CN105646193A - Method used for separating and extracting lactic acid from fermentation broth - Google Patents
Method used for separating and extracting lactic acid from fermentation broth Download PDFInfo
- Publication number
- CN105646193A CN105646193A CN201410731197.6A CN201410731197A CN105646193A CN 105646193 A CN105646193 A CN 105646193A CN 201410731197 A CN201410731197 A CN 201410731197A CN 105646193 A CN105646193 A CN 105646193A
- Authority
- CN
- China
- Prior art keywords
- lactic acid
- solution
- precipitate
- alcohol
- acetate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a method used for separating and extracting lactic acid from a fermentation broth. The method comprises following steps: (1) the fermentation broth is subjected to filtering, acidolysis, and heating concentration dehydration so as to obtain a preliminarily concentrated lactic acid solution; (2) active carbon is used for decolouring of the preliminarily concentrated lactic acid solution, a small amount of an alcohol with a high boiling point is added, and concentration dehydration is carried out until lactic acid content is higher than 90%; (3) the lactic acid concentrated solution is cooled to 10 to 15 DEG C, an acetate is added, an alcohol precipitation agent is added with stirring until temperature is reduced to 4 to 10 DEG C, and a lactic acid filtrate and a solid substance are obtained via filtering; (4) the solid substance is washed with ethyl alcohol, and a precipitate and a lactic acid filtered solution are obtained via filtering; (5) the lactic acid filtrate obtained in step (3) and the lactic acid filtered solution obtained in step (4) are subjected to distillation; and (6) a lactic acid liquor obtained in step (5) is subjected to molecular distillation refining so as to obtain a lactic acid product. In the method, conventional desalting and deproteinization processes such as ion exchange and ultrafiltration are avoided, so that lactic acid loss in the fermentation broth is reduced, and lactic acid yield and quality are improved.
Description
Technical field
The invention belongs to biological technical field, relate to fermentable product separation method, particularly to a kind of method of separation and Extraction lactic acid from fermentation liquid.
Background technology
Lactic acid is as polylactic acid synthon and a kind of important organic acid, and its market demand constantly expands, and purposes is further extensive, can be applicable to the fields such as food, medicine, medical macromolecular materials, chemical engineering industry. Current industrial many employing Production by Microorganism Fermentation lactic acid, with saccharides such as starch (such as Semen Maydis powder, rice meal, sweet potato powder etc.), glucoses for raw material, microbe inoculation (such as Rhizopus oryzae, lactic acid bacteria class etc.), generate containing lactic acid or Lactated fermentation liquid by fermenting, obtain lactic product then through separation and Extraction. In sweat, the generation of lactic acid can make fermentation system pH value reduce, thus suppressing the normal growth of thalline and producing acid, it is necessary to by adding acid neutralizing agent such as carbonate or hydroxide (such as CaCO3, NaOH, ammonia etc.) control the pH value of fermentation system, make sweat smooth.
Lactic fermentation liquid is the mixture that a kind of composition is extremely complex, except containing lactic acid, also have the impurity such as substantial amounts of thalline and fragment, protein, residual sugar, pigment, inorganic salt, fermentation byproduct and unconverted starch, and they multi-sources are in raw material, the intermediate by-products not consuming culture medium and fermentation completely. The existing for the follow-up separation of lactic acid, refining bring very big difficulty of these impurity, and in actual production, the extraction cost of lactic acid has also accounted for the 50%��60% of total cost of production. Therefore the separation and Extraction of lactic acid just becomes particularly important, and it is the technical bottleneck in restriction lactic acid production process and difficult point place; Especially albumen, saccharide, inorganic salt are difficult to be removed in lactic acid purification process, and the presence of which can make follow-up subtractive process (such as molecular distillation) be difficult to, and gained lactic product yield is low, and product quality is not high yet.
The main method extracting lactic acid from fermentation liquid has calcium salt method, extraction, absorption method, esterification process and membrane separation process etc., consider the problems such as production cost, environmental pollution and production stability, current industrialized production adopts calcium salt method mostly, i.e. calcium lactate crystallization-acidolysis process.This technological process is: first the calcium lactate in fermentation liquid is carried out condensing crystallizing, it is subsequently added into sulphuric acid to carry out acidifying, add after activated carbon decolorizing, destaining solution containing lactic acid is carried out hyperfiltration treatment, remove part saccharide therein and macromolecular compound etc., foreign ion therein is removed then through anion and cation exchange resin, concentration, finished product lactic acid after molecular distillation can be refined after. This technique relative maturity, equipment are simple, and the subject matter existed has ion exchange process to consume substantial amounts of soda acid, and produces substantial amounts of waste water; Adopting ultrafiltration technology to remove saccharide therein and macromolecular compound, removal efficiency is not high, and effect is unsatisfactory; Whole technique lactic acid loss amount is big, yield is low, and products obtained therefrom purity is low, does not reach polymer grade quality index requirement.
For tradition calcium salt method Problems existing, researcheres propose some improved plans.
CN201010046522.7 discloses a kind of method producing Pfansteihl, this method adopts calcium salt method to extract the lactic acid in fermentation liquid with membrance separation, ion exchange integrated technology, lactic fermentation liquid is by ultrafiltration removing protein, the de-divalent salts of nanofiltration and pigment, after reverse osmosis concentration, enter the zwitterion in anion-cation exchange resin elimination fermentation liquid, obtain the lactic product of 85% then through rectification under vacuum concentration. The program uses multiple membrane separation techniques, for the fermentation liquid that composition is so complicated, the especially easy blocking causing film in operation, operating difficulties, need to clean continually, change membrane module, complex steps, separation costs are high, and final products obtained therefrom purity is only capable of meeting food grade lactic acid quality index and requires (food grade lactic acid colourity to lactic acid, the requirement of contained iron salt and chloride ion, sulfate ion is all relatively low).
CN201110421584.6 discloses a kind of Pfansteihl and/or the preparation method of Pfansteihl salt, first with flocculation, filtration, centrifugal or hyperfiltration treatment fermentation liquid, then carries out acidifying, anion exchange etc. and obtains lactic acid or Lactated technology. The step of concentration, molecular distillation is saved in this invention, but has used ion exchange process, finally can only obtain the lactic acid aqueous solution that concentration is 160g/L, and can not get real lactic product.
CN01109903.8 discloses a kind of suction-joint method separating-purifying and manufactures fine purification of lactic acid method, the basis of tradition calcium salt method with the addition of " inhale and hand over agent ", the lactic acid in " inhale and hand over agent " absorption exchange fermentation liquid is added after fermentation liquor acidolysis, it is separated with the dissolved organic matter in fermentation liquid, then through the lactic acid aqueous solution obtaining 20%��30% after soda acid eluting, cation and anion exchange, decolouring, after concentrated, product yield is about 44.6%. This technology have employed " inhale and hand over agent " and ion exchange process, need to consume more soda acid, produce substantial amounts of waste water, make the operation cycle be greatly prolonged, and the yield of final products is not high yet.
CN201010150058.6 discloses a kind of method of clean production of lactic acid by calcium salt process, CN201010177402.0 discloses a kind of method that calcium salt method couples cleanly producing lactic acid with electrodialysis, the carbonate of above-mentioned patent solubility removes the calcium ion in fermentation liquid, then carry out ion exchange respectively and obtained the technical scheme of lactic acid by bipolar membrane electrodialysis, relating separately to ion exchange and electrodialytic technique in the two process program, processing procedure can produce a large amount of waste water, a large amount of acid of consumption or alkali, energy consumption is high, cost is high;Meanwhile, using bipolar membrane electrodialysis technology, it is necessary to clean continually or change film, the operation cycle is short, poor stability.
CN201310692379.2 discloses a kind of method utilizing molecular distillation technique industrial production of lactic acid, by the lactic acid of food stage through acidolysis, decolouring, ion exchange, falling film evaporation and thin film evaporation process, in lactic acid material after water content��2%, lactic acid material is carried out molecular distillation and obtains high-pure lactic acid. Although the lactic acid purity after refining has reached 98.0%��99.2%, but is suitable only for food grade lactic acid raw material, meanwhile, ion exchange process need to consume a large amount of soda acid, produce a large amount of waste water, and evaporation process energy consumption is also higher.
CN03122584.5 discloses in a kind of microbial fermentation solution and extracts separation 1, the method of ammediol, the nucleic acid in fermentation liquid, albumen and partial salts material etc. are removed by the method for the organic solvent deposits such as ethanol or methanol, isopropanol, acetone, butanone, process route is simple, cost is low, product loss is little, solves decompression distillation later stage salt-pepper noise and stickum affects the problem that 1,3-PD evaporates. Although lactic fermentation liquid also has the existence of saccharide, albumen and inorganic salts, if being applied to the method for organic solvent deposit extract separation 1, ammediol system, alcohols can with lactic acid generation esterification, generate a small amount of carboxylate, affect follow-up molecular distillation subtractive process and the quality of final lactic product.
Summary of the invention
In order to solve in prior art exist lactic acid loss amount big, yield is low, lactic acid quality is low, acid and alkali consumption amount and sewage load big, polysaccharose substance and macromolecular compound are difficult to the problems such as elimination, the invention provides a kind of method of separation and Extraction lactic acid from fermentation liquid.
The present invention is the method for separation and Extraction lactic acid from fermentation liquid, comprises the following steps:
(1) by lactic fermentation liquid filtration, acidolysis, heating concentration elimination 70%��80% moisture, obtain the lactic acid solution of initial concentration;
(2) adopt activated carbon that lactic acid solution is decoloured, and after decolouring, lactic acid clear liquid adds a small amount of high-boiling point alcohol, carry out secondary concentration dehydration, make lactic acid content reach more than 90%;
(3) step (2) gained lactic acid concentrated solution is cooled to 10��15 DEG C, add a certain amount of acetate, and it is slowly added to precipitate with ethanol agent while stirring wherein, the albumen in concentrated solution, residual sugar and inorganic salts is made to precipitate out, when system temperature is down to 4��10 DEG C, stop cooling, be filtrated to get lactic acid filtrate and insoluble solid content;
(4) in step (3) gained solid content, add washing with alcohol, be filtrated to get precipitate and lactic acid filtrate;
(5) step (3) and (4) gained lactic acid filtrate are distilled, obtain lactic acid solution after desolventizing;
(6) step (5) gained lactic acid solution adopts molecular distillation carry out refining purification, the lactic product of high chemical purity and high-optical-purity can be obtained.
Lactic acid fermenting bacteria used by step of the present invention (1) is lactobacillus casei, and fermenting carbon source is Semen Maydis powder, and fermentation temperature is 40��50 DEG C, and the omnidistance blowing air of fermentation, volume of air flow velocity is 1.0��20h-1, calcium carbonate is as pH adjusting agent, and final Lactic Acid from Fermentation Broth content is at 120��180g/L, and it is 6.0��8.0 that fermentation terminates pH value.
Step of the present invention (1) adopts common filtration or centrifugation that fermentation liquid is filtered, and removes solid insoluble matter, obtains calcium lactate solution.Then adding sulfuric acid solution in calcium lactate solution, the mass fraction of sulphuric acid is 30%��70%, it is preferred to 40%��60%, and treatment temperature is 60��80 DEG C, more complete for what make acid hemolysis process carry out, and the pH value controlling final acidolysis system is 1.0��2.5. Being filtered after acidolysis, obtain lactic acid solution after acidolysis, heating concentration removes the moisture of 70%��80% in lactic acid solution, obtains the lactic acid solution of initial concentration.
Step of the present invention (2) adds activated carbon in lactic acid solution and carries out desolventing technology, addition is the 0.5%��2.5% of reaction system quality, it is preferably 0.5%��1.5%, treatment temperature is 55��75 DEG C, it is preferably 60��70 DEG C, mixing time 20��40min, activated carbon used is Powdered, pore-size about 10-6��10-4Mm. Lactic acid solution is preferably flowed through carbon post by certain flow velocity by the present invention, filling the activated carbon used by carbon post is granular active carbon, charging rate is 1��4BV/h, feeding temperature 30��50 DEG C, can remove the part larger molecular organics in lactic acid solution while decolouring. After activated carbon decolorizing processes, the light transmittance of lactic acid solution promotes more than 75%.
The high-boiling point alcohol that step of the present invention (2) uses is n-butyl alcohol, n-amyl alcohol, isobutanol or isoamyl alcohol, it is preferred to isobutanol, and addition is lactic acid supernatant volume 0.01��0.1 times. Thickening can adopt air-distillation, decompression distillation or thin film evaporation mode, and the vacuum controlling decompression distillation or thin film evaporation is 80��90kPa. After concentrated dehydration, it is thus achieved that lactic acid content (mass fraction) is the lactic acid concentrated solution of 90%��95%.
Acetate described in step of the present invention (3) is monovalence acetate or bivalence acetate, as being ammonium acetate, potassium acetate, sodium acetate, zinc acetate, calcium acetate, barium acetate, manganese acetate etc., being preferably zinc acetate, addition is the 0.1%��0.5% of lactic acid concentrated solution quality.
The precipitate with ethanol agent that step of the present invention (3) uses is low-boiling point alcohol solvent, and such as methanol, ethanol, normal propyl alcohol, isopropanol etc., addition is 1��5 times of step (2) gained lactic acid concentrated solution volume, it is preferred to 2��3 times. The present invention is preferably simultaneously introduced the ketone solvents such as a certain amount of acetone, butanone what add alcoholic solvent, and the volume ratio controlling alcohol and ketone is 1:3��3:1. Consider yield and quality, the industrial exploitativeness amplified of the effect of desalination, deproteinization etc., final products, it is preferred to use the mixed solvent that ethanol forms with acetone is precipitate with ethanol agent, and the volume ratio of the two is 2:1. In the present invention, precipitate with ethanol agent can once add or add several times, it is preferable that above addition at twice. Specifically, when precipitate with ethanol agent total addition level is certain, first a part of precipitate with ethanol agent is slowly added in lactic acid concentrated solution, stirring, after system temperature is down to 4 ~ 10 DEG C, filter; The filtrate obtained is mixed with Part II precipitate with ethanol agent by aforesaid operations process, stirring, after being cooled to 4 ~ 10 DEG C, again filter; Repeat aforesaid operations, until precipitate with ethanol agent whole after multi-pass operation is completely added in lactic acid concentrated solution. The present invention adopts and adds precipitate with ethanol agent several times, avoid long alcohol excess on the one hand and contact generation esterification with lactic acid, the reaction forward promoted carries out, being gradually added into precipitant carries out fractional precipitation on the other hand, the materials such as the albumen in lactic acid concentrated solution, saccharide can be made better to precipitate out, gradually reduced inorganic salts dissolubility in lactic acid solution.
Step of the present invention (4) adds washing with alcohol in step (3) gained solid content, and addition is 0.6��0.8 times that step (3) uses solvent total amount, is precipitated thing and lactic acid filtrate after filtration.
Mixed solvent in step (3) and (4) gained lactic acid filtrate and residual water are carried out distillation elimination by step of the present invention (5), it is possible to taking decompression distillation or thin film evaporation, vacuum is 85��95kPa.
The lactic acid concentrated solution obtained is purified by step of the present invention (6) by molecular distillation apparatus is refining further, and the temperature of molecular distillation controls at 65��85 DEG C, it is preferred to 65��75 DEG C, and system pressure (absolute pressure) controls at 10��100Pa, it is preferred to 10��60Pa.
After the inventive method processes, the salt rejection rate of lactic fermentation liquid reaches 97.5%��99.0%, and deproteinizing rate has reached 98.5%��99.5%, and the calcium salt method extraction process that the yield of lactic acid is more traditional improves 5%��10%.
Compared with prior art, beneficial effects of the present invention is embodied in:
1, secondary concentration dewatering process is adopted, and before second time thickening, add high-boiling point alcohol solvent, not only solve salt-pepper noise and stickum obstruction evaporation problems that vacuum distillation process occurs, and the excessive volatilization loss of reagent in heating concentration and follow-up use procedure can be avoided, reduce cost, separate the product purity height, the yield height that obtain;
2, the present invention is before adding low boiling precipitate with ethanol agent, it is firstly added a certain amount of acetate, the two combined effect can well remove in lactic fermentation liquid the materials such as the salt of solubility, albumen, residual sugar, follow-up molecular distillation process can be smoothed out, the residual heavy constituent of still can't detect the existence of salt or albumen;
3, adopt the mixed solvent that low mass molecule alcohol and acetone prepare to carry out remove impurity at low temperatures, be possible not only to suppress the carrying out of esterification between alcohols and lactic acid, it is ensured that the yield of lactic acid; And solve that the simple precipitate viscosity formed in acetone treatment lactic fermentation liquid process is excessive and wall built-up and stick on stirring paddle, the problem being unfavorable for mass transfer and subsequent operation;
4, present invention eliminates the technical process of traditional desalinations such as ion exchange, electrodialysis, ultrafiltration, nanofiltration and the macromole such as deproteinization, residual sugar, the loss amount reducing Lactic Acid from Fermentation Broth, the treating capacity saving sewage, decrease making consumption, simplifying process route, improve yield and the quality of lactic acid of soda acid; Meanwhile, the organic solvent in whole process can be recycled, and saves production cost. The chemical purity of the lactic product obtained reaches more than 92%, and optical purity has reached 98%��99.5%, can meet normal food level quality index requirement, can meet again polymer grade quality index requirement, can be used for preparing the poly-lactic acid material of high-quality.
Detailed description of the invention
By the examples below the inventive method is described in detail, but does not constitute limitation of the invention.
Lactic fermentation liquid handled by the present invention is with Semen Maydis powder for carbon source, and the lactic fermentation liquid that employing lactobacillus casei ferments and obtains, fermentation temperature is 50 DEG C, the omnidistance blowing air of fermentation, and volume of air flow velocity is 5.0h-1, calcium carbonate is as pH adjusting agent, and final Lactic Acid from Fermentation Broth content is 150g/L, and it is 7.2 that fermentation terminates pH value.
Embodiment 1
Take the above-mentioned fermentation liquid of 2L, lactic fermentation liquid is filtered to remove solid insoluble matter, obtains calcium lactate solution; Then adding sulfuric acid solution in calcium lactate solution, the mass fraction of sulphuric acid is 50%, and treatment temperature is 70 DEG C, and the pH value controlling final acidolysis system is 1.0.Being filtered after acidolysis, obtain lactic acid solution after acidolysis, heating concentration removes the moisture of 80% in lactic acid solution, obtains the lactic acid solution of initial concentration. The lactic acid solution of initial concentration is heated to 40 DEG C, flow through carbon post with the flow velocity of 2BV/h and carry out desolventing technology, lactic acid clear liquid after being decoloured, above-mentioned clear liquid adds the isobutanol of 0.05 times of volume, thin film evaporation is adopted to carry out secondary concentration dehydration, control vacuum is 90kPa, and to lactic acid clear liquid, lactic acid content is 90%, lactic acid concentrated solution after being decoloured. Above-mentioned lactic acid concentrated solution is placed in ice-water bath, when temperature is down to 10 DEG C, it is added thereto to the zinc acetate of concentrated solution quality 0.25%, and it is slowly added to the ethanol of 3 times of volumes of concentrated solution while stirring, through about 25min, the temperature of system is down to 5 DEG C, stops cooling, is filtrated to get insoluble solid content and lactic acid filtrate. To add washing with alcohol in gained solid content, addition is 0.6 times that above-mentioned ethanol makes consumption, is precipitated thing and lactic acid filtrate after filtration. Two parts lactic acid filtrate is mixed, under vacuum 90kPa, carries out decompression distillation, remove organic solvent therein (isobutanol, ethanol) and residual moisture. Finally, being refined by molecular distillation, temperature is 70 DEG C, and pressure is 20Pa. In molecular distillation process, lactic acid solution film-formation result on evaporating surface is better, liquid film covers uniformly, molecular distillation process can be smoothed out, the final more traditional calcium salt method extraction process of gained lactic product yield improves 7.7%, and the chemical purity of lactic acid is 93%, and optical purity is 99.2%, product purity can meet normal food level quality index requirement, can meet again polymer grade quality index requirement.
Being mixed by insoluble for two parts solid content, after drying precipitate, quality is 200.2g, and after precipitate with ethanol, the extrusion rate of salt and albumen has respectively reached 98.5% and 99.1%.
Embodiment 2
Take the above-mentioned fermentation liquid of 2L, lactic fermentation liquid is filtered to remove solid insoluble matter, obtains calcium lactate solution; Then adding sulfuric acid solution in calcium lactate solution, the mass fraction of sulphuric acid is 30%, and treatment temperature is 80 DEG C, and the pH value controlling final acidolysis system is 2.5. Being filtered after acidolysis, obtain lactic acid solution after acidolysis, heating concentration removes the moisture of 80% in lactic acid solution, obtains the lactic acid solution of initial concentration. The lactic acid solution temperature of initial concentration is risen to 65 DEG C, add the activated carbon of lactic acid solution quality 1.5%, continuously stirred 25min carries out desolventing technology, lactic acid clear liquid after being decoloured, adding the isoamyl alcohol of 0.02 times of volume in above-mentioned clear liquid, by adopting thin film evaporation to carry out secondary concentration dehydration, control vacuum is 85kPa, to lactic acid clear liquid, lactic acid content is 91%, lactic acid concentrated solution after being decoloured. Above-mentioned lactic acid concentrated solution is placed in ice-water bath, when temperature is down to 15 DEG C, it is added thereto to the sodium acetate of concentrated solution quality 0.5%, and it is slowly added to the isopropanol of 2 times of volumes of concentrated solution while stirring, through about 25min, the temperature of system is down to 5 DEG C, stops cooling, is filtrated to get insoluble solid content and lactic acid filtrate. To add washing with alcohol in gained solid content, addition is 0.8 times that above-mentioned ethanol makes consumption, is precipitated thing and lactic acid filtrate after filtration. Two parts lactic acid filtrate is mixed, under vacuum 95kPa, carries out decompression distillation, remove organic solvent therein (isoamyl alcohol, isopropanol) and residual moisture. Finally, being refined by molecular distillation, temperature is 65 DEG C, and pressure is 60Pa.In molecular distillation process, lactic acid solution film-formation result on evaporating surface is better, and liquid film covers uniformly, molecular distillation process can be smoothed out, the final more traditional calcium salt method extraction process of gained lactic product yield improves 7.3%, and the chemical purity of lactic acid is 92.8%, and optical purity is 99.1%.
Being mixed by insoluble for two parts solid content, after drying precipitate, quality is 192.1g, and after precipitate with ethanol, the extrusion rate of salt and albumen has respectively reached 98.3% and 99.0%.
Embodiment 3
Take the above-mentioned fermentation liquid of 2L, lactic fermentation liquid is filtered to remove solid insoluble matter, obtains calcium lactate solution; Then adding sulfuric acid solution in calcium lactate solution, the mass fraction of sulphuric acid is 70%, and treatment temperature is 60 DEG C, and the pH value controlling final acidolysis system is 2.0. Being filtered after acidolysis, obtain lactic acid solution after acidolysis, heating concentration removes the moisture of 80% in lactic acid solution, obtains the lactic acid solution of initial concentration. The lactic acid solution temperature of initial concentration is risen to 55 DEG C, add the activated carbon of lactic acid solution quality 0.5%, continuously stirred 35min carries out desolventing technology, lactic acid clear liquid after being decoloured, adding the n-butyl alcohol of 0.1 times of volume in above-mentioned clear liquid, by adopting thin film evaporation to carry out secondary concentration dehydration, control vacuum is 85kPa, to lactic acid clear liquid, lactic acid content is 92%, lactic acid concentrated solution after being decoloured. Above-mentioned lactic acid concentrated solution is placed in ice-water bath, when temperature is down to 12 DEG C, it is added thereto to the ammonium acetate of concentrated solution quality 0.1%, and it is slowly added to the methanol of 5 times of volumes of concentrated solution while stirring, through about 25min, the temperature of system is down to 5 DEG C, stops cooling, is filtrated to get insoluble solid content and lactic acid filtrate. To add washing with alcohol in gained solid content, addition is 0.7 times that above-mentioned ethanol makes consumption, is precipitated thing and lactic acid filtrate after filtration. Two parts lactic acid filtrate is mixed, under vacuum 85kPa, carries out decompression distillation, remove organic solvent therein (n-butyl alcohol, methanol) and residual moisture. Finally, being refined by molecular distillation, temperature is 85 DEG C, and pressure is 100Pa. In molecular distillation process, lactic acid solution film-formation result on evaporating surface is better, and liquid film covers uniformly, molecular distillation process can be smoothed out, the final more traditional calcium salt method extraction process of gained lactic product yield improves 6.6%, and the chemical purity of lactic acid is 92.2%, and optical purity is 98.8%.
Being mixed by insoluble for two parts solid content, after drying precipitate, quality is 164.3g, and after precipitate with ethanol, the extrusion rate of salt and albumen has respectively reached 97.8% and 98.5%.
Embodiment 4
Other conditions are with embodiment 1, simply change precipitate with ethanol agent ethanol in embodiment 1 mixed solvent of ethanol and acetone into, wherein ethanol and acetone volume ratio are 2:1, and the sedimentary quality of final gained is 215.6g, and after blended solvent deposition, the extrusion rate of salt and albumen has respectively reached 98.9% and 99.4%; And in molecular distillation process, lactic acid solution film-formation result on evaporating surface is better, liquid film covers uniformly, molecular distillation process can be smoothed out, the final more traditional calcium salt method extraction process of gained lactic product yield improves 8.5%, the chemical purity of lactic acid is more than 93.5%, and optical purity is 99.5%.
Embodiment 5
Other conditions are with embodiment 2, simply the precipitate with ethanol agent isopropanol in embodiment 2 is changed into the mixed solvent of isopropanol and butanone, wherein isopropanol and butanone volume ratio are 3:1, the sedimentary quality of final gained is 203.5g, and after blended solvent deposition, the extrusion rate of salt and albumen has respectively reached 98.7% and 99.2%.And in molecular distillation process, lactic acid solution film-formation result on evaporating surface is better, liquid film covers uniformly, molecular distillation process can be smoothed out, the final more traditional calcium salt method extraction process of gained lactic product yield improves 8.1%, the chemical purity of lactic acid is 93.2%, and optical purity is 99.3%.
Embodiment 6
Other conditions, with embodiment 4, are different in that point 2 additions are taked in precipitate with ethanol agent (mixed solvent of ethanol and acetone), are firstly added the mixed solvent of 2 times of volumes, add the mixed solvent of 1 times of volume after filtration. The sedimentary quality of final gained is 221.3g, and after blended solvent deposition, the extrusion rate of salt and albumen has respectively reached 99.0% and 99.5%; And in molecular distillation process, lactic acid solution film-formation result on evaporating surface is better, liquid film covers uniformly, molecular distillation process can be smoothed out, the final more traditional calcium salt method extraction process of gained lactic product yield improves 9.8%, the chemical purity of lactic acid is 94.1%, and optical purity is 99.5%.
Comparative example 1
Other conditions, with embodiment 1, are different in that and do not add acetate zinc acetate in this embodiment, and the sedimentary quality of final gained is 180.6g, and after precipitate with ethanol, the extrusion rate of salt and albumen has respectively reached 97.4% and 98.3%; The final more traditional calcium salt method extraction process of gained lactic product yield improves 4.8%, and the chemical purity of lactic acid is 92.3%, and optical purity is 98.5%.
Comparative example 2
Other conditions are with embodiment 1, high-boiling point alcohol is not added before being different in that secondary concentration dehydration in this embodiment, owing to fermentation system has bigger viscosity, when concentrating water removal more than 90%, these impurity solid contents substantial amounts of are precipitated out, producing wall sticking phenomenon, material loses flowability even carbonization, so that process has some setbacks. The quality of final gained solid content is 250.2g, and after precipitate with ethanol, the extrusion rate of salt and albumen has respectively reached 95.0% and 96.8%; The final more traditional calcium salt method extraction process of gained lactic product yield improves 4.5%, and the chemical purity of lactic acid is 92.3%, and optical purity is 98.0%.
Claims (14)
1. the method for separation and Extraction lactic acid from fermentation liquid, it is characterised in that comprise the following steps:
(1) by lactic fermentation liquid filtration, acidolysis, heating concentration elimination 70%��80% moisture, obtain the lactic acid solution of initial concentration;
(2) adopt activated carbon that lactic acid solution is decoloured, and after decolouring, lactic acid clear liquid adds a small amount of high-boiling point alcohol, carry out secondary concentration dehydration, make lactic acid content reach more than 90%;
(3) step (2) gained lactic acid concentrated solution is cooled to 10��15 DEG C, add a certain amount of acetate, and it is slowly added to precipitate with ethanol agent while stirring wherein, the albumen in concentrated solution, residual sugar and inorganic salts is made to precipitate out, when system temperature is down to 4��10 DEG C, stop cooling, be filtrated to get lactic acid filtrate and insoluble solid content;
(4) in step (3) gained solid content, add washing with alcohol, be filtrated to get precipitate and lactic acid filtrate;
(5) step (3) and (4) gained lactic acid filtrate are distilled, obtain lactic acid solution after desolventizing;
(6) step (5) gained lactic acid solution adopts molecular distillation carry out refining purification, the lactic product of high chemical purity and high-optical-purity can be obtained.
2. method according to claim 1, it is characterised in that: lactic acid fermenting bacteria used by step (1) lactic fermentation liquid is lactobacillus casei, and fermenting carbon source is Semen Maydis powder, and fermentation temperature is 40��50 DEG C, and the omnidistance blowing air of fermentation, volume of air flow velocity is 1.0��20h-1, calcium carbonate is as pH adjusting agent, and final Lactic Acid from Fermentation Broth content is at 120��180g/L, and it is 6.0��8.0 that fermentation terminates pH value.
3. method according to claim 1, it is characterized in that: step (1) described acidolysis is addition sulfuric acid solution in calcium lactate solution, the mass fraction of sulphuric acid is 30%��70%, and treatment temperature is 60��80 DEG C, and the pH value controlling final acidolysis system is 1.0��2.5.
4. method according to claim 1, it is characterized in that: step (2) adds activated carbon in lactic acid solution and carries out desolventing technology, addition is the 0.5%��2.5% of reaction system quality, it is preferably 0.5%��1.5%, treatment temperature is 55��75 DEG C, being preferably 60��70 DEG C, mixing time is 20��40min.
5. method according to claim 1, it is characterised in that: lactic acid solution is flowed through carbon post by certain flow velocity by step (2), and filling the activated carbon used by carbon post is granular active carbon, and charging rate is 1��4BV/h, feeding temperature 30��50 DEG C.
6. method according to claim 1, it is characterised in that: the high-boiling point alcohol that step (2) uses is n-butyl alcohol, n-amyl alcohol, isobutanol or isoamyl alcohol, and addition is lactic acid supernatant volume 0.01��0.1 times.
7. method according to claim 1, it is characterised in that: step (2) thickening adopts decompression distillation or thin film evaporation, and control vacuum is 80��90kPa, obtains the lactic acid concentrated solution that lactic acid content is 90%��95% after thickening.
8. method according to claim 1, it is characterised in that: the acetate described in step (3) is ammonium acetate, potassium acetate, sodium acetate, zinc acetate, calcium acetate, barium acetate or manganese acetate, and addition is the 0.1%��0.5% of lactic acid concentrated solution quality.
9. method according to claim 1, it is characterized in that: the precipitate with ethanol agent that step (3) uses is low-boiling point alcohol solvent, preferred methanol, ethanol, normal propyl alcohol or isopropanol, addition is 1��5 times of step (2) gained lactic acid concentrated solution volume, it is preferred to 2��3 times.
10. method according to claim 1, it is characterised in that: step (3) is simultaneously introduced a certain amount of acetone or butanone as precipitate with ethanol agent what add alcoholic solvent, and the volume ratio controlling alcohol and ketone is 1:3��3:1.
11. method according to claim 10, it is characterised in that: step (3) is simultaneously introduced a certain amount of acetone addition ethanol, and the volume ratio of the two is 2:1.
12. the method according to claim 1 or 10, it is characterised in that: when precipitate with ethanol agent total addition level is certain, first a part of precipitate with ethanol agent is slowly added in lactic acid concentrated solution, stirring, after system temperature is down to 4 ~ 10 DEG C, filter; The filtrate obtained is mixed with Part II precipitate with ethanol agent by aforesaid operations process, stirring, after being cooled to 4 ~ 10 DEG C, again filter; Repeat aforesaid operations, until precipitate with ethanol agent whole after multi-pass operation is completely added in lactic acid concentrated solution.
13. method according to claim 1, it is characterised in that: decompression distillation or thin film evaporation are taked in the distillation of step (5), and control vacuum is 85��95kPa.
14. method according to claim 1, it is characterised in that: the temperature of step (6) molecular distillation controls at 65��85 DEG C, and system pressure controls at 10��100Pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410731197.6A CN105646193B (en) | 2014-12-05 | 2014-12-05 | A kind of method of the separation and Extraction lactic acid from zymotic fluid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410731197.6A CN105646193B (en) | 2014-12-05 | 2014-12-05 | A kind of method of the separation and Extraction lactic acid from zymotic fluid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105646193A true CN105646193A (en) | 2016-06-08 |
| CN105646193B CN105646193B (en) | 2018-04-10 |
Family
ID=56481169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410731197.6A Active CN105646193B (en) | 2014-12-05 | 2014-12-05 | A kind of method of the separation and Extraction lactic acid from zymotic fluid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105646193B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106431895A (en) * | 2016-09-18 | 2017-02-22 | 宁波工程学院 | Method for extracting lactic acid from fermentation liquor through combination of molecular distillation and extraction |
| CN107805251A (en) * | 2017-12-07 | 2018-03-16 | 内蒙古金达威药业有限公司 | A kind of method that riboflavin is extracted from Lactochrome fermentation liquor |
| CN109678696A (en) * | 2019-01-31 | 2019-04-26 | 华熙福瑞达生物医药有限公司 | A method of extracting lactic acid from hyaluronic acid fermentation liquor |
| CN110857446A (en) * | 2018-08-23 | 2020-03-03 | 滨州市华康梦之缘生物科技有限公司 | Production process of high-purity lactic acid |
| CN112028224A (en) * | 2020-09-16 | 2020-12-04 | 广东恩维乐环境科技有限公司 | Processing technology for preparing carbon source for high-quality sewage treatment from waste sugar |
| CN113773189A (en) * | 2021-08-02 | 2021-12-10 | 合肥信达膜科技有限公司 | Application of membrane process in lactic acid production |
| CN114014752A (en) * | 2021-12-07 | 2022-02-08 | 河南星汉生物科技有限公司 | Process for decoloring crude lactic acid by using activated carbon |
| CN114591164A (en) * | 2022-01-29 | 2022-06-07 | 安徽丰原发酵技术工程研究有限公司 | Lactic acid purification method |
| CN114907205A (en) * | 2021-02-07 | 2022-08-16 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Method for reducing residual sugar and extracellular polymeric substances in lactic acid product by fermentation method |
| CN115991646A (en) * | 2021-10-18 | 2023-04-21 | 上海凯赛生物技术股份有限公司 | Method for separating and extracting lactic acid, lactic acid product and preparation method thereof |
| CN115991643A (en) * | 2021-10-18 | 2023-04-21 | 上海凯赛生物技术股份有限公司 | Method for separating and extracting lactic acid |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6272646A (en) * | 1985-09-25 | 1987-04-03 | Taki Chem Co Ltd | Separation and purification of lactic acid |
| US5641406A (en) * | 1993-02-18 | 1997-06-24 | Vogelbusch Gesellschaft M.B.H. | Lactic acid extraction and purification process |
| CN1603298A (en) * | 2004-08-03 | 2005-04-06 | 合肥工业大学 | Process for extracting lactic acid from fermentation liquid |
| CN101234962A (en) * | 2008-03-04 | 2008-08-06 | 江苏道森生物化学有限公司 | Technique for separating and purifying L-lactic acid |
| CN101979368A (en) * | 2010-10-19 | 2011-02-23 | 大连理工大学 | Method for extracting and salting organic acids out of fermentation liquor |
| CN103724183A (en) * | 2013-12-16 | 2014-04-16 | 河南金丹乳酸科技股份有限公司 | Method of industrial production of lactic acid by employing molecular distillation technology |
-
2014
- 2014-12-05 CN CN201410731197.6A patent/CN105646193B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6272646A (en) * | 1985-09-25 | 1987-04-03 | Taki Chem Co Ltd | Separation and purification of lactic acid |
| US5641406A (en) * | 1993-02-18 | 1997-06-24 | Vogelbusch Gesellschaft M.B.H. | Lactic acid extraction and purification process |
| CN1603298A (en) * | 2004-08-03 | 2005-04-06 | 合肥工业大学 | Process for extracting lactic acid from fermentation liquid |
| CN101234962A (en) * | 2008-03-04 | 2008-08-06 | 江苏道森生物化学有限公司 | Technique for separating and purifying L-lactic acid |
| CN101979368A (en) * | 2010-10-19 | 2011-02-23 | 大连理工大学 | Method for extracting and salting organic acids out of fermentation liquor |
| CN103724183A (en) * | 2013-12-16 | 2014-04-16 | 河南金丹乳酸科技股份有限公司 | Method of industrial production of lactic acid by employing molecular distillation technology |
Non-Patent Citations (1)
| Title |
|---|
| 王甲卫: "从发酵液中分离提纯L-乳酸的工艺研究", 《北京化工大学硕士研究生学位论文》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106431895A (en) * | 2016-09-18 | 2017-02-22 | 宁波工程学院 | Method for extracting lactic acid from fermentation liquor through combination of molecular distillation and extraction |
| CN106431895B (en) * | 2016-09-18 | 2018-06-05 | 宁波工程学院 | Molecular distillation combines extraction for the method for extracting Lactic Acid from Fermentation Broth |
| CN107805251A (en) * | 2017-12-07 | 2018-03-16 | 内蒙古金达威药业有限公司 | A kind of method that riboflavin is extracted from Lactochrome fermentation liquor |
| CN110857446A (en) * | 2018-08-23 | 2020-03-03 | 滨州市华康梦之缘生物科技有限公司 | Production process of high-purity lactic acid |
| CN109678696A (en) * | 2019-01-31 | 2019-04-26 | 华熙福瑞达生物医药有限公司 | A method of extracting lactic acid from hyaluronic acid fermentation liquor |
| CN112028224A (en) * | 2020-09-16 | 2020-12-04 | 广东恩维乐环境科技有限公司 | Processing technology for preparing carbon source for high-quality sewage treatment from waste sugar |
| CN114907205A (en) * | 2021-02-07 | 2022-08-16 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Method for reducing residual sugar and extracellular polymeric substances in lactic acid product by fermentation method |
| CN114907205B (en) * | 2021-02-07 | 2024-05-31 | 中科南京绿色制造产业创新研究院 | Method for reducing residual sugar and extracellular polymer in lactic acid product by fermentation method |
| CN113773189A (en) * | 2021-08-02 | 2021-12-10 | 合肥信达膜科技有限公司 | Application of membrane process in lactic acid production |
| CN115991646A (en) * | 2021-10-18 | 2023-04-21 | 上海凯赛生物技术股份有限公司 | Method for separating and extracting lactic acid, lactic acid product and preparation method thereof |
| CN115991643A (en) * | 2021-10-18 | 2023-04-21 | 上海凯赛生物技术股份有限公司 | Method for separating and extracting lactic acid |
| CN114014752A (en) * | 2021-12-07 | 2022-02-08 | 河南星汉生物科技有限公司 | Process for decoloring crude lactic acid by using activated carbon |
| CN114591164A (en) * | 2022-01-29 | 2022-06-07 | 安徽丰原发酵技术工程研究有限公司 | Lactic acid purification method |
| CN114591164B (en) * | 2022-01-29 | 2023-11-24 | 安徽丰原发酵技术工程研究有限公司 | Purification method of lactic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105646193B (en) | 2018-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105646193A (en) | Method used for separating and extracting lactic acid from fermentation broth | |
| CN102976923B (en) | New process for extracting lactic acid from lactic acid fermentation liquid | |
| Gonzalez et al. | Economic evaluation of an integrated process for lactic acid production from ultrafiltered whey | |
| CN101979368B (en) | Method for extracting and salting organic acids out of fermentation liquor | |
| CN102958893B (en) | Process for removing, isolating and purifying dicarboxylic acids | |
| CN110272341B (en) | Purification method of long-chain dibasic acid | |
| CN102952831A (en) | Manufacturing process of purified lactic acid | |
| CN104788288A (en) | Method for purifying 1,3-propylene glycol from 1,3-propylene glycol fermentation liquor and application thereof | |
| CN101633634A (en) | Method for extracting L-proline from fermentation liquor by membrane separation technology | |
| CN102040476B (en) | Method for separating and purifying 1,3-propylene glycol from fermentation liquor | |
| CN103804173B (en) | A kind of process for purification of fermentation organic acid | |
| CN105837488B (en) | A kind of hydroxyproline fermentation manufacturing technique | |
| CN103804172A (en) | Method for improving organic acid product quality | |
| CN102603814B (en) | Method for increasing crystalizing efficiency of xylose in xylose mother solution | |
| CN105585431A (en) | Desalination method for salt-containing fermentation liquid | |
| CN104556495B (en) | The processing method of 1,3 propanediol fermentation liquor desalination acid-basic regenerated waste liquids in water | |
| CN104592004B (en) | A kind of method of refining long-chain organic acid | |
| CN107201384A (en) | A kind of method of separation and Extraction D-ALPHA-Hydroxypropionic acid in sodium zymotic fluid from D-ALPHA-Hydroxypropionic acid | |
| CN104789607B (en) | A kind of method that Integrated process prepares lactic acid and/or lactate | |
| CN104591999A (en) | Long chain organic acid purifying method | |
| WO2023109027A1 (en) | Method for desalting and purifying 1,3-propanediol fermentation broth | |
| CN104556496B (en) | Treatment method of fermentation broth desalinated resin regenerated wastewater | |
| CN103804174A (en) | Organic acid refining method | |
| CN105712841B (en) | A kind of method of the propane diols of the separation and Extraction from zymotic fluid 1,3 | |
| CN103695488B (en) | A kind of arginine preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |