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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- ammediol
- fermented liquid
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- 239000007788 liquid Substances 0.000 title claims abstract description 60
- 238000000605 extraction Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000000926 separation method Methods 0.000 title claims abstract description 23
- 239000006227 byproduct Substances 0.000 title claims description 16
- 238000000855 fermentation Methods 0.000 title abstract description 14
- 230000004151 fermentation Effects 0.000 title abstract description 14
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title abstract description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 70
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012071 phase Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 8
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract description 7
- 125000002091 cationic group Chemical group 0.000 claims abstract description 7
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 7
- 239000011973 solid acid Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 5
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 48
- 235000011187 glycerol Nutrition 0.000 claims description 28
- -1 alcohol forms acetal Chemical class 0.000 claims description 21
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 20
- 150000001299 aldehydes Chemical class 0.000 claims description 13
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000066 reactive distillation Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 claims description 6
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 6
- 241000047703 Nonion Species 0.000 claims description 6
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical class CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 238000005189 flocculation Methods 0.000 claims description 5
- 230000016615 flocculation Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- BJLRVFDWAOVFCI-UHFFFAOYSA-N 1h-imidazole;quinoline Chemical compound C1=CNC=N1.N1=CC=CC2=CC=CC=C21 BJLRVFDWAOVFCI-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- HNCGGGHOEMOHFA-UHFFFAOYSA-M S(=O)(=O)(OC)[O-].C(C)OC(=O)[N+](C)(C)C.C(C=C)(=O)O.C(C=C)(=O)N Chemical compound S(=O)(=O)(OC)[O-].C(C)OC(=O)[N+](C)(C)C.C(C=C)(=O)O.C(C=C)(=O)N HNCGGGHOEMOHFA-UHFFFAOYSA-M 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 229920006322 acrylamide copolymer Polymers 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000005341 cation exchange Methods 0.000 claims description 2
- 239000003729 cation exchange resin Substances 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- PRAHCKGOTFKWKD-UHFFFAOYSA-N dimethyl(propyl)azanium;chloride Chemical compound Cl.CCCN(C)C PRAHCKGOTFKWKD-UHFFFAOYSA-N 0.000 claims description 2
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 2
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 claims description 2
- XDFYWAPQDKBIHB-UHFFFAOYSA-N ethyl prop-2-enoate;prop-2-enamide Chemical compound NC(=O)C=C.CCOC(=O)C=C XDFYWAPQDKBIHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011964 heteropoly acid Substances 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N mono-n-propyl amine Natural products CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 2
- ITFGZZGYXVHOOU-UHFFFAOYSA-N n,n-dimethylmethanamine;methyl hydrogen sulfate Chemical compound C[NH+](C)C.COS([O-])(=O)=O ITFGZZGYXVHOOU-UHFFFAOYSA-N 0.000 claims description 2
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 claims description 2
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 229920000166 polytrimethylene carbonate Polymers 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000003311 flocculating effect Effects 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 229940035437 1,3-propanediol Drugs 0.000 abstract 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 3
- 239000008346 aqueous phase Substances 0.000 abstract 2
- 239000008394 flocculating agent Substances 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 238000011027 product recovery Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 5
- RCORSHSFJCXHTF-UHFFFAOYSA-N 2-ethenyl-1,3-dioxan-5-ol Chemical compound OC1COC(C=C)OC1 RCORSHSFJCXHTF-UHFFFAOYSA-N 0.000 description 4
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 4
- 241000282326 Felis catus Species 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 241000193403 Clostridium Species 0.000 description 2
- 241000193171 Clostridium butyricum Species 0.000 description 2
- 241000588747 Klebsiella pneumoniae Species 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- MFJDFPRQTMQVHI-UHFFFAOYSA-N 3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical class O=C1OCOC(=O)C2=CC=C1C=C2 MFJDFPRQTMQVHI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000193469 Clostridium pasteurianum Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 235000008504 concentrate Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000012262 fermentative production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012269 metabolic engineering Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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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| CN100364947C (en) * | 2006-08-16 | 2008-01-30 | 华东理工大学 | Method of continuous and high-yield separating and extracting 1,3-dihydroxypropane from fermentation liquid |
| CN101898935A (en) * | 2010-07-09 | 2010-12-01 | 华东理工大学 | Method for extracting and separating 1,3-propylene glycol from fermentation liquor |
| CN102816048A (en) * | 2012-09-04 | 2012-12-12 | 华东理工大学 | Method for extracting and separating 1,3-propanediol from fermentation liquid |
| RU2679644C2 (en) * | 2014-12-08 | 2019-02-12 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Method for separating glycols |
| BR112018074034B1 (en) | 2016-05-23 | 2022-06-28 | Shell Internationale Research Maatschappij B.V. | PROCESS FOR SEPARATION OF DIOLS |
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| US11203561B2 (en) | 2018-02-21 | 2021-12-21 | Shell Oil Company | Stabilization of polyhydric alcohols by steam injection |
| CN108893497A (en) * | 2018-07-18 | 2018-11-27 | 大连理工大学 | A kind of many cells system and fermentation process changing aeration condition regulation product |
| CN113773174B (en) * | 2021-09-15 | 2022-07-15 | 花安堂生物科技集团有限公司 | Method for simultaneously extracting dihydric alcohol and organic acid ester from microbial fermentation broth |
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