CN1351650A - Utilisation of microemulsions in fermentation processes - Google Patents

Utilisation of microemulsions in fermentation processes 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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    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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    • C09K23/018—Mixtures of two or more different organic oxygen-containing compounds
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    • 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
    • C12N1/26—Processes using, or culture media containing, hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/56—Glucosides; Mucilage; Saponins

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Abstract

The invention relates to the utilization of O/W emulsions in fermentation processes, said emulsions containing at least water, emulsifying agents and an oil phase that contains one or more compounds selected from the group consisting of: a) fatty acid alkyl ester and/or b) triglycerides of vegetable origin, wherein the emulsions have an average drop size ranging from 1 to 100 nm.

Description

Micro emulsion application during the fermentation
The present invention relates to micro emulsion application during the fermentation.
When synthetic complicated crude substance or other organic compound such as microbiotic, people adopt microbiological method more and more.When microorganism or part microorganism, when particularly having bacterium or fungi to participate in, just relate to the material conversion under anaerobism or the aerobic condition.With regard to these methods, each professional domain difference, boundary are also always smudgy, as used " bio-transformation ", " biotransformation " or " fermentation ".The latter also is the term of this method in the application's scope, at this moment, if the microbial host bacterium is used to change or the synthetic chemistry compound.
For the exploitation and the optimization of fermenting process, especially, the reaction medium that the microorganism transformation takes place therein has meaning.In general, reaction medium all is a kind of watery solution or water dispersion, has influence on the income and the efficient of method especially.Microorganism needs trace elements that carbon, nitrogen and some exist with combining form such as calcium, iron, phosphorus or zinc as nutriment, so that carry out metabolism, reaches desired product as far as possible.To often keep certain in addition and majority is the temperature and the pH-scope of close limit.See also the textbook of W. Kruegel (Crueger)/A. Kruegel as for other detailed circumstances: " biotechnology-applied microbiology study course ", 1984 the 2nd edition, R.Oldenbourg press publishes.This book chapter 5 has been discussed the basis of fermentation technique specially.Therefore this document also belongs to the disclosed content of the application.As the nutriment of microorganism, except that energy rich saccharide and derivative thereof, in many methods, all add natural fat and oils, and the derivative of this class material, as glycerine, glyceryl ester, lipid acid or fatty ester.Certainly in the substratum any inclusion should not be arranged, it has negative impact to the metabolism of microorganism.
Known from German patent DE 3738812A1, for example utilize microorganism to make the method for α-Ω-dicarboxylic acid, this method uses candida tropicalis (Candida tropicalis) bacillus that dodecyl acid methyl esters is converted into desired dicarboxylic acid.Conversion is in aqueous medium, and the pH value is 6.0, and temperature produces down for 30 ℃.Except giving the glucose of microorganism supplying energy, medium also contains as the dehydrated sorbitol mono-fatty acid ester of the ethoxylation of emulsifying agent, yeast extract, corn steep liquor and inorganic nitrogenous source and phosphorus source.Then, quantitatively add Laurate methyl for medium.Document do not mention emulsion type, it generates in fermented product or quantitatively add Laurate methyl to medium therein.0 535 939A1 are known by European patent EP, the method that a kind of Ω of preparation-many kinds of unsaturated fatty acidss of 9-are arranged, wherein, in aqueous culture medium, suitable microorganism is having carbohydrate to exist as the energy supplier and inorganic or organic nitrogenous source is being arranged and the desired multiple unsaturated fatty acids of production in the presence of the fatty acid methyl ester is arranged.
And also having certain methods, the fatty substance that wherein only utilizes above-mentioned prior art is as the energy supplier.This is to have economic benefit especially, because this fatty substance is cheaper than its valency of sugar, starch and similar compounds usually.Parker people such as (Park) (people such as Parker, " fermentation and biotechnology magazine ", the 82nd volume, the 2nd phase, the 183rd～186 page, 1996) once describing a kind of fermenting process to make tylosin (Tylosin), wherein is the microorganism of using streptomyces fradiae strain (Streptomyces fradiae) in aqueous medium, approximately contains 60 gram/litres as the original consumption of the rapeseed oil of sole carbon source.
In addition, during the fermentation, the oxygen level decisive role in medium or the fermented juice.Therefore, oxygen has the effect of matrix in Aerobic processes.Whether can make the oxygen that is rich in carry out the transition to the liquid phase that contains microorganism by gas phase to the whole bag of tricks is crucial.An important parameter shows special exchange surface, and in general exchange surface is (the seeing also the document of Kruegel, the 5th chapter, the 71st page) determined by the transfer coefficient kLa of oxygen indirectly.Usually can regulate infeeding to the best of oxygen by stirring fermented juice, wherein oxygen or air and liquid mixing make the interface produce gaseous interchange.Stir by intensive, infeeding of tangible mechanical energy arranged, implement as people such as Parkers, but also can destroy the part substratum, and the yield of this method is reduced.In addition, downright bad microorganism itself continues cracking, can cause poisoning of substratum by formed split product, so can not produce economically.Work (G. dagger-axe agate at dagger-axe agate (Goma) and Luo Ersi (Rols), J.L. Luo Ersi, " bioprocess technology communication ", the 13rd volume, the 1st phase, the 7th～12 page, 1991) know in, when using soya-bean oil to make microbiotic in the fermenting process, can improve the transfer coefficient kLa of oxygen, under the situation that drops into identical energy (stirring), can improve the productive rate of total process.
Task of the present invention is to improve fermenting process, uses cheap carbon source on the one hand, will ensure to microorganism on the other hand with abundant oxygen supply, and not by stirring so that microorganism has high machinery burden.Must seek a method, the mechanical energy in the fermenting process is reduced to a minimum, thereby be unlikely the reduction yield.Even mainly be to reduce the energy input, also can improve yield.
Find that the emulsion of using oil specific, little particulate to be suspended in water (oil/water) can solve above-mentioned task.
In the original adoption scheme, when using the emulsion of oil/water during the fermentation, require emulsion wherein to contain water, emulsifying agent and oil phase at least, and oil phase contains one or more and is selected from following compound:
A) fatty acid alkyl ester and/or
The drop size of the b) triglyceride level of plant-sourced, and emulsion is 1 to 100 nanometer.
Little according to its fineness of emulsion spy that the present invention makes.Thereby relate to so-called microemulsion, its definition be on the macroscopic view be uniformly, on the optics be transparent, often be low viscosity, be stable mixture on thermodynamics, it is made up of two kinds of mutual immiscible liquid, and have a kind of non-ionic or ionic surfactant at least, especially contain two hydrophobic groups.The condition of the formation of micro emulsion is that oil-water-interfacial tension almost is bordering on zero.In general, must add a kind of nonionogenic tenside at least, and then add a kind of cosurfactant, to reach this specific emulsion form.This is seen also document " colloid and surface chemistry introduction, D.J.Shaw, Butferworth, 1992, the 269 and 270 pages ".Size according to the used emulsion droplet of the present invention is 1～100 nanometer.Preferably in the scope of 10～80 nanometers, particularly in the scope of 10～30 nanometers.The fineness of oil droplet makes between oil phase and the water and to form a very big surface, and so just making the water that contains microorganism and contain can very fast contact between the oil phase of nutrient.Can also simplify exchange gas by big surface, especially oxygen and CO 2Exchange.Emulsion viscosity also additionally reduces, so that involves whole fermentation medias.So, can reduce the stirring velocity of fermentation media significantly with that, thereby be expected to improve the yield of fermenting process.
According to the present invention, micro emulsion is the aqueous ferment medium, and it contains microorganism, and in case of necessity other auxiliary agents and additive.The details of this method particularly quantitatively adds the speed and the amount of emulsion, is that the professional can adapt to particular case by kind of microorganism and the fermentation process decision of being selected.
Dewater, outside the oil phase, micro emulsion also contains: a) by the compound or the b of fatty acid alkyl ester class) crude vegetal and derivative thereof.This relates to a) and b) class hydrophobic, water insoluble or only be slightly soluble in the compound of water, the nutrient that they both can be used as used bacterium during the fermentation also can be used as the energy supplier, and it also can be used as raw material (matrix) to make desired product by bio-transformation.
The methyl ester of suitable a) class particularly is the methyl esters of fatty acid derived of saturated, undersaturated, straight chain or the side chain of 7 to 23 carbon atoms from total amount.The compound that this is represented by formula (I):
R 1-COO-R 2(I) R wherein 1Representative has the alkyl of 6-22 carbon atom, R 2Representative has the alkyl of 1-4 carbon atom, preferentially is methyl and ethyl.The preferential especially methyl esters that is to use is as a) composition.The ester class of formula (I) or methyl esters obtain with usual method, for example by the esterification of triglyceride level and methyl alcohol and the distillation of following.Suitable lipid acid has: caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, undecyl acid, lauric acid, tridecyl acid, tetradecanoic acid, pentadecyl acid, palmitinic acid, heptadecyl acid, stearic acid, nonadecyl acid, eicosanoic acid are with docosoic.The representative of unsaturated acid has, for example, and lauroleic acid, myristoleic acid, palmitolic acid, petroselinum olefin(e) acid, oleic acid, elaidic acid, ricinolic acid, linolic acid, trans,trans-Linoleic acid, linolenic acid, suitable (formula)-9-eicosenoic acid, arachidonic acid and erucic acid.Also have, the mixture of the methyl esters that these are sour also suits.The micro emulsion that use contains the methyl esters of Witconol 2301, Uniphat A60, methyl stearate and/or methyl pelargonate class is preferential especially.Based on natural acid mixture, for example also can use by the methyl esters that obtains in Toenol 1140, Oleum Cocois, plam oil, palm-kernel oil, sweet oil, Viscotrol C, rapeseed oil, sesame oil, soya-bean oil or the Trisun Oil R 80 (rapeseed oil and Trisun Oil R 80 have kind new and the old law cultivation sometimes).
B) the class suitable compounds is the natural oils of plant-sourced.Therefore relate generally to the mixture of triglyceride level, wherein glycerine sometimes with longer chain fatty acid esterification fully.Shi Yi vegetables oil then is selected from especially: peanut oil, Oleum Cocois, Toenol 1140, plam oil, sweet oil, palm-kernel oil, Viscotrol C, rapeseed oil, sesame oil, soya-bean oil and Trisun Oil R 80.
Peanut oil (based on lipid acid) on average contains the stearic acid of palmitinic acid and 4 (weight) % of linolenic acid, 1 (weight) % eicosanoic acid, 10 (weight) % of linolic acid, 1 (weight) % of oleic acid, 24 (weight) % of 54 (weight) %.Fusing point is 2～3 ℃.
Toenol 1140 generally contains the linolenic acid of linolic acid and 52 (weight) % of oleic acid, 17 (weight) % of stearic acid, 22 (weight) % of palmitinic acid, 4 (weight) % of 5 (weight) %.Iodine number is positioned at 155～205 scope.Saponification value is 188～196, and fusing point is about-20 ℃.
Oleum Cocois in lipid acid, contain 0.2～1 (weight) % that has an appointment caproic acid, 5～8 (weight) % sad, 6～9 (weight) % capric acid, 45～51 (weight) % lauric acid, 16～19 (weight) % tetradecanoic acid, 9～11 (weight) % palmitinic acid, 2～3 (weight) % stearic acid, be less than oleic acid and the linolic acid of 1 (weight) % at the most of docosoic, 8～10 (weight) % of 0.5 (weight) %.Iodine number is positioned at 7.5～9.5 scope, and saponification value is 0.88～0.90.20～23 ℃ of fusing points.
Sweet oil mainly contains oleic acid (seeing also Lebensmittelchem.Gerichtl.Chem., 39,112～114,1985).Plam oil contains the linolic acid of oleic acid, 10 (weight) % of stearic acid, 41 (weight) % of palmitinic acid, 5 (weight) % of tetradecanoic acid, 42 (weight) % of 2 (weight) % that has an appointment as the lipid acid composition.Palm-kernel oil, following composition is arranged usually: caproic acid/caprylic/capric of 9 (weight) %, the linolic acid of oleic acid and 1 (weight) % of stearic acid, 15 (weight) % of palmitinic acid, 2 (weight) % of tetradecanoic acid, 7 (weight) % of lauric acid, 15 (weight) % of 50 (weight) % with regard to lipid acid spectrum.
Rapeseed oil contains the docosane diolefinic acid of gaidic acid and 1 (weight) % of palmitinic acid, 2 (weight) % of eicosenoic acid, 3 (weight) % of linolenic acid, 5 (weight) % of linolic acid, 8 (weight) % of oleic acid, 14 (weight) % of erucic acid, 15 (weight) % of 48 (weight) % that has an appointment usually as the lipid acid composition.Rapeseed oil with new method cultivation is to be rich in unsaturated composition.Usually the component of lipid acid is erucic acid 0.5 (weight) %, oleic acid 63 (weight) %, linolic acid 20 (weight) %, linolenic acid 9 (weight) %, eicosenoic acid 1 (weight) %, palmitinic acid 4 (weight) %, gaidic acid 2 (weight) % and docosane diolefinic acid 1 (weight) %.
Viscotrol C contains the glyceryl ester of the ricinoleate acid of 80～85 (weight) %, contains the linoleic glyceryl ester of oleic glyceryl ester, 3 (weight) % of 7 (weight) % that has an appointment and palmitinic acid and the stearic glyceryl ester of about 2 (weight) % in addition.
Soya-bean oil contains the multiple unsaturated acid, particularly linoleic acid plus linolenic acid of 55～65 (weight) % of total fatty acids.Trisun Oil R 80 has similar situation, and based on total fatty acids, common lipid acid spectrum is: the linolic acid of oleic acid and 20～75 (weight) % of palmitinic acid, 14～65 (weight) % of tetradecanoic acid, 3～10 (weight) % of about 1 (weight) %.
All data of lipid acid composition all are known in the relevant above-mentioned triglyceride level, and it depends on the quality of raw material, so have deviation on the numeral.Preferential especially is to contain the b that is selected from Oleum Cocois, Trisun Oil R 80 and/or rapeseed oil) micro emulsion of class nutriment.
The important composition of the micro emulsion of using according to the present invention is emulsifying agent or the emulsifier system that adds.What at first use as emulsifying agent is the fatty alcohol and the lipid acid of non-ionization emulsifying agent, especially ethoxylation.
Fatty alcohol ethoxylate according to connotation of the present invention has general formula (II):
R 3-O-(CH 2CH 2O) n-H (II) is R wherein 3Representative has alkyl straight chain or side chain, saturated or unsaturated of 6 to 24 carbon atoms, and n represents 1～50 numerical value.Preferential especially is that the numerical value of the n in the formula (II) is 1～35, especially those compounds of 1～15.In addition, preferential especially is R in the formula (II) 3Those compounds for alkyl that 16～22 carbon atoms are arranged.
Compound in the formula (II) in accordance with known methods by fatty alcohol and oxyethane at pressure, having to transform in the presence of acidity or the basic catalyst and obtaining in case of necessity.Representational example is a hexane alcohol, octane alcohol, 2-ethylhexyl alcohol, decane alcohol, lauryl alcohol, different tridecyl alcohol, tetradecyl alcohol, hexadecanol, Palmitoleyl alcohol, stearyl alcohol, isooctadecanol, oleyl alcohol, anti-oleyl alcohol, petroselinum alcohol, inferior oleyl alcohol, linolenyl alcohol, paulownia alcohol, n-Eicosanol, suitable-9-20 (carbon) enol behenyl alcohol, erucyl alcohol and Brazilian enol with and cuts, produced during during for example based on the high-pressure hydrogenation of greasy industrial methyl esters or by the synthetic legal system aldehyde of Lauren (Roelen) hydroxyl and when in unsaturated aliphatic alcohol dimerisation, doing the monomer fractionation.Preferential is the industrial fatty alcohol that 12～18 carbon atoms are arranged, for example coconut alcohol, palmityl alcohol, palm-kernel alcohol or stearyl alcohol.
Fatty acid ethoxylate also can be considered as emulsifying agent or emulsifying agent composition, and they are mainly formula (III):
R 4CO 2(CH 2CH 2O) mH (III) is R wherein 4Expression has alkyl straight chain or side chain of 12～22 carbon atoms, and m represents 5～50 numeral, and preferably 15～35.Typical example be by the adduct of 20～30 moles oxyethane and lauric acid, different ficocerylic acid, tetradecanoic acid, palmitinic acid, Zoomeric acid, stearic acid, Unimac 5680, oleic acid, elaidic acid, petroselinic acid, linolic acid, linolenic acid, eleostearic acid, eicosanoic acid, eicosenoic acid, docosoic and erucic acid with and cuts, produced during for example when the pressurization cracking of natural fat and oil or by the synthetic reduction of Luo Lunshi carbonylation aldehyde.20～30 moles oxyethane and the adduct of the lipid acid of 16～18 carbon atoms is arranged preferably.
Partial glyceride can be considered as emulsifying agent, is mainly formula (IV):
Figure A0080800900081
COR wherein 5Representative has the acyl group of straight or branched of 12～22 carbon atoms, and the summation of x, y and z represents 0 or from 1～50 numeral, and particularly 15～35.Example to the suitable partial glyceride of implication of the present invention has: lauric monoglyceride, coconut fatty acid direactive glyceride, hexadecanoic acid direactive glyceride, glyceryl monostearate, Unimac 5680 direactive glyceride, monoolein and glyceryl monostearate with and and 5～50 20～30 moles adducts of oxyethane particularly.At first be to use the single glycerine/mixture of two glyceryl ester and the component of the direactive glyceride of excessive formula (IV), the wherein COR of direactive glyceride or industry 5Representative has the straight chain acyl group of 16～18 carbon atoms.
As other examples of suitable emulsifiers, can be by for example being selected from following nonionogenic tenside:
(I) propylene oxide of 2～30 moles oxyethane and/or 0～5 mole and the adduct of the straight-chain fatty alcohol of 8～22 carbon atoms is arranged;
(II) monoglyceride of saturated and unsaturated fatty acids of 6～22 carbon atoms and the adduct of triglyceride and sorbitan monoesters and sorbitan diester and its ethylene oxide are arranged;
(III) the alkyl list glycosides of 8～22 carbon atoms and the analogue of few glycosides of alkyl and ethoxylation thereof are arranged in the alkyl;
(IV) adduct of 15～60 moles oxyethane and Viscotrol C and/or hardened Viscotrol C;
(V) poly-grease particularly polyglycerol ester such as polyglycerol polyricinoleate or Polyglycerine poly--the 12-hydroxy stearic acid ester.Suitable is the mixture that the compound that is made of multiple this class material is arranged simultaneously:
(VI) adduct of 2～15 moles oxyethane and Viscotrol C and/or hardened castor oil;
(VII) based on straight chain, side chain, unsaturated or saturated C 12/22The partial ester class of-lipid acid, ricinolic acid and 12-oxystearic acid and glycerine, Polyglycerine, tetramethylolmethane, Dipentaerythritol, sugar alcohol (as sorbyl alcohol) and poly-glycosides (as Mierocrystalline cellulose);
(VIII) wool wax alcohol;
(IX) poly-alkylene glycol.
The sorbitan monoesters of oxyethane and/or propylene oxide and monoglyceride and triglyceride and lipid acid and the adduct of sorbitan diester or Viscotrol C all are the known and commercial commodity that can buy.Thereby relating to homologous mixture, its average degree of alkoxylation is the ratio of amount that is equivalent to oxyethane and/or propylene oxide and carries out the matrix of addition reaction with it.
Preferential especially is the emulsifying agent of common use (III) class, just alkylglycoside.Few glycosides of alkyl and the few glycosides of thiazolinyl all are known nonionogenic tensides, and it is a formula V
R 6O-[G] p(V) R wherein 6Representative has the alkyl and/or the thiazolinyl of 4～22 carbon atoms, and the G representative has the glycosyl of 5～6 carbon atoms, and P then represents the numeral between 1～10.They are to make by the methods involving of organic chemistry preparation.Here by enumerating some representative documents in many reference: people's such as Biermann " Starch/Starke " 45,281 (1993), B.Salka people such as " makeup " 108,89 (1993) and J.Kahre at the SOFW magazine, the 8th, 598 (1995).
Few glycosides of alkyl and/or the few glycosides of thiazolinyl are especially to derive from glucose from aldose and ketose that 5 or 6 carbon atoms are arranged.Few glycosides of preferential alkyl and/or the few glycosides of thiazolinyl are few glucoside of alkyl and/or the few glucoside of thiazolinyl.Indices P in logical formula V is oligomerization degree (DP), that is to say, and the distribution of single glycosides and few glycosides, and represent numeral between 1 to 10.And P must be an integer in the compound of enumerating, and at first can suppose P value=1 here to 6, is by analysis average juice calculation value for the few glycosides P of certain alkyl value, so great majority are marks.Particularly the average oligomerization degree P of few glycosides of alkyl and/or the few glycosides of thiazolinyl is 1.1 to 3.0.From the angle of utilisation technology, few glycosides of this alkyl and/or the few glycosides of thiazolinyl are preferential, and its oligomerization degree is less than 1.7, especially between 1.2 and 1.4.Alkyl or alkenyl R 6Be the primary alconol deutero-of 8 to 10 carbon atoms preferably by 4 to 11 carbon atoms are arranged.Representative example have butanols, hexanol, octanol, decyl alcohol, hendecanol with and cuts, for example when the hydrogenation of commercial fatty acids methyl esters or obtain in the hydrogenation process of the aldehyde in the Luo Lunshi hydroxyl is synthetic.Preferential is that chain length is C 8-C 10The few glycosides of the alkyl of (DP=1～3) is at industrialness C 8-C 10Produce as singlings when the coconut lipidol carries out fractionation by distillation, and can be doped with the C that is less than 6 (weight) % 12-alcohol, and based on industrial C 9/11The few glycosides of the alkyl of-oxo-alcohols (DP=1～3).Alkyl or alkenyl R 6Also can be further by there being 12～22 carbon atoms especially to derive in the primary alconol of 12～14 carbon atoms.Representative example be lauryl alcohol, tetradecyl alcohol, hexadecanol, Palmitoleyl alcohol, stearyl alcohol, isooctadecanol, oleyl alcohol, anti-oleyl alcohol, petroselinum alcohol, n-Eicosanol, cis 9-gadoleyl alcohol, behenyl alcohol, erucyl alcohol, Brazilian enol with and cuts, as mentioned above, they can both as above obtain.The preferential hardened DP that is based on is 1～3 C 12/14The few glycosides of the alkyl of coconut alcohol.If the alkylglycoside of formula V is as emulsifying agent, so its advantage just be to use a small amount of polyhydroxycarboxyliacid acid especially citric acid as formulation auxiliary agents.And in general, at this moment the consumption of polyhydroxy acid is 0.1～3.0 (weight) %, is preferably 0.1～1.0 (weight) %.
Mainly contain 20～90 (weight) % according to the used micro emulsion of the present invention, especially the water of 30～80 (weight) %, prepreerence then is the water of 30～60 (weight) %, and the rest part among the 100 weight % is oil phase and emulsifying agent, in case of necessity other auxiliary agents and additive can also be arranged.The preferential content of oil phase itself is 10～80 (weight) %, 20～70 (weight) % especially, and preferential especially then is 25～55 (weight) %.Oil phase mainly be contain composition a) or b) and the mixture of these compositions.Utilizing these emulsions especially preferentially is that the weight ratio of its oil phase and water is 1: 1.The preferential content of emulsifying agent or emulsifying system is 10～50 (weight) %, content 15～45 (weight) % preferably, and preferential especially content then is 20～40 (weight) %.
Micro emulsion of the present invention can be used for various fermenting processs.During the method that can be used for all professionals in addition and be familiar with is arranged, as batchwise or batch charging fermentation method, and continuous fermentation method.The fermentation system that all professionals are familiar with can adopt.Details sees also the particular of Crueger, the 50th～70 page.The purposes of micro emulsion is not limited to certain micro-organisms, and the compound that all professionals are familiar with by fermentation all can use emulsion to make or change.Except the classical fermentation process that adopts based on synthetic antibiotic, (see also the works of Crueger, the 197th～242 page), above-mentioned emulsion also is applicable to microbial transformation (" biotransformation "), conversion as steroide and sterol, the conversion of microbiotic and sterilant, the perhaps manufacturing of VITAMIN (seeing also the works of Kruegel, the 254th～273 page).And preferably be used to make antibiotic fermenting process, as cephamycin, tylosin or erythromycin.
Usually micro emulsion is an aqueous ferment juice, and it contains microorganism and nitrogenous source and trace elements, also has other auxiliary agents, especially defoaming agents in case of necessity and prepares with proper method.For example can consider to have as nitrogenous source: peptone, yeast extract or malt extract, corn steep liquor, urea or Yelkin TTS.Trace elements can be used the form of inorganic salt, for example SODIUMNITRATE or saltpetre, ammonium nitrate, sulfuric acid amine, ferric sulfate or the like.Another advantage is exactly that micro emulsion itself can add as defoaming agents or nitrogenous source with other additive.
Embodiment
Make different micro emulsions by the mixing raw material thing.Composition is listed in table 1.The available Malvern Mastersizer 2000 of drop size measures.Emulsion is suitable for doing the independent nutriment source in the fermenting process, also can directly mix in the aqueous ferment juice.
Table 1a
Weight % Weight % Weight % Weight %
Witconol 2301 ??32.44
Laurate methyl ????30.95
Methyl pelargonate ????29.61
The rapeseed oil fatty acid methyl esters ????32.35
Water ????34.27 ????32.04 ????30.24 ????34.18
Alkylglycoside ????25.22 ????31.55 ????30.95 ????25.3
Olein ????7.91 ????6.55 ????7.62 ????7.84
Citric acid ????0.25 ????0.24 ????0.24 ????0.24
Outward appearance Clarification Clarification Clarification Clarification
Droplet size ????＜80nm ????＜80nm ????＜80nm ????＜80nm

Claims (10)

1. the application of oil/water miscible liquid, it contains water, emulsifying agent at least, and oil phase, and this oil phase contains one or more that are selected from following compound:
A) fatty acid alkyl ester and/or
B) triglyceride level of plant-sourced,
It is characterized by, the drop magnitude range of emulsion is 1～100 nanometer in the fermenting process.
2. according to the application of claim 1, it is characterized by, a) use fatty acid methyl ester as composition.
3. according to the application of claim 1 or 2, it is characterized by, the average droplet size of used emulsion is 10～80 nanometers, preferably in the scope of 10～50 nanometers.
4. according to the application in the claim 1 to 3, it is characterized by, the water content of used emulsion is 20～90 (weight) %, 30～80 (weight) % preferably, and especially preferentially be 30～60 (weight) %.
5. according to the application of claim 1 to 4, it is characterized by, the oil phase amount of used emulsion is 10～80 (weight) %, preferred 20～70 (weight) %, and especially preferentially be 25～55% weight.
6. according to the application of claim 1 to 5, it is characterized by, contain the fatty acid methyl ester of formula (I) in the oil phase of used emulsion:
R 1-COO-R 2????(I)
R wherein 1Representative has the alkyl of 6 to 22 carbon atoms, R 2Then represent methyl.
7. according to the application in the claim 1 to 6, it is characterized by, contain Witconol 2301, Uniphat A60, methyl stearate and/or methyl pelargonate in the oil phase of used emulsion.
8. according to the application in the claim 1 to 7, it is characterized by, contain Oleum Cocois, Trisun Oil R 80 and/or rapeseed oil in the oil phase of used emulsion.
9. according to the application in the claim 1 to 8, it is characterized by, used emulsion contains as the few glycosides of the alkyl of emulsifying agent.
10. according to the application in the claim 1 to 9, it is characterized by, the contained emulsification dosage of used emulsion is 10～50% weight, and preferably 15～40% weight are preferably 20～35% weight especially.
CN00808009A 1999-05-25 2000-05-16 Utilisation of microemulsions in fermentation processes Pending CN1351650A (en)

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