CN1570124A - Long chain normal dibasic acid production method - Google Patents
Long chain normal dibasic acid production method Download PDFInfo
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- CN1570124A CN1570124A CN 200410018255 CN200410018255A CN1570124A CN 1570124 A CN1570124 A CN 1570124A CN 200410018255 CN200410018255 CN 200410018255 CN 200410018255 A CN200410018255 A CN 200410018255A CN 1570124 A CN1570124 A CN 1570124A
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Abstract
The invention discloses a method for preparing a normal long chain binary acid. The method comprises the following steps: C9-C18 alkane or fatty acid is served as substrate and converted to relative long chain binary acid by fermentation method or enzyme method; the reaction liquid is pretreated for removing the thallus and residual alkane or fatty acid, a binary acid clear liquid is obtained, acidification crystallization is carried out, the acidification crystallization liquid is filtered by pressing, and the binary acid crude product is obtained; the binary acid crude product is refined by using knifing vaporization and short path distillation device under the vacuum condition or by using organic solvent. The normal long chain binary acid prepared by the method has high thermal stability and can be used for preparing nylon, thermosol, and polyester materials.
Description
Technical field
The present invention relates to the production method of positive long-chain biatomic acid, specifically, the present invention relates to a kind of method of utilizing biological process to produce the positive long-chain biatomic acid of high thermal stability.
Background technology
Long-chain biatomic acid (DCA) is the base monomer raw material of a series of extraordinary synthetic materialss, long-chain biatomic acid and derivative monomer thereof can be produced extraordinary nylon, polycarbonate, powder coating, spices, hot melt adhesive, extraordinary lubricant etc., are the important source material of synthetic perfume, engineering plastics, cold resistant plasticizer, senior lubricant and products such as polyamide hot, powder coating.
E.I.Du Pont Company is with chemical synthesis production SL-AH at present, this method is raw material with the n-butene, this chemical synthesis process needs the chemical reaction through seven step High Temperature High Pressure, there is significant disadvantages in this method: organic single acid exists as impurity, because it can stop polyreaction, removing single acid will increase production cost, and this is a stubborn problem; Can not the longer diprotic acid of production carbochain.
Fermentative Production DCA is the application at petrochemical industry of the microbial fermentation technology that rises the seventies, has that raw material sources are wide, the reaction specificity is strong and advantage such as reaction conditions gentleness, at home and abroad is subjected to generally paying attention to.Have only chemical method production SL-AH and semi-synthesis method to produce nine carbon and 11 carbon long-chain biatomic acid monomers in the market, on technical scale, be applied in the above product.And biological process can provide from C
9To C
18Even C
22Serial long-chain biatomic acid monomer.The existing long-chain biatomic acid market that these new special long-chain biatomic acid monomers can be produced with better performance competition chemical method, simultaneously, the extraordinary long-chain biatomic acid monomer of series of different nature a series of new functional materialss of different nature that have of will deriving.
The long-chain biatomic acid that extensive in the world at present industry is used mainly is nonane diacid (U.S. CORNING, about 2.5 ten thousand tons), sebacic acid (China, about 30,000 tons/year) and SL-AH (Dupont, Ube, Degussa etc., about 100,000 tons/year).Nonane diacid is oleic acid cracking and getting.The raw material that sets out of sebacic acid is a Viscotrol C.SL-AH is the product that adopts chemical method to produce, and minority manufacturer occupies monopoly position in the world, and price is high for a long time, has a strong impact on the cost of derived product; Simultaneously because chemical method other long-chain biatomic acid beyond can not the production SL-AH makes the derived product Application Areas limit to some extent.
The patented technology of long-chain biatomic acid production at present both at home and abroad all is to be substrate utilization biological fermentation process production or to utilize lipid acid be that substrate is with the synthetic diprotic acid of chemical method with alkane, domestic fermentative Production long-chain biatomic acid is substrate with alkane, but in patent, do not propose the notion of substrate conversion efficiency, and the transformation efficiency of substrate alkane is vital for the production cost of diprotic acid.Abroad having with lipid acid is the report that fermenting substrate is produced diprotic acid, shake a bottle scale but all rest on, and level is lower, and as United States Patent (USP) 4,965,201 have reported with C
8-C
14Lipid acid is substrate, fermentative production C
8-C
10Diprotic acid, acid yield only has 10g/L, and can not produce C
11-C
18Diprotic acid.Though it is many that the extraction of diprotic acid both at home and abroad, refining patent also have, all fail to solve product quality problem, the product that the technology of carrying obtains all is difficult to be applied to fields such as nylon, polyester.International major companies such as external Du Pont, Henkel have also dropped into lot of manpower and material resources, finally abandon producing long-chain biatomic acid with biological process.Domesticly tackle key problems from the Seventh Five-Year Plan, always with the industrialization production of long-chain biatomic acid as brainstorm subject, drop into a large amount of manpower and materials until 15 tackling key problem Kai Sai companies, final quality product and the cost problem that has successfully solved the long-chain biatomic acid of biological process production realized being applied to a plurality of productions that the diprotic acid quality had the particular requirement field such as nylon, polyester, hot melt adhesive at industrially scalable.
Summary of the invention
Purpose of the present invention just is to provide a kind of biological process that utilizes, and comprises fermentation method and enzyme process, produces the method for long-chain biatomic acid.
The method that biological process of the present invention is produced long-chain biatomic acid may further comprise the steps:
1) fermentation method transforms: with C
9～C
18Alkane or lipid acid be substrate, be converted into the corresponding long chain diprotic acid by microbe fermentation method;
Wherein, microorganism is adopted candida tropicalis (Candida Tropicalis), and the prescription of fermentation tank culture medium is: KH
2PO
4: 0.2～1.5%; NaCl:0～0.2%; Yeast extract paste: 0.1～2.0%; Urea: 0.2～1.5%; Glucose: 1.0～5.0%; (NH
4)
2SO
4: 0～2.0%; MgSO
47H
2O:0～0.3%; Defoamer: 0.005%;
Fermentation condition is: inoculum size: 20%; Jar temperature: 29.0 ± 1.0 ℃; Ventilation: 1: 1.0～0.2vvm; Tank pressure: 0.05～0.1Mpa; PH: earlier fermentation thalli growth 3.5～6.5; The fermentation middle and later periods transforms 7.0～8.5; Incubation time: 140～170 hours;
The feed supplement controlled variable:
--alkane/lipid acid: as thalli growth optical density(OD) (OD
600) greater than 0.6, begin to add 5～10% alkane or lipid acid, adding in the alkane lipid acid control fermented liquid alkane or fatty acid concentration thereafter is 2～10%, fermentation ends stopped feed supplement in preceding 24 hours;
--the secondary carbon source: batch formula is added glucose or sucrose in the fermenting process, and perhaps stream adds glucose or sucrose;
1 ') above step 1) also can replace by enzyme process, be specially: the seed liquor of heat-obtaining band candiyeast (CandidaTropicalis), the separated and collected thalline, after direct or process immobilization is handled, add damping fluid and substrate (alkane or lipid acid) and transform, also can suitably add the secondary carbon source with alkali control pH 7.0～8.5 in the process;
2) pre-treatment of fermented liquid or enzyme process reaction solution: fermented liquid or enzyme process reaction solution are added adjusting PH with base to 8～10, be heated to 60～100 ℃, utilize centrifuging or membrane filter method separating thallus then, diprotic acid clear liquid and the remaining substrate of fermentation; The diprotic acid clear liquid that obtains adds 0～5% gac according to circumstances, 60～95 ℃ of decolourings 20～180 minutes, removes by filter gac, destainer is heated to 60～100 ℃ then, uses H
2SO
4Regulate pH to 2～5 and carry out acidizing crystal, acidizing crystal liquid obtains the diprotic acid crude product through filter press again;
3) distillation method is refining: the above-mentioned diprotic acid crude product that obtains, and use luwa evaporator at vacuum 10～600Pa earlier, remove light constituent under 120～250 ℃ of conditions of temperature; Material after removing light constituent uses short course distillation device to remove heavy constituent at vacuum 3～100Pa under 180～240 ℃ of conditions of temperature; Material carries out distillation procedure under molten state, material add thermal recovery steam or thermal oil; The entire operation process adopts gap or successive mode;
3 ') the secondary solvent crystallization process is refining: the diprotic acid crude product that obtains is put in a certain proportion of solvent, employed solvent can be alcohols (methyl alcohol, ethanol, Virahol, propyl carbinol), acids (acetate), ketone (acetone), ester class (ethyl acetate, butylacetate) etc., heating makes its dissolving, in 60-100 ℃ of insulation postcooling crystallization in 30-180 minute, solid-liquid separation, drying obtains product;
Above step 3), 3 ') also can be after fermentation ends direct acidifying feed liquid, adopt the secondary solvent crystallization process to make with extra care the crude product that obtains after thalline and the diprotic acid coprecipitation.
The positive long-chain biatomic acid that biological process production of the present invention obtains has the thermostability of height, thereby can be used as the preparation of monomer applications in materials such as high-grade nylon, thermosol, polyester; Realized can be used in the long-chain biatomic acid in fields such as high-grade nylon, hot melt adhesive, polyester in the world first with biological process production, and the above novel long-chain biatomic acid of C13 that can provide chemical method to produce has been expanded the application of diprotic acid at industrial circle greatly.
Embodiment
Below in conjunction with specific embodiment the present invention is further described.It may be noted that following examples only to be used to the present invention is described and be not used in and limit the scope of the invention.
Embodiment 1: the preparation of seed liquor
1) the glycerine pipe bacterial classification of heat-obtaining band candiyeast (CCTCC NO:M203052) is inoculated in 200mL liquid nutrient medium (peptone 10g/kg, yeast extract paste 5g/kg is housed, glucose 10g/kg, the pH nature) in the 500mL seed bottle, 35 ℃, the 300rpm shaking table was cultivated 10～15 hours;
2) get above-mentioned shake-flask seed, insert in the 10L fermentor tank that 5L seed culture medium (peptone 10g/kg, yeast extract paste 10g/kg, glucose 10g/kg, pH nature) is housed, in 35 ℃ of cultivations 24 hours, it was standby to make primary seed solution.
3) 16M is being housed
3The 20M of substratum
3In the fermentor tank, insert above-mentioned primary seed solution, beginning secondary seed jar is cultivated.Fermentative medium formula is with the one-level seeding tank.In 29 ℃ of cultivations 16 hours, it was standby to make secondary seed solution.
Embodiment 2The oleic acid fermentation
In the 30L fermentor tank of 15L substratum was housed, the primary seed solution that inserts 1.5L embodiment 1 respectively began fermentation.The fermention medium of fermentor tank is: potassium primary phosphate 10g/kg, and sal epsom 0.5g/kg, urea 5.0g/kg, corn steep liquor 10g/kg, glucose 40g/kg, pH5.8 sterilized 20 minutes for 121 ℃.Oleic acid, feed supplement sugar and alkali branch disappear.Under 35 ℃, rotating speed 500rpm, air flow 7.5vvm, tank pressure 0.05Mpa condition, cultivate, ferment and began stream in 3 hours and add glucose, speed is 100g/hr, sugared flow acceleration is turned down to 70g/hr after 48 hours, sugared flow acceleration is turned down to 40g/hr after 96 hours, and 5h stops to mend sugar before the fermentation ends; After glucose stream adds 3h, begin stream and add oleic acid, flow acceleration is 30g/hr, stops stream about 20h before the fermentation ends and adds oleic acid.From being inoculated into fermentation ends, total incubation time is 120 hours.Put tank volume 16.4kg, add oleic acid total amount 2374.7g, measure 18 carbon dicarboxylic acid (DC in the fermenation raw liquid with gas phase
18) content is 77.5g/kg, oleic acid is 67% to the weight transformation efficiency of diprotic acid.
Embodiment 311 carbon normal alkane (DC
11) fermentation
100M is being housed
3The 200M of substratum
3In the fermentor tank, insert primary seed solution and begin fermentation.The fermentation culture based component is: glucose 10g/L, KH
2PO
415g/L, yeast extract paste 10g/L, corn steep liquor 5g/L, urea 4.5g/L, NaCl 1g/L, KNO
37g/L, the pH nature, 121 ℃ of sterilizations even disappear.Alkane and feed supplement sugar disappear.Under 29 ℃ of air flow 0.5vvm, tank pressure 1.0Mpa condition, cultivate.The preceding 20 hours pH that ferment are natural, based on thalli growth, as thalli growth optical density(OD) (OD
600) greater than 0.6, begin stream and add C
11Alkane, C in the control fermented liquid
11Alkane concentration maintains 5% (V: V), regulate pH to 7.0 simultaneously, in 48 hours, regulate pH to 7.0 with NaOH solution in per 4 hours, and 48-72 hour, regulated pH to 7.5 with NaOH solution in per 4 hours, 72-120 hour, regulated pH to 7.8 with NaOH solution in per 4 hours, 120 hours to putting jar, regulated pH to 8.0 with NaOH solution in per 4 hours.Fermentation to 24,48,72 hours batches of formulas add 1%, and (W: glucose V), 2% (W: yeast extract paste V) was added in fermentation to 96 hours.From being inoculated into fermentation ends, total incubation time is 167 hours, mends C altogether
1130.85 tons of alkane are with extracted with diethyl ether NaOH titration measuring fermenation raw liquid DC
11Content is 120.4g/L, 19.914 tons of fermentation total acids, and alkane is 64.55% to the weight transformation efficiency of diprotic acid.
Embodiment 4DC
12Fermentation
100M is being housed
3The 200M of substratum
3In the fermentor tank, the secondary seed solution that inserts embodiment 1 begins fermentation.The fermentation culture based component is: glucose 30g/L, KH
2PO
45g/L, yeast extract paste 20g/L, corn steep liquor 15g/L, urea 2.5g/L, NaCl 2.0g/L, KNO
37g/L, the tap water preparation, the pH nature, 121 ℃ of sterilizations even disappear.C
12Alkane and feed supplement sugar disappear.Under 29 ℃ of air flow 0.5vvm, tank pressure 1.0Mpa condition, cultivate.Preceding 20 hours pH nature that ferments, based on thalli growth, when thalli growth optical density(OD) (OD) greater than 0.6, begin batch formula and add C
12Alkane 8%, after this added that alkane concentration maintains 5% (V: V) in alkane control fermented liquid in per 8 hours, regulate pH to 6.5 simultaneously, after 48 hours, regulated pH to 7.0 with NaOH solution in per 4 hours, 48-72 hour, regulate pH to 7.5 with NaOH solution in per 4 hours, and 72-120 hour, regulated pH to 7.8 with NaOH solution in per 4 hours, 120 hours to putting jar, regulated pH to 8.0 with NaOH solution in per 4 hours.Fermentation to 24,48,72 hours batches of formulas add 1%, and (W: glucose V), from being inoculated into fermentation ends, total incubation time is 138 hours, mends C altogether
1234.33 tons of alkane are with extracted with diethyl ether NaOH titration measuring fermenation raw liquid DC
12Content is 168.4g/L, 24.79 tons of fermentation total acids, and alkane is 72.21% to the weight transformation efficiency of diprotic acid.
Embodiment 5DC
13Fermentation
100M is being housed
3The 200M of substratum
3In the fermentor tank, the secondary seed solution of access begins fermentation.The fermentation culture based component is: glucose 40g/L, KH
2PO
48g/L, yeast extract paste 10g/L, corn steep liquor 5g/L, urea 3.5g/L, NaCl 1.0g/L, KNO
37g/L, the pH nature, 121 ℃ of sterilizations even disappear.Alkane and feed supplement sugar disappear.Under 29 ℃ of air flow 0.6vvm, tank pressure 1.0Mpa condition, cultivate.Preceding 20 hours pH nature that ferments, based on thalli growth, when thalli growth optical density(OD) (OD) greater than 0.6, begin batch formula and add C
13Alkane 5% added that alkane concentration maintains 5% (V: V), regulate pH to 6.5 and automatic control simultaneously, pH automatic control 7.0 in 48 hours in alkane control fermented liquid in after this per 8 hours, 72 hours, pH automatic control 7.5,120 hours, pH automatic control 7.8,120 hours is to putting jar, pH automatic control 8.0.Fermentation to 16,32,72 hours batches of formulas add 1%, and (W: glucose V), from being inoculated into fermentation ends, total incubation time is 160 hours, mends C altogether
1330.306 tons of alkane are with extracted with diethyl ether NaOH titration measuring fermenation raw liquid DC
13Content is 165.4g/L, 24.45 tons of fermentation total acids, and alkane is 80.67% to the weight transformation efficiency of diprotic acid.
Embodiment 6DC
14Fermentation
100M is being housed
3The 200M of substratum
3In the fermentor tank, insert secondary seed solution and begin fermentation.The fermentation culture based component is: glucose 20g/L, KH
2PO
46g/L, yeast extract paste 7g/L, corn steep liquor 10g/L, urea 2.5g/L, NaCl 1.0g/L, the pH nature, 121 ℃ of sterilizations even disappear.Alkane and feed supplement sugar disappear.Under 29 ℃ of air flow 0.6vvm, tank pressure 1.0Mpa condition, cultivate.Preceding 20 hours pH nature that ferments, based on thalli growth, when thalli growth optical density(OD) (OD) greater than 0.6, begin batch formula and add C
14Alkane 5% added that alkane concentration maintains 5% (V: V), regulate pH to 6.5 and automatic control simultaneously, pH automatic control 7.0 in 48 hours in alkane control fermented liquid in after this per 8 hours, 72 hours, pH automatic control 7.5,120 hours, pH automatic control 7.8,120 hours is to putting jar, pH automatic control 8.0.Fermentation to 20,38,68 hours batches of formulas add 1%, and (W: glucose V), from being inoculated into fermentation ends, total incubation time is 143 hours, mends C altogether
1428.235 tons of alkane are with extracted with diethyl ether NaOH titration measuring fermenation raw liquid DC
14Content is 194.6g/L, 23.67 tons of fermentation total acids, and alkane is 83.83% to the weight transformation efficiency of diprotic acid.
Embodiment 7DC
15Fermentation
3M is being housed
3The 5M of substratum
3In the fermentor tank, insert secondary seed solution and begin fermentation.The fermentation culture based component is: sucrose 20g/L, KH
2PO
415g/L, yeast extract paste 10g/L, corn steep liquor 4.5g/L, urea 10g/L, the tap water preparation, the pH nature was sterilized 20 minutes for 121 ℃.C
15Alkane and feed supplement sugar disappear.Under 29 ℃, air flow 0.8vvm, tank pressure 1.0Mpa condition, cultivate.Preceding 20 hours pH nature that ferments, based on thalli growth, when thalli growth optical density(OD) (OD) greater than 0.6, begin to add C
15Alkane 10%, added that alkane concentration maintains 8% (V: V) in alkane control fermented liquid in per during the fermentation then 12 hours, regulate pH to 7.0 simultaneously, in 48 hours, regulated pH to 7.0 with NaOH solution in per 4 hours, 48-72 hour, regulate pH to 7.5 with NaOH solution in per 4 hours, and 72-120 hour, regulated pH to 7.8 with NaOH solution in per 4 hours, 120 hours to putting jar, regulated pH to 8.0 with NaOH solution in per 4 hours.From being inoculated into fermentation ends, total incubation time is 166 hours, adds C
15Alkane total amount 711kg is with extracted with diethyl ether NaOH titration measuring fermenation raw liquid DC
15Content is 142.3g/L, and alkane is 80.1% to the weight transformation efficiency of diprotic acid.
Embodiment 8DC
16Fermentation
In the 10L fermentor tank of 6L substratum is housed, inserts the 1.0L primary seed solution and begin fermentation.The fermentation culture based component is: glucose 10g/L, KH
2PO
48g/L, yeast extract paste 1g/L, corn steep liquor 1.5g/L, urea 1g/L, NaCl 1g/L, KNO
37g/L, the tap water preparation, the pH nature was sterilized 20 minutes for 121 ℃.Alkane and feed supplement sugar disappear.Under 29 ℃, air flow 0.8vvm, tank pressure 1.0Mpa condition, cultivate.Preceding 20 hours pH nature that ferments, based on thalli growth, when thalli growth optical density(OD) (OD) greater than 0.6, add 10%C
16Alkane, added 5% alkane in then per 12 hours, alkane concentration maintains 7% (V: V), regulate pH to 7.0 simultaneously in the control fermented liquid, in 48 hours, regulate pH to 7.0 with NaOH solution in per 4 hours, and 48-72 hour, regulated pH to 7.5 with NaOH solution in per 4 hours, 72-120 hour, regulated pH to 7.8 with NaOH solution in per 4 hours, 120 hours to putting jar, regulated pH to 8.0 with NaOH solution in per 4 hours.Fermentation to 24, criticize formula 48,72 hours the time and add 1% (W: glucose V).From being inoculated into fermentation ends, total incubation time is 165 hours, adds C
16Alkane total amount 1500g is with extracted with diethyl ether NaOH titration measuring fermenation raw liquid DC
16Content is 106.2g/L, and alkane is 66.4% to the weight transformation efficiency of diprotic acid.
Embodiment 9DC
17Fermentation
Get inclined-plane candida tropicalis bacterial classification, be inoculated in the seed bottle of the 500mL that the 200mL liquid nutrient medium is housed 30 ℃, the 300rpm shaking table was cultivated 15 hours, shake-flask culture based formulas: peptone 10g/kg, yeast extract paste 5g/kg, glucose 10g/kg, tap water preparation, pH nature.
Shake in the bottle at the 500mL that the 15ml substratum is housed, insert the bacterial classification in the above-mentioned seed liquor of 3mL respectively, add simultaneously and divide the urea that disappears, begin fermentation.The fermentation culture based component is: glucose 30g/kg, KH
2PO
410g/kg, yeast extract paste 1.5g/kg, corn steep liquor 2.5g/kg, urea 3.0g/kg, KNO
310g/kg, C
17Alkane 15%, tap water preparation, pH7.5,121 ℃ of sterilizations 20 minutes are cultivated under 29 ℃, 220rpm condition, regulate pH to 7.5～8.0,96 a hour following shaking table every 24 hours after 48 hours and detect.From being inoculated into fermentation ends, total incubation time is 96 hours.Measure fermenation raw liquid 17 carbon dicarboxylic acid (DC
17) content is up to 62.3g/L.
Embodiment 10The mixed alkanes fermentation
In the 10L fermentor tank of 6L substratum is housed, insert the secondary seed solution of embodiment 1, begin fermentation.The fermentation culture based component is: glucose 10g/L, KH
2PO
48.5g/L, yeast extract paste 1.5g/L, corn steep liquor 1.5g/L, urea 1g/L, NaCl 1g/L, KNO
38g/L, the tap water preparation, the pH nature was sterilized 20 minutes for 121 ℃.Alkane and feed supplement sugar disappear.Under 29 ℃, 600rpm, air flow 0.8vvm, tank pressure 1.0Mpa condition, cultivate.Preceding 20 hours pH nature that ferments, based on thalli growth, when thalli growth optical density(OD) (OD) greater than 0.6, begin stream and add and mix normal alkane C
9-11Alkane concentration maintains 5% (V: V) in the control fermented liquid, regulate pH to 7.0 simultaneously, in 48 hours, regulated pH to 7.0 with NaOH solution in per 4 hours, 48-72 hour, regulate pH to 7.5 with NaOH solution in per 4 hours, and 72-120 hour, regulated pH to 7.8 with NaOH solution in per 4 hours, 120 hours to putting jar, regulated pH to 8.0 with NaOH solution in per 4 hours.Fermentation to 24, criticize formula 48,72 hours the time and add 1% (W: glucose V).From being inoculated into fermentation ends, total incubation time is 144 hours, and measuring the fermenation raw liquid acid content with vapor phase process is 87.2g/L, and the content distribution of diprotic acid is DC
9: 25.45%, DC
10: 39.74%, DC
11: 31.37%.
Embodiment 11The mixed alkanes fermentation
In the 10L fermentor tank of 6L substratum is housed, insert the 1.0L primary seed solution, begin fermentation.The fermentation culture based component is: glucose 10g/L, KH
2PO
48g/L, yeast extract paste 1g/L, corn steep liquor 1.5g/L, urea 1g/L, NaCl 1g/L, KNO
37g/L, the tap water preparation, the pH nature was sterilized 20 minutes for 121 ℃.Alkane and feed supplement sugar disappear.Under 29 ℃, 600rpm, air flow 0.8vvm, tank pressure 1.0Mpa condition, cultivate.Preceding 20 hours pH nature that ferments, based on thalli growth, when thalli growth optical density(OD) (OD) greater than 0.6, begin stream and add normal alkane C
11-14Alkane concentration maintains 5% (V: V), regulate pH to 7.0 simultaneously, in 48 hours in the control fermented liquid, regulated pH to 7.0 with NaOH solution in per 4 hours, 48-72 hour, regulated pH to 7.5,72-120 hour with NaOH solution in per 4 hours, regulated pH to 7.8 with NaOH solution in per 4 hours, 120 hours to putting jar, regulated pH to 8.0 with NaOH solution in per 4 hours.Fermentation to 24, criticize formula 48,72 hours the time and add 1% (W: glucose V).From being inoculated into fermentation ends, total incubation time is 140 hours, is 95.6g/L with extracted with diethyl ether NaOH titration measuring fermenation raw liquid diprotic acid content, and alkane is 63.7% to the weight transformation efficiency of diprotic acid.
Embodiment 12Dodecylic acid (lauric acid, Lauric acid) is as the shake flask fermentation of substrate
Get glycerine pipe candida tropicalis bacterial classification, be inoculated in the seed bottle of the 500mL that the 200mL liquid nutrient medium is housed 30 ℃, the 300rpm shaking table was cultivated 15 hours, shake-flask culture based formulas: peptone 10g/kg, yeast extract paste 5g/kg, glucose 10g/kg, tap water preparation, pH nature.
Shake in the bottle at the 500mL that the 15ml substratum is housed, insert the bacterial classification in the above-mentioned seed liquor of 3mL respectively, add simultaneously and divide the lauric acid that disappears, begin fermentation.The fermentation culture based component is: glucose 25g/kg, KH
2PO
410g/kg, yeast extract paste 0.5g/kg, corn steep liquor 2.5g/kg, urea 3.0g/kg, KNO
310g/kg, lauric acid 15%, tap water preparation, pH7.5,121 ℃ of sterilizations 20 minutes are cultivated under 29 ℃, 220rpm condition, regulate pH to 7.5～8.0,96 a hour following shaking table every 24 hours after 48 hours and detect.From being inoculated into fermentation ends, total incubation time is 96 hours.Be up to 47.7g/L with gas phase internal mark method determination fermenation raw liquid SL-AH content.
Embodiment 13The fermentation of tetradecacarbon fatty acid (tetradecanoic acid, Myristic acid)
According to the fermentation of the method for embodiment 12 control tetradecacarbon fatty acid Myristic acid (tetradecanoic acid), the content that vapor phase process detects ten four-carbon dicarboxylic acids in the liquid of fermentation source after the fermentation ends is up to 35.6g/l.
Embodiment 14The fermentation of 16 carbon fatty acids (palmitinic acid, Palmiticacid, Palmitic acid)
Control the fermentation of 16 carbon fatty acids (palmitinic acid, Palmiticacid, Palmitic acid) according to the method for embodiment 12, the content that vapor phase process detects 16-dicarboxylic acid in the liquid of fermentation source after the fermentation ends is up to 38.6g/l.
Embodiment 15The fermentation of 18 carbon fatty acids (stearic acid, Stearic acid)
Control the fermentation of 18 carbon fatty acids (stearic acid, Stearic acid) according to the method for embodiment 12, the content that vapor phase process detects 18 carbon dicarboxylic acids in the liquid of fermentation source after the fermentation ends is up to 29.7g/l.
Embodiment 16C
12The enzymatic conversion of normal alkane
It is centrifugal to get the 6L secondary seed solution, collects thalline, the KCl washing with 0.1% one time, and recentrifuge, the thalline of collecting add potassium primary phosphate-Sodium phosphate dibasic damping fluid 5L altogether that pH is 7.5 0.1M, the C of adding 10%
12Normal alkane begins enzymatic conversion, adds 30g glucose in the conversion process in per 6 hours, adds 8% C in per 12 hours
12Alkane, process is 7.5 with sodium hydroxide control pH, transforms 120 hours, and producing acid is 115g/L, and alkane conversion is 77%.
Embodiment 17C
12The enzymatic conversion of normal alkane
It is centrifugal to get the 6L secondary seed solution, collects thalline, the KCl washing with 0.1% one time, and recentrifuge, with the thalline that the sodium alginate method fixedly is collected, adding pH is that potassium primary phosphate-Sodium phosphate dibasic damping fluid of 7.5 0.01M is total to 5L, the C of adding 10%
12Normal alkane begins enzymatic conversion, adds 30g glucose in the conversion process in per 6 hours, adds 8% C in per 12 hours
12Alkane, process is 7.5 with sodium hydroxide control pH, transforms 80 hours, and producing acid is 45g/L, and alkane conversion is 84%.
Embodiment 18Broth extraction
One times of the fermented liquid thin up that embodiment 8 is obtained adds adjusting PH with base to 10.0, is heated to 90 ℃, and is centrifugal while hot, removes thalline and residual hydrocarbon.Centrifugal clear liquid adds 2.5% activated carbon decolorizing elimination gac after 20 minutes, regulates pH to 3.0 with sulfuric acid and carries out acidizing crystal, and acidizing crystal liquid is cooled to room temperature, filter, wash to neutral, dried 12 hours, and obtained product 850g for 80 ℃, analyzing total acid is 99.0%, DC
16Gas chromatographic purity is 98.1%, and extract yield is 85%.
Embodiment 19Membrane filtration
Get the fermented liquid that 30 liters of embodiment 10 obtain, regulating pH with liquid caustic soda is 8.0, and feed temperature is heated to 70 ℃;
The fermented liquid of handling is placed ceramic super-filtering film filtration cycle jar, starts product pump, keep going into film pressure at 0.7Mpa, go out under the state of film pressure at 0.3Mpa, the filtration flux of film is 95L/ square metre hour;
At material liquid volume during at 5 liters, beginning adds 75 ℃, pH in storage tank be 10 liters of 9.0 hot water, when material liquid volume is 25 liters, quits work 1.8 hours process operation time.Analytical results shows that the content of long-chain biatomic acid is 67.3 grams per liters in the filtrate, and long-chain biatomic acid content is 12.3 grams per liters in the concentrated solution.
Embodiment 20Membrane filtration
Get the fermented liquid of 100 liters of embodiment 8, regulating PH with liquid caustic soda is 8.0, and feed temperature is heated to 80 ℃;
The fermented liquid of handling is placed organic ultrafiltration membrance filter circulation tank, starts product pump, keep going into film pressure at 0.7Mpa, go out under the state of film pressure at 0.3Mpa, the filtration flux of film is 95L/ square metre hour;
At material liquid volume during at 25 liters, beginning adds 75 ℃, pH in storage tank be 60 liters of 9.0 hot water, when material liquid volume is 25 liters, quits work 1.8 hours process operation time.Analytical results shows that the content of long-chain biatomic acid is 85.5 grams per liters in the filtrate, and long-chain biatomic acid content is 18 grams per liters in the concentrated solution.
Embodiment 21Membrane filtration
With 150 tons of fermented liquids after embodiment 4 fermentation ends, regulating pH with liquid caustic soda is 10.5, and feed temperature is heated to 90 ℃.
The fermented liquid of handling is placed the membrane filtration circulation tank, starts product pump, keep going into film pressure at 0.75Mpa, go out under the state of film pressure at 0.2Mpa, the filtration flux of film is 155 liters/square metre hours.
At material liquid volume during at 30 cubic metres, in storage tank, add 75 ℃, pH and be 100 cubic metres of 9.0 hot water, when material liquid volume is 30 cubic metres, quit work 20 hours process operation time.Analytical results shows that the content of long-chain biatomic acid is 67.8 grams per liters in the filtrate; Long-chain biatomic acid content is 5.25 grams per liters in the concentrated solution.
Embodiment 22Product purification---distillation
45 kilograms of crude product diprotic acid getting embodiment 19 are in the fusion jar, and the fusion jar adopts heat-conducting oil heating, 180 ℃ of temperature, 1 hour fusion time spent.With pump material is squeezed into luwa evaporator after the fusion, temperature of charge is 176 ℃ when advancing luwa evaporator, and luwa evaporator passes in and out oily temperature and is respectively 185 ℃ and 189 ℃, and vacuum tightness 500Pa took off light constituent 5 minutes consuming time.
The material that will take off behind the light constituent is squeezed into short course distillation device with pump, and short course distillation device hot side and huyashi-chuuka (cold chinese-style noodles) temperature are respectively 222-230 ℃ and 134-143 ℃, system vacuum degree 15-19Pa, 180 ℃ of feeding temperatures, 1.5 hours consuming time of process.
The product purity that obtains through above-mentioned purifying process is 98.12%, and thermostability is 86/92, obtains 39 kilograms of products, and product is a white plates, and yield is 86.7%; 4.0 kilograms of distillation residue, residual 2.0 kilograms of pipeline.
Embodiment 23Product purification---distillation
Get 43 kilograms of crude product diprotic acid in the fusion jar, the fusion jar adopts heat-conducting oil heating, 160 ℃ of temperature, 1 hour fusion time spent.With pump material is squeezed into luwa evaporator after the fusion, temperature of charge is 156.6 ℃ when advancing luwa evaporator, and luwa evaporator passes in and out oily temperature and is respectively 193 ℃ and 190 ℃, and vacuum tightness 210-230Pa took off light constituent 13 minutes consuming time.
The material that will take off behind the light constituent is squeezed into short course distillation device with pump, and short course distillation device hot side and huyashi-chuuka (cold chinese-style noodles) temperature are respectively 216-219 ℃ and 137-154 ℃, system vacuum degree 18Pa, 180 ℃ of feeding temperatures, 1.8 hours consuming time of process.
The product purity that obtains through above-mentioned purifying process is 98.24%, and the product thermostability is 87/93, obtains 37 kilograms of products, and product is a white plates, and yield is 86%; 3.5 kilograms of distillation residue, residual 2.5 kilograms of pipeline.
Embodiment 24Product purification---solvent method
The diprotic acid crude product DC that makes
12300kg adds ethanol 1000L, is heated to 70 ℃ and makes the diprotic acid dissolving, be incubated 90 minutes, in 1 hour, it be cooled to 15 ℃ of crystallizations, centrifugal with centrifugal basket drier, the product of the primary crystallization that obtains adds 800L ethanol again, be heated to 70 ℃ and make diprotic acid dissolving, be incubated 60 minutes, in 2 hours, it is cooled to 15 ℃ of crystallizations, obtain with centrifugal basket drier is centrifugal, drying, product 285kg, yield are 95%.Product thermostability behind the solvent crystallization is 88/92, and the purity of vapor detection diprotic acid is 98.15%.
Embodiment 25Product purification---solvent method
The diprotic acid crude product DC that makes
12150g adds methyl alcohol 1000mL, is heated to 60 ℃ and makes the diprotic acid dissolving, be incubated 90 minutes, in 1 hour, it be cooled to 15 ℃ of crystallizations, filter, the product of the primary crystallization that obtains adds 800mL methyl alcohol again, be heated to 60 ℃ and make diprotic acid dissolving, be incubated 60 minutes, in 2 hours, it is cooled to 15 ℃ of crystallizations, filter, drying, product 136g, yield are 90.6%.Product thermostability behind the solvent crystallization is 86/91, and the purity of vapor detection diprotic acid is 97.05%.
Embodiment 26Product purification---solvent method
The diprotic acid crude product DC that makes
12300g adds ethyl acetate 1500mL, is heated to 70 ℃ and makes the diprotic acid dissolving, be incubated 60 minutes, in 2 hours, it be cooled to 15 ℃ of crystallizations, filter, the product of the primary crystallization that obtains adds the 1200mL ethyl acetate again, be heated to 70 ℃ and make diprotic acid dissolving, be incubated 30 minutes, in 2 hours, it is cooled to 15 ℃ of crystallizations, filter, drying, product 270g, yield are 90%.Product thermostability behind the solvent crystallization is 87/93, and the purity of vapor detection diprotic acid is 98.75%.
Embodiment 27Product purification---solvent method
The diprotic acid crude product DC that makes
12300g adds butylacetate 1500mL, is heated to 80 ℃ and makes the diprotic acid dissolving, be incubated 60 minutes, in 2 hours, it be cooled to 15 ℃ of crystallizations, filter, the product of the primary crystallization that obtains adds the 1200mL butylacetate again, be heated to 90 ℃ and make diprotic acid dissolving, be incubated 30 minutes, in 2 hours, it is cooled to 15 ℃ of crystallizations, filter, drying, product 264g, yield are 88%.Product thermostability behind the solvent crystallization is 86/90, and the purity of vapor detection diprotic acid is 98.35%.
Embodiment 28Product purification---solvent method
The diprotic acid crude product DC that makes
12200g adds acetone 1500mL, is heated to 50 ℃ and makes the diprotic acid dissolving, be incubated 60 minutes, in 1 hour, it be cooled to 15 ℃ of crystallizations, filter, the product of the primary crystallization that obtains adds 1200mL acetone again, be heated to 50 ℃ and make diprotic acid dissolving, be incubated 30 minutes, in 1 hour, it is cooled to 15 ℃ of crystallizations, filter, drying, product 175g, yield are 87.5%.Product thermostability behind the solvent crystallization is 87/91, and the purity of vapor detection diprotic acid is 97.45%.
Embodiment 29Product purification---solvent method
The diprotic acid crude product DC that makes
12200g adds butanone 1500mL, is heated to 70 ℃ and makes the diprotic acid dissolving, be incubated 60 minutes, be cooled to 15 ℃ of crystallizations rapidly, filter, the product of the primary crystallization that obtains adds the 1200mL butanone again, be heated to 70 ℃ and make the diprotic acid dissolving, be incubated 30 minutes, be cooled to 15 ℃ of crystallizations rapidly, filter, drying, product 164g, yield are 82%.Product thermostability behind the solvent crystallization is 85/90, and the purity of vapor detection diprotic acid is 97.25%.
Embodiment 30Product purification---solvent method
The diprotic acid crude product DC that makes
12250g adds acetate 1000mL, is heated to 90 ℃ and makes the diprotic acid dissolving, be incubated 90 minutes, in 1 hour, it be cooled to 15 ℃ of crystallizations, filter, the product of the primary crystallization that obtains adds 800mL acetate again, be heated to 80 ℃ and make diprotic acid dissolving, be incubated 60 minutes, in 2 hours, it is cooled to 15 ℃ of crystallizations, filter, drying, product 204kg, yield are 81.6%.Product thermostability behind the solvent crystallization is 86/92, and the purity of vapor detection diprotic acid is 98.55%.
Embodiment 31Product purification---solvent method
The diprotic acid crude product DC that makes
12200g adds Virahol 1000mL, is heated to 80 ℃ and makes the diprotic acid dissolving, be incubated 60 minutes, in 2 hours, it be cooled to 15 ℃ of crystallizations, filter, the product of the primary crystallization that obtains adds the 800mL Virahol again, be heated to 70 ℃ and make diprotic acid dissolving, be incubated 30 minutes, in 2 hours, it is cooled to 15 ℃ of crystallizations, filter, drying, product 171g, yield are 85.5%.Product thermostability behind the solvent crystallization is 89/91, and the purity of vapor detection diprotic acid is 97.85%.
Embodiment 32Product purification---solvent method
The diprotic acid crude product DC that makes
12200g adds propyl carbinol 1200mL, is heated to 90 ℃ and makes the diprotic acid dissolving, be incubated 60 minutes, in 2 hours, it be cooled to 15 ℃ of crystallizations, filter, the product of the primary crystallization that obtains adds the 1000mL propyl carbinol again, be heated to 90 ℃ and make diprotic acid dissolving, be incubated 60 minutes, in 2 hours, it is cooled to 15 ℃ of crystallizations, filter, drying, product 168g, yield are 84%.Product thermostability behind the solvent crystallization is 88/92, and the purity of vapor detection diprotic acid is 97.95%.
Embodiment 33Product purification---solvent method
The diprotic acid crude product DC that makes
12200g adds ethylene glycol 1500mL, is heated to 60 ℃ and makes the diprotic acid dissolving, be incubated 30 minutes, be cooled to 15 ℃ of crystallizations rapidly, filter, the product of the primary crystallization that obtains adds 1200L ethylene glycol again, be heated to 60 ℃ and make the diprotic acid dissolving, be incubated 30 minutes, be cooled to 15 ℃ of crystallizations rapidly, filter, drying, product 153, yield are 76.5%.Product thermostability behind the solvent crystallization is 87/93, and the purity of vapor detection diprotic acid is 98.75%.
Embodiment 34The thermostability experiment of long-chain biatomic acid
The color and luster of polymkeric substance is a very important index, the long-chain biatomic acid that the traditional biological method is produced is owing to contain albumen, thermolability materials such as carbohydrate, therefore in polymer processing,, needs make color and luster become very dark because passing through pyroprocess, applicant of the present invention has added this index of thermostability for the control of long-chain biatomic acid quality on stream, by investigating the thermostability of diprotic acid variation quantitatively characterizing product of transmittance after heating for some time under the blowing air state, thereby by the optimization innovation of technology, final production has gone out to satisfy production nylon, high-grade hot melt adhesive, the qualified product of polymkeric substance such as polyester.
Take by weighing the long-chain biatomic acid sample (being designated as sample 1,2 and 3) of the embodiment 22,23,26 of 30.00 ± 0.05g and the comparison that existing like product is made thermostability respectively, each sample is placed the clean colorimetric cylinder of exsiccant, place 150 ± 2 ℃ oil bath then, bubbling air is to the colorimetric cylinder bottom, stopped bubbling air in 30 ± 1 minutes immediately, afterwards all samples is transferred in the beaker of methyl-sulphoxide (DMSO) of 100ml, be cooled to room temperature and make the blank transmittance of surveying each sample at the 440/550nm place with DMSO, its result is as shown in table 1:
Table 1: each DC12 of manufacturer product thermostability index contrast
| Manufacturer | Production technique | Total acid (%) | Single acid (%) | Fusing point (℃) | Thermostability 440/550nm |
| ??Dupont | Chemical method | ??99.78 | ??99.27 | ????129.5-130.6 | ??87/93 |
| ??Ube | Chemical method | ??99.58 | ??98.60 | ????129.4-130.6 | ??85/92 |
| Zibo is extensively logical | Fermentation method | ??99.21 | ??98.13 | ????128.9-130.0 | ??81/85 |
| Sample 1 | Biological process | ??99.31 | ??98.12 | ????129.2-130.3 | ??86/92 |
| Sample 2 | Biological process | ??99.45 | ??98.24 | ????129.1-130.2 | ??87/93 |
| Sample 3 | Biological process | ??99.72 | ??99.23 | ????129.4-130.5 | ??87/93 |
As seen from the above table, the thermostability of the long-chain biatomic acid that method of the present invention prepares obviously is better than the like product of existing biological process preparation, and is equally matched with the quality product that is widely used at present polymer production in the world of chemical method preparation with E.I.Du Pont Company.And compare with chemical method, there is reaction conditions gentleness---normal temperature and pressure in this biological process production technique, reaction process is simple---and a step transforms, advantage such as fatty acids not, be lower than chemical method and successfully realize industrialization production obtaining under the condition of same quality product production cost, it is leading in the world that level reaches.
Claims (29)
1, a kind of production method of positive long-chain biatomic acid may further comprise the steps:
One, with C
9～C
18Alkane or lipid acid be substrate, be converted into corresponding positive long-chain biatomic acid by biological process;
Two, reaction solution is carried out pre-treatment, to remove thalline and residual alkane or lipid acid wherein, obtain the diprotic acid clear liquid, carry out acidizing crystal then, acidizing crystal liquid obtains the diprotic acid crude product through filter press again;
Three, with the diprotic acid crude product that obtains by adopting wiped film vaporization, short course distillation device refining or adopt organic solvent refining under high vacuum condition.
2, the method for claim 1 is characterized in that, described biological process is a fermentation method.
3, method as claimed in claim 2 is characterized in that, the employed bacterial classification of fermentation method is candida tropicalis (Candida Tropicalis).
4, method as claimed in claim 2 is characterized in that, the prescription of fermention medium is:
KH
2PO
4：0.2～1.5％；????NaCl：0～0.2％；
Yeast extract paste: 0.1～2.0%; Urea: 0.2～1.5%;
Glucose: 1.0～5.0%; (NH
4)
2SO
4: 0～2.0%;
MgSO
47H
2O:0～0.3%; Defoamer: 0.005%.
5, method as claimed in claim 2 is characterized in that, the mode of adding is adopted in the adding of substrate.
6, method as claimed in claim 5, it is characterized in that, the additional way of substrate is as follows: when the thalli growth optical density(OD) greater than 0.6 the time, begin to add 5～10% alkane or lipid acid, add thereafter that alkane concentration is 2～10% in alkane or the lipid acid control fermented liquid.
7, method as claimed in claim 2 is characterized in that, also adds the secondary carbon source in the fermenting process.
8, method as claimed in claim 7 is characterized in that, described secondary carbon source is glucose or sucrose.
9, the method for claim 1 is characterized in that, described biological process is an enzyme process.
10, method as claimed in claim 9 is characterized in that, described enzyme process is directly to utilize the thalline of candida tropicalis (Candida Tropicalis) seed liquor or carry out in buffer system through the thalline after the immobilization.
11, method as claimed in claim 9 is characterized in that, described buffer system is potassium primary phosphate-Sodium phosphate dibasic damping fluid.
12, method as claimed in claim 9 is characterized in that, the method that in batches adds is adopted in the adding of substrate.
13, method as claimed in claim 9 is characterized in that, also adds the secondary carbon source in the conversion process.
14, method as claimed in claim 13 is characterized in that, described secondary carbon source is glucose or sucrose.
15, the method for claim 1 is characterized in that, can be single alkane or lipid acid as the normal alkane or the lipid acid of substrate, also can be blended alkane or lipid acid.
16, the method for claim 1, it is characterized in that, the pre-treatment of fermented liquid comprises that fermented liquid is added alkali regulates pH to 8～12 in the step 2, be heated to 60～100 ℃, utilize breakdown of emulsion layering settled process, centrifuging or membrane filter method to remove thalline in the fermented liquid and residual alkane or lipid acid then.
17, method as claimed in claim 16 is characterized in that, the employed film of membrane filtration can be organic membrane or mineral membrane, can be ultra-filtration membrane or microfiltration membrane.
18, method as claimed in claim 16 is characterized in that, the film pressure of going into of membrane filtration is controlled at 0.1-0.7Mpa, and the membrane pressure-controlling is at 0.0-0.4Mpa.
19, the method for claim 1 is characterized in that, the diprotic acid clear liquid that obtains through pre-treatment in the step 2 can add activated carbon decolorizing according to circumstances.
20, method as claimed in claim 19 is characterized in that, the dosage of gac is 0～5% in the step 2, and the temperature of decolouring is 60～95 ℃, and the time is 20-180 minute.
21, the method for claim 1 is characterized in that, the acidizing crystal of step 2 comprises destainer is heated to 60～100 ℃, carries out acidizing crystal with acid for adjusting pH to 2～5.
22, the method for claim 1, it is characterized in that, adopt wiped film vaporization, short course distillation device to use luwa evaporator at vacuum 10～600Pa refining comprising under high vacuum condition in the step 3, remove light constituent under 120～250 ℃ of conditions of temperature, at vacuum 3～100Pa, use short course distillation device to remove heavy constituent under 180～240 ℃ of conditions of temperature then.
23, the method for claim 1 is characterized in that, adopts organic solvent purified step to comprise in the step 3 diprotic acid crude product is put in the organic solvent, and heating makes its dissolving, insulation for some time, crystallisation by cooling, solid-liquid separation, drying.
24, method as claimed in claim 23 is characterized in that, employed organic solvent can be alcohols, acids, ketone or ester class.
25, method as claimed in claim 24 is characterized in that, described alcohols can be methyl alcohol, ethanol, ethylene glycol, Virahol or propyl carbinol.
26, method as claimed in claim 24 is characterized in that, described acids is an acetate.
27, method as claimed in claim 24 is characterized in that, described ketone is acetone or butanone.
28, method as claimed in claim 24 is characterized in that, described ester class is ethyl acetate or butylacetate.
29, the method for claim 1 is characterized in that, adopts the step 2 of fermentation method also can following step to replace:
Direct acidifying feed liquid obtains the diprotic acid crude product with thalline and diprotic acid coprecipitation after the fermentation ends.
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