CN1030146C - Method of preparation long chain a,w-dicarboxylic acid with microorganism fermentation n-paraffins - Google Patents

Method of preparation long chain a,w-dicarboxylic acid with microorganism fermentation n-paraffins Download PDF

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Publication number
CN1030146C
CN1030146C CN94100594A CN94100594A CN1030146C CN 1030146 C CN1030146 C CN 1030146C CN 94100594 A CN94100594 A CN 94100594A CN 94100594 A CN94100594 A CN 94100594A CN 1030146 C CN1030146 C CN 1030146C
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dicarboxylic acid
fermentation
long chain
carbon
alkane
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CN94100594A
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CN1092108A (en
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陈远童
刘挺
庞月川
郝秀珍
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Institute of Microbiology of CAS
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Institute of Microbiology of CAS
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Priority to CN94100594A priority Critical patent/CN1030146C/en
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Priority to PCT/IB1995/000093 priority patent/WO1995021145A2/en
Priority to AU15446/95A priority patent/AU1544695A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
    • C07C55/02—Dicarboxylic acids
    • 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
    • C12N1/14—Fungi; Culture media therefor
    • C12N1/16—Yeasts; Culture media therefor
    • C12N1/165—Yeast isolates
    • 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
    • C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C12P7/44—Polycarboxylic acids
    • C12P7/46—Dicarboxylic acids having four or less carbon atoms, e.g. fumaric acid, maleic acid
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12R—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES C12C - C12Q, RELATING TO MICROORGANISMS
    • C12R2001/00—Microorganisms ; Processes using microorganisms
    • C12R2001/645—Fungi ; Processes using fungi
    • C12R2001/72—Candida
    • C12R2001/74—Candida tropicalis

Abstract

The present invention discloses a method for producing long-chain alpha, W-dicarboxylic acid by means of microorganism fermentation, particularly a method for producing 15 carbon-dicarboxylic acid (DC15). The present invention comprises the following steps that single long-chain dicarboxylic acid or mixed long-chain dicarboxylic acid which can be formed and accumulated in a culture medium with various kinds of C11 to C17 n-alkane or mixed n-alkane as a matrix and has the same chain length as that of the matrix is fermented, particularly candida tropicalis NP-6-126 which forms and accumulates DC15 in a culture medium with n-pentadecane (nC15) as a matrix is fermented, and then, dicarboxylic acid formed in fermentation liquid is recovered.

Description

Method of preparation long chain a,w-dicarboxylic acid with microorganism fermentation n-paraffins
The present invention relates to microorganism fermentation n-paraffins and produce long-chain alpha, omega-dicarboxylic acid, the Pentadecane that especially ferments, the method for high yield 15 carbon dicarboxylic acid.
Long chain dicarboxylic acid is a synthetic perfume, and the Buddhist nun becomes the important source material of engineering plastics, hot melt adhesive, resin, cold-resistant plasticizer etc.12 long chain dicarboxylic acids that carbon is above, occurring in nature does not exist, yet there is not economically viable synthetic method on the chemical industry, therefore utilize the special oxidation capacity of microorganism, at normal temperatures and pressures, transform the normal alkane in the oil, produce attention and further investigation that long chain dicarboxylic acid causes scientists already.
15 carbon dicarboxylic acid are important source material of synthetic famous and precious spices cyclopentadecanone and muskone (being 3-methyl-cyclopentadecanone), and the latter is one of main component of natural musk.Muskone with synthetic replaces rare rare natural musk, prepares multiple Chinese patent medicine, and the clinical application test shows that curative effect is the same with natural musk remarkable.
Pentadecane also is microorganism a kind of alkene of assimilation easily, therefore forms and accumulate relatively difficulty of 15 carbon dicarboxylic acid, particularly high yield 15 carbon dicarboxylic acid.
In patent documentation, though the relevant method of microorganism from normal alkane fermentative production long chain dicarboxylic acid of utilizing is also not relevant to Pentadecane fermentative production 15 carbon dicarboxylic acid, the particularly method of high yield 15 carbon dicarboxylic acid.In US4339536, have only the embodiment that produces 12 carbon and 13 carbon dicarboxylic acid, and acid yield is not high, only reaches 45g/L; And in US4624920, only shake the embodiment that bottle is produced 14 carbon and 16 carbon dicarboxylic acid at 50ml and 500ml, and acid yield is too low, has only 3mg in every liter of fermented liquid; Application number is 87105445 and 89102548 Chinese patent application, mainly is about producing the method for 16 carbon and 17 carbon dicarboxylic acid, on the 16L jar, produces the acid amount and is respectively 120g/L and 133g/L.
People such as Japan tree planting South Sea man reported with a strain candida tropicalis mutant strain M 2030Produce 15 carbon dicarboxylic acid from Pentadecane, on 3 liters of jars, produce acid and reach about 90g/L; Shanghai Shen Yong waits the people to report that (bacterium is dense to be 15 * 10 for high density resting cell with a strain candida tropicalis N-15 by force 8Individual/milliliter) transform and to reach 109g/L when Pentadecane is 15 carbon dicarboxylic acid, (" plant physiology journal " 1980.Vol.6, No:1).But during laboratory test fermentation, fermented DC 8 days 15Output only reach 77.2g/L.The report of other relevant fermentative production 15 carbon dicarboxylic acid all has only 40-50g/L.Therefore produce DC with microbial fermentation high production ground 15Be a problem that still need solve, the purpose of this invention is to provide a kind of production C 11-C 17The method of single long chain dicarboxylic acid and hybrid long chain dicarboxylic acid, particularly high production ground produces DC 15Method.
The used bacterial strain of the present invention is candida tropicalis (Candida tropicalis) NP-6-126, be the candida tropicalis (referring to " microorganism journal " 20(1) that produces mixed dicarboxylic acid with a strain oxidation normal alkane: 88-93,1980) be starting strain, by nitrous acid and ultraviolet repeatedly repeatedly mutagenesis screening cultivate, can be from C 11-C 17Various single normal alkane and mix normal alkane, especially Pentadecane, the dicarboxylic acid of high production ground production respective chain length.Candida tropicalis NP-6-126(is hereinafter to be referred as NP-6-126) be deposited in China Committee for Culture Collection of Microorganisms common micro-organisms center, preserving number is: CGMCC NO.0206.
The physiological property of NP-6-126 is as follows:
One, the fermentation of carbohydrate: glucose+, semi-lactosi+, sucrose+, maltose+, lactose-.
Two, assimilation: glucose+, semi-lactosi+, sorbose-, sucrose+, maltose+, cellobiose+, trehalose+, lactose-, close disaccharides-, raffinose-, melizitose+, levulin-, Zulkovsky starch+, wood sugar+, the L-arabinose+, D-arabinose-ribose-, rhamnosyl-, α-Jia Jiputaotanggan+, glycerine+, ethanol+, tetrahydroxybutane-, N.F,USP MANNITOL+, inositol-, ribitol+, melampyrum-, sorbitol+, Trisodium Citrate-, Soduxin+, calcium lactate-.
Three, the needs of growth hormone: vitamin H ++, vitamins B 1++, vitamins B 2+, vitamins B 6+, vitamins B 12+, folic acid+, nicotinic acid+, pantothenic acid+, inositol+, para-amino benzoic acid+.
Four, other: nitrate-, freezing milk-, ursolic acid decomposes-, solidify the ox level-, the grease enzyme-.
Morphological specificity: creamy-white, gauffer type, bacterium colony are the crisp shape of cake shape and peach.
Cultural characteristic:
When cultivating in malt juice liquid medium, pseudohypha is many and grow; When in the alkane seed culture medium, cultivating, the short pseudohypha of some amount is arranged; And when fermenting in fermention medium, major part is a single ellipse garden cell.
Seed culture medium of the present invention: the wort of (1), 10 Bahrain's pols adds the solid inclined-plane that 2% agar is made; (2), the malt juice liquid medium of 10 Bahrain; (3) the alkane seed culture medium comprises: KH 2PO 46-12g/L, corn steep liquor 3-8g/L, yeast extract paste 3-8g/L, sucrose 3-8g/L, urea 3-6g/L, heavy wax or Pentadecane 40-70ml/L, tap water preparation, natural pH.
The process of cultivating seed is: get a transfering loop NP-6-126 yeast thalline, be coated on by (15 * 180 test tubes, every dress 6-7ml substratum is put into the inclined-plane) on the wort solid inclined-plane, cultivated 40 hours in 28-30 ℃.Getting an above-mentioned cultured NP-6-126 bacterial classification all scrapes in the 250ml triangular flask that 25ml alkane seed culture medium is housed, on 28-30 ℃ 220 rev/mins rotary shaker, cultivated 40-48 hour, as the shake flask fermentation seed or get two above-mentioned cultured NP-6-126 bacterial classifications and all scrape in the 5000ml triangular flask that the 500ml substratum is housed, on 180 rev/mins of rotary shakers, cultivated 44-48 hour for 28-30 ℃, as the seed of first class seed pot.
Produce long chain dicarboxylic acid with NP-6-126 bacterial strain of the present invention, particularly the concrete grammar of 15 carbon dicarboxylic acid is: ferment-seeded is inserted pH5.5-9.0, be preferably the 15-45%(V/V that contains of 6.5-7.5) C 11-C 19Normal alkane and 85-55%(V/V) in the mixed solution of fermention medium.Consisting of of fermention medium: alkali metal phosphate 6-14g/L, be preferably 7-10g/L, sodium-chlor 0.5-2.0g/L, yeast extract paste 1-6g/L, be preferably 3-5g/L, corn steep liquor 0.5-2g/L, urea 0.5-2.5g/L, be preferably 1.0-2.0g/L, nitrate 5-15g/L is preferably 6-12g/L, dimethyl sulfoxide (DMSO) 10-20ml, defoamer 400-1200ppm and some other known nutrition sources, under pH6.5-7.5 with said mixture at 25-35 ℃, be preferably in 27-31 ℃ of aerobic fermentation 48-170 hour, transferred a pH value every 6-8 hour with NaOH solution, the pH value is controlled between the 7.5-8.5.Then the dicarboxylic acid that produces is separated from fermented liquid.In when beginning fermentation, normal alkane content is 10-20%(V/V in the mixed solution), add normal alkane between in due course later on, make that normal alkane concentration is as the criterion all the time 〉=5%(V/V) in the fermented liquid.Alkali metal phosphate can be from KH 2PO 4, NaH 2PO 4, K 2HPO 4And Na 2HPO 4In select a kind of.Nitrate can select a kind of from potassium or sodium salt.
After the fermentation ends, add an amount of water, add alkali to pH10-12, be heated to 85-90 ℃, carry out the breakdown of emulsion layering, the upper strata is a Residual oil, reclaim usefulness again, clear liquid in the middle of emitting, lower floor's thalline layer is handled once or press filtration or centrifugal again, merge clear liquid, add proper amount of active carbon, 85-90 ℃ of decolouring 30 minutes, remove gac after, destainer is heated to 60-70 ℃, adds HCl or H 2SO 4Carry out acidizing crystal to pH4-5, be cooled to 30 ℃ after, air blow drying is used in press filtration, 60 ℃ of oven dry, white 15 carbon dicarboxylic acid crystallizates.
With NP-6-126 bacterial strain of the present invention and fermentation process, can produce C 11-C 19Various single and mixed dicarboxylic acid.Wherein on 2.5 tons of jars, from Pentadecane fermentative production 15 carbon dicarboxylic acid, fermented 6 days, produce the acid amount up to 170-180g/L, the aftertreatment total recovery reaches 80%, and purity reaches about 96%.
Example one
(1), get a transfering loop NP-6-126 bacterial classification, be coated on 15 * 180 Boiling tube wort solid inclined-planes, cultivated two days for 30 ℃.
(2), get one of above-mentioned bacterial classification, insert in the 250ml triangular flask that 25ml alkane seed culture medium is housed and on 220 rev/mins rotary shaker, cultivated 48 hours in 30 ℃.KH in the alkane seed culture medium 2PO 48g/l, yeast extract paste 5g/l, corn steep liquor 3g/l, sucrose 5g/l, urea 3g/l, heavy wax 50ml/l, tap water preparation, pH5.0.
(3), in the 500ml triangular flask of 15ml fermention medium is housed, insert the above-mentioned seed liquor of 3.5ml, 200 rev/mins of rotary shaker top fermentations 4 days, transferred a pH to 7.5-8.0 with NaOH in per 24 hours.Fermention medium contains KH 2PO 48g/l, yeast extract paste 2g/l, corn steep liquor 1g/l, sodium-chlor 1.5g/l, urea 1g/l, Pentadecane 200ml/l, bubble enemy 500ppm, KNO 36g/l, the tap water preparation, pH7.5 sterilized 30 minutes down at 110 ℃.After the fermentation ends, transfer pH to 3, use the 100ml ether extraction, remove ether, get white crystals,, calculate dicarboxylic acid content with the titration of standard NaOH solution with HCl.DC as a result 11Output is 53.6g/l, through gas chromatographic analysis, and DC 11Purity is 98.11%.
Example 2
According to the method for example 1, be normal alkane nC 15, DC as a result 15Output be 73.5g/l, purity is 96.31%.
Example 3
According to the method for example 1, be normal alkane nC 17, DC as a result 17Output be 53.9g/l, purity is 98.2%.
Example 4
Seed culture medium and cultural method are with example 1, and fermention medium is KH 2PO 48g/l, NaCl1g/l, yeast extract paste 2g/l, corn steep liquor 1g/l, KNO 39g/l, dimethyl sulfoxide (DMSO) 6ml/l, bubble enemy 600ppm, urea 1.2g/l, Pentadecane 200ml/l, tap water preparation, pH7.5.1.5L was cultivated two days, and the NP-6-126 bacterial strain kind liquid that microscopy does not have an assorted bacterium inserts the 8L fermention medium is housed, in 121 ℃ of automatic controlling tank of 16L of sterilizing 30 minutes, and at 29 ℃, 800 rev/mins, tank pressure 1Kg/cm 2, air flow 1: 1, pH is controlled at 7.5 after 24 hours, ferments DC 165 hours 15Output reach 130.1g/L.
Example 5
Seed culture medium and cultural method are with example one, and fermention medium is with example two.Cultivating two days, there is not the 400L of assorted bacterium through microscopy, NP-6-126 kind liquid inserts the 1500L fermention medium is housed, in 121 ℃ of 2500L fermentor tanks of sterilizing 40 minutes, 29 ℃, 200 rev/mins, tank pressure 0.8Kg/cm 2, air flow 1: 0.8, during beginning, Pentadecane 300L, after 24 hours,, transfer a pH to 7.5 with NaOH solution, since the 3rd day every 8-6 hour, add Pentadecane 120L every day, totally 3 times, ferment 6 days (144 hours), 15 carbon dicarboxylic acid content are 178g/L in the fermentation clear liquid.After the fermentation ends, add the long-pending tap water of monoploid, be heated to 90 ℃, add adjusting PH with base to 10, cool after 50 ℃, put into layering jar standing demix one day, emit the upper strata Residual oil, 60L altogether, lower floor's bacterium layer by press filtration, remove thalline, cleaner liquid and middle level clear liquid merge, add 0.7% gac, 90 ℃ decoloured 15 minutes, and gac is removed in press filtration, the decolouring cleaner liquid is squeezed in the souring tank, adds water to DC 15Concentration is 4%, is heated to 70 ℃, adds dense HCl and is acidified to pH4, cool to about 30 ℃, and filter press, air blow drying, solid substance gets white DC 60 ℃ of oven dry 15229Kg, aftertreatment total recovery 85.76%, purity are 96.5%.

Claims (2)

1, a kind of microbial fermentation that utilizes is produced α, the method of ω-15 carbon dicarboxylic acid, it is characterized in that being in the substratum of matrix with the Pentadecane,, reclaim formed dicarboxylic acid then with candida tropicalis (Candidatropicalis) NP-6-126 (CGMCCNO.0206) fermentation.
2, candida tropicalis (Candida tropicalis) NP-6-126(CGMCCNO.0206 bacterial strain).
CN94100594A 1994-01-28 1994-01-28 Method of preparation long chain a,w-dicarboxylic acid with microorganism fermentation n-paraffins Expired - Lifetime CN1030146C (en)

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CN94100594A CN1030146C (en) 1994-01-28 1994-01-28 Method of preparation long chain a,w-dicarboxylic acid with microorganism fermentation n-paraffins
PCT/IB1995/000093 WO1995021145A2 (en) 1994-01-28 1995-01-27 FERMENTATION PRODUCTION OF LONG CHAIN α,φ-DICARBOXYLIC ACIDS FROM ALKANES BY USE OF A MICROORGANISM
AU15446/95A AU1544695A (en) 1994-01-28 1995-01-27 Fermentation production of long chain alpha,omega-dicarboxylic acids from alkanes by use of a microorganism

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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1049688C (en) * 1995-10-05 2000-02-23 中国石油化工总公司 Method for treatment of alpha, omega dibasic acid fermentation liquor
CN1048754C (en) * 1995-11-09 2000-01-26 中国科学院微生物研究所 Process for producing long-chain alpha, omega-dicarboxylic acid by synchronous fermentation of microbe
MXPA01002579A (en) * 1998-09-17 2002-04-08 Cognis Corp Process for making polycarboxylic acids.
ATE332389T1 (en) * 1999-09-30 2006-07-15 Cognis Ip Man Gmbh IMPROVED FERMENTATION PROCESS
KR100528804B1 (en) * 2003-12-08 2005-11-15 씨제이 주식회사 Method for preparing xylitol with high yield using recycing microorganism
WO2007077568A1 (en) * 2005-12-30 2007-07-12 Council Of Scientific And Industrial Research Process for preparing long-chain dicarboxylic acids
CN101899412B (en) * 2009-08-12 2012-02-22 青岛生物能源与过程研究所 Engineering colon bacillus for preparing biological gasoline
CN109913512A (en) * 2017-12-13 2019-06-21 上海凯赛生物技术研发中心有限公司 The method of biofermentation production long-chain biatomic acid
WO2023224418A1 (en) * 2022-05-18 2023-11-23 안정오 Method for producing from fatty alcohols monomers for producing various synthetic resins

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Publication number Priority date Publication date Assignee Title
US3843466A (en) * 1969-11-10 1974-10-22 Ajinomoto Kk Method of producing dicarboxylic acids by fermentation
US4339536A (en) * 1979-06-08 1982-07-13 Nippon Mining Co., Ltd. Process for the preparation of long-chain dicarboxylic acids by fermentation
DE3721119A1 (en) * 1987-06-26 1989-01-05 Henkel Kgaa FERMENTATIVE PRODUCTION OF DICARBONIC ACIDS

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