends on the quality of the raw material and therefore the figures may be biased. Particular preference is given to microemulsions containing nutrients of type b) selected from coconut oil, sunflower oil and/or rapeseed oil.

按照本发明应用的微乳的重要成份是加入的乳化剂或乳化剂系统。首先作为乳化剂使用的是非离子化乳化剂,尤其是乙氧基化的脂族醇和脂肪酸。An essential constituent of the microemulsions used according to the invention are the added emulsifiers or emulsifier systems. Firstly used as emulsifiers are nonionic emulsifiers, especially ethoxylated aliphatic alcohols and fatty acids.

按照本发明含意的脂肪醇乙氧基化物具有通式(II):Fatty alcohol ethoxylates within the meaning of the invention have the general formula (II):

R3-O-(CH2CH2O)n-H  (II)其中R3代表有6至24个碳原子的直链的或支链的、饱和的或不饱和的烷基,n表示1~50的数值。特别优先的是式(II)中的n的数值为1~35,尤其是1~15的那些化合物。此外,特别优先的是式(II)中的R3为有16~22碳原子的烷基的那些化合物。R 3 -O-(CH 2 CH 2 O) n -H (II) wherein R 3 represents a linear or branched, saturated or unsaturated alkyl group having 6 to 24 carbon atoms, and n represents 1 A value of ~50. Particular preference is given to those compounds in which n in formula (II) has a value from 1 to 35, especially from 1 to 15. Furthermore, particular preference is given to those compounds in formula (II) in which R 3 is an alkyl group having 16 to 22 carbon atoms.

式(II)中的化合物是按照已知的方法通过脂族醇和环氧乙烷在压力、必要时在有酸性或碱性催化剂存在下进行转化而获得的。代表性的实例是己烷醇、辛烷醇、2-乙基己基醇、癸烷醇、月桂醇、异十三烷醇、肉豆蔻醇、鲸蜡醇、棕榈油醇、硬脂醇、异硬脂醇、油醇、反油醇、岩芹醇、亚油醇、亚麻醇、桐醇、花生醇、顺-9-二十(碳)烯醇、山萮醇、瓢儿菜醇和巴西烯醇以及其工业混合物,例如基于油脂的工业甲酯的高压氢化时或由罗伦(Roelen)羟基合成法制醛时以及在不饱和脂肪族醇二聚作用中作单体分馏时所产生的。优先的是有12~18个碳原子的工业脂族醇,例如椰子醇、棕榈醇、棕榈仁醇或硬脂醇。The compounds of formula (II) are obtained according to known methods by conversion of aliphatic alcohols and ethylene oxide under pressure, if necessary in the presence of acidic or basic catalysts. Representative examples are hexane alcohol, octanol, 2-ethylhexyl alcohol, decanol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isotridecyl alcohol, Stearyl alcohol, oleyl alcohol, elaidic alcohol, petracel alcohol, linoleyl alcohol, linolenyl alcohol, tungyl alcohol, arachidyl alcohol, cis-9-eicosenol, behenyl alcohol, ericyl alcohol, and braziene Alcohols and their industrial mixtures are produced, for example, in the high-pressure hydrogenation of oil-based industrial methyl esters or in the production of aldehydes by the Roelen hydroxyl synthesis and in monomer fractionation in the dimerization of unsaturated aliphatic alcohols. Preference is given to technical aliphatic alcohols having 12 to 18 carbon atoms, such as coconut alcohol, palmityl alcohol, palm kernel alcohol or stearyl alcohol.

脂肪酸乙氧基化物也可考虑作为乳化剂或乳化剂成份,它们主要为式(III):Fatty acid ethoxylates can also be considered as emulsifiers or emulsifier ingredients, which are mainly of formula (III):

R4CO2(CH2CH2O)mH    (III)其中R4表示有12~22个碳原子的直链的或支链的烷基,m代表5~50的数字,优选是15~35。典型的实例是由20~30摩尔的环氧乙烷和月桂酸、异十三碳酸、肉豆蔻酸、棕榈酸、棕榈油酸、硬脂酸、异硬脂酸、油酸、反油酸、岩芹酸、亚油酸、亚麻酸、桐酸、花生酸、二十碳烯酸、山萮酸和芥酸的加成产物以及其工业混合物,例如在天然脂肪和油的加压裂解时或由罗伦氏羰基化合成还原醛时所产生的。优选是20~30摩尔的环氧乙烷和有16~18个碳原子的脂肪酸的加成产物。R 4 CO 2 (CH 2 CH 2 O) m H (III) wherein R 4 represents a linear or branched chain alkyl group with 12 to 22 carbon atoms, and m represents a number from 5 to 50, preferably 15 to 50 35. A typical example is composed of 20 to 30 moles of ethylene oxide and lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, Addition products of petroselinic acid, linoleic acid, linolenic acid, erucic acid, arachidic acid, eicosenoic acid, behenic acid and erucic acid and their industrial mixtures, for example in the pressure cracking of natural fats and oils or Produced during the synthesis of reduced aldehydes by Rorent's carbonylation. Preference is given to addition products of 20-30 moles of ethylene oxide and fatty acids having 16-18 carbon atoms.

偏甘油酯可以考虑作为乳化剂,主要为式(IV):

Figure A0080800900081
其中COR5代表有12~22个碳原子的直链或支链的酰基,x、y和z的总和表示0或者从1~50的数字,特别是15~35。对本发明含义的合适偏甘油酯的实例有:月桂酸单甘油酯、椰子脂肪酸单甘油酯、棕榈酸单甘油酯、硬脂酸单甘油酯、异硬脂酸单甘油酯、油酸单甘油酯和硬脂酸单甘油酯以及其和5~50特别是20~30摩尔的环氧乙烷的加成产物。首先是使用单甘油酯或工业的单甘油/二甘油酯的混合物和过量的式(IV)的单甘油酯的组份,其中COR5代表有16~18个碳原子的直链酰基。Partial glycerides can be considered as emulsifiers, mainly of formula (IV):
Figure A0080800900081
Wherein COR 5 represents a linear or branched acyl group with 12-22 carbon atoms, and the sum of x, y and z represents 0 or a number from 1-50, especially 15-35. Examples of suitable partial glycerides within the meaning of the present invention are: monoglyceride laurate, monoglyceride coconut fatty acid, monoglyceride palmitate, monoglyceride stearate, monoglyceride isostearate, monoglyceride oleate And stearic acid monoglyceride and its addition product with 5-50, especially 20-30 moles of ethylene oxide. The first is the use of monoglycerides or commercial monoglyceride/diglyceride mixtures and excess monoglyceride components of formula (IV), in which COR 5 represents a linear acyl group having 16-18 carbon atoms.

作为其他适宜的乳化剂,可以是由例如选自以下的非离子表面活性剂:As other suitable emulsifiers, nonionic surfactants can be selected from, for example, the following:

(I)2~30摩尔的环氧乙烷和/或0~5摩尔的氧化丙烯和有8~22个碳原子的直链脂族醇的加成产物;(1) The addition product of 2~30 moles of oxirane and/or 0~5 moles of propylene oxide and the linear aliphatic alcohol of 8~22 carbon atoms;

(II)有6~22个碳原子的饱和与不饱和脂肪酸的甘油单酯和甘油二酯以及脱水山梨糖醇单酯和脱水山梨糖醇二酯和其氧化乙烯的加成产物;(II) Monoglycerides and diglycerides of saturated and unsaturated fatty acids having 6 to 22 carbon atoms, as well as sorbitan monoesters and sorbitan diesters and their addition products of ethylene oxide;

(III)烷基中有8~22个碳原子的烷基单苷和烷基寡苷及其乙氧基化的类似物;(III) Alkyl monoglycosides and alkyl oligoglycosides with 8 to 22 carbon atoms in the alkyl group and their ethoxylated analogues;

(IV)15~60摩尔的环氧乙烷和蓖麻油和/或硬化的蓖麻油的加成产物;(IV) addition products of 15-60 moles of ethylene oxide and castor oil and/or hardened castor oil;

(V)聚油酯特别是聚甘油酯如聚甘油聚蓖麻油酸酯或聚甘油聚-12-羟基硬脂酸酯。同时适宜的是有由多种这类物质构成的化合物的混合物:(V) Polyoleyl esters, especially polyglycerol esters such as polyglycerol polyricinoleate or polyglycerol poly-12-hydroxystearate. Also suitable are mixtures of compounds consisting of several of these substances:

(VI)2~15摩尔的环氧乙烷和蓖麻油和/或硬化蓖麻油的加成产物;(VI) addition products of 2 to 15 moles of ethylene oxide and castor oil and/or hardened castor oil;

(VII)基于直链、支链、不饱和或饱和的C12/22-脂肪酸、蓖麻油酸以及12-羟基硬脂酸和甘油、聚甘油、季戊四醇、二季戊四醇、糖醇(如山梨醇)以及聚苷(如纤维素)的偏酯类;(VII) Based on linear, branched, unsaturated or saturated C 12/22 -fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (such as sorbitol) and partial esters of polyglycosides (such as cellulose);

(VIII)羊毛蜡醇;(VIII) wool wax alcohol;

(IX)聚亚烷二醇。(IX) Polyalkylene glycols.

环氧乙烷和/或氧化丙烯和甘油单酯和甘油二酯以及脂肪酸的脱水山梨糖醇单酯和脱水山梨糖醇二酯或蓖麻油的加成产物都是已知的并商业上可以购买的商品。因而涉及到同系的混合物,其平均烷氧基化度是相当于环氧乙烷和/或氧化丙烯和与其进行加成反应的基质的物质量的比例。Addition products of ethylene oxide and/or propylene oxide and mono- and diglycerides and sorbitan mono- and diesters of fatty acids or castor oil are known and commercially available Products of. These are thus homologous mixtures, the average degree of alkoxylation of which corresponds to the ratio of the amount of substance to ethylene oxide and/or propylene oxide and the substrate which undergoes an addition reaction therewith.

特别优先的是共同使用(III)类的乳化剂,也就是烷基苷。烷基寡苷和烯基寡苷都是已知的非离子表面活性剂,其为式(V)Particular preference is given to the co-use of emulsifiers of class (III), ie alkyl glycosides. Alkyl oligosides and alkenyl oligosides are known nonionic surfactants of formula (V)

R6O-[G]p  (V)其中R6代表有4~22个碳原子的烷基和/或烯基,G代表有5~6个碳原子的糖基,而P则表示1~10之间的数字。它们是可以按有机化学制剂的相关方法制得的。这里由许多参考文献中列举一些代表性文献:Biermann等人的“Starch/Starke”45,281(1993),B.Salka在“化妆品”108,89(1993)以及J.Kahre等人在SOFW杂志,第8册,598(1995)。R 6 O-[G] p (V) wherein R 6 represents an alkyl and/or alkenyl group with 4 to 22 carbon atoms, G represents a sugar group with 5 to 6 carbon atoms, and P represents 1 to 6 Numbers between 10. They can be prepared according to the relevant methods of organic chemical preparations. Some representative documents are listed here from many references: Biermann et al. "Starch/Starke" 45, 281 (1993), B. Salka in "Cosmetics" 108, 89 (1993) and J. Kahre et al. in SOFW magazine , Volume 8, 598 (1995).

烷基寡苷和/或烯基寡苷是能够从有5或6个碳原子的醛糖及酮糖尤其是从葡萄糖中衍生。优先的烷基寡苷和/或烯基寡苷是烷基寡葡糖苷和/或烯基寡葡糖苷。在通式(V)中的指数P是寡聚度(DP),也就是说,单苷和寡苷的分配,并代表1至10之间的数字。而在列举的化合物中P必须是整数,在这里首先可假设P值=1至6,对某个烷基寡苷而言P值是经过分析的平均汁算值,所以大多数是分数。特别是烷基寡苷和/或烯基寡苷的平均寡聚度P为1.1至3.0。从应用技术的角度来看,这种烷基寡苷和/或烯基寡苷是优先的,其寡聚度小于1.7,尤其是在1.2和1.4之间。烷基或烯基R6是由有4至11个碳原子而优选是8至10个碳原子的伯醇衍生的。代表性实例有丁醇、己醇、辛醇、癸醇、十一烷醇以及其工业混合物,例如在工业脂肪酸甲酯氢化时或在罗伦氏羟基合成中的醛的氢化过程中获得的。优先的是链长为C8-C10(DP=1~3)的烷基寡苷,在工业性C8-C10椰子脂醇进行蒸馏分离时作为初馏物而产生,并可掺杂有少于6(重量)%的C12-醇,以及基于工业C9/11-羰基醇(DP=1~3)的烷基寡苷。烷基或烯基R6也可进一步由有12~22个碳原子尤其是12~14个碳原子的伯醇中衍生。代表性实例是月桂醇、肉豆蔻醇、鲸蜡醇、棕榈油醇、硬脂醇、异硬脂醇、油醇、反油醇、岩芹醇、花生醇、顺式9-二十碳烯醇、山萮醇、瓢儿菜醇、巴西烯醇以及其工业混合物,如上所述,它们都能如上获得的。优先的是基于硬化的DP为1~3的C12/14椰子醇的烷基寡苷。如果式(V)的烷基苷用作乳化剂,那么它的优点就是使用少量聚羟基羧酸尤其是柠檬酸作为制剂助剂。而一般来讲,这时聚羟基酸的用量是0.1~3.0(重量)%,优先为0.1~1.0(重量)%。Alkyl and/or alkenyl oligosides can be derived from aldoses and ketoses having 5 or 6 carbon atoms, especially glucose. Preferred alkyl and/or alkenyl oligosides are alkyl and/or alkenyl oligoglucosides. The index P in the general formula (V) is the degree of oligomerization (DP), that is to say, the distribution of monoglycosides and oligoglycosides, and represents a number between 1 and 10. In the listed compounds, P must be an integer, and here at first it can be assumed that the P value=1 to 6. For a certain alkyl oligoglycoside, the P value is the calculated average value after analysis, so most of them are fractions. In particular the average degree of oligomerization P of the alkyl and/or alkenyl oligosides is from 1.1 to 3.0. From an applied technical point of view, such alkyl and/or alkenyl oligosides are preferred with a degree of oligomerization of less than 1.7, especially between 1.2 and 1.4. Alkyl or alkenyl R6 is derived from a primary alcohol having 4 to 11 carbon atoms, preferably 8 to 10 carbon atoms. Representative examples are butanol, hexanol, octanol, decanol, undecanol and industrial mixtures thereof, as obtained, for example, during the hydrogenation of industrial fatty acid methyl esters or during the hydrogenation of aldehydes in the Lorenzo hydroxyl synthesis. Alkyl oligosides with a chain length of C 8 -C 10 (DP=1~3) are preferred, which are produced as foreruns during the distillation and separation of industrial C 8 -C 10 coconut oil alcohols, and can be doped There are less than 6% by weight of C 12 -alcohols, and alkyl oligosides based on industrial C 9/11 -carbonyl alcohols (DP=1-3). Alkyl or alkenyl R 6 may also be further derived from primary alcohols having 12 to 22 carbon atoms, especially 12 to 14 carbon atoms. Representative examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidic alcohol, petracel alcohol, arachidyl alcohol, cis-9-eicosene Alcohol, Behenyl Alcohol, Behenyl Alcohol, Bascenyl Alcohol, and industrial mixtures thereof, all of which are obtainable as described above. Preference is given to alkyl oligosides based on hardened C 12/14 coconut alcohols with a DP of 1-3. If the alkylglycosides of the formula (V) are used as emulsifiers, it has the advantage of using small amounts of polyhydroxycarboxylic acids, especially citric acid, as formulation aids. Generally speaking, the amount of polyhydroxy acid used at this time is 0.1-3.0% by weight, preferably 0.1-1.0% by weight.

按照本发明所用的微乳主要含有20~90(重量)%,尤其是30~80(重量)%的水,而最优先的则是30~60(重量)%的水,100重量%中的其余部分为油相以及乳化剂,必要时还可以有其他助剂和添加剂。油相本身的优先含量是10~80(重量)%,尤其是20~70(重量)%,而特别优先的则是25~55(重量)%。油相主要是含有成分a)或b)以及这些成份的混合物。利用这些乳液特别优先是其油相和水相的重量比为1∶1。乳化剂或者乳化系统的优先含量是10~50(重量)%,优选是含量15~45(重量)%,特别优先的含量则是20~40(重量)%。The microemulsion used according to the present invention mainly contains 20-90 (weight) %, especially 30-80 (weight) % of water, and the most preferred is 30-60 (weight) % of water, 100 % by weight The rest is the oil phase and emulsifier, and other auxiliary agents and additives if necessary. The preferred content of the oil phase itself is 10-80% by weight, especially 20-70% by weight, and particularly preferably 25-55% by weight. The oily phase mainly contains ingredients a) or b) and mixtures of these ingredients. It is particularly preferred to use these emulsions with a weight ratio of oil phase to water phase of 1:1. The preferred content of emulsifier or emulsifying system is 10-50% by weight, preferably 15-45% by weight, and particularly preferred content is 20-40% by weight.

本发明所述的微乳可用于各种发酵过程。此外还可用于一切专业人员所熟悉的方法布置中,如分批发酵法或分批加料发酵法,以及连续发酵法。凡专业人员熟悉的发酵系统都可以采用。详细情况请参阅Crueger的个别部分,第50~70页。微乳的用途不限于某些微生物,所有专业人员通过发酵所熟悉的化合物,都可使用乳液进行制造或转换。除了以合成抗生素为主而采用的经典发酵方法以外(请参阅Crueger的著作,第197~242页),上述乳液还适用于微生物的转化(“生物转换”),如甾族化合物和甾醇的转换,抗生素和杀虫剂的转换,或者维生素的制造(请参阅克鲁格尔的著作,第254~273页)。而优选是用于制造抗生素的发酵过程,如头孢霉素、太乐菌素或红霉素。The microemulsion of the present invention can be used in various fermentation processes. Furthermore, it can be used in all process arrangements familiar to the skilled person, such as batch or fed-batch fermentation, as well as continuous fermentation. Any fermentation system familiar to professionals can be used. For details, see the individual sections of Crueger, pp. 50-70. The use of microemulsions is not limited to certain microorganisms, all compounds familiar to professionals through fermentation can be produced or transformed using emulsions. In addition to the classical fermentation methods used mainly for the synthesis of antibiotics (see Crueger, pp. 197-242), the above emulsions are also suitable for microbial transformations ("biotransformations"), such as steroids and sterols , the conversion of antibiotics and pesticides, or the manufacture of vitamins (see Kruger, pp. 254-273). Rather, it is preferably a fermentation process for the manufacture of antibiotics, such as cephalosporins, telosin or erythromycin.

通常微乳是水性发酵汁,它含有微生物以及氮源和痕量元素,必要时还有其他助剂,尤其是去泡剂并以适当方法配制。作为氮源例如可考虑有:胨、酵母提取物或麦芽提取物、玉米浆、尿素或卵磷脂。痕量元素可以用无机盐的形式,例如硝酸钠或硝酸钾、硝酸胺、硫酸胺、硫酸铁等等。另一个优点,就是微乳本身能以另外的添加剂,如去泡剂或氮源加入。Usually microemulsions are aqueous fermented juices which contain microorganisms as well as nitrogen sources and trace elements and, if necessary, other auxiliaries, especially defoamers, and are formulated in an appropriate manner. Examples of nitrogen sources are: peptone, yeast extract or malt extract, corn steep liquor, urea or lecithin. Trace elements can be used in the form of inorganic salts such as sodium or potassium nitrate, ammonium nitrate, ammonium sulfate, iron sulfate, and the like. Another advantage is that the microemulsion itself can be added with additional additives such as defoamers or nitrogen sources.

实施例Example

通过混合原料物而制成不同的微乳。组成成份列于表1。液滴大小可用Malvern Mastersizer 2000进行测量。乳液适于作发酵过程中的单独养料源,亦可直接掺入水性发酵汁内。Different microemulsions are made by mixing raw materials. The composition is listed in Table 1. Droplet size can be measured with a Malvern Mastersizer 2000. The emulsion is suitable as an independent nutrient source in the fermentation process, and can also be directly mixed into the aqueous fermentation juice.

                             表1a   重量%   重量%   重量%   重量%   油酸甲酯   32.44   月桂酸甲酯     30.95   壬酸甲酯     29.61 菜籽油脂肪酸甲酯     32.35       水     34.27     32.04     30.24     34.18     烷基苷     25.22     31.55     30.95     25.3   油酸甘油酯     7.91     6.55     7.62     7.84     柠檬酸     0.25     0.24     0.24     0.24      外观     澄清     澄清     澄清     澄清    小滴大小     <80nm     <80nm     <80nm     <80nm Table 1a weight% weight% weight% weight% methyl oleate 32.44 Methyl laurate 30.95 Methyl nonanoate 29.61 Rapeseed Fatty Acid Methyl Esters 32.35 water 34.27 32.04 30.24 34.18 Alkyl glycosides 25.22 31.55 30.95 25.3 Glyceryl Oleate 7.91 6.55 7.62 7.84 citric acid 0.25 0.24 0.24 0.24 Exterior clarify clarify clarify clarify droplet size <80nm <80nm <80nm <80nm

Claims (10)

1.油/水乳液的应用,它至少含有水、乳化剂,以及油相,该油相含有选自以下化合物的一种或多种:1. The application of oil/water emulsion, it contains water, emulsifying agent at least, and oil phase, and this oil phase contains one or more selected from following compounds: a)脂肪酸烷基酯和/或a) fatty acid alkyl esters and/or b)植物源的甘油三酯,b) triglycerides of vegetable origin, 其特征为,发酵过程中乳液的液滴大小范围为1~100纳米。It is characterized in that the droplet size range of the emulsion in the fermentation process is 1-100 nanometers. 2.按照权利要求1的应用,其特征为,作为成份a)使用脂肪酸甲酯。2. Use according to claim 1, characterized in that fatty acid methyl esters are used as component a). 3.按照权利要求1或2的应用,其特征为,所用乳液的平均液滴大小为10~80纳米,优选是在10~50纳米的范围内。3. Use according to claim 1 or 2, characterized in that the average droplet size of the emulsion used is in the range of 10 to 80 nm, preferably in the range of 10 to 50 nm. 4.按照权利要求1至3中的应用,其特征为,所用乳液的含水量为20~90(重量)%,优选是30~80(重量)%,而特别优先是30~60(重量)%。4. According to the application in claims 1 to 3, it is characterized in that the water content of the emulsion used is 20-90 (weight) %, preferably 30-80 (weight) %, and particularly preferably 30-60 (weight) %. 5.按照权利要求1至4的应用,其特征为,所用乳液的油相含有量为10~80(重量)%,优选20~70(重量)%,而特别优先是25~55%重量。5. Use according to claims 1 to 4, characterized in that the emulsion used has an oil phase content of 10-80% by weight, preferably 20-70% by weight and particularly preferably 25-55% by weight. 6.按照权利要求1至5的应用,其特征为,所用乳液的油相中含有式(I)的脂肪酸甲酯:6. According to the application of claims 1 to 5, it is characterized in that the fatty acid methyl ester of formula (I) is contained in the oil phase of the emulsion used: R1-COO-R2    (I)R 1 -COO-R 2 (I) 其中R1代表有6至22个碳原子的烷基,R2则表示甲基。Wherein R 1 represents an alkyl group having 6 to 22 carbon atoms, and R 2 represents a methyl group. 7.按照权利要求1至6中的应用,其特征为,所用乳液的油相中含有油酸甲酯、棕榈酸甲酯、硬脂酸甲酯和/或壬酸甲酯。7. According to the application in claims 1 to 6, it is characterized in that the oil phase of the emulsion used contains methyl oleate, methyl palmitate, methyl stearate and/or methyl nonanoate. 8.按照权利要求1至7中的应用,其特征为,所用乳液的油相中含有椰子油、葵花油和/或菜籽油。8. Use according to claims 1 to 7, characterized in that the oily phase of the emulsion used contains coconut oil, sunflower oil and/or rapeseed oil. 9.按照权利要求1至8中的应用,其特征为,所用乳液含有作为乳化剂的烷基寡苷。9. Use according to claims 1 to 8, characterized in that the emulsion used contains alkyl oligoglycosides as emulsifiers. 10.按照权利要求1至9中的应用,其特征为,所用乳液所含的乳化剂量为10~50%重量,优选是15~40%重量,特别优先为20~35%重量。10. Use according to claims 1 to 9, characterized in that the emulsifier used in the emulsion contains 10-50% by weight, preferably 15-40% by weight, particularly preferably 20-35% by weight.
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