CN105218346A - The preparation method of bio-based fumaric acid - Google Patents

The preparation method of bio-based fumaric acid Download PDF

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CN105218346A
CN105218346A CN201510604008.3A CN201510604008A CN105218346A CN 105218346 A CN105218346 A CN 105218346A CN 201510604008 A CN201510604008 A CN 201510604008A CN 105218346 A CN105218346 A CN 105218346A
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fumaric acid
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邹祥
李虹庆
李正华
李云政
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ANHUI SEALONG BIOTECHNOLOGY Co Ltd
Southwest University
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ANHUI SEALONG BIOTECHNOLOGY Co Ltd
Southwest University
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Abstract

The invention discloses the preparation method of bio-based fumaric acid, concrete grammar is: by quality volume fraction be 40 ~ 80% L MALIC ACID solution temperature be 160 ~ 190 DEG C, pressure be 0.7 ~ 1MPa condition under dehydration reaction 5 ~ 10 hours, fumaric acid crystal is collected after dehydration reaction, the method utilizes the molecule inner dewatering reaction between oxysuccinic acid and fumaric acid, and fumaric acid low solubility characteristic, industry is simple, and oxysuccinic acid transformation efficiency is high, transformation efficiency can realize more than 95%, and the product purity of acquisition is high.

Description

The preparation method of bio-based fumaric acid
Technical field
The invention belongs to biological chemical field, be specifically related to a kind of preparation method of bio-based fumaric acid.
Background technology
Fumaric acid has another name called FUMARIC ACID TECH GRADE, fumaric acid, is a kind of important platform chemicals and medicine intermediate, is widely used in the fields such as food, medicine, chemical industry, coating, resin, softening agent.The derivative dimethyl fumarate of fumaric acid has been developed to the medicine for the treatment of diversity sclerosis.Along with the purposes at food and field of medicaments is expanded, the fumaric acid demand of the good biogenetic derivation of security is also increased day by day.
The fumaric acid of current industrial production is mainly derived from the cis-butenedioic anhydride of petroleum resources, produce through isomerate process, this technique is subject to the restriction of petroleum resources, in the application in food and medicine field, its biological safety is under suspicion, therefore, biological fermentation process production bio-based fumaric acid is adopted to come into one's own in recent years, the bacterial strain that fumaric acid is produced in current direct fermentation is mainly rhizopus and genetic engineering modified intestinal bacteria etc., as patent a kind of (method of preparing fumaric acid through direct starchy material fermentation with rhizopus that Deng Li etc. reports, license numbers 201110275974.7), Jiang Min etc. report the patent (method of its production fumaric acid of the new high-yield fumaric acid gene engineering bacterium agent built, license ZL200810019216.7).But adopt these bacterial strain direct fermentation production fumaric acid to there is the problems such as heteroacid is high, fermentation period is long, glucose acid invert ratio is low, in fermented liquid except fumaric acid, there are other heteroacid (comprising succsinic acid, oxysuccinic acid, lactic acid, acetic acid etc.) of about 10-40% simultaneously, downstream extraction is caused to be separated fumaric acid cost high, cannot compete with existing production technique, up to now, adopt above-mentioned bacterial strains direct fermentation to produce fumaric acid and not yet realize industrialization.
Therefore, be badly in need of a kind of novel process of producing fumaric acid of exploitation, method is simple, is convenient to realize industrialization.
Summary of the invention
In view of this, the object of the present invention is to provide the preparation method of bio-based fumaric acid, the method is simple, and condition is controlled, is convenient to realize industrialization.
For achieving the above object, the invention provides following technical scheme:
The preparation method of bio-based fumaric acid, by quality volume fraction be 40 ~ 80% L MALIC ACID solution temperature be 160 ~ 190 DEG C, pressure be 0.7 ~ 1MPa condition under dehydration reaction 5 ~ 10 hours, collect fumaric acid crystal after dehydration reaction.
Preferably, the quality volume fraction of adding L MALIC ACID solution maintenance L MALIC ACID solution in described dehydration reaction process is 40 ~ 80%.When L MALIC ACID quality volume fraction is lower than 40%, the efficiency that L MALIC ACID dehydration generates bio-based fumaric acid is low, and when L MALIC ACID concentration is higher than 80%, L MALIC ACID meeting crystallization, is unfavorable for that dehydration generates fumaric acid equally.
Preferred, the quality volume fraction of described L MALIC ACID solution is 40 ~ 60%.
Preferred, described L MALIC ACID solution is obtained by polymalic acid acid hydrolysis.Wherein the acid-hydrolyzed method of polymalic acid adds in the sulfuric acid or hydrochloric acid that concentration is 0.5 ~ 2M by the solution containing polymalic acid salt or polymalic acid, and acid hydrolysis 4 ~ 10 hours under 70 ~ 95 DEG C of conditions, obtains the L MALIC ACID that quality volume fraction is 40 ~ 80%.
In order to reduce production cost, described polymalic acid salt or polymalic acid are obtained by fermentation, preferably obtain with Aureobasidium pullulans fermentation, also can obtain with the strain fermentation that other can produce polymalic acid, then filtering fermentation liquor removed fermentation thalli and obtain, filtration can adopt Plate Filtration or membrane sepn to filter (ultra-filtration membrane or inorganic ceramic film).
In the present invention, the Aureobasidium pullulans (Aureobasidiumpullulans) that the Aureobasidium pullulans that the present invention uses is CCTCCNO:M2012223 for preserving number, also can use and derive from USDA DSMZ (NRRL), American type culture collection (ATCC), the Aureobasidium that the Culture Collection such as China General Microbiological culture presevation administrative center (CGMCC) or natural separation produce polymalic acid belongs to or Physarum genus bacterial classification.
In the present invention, described Aureobasidium pullulans fermented liquid is prepared by following methods: be inoculated in fermention medium by the Aureobasidium pullulans of activation, temperature be 23 ~ 30 DEG C, ventilation volume than in 1:0.8 ~ 1.6, remaining sugar concentration when little higher than 20g/L bottom fermentation 96 ~ 200, in fermenting process, stream adds calcium carbonate or calcium hydroxide control pH is 5 ~ 6.5; Sugary 50 ~ 200g/L, nitrogenous source 1 ~ 5g/L, KH in described fermention medium 2pO 40.005 ~ 0.3g/L, ZnSO 40.005 ~ 0.3g/L, MgSO 40.005 ~ 0.3g/L, surplus is water.
In the present invention, the method for activation Aureobasidium pullulans is inoculated in seed culture medium by Aureobasidium pullulans, is then 23 ~ 30 DEG C in temperature, cultivates 36 ~ 96 hours under rotating speed 180 ~ 300rpm condition; The each component of described seed culture medium is as follows: glucose 40 ~ 100g/L, ammonium nitrate 1 ~ 5g/L, KH 2pO 40.005 ~ 0.3g/L, ZnSO 40.005 ~ 0.3g/L, MgSO 40.005 ~ 0.3g/L corn steep liquor, 0.05 ~ 0.3g/L and CaCO 310 ~ 50g/L, solvent is water.
Beneficial effect of the present invention is: disclosed by the invention is deficiency for existing fumaric acid production technique, develop a kind of production technique of new bio base fumaric acid, utilize the molecule inner dewatering reaction between oxysuccinic acid and fumaric acid, and fumaric acid low solubility characteristic, prepare fumaric acid, fumaric acid can separate out by direct crystallization, and technique is simple, in the present invention, oxysuccinic acid adopts the strain fermentation of high yield polymalic acid to obtain polymalic acid, then polymalic acid is hydrolyzed to L MALIC ACID, L MALIC ACID is prepared in the polymalic acid hydrolysis of producing by utilizing direct fermentation, production cost can be reduced on the one hand, widen the Application Areas of Aureobasidium pullulans tunning polymalic acid on the other hand, improve the added value of product of polymalic acid, and Aureobasidium pullulans fermentative production polymalic acid has the advantage of not producing heteroacid, succsinic acid is not contained equally in hydrolyzed solution after polymalic acid hydrolysis, acetic acid, the heteroacid such as lactic acid, oxysuccinic acid output is high, purity is much better than the oxysuccinic acid that microorganism direct fermentation is produced, therefore there is higher transformation efficiency when preparing fumaric acid and do not produce impurity, can more than 95% be reached in oxysuccinic acid transformation efficiency, and cost is low, the product purity obtained is high, there is good prospects for commercial application.
Embodiment
To be described in detail the preferred embodiments of the present invention below.The experimental technique of unreceipted actual conditions in embodiment, the usually conveniently conditioned disjunction condition of advising according to manufacturer.
Embodiment 1
The preparation method of bio-based fumaric acid, concrete steps are as follows: be that the L MALIC ACID solution of (the unit g/mL) of 50% adds in reactor by quality volume fraction, then 170 DEG C are warming up to, maintaining pressure is that 0.7Mpa dehydration reaction produces fumaric acid in 7 hours, after fumaric acid is separated out, collect fumaric acid crystal, continue to add L MALIC ACID simultaneously and maintain starting point concentration, driving a reaction carries out to fumaric acid direction.Then detect fumaric acid output, result display fumaric acid output is 42% (unit g/mL), and in oxysuccinic acid, the transformation efficiency of oxysuccinic acid is greater than 98%.
In the present embodiment, L MALIC ACID directly can buy commercial prod, and existing L MALIC ACID of can producing also can be adopted to adopt with the polymalic acid acid hydrolysis of fermentative Production obtained, and the present embodiment is adopted with the following method:
(1) bacterial classification seed culture: get in the shaking flask that Aureobasidium pullulans (Aureobasidiumpullulans) that preserving number is CCTCCNO:M2012223 is inoculated in containing 50mL seed culture medium (Flask volume is 500mL), be 25 DEG C in temperature, rotating speed is cultivate 48 hours under 220rpm condition; Seed culture medium adopts glucose 60g/L, ammonium chloride 3g/L, KH 2pO 40.2g/L, ZnSO 40.1g/L; MgSO 40.15g/L, corn steep liquor 2g/L and CaCO 320g/L;
(2) polymalic acid fermentation: the nutrient solution getting step (1) is in the 10% 300L fermentor tank be inoculated in containing 220L fermention medium by inoculum size, then temperature be 25 DEG C, ventilation ratio at more than 1:1 (v/v), remaining sugar concentration at 20g/L with top fermentation 164 hours, in fermenting process, stream adds CaCO 3solution control pH is 6.0; Detect polymalic acid output after fermentation, the output that result shows the present embodiment polymalic acid is 189g/L; Fermentating formula is glucose 120g/L, ammonium sulfate 3g/L, KH 2pO 40.2g/L, ZnSO 40.15g/L, MgSO 40.2g/L;
(3) L MALIC ACID preparation: by polymalic acid fermented liquid obtained for step (2) with ultra-filtration membrane (molecular weight 10KDa), remove fermentation thalli, obtain the fermentation clear liquid containing polymalic acid salt, the sulfuric acid of 2M is added after fermentation clear liquid concentrates, acid hydrolysis 7 hours under 85 DEG C of conditions, obtains the L MALIC ACID solution that quality volume fraction is 50% (g/ml) concentration.
Embodiment 2
The preparation method of bio-based fumaric acid, concrete steps are as follows: be that the L MALIC ACID solution of (the unit g/mL) of 60% adds in reactor by quality volume fraction, be warming up to 180 DEG C, maintaining pressure is that 0.9Mpa reacts 8 hours dehydration production fumaric acid, after fumaric acid is separated out, collect fumaric acid crystal, continue to add L MALIC ACID simultaneously and maintain starting point concentration, driving a reaction carries out to fumaric acid direction.Then detect fumaric acid output, result display fumaric acid output is 50.8% (unit g/mL), and in oxysuccinic acid, the transformation efficiency of oxysuccinic acid is greater than 98.5%.
In the present embodiment, L MALIC ACID can directly be bought, and existing L MALIC ACID of can producing also can be adopted to adopt with the polymalic acid acid hydrolysis of fermentative Production obtained, and the present embodiment is adopted with the following method:
(1) bacterial classification seed culture: get in the shaking flask that Aureobasidium pullulans (Aureobasidiumpullulans) that preserving number is CCTCCNO:M2012223 is inoculated in containing 50mL seed culture medium (Flask volume is 500mL), be 25 DEG C in temperature, rotating speed is cultivate 48 hours under 220rpm condition; Seed culture medium adopts glucose 60g/L, ammonium chloride 3g/L, KH2PO40.2g/L, ZnSO40.1g/L; MgSO40.15g/L, corn steep liquor 2g/L and CaCO320g/L;
(2) polymalic acid fermentation: the nutrient solution getting step (1) is in the 10% 300L fermentor tank be inoculated in containing 220L fermention medium by inoculum size, then temperature be 25 DEG C, ventilation ratio at more than 1:1 (v/v), remaining sugar concentration at 20g/L with top fermentation 170 hours, in fermenting process, stream adds CaCO 3solution control pH is 6.0; Detect polymalic acid output after fermentation, it is 205g/L that result shows the present embodiment polymalic acid output; Fermentating formula is glucose 120g/L, ammonium sulfate 3g/L, KH 2pO 40.2g/L, ZnSO 40.15g/L, MgSO 40.2g/L;
(3) L MALIC ACID preparation: by polymalic acid fermented liquid obtained for step (2) with inorganic ceramic film (membrane pore size 0.1 μm), remove fermentation thalli, obtain the fermentation clear liquid containing polymalic acid salt, the sulfuric acid of 0.5M is added after fermentation clear liquid concentrates, acid hydrolysis 9 hours under 75 DEG C of conditions, obtains the L MALIC ACID solution that quality volume fraction is 60% (g/mL) concentration.
Embodiment 3
The preparation method of bio-based fumaric acid, concrete steps are as follows: be that the L MALIC ACID solution of (the unit g/mL) of 55% adds in reactor by quality volume fraction, be warming up to 190 DEG C, maintaining pressure is that 1Mpa reacts 5 hours dehydration production fumaric acid, after fumaric acid is separated out, collect fumaric acid crystal, continue to add L MALIC ACID simultaneously and maintain starting point concentration, driving a reaction carries out to fumaric acid direction.Then detect fumaric acid output, result display fumaric acid output is 46.8% (unit g/mL), and in oxysuccinic acid, the transformation efficiency of oxysuccinic acid is greater than 99%.
In the present embodiment, L MALIC ACID can directly be bought, and existing L MALIC ACID of can producing also can be adopted to adopt with the polymalic acid acid hydrolysis of fermentative Production obtained, and the present embodiment is adopted with the following method:
(1) bacterial classification seed culture: get in the shaking flask that Aureobasidium pullulans (Aureobasidiumpullulans) that preserving number is CCTCCNO:M2012223 is inoculated in containing 50mL seed culture medium (Flask volume is 500mL), be 25 DEG C in temperature, rotating speed is cultivate 48 hours under 220rpm condition; Seed culture medium adopts glucose 60g/L, ammonium chloride 3g/L, KH2PO40.2g/L, ZnSO40.1g/L; MgSO40.15g/L, corn steep liquor 2g/L and CaCO320g/L;
(2) polymalic acid fermentation: the nutrient solution getting step (1) is in the 10% 300L fermentor tank be inoculated in containing 220L fermention medium by inoculum size, then temperature be 25 DEG C, ventilation ratio at more than 1:1 (v/v), remaining sugar concentration at 20g/L with top fermentation 168 hours, in fermenting process, stream adds CaCO 3solution control pH is 6.0; Detect polymalic acid output after fermentation, the output that result shows the present embodiment polymalic acid is 194g/L; Fermentating formula is glucose 120g/L, ammonium sulfate 3g/L, KH 2pO 40.2g/L, ZnSO 40.15g/L, MgSO 40.2g/L;
(3) L MALIC ACID preparation: by polymalic acid fermented liquid obtained for step (2) with ultra-filtration membrane (molecular weight 10KDa), remove fermentation thalli, obtain the fermentation clear liquid containing polymalic acid salt, the sulfuric acid of 1M is added after fermentation clear liquid concentrates, acid hydrolysis 5 hours under 90 DEG C of conditions, obtains the L MALIC ACID solution that quality volume fraction is 55% (g/ml) concentration.
Embodiment 4
The preparation method of bio-based fumaric acid, concrete steps are as follows: be that the L MALIC ACID solution of (the unit g/mL) of 40% adds in reactor by quality volume fraction, be warming up to 160 DEG C, maintain pressure 0.8Mpa and react 9 hours dehydration production fumaric acid, after fumaric acid is separated out, collect fumaric acid crystal, continue to add L MALIC ACID simultaneously and maintain starting point concentration, driving a reaction carries out to fumaric acid direction.Then detect fumaric acid output, result display fumaric acid output is 33.4% (unit g/mL), and in oxysuccinic acid, the transformation efficiency of oxysuccinic acid is greater than 97%.
In the present embodiment, L MALIC ACID can directly be bought, and existing L MALIC ACID of can producing also can be adopted to adopt with the polymalic acid acid hydrolysis of fermentative Production obtained, and the present embodiment is adopted with the following method:
(1) bacterial classification seed culture: get in the shaking flask that Aureobasidium pullulans (Aureobasidiumpullulans) that preserving number is CCTCCNO:M2012223 is inoculated in containing 50mL seed culture medium (Flask volume is 500mL), be 25 DEG C in temperature, rotating speed is cultivate 48 hours under 220rpm condition; Seed culture medium adopts glucose 60g/L, ammonium chloride 3g/L, KH2PO40.2g/L, ZnSO40.1g/L; MgSO40.15g/L, corn steep liquor 2g/L and CaCO320g/L;
(2) polymalic acid fermentation: the nutrient solution getting step (1) is in the 10% 300L fermentor tank be inoculated in containing 220L fermention medium by inoculum size, then temperature be 25 DEG C, ventilation ratio at more than 1:1 (v/v), remaining sugar concentration at 20g/L with top fermentation 160 hours, in fermenting process, stream adds CaCO 3solution control pH is 6.0; Detect polymalic acid output after fermentation, the output that result shows the present embodiment polymalic acid is 195g/L; Fermentating formula is glucose 120g/L, ammonium sulfate 3g/L, KH 2pO 40.2g/L, ZnSO 40.15g/L, MgSO 40.2g/L;
(3) L MALIC ACID preparation: by polymalic acid fermented liquid obtained for step (2) with ultra-filtration membrane (molecular weight 10KDa), remove fermentation thalli, obtain the fermentation clear liquid containing polymalic acid salt, the sulfuric acid of 1M is added after fermentation clear liquid concentrates, acid hydrolysis 4 hours under 95 DEG C of conditions, obtains the L MALIC ACID solution that quality volume fraction is 40% (g/ml) concentration.
Embodiment 5
The preparation method of bio-based fumaric acid, concrete steps are as follows: the L MALIC ACID solution by quality volume fraction being (the unit g/ml) of 80%, 160 DEG C are warming up in reactor, maintain pressure 0.8Mpa and react 10 hours dehydration production fumaric acid, after fumaric acid is separated out, collect fumaric acid crystal, continue to add L MALIC ACID simultaneously and maintain starting point concentration, driving a reaction carries out to fumaric acid direction.The transformation efficiency of the condition oxysuccinic acid of the present embodiment can realize more than 98%.
In the present embodiment, L MALIC ACID can directly be bought, and existing L MALIC ACID of can producing also can be adopted to adopt with the polymalic acid acid hydrolysis of fermentative Production obtained, and the present embodiment is adopted with the following method:
(1) bacterial classification seed culture: get in the shaking flask that Aureobasidium pullulans (Aureobasidiumpullulans) that preserving number is CCTCCNO:M2012223 is inoculated in containing 50mL seed culture medium (Flask volume is 500mL), be 25 DEG C in temperature, rotating speed is cultivate 48 hours under 220rpm condition; Seed culture medium adopts glucose 60g/L, ammonium chloride 3g/L, KH2PO40.2g/L, ZnSO40.1g/L; MgSO40.15g/L, corn steep liquor 2g/L and CaCO320g/L;
(2) polymalic acid fermentation: the nutrient solution getting step (1) is in the 10% 300L fermentor tank be inoculated in containing 220L fermention medium by inoculum size, then temperature be 25 DEG C, ventilation ratio at more than 1:1 (v/v), remaining sugar concentration at 20g/L with top fermentation 170 hours, in fermenting process, stream adds CaCO 3solution control pH is 6.0; Detect polymalic acid output after fermentation, the output that result shows the present embodiment polymalic acid is 219g/L; Fermentating formula is glucose 120g/L, ammonium nitrate 3g/L, KH 2pO 40.2g/L, ZnSO 40.15g/L, MgSO 40.2g/L.
(3) L MALIC ACID preparation: by polymalic acid fermented liquid obtained for step (2) with inorganic ceramic film (membrane pore size 0.1 μm), remove fermentation thalli, obtain the fermentation clear liquid containing polymalic acid salt, the sulfuric acid of 0.5M is added after fermentation clear liquid concentrates, acid hydrolysis 10 hours under 70 DEG C of conditions, obtains the L MALIC ACID solution that quality volume fraction is 80% (g/mL) concentration.
Embodiment 6
The preparation method of bio-based fumaric acid, concrete steps are as follows: the L MALIC ACID solution by quality volume fraction being (the unit g/mL) of 70%, 180 DEG C are warming up in reactor, maintain pressure 0.8Mpa and react 8 hours dehydration production fumaric acid, after fumaric acid is separated out, collect fumaric acid crystal, continue to add L MALIC ACID simultaneously and maintain starting point concentration, driving a reaction carries out to fumaric acid direction.The transformation efficiency of the condition oxysuccinic acid of the present embodiment can realize more than 96%.
In the present embodiment, L MALIC ACID can directly be bought, and existing L MALIC ACID of can producing also can be adopted to adopt with the polymalic acid acid hydrolysis of fermentative Production obtained, and the present embodiment is adopted with the following method:
(1) bacterial classification seed culture: get in the shaking flask that Aureobasidium pullulans (Aureobasidiumpullulans) that preserving number is CCTCCNO:M2012223 is inoculated in containing 50mL seed culture medium (Flask volume is 500mL), be 25 DEG C in temperature, rotating speed is cultivate 48 hours under 220rpm condition; Seed culture medium adopts glucose 60g/L, ammonium chloride 3g/L, KH2PO40.2g/L, ZnSO40.1g/L; MgSO40.15g/L, corn steep liquor 2g/L and CaCO320g/L;
(2) polymalic acid fermentation: the nutrient solution getting step (1) is in the 10% 300L fermentor tank be inoculated in containing 220L fermention medium by inoculum size, then temperature be 25 DEG C, ventilation ratio at more than 1:1 (v/v), remaining sugar concentration at 20g/L with top fermentation 170 hours, in fermenting process, stream adds CaCO 3solution control pH is 6.0; Detect polymalic acid output after fermentation, the output that result shows the present embodiment polymalic acid is 208g/L; Fermentating formula is glucose 120g/L, ammonium nitrate 3g/L, KH 2pO 40.2g/L, ZnSO 40.15g/L, MgSO 40.2g/L;
(3) L MALIC ACID preparation: by polymalic acid fermented liquid obtained for step (2) with inorganic ceramic film (membrane pore size 0.1 μm), remove fermentation thalli, obtain the fermentation clear liquid containing polymalic acid salt, the sulfuric acid of 1.5M is added after fermentation clear liquid concentrates, acid hydrolysis 10 hours under 85 DEG C of conditions, obtains the L MALIC ACID solution that quality volume fraction is 70% (g/ml) concentration.
In above-described embodiment, Aureobasidium pullulans activation is 23 ~ 30 DEG C in temperature, cultivates 36 ~ 96 hours under rotating speed 180 ~ 300rpm condition; Fermentation culture temperature be 23 ~ 30 DEG C, ventilation volume than in 1:0.8 ~ 1.6, remaining sugar concentration when little higher than 20g/L bottom fermentation 96 ~ 200, in fermenting process, stream adds calcium carbonate or calcium hydroxide control pH is 5 ~ 6.5; The each component of seed culture medium all can realize goal of the invention as follows: glucose 40 ~ 100g/L, ammonium nitrate 1 ~ 5g/L, KH 2pO 40.005 ~ 0.3g/L, ZnSO 40.005 ~ 0.3g/L, MgSO 40.005 ~ 0.3g/L, corn steep liquor 0.05 ~ 0.3g/L and CaCO 310 ~ 50g/L, solvent is water; The each component of fermention medium all can realize goal of the invention as follows, sugary 50 ~ 200g/L, nitrogenous source 1 ~ 5g/L, KH 2pO 40.005 ~ 0.3g/L, ZnSO 40.005 ~ 0.3g/L, MgSO 40.005 ~ 0.3g/L, surplus is water.
What finally illustrate is, above preferred embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although by above preferred embodiment to invention has been detailed description, but those skilled in the art are to be understood that, various change can be made to it in the form and details, and not depart from claims of the present invention limited range.

Claims (8)

1. the preparation method of bio-based fumaric acid, it is characterized in that: by quality volume fraction be 40 ~ 80% L MALIC ACID solution temperature be 160 ~ 190 DEG C, pressure be 0.7 ~ 1MPa condition under dehydration reaction 5 ~ 10 hours, collect fumaric acid crystal after dehydration reaction.
2. the preparation method of bio-based fumaric acid according to claim 1, is characterized in that: adding the quality volume fraction that L MALIC ACID solution maintains L MALIC ACID solution in described dehydration reaction process is 40 ~ 80%.
3. the preparation method of bio-based fumaric acid according to claim 1, is characterized in that: the quality volume fraction of described L MALIC ACID solution is 40 ~ 60%.
4. the preparation method of bio-based fumaric acid according to claim 1, is characterized in that: described L MALIC ACID solution is obtained by polymalic acid acid hydrolysis.
5. the preparation method of bio-based fumaric acid according to claim 3, it is characterized in that: the acid-hydrolyzed method of described polymalic acid adds in the sulfuric acid or hydrochloric acid that concentration is 0.5 ~ 2M by the solution containing polymalic acid salt or polymalic acid, acid hydrolysis 4 ~ 10 hours under 70-95 DEG C of condition, obtains the L MALIC ACID that quality volume fraction is 40 ~ 80%.
6. the preparation method of bio-based fumaric acid according to claim 4 or 5, is characterized in that: described polymalic acid salt or polymalic acid are removed fermentation thalli by Aureobasidium pullulans filtering fermentation liquor and obtain.
7. the preparation method of bio-based fumaric acid according to claim 6, it is characterized in that: described Aureobasidium pullulans fermented liquid is prepared by following methods: be inoculated in fermention medium by the Aureobasidium pullulans of activation, temperature be 23 ~ 30 DEG C, ventilation volume than in 1:0.8 ~ 1.6, remaining sugar concentration when little higher than 20g/L bottom fermentation 96 ~ 200, in fermenting process, stream adds calcium carbonate or calcium hydroxide control pH is 5 ~ 6.5; Sugary 50 ~ 200g/L, nitrogenous source 1 ~ 5g/L, KH in described fermention medium 2pO 40.005 ~ 0.3g/L, ZnSO 40.005 ~ 0.3g/L, MgSO 40.005 ~ 0.3g/L, surplus is water.
8. the preparation method of bio-based fumaric acid according to claim 6, it is characterized in that: the method for activation Aureobasidium pullulans is inoculated in seed culture medium by Aureobasidium pullulans, be then 23-30 DEG C in temperature, cultivate 36-96 hour under rotating speed 180-300rpm condition; The each component of described seed culture medium is as follows: glucose 40-100g/L, ammonium nitrate 1-5g/L, KH 2pO 40.005-0.3g/L, ZnSO 40.005-0.3g/L, MgSO 40.005-0.3g/L, corn steep liquor 0.05-0.3g/L and CaCO 310-50g/L, solvent is water.
CN201510604008.3A 2015-09-18 2015-09-18 The preparation method of bio-based fumaric acid Pending CN105218346A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05262692A (en) * 1992-03-19 1993-10-12 Nippon Shokubai Co Ltd Production of fumaric acid crystal form
CN102492734A (en) * 2011-12-20 2012-06-13 西南大学 Method for producing malic acid

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05262692A (en) * 1992-03-19 1993-10-12 Nippon Shokubai Co Ltd Production of fumaric acid crystal form
CN102492734A (en) * 2011-12-20 2012-06-13 西南大学 Method for producing malic acid

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