CN1304345C - Method for separation and extraction of 1,3-propylene glycol and its byproducts from fermentation liquid - Google Patents
Method for separation and extraction of 1,3-propylene glycol and its byproducts from fermentation liquid Download PDFInfo
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- CN1304345C CN1304345C CN 200410083940 CN200410083940A CN1304345C CN 1304345 C CN1304345 C CN 1304345C CN 200410083940 CN200410083940 CN 200410083940 CN 200410083940 A CN200410083940 A CN 200410083940A CN 1304345 C CN1304345 C CN 1304345C
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Abstract
The present invention discloses a downstream separating and extracting process for preparing 1, 3-propanediol by a fermentation method, which belongs to the technical field of biochemical separation. The process comprises: firstly separating ethanol in fermentation liquid through rectification; then flocculating a cationic flocculating agent and a nonionic flocculating agent in a compound mode for separating solid substances in the fermentation liquid and dissolving protein in the fermentation liquid; regulating the pH valve of the clear liquid by acid, and then processing the clear liquid by aldehyde through reaction extraction; processing 1, 3-propanediol, 2, 3-butanediol, glycerol and the aldehyde through acetal reaction, and then separating the generated annular acetal from aqueous phases; separating salts and other dissoluble impurities in the fermentation liquid from the 1, 3-propanediol, the 2, 3-butanediol and the glycerol along with the aqueous phases; processing the acetal by hydrolyzing through reaction rectification to obtain a high-concentration mixture of the 1, 3-propanediol, the 2, 3-butanediol and the glycerol by using a solid acid catalyst; separating the mixture of the 1, 3-propanediol, the 2, 3-butanediol and the glycerol through ordinary rectification; recovering excessive aldehyde in raffinate phases through rectification. The present invention has the advantages of simple extraction process and separation process, low energy consumption, high product recovery rate, less equipment investment and less land occupation.
Description
Technical field
The invention belongs to the bioseparation technology field, particularly a kind of from fermented liquid separation and Extraction 1, the method for ammediol and by product thereof.
Background technology
1, ammediol (1,3-Propandiol is called for short PDO) is the monomer of production Poly(Trimethylene Terephthalate) (PTT).At document " Smith; J.G.Polym.Sci.; Part A-1.1966; 4; " the Preparation and properties of poly (methylene terephthalates) " of 1851-1859 " and " Witt U; et al J, Makromol Chem Phys, 1994,195:793 ~ 802, " Synthesisproperties and biodegradability of polyesters based on 1,3-propanediol " " middle report; PTT is a kind of biodegradable polyester material, is applied to senior textile materials.Compare with polybutylene terephthalate (PDT) with polyethylene terephthalate (PET), 1, the odd numbers of carbon atoms number of ammediol makes PTT have special performances.Existing PDO production method mainly contains propenal method and epoxyethane method, but problems such as these two kinds of methods exist, and side reaction is many, severe reaction conditions and environmental pollution, and output is less, production and the application of PDO have greatly been restricted, utilize glycerine or glucose fermentation method to produce PDO and have mild condition, raw materials for production, be subjected to increasing attention for advantages such as renewable resources, environmental pollution are little.
Qi Wentao, repair " the glycerine disproportionation produces 1; metabolism of ammediol process and gene regulating mechanism progress " and Zhang Jian that the will dragon is delivered in " Chinese biological engineering magazine; 2003; 23; 64-68 ", Zhao Hongying, " Metabolic engineering for themicrobial production of 1, the 3-propanediol " that " glucose is as cosubstrate fermentative production 1; research of ammediol " Charles E Nakamura that Liu Hongjuan etc. deliver on " modern chemical industry; 2002; 22; 32-35 " delivers in " Current Opinion inBiotechnology 2003; 14:454-459 "; " Microbial production of 1; 3-propanediol " Biebl that H.BieblK.MenzelA.-P.ZengW.-D.Deckwer delivers in " Appl Microbiol Biotechnol (1999) 52:289-297 ", H. " Glycerol fermentationof 1, the 3-propanediol by Clostridium butyricum.Measurement of productinhibition by use of a pH-auxostat " that in " Appl.Microbiol.Biotechnol.1991; 35; 701-705 ", delivers; Laffend; Lisa Anne; Nagarajan; Vasantha; Nakamura; " Bioconversion of a fermentable carbon source to1; 3-propanediol by a single microorganism " that Charles Edwin. delivers in " United States Patent 5; 686; 276; 1997 " shows, with glycerine or glycerol fermented broth or glucose is raw material, when utilizing Cray Bai Shi pneumobacillus (Klebsiella pneumoniae) clostridium butylicum (Clostridium pasteurianum) recombination bacillus coli bacterial classifications such as (E.coli K12) to ferment, during fermentation ends 1, the concentration of ammediol in fermented liquid is about 5～13%.Also contain a lot of by-product acetic acid salt, lactic acid salt, succinate, glycerine, ethanol, 2 in the fermented liquid simultaneously, 3-butyleneglycol and thalline and remaining components such as substratum.Want to extract 1 from fermented liquid, ammediol, glycerine, 2,3-butyleneglycol just must separate with water these materials with impurity.
Existing from fermented liquid separation and Extraction 1, the method for ammediol mainly contains:
1. concentrate distillation method, at first germ-carrying fermented liquid straight run distillation is concentrated; After the cooling, add ethanol or methyl alcohol, n-propyl alcohol, Virahol, acetone, butanone etc. by a certain percentage, by sedimentation or filtration or centrifugation precipitation, get supernatant liquor then; Use same alcohol or ketone washing precipitation again, by sedimentation or filtration or centrifugation precipitation, get supernatant liquor then; The gained supernatant liquor is reclaimed alcohol by distillation or rectifying or ketone (is repaiied the will dragon; Zhang Daijia; Gao Sujun etc., extraction separation 1 in the microbial fermentation solution, the method CN14606712003.12.10 of ammediol).
2. use ion exchange method by Zeo-karb, again by solvent elution, collects 1, ammediol component (Hilaly with fermented liquid; Ahmad K; Binder; Thomas P., Method of recovering1,3-propanediol from fermentation broth, US 6,479,716, and November 12,2002; Roturier; Jean-Michel; Fouache; Catherine; Berghmans; Elie, Process forthe purification of 1,3-propanediol from a fermentation medium, US6,428,992, August 6,2002).
3. alkali is regulated fermented liquid pH, separates by additive method again, comprises distillation, rectifying, operation such as filtration, extraction and crystallization (Ames; Tyler T., Process for the isolation of1,3-propanediol from fermentation broth US 6,361,983, March 26,2002).
4. use the simple liquid-liquid extraction of alcohols from fermented liquid, to extract 1, ammediol (Janusz J.Malinowski, Evaluation of liquid extraction potentials for downstreamseparation of1,3-propanediol, Biotechnology Techniques 13:127-130,1999.).
5. use formaldehyde, acetaldehyde and 1, ammediol reacts, and product restores with organic solvent extraction; Janusz J.Malinowski, Reactive Extraction for Downstream Separation of1,3-Propanediol, Biotechnol.Prog.2000,16,76-79 is to great waves, Chen Shufeng, Liu Dehua, in the fermented liquid 1, the extracting and separating of ammediol, Tsing-Hua University's journal (natural science edition) 2001,41 (12) 53-55.
6. fermented liquid concentrates by electrodialytic desalting, and rectification under vacuum obtains product; Yan Gong, Yu Tang, The possibility of the desalination of actual 1,3-propanediolfermentation broth by electrodialysis, Desalination 2004.161:169 ~ 178.
From fermented liquid, extract 1 for listed above, the method for ammediol, 1,3 methods exist energy consumption big, consume the shortcoming of a large amount of organic solvents; 2, the method commercial viability in 4 is relatively poor; Method formaldehyde, acetaldehyde boiling point in 5 are low, and easily form polymer and reclaim difficulty, and use organic solvent extraction toxicity such as benzene bigger; Electrodialytic desalting 1 in 6, and the ammediol loss is big, and the high floor space of cost of equipment is big.All extracting method listed above do not have complete extraction separation from fermented liquid 1, ammediol, glycerine, 2, the technology of 3-butyleneglycol.
Summary of the invention
The purpose of this invention is to provide a kind of from fermented liquid separation and Extraction 1, the method for ammediol and by product thereof.It is characterized in that: utilize rectifying, composite flocculation, reaction, extraction and reaction rectification method, separation and Extraction 1 from fermented liquid, ammediol and by product ethanol thereof, glycerine and 2, and the technological process of 3-butyleneglycol is:
1) will contain 1, the fermented liquid of ammediol is isolated the ethanol in the fermented liquid by rectifying tower;
2) fermented liquid adds the flocculant in non-ion type of 50～400ppm cationic flocculant and 20～300ppm, removes thalline solid substance and protein;
3) pH with acid adjusting fermented liquid is 1-3;
4) fermented liquid carries out reaction, extraction with 15wt%～40wt% propionic aldehyde, butyraldehyde, isobutyric aldehyde or isovaleric aldehyde butyraldehyde, and alcohol forms acetal with aldehyde generation aldolization, and is extracted to organic phase;
5) add the water of 5wt%～15wt% in the extraction phase, carry out reactive distillation, make the acetal hydrolysis reaction be able to forward after aldehydes is isolated and carry out by the rectifying tower that is filled with solid acid, obtain 1, ammediol, glycerine and 2, the 3-mixture of butanediols reclaims aldehydes simultaneously;
6) 1, ammediol, glycerine and 2, the 3-mixture of butanediols obtains 1 respectively by rectifying, ammediol, glycerine and 2,3-butyleneglycol product;
7) extracting phase with in calcium hydroxide or the sodium hydroxide and after, wherein excessive aldehyde reclaims by rectifying.
The pH acid of described adjusting fermented liquid is sulfuric acid or hydrochloric acid.
Described fermented liquid is: with glycerine or glucose be substrate utilize Cray Bai Shi pneumobacillus (Klebsiella pneumoniae), clostridium butylicum (Clostridium butyricum) or recombination bacillus coli (E.coli) the resulting fermented liquid that ferments.
Described cationic flocculant is: acrylamide-methacrylic acid-2-hydroxy propyl ester base trimethyl ammonium chloride multipolymer, acrylamide-Jia Jibingxisuanyizhi base trimethyl ammonium chloride multipolymer, acrylamide-Jia Jibingxisuanyizhi base trimethyl ammonium methyl sulfate multipolymer, acrylamide-acrylicacid ethoxycarbonyl trimethyl ammonium methyl sulfate multipolymer, Poly Dimethyl Diallyl Ammonium Chloride, acrylamide-dimethyl diallyl ammonium chloride copolymer, 2-hydroxypropyl alkyl dimethyl ammonium chloride-two (2-hydroxypropyl) alkyl ammomium chloride multipolymer, apart from 2-hydroxypropyl alkyl dimethyl ammonium chloride, poly-trimeric cyanamide formal, acrylamide-acrylicacid ethyl ester multipolymer, alkene acid amides-methacrylic acid-N-dimethyl amine ester copolymer, alkene acid amides-N, N-dimethyl amido acrylamide copolymer, poly-N, N-dimethyl amido-1-hydroxyethyl-2-hydroxyl propylamine, poly-imines, poly-ring is narrowed basic ethene, polystyrene tetramethyl-ammonia chloride, the polyvinyl imidazole quinoline, poly--2-hydroxypropyl-N-dimethyl chlorination amine, polydiene propyl-dimethyl ammonia chloride or chitosan.
Described flocculant in non-ion type is: polyvinyl alcohol, polyvinyl methyl ether, polyacrylamide, polyoxyethylene, polyvinylpyrrolidone, polyvinyl acetate hydrolyzate, poly-methyl or poly-alkylphenol-oxyethane.
Described solid acid comprises: gel strongly acidic cation-exchange, large porous strong acid cation exchange resin or heteropolyacid.
Beneficial effect of the present invention is that operational path is simple, and energy consumption is lower, and labour intensity is low, and equipment cost is low, and occupation area of equipment is little, and 1 in the fermented liquid, ammediol and 2,3-butyleneglycol total yield can reach 95%, the glycerine yield can reach 40%.Save filtration, desalination and concentration process, do not use extraction agents such as benzene, pollute characteristics such as lower.
Embodiment
The invention provides a kind of from fermented liquid separation and Extraction 1, the method for ammediol and by product thereof.Be to utilize rectifying, composite flocculation, reaction, extraction and reactive distillation to 1, the novel process that various products, separation of by-products are extracted in the ammediol fermented liquid.Described composite flocculation utilizes cationic flocculant and flocculant in non-ion type composite flocculation fermented liquid to remove solid substance and most of soluble protein such as thalline.The reaction, extraction method method that reaction, extraction step aldolization and extraction are carried out simultaneously.The reactive distillation step is utilized solid acid catalyst, and the acetal hydrolysis reaction combines with the rectifying separation process, makes hydrolysis reaction to carry out thoroughly by forward.Various soluble impurities in the fermented liquid enter aldehyde with extracting phase and reclaim rectifying tower, and by the mash discharging, separation and Extraction 1 from fermented liquid at last, ammediol and by product ethanol thereof, glycerine and 2, and the technological process of 3-butyleneglycol is:
1) will contain 1, the fermented liquid of ammediol is isolated the ethanol in the fermented liquid by rectifying tower;
2) fermented liquid adds the flocculant in non-ion type of 50～400ppm cationic flocculant and 20～300ppm, removes thalline solid substance and protein;
3) pH with acid adjusting fermented liquid is 1-3;
4) fermented liquid carries out reaction, extraction with 15wt%～40wt% propionic aldehyde, butyraldehyde, isobutyric aldehyde or isovaleric aldehyde butyraldehyde, and alcohol forms acetal with aldehyde generation aldolization, and is extracted to organic phase;
5) add the water of 5wt%～15wt% in the extraction phase, carry out reactive distillation, make the acetal hydrolysis reaction be able to forward after aldehydes is isolated and carry out by the rectifying tower that is filled with solid acid, obtain 1, ammediol, glycerine and 2, the 3-mixture of butanediols reclaims aldehydes simultaneously;
6) 1, ammediol, glycerine and 2, the 3-mixture of butanediols obtains 1 respectively by rectifying, ammediol, glycerine and 2,3-butyleneglycol product;
7) extracting phase with in calcium hydroxide or the sodium hydroxide and after, wherein excessive aldehyde reclaims by rectifying.
Lifting specific examples is below again illustrated the inventive method.
Example 1
(1) fermented liquid: 1, ammediol 53.5g/L; 2,3-butyleneglycol 7.5g/L; Glycerine 27.6g/L; Ethanol 8.1g/L; Lactic acid 5.9g/L; Acetic acid 10.5g/L; Succsinic acid 5.6g/L; OD 4.7; Soluble proteins 0.4g/L.
(2) rectifying separation ethanol condition: sieve-tray tower, middle part charging, 100 ℃ of column bottom temperatures, reflux ratio 3: 1 (volume ratio).
(3) flocculating conditions: the 100ppm chitosan, the 200ppm polyacrylamide, fermentation OD reduces to 0, and soluble protein content is reduced to 0.16g/L, the fermented liquid rate of recovery 98%.
(4) fermented liquid is transferred pH: sulfuric acid is transferred pH to 2.
(5) reaction, extraction condition: extractive reaction agent, butyraldehyde-n, consumption, the extraction of 15%, 4 stage countercurrent.
(6) reaction, extraction result: gained extraction phase, 1, ammediol acetal 650g/L; 2,3-butyleneglycol acetal 120g/L; Glycerine acetal 60g/L.1, ammediol acetal, 2, the 3-butyleneglycol acetal rate of recovery 95%, the glycerine acetal rate of recovery 30%.
(7) reactive distillation condition: packing tower, catalyzer, large porous strong acid type H type Zeo-karb, middle part charging, 160 ℃ of column bottom temperatures, reflux ratio 3: 1.
(8) reactive distillation result: the pure butyraldehyde of cat head gained, gained at the bottom of the tower, 1, ammediol 580g/L; 2,3-butyleneglycol 100g/L; Glycerine 60g/L, 1, ammediol, 2, the 3-butyleneglycol rate of recovery 98%, the glycerine rate of recovery 80%.
(9) the extracting phase butyraldehyde-n reclaims: sieve-tray tower, and the middle part charging, 100 ℃ of column bottom temperatures, reflux ratio 3: 1 (volume ratio), cat head obtains pure butyraldehyde.
Example 2
(1) fermented liquid: 1, ammediol 53.5g/L; 2,3-butyleneglycol 7.5g/L; Glycerine 27.6g/L; Ethanol 8.1g/L; Lactic acid 5.9g/L; Acetic acid 10.5g/L; Succsinic acid 5.6g/L; OD 4.7; Soluble proteins 0.4g/L.
(2) rectifying separation ethanol condition: sieve-tray tower, middle part charging, 100 ℃ of column bottom temperatures, reflux ratio 3: 1 (volume ratio).
(3) flocculating conditions: the 150ppm chitosan, the 150ppm polyacrylamide, fermentation OD reduces to 0, and soluble protein content is reduced to 0.13g/L, the fermented liquid rate of recovery 99%.
(4) fermented liquid is transferred pH: sulfuric acid is transferred pH to 1.5.
(5) reaction, extraction condition: extractive reaction agent, butyraldehyde-n, consumption, the extraction of 20%, 4 stage countercurrent.
(6) reaction, extraction result: gained extraction phase, 1, ammediol acetal 580g/L; 2,3-butyleneglycol acetal 110g/L; Glycerine acetal 50g/L.1, ammediol acetal, 2, the 3-butyleneglycol acetal rate of recovery 98%, the glycerine acetal rate of recovery 50%.
(7) reactive distillation condition: packing tower, catalyzer, gel strong acid type H type Zeo-karb, middle part charging, 160 ℃ of column bottom temperatures, reflux ratio 3: 1 (volume ratio).
(8) reactive distillation result: the pure butyraldehyde of cat head gained, gained at the bottom of the tower, 1, ammediol 580g/L; 2,3-butyleneglycol 100g/L; Glycerine 60g/L, 1, ammediol, 2, the 3-butyleneglycol rate of recovery 98% glycerine rate of recovery 80%.
(9) the extracting phase butyraldehyde-n reclaims: sieve-tray tower, and the middle part charging, 100 ℃ of column bottom temperatures, reflux ratio 3: 1 (volume ratio), cat head obtains pure butyraldehyde.
Claims (5)
1. separation and Extraction 1 from fermented liquid, the method for ammediol and by product thereof utilizes rectifying will contain 1, and the fermented liquid of ammediol is isolated the ethanol in the fermented liquid by rectifying tower; Through composite flocculation, reaction, extraction and reaction rectification method, separation and Extraction 1 from fermented liquid, ammediol and by product ethanol thereof, glycerine and 2, and the 3-butyleneglycol is characterized in that, is extracting 1, in the process of ammediol and by product thereof:
1) in isolating the alcoholic acid fermented liquid, adds the flocculant in non-ion type of 50～400ppm cationic flocculant and 20～300ppm, remove thalline solid substance and protein;
2) pH with acid adjusting fermented liquid is 1-3;
3) fermented liquid carries out reaction, extraction with 15wt%～40wt% propionic aldehyde, butyraldehyde, isobutyric aldehyde or isovaleric aldehyde butyraldehyde, and alcohol forms acetal with aldehyde generation aldolization, and is extracted to organic phase;
4) add the water of 5wt%～15wt% in the extraction phase, carry out reactive distillation, make the acetal hydrolysis reaction be able to forward after aldehydes is isolated and carry out by the rectifying tower that is filled with solid acid, obtain 1, ammediol, glycerine and 2, the 3-mixture of butanediols reclaims aldehydes simultaneously;
5) 1, ammediol, glycerine and 2, the 3-mixture of butanediols obtains 1 respectively by rectifying, ammediol, glycerine and 2,3-butyleneglycol product;
6) extracting phase with in calcium hydroxide or the sodium hydroxide and after, wherein excessive aldehyde reclaims by rectifying.
According to claim 1 described from fermented liquid separation and Extraction 1, the method for ammediol and by product thereof is characterized in that: the pH acid of described adjusting fermented liquid is sulfuric acid or hydrochloric acid.
According to claim 1 described from fermented liquid separation and Extraction 1, the method of ammediol and by product thereof is characterized in that: described cationic flocculant is: acrylamide-methacrylic acid-2-hydroxy propyl ester base trimethyl ammonium chloride multipolymer, acrylamide-Jia Jibingxisuanyizhi base trimethyl ammonium chloride multipolymer, acrylamide-Jia Jibingxisuanyizhi base trimethyl ammonium methyl sulfate multipolymer, acrylamide-acrylicacid ethoxycarbonyl trimethyl ammonium methyl sulfate multipolymer, Poly Dimethyl Diallyl Ammonium Chloride, acrylamide-dimethyl diallyl ammonium chloride copolymer, 2-hydroxypropyl alkyl dimethyl ammonium chloride-two (2-hydroxypropyl) alkyl ammomium chloride multipolymer, apart from 2-hydroxypropyl alkyl dimethyl ammonium chloride, poly-trimeric cyanamide formal, acrylamide-acrylicacid ethyl ester multipolymer, alkene acid amides-methacrylic acid-N-dimethyl amine ester copolymer, alkene acid amides-N, N-dimethyl amido acrylamide copolymer, poly-N, N-dimethyl amido-1-hydroxyethyl-2-hydroxyl propylamine, poly-imines, poly-ring is narrowed basic ethene, polystyrene tetramethyl-ammonia chloride, the polyvinyl imidazole quinoline, poly--2-hydroxypropyl-N-dimethyl chlorination amine, polydiene propyl-dimethyl ammonia chloride or chitosan.
According to claim 1 described from fermented liquid separation and Extraction 1, the method of ammediol and by product thereof is characterized in that: described flocculant in non-ion type is: polyvinyl alcohol, polyvinyl methyl ether, polyacrylamide, polyoxyethylene, polyvinylpyrrolidone, polyvinyl acetate hydrolyzate, poly-methyl or poly-alkylphenol-oxyethane.
According to claim 1 described from fermented liquid separation and Extraction 1, the method for ammediol and by product thereof is characterized in that: described solid acid is: gel strongly acidic cation-exchange, large porous strong acid cation exchange resin or heteropolyacid.
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| WO2024121703A1 (en) * | 2022-12-06 | 2024-06-13 | Eni S.P.A. | Separation process of alcohol mixtures with high water content by liquid-liquid extraction |
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