CN101182455A - Device and technique for producing propanoic acid by coupling of fibrous bed bioreactor with extraction separation - Google Patents
Device and technique for producing propanoic acid by coupling of fibrous bed bioreactor with extraction separation Download PDFInfo
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- CN101182455A CN101182455A CNA2007101907548A CN200710190754A CN101182455A CN 101182455 A CN101182455 A CN 101182455A CN A2007101907548 A CNA2007101907548 A CN A2007101907548A CN 200710190754 A CN200710190754 A CN 200710190754A CN 101182455 A CN101182455 A CN 101182455A
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 235000019260 propionic acid Nutrition 0.000 title claims abstract description 100
- 238000000605 extraction Methods 0.000 title claims abstract description 94
- 238000000926 separation method Methods 0.000 title claims abstract description 15
- 230000008878 coupling Effects 0.000 title claims abstract description 14
- 238000010168 coupling process Methods 0.000 title claims abstract description 14
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 14
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 title claims description 11
- 238000000034 method Methods 0.000 title abstract description 15
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 89
- 239000012528 membrane Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 241000186429 Propionibacterium Species 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000010828 elution Methods 0.000 claims abstract description 20
- 238000005516 engineering process Methods 0.000 claims abstract description 15
- 238000009833 condensation Methods 0.000 claims abstract description 10
- 230000005494 condensation Effects 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 239000007788 liquid Substances 0.000 claims description 41
- 239000000835 fiber Substances 0.000 claims description 34
- 239000012074 organic phase Substances 0.000 claims description 30
- 239000006052 feed supplement Substances 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 230000001276 controlling effect Effects 0.000 claims description 7
- 239000000523 sample Substances 0.000 claims description 7
- 239000008346 aqueous phase Substances 0.000 claims description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical group 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 150000003512 tertiary amines Chemical group 0.000 claims description 4
- 235000013311 vegetables Nutrition 0.000 claims description 4
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical group CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 claims description 3
- 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 3
- 241000894006 Bacteria Species 0.000 claims description 3
- WONCHGDEGMFLPR-UHFFFAOYSA-N [Cl-].[NH4+].CC(CCCCCCC)P(CCCCCCCC)CCCCCCCC Chemical compound [Cl-].[NH4+].CC(CCCCCCC)P(CCCCCCCC)CCCCCCCC WONCHGDEGMFLPR-UHFFFAOYSA-N 0.000 claims description 3
- 238000007444 cell Immobilization Methods 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical group [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 229940055577 oleyl alcohol Drugs 0.000 claims description 3
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 claims description 3
- 125000005270 trialkylamine group Chemical group 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- BJVWCKXHSNBHGB-UHFFFAOYSA-L disodium;chloride;hydroxide Chemical compound [OH-].[Na+].[Na+].[Cl-] BJVWCKXHSNBHGB-UHFFFAOYSA-L 0.000 claims description 2
- 238000012262 fermentative production Methods 0.000 claims description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical group CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 37
- 238000000855 fermentation Methods 0.000 abstract description 34
- 230000004151 fermentation Effects 0.000 abstract description 34
- 230000005764 inhibitory process Effects 0.000 abstract description 5
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- 239000002609 medium Substances 0.000 description 20
- 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 17
- 239000008103 glucose Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 14
- 239000001963 growth medium Substances 0.000 description 12
- 238000011218 seed culture Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 239000002054 inoculum Substances 0.000 description 9
- 241000186428 Propionibacterium freudenreichii Species 0.000 description 8
- 230000001580 bacterial effect Effects 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 108090000623 proteins and genes Proteins 0.000 description 6
- 102000004169 proteins and genes Human genes 0.000 description 6
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 6
- 235000010334 sodium propionate Nutrition 0.000 description 6
- 239000004324 sodium propionate Substances 0.000 description 6
- 229960003212 sodium propionate Drugs 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 239000004744 fabric Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 210000002268 wool Anatomy 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
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- 239000012510 hollow fiber Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
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- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004113 cell culture Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 210000001822 immobilized cell Anatomy 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 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 1
- 230000031018 biological processes and functions Effects 0.000 description 1
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- 229940041514 candida albicans extract Drugs 0.000 description 1
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- 150000001868 cobalt Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 239000004310 lactic acid Substances 0.000 description 1
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- 238000000409 membrane extraction Methods 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
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- Apparatus Associated With Microorganisms And Enzymes (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a fibrous bed reactor and the equipment and process for extracting separation and coupling production of propionic acid. The invention utilizes an immobilized fibrous bed reactor unit, a membrane separation unit, an extraction and anti-extraction unit and an elution and condensation unit to realize the efficient production of propionic acid. The device has strong feasibility, simple operation, easy realization of automation, immobilized materials, long using life of the membrane and the matching equipment, convenient maintenance and good application prospect. Through extracting separation and coupling production technology, the separation of propionic acid is realized. The invention radically eliminates the feedback inhibition of propionic acid, implements the high density fermentation of propionibacterium and greatly improves the production efficiency of propionic acid through the fermentation method. The extracted water phase is returned to the reactor for recycle after elution and condensation by an elution device, which eliminates the harm of extractant for propionibacterium from the root.
Description
Technical field
The invention belongs to fermentation engineering and separation engineering technical field, relate to the device and the technology of a kind of fibre bed reactor and extracting and separating producing propanoic acid by coupling.
Background technology
Propionic acid is a kind of important fine chemical product and basic chemical raw materials, is widely used in fields such as food, feed, rubber, plastics, paint, coating, spices, medicine, agricultural chemicals, printing.At present to adopt with the oil be the chemical synthesis of raw material to the suitability for industrialized production of propionic acid, and for a long time, because propionic acid manufacturing condition harshness, technical difficulty is big, and China's scale operation of always failing to realize mainly depends on import; On the other hand, because the world petroleum price rising all the way, be that the propionic acid production cost of raw material constantly raises with the oil.In the long run, along with petroleum resources are exhausted day by day, environmental protection requirement is strict day by day, all multifactor production developments that is restricting the oil propionic acid.Therefore, biological process prepares propionic acid technology that is worth exploration beyond doubt.
Owing to reasons such as the propionibacterium growth velocity are slow, the end product feedback inhibition is serious, it is low that the traditional zymotic method is produced the propionic acid productive rate, can't compete with chemical synthesis.In order to improve propionic acid production efficiency, eliminate the propionic acid feedback inhibition, the extractive fermentation method is applied to the fermentation of propionic acid.Yang ST etc. has made up a cover free cell two steps extractive fermentation device, utilizes hollow-fibre membrane to realize the extraction of propionic acid, and propionic acid output reaches 75g/l (production efficiency 0.63g/l/h), is the maximum of present propionic acid output report.Similar with other organic acid extractive fermentation, in the extractive fermentation propionic acid process, extraction agent is an insoluble problem for the toxicity of propionibacterium.Utilize hollow fiber membrane extraction can reduce the influence of extraction agent to fermentation, but along with the carrying out that extracts, still be difficult to avoid because extraction agent toxicity causes production efficiency to reduce, production is extremely disadvantageous to propionic acid for this.Have only a kind of toxic extractive fermentation technology that can fundamentally eliminate extraction agent to propionibacterium of searching, could fundamentally improve the production efficiency and the production stability of propionic acid.Except that extractive fermentation, the immobilization propionibacterium also is used to propionic acid production to improve the output of propionic acid.Studies show that immobilized cell has higher propionic acid of specific ionization cell and organic solvent tolerance.The cover fibre bed reactor that Yang ST etc. make up, propionic acid output reaches 71.8g/l (production efficiency 0.08g/l/h), produce the maximum of propionic acid output for immobilization, similar with other process for fixation, fibre bed reactor method fermenting propionic acid can be to a certain degree the tolerance of raising propionic acid, but the propionic acid increase of production is slow under high density propionic acid condition.In order further to improve propionic acid output, novel propionibacterium immobilization way is explored in the industrialization of realization production of Propionic Acid by Fermentation Process and novel propionic acid extraction and separation technology is imperative.
Summary of the invention
The device and the technology that the objective of the invention is to avoid above-mentioned the deficiencies in the prior art and provide a kind of fibre bed reactor and extracting and separating coupling (FBES) to produce propionic acid.Promptly in a covering device, realize the immobilization fermentation of propionic acid and the ON-LINE SEPARATION of propionic acid.Can fundamentally eliminate the propionic acid feedback inhibition by this cover technology, realize the propionibacterium high density fermentation, avoid the murder by poisoning of extraction agent simultaneously, realize the production of propionic acid propionibacterium.
The object of the invention can reach by following measures:
This device comprises immobilization fibre bed reactor unit, film separation unit, extraction and reextraction unit and elution and condensing unit, the immobilization fibre bed reactor unit mainly is made of reactor 9, filamentary material 8, whipping appts 10-1, pH automatic control device and feed supplement device, wherein filamentary material is fixed in inside reactor as cell immobilization carrier, the pH automatic control device links to each other with reactor 9 with the feed supplement device, whipping appts 10-1 position hangs on reactor 9 inside, and does not contact mutually with filamentary material 8;
The pH automatic control device is by pH probe 7, pH detector 6, constant flow pump 5-1, alkali lye bottle 2, air filter 1-1 and interconnect pipeline and constituted, pH probe 7 is connected on the reactor 9, when pH in the reactor 9 be lower than when controlling pH, in reactor 9, mend to go into alkali lye and control pH automatically by constant flow pump 5-1; The feed supplement device is made of constant flow pump 5-2, feed supplement bottle 3, air filter 1-2 and interconnective pipeline, by constant flow pump 5-2 the substratum in the feed supplement bottle 3 is mended into reactor 9 by the pipeline that is connected on the reactor 9;
Film separation unit is made of membrane module 14, constant flow pump 5-3 and constant flow pump 5-4, tensimeter 12, pressure regulating switch 13 and relevant connection pipeline, after the propionic acid concentration in the reactor 9 reaches 20-60g/l, the fermented liquid in the reactor 9 is pumped in the membrane module 14 that links to each other with reactor 9 by constant flow pump 5-3, and regulate the pressure of pressure regulating switch 13 controlling diaphragm assemblies 14 according to tensimeter 12 readings, seen through liquid by the film of membrane module 14 and pump in the extraction kettle 16 by constant flow pump 5-4;
Above-mentioned extraction and reextraction unit are made of extraction kettle 16, reextraction still 17, strippant reservoir 19, whipping appts 10-2 and 10-3, constant flow pump 5-5,5-6,5-7 and associated pipe, described strippant reservoir 19 and reextraction still 17 are connected by pipeline, by constant flow pump 5-6 strippant (strippant is stored in the strippant reservoir 19) are added reextraction still 17; Film in the extraction kettle 16 sees through liquid gained water (containing a small amount of organic phase) after extracting and pumps into elution and condensing unit through constant flow pump 5-5; Membrane module 14 sees through liquid propionic acid after extraction kettle 16 extractions and enters organic phase, and organic phase obtains propionic acid or Sodium Propionate after entering 17 reextraction of reextraction still.
Above-mentioned elution and condensing unit are made of elutriator 20 and condenser 21, elutriator 20 and condenser 21 are connected by pipeline, extraction back gained water contains a small amount of organic phase in the described extraction kettle 16, water is after elutriator 20 elutions, the organic phase of aqueous phase is returned extraction kettle 16, water enters condenser 21, water inflow reactor 9 after condensation.
Filamentary material 8 in the above-mentioned fibre bed reactor can be vegetable fibre (as gauze, cotton), animal fibre (as wool fabric) or synthon (as polyester piece good).
So-called high density fermentation is meant the high bacteria concentration fermentation that utilizes this method can realize comprising propionibacterium, and dry cell weight is up to 20-45g/l, has remarkable advantages with general free cell culture comparing (dry cell weight is less than 10g/l).
Described membrane module 14 can be inorganic ceramic film or organic membrane.The material of inorganic ceramic film is aluminum oxide or zirconium white, and membrane pore size is 0.1-0.2 μ m; The material of organic membrane is a polyvinylidene difluoride (PVDF).
Described extraction agent and strippant is characterized in that extraction agent selects tertiary amine (preferred trioctylamine or trialkylamine) or quaternary amine (preferred palmityl trimethyl ammonium chloride, methyl trioctylphosphine ammonium chloride or trimethyl ammonium chloride) for use; Thinner is selected oleyl alcohol, kerosene or n-Octanol for use; Strippant is selected sodium-chlor, sodium hydroxide or hydrochloric acid for use.
This production technique is:
Propionibacterium is inoculated in the reactor 9 that seed culture medium is housed in advance and cultivates 12-60h, bacterial strain is adsorbed on the immobilization that realizes bacterial strain on the filamentary material 8, seed liquor in the reactor 9 is replaced with fermention medium, utilize the pH automatic control device to mend fermented liquid pH value in the alkali lye controlling reactor, start whipping appts 10-1 reactor 9 interior materials are fully contacted, realize propionibacterium fermentation productions of ethylformic acid in immobilization fibre bed reactor.
After propionibacterium fermented in immobilization fibre bed reactor, fermented liquid in the reactor 9 filters by membrane module 14 earlier, bacterium produced by free propionic acid in the reactor of being held back by membrane module 14 9 and albumen is trapped Returning reactor 9, while afterfermentation substratum in reactor 9, the film that contains propionic acid sees through liquid to be continued to realize the separating of propionic acid with reextraction unit, elution with condensing unit by extraction successively.
The gained water entered elutriator 20 after above-mentioned film saw through the extraction agent extraction of liquid in extraction kettle 16, the water of aqueous phase forms steam and enters Returning reactor 9 after condenser 21 condensations, the extraction agent that water contains is separated and returns extraction kettle 16, the propionic acid of fermentative production enters organic phase after extraction, the organic phase that contains propionic acid enters reextraction still 17, strippant in reextraction still 17 is stripped, and reclaims the propionic acid in the organic phase.
The used alkali lye of the present invention can be sodium hydroxide or the 3-8mol/l sodium bicarbonate aqueous solution of 3-8mol/l.
Seed liquor of the present invention is a seed culture medium of having inoculated bacterial strain.
Fermented liquid of the present invention is a fermention medium of having inoculated bacterial strain.
Described seed culture medium and fermention medium mainly contained carbon source (in glucose, lactic acid, the glycerine one or more), nitrogenous source (extractum carnis, peptone, yeast extract paste, corn steep liquor, soybean cake powder, cottonseed meal, urea, (NH when the present invention produced propionic acid
4)
2SO
4, NH
4Among the Cl one or more) and inorganic salt (one or more in sylvite, cobalt salt, sodium salt, phosphoric acid salt, dihydrogen phosphate, the hydrochloride, as: SODIUM PHOSPHATE, MONOBASIC).Their ratio can specifically be regulated according to practical situation, and wherein the carbon source of fermention medium (as glucose) add-on is 40～120g/l.
This production technique is specially:
The propionibacterium seed liquor is inoculated in the reactor 9 that the 3L seed culture medium is housed in advance with 5-20% (v/v) inoculum size, temperature 30-37 ℃, rotating speed 0-400r/min, N
2Feeding amount 0.05-0.3L/min (feeding) pH automatic control device control pH from inert gas entrance 4, cultivate 24-48h and realize that the absorption of bacterial strain on filamentary material 8 is with fixing, seed liquor in the reactor 9 is replaced with fermention medium, at initial glucose concentration is under the condition of 50-120g/l, after cultivating 36-100h, fermented liquid pumps into film separation unit by constant flow pump 5-3, under the operating pressure of 0.02-0.10MPa, realize the filtration of propionic fermentation liquid on membrane module 14, held back by membrane module 14 in the albumen Returning reactor 9 of propionibacterium cell in the fermented liquid and fermented liquid, while afterfermentation substratum in reactor 9, the high density fermentation of propionibacterium in the realization response device 9.Film pumps into by constant flow pump 5-4 through liquid and enters extraction kettle 16, after tertiary amine after the thinner dilution or quaternary amine extraction, water and organic phase layering, the water that contains a small amount of extraction agent pumps into elutriator 20 by constant flow pump 5-5, after water formation water vapour enters condenser 21 condensations under 80-110 ℃ the condition, pass through constant flow pump 5-8 Returning reactor 9, a small amount of extraction agent that aqueous phase contains, thinner returns extraction kettle 16, the organic phase that contains propionic acid after extraction enters reextraction still 17, strip through strippant, after the layering, become propionic acid or Sodium Propionate to pump into from propionic acid through constant flow pump 5-7 and reclaim mouthful 18 recovery, organic phase is then returned extraction kettle 16 and is carried out the next batch extraction.
Beneficial effect of the present invention:
1, this device and technology utilization immobilization fibre bed reactor have been realized the efficient absorption of propionibacterium and the efficient fermentation of propionic acid, with general free cell culture comparing, this immobilized cell self has higher production efficiency, reach 0.50g/l/h, the production efficiency (being generally less than 0.25g/l/h) that can reach far above general free cell is for the High-efficient Production of complete assembly is laid a good foundation.
2, this device and process using original position isolation technique (ISPR), free cell can effectively be separated with the fermented liquid that contains propionic acid, fundamentally eliminated the feedback inhibition of propionic acid to propionibacterium, realize the accumulation of free cell in the cell Returning reactor, reach the high density fermentation of propionibacterium, the production efficiency of propionibacterium will be further enhanced, and can reach 1.00-1.25g/l/h.
3, this device and technology utilization water (about 100 ℃) are than organic phase boiling point (greater than 150 ℃) the low characteristics of comparing, the Returning reactor reuse after elutriator elution, cooling of water after the extraction, the utilization elutriator has been realized separating of organic phase and water, fundamentally avoided organic phase to enter reactor and caused murder by poisoning, made organic phase obtain reuse simultaneously thalline.
4, this device and process using extraction kettle and reextraction still combined apparatus, the extraction and the reextraction of propionic acid have been realized, extraction agent and direct the contact extraction efficiency that improved propionic acid of propionic acid through liquid, in the less time (10-15min), just can reach extraction equilibrium, improve the extraction efficiency of propionic acid.
5, this device and technological operation are simple, easily realize automatization, and immobilization material, film and support equipment long service life, convenience for device maintenance have good utilization prospect.
Description of drawings:
Fig. 1 is the apparatus structure synoptic diagram of fibre bed reactor of the present invention and extracting and separating producing propanoic acid by coupling.
Among the figure
1-1,1-2,1-3. air filter, 2. alkali lye bottle, 3. feed supplement bottle, 4. inert gas entrance, 5-1,5-2,5-3,5-4,5-5,5-6,5-7,5-8. constant flow pump, 6.pH detector, 7.pH probe, 8. filamentary material, 9. reactor, 10-1,10-2,10-3. whipping appts, the outlet of 11. tail gas, 12. tensimeter, 13. pressure regulating switch, 14. membrane modules, 15-1,15-2,15-3,15-4. switch, 16. extraction kettle, 17. the reextraction still, 18. propionic acid reclaim mouth, 19. strippant reservoirs, 20. elutriator, 21. condensers
Embodiment
The invention will be further described by the following examples, but to the present invention without limits.
This device mainly is made of immobilization fibre bed reactor unit, film separation unit, extraction and reextraction unit and elution and condensing unit, the immobilization fibre bed reactor unit mainly is made of reactor 9, filamentary material 8, whipping appts 10-1, pH automatic control device and feed supplement device, wherein filamentary material is fixed in inside reactor as cell immobilization carrier, the pH automatic control device links to each other with reactor 9 with the feed supplement device, whipping appts 10-1 position hangs on reactor 9 inside, and does not contact mutually with filamentary material 8; Reactor 9 tops also are provided with an inert gas entrance 4 and a tail gas outlet 11 by pipeline;
The pH automatic control device is by pH probe 7, pH detector 6, constant flow pump 5-1, alkali lye bottle 2, air filter 1-1 and interconnect pipeline and constituted, pH probe 7 is connected on the reactor 9, when pH in the reactor 9 be lower than when controlling pH, in reactor 9, mend to go into alkali lye and control pH automatically by constant flow pump 5-1; The feed supplement device is made of constant flow pump 5-2, feed supplement bottle 3, air filter 1-2 and interconnective pipeline, by constant flow pump 5-2 the substratum in the feed supplement bottle 3 is mended into reactor 9 by the pipeline that is connected on the reactor 9;
Film separation unit is made of membrane module 14, constant flow pump 5-3 and constant flow pump 5-4, tensimeter 12, pressure regulating switch 13 and relevant connection pipeline, after the propionic acid concentration in the reactor 9 reaches 20-60g/l, the fermented liquid in the reactor 9 is pumped in the membrane module 14 that links to each other with reactor 9 by constant flow pump 5-3, and regulate the pressure of pressure regulating switch 13 controlling diaphragm assemblies 14 according to tensimeter 12 readings, seen through liquid by the film of membrane module 14 and pump in the extraction kettle 16 by constant flow pump 5-4;
Above-mentioned extraction and reextraction unit are made of extraction kettle 16, reextraction still 17, strippant reservoir 19, whipping appts 10-2 and 10-3, constant flow pump 5-5,5-6,5-7 and associated pipe, described strippant reservoir 19 and reextraction still 17 are connected by pipeline, by constant flow pump 5-6 strippant (strippant is stored in the strippant reservoir 19) are added reextraction still 17; Film in the extraction kettle 16 sees through liquid gained water (containing a small amount of organic phase) after extracting and pumps into elution and condensing unit through constant flow pump 5-5; Membrane module 14 sees through liquid propionic acid after extraction kettle 16 extractions and enters organic phase, and organic phase obtains propionic acid or Sodium Propionate after entering 17 reextraction of reextraction still.
Above-mentioned elution and condensing unit are made of elutriator 20 and condenser 21, elutriator 20 and condenser 21 are connected by pipeline, extraction back gained water contains a small amount of organic phase in the described extraction kettle 16, water is after elutriator 20 elutions, the organic phase of aqueous phase is returned extraction kettle 16, water enters condenser 21, water inflow reactor 9 after condensation.
On pipeline, be provided with switch 15-1 between condenser 21 and the reactor 9, on pipeline, be provided with switch 15-2 between extraction kettle 16 and the elutriator 20, on pipeline, be provided with switch 15-3 between membrane module 14 and the extraction kettle 16, on pipeline, be provided with switch 15-4 between reextraction still 17 and the strippant reservoir 19.
Below specify implementing procedure:
Embodiment 1
Propionibacterium freudenreichii NX-4 (the Propionibacteriumfreudeenreichii NX-4 that this laboratory is had independent intellectual property right, the patent No.: 200710020579.8, open on October 3rd, 2007) seed liquor is inoculated in the reactor 9 that the 3L seed culture medium is housed in advance with 5% (v/v) inoculum size, 30 ℃ of temperature feed 0.05L/min N from inert gas entrance 4
2, utilize constant flow pump 5-1 in reactor 9, to mend simultaneously and go into 8mol/l aqueous sodium hydroxide solution control pH 6.0, leave standstill and cultivate the absorption of 48h realization bacterial strain on vegetable fibre (gauze) 8 with fixing.Seed liquor in the reactor 9 is replaced with fermention medium, initial pH is 6.9, utilize constant flow pump 5-1 to mend in reactor 9 and go into 8mol/l aqueous sodium hydroxide solution control pH 6.0, initial glucose concentration 50g/l is that glucose is added in the fermention medium, feeds 0.1L/min N
2, 30 ℃ of culture temperature leave standstill and cultivate 70h, propionic acid output 17.5g/l, and production efficiency reaches 0.25g/l/h.
Embodiment 2
Propionibacterium freudenreichii NX-4 seed liquor is equipped with in the reactor 9 of 3L seed culture medium in advance with the inoculum size access of 10% (v/v), and 35 ℃ of temperature feed 0.2L/min N
2, utilize whipping appts 10-1 to stir (rotating speed 200r/min), utilize constant flow pump 5-1 to mend simultaneously into 3mol/l aqueous sodium hydroxide solution control pH 6.0, cultivate 36h and realize cell fixing on vegetable fibre 8 (cotton).Seed liquor in the reactor 9 is replaced with fermention medium, and initial pH is 6.9, utilizes constant flow pump 5-1 to mend into 3mol/l aqueous sodium hydroxide solution control pH 6.0 simultaneously, initial glucose concentration 120g/l, and 35 ℃ of temperature feed 0.2L/min N
2, utilize whipping appts 10-1 to stir (rotating speed 200r/min), fermentation 150h, propionic acid output 57.5g/l, production efficiency reaches 0.38g/l/h.
Propionibacterium freudenreichii NX-4 seed liquor is equipped with in the reactor 9 of 3L seed culture medium in advance with the inoculum size access of 15% (v/v), and 37 ℃ of temperature feed 0.3L/min N from inert gas entrance 4
2, utilize whipping appts 10-1 to stir (rotating speed 400r/min), utilize constant flow pump 5-1 in reactor 9, to mend simultaneously and go into 5mol/l sodium bicarbonate aqueous solution control pH 6.0, cultivate 30h and realize cell fixing on animal fibre (wool fabric) 8.Seed liquor in the reactor 9 is replaced with fermention medium, and initial pH is 6.9,, utilize constant flow pump 5-1 to mend simultaneously into 5mol/l sodium bicarbonate aqueous solution control pH 6.0, initial glucose concentration 80g/l feeds 0.1L/min N from inert gas entrance 4
2Utilize whipping appts 10-1 to stir (rotating speed 400r/min), after cultivating 80h, fermented liquid utilizes constant flow pump 5-3 to pump into membrane module 14 (the aluminum oxide inorganic ceramic film of 0.2 μ m) at 0.02MPa, filter under 37 ℃ of conditions, free cell and Partial Protein in the reactor of being held back by membrane module 14 9 are trapped Returning reactor 9, utilize constant flow pump 5-2 that the fermention medium in the feed supplement bottle 3 is mended (glucose concn 80g/l) in the reactor 9 simultaneously, realize the high density fermentation of propionibacterium in reactor 9, propionic acid production efficiency increases gradually, batch production time reduces gradually, through 10 batches of fermentations (total time 470h), propionic acid accumulative total concentration reaches 385g/l, production efficiency reaches 0.82g/l/h, and wherein the dry cell weight in the reactor 9 is finally up to 23.3g/l.
Propionibacterium freudenreichii NX-4 seed liquor is equipped with in the reactor of 3L seed culture medium in advance with the inoculum size access of 20% (v/v), and 35 ℃ of temperature feed 0.15L/min N
2, utilize whipping appts 10-1 to stir (rotating speed 200r/min), sodium bicarbonate aqueous solution control pH 6.0 cultivates 24h and realizes cell fixing on animal fibre (wool fabric) 8.Seed liquor in the reactor 9 is replaced with fermention medium, and initial pH is 6.9,, utilize constant flow pump 5-1 to mend simultaneously into 4mol/l sodium bicarbonate aqueous solution control pH 6.0, initial glucose concentration 80g/l feeds 0.1L/min N
2Utilize whipping appts 10-1 to stir (rotating speed 200r/min), after cultivating 72h, fermented liquid utilizes constant flow pump 5-3 to pump into membrane module 14 (the polyvinylidene difluoride (PVDF) hollow fiber microfiltration membrane of 0.1 μ m) at 0.10MPa, filter under 35 ℃ of conditions, free cell and Partial Protein in the reactor of being held back by membrane module 14 9 are trapped Returning reactor 9, utilize constant flow pump 5-2 that the fermention medium in the feed supplement bottle 3 is mended (glucose concn 80g/l) in the reactor 9 simultaneously, realize the high density fermentation of propionibacterium in reactor 9, propionic acid production efficiency increases gradually, batch production time reduces gradually, through 10 batches of fermentations (405h), propionic acid accumulative total concentration reaches 394g/l, production efficiency reaches 0.97g/l/h, and wherein the dry cell weight in the reactor 9 is finally up to 30.5g/l.
Embodiment 5
Propionibacterium freudenreichii NX-4 seed liquor is equipped with in the reactor of 3L seed culture medium in advance with the inoculum size access of 15% (v/v), and 33 ℃ of temperature feed 0.25L/min N
2, utilize whipping appts 10-1 to stir (rotating speed 100r/min), aqueous sodium hydroxide solution control pH 6.0 cultivates 28h and realizes cell fixing on synthon (polyester piece good) 8.Seed liquor in the reactor 9 is replaced with fermention medium, and initial pH is 6.9, utilizes constant flow pump 5-1 to mend into 4mol/l aqueous sodium hydroxide solution control pH 6.0 simultaneously, and initial glucose concentration 80/l feeds 0.25L/min N
2Utilize whipping appts 10-1 to stir (rotating speed 200r/min), after cultivating 75h, fermented liquid utilizes constant flow pump 5-3 to pump into membrane module 14 (the polyvinylidene difluoride (PVDF) hollow fiber microfiltration membrane of 0.2 μ m) at 0.04MPa, filter under 35 ℃ of conditions, free cell and Partial Protein in the reactor of being held back by membrane module 14 9 are trapped Returning reactor 9, utilize constant flow pump 5-2 that the fermention medium in the feed supplement bottle 3 is mended the high density fermentation of (glucose concn 80g/l) realization propionibacterium in reactor 9 in the reactor 9 simultaneously, see through liquid and enter extraction kettle 16, utilize 40% trialkylamine+60% n-Octanol (v/v) extraction through the propionic acid in the liquid (the not reuse of extraction residue water), organic phase after the extraction enters reextraction still 17, propionic acid in the organic phase generates Sodium Propionate via constant flow pump 5-6 pumps into reextraction still 17 from strippant holder 19 sodium-chlor reextraction back, and recovery obtains extraction agent and is used for extracting next time.Propionic acid production efficiency increases gradually, and a batch production time reduces gradually, and through 10 batches of fermentations and extraction/reextraction (395h), propionic acid accumulative total concentration reaches 393g/l, and production efficiency reaches 0.99g/l/h, and wherein the dry cell weight in the reactor 9 is finally up to 32.8g/l.
Embodiment 6
Propionibacterium freudenreichii NX-4 seed liquor is equipped with in the reactor of 3L seed culture medium in advance with the inoculum size access of 10% (v/v), and 35 ℃ of temperature feed 0.20L/min N
2, utilize whipping appts 10-1 to stir (rotating speed 150r/min), aqueous sodium hydroxide solution control pH 6.0 cultivates 36h and realizes cell fixing on animal fibre (wool fabric) 8.Seed liquor in the reactor 9 is replaced with fermention medium, and initial pH is 6.9, utilizes constant flow pump 5-1 to mend into 5mol/l aqueous sodium hydroxide solution control pH 6.0 simultaneously, and initial glucose concentration 100g/l feeds 0.20L/min N
2Utilize whipping appts 10-1 to stir (rotating speed 150r/min), after cultivating 85h, fermented liquid utilizes constant flow pump 5-3 to pump into membrane module 14 (the aluminum oxide inorganic ceramic film of 0.1 μ m) at 0.08MPa, filter under 35 ℃ of conditions, free cell and Partial Protein in the reactor of being held back by membrane module 14 9 are trapped Returning reactor 9, utilize constant flow pump 5-2 that the fermention medium in the feed supplement bottle 3 is mended the high density fermentation of (initial sugared concentration 100g/l) realization propionibacterium in reactor 9 in the reactor 9 simultaneously, see through liquid and enter extraction kettle 16, utilize 40% palmityl trimethyl ammonium chloride+60% kerosene (v/v) extraction through the propionic acid in the liquid (the not reuse of extraction residue water), organic phase after the extraction enters reextraction still 17, propionic acid in the organic phase becomes Sodium Propionate via constant flow pump 5-6 pumps into reextraction still 17 from strippant holder 19 sodium hydroxide reextraction back, and recovery obtains extraction agent and is used for extracting next time.Through 10 batches of fermentations and extraction/reextraction (480h), propionic acid accumulative total concentration reaches 500g/l, and production efficiency reaches 1.04g/l/h, and wherein the dry cell weight in the reactor 9 is finally up to 34.5g/l.
Embodiment 7
Propionibacterium freudenreichii NX-4 seed liquor is equipped with in the reactor of 3L seed culture medium in advance with the inoculum size access of 15% (v/v), and 33 ℃ of temperature feed 0.10L/min N
2, utilize whipping appts 10-1 to stir (rotating speed 300r/min), aqueous sodium hydroxide solution control pH 6.0 cultivates 30h and realizes cell fixing on synthon (polyester piece good) 8.Seed liquor in the reactor 9 is replaced with fermention medium, and initial pH is 6.9, utilizes constant flow pump 5-1 to mend into 8mol/l aqueous sodium hydroxide solution control pH 6.0 simultaneously, and initial glucose concentration 100g/l feeds 0.15L/min N
2Utilize whipping appts 10-1 to stir (rotating speed 300r/min), after cultivating 80h, fermented liquid utilizes constant flow pump 5-3 to pump into membrane module 14 (the zirconium white inorganic ceramic film of 0.2 μ m) at 0.06MPa, filter under 33 ℃ of conditions, free cell and Partial Protein in the reactor of being held back by membrane module 14 9 are trapped Returning reactor 9, utilize constant flow pump 5-2 that the fermention medium in the feed supplement bottle 3 is mended the high density fermentation of (glucose concn 100g/l) realization propionibacterium in reactor 9 in the reactor 9 simultaneously, see through liquid and enter extraction kettle 16, utilize 50% methyl trioctylphosphine ammonium chloride+50% oleyl alcohol (v/v) extraction to see through the propionic acid in the liquid, extraction residue water is through elutriator 20 elutions (80 ℃), and after condenser 21 condensations, pump into reuse in the reactor 9 by constant flow pump 5-8.Propionic acid in the organic phase pumps into reextraction still 17 via constant flow pump 5-6 and obtains separating after hydrochloric acid is stripped from strippant holder 19, recovery obtains extraction agent and is used for extracting next time.Through 10 batches of fermentations and extraction/reextraction (340h), propionic acid accumulative total concentration reaches 504g/l, and production efficiency reaches 1.48g/l/h, and wherein the dry cell weight in the reactor 9 is finally up to 34.5g/l.
Embodiment 8
Propionibacterium freudenreichii NX-4 seed liquor is equipped with in the reactor of 3L seed culture medium in advance with the inoculum size access of 15% (v/v), and 35 ℃ of temperature feed 0.15L/min N
2, utilize whipping appts 10-1 to stir (rotating speed 100r/min), utilize constant flow pump 5-1 to mend simultaneously into 8mol/l aqueous sodium hydroxide solution control pH 6.0, cultivate 32h and realize cell fixing on synthon (polyester piece good) 8.Seed liquor in the reactor 9 is replaced with fermention medium, and initial pH is 6.9, utilizes constant flow pump 5-1 to mend into 8mol/l aqueous sodium hydroxide solution control pH 6.0 simultaneously, and initial glucose concentration 100g/l feeds 0.15L/min N
2Utilize whipping appts 10-1 to stir (rotating speed 100r/min), after cultivating 80h, fermented liquid utilizes constant flow pump 5-3 to pump into membrane module 14 (the zirconium white inorganic ceramic film of 0.1 μ m) at 0.04MPa, filter under 35 ℃ of conditions, free cell and Partial Protein in the reactor of being held back by membrane module 14 9 are trapped Returning reactor 9, utilize constant flow pump 5-2 that the fermention medium in the feed supplement bottle 3 is mended the high density fermentation of (glucose concn 100g/l) realization propionibacterium in reactor 9 in the reactor 9 simultaneously, see through liquid and enter extraction kettle 16, utilize 60% trimethyl ammonium chloride+40% kerosene (v/v) extraction to see through the propionic acid in the liquid, extraction residue water is through elutriator 20 elutions (110 ℃), and after condenser 21 condensations, pump into reuse in the reactor 9 by constant flow pump 5-8.Propionic acid in the organic phase pumps into reextraction still 17 via constant flow pump 5-6 and become Sodium Propionate after sodium-chlor is stripped from strippant holder 19, recovery obtains extraction agent and is used for extracting next time.Through 10 batches of fermentations and extraction/reextraction (352h), propionic acid accumulative total concentration reaches 497g/l, and production efficiency reaches 1.41g/l/h, and wherein the dry cell weight in the reactor 9 is finally up to 33.7g/l.
Claims (10)
1. the device of fibre bed reactor and extracting and separating producing propanoic acid by coupling comprises immobilization fibre bed reactor unit, film separation unit, extraction and reextraction unit and elution and condensing unit, it is characterized in that:
Described immobilization fibre bed reactor unit mainly is made of reactor (9), filamentary material (8), whipping appts (10-1), pH automatic control device and feed supplement device, wherein filamentary material (8) is fixed in reactor (9) inside as cell immobilization carrier, the pH automatic control device links to each other with reactor (9) with the feed supplement device, and whipping appts (10-1) hangs on reactor (9) inside;
Described film separation unit mainly is made of membrane module (14), constant flow pump (5-3) and constant flow pump (5-4), tensimeter (12), pressure regulating switch (13) and connecting pipeline, after the propionic acid concentration in the reactor (9) reaches 20-60g/l, the fermented liquid in the reactor (9) is pumped in the membrane module (14) that links to each other with reactor (9) by constant flow pump (5-3), and regulate the pressure of pressure regulating switch (13) controlling diaphragm assembly (14) according to tensimeter (12) reading, see through liquid through the film of membrane module (14) and pump in the extraction kettle (16) by constant flow pump (5-4);
Described extraction and reextraction unit are mainly by extraction kettle (16), reextraction still (17), strippant reservoir (19), whipping appts (10-2) and (10-3), constant flow pump (5-5), constant flow pump (5-6), constant flow pump (5-7) and associated pipe constitute, described strippant reservoir (19) is connected by pipeline with reextraction still (17), by constant flow pump (5-6) strippant in the strippant reservoir (19) is added in the reextraction still (17); Film in the extraction kettle (16) sees through liquid gained water after extracting and pumps into elution and condensing unit through constant flow pump (5-5);
Described elution and condensing unit mainly are made of elutriator (20) and condenser (21), elutriator (20) is connected by pipeline with condenser (21), extraction back gained water contains a small amount of organic phase in the described extraction kettle (16), water is after elutriator (20) elution, the organic phase of aqueous phase is returned extraction kettle (16), water enters condenser (21), water inflow reactor (9) after condensation.
2. the device of fibre bed reactor according to claim 1 and extracting and separating producing propanoic acid by coupling, it is characterized in that: described pH automatic control device is by pH probe (7), pH detector (6), constant flow pump (5-1), alkali lye bottle (2), air filter (1-1) and interconnect pipeline and constituted, pH probe (7) is connected on the reactor (9), when pH in the reactor (9) be lower than when controlling pH, mend alkali lye by constant flow pump (5-1) to reactor (9).
3. the device of fibre bed reactor according to claim 1 and extracting and separating producing propanoic acid by coupling, it is characterized in that: described feed supplement device is made of constant flow pump (5-2), feed supplement bottle (3), air filter (1-2) and interconnective pipeline, by constant flow pump (5-2) substratum in the feed supplement bottle (3) is mended into reactor (9) by the pipeline that is connected on the reactor (9).
4. the device of fibre bed reactor according to claim 1 and extracting and separating producing propanoic acid by coupling is characterized in that described filamentary material is vegetable fibre, animal fibre or synthon.
5. the device of fibre bed reactor according to claim 1 and extracting and separating producing propanoic acid by coupling is characterized in that described membrane module (14) material therefor is inorganic ceramic film and organic membrane.
6. the device of fibre bed reactor according to claim 5 and extracting and separating producing propanoic acid by coupling, the material that it is characterized in that described inorganic ceramic film is aluminum oxide or zirconium white, membrane pore size is 0.1-0.2 μ m; The material of organic membrane is a polyvinylidene difluoride (PVDF).
7. one kind is utilized claim 1, the device of 2 or 3 described fibre bed reactors and extracting and separating producing propanoic acid by coupling is produced the technology of propionic acid, it is characterized in that propionibacterium ferments in immobilization fibre bed reactor after, fermented liquid in the reactor (9) filters by membrane module (14) earlier, bacterium produced by free propionic acid in the fermented liquid and albumen is held back Returning reactor (9) by membrane module (14), while afterfermentation substratum in reactor (9), the film that contains propionic acid sees through liquid to be continued successively by extraction and reextraction unit, elution realizes separating of propionic acid with condensing unit.
8. technology according to claim 7, the gained water enters elutriator (20) after it is characterized in that seeing through liquid by described film extraction agent extracting through extraction kettle (16) in, the water of aqueous phase forms steam and enters Returning reactor (9) after condenser (21) condensation, the extraction agent that water contains is separated and returns extraction kettle (16), the propionic acid of fermentative production enters organic phase after extraction, the organic phase that contains propionic acid enters reextraction still (17), after strippant in reextraction still (17) is stripped, reclaim and obtain propionic acid.
9. technology according to claim 7 is characterized in that extraction agent is tertiary amine or the quaternary amine after the thinner dilution; Strippant is selected sodium-chlor, sodium hydroxide or hydrochloric acid for use.
10. technology according to claim 9 is characterized in that described thinner is oleyl alcohol, kerosene or n-Octanol; Tertiary amine is trioctylamine or trialkylamine, and quaternary amine is palmityl trimethyl ammonium chloride, methyl trioctylphosphine ammonium chloride or trimethyl ammonium chloride.
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