CN103805643A - Production method for long-chain dicarboxylic acids - Google Patents
Production method for long-chain dicarboxylic acids Download PDFInfo
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- CN103805643A CN103805643A CN201210439800.4A CN201210439800A CN103805643A CN 103805643 A CN103805643 A CN 103805643A CN 201210439800 A CN201210439800 A CN 201210439800A CN 103805643 A CN103805643 A CN 103805643A
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Abstract
The invention discloses a production method for long-chain dicarboxylic acids. The method includes: subjecting a dicarboxylic acid strain to enlargement culture to obtain a seed solution, conducting enlargement fermentation on the seed solution, adding emulsified alkane, removing mycoprotein at the end of reaction, and carrying out crystallization to obtain a long-chain dicarboxylic acid product. The method provided by the invention improves the compatibility of the aqueous phase and oil phase in the fermentation system, and enhances the conversion rate of alkane in the fermentation system and the yield of the dicarboxylic acid product.
Description
Technical field
The invention belongs to biological chemical field, relate generally to a kind of method of utilizing fermentation mode to produce long-chain biatomic acid.
Background technology
Long-chain biatomic acid (Long chain dicarboxylic acids) refers to the aliphatic dicarboxylic acid (being called for short DCn) that contains more than 10 carbon atom in carbochain, comprising saturated and unsaturated dicarboxylic acid, is the fine chemical product that a class has important and extensive industrial use.Also be in chemical industry, to synthesize the important source material such as senior spices, high performance nylon engineering plastics, high-grade nylon hot-melt adhesive, high-temperature electric medium, senior paint and coating, senior lubricant, cold-resistant plasticizer, resin, medicine and agricultural chemicals simultaneously.
Production of Long-chain Dicarboxylic Acids by Fermentation Methods is the effect that utilizes the distinctive oxidation capacity of microorganism and extracellular microbial endoenzyme, at normal temperatures and pressures respectively by α, omega oxidation, the methyl oxidation at long-chain normal alkane two ends is become to carboxyl, generate the various long-chain biatomic acids of respective chain length.Can utilize bacterium, mould and the actinomycetic kind of petroleum hydrocarbon a lot, wherein the yeast of mycocandida (candida) is the high producing microbial of normal alkane fermentative production diprotic acid.Long-chain biatomic acid fermentation is typical gas phase (oxygen)-water (fermented liquid)-oil phase (alkane)-solid phase (thalline) four phase systems, in order to maintain the homogeneity of four phase systems, conventionally in substratum, adds during the fermentation emulsifying agent.
CN102115768A discloses a kind of method that microbial synchronous fermentation n-hexadecane is produced 16-dicarboxylic acid, adds tensio-active agent (polysorbate60) 0.1～2 g/L to strengthen the emulsifying effectiveness of oil phase.Generally emulsifying agent is not the required composition of microbial metabolism, and therefore the mode of this additional emulsifying agent can have a negative impact to normal microorganism fermentation.
The present stage fermentation of long-chain biatomic acid generally adopts batch fermentation, adds the form of alkane in fermenting process.CN102115767A discloses a kind of microbial synchronous fermentation n-undecane and has produced 11 carbon dicarboxylic acid methods, by adding n-hexadecane at 60,90,120 hours, make in fermented liquid normal alkane concentration all the time >=5%(V/V).In actual production process, mixed with water even fast for the alkane that makes to add, general employing improves the method for stirring velocity, but the raising of stirring velocity can make shearing force increase, thereby affects the growth of fermentation thalline.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method of producing long-chain biatomic acid.The method has been improved the consistency between water and oil phase in fermentation system, has improved the efficiency of fermentation.
A kind of method of producing long-chain biatomic acid, comprise following content: the diprotic acid strain expanded culture of preservation is obtained to seed liquor, and seed liquor expands fermentation, adds emulsification alkane in fermenting process, after reaction finishes, remove tropina, crystallization obtains long-chain biatomic acid product.
In the inventive method, described diprotic acid bacterial classification is selected from the microorganism that can utilize normal alkane growth or the microorganism with complete α, omega oxidation approach, the preferably one in mycocandida, Cryptococcus, Endomyces, Hansenula anomala genus, pichia genus, Rhodotorula, torulopsis or Trichosporon etc.
In the inventive method, described enlarged culturing, carries out enlarged culturing, preferably 9 ~ 12 times of enlarged culturing according to 7～15 times.
In the inventive method, the each component concentration of minimum medium is as follows: sucrose 20～50g/L, corn steep liquor 1～3g/L, yeast extract paste 1～2g/L, sodium-chlor 0.5～1.5g/L, potassium primary phosphate 3～8g/L, magnesium sulfate 1～2g/L, urea 1～5g/L.
In the inventive method, the volume of described expansion fermentation is 7～15 times of seed liquor volume, preferably 9 ~ 12 times.
In the inventive method, fermentation condition is: mixing speed is 100～700rpm, and air flow is 0.6～1.0VVM, and leavening temperature is 29～32 ℃, and fermentation time is 138～144 hours.
In the inventive method, described fermenting process regulates and controls by the mode of adjust pH step by step, and fermentation starts, hierarchy of control pH value is, after 4～5,24 hours, system pH is adjusted to 6.8～7, then at interval of a pH value of raising in 24 hours, each raising 0.1～0.5, until fermentation ends.
In the inventive method, add during the fermentation alkane concentration in emulsification alkane maintenance system to be not less than 4%, the volume that at every turn adds emulsification alkane is 3%～12% of fermentation cumulative volume.
In the inventive method, described emulsification alkane is that long chain alkane mixes with water, carries out that microwave treatment obtains.
Wherein long chain alkane is the alkane that contains 10～16 carbon atoms in carbochain, and the volume ratio of long chain alkane and water is 3:1～10:1.
Wherein the power density of microwave treatment is the microwave power of every liter of oil-water mixture of 100～10kW/L(), microwave frequency is 300～3000MHz, microwave treatment time is 10～30 minutes.
Compared with prior art, a kind of method tool of producing long-chain biatomic acid of the present invention has the following advantages:
Adopt microwave treatment that alkane and water are processed, microwave treatment can produce heat effect, utilize the feature of water molecules fast propagation microwave radiation energy, strengthen moving upward of water molecules, both mixed effects are improved, promote the emulsification between oil phase and water, improve the emulsifying effectiveness of alkane, improve the homogeneity of gas phase (oxygen)-water (fermented liquid)-oil phase (alkane)-solid phase (thalline) four phase systems, avoided emulsifying agent and the impact of high-speed stirring on fermenting process added.Improve the transformation efficiency of alkane in fermentation system by the emulsification pre-treatment to alkane, and improved the yield of dicarboxylic acid product.
Embodiment
Detailed process and the effect of the present invention being sent out to method below in conjunction with embodiment describe, but are not limited to following examples.
In the present embodiment, select candida tropicalis (Candida tropicalis) mutant strain PF-UV-56 to carry out the experiment of long chain alkane fermentative production long-chain biatomic acid as fermentation strain, this mutant strain is deposited in China Committee for Culture Collection of Microorganisms's common micro-organisms center, and deposit number is CGMCC NO.0356.
Embodiment 1
The each component concentration of minimum medium is as follows: sucrose 30g/L, corn steep liquor 3g/L, yeast extract paste 2g/L, sodium-chlor 1g/L, potassium primary phosphate 5g/L, magnesium sulfate 1g/L, urea 4g/L.
(1) fermentation seed liquid is cultivated: slant preservation bacterial classification is inoculated in to 3000mL shaking flask and carries out strain activation and culture, activation culture liquid amasss as 500mL, and culture temperature is 32 ℃, and shaking table revolution is 120rpm, cultivates 48 hours.
(2) alkane pre-treatment: get 12 carbon alkane 3000mL and mix with 600mL water, microwave treatment 10 minutes, microwave frequency is 2450MHz, power density is 4.2kW/L.
(3) diacid fermentation: the bacterial classification seed liquor 1000mL of activation is added in 6000mL fermention medium, then add ten two carbon alkanes of 600mL through microwave emulsification, pH value is 4.3, and stirring revolution is 400rpm, ventilation is set to 7000mL/min; PH value was adjusted to 7.2 in 24 hours, and adds ten two carbon alkanes of 1200mL through microwave emulsification; Respectively pH value was raised to 0.2 in 48 hours, 72 hours, and add respectively ten two carbon alkanes of 600mL through microwave emulsification, respectively pH value was raised to 0.2 in 96 hours, 120 hours, until reaction in 144 hours finishes.In final fermentation system, SL-AH concentration is 150.1g/L, and the transformation efficiency of 12 carbon alkanes is 75.5%.
Embodiment 2
The each component concentration of minimum medium is as follows: sucrose 20g/L, corn steep liquor 1g/L, yeast extract paste 2g/L, sodium-chlor 1.5g/L, potassium primary phosphate 3g/L, magnesium sulfate 2g/L, urea 3g/L.
(1) fermentation seed liquid is cultivated: slant preservation bacterial classification is inoculated in to 3000mL shaking flask and carries out strain activation and culture, activation culture liquid amasss as 500mL, and culture temperature is 32 ℃, and shaking table revolution is 120rpm, cultivates 48 hours.
(2) alkane pre-treatment: get triclecane 3000mL and mix with 300mL water, microwave treatment 15 minutes, microwave frequency is 915MHz, power density is 300W/L.
(3) diacid fermentation: the bacterial classification seed liquor 1000mL of activation is added in 6450mL fermention medium, and add the triclecane of 550mL through microwave emulsification, pH value is made as 4.5, and stirring revolution is 500rpm, ventilation is set to 8000mL/min; PH value was adjusted to 7 in 24 hours, and adds the triclecane of 1100mL through microwave emulsification.Respectively pH value was raised to 0.2 in 48 hours, 72 hours, and add respectively the triclecane of 550mL through microwave emulsification, respectively pH value was raised to 0.2 in 96 hours, 120 hours, until reaction in 144 hours finishes.In final fermentation fermentation system, tridecanyldicarboxylic acid concentration is 138.6g/L, and the transformation efficiency of 12 carbon alkanes is 72.8%.
Embodiment 3
The each component concentration of minimum medium is as follows: sucrose 50g/L, corn steep liquor 2g/L, yeast extract paste 2g/L, sodium-chlor 1.5g/L, potassium primary phosphate 3g/L, magnesium sulfate 2g/L, urea 1g/L.
(1) fermentation seed liquid is cultivated: slant preservation bacterial classification is inoculated in to 5000mL shaking flask and carries out strain activation and culture, activation culture liquid amasss as 900mL, and culture temperature is 32 ℃, and shaking table revolution is 180rpm, cultivates 48 hours.
(2) alkane pre-treatment: get hexadecane hydrocarbon 3000mL and mix with 600mL water, microwave treatment 30 minutes, microwave frequency is 896MHz, power density is 140W/L.
(3) diacid fermentation: the bacterial classification seed liquor 1000mL of activation is added in 5400mL fermention medium, and add the hexadecane hydrocarbon of 600mL through microwave emulsification, pH value is 4.3, and stirring revolution is 400rpm, ventilation is set to 7000mL/min; 24 hours time, pH value is adjusted to 7, and adds respectively the hexadecane hydrocarbon of 1200mL through microwave emulsification.Respectively pH value was raised to 0.2 in 48 hours, 72 hours, and add the hexadecane hydrocarbon of 600mL through microwave emulsification, respectively pH value was raised to 0.2 in 96 hours, 120 hours, until reaction in 144 hours finishes.In final fermentation system, 16-dicarboxylic acid concentration is 123.1g/L, and the transformation efficiency of 12 carbon alkanes is 61.6%.
Comparative example 1
According to the experimental technique in embodiment 1, but the alkane adding is without microwave emulsification.
(1) fermentation seed liquid is cultivated: slant preservation bacterial classification is inoculated in to 3000mL shaking flask and carries out strain activation and culture, activation culture liquid amasss as 500mL, and culture temperature is 32 ℃, and shaking table revolution is 120rpm, cultivates 48 hours.
(2) diacid fermentation: the bacterial classification seed liquor 1000mL of activation is added in 6000mL fermention medium (add polysorbate60 in substratum, concentration is 0.1g/L), and add 500mL 12 carbon alkanes and 100mL water.PH value is made as 4.3, and stirring revolution is 700rpm, and ventilation is set to 7000mL/min.PH value was adjusted to 7.2 in 24 hours, and adds 1000mL 12 carbon alkanes and 200mL water.Respectively pH value was raised to 0.2 in 48 hours, 72 hours, and add respectively 500mL 12 carbon alkanes and 100mL water, respectively pH value was raised to 0.2 in 96 hours, 120 hours, until reaction in 144 hours finishes.In final fermentation system, SL-AH concentration is 125.7g/L, and the transformation efficiency of 12 carbon alkanes is 70.2%.
Claims (11)
1. produce the method for long-chain biatomic acid for one kind, it is characterized in that comprising following content: diprotic acid strain expanded culture is obtained to seed liquor, and seed liquor expands fermentation, adds emulsification alkane in fermenting process, after reaction finishes, remove tropina, crystallization obtains long-chain biatomic acid product.
2. method according to claim 1, is characterized in that: described diprotic acid bacterial classification is selected from the microorganism that can utilize normal alkane growth or the microorganism with complete α, omega oxidation approach.
3. method according to claim 1 and 2, is characterized in that: described diprotic acid bacterial classification is selected from the one in mycocandida, Cryptococcus, Endomyces, Hansenula anomala genus, pichia genus, Rhodotorula, torulopsis or Trichosporon.
4. method according to claim 1, is characterized in that: described enlarged culturing, carry out enlarged culturing according to 7～15 times.
5. method according to claim 1, is characterized in that: the volume of described expansion fermentation is 7～15 times of seed liquor volume.
6. method according to claim 1, is characterized in that: fermentation condition is: mixing speed is 100～700rpm, and air flow is 0.6～1VVM, and leavening temperature is 29～32 ℃, and fermentation time is 138～144 hours.
7. according to the method described in claim 1 or 6, it is characterized in that: described fermenting process regulates and controls by the mode of adjust pH step by step, fermentation starts, hierarchy of control pH value is adjusted to 6.8～7.2 by system pH after being 4～5,15～24 hours, then at interval of 20～24 hours, improve one time pH value, improve 0.1～0.5 at every turn, until fermentation ends.
8. method according to claim 1, is characterized in that: add during the fermentation alkane concentration in emulsification alkane maintenance system to be not less than 4%, the volume that at every turn adds emulsification alkane is 3%～12% of fermentation cumulative volume.
9. method according to claim 1, is characterized in that: described emulsification alkane is that long chain alkane mixes with water, carries out that microwave treatment obtains.
10. method according to claim 9, is characterized in that: described long chain alkane is the alkane that contains 10～16 carbon atoms in carbochain, and the volume ratio of long chain alkane and water is 3:1～10:1.
11. methods according to claim 9, is characterized in that: the power density of microwave treatment is 100W/L～10kW/L, and microwave frequency is 300MHz～3000MHz, and microwave treatment time is 10～30 minutes.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100884A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Method for preparing long-chain dicarboxylic acid by fermentation |
| CN112725385A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Method for preparing long-chain dicarboxylic acid by fermentation |
| WO2021083079A1 (en) | 2019-10-28 | 2021-05-06 | 中国石油化工股份有限公司 | Long-chain composition, combination of long-chain composition, manufacturing method, and application thereof |
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| CN1147016A (en) * | 1995-10-05 | 1997-04-09 | 中国石油化工总公司 | Method for treatment of alpha, omega dibasic acid fermentation liquor |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100884A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Method for preparing long-chain dicarboxylic acid by fermentation |
| CN111100884B (en) * | 2018-10-26 | 2022-03-08 | 中国石油化工股份有限公司 | Method for preparing long-chain dicarboxylic acid by fermentation |
| CN112725385A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Method for preparing long-chain dicarboxylic acid by fermentation |
| WO2021083079A1 (en) | 2019-10-28 | 2021-05-06 | 中国石油化工股份有限公司 | Long-chain composition, combination of long-chain composition, manufacturing method, and application thereof |
| CN112725385B (en) * | 2019-10-28 | 2022-09-09 | 中国石油化工股份有限公司 | Method for preparing long-chain dicarboxylic acid by fermentation |
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