CN107794219A - A kind of bioreactor for fermentation of gaseous substrates - Google Patents
A kind of bioreactor for fermentation of gaseous substrates Download PDFInfo
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- CN107794219A CN107794219A CN201610780231.8A CN201610780231A CN107794219A CN 107794219 A CN107794219 A CN 107794219A CN 201610780231 A CN201610780231 A CN 201610780231A CN 107794219 A CN107794219 A CN 107794219A
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- film
- fermentation
- bioreactor
- membrane module
- gas
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- 238000000855 fermentation Methods 0.000 title claims abstract description 161
- 230000004151 fermentation Effects 0.000 title claims abstract description 156
- 239000000758 substrate Substances 0.000 title claims abstract description 20
- 239000012528 membrane Substances 0.000 claims abstract description 101
- 210000004534 cecum Anatomy 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims description 27
- 238000010899 nucleation Methods 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000003034 coal gas Substances 0.000 claims description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 15
- 239000012530 fluid Substances 0.000 claims description 15
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- 239000006052 feed supplement Substances 0.000 claims description 10
- 230000002401 inhibitory effect Effects 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000001963 growth medium Substances 0.000 claims description 9
- 241000589516 Pseudomonas Species 0.000 claims description 8
- 230000019522 cellular metabolic process Effects 0.000 claims description 8
- 241000589220 Acetobacter Species 0.000 claims description 7
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- 238000001471 micro-filtration Methods 0.000 claims description 7
- 244000005700 microbiome Species 0.000 claims description 7
- 239000003002 pH adjusting agent Substances 0.000 claims description 7
- 230000029219 regulation of pH Effects 0.000 claims description 7
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims description 6
- 235000011054 acetic acid Nutrition 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
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- 241000588807 Bordetella Species 0.000 claims description 4
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- 241001223493 Acetoanaerobium noterae Species 0.000 claims description 3
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- 239000005711 Benzoic acid Substances 0.000 claims description 3
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- 241000205142 Desulfobacterium autotrophicum Species 0.000 claims description 3
- 241000186394 Eubacterium Species 0.000 claims description 3
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 241000204649 Thermoanaerobacter kivui Species 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 235000015097 nutrients Nutrition 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- 229940107700 pyruvic acid Drugs 0.000 claims description 3
- 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 description 3
- 229940005605 valeric acid Drugs 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 241000193830 Bacillus <bacterium> Species 0.000 claims description 2
- 239000000571 coke Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000013589 supplement Substances 0.000 claims description 2
- 235000009499 Vanilla fragrans Nutrition 0.000 claims 1
- 244000263375 Vanilla tahitensis Species 0.000 claims 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 78
- 239000007788 liquid Substances 0.000 description 19
- 239000000306 component Substances 0.000 description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 5
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- 239000005695 Ammonium acetate Substances 0.000 description 4
- 235000019257 ammonium acetate Nutrition 0.000 description 4
- 229940043376 ammonium acetate Drugs 0.000 description 4
- BQJCRHHNABKAKU-KBQPJGBKSA-N morphine Chemical compound O([C@H]1[C@H](C=C[C@H]23)O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4O BQJCRHHNABKAKU-KBQPJGBKSA-N 0.000 description 4
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 239000012510 hollow fiber Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012549 training Methods 0.000 description 3
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 241001052560 Thallis Species 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 229940041514 candida albicans extract Drugs 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- 229960005181 morphine Drugs 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 0.000 description 2
- TUUBOHWZSQXCSW-UHFFFAOYSA-N vanillic acid Natural products COC1=CC(O)=CC(C(O)=O)=C1 TUUBOHWZSQXCSW-UHFFFAOYSA-N 0.000 description 2
- 239000012138 yeast extract Substances 0.000 description 2
- 241001464894 Blautia producta Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 241000194017 Streptococcus Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229940091250 magnesium supplement Drugs 0.000 description 1
- 239000012533 medium component Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002101 nanobubble Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M29/00—Means for introduction, extraction or recirculation of materials, e.g. pumps
- C12M29/04—Filters; Permeable or porous membranes or plates, e.g. dialysis
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M27/00—Means for mixing, agitating or circulating fluids in the vessel
- C12M27/02—Stirrer or mobile mixing elements
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M27/00—Means for mixing, agitating or circulating fluids in the vessel
- C12M27/18—Flow directing inserts
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M29/00—Means for introduction, extraction or recirculation of materials, e.g. pumps
- C12M29/24—Recirculation of gas
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M41/00—Means for regulation, monitoring, measurement or control, e.g. flow regulation
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M41/00—Means for regulation, monitoring, measurement or control, e.g. flow regulation
- C12M41/26—Means for regulation, monitoring, measurement or control, e.g. flow regulation of pH
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
Abstract
The present invention relates to a kind of bioreactor for fermentation of gaseous substrates.Specifically, bioreactor of the invention includes (1) fermentation tank；(2) membrane module being placed in fermentation tank；Wherein, the membrane module includes film and the connecting pipe for being used to make film connect with exterior line positioned at one end of the film；Wherein, the other end of film is cecum.Present invention additionally comprises the Zymolysis Equipment of the bioreactor, and the method fermented using the bioreactor and Zymolysis Equipment.The present invention can efficiently generate tunning from closing Synthesis gas fermentation system, and continuously isolate tunning, it is therefore prevented that Product inhibiton.
Description
Technical field
The invention belongs to biotechnology equipment and microbiological art.More particularly it relates to a kind of be used to synthesize
The bioreactor of gas fermentation.
Background technology
Traditional batch culture fermentations process, because the metabolite of cell has inhibitory action to cell, as metabolism is produced
The accumulation of thing, the specific growth rate of cell will be gradually reduced.Therefore, thalline just stops breeding to a certain extent for fermentation progress.
This area still needs during the fermentation, under conditions of microbial activity is not influenceed, will suppress thalli growth
Target product or metabolic by-product original position are separated, and make thalline fast-growth to very high concentration, and keep fermentation process
It is carried out continuously, improves target product yield.
The content of the invention
The present invention provides a kind of the synthesis gas fermenting organism reactor and its component of the separation of high-efficiency fermenting and product, especially
Membrane module.
Specifically, membrane module of the invention includes：
Film；With
Connecting pipe positioned at one end of the film, for making film be connected with exterior line；
Wherein, the other end of film is cecum.
In one or more embodiments, the film is organic film, ceramic membrane or metal film.
In one or more embodiments, the structure of the film is tubular type, board-like or rolling.
In one or more embodiments, the film is milipore filter or microfiltration membranes.
In one or more embodiments, the film is hollow fiber form milipore filter or microfiltration membranes.
In one or more embodiments, the other end of the film is sealed using fixed seal head, forms the cecum.
In one or more embodiments, the membrane module includes more than 2, such as 2~20 films in parallel, each film
One end is cecum, and the other end each includes being used to make the connecting pipe that film connects with exterior line.
It is described to contain in more than 2, such as the membrane module of 2~20 films in parallel in one or more embodiments, warp
Each film is fixed on symmetrical position by fixture.
The bioreactor of the present invention includes：
(1) fermentation tank；With
(2) membrane module being placed in fermentation tank；
Wherein, the membrane module includes：
Film；With
Connecting pipe positioned at one end of the film, for making film be connected with exterior line；
Wherein, the other end of film is cecum.
In one or more embodiments, the film is organic film, ceramic membrane or metal film.
In one or more embodiments, the structure of the film is tubular type, board-like or rolling.
In one or more embodiments, the film is milipore filter or microfiltration membranes.
In one or more embodiments, the film is hollow fiber form milipore filter or microfiltration membranes.
In one or more embodiments, the other end of the film is sealed using fixed seal head, forms the cecum.
In one or more embodiments, the membrane module includes more than 2, such as 2~20 films in parallel, each film
One end is cecum, and the other end each includes being used to make the connecting pipe that film connects with exterior line.
It is described to contain in more than 2, such as the membrane module of 2~20 films in parallel in one or more embodiments, warp
Each film is fixed on symmetrical position by fixture.
In one or more embodiments, the film is releasably secured together with the connecting pipe.
In one or more embodiments, the bioreactor also includes the bubble generator being placed in fermentation tank.
In one or more embodiments, the bubble generator is located at fermenter base, and quantity is 1~8.
In one or more embodiments, the bubble generator be porous venturi-type, online mixer formula or
Vortex bubble generator.
In one or more embodiments, the bioreactor also includes the guide shell being placed in fermentation tank.
In one or more embodiments, the membrane module, which is located at, to be placed in the guide shell in fermentation tank.
In one or more embodiments, there is stationary grizzly in the guide shell, for fixing the membrane module.
In one or more embodiments, the membrane module is detachably fixed with the guide shell, or is used in membrane module
It is integrally formed in the component of fixed film with the guide shell.
In one or more embodiments, the membrane module is placed in the middle and lower part of the guide shell.
In one or more embodiments, there is through hole on the water conservancy diversion barrel, to allow to connect membrane module and outside
The pipeline of equipment passes through.
In one or more embodiments, there is through hole in the fermentor walls, to allow to connect membrane module and outside
The pipeline of equipment passes through.
In one or more embodiments, the pipeline for connecting membrane module and external equipment is via fermentation cover and outside
Portion's equipment connection.
In one or more embodiments, triple valve is set on the part outside the pipeline fermentation tank.
In one or more embodiments, the bubble generator is arranged to inside guide shell.
In one or more embodiments, the fermentation tank is stirred type or gas lift type fermentation tank.
In one or more embodiments, the fermentation tank also include seed liquor import, gas access, gas vent,
PH adjusting agent entrance and culture medium import.
In one or more embodiments, the bioreactor includes：Fermentation tank and the bubble being placed in fermentation tank
Generator, membrane module and guide shell；Wherein, the bubble generator quantity is 1~8, positioned at fermenter base；The film group
Part has more than 2, such as 2~20 films, is distributed on inside the guide shell, and the film bottom is cecum, and top has
For the connecting pipe connected with exterior line.
The present invention also provides a kind of Zymolysis Equipment, and the Zymolysis Equipment includes：
(1) bioreactor as described herein；With
(2) feeder.
In one or more embodiments, it is cold that the feeder includes coal gas surge tank, gas compressor and gas
But device.
In one or more embodiments, the equipment also includes seeding tank, the seeding tank and gas cooler and
Bioreactor connects, for providing seed liquor to bioreactor.
In one or more embodiments, the air-turbocooler provides gas to seeding tank, and via biological respinse
Device bottom and via the membrane module to the fermentation tank provide gas.
In one or more embodiments, the equipment also includes circulating fan, for that will come from seeding tank and biology
The gas circulation of reactor is into seeding tank or bioreactor.
In one or more embodiments, the equipment also includes pH regulation tanks, for the culture to bioreactor
Liquid provides the reagent for adjusting its pH.
In one or more embodiments, the equipment also includes feed supplement tank, is fermented for being added to bioreactor
Liquid.
In one or more embodiments, the equipment also includes measuring pump, for seed liquor, pH adjusting agent or training
It is added to after supporting base metering in bioreactor.
In one or more embodiments, the equipment also includes product reservoir, via the triple valve and the film
Component is connected.
The present invention also provides a kind of fermentation process, bioreactor or Zymolysis Equipment of the methods described including the use of the present invention
The step of fermentative microorganism.
In one or more embodiments, fermentation substrate is used as using coke-stove gas.
In one or more embodiments, the bioreactor or the process fermented of Zymolysis Equipment of the present invention are used
In, the coke-stove gas as fermentation substrate is passed through via the membrane module, and filter out cell growth via the membrane module to have
The products of cellular metabolism of inhibitory action.
In one or more embodiments, the products of cellular metabolism that the cell growth has inhibitory action includes：First
Acid, acetic acid, propionic acid, butyric acid, isobutyric acid, succinic acid, lactic acid, pyruvic acid, malic acid, citric acid, benzoic acid, vanillic acid, caproic acid,
Valeric acid, or the combination of they two or more.
In one or more embodiments, when cell growth has the products of cellular metabolism of inhibitory action in fermentation tank
When concentration reaches 1% or more, stop being passed through coke-stove gas via the membrane module, then filtered out to cell by the membrane module
Growth has the products of cellular metabolism of inhibitory action.
In one or more embodiments, the pressure in fermentation tank is in the range of 0~2MPa.
In one or more embodiments, fermentation tank exit gas is circulated, and recycle ratio is 2~10.
In one or more embodiments, membrane module is rotated and switches out liquid and ventilating mode.
In one or more embodiments, the fermentative microorganism is selected from：Fusobacterium (such as Clostridium
Ljungdahlii), Moore Bordetella (such as Moorella thermoacetica), Pyrococcus (such as Pyrococcus
Furiosus), Eubacterium (such as Eubacterium limosum), Desulfobacter (such as Desulfobacterium
Autotrophicum), the thermophilic Pseudomonas of carbonoxide (such as Carboxydothermus hydrogenoformans), production acetobacter
(such as Acetogenium kivui), acetobacter (such as Acetobacterium woodii), anaerobism acetobacter are (such as
Acetoanaerobium noterae), Butyribacterium (such as Butyribaceterium methylotrophicum), digestion
Streptococcus (such as Peptostreptococcus productus) and Raul's formula Pseudomonas (such as Ralstonia eutropha).
In one or more embodiments, the pH value of fermentation culture is 6.0-8.0.
In one or more embodiments, fermentation temperature is 25-75 DEG C.
Other aspects of the present invention are apparent to those skilled in the art due to this disclosure
's.
Brief description of the drawings
Fig. 1 is the structure chart of synthesis gas bioreactor 10, including：11, ferment tank；21, membrane module；31,
Guide shell；41, air inlet pipe；51, film connecting tube；61, stationary grizzly；71, bubble generator.
Fig. 2 is the structure chart of single membrane module, and composition includes：210, film；61, stationary grizzly；51, film connecting tube；220,
Connector；230, fixed seal head.
Fig. 3 is that synthesis gas is fermentation substrate, and anaerobe realizes fermentation, product isolation integral in bioreactor
The process chart of fermentation process.Device includes：1, coal gas surge tank；2, gas compressor；3, air-turbocooler；4, circulated air
Machine；5, seeding tank；6, pH regulation tanks；7, feed supplement tank；8, product reservoir；9, measuring pump；10, bioreactor.
Embodiment
It is contemplated that improving fermentation of gaseous substrates particularly contains CO, H2And CO2Coke-stove gas substrate microbial fermentation
Efficiency, and realize the separation for realizing product during the fermentation.The present invention can efficiently give birth to from closing Synthesis gas fermentation system
Into tunning, and continuously isolate tunning, it is therefore prevented that Product inhibiton.
By using provided herein is bioreactor and Zymolysis Equipment realize this paper each side purposes.
The bioreactor of the present invention includes：
(1) fermentation tank；With
(2) membrane module being placed in fermentation tank；
Wherein, the membrane module includes：
Film；With
Connecting pipe positioned at one end of the film, for making film be connected with exterior line；
Wherein, the other end of film is cecum.
In certain embodiments, bioreactor of the invention is fermentation tank.
There can be the tank body of conventional fermentation tank suitable for the fermentation tank of the present invention, and phase is made according to the requirement of the present invention
The structural modification answered.For example, fermentation tank can have the tank body of conventional stirred type or gas lift type fermentation tank.Generally, fermentation tank
Including tank body, cover and corresponding outlet and entrance, such as gas access, gas vent, zymotic fluid (culture medium) entrance, seed
Liquid entrance, pH adjusting agent entrance etc..
Membrane module is usually located at the middle and lower part of fermentation tank.Film in membrane module can be commonly used in the art in separation and fermentation production
The various films of thing, including but not limited to organic film, ceramic membrane or metal film, its structure can be tubular type, board-like or rolling.Film
Can be milipore filter or microfiltration membranes.In certain embodiments, film is hollow fiber form milipore filter or microfiltration membranes.In some implementations
In scheme, the average pore size of film is in the range of 4~100nm, such as in the range of 30~70nm.The diameter of film can 2~
In the range of 10cm, such as 2~7cm.The height of film can be the 1/6~2/3 of fermentation tank height, such as 1/6 to 1/3.Generally, film
Component should be under the liquid level of zymotic fluid.The diameter and height of film can be determined according to the volume etc. of the quantity of film in membrane module, fermentation tank
Degree etc..
In the present invention, one end of film is cecum, and generally usable fixed seal head is sealed.The other end of film is fixed with company
Jointed tubular workpieces, for making film be connected with exterior line.Connecting pipe can have any appropriate structure, and removably connect with film
Connect.For example, connecting pipe can have pedestal, for fixing (such as banding) film, and the pipe fitting to be extended out from the pedestal.
Fig. 2 shows an example of inventive film component, including film 210, connecting pipe 220 and fixed seal head 230.
The membrane module may include more than 2, such as 2~20 (such as 2~15,2~10,2~8) are in parallel
Film, each film one end are cecum, and the other end each includes being used to make the connecting pipe that film connects with exterior line.The quantity of film can
Determined according to the capacity of fermentation tank.In this kind of membrane module, each film can be fixed up via fixture, be preferably integrally fixed at relative
On the position of title.For example, each fixed seal head can be together in series by fixture, or the pedestal of each connecting pipe is together in series.
Herein, it is equal to refer to the mutual air line distance of film for the symmetrical position.For example, in the case where using 3 films, from
Seen on cross section, 3 films are located at three summits of equilateral triangle respectively.Generally, nothing outside the film in membrane module of the invention
The structure of shell etc.
The connecting pipe of film can connect with exterior line.The exterior line is often referred to other pipeline knots beyond membrane module
Structure.There can be through hole on tank body or cover, to allow exterior line to may pass through the tank body of fermentation tank, or the tank through fermentation tank
Cover and connected with external equipment.Or also the connecting pipe can be designed to long enough, so as to pass through tank by the connecting pipe
Body or cover, then be connected with exterior line.
Guide shell can be provided with fermentation tank.Guide shell two open ends, fermenter base can be placed in.Now, membrane module leads to
It is frequently located in guide shell, and is usually located at the middle and lower part of guide shell.Grid can be set on the inwall of guide shell, for fixing film group
Part.Generally, the thickness of water conservancy diversion barrel is no more than 1cm.The external diameter of guide shell is between fermentation tank internal diameter 1/3 to 2/3.Guide shell
The height of fermentation tank is highly should not exceed, usually between 2/3 to the 3/4 of fermentation tank height.Generally, the height of guide shell also should
Under the liquid level of zymotic fluid.In certain embodiments, membrane module and guide shell are detachable；In other embodiments, film
The component for being used to fix film in component is integrally formed with guide shell.Herein, the component for fixing film is membrane removal in membrane module
Other parts in addition, including but not limited to previously described fixed seal head, fixed seal head or the pedestal of connecting pipe connected
Fixture to get up etc..
In the case where pipeline passes through tank body, through hole can be set on guide shell, it is allowed to which exterior line or connecting pipe are worn
The through hole is crossed, and passes through tank body.
Generally, the through hole on guide shell, tank body and cover and pipeline are combined closely, to prevent zymotic fluid from passing through the through hole.
In certain embodiments, connecting pipe can be set in the through hole of guide shell, tank body or cover, the connecting pipe is with leading
Flow cartridge, tank body or cover are tightly connected via seal, or are integrally formed with guide shell, tank body or cover.In these embodiment party
In case, the connecting pipe on membrane module directly can be tightly connected with the connecting pipe on guide shell, or can be via independent company
Jointed tubular workpieces are tightly connected with the connecting pipe on guide shell.Similarly, the connecting pipe of guide shell and the connecting pipe of tank body it
Between can directly be tightly connected, can also pass through independent connecting pipe and be tightly connected.Pipeline outside tank body or cover can pass through tank
Connecting pipe on body or cover is tightly connected.The mode of sealed connection is well known in the art, such as conventional using this area
Thread seal.
Bubble generator is also provided with fermentation tank.Bubble generator is usually located at fermenter base, and quantity is 1~8
It is individual.Bubble generator can be various bubble generators well known in the art, including but not limited to porous venturi-type, online
Mixer type or vortex bubble generator.In the case of with guide shell, bubble generator is usually arranged as being located at water conservancy diversion
Cylinder is internal.The coke-stove gas that gas in bubble generator uses for the present invention.
In certain embodiments, triple valve is provided with the pipeline outside the fermentation tank connected with film.Generally, triple valve
Quantity is identical with the quantity of film.In every film fluid circulation and switching controlled by respective triple valve.Prolong from each triple valve
The pipeline stretched can accumulate a pipeline, be connected with other external equipments.Triple valve be used for controlling film and feeder with
And the connection of film and product reservoir.
Fig. 1 shows a specific embodiment of bioreactor 10 of the present invention.The bioreactor 10 includes fermentation tank
Tank body 11, membrane module 21, guide shell 31, air inlet pipe 41, film connecting tube 51, stationary grizzly 61 and bubble generator 71.
In certain embodiments, bioreactor of the invention includes：Fermentation tank and the bubble hair being placed in fermentation tank
Raw device, membrane module and guide shell；Wherein, the bubble generator quantity is 1~8, positioned at fermenter base and is located at water conservancy diversion
Cylinder is internal；The membrane module has more than 2, such as 2~20 films, is distributed on inside the guide shell, and the film bottom
For cecum, top has the connecting pipe for being used for connecting with exterior line.
In preferred embodiments, allow the pipeline for connecting the membrane module and external equipment close on guide shell and tank body
Seal through through hole.In a further preferred embodiment, connecting pipe is set in the through hole on guide shell and tank body,
The connecting pipe is tightly connected with guide shell, tank body or cover via seal, or with guide shell, tank body or cover one into
Type.In preferred embodiments, membrane module and guide shell are detachable.In a further preferred embodiment, for fixing film
Component be integrally formed with guide shell.In preferred embodiments, it is provided with the pipeline outside the fermentation tank connected with film
Triple valve, for controlling the circulation and switching of fluid in every film.
The Zymolysis Equipment of the present invention contains bioreactor and feeder as described herein.In certain embodiments,
The feeder includes coal gas surge tank, gas compressor and gas cooler.In certain embodiments, the equipment is also
Including seeding tank, for providing seed liquor.Measuring pump can be connected between seed liquor and fermentation tank, seed liquor is via the measuring pump
It is added to after metering in the fermentation tank.Feeder can provide gas to seeding tank and fermentation tank.In certain embodiments, gas
Body provides gas via air-turbocooler to seeding tank.Similarly, air-turbocooler is from the bottom of the fermentation tank of bioreactor
Supply to the fermentation tank, and/or supplied via the triple valve to the membrane module, supplied so as to realize to fermentation tank.
The Zymolysis Equipment of the present invention may also include circulating fan, in the fermentation tank for circulating seeding tank and bioreactor
Gas.Specifically, the gas in the gas and fermentation tank in seeding tank can be circulated back to seeding tank via circulating fan
And fermentation tank.The gas of circulation can return to the fermentation with being passed through after the gas mixing of air-turbocooler by identical pipeline
In tank.
The Zymolysis Equipment of the present invention may also include pH regulation tanks, for being provided to the nutrient solution of bioreactor for adjusting
Its pH reagent；And feed supplement tank, for adding zymotic fluid to bioreactor.Zymotic fluid at the beginning of fermentation in bioreactor
Also can be provided by the feed supplement tank.PH adjusts tank and feed supplement tank can all be connected via measuring pump with fermentation tank.
The Zymolysis Equipment of the present invention may also include product reservoir, be connected via the triple valve with the membrane module.
Fig. 3 shows a specific embodiment of Zymolysis Equipment of the present invention.The set Zymolysis Equipment includes coal gas surge tank 1,
Gas compressor 2, air-turbocooler 3, circulating fan 4, seeding tank 5, pH regulation tanks 6, feed supplement tank 7, product reservoir 8, measuring pump
9, and bioreactor 10.
Coke-stove gas after purification enters in coal gas surge tank 1 after being mixed in the proper ratio with carbon dioxide, via gas
Gas compressor 2, which is compressed to enter in air-turbocooler 3 after appropriate pressure, is cooled to suitable temperature, is then respectively supplied to seed
Tank and fermentation tank, the fermentation substrate as microorganism in the fermentation substrate and fermentation tank of the seed liquor in seeding tank 5.Gas can lead to
Cross the bottom of bioreactor 10 and enter membrane module via triple valve and be supplied to the fermentation tank of bioreactor 10.Seed
Seed liquor in tank 5 is supplied to fermentation tank after the metering of measuring pump 9, it is fermented in seeding tank caused by gas via circulating fan
Seeding tank 5 and bioreactor 10 are again supplied to after circulation, with the gas mixing of the offer of air-turbocooler 3.In suitable bar
Fermented under part after certain time, the gas in bioreactor 10 is discharged at the top of fermentation tank, is circulated via circulating fan, with gas
Seeding tank 5 and biological respinse are again supplied to after the gas mixing discharged in gas and/or seeding tank 5 that body cooler 3 provides
Device 10.When needed, tank can be adjusted by pH and suitable pH adjusting agent is provided into fermentation tank, to adjust the pH of zymotic fluid；Together
Sample, can be by feed supplement tank to fermentation tank afterfermentation liquid.In fermentation process, all membrane modules can be made by switching three-way valve
Gaspipe line is all connected to, for providing gas to fermentation tank., can be by the part film in membrane module with the progressively progress of fermentation
Liquid pattern, i.e. regulating three-way valve are switched to out, stops supplying gas to these films, these films is connected with product reservoir 8, pass through
Fermentation tank inside and outside differential pressure, which produces, filters power, and gas-liquid cycle flows in fermentation tank is washed away to membrane module generation cross-flow, and these films are held
It is continuous to filter out tunning, such as ammonium acetate solution., it is necessary to be backwashed to membrane module during continuing fermentation.At interval of number
Hour (such as 4~6 hours), each film in membrane module is rotated and switches out liquid and ventilating mode, i.e., membrane module is entered by coal gas
Row backwash, make the filter cake for being attached to film surface in filter process is broken to come off, recover membrane flux.
It should be understood that the material and its size of all parts that bioreactor of the present invention and Zymolysis Equipment are related to
To be the conventional material in this area and size.For example, the height of guide shell can be designed according to the depth and width of the tank body of fermentation tank
Degree and width.Guide shell can be metal material or ceramic material.Each pipeline can be plastic material or
Metal material, or ceramic material.In addition, in Zymolysis Equipment of the present invention in addition to the bioreactor of the present invention, remaining device,
Such as coal gas surge tank, gas compressor, circulating fan, seeding tank, pH regulation tank, feed supplement tank, product reservoir, measuring pump, three
Port valve and the connecting pipeline between them etc. can be device commonly used in the art.
Therefore, the present invention also provides a kind of fermentation process, bioreactor or hair of the methods described including the use of the present invention
The step of ferment equipment fermentative microorganism.
The fermentation process of the present invention is anaerobic fermentation, and fermentation substrate is used as using coke-stove gas.This area can be used conventional
Coke-stove gas as fermentation substrate.In certain embodiments, in terms of percent by volume (v/v), coke oven that purified treatment is crossed
Coal gas contains 20~30% CH4, 55~65% H2, 1~5% CO2, 2~6% CO, 7~10% other compositions
(such as N2).In certain embodiments, with volume percentage, the coke-stove gas that purified treatment is crossed is containing 22~26%
CH4, 58~63% H2, 2~4% CO2, 3~5% CO, 8~10% other composition (such as N2)。
The coke-stove gas crossed to purified treatment supplements CO2, make gas fully mixed in gas reservoir 1 of the invention
Close.Generally, CO2The amount of filling into should cause gained gas in, H2With CO2Mol ratio 1.0~5.0：In the range of 1, such as
1.5~4.5：In the range of 1, or 1.5~4.0：In the range of 1, or 1.5~3.5：In the range of 1, Huo Zhe
1.5~3.0：In the range of 1, or 2.0~3.5：In the range of 1, or 2.0~3.0：In the range of 1.
In certain preferred aspects, with volume percentage, the coke-stove gas that the present invention is used to ferment contains 16
~23% CH4, 44~51% H2, 18~30% CO2, 2.5~4.0% CO, 4.5~6.5% N2And surplus is miscellaneous
Matter (including O2).It is highly preferred that with volume percentage, the coke-stove gas for fermentation contains 18~20% CH4, 45~
49% H2, 20~27% CO2, 2.8~3.6% CO, 5.0~6.0% N2And impurity (including the O of surplus2)。
It is 0.1~2.0MPa by gas compression (such as gas compressor 2 in the present invention) to pressure after being sufficiently mixed,
Such as 0.1~1.0MPa, 0.1~0.5MPa, 0.3~2.0MPa, 0.5~2.0MPa, 1.0~2.0MPa, 1.0~1.5MPa are not
Deng.Then by the temperature control of gas between 30~50 DEG C or 35~45 DEG C.This control can be in the gas cooler 3 of the present invention
Middle progress.
Afterwards, the gas is passed through in fermentation tank via fermenter base and membrane module, sent out as fermentation substrate
Ferment.
The microorganism fermented suitable for the present invention may be selected from：Fusobacterium (such as Clostridium ljungdahlii), Moore
Bordetella (such as Moorella thermoacetica), Pyrococcus (such as Pyrococcus furiosus), Eubacterium are (such as
Eubacterium limosum), Desulfobacter (such as Desulfobacterium autotrophicum), carbonoxide is thermophilic
Pseudomonas (such as Carboxydothermus hydrogenoformans), production acetobacter (such as Acetogenium kivui), acetic acid
Bacillus (such as Acetobacterium woodii), anaerobism acetobacter (such as Acetoanaerobium noterae), butyric acid bar
Pseudomonas (such as Butyribaceterium methylotrophicum), Peptostreptococcus (such as Peptostreptococcus
) and Raul's formula Pseudomonas (such as Ralstonia eutropha) productus.
It can be selected to be applied to the fermentation training that the anaerobe grows and fermented according to specifically used anaerobe
Support base.Such as, it is generally the case that culture medium main component is：Potassium dihydrogen phosphate, dipotassium hydrogen phosphate, ammonium sulfate, seven hydrated sulfuric acids
Magnesium, yeast extract, morphine ethyl sulfonic acid and trace element solution ATCC 1754PETC.The dosage of each main component is this in culture medium
The conventional content in field, those skilled in the art can be according to culture medium content known in the art, fermentation situation etc. to culture medium
In the content of each composition make the appropriate adjustments.
Generally, the pressure in fermentation tank is in the range of 0~2MPa, such as 0.1~2MPa or 0.1~1MPa；Fermentation training
The pH value of nutrient solution is 6.0-8.0, such as 6.0~7.0；Fermentation temperature is 25~75 DEG C, such as 45~60 DEG C.
The fermentation of the present invention can be continuously fermented.Therefore, during the fermentation, coke-stove gas is continuously passed through as micro- life
The substrate of thing fermentation so that anaerobe constantly grows.Generally, in fermentation process, the amount for the coke-stove gas being passed through can make
Anaerobic fermentation tank operating pressure in the range of 0.1~2.0MPa, such as 0.1~2.0MPa, 0.1~0.5MPa, 0.3~
2.0MPa, 0.5~2.0MPa, 1.0~2.0MPa, 1.0~1.5MPa.
When measure the total concentration of organic acid and/or alcohol in anaerobic fermentation tank reach more than 1% (such as more than 2%, 3% with
Above, more than 5%, different choice can be made according to different anaerobes) when, the film of part membrane module is switched via triple valve
Into liquid pattern is gone out, filtering power is produced by fermentation tank inside and outside differential pressure, these films is persistently filtered out tunning, as ammonium acetate is molten
Liquid.While fermentation tank continuous discharge, the portion gas that fermentation tank exports is circulated, recycle ratio can be 2~10, such as
2~8,2~6,2~5,3~10,3~8,3~6,5~10,6~8.In certain embodiments, using high fermentation tank pressure
Power and high circulation ratio are fermented.In other embodiments, fermented using low fermentation pressure tank and high circulation ratio.
, can be according to actual conditions while the fresh anaerobe of continuous supplementation and culture medium in fermentation tank continuous discharge
(such as via seeding tank 5 and feed supplement tank 7), controls the constancy of volume of zymotic fluid.When needing, it is suitable also tank addition can be adjusted by pH
When pH adjusting agent, such as ammoniacal liquor, by the pH regulations of the zymotic fluid in fermentation tank to suitable scope.Routine can be used
The total concentration of organic acid and/or alcohol in the volume of zymotic fluid, pH and zymotic fluid in method monitoring fermentation tank.
, it is necessary to be backwashed to membrane module during continuing fermentation.It is right at interval of a few hours (such as 4~6 hours)
Each film in membrane module, which is rotated, switches out liquid and ventilating mode, i.e., membrane module is backwashed by coal gas, made in filter process
Be attached to film surface filter cake it is broken come off, recover membrane flux.
Therefore, can be via the film group during being fermented using the bioreactor or Zymolysis Equipment of the present invention
Part is passed through the coke-stove gas as fermentation substrate, and filters out cell growth via the membrane module and have the cell generation of inhibitory action
Thank to product.
Herein, organic acid or alcohol are CO, CO in coke-stove gas2And H2With one kind or more of anaerobe reaction generation
Kind organic acid or alcohol, including formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, succinic acid, lactic acid, pyruvic acid, malic acid, citric acid,
The combination of benzoic acid, vanillic acid, caproic acid, valeric acid, methanol, ethanol, propane diols, butanol, amylalcohol, or they two or more.
Advantage of the invention is that micro-nano bubble generator, fermentation of gaseous substrates tank, film separation system are integrated into
In a set of synthesis gas fermentation reactor, using the pressure and flow regime of zymotic fluid, realize high-efficiency fermenting and realize that product separates,
Prevent Product inhibiton.
Hereafter the present invention will be illustrated in a manner of specific embodiment.It should be understood that these embodiments are only illustrative, and
The unrestricted present invention.Unless otherwise noted, all numbers occurred in this specification, claims and specific implementation case
Working pressure range, temperature range, pH value range, the gas componant numerical value of word, such as fermentation tank should not be construed definitely
Exact value, the numerical value are that those of ordinary skill in the art is understood, the error range that known technology is allowed.
Embodiment
The present embodiment uses Moore Bordetella Moorella thermoacetica, ATCC 49707.
Medium component：Potassium dihydrogen phosphate, dipotassium hydrogen phosphate, ammonium sulfate, bitter salt, yeast extract, morphine second sulphur
Acid, trace element solution ATCC 1754PETC.
Bioreactor fermentation tank used in fermentation uses 2m3Gas-lifting type anaerobic fermentation tank, it is internally provided with guide shell, bottom
4 vortex bubble generators are disposed with, the uniform 6 metal hyperfiltration membrane assemblies in guide shell inside, average pore size 50nm, bottom is
Cecum, it is fixed on by grid on fermentation tank guide shell, top difference connecting line, through respective triple valve, is communicated to product storage
Tank and gas piping, as shown in Figure 1 and Figure 2.
Fermentation gas substrate uses purified treated coke-stove gas, the main component such as table 1 of coal gas：
The main component (%, v/v) of the coal gas of table 1.
| CO | H2 | CO2 | CH4 | Other (N2Deng) | Amount to |
| 4% | 60% | 2.5% | 24% | 9.5% | 100% |
To coke-stove gas supplementary carbon source CO2Gas, be sufficiently mixed in gas reservoir so that H2With CO2Molar ratio
About 2.5, then gaseous mixture is carried out to be forced into 0.3MPa, gas temperature is 55 DEG C.By 10Nm3/ h gaseous substrates, which are passed through, have been connect
The airlift fermentor of the triumphant 5 productions vinegar bacterium of kind, keeps fermentation pressure tank 0.3MPa, 55 DEG C of temperature, pH 6.4, fermentation tank is worked off one's feeling vent one's spleen
Body is circulated, recycle ratio 2.Meanwhile 6 membrane modules are also communicated to gaspipe line, and coal gas is blasted into fermentation tank.
During coal gas is passed through, fermentation thalli quantity constantly increases, while produces metabolism acetic acid product, by supplementing ammoniacal liquor
After maintaining pH 6.4, fermentation to proceed to 72h, after generation acetic acid ammonium concentration reaches 5.5wt%, by 5 switchings in 6 membrane modules
To liquid pattern is gone out, regulating three-way valve to the storage tank that discharges, filtering power is produced by fermentation tank inside and outside differential pressure, gas-liquid is followed in fermentation tank
Circulation is dynamic to be washed away to membrane module generation cross-flow, and membrane module persistently filters out ammonium acetate solution, and it is about 100L/h to go out liquid speed rate.
, it is necessary to be backwashed to membrane module during continuing fermentation.At interval of 4 hours, 6 membrane modules are rotated
Liquid and ventilating mode are switched out, i.e., membrane module is backwashed by coal gas, uses the filter cake that film surface is attached in filter process
It is broken to come off, recover membrane flux.Through testing the membrane module by gas back-flushing, in continuously fermenting for a long time, its flux can
Return to more than the 80% of initial flux.
Bioreactor of the present invention realizes that in-situ fermentation product separates, stable discharge concentration is 5.5wt% through continuous operation
Left and right ammonium acetate feed liquid, and filter out in feed liquid without anaerobic fermentation bacterial strain.Reactor of the present invention reduces external membrane filtration system
Pump and complex pipeline, it is easy to overall sterilizing, reduces miscellaneous bacteria and infect risk.
Claims (10)
1. a kind of bioreactor, it is characterised in that the bioreactor includes：
(1) fermentation tank；With
(2) membrane module being placed in fermentation tank；
Wherein, the membrane module includes：
Film；With
Connecting pipe positioned at one end of the film, for making film be connected with exterior line；
Wherein, the other end of film is cecum.
2. bioreactor as claimed in claim 1, it is characterised in that the membrane module has following one or more special
Sign：
(1) film is organic film, ceramic membrane or metal film；
(2) structure of the film is tubular type, board-like or rolling；
(3) film is milipore filter or microfiltration membranes；
(4) other end of the film is sealed using fixed seal head, forms the cecum；
(5) membrane module includes more than 2, such as 2~20 films in parallel, each film one end are cecum, and the other end is each
Including the connecting pipe for making film be connected with exterior line；Preferably, each film is fixed on to symmetrical position via fixture
Put；
(6) film is releasably secured together with the connecting pipe.
3. bioreactor as claimed in claim 1 or 2, it is characterised in that
(1) bioreactor also includes the bubble generator being placed in fermentation tank, it is preferable that the bubble generator is located at
Fermenter base, quantity are 1~8；It is highly preferred that the bubble generator is porous venturi-type, online mixer formula
Or vortex bubble generator；And/or
(2) bioreactor also includes the guide shell being placed in fermentation tank；And/or
(3) fermentation tank is stirred type or gas lift type fermentation tank；And/or
(4) fermentation tank also includes seed liquor import, gas access, gas vent, pH adjusting agent entrance and culture medium import.
4. bioreactor as claimed in claim 3, it is characterised in that
(1) membrane module is located in guide shell, is preferably disposed in the middle and lower part of the guide shell；And/or
(2) there is stationary grizzly in the guide shell, for fixing the membrane module；And/or
(3) membrane module is detachably fixed with the guide shell, or is used to fix the component of film and the water conservancy diversion in membrane module
Cylinder is integrally formed；And/or
(4) there is through hole, to allow the pipeline for connecting membrane module and external equipment to pass through on the water conservancy diversion barrel；The fermentation tank
There is through hole, to allow the pipeline for connecting membrane module and external equipment to pass through on wall；And/or
(5) bubble generator is arranged to inside guide shell.
5. bioreactor as claimed in claim 1, it is characterised in that the bioreactor includes：Fermentation tank and it is placed in
Bubble generator, membrane module and guide shell in fermentation tank；Wherein, the bubble generator quantity is 1~8, positioned at fermentation
Pot bottom；The membrane module has more than 2, such as 2~20 films, is distributed on inside the guide shell, and the film bottom
For cecum, top has the connecting pipe for being used for connecting with exterior line.
6. a kind of Zymolysis Equipment, it is characterised in that the Zymolysis Equipment includes：
(1) bioreactor any one of claim 1-5；With
(2) feeder.
7. Zymolysis Equipment as claimed in claim 6, it is characterised in that
(1) feeder includes coal gas surge tank, gas compressor and gas cooler；And/or
(2) equipment also includes seeding tank, and the seeding tank connects with gas cooler and bioreactor, for biology
Reactor provides seed liquor；And/or
(3) equipment also includes circulating fan, for by the gas circulation from seeding tank and bioreactor to seeding tank
Or in bioreactor；And/or
(4) equipment also includes pH regulation tanks, for providing the reagent for adjusting its pH to the nutrient solution of bioreactor；
And/or
(5) equipment also includes feed supplement tank, for adding zymotic fluid to bioreactor；And/or
(6) equipment also includes measuring pump, for being added to bioreactor after being measured to seed liquor, pH adjusting agent or culture medium
It is interior；And/or
(7) equipment also includes product reservoir, is connected via the triple valve with the membrane module.
A kind of 8. fermentation process, it is characterised in that methods described including the use of the bioreactor described in claim 1-5 or
The step of Zymolysis Equipment fermentative microorganism described in claim 6 or 7.
9. method as claimed in claim 8, it is characterised in that
Fermentation substrate is used as using coke-stove gas；Preferably, in terms of percent by volume (v/v), coke-stove gas that purified treatment is crossed
Contain 20~30% CH4, 55~65% H2, 1~5% CO2, 2~6% CO, 7~10% other compositions；It is more excellent
Selection of land, with volume percentage, the coke-stove gas that purified treatment is crossed contains 22~26% CH4, 58~63% H2, 2~
4% CO2, 3~5% CO, 8~10% other compositions；
The coke-stove gas crossed to purified treatment supplements CO2, CO2The amount of filling into should cause gained gas in, H2With CO2Mol ratio exist
1.0~5.0：In the range of 1, such as 1.5~4.5：In the range of 1, or 1.5~4.0：In the range of 1, Huo Zhe
1.5~3.5：In the range of 1, or 1.5~3.0：In the range of 1, or 2.0~3.5：In the range of 1, Huo Zhe
2.0~3.0：In the range of 1；
Preferably, the coke-stove gas for fermentation contains 16~23% CH4, 44~51% H2, 18~30% CO2、2.5
~4.0% CO, 4.5~6.5% N2And the impurity of surplus；It is highly preferred that with volume percentage, the coke oven for fermentation
Coal gas contains 18~20% CH4, 45~49% H2, 20~27% CO2, 2.8~3.6% CO, 5.0~6.0% N2
And the impurity of surplus.
10. method as claimed in claim 8 or 9, it is characterised in that methods described has following one or more features：
(1) coke-stove gas as fermentation substrate is passed through via the membrane module, and is filtered out via the membrane module and cell is given birth to
Products of cellular metabolism with inhibitory action；Preferably, when the cell metabolism that cell growth has inhibitory action in fermentation tank is produced
When the concentration of thing reaches 1% or more, stop being passed through coke-stove gas via the membrane module, then filtered out pair by the membrane module
Cell growth has the products of cellular metabolism of inhibitory action；Wherein, the cell growth has the products of cellular metabolism of inhibitory action
Including：Formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, succinic acid, lactic acid, pyruvic acid, malic acid, citric acid, benzoic acid, vanilla
The combination of acid, caproic acid, valeric acid, or they two or more；
(2) fermentation is to continuously ferment；
(3) pressure in fermentation tank is in the range of 0~2MPa；
(4) fermentation tank exit gas is circulated, and recycle ratio is 2~10；
(5) fermentative microorganism is selected from：Fusobacterium (such as Clostridium ljungdahlii), Moore Bordetella are (such as
Moorella thermoacetica), Pyrococcus (such as Pyrococcus furiosus), Eubacterium (such as
Eubacterium limosum), Desulfobacter (such as Desulfobacterium autotrophicum), carbonoxide is thermophilic
Pseudomonas (such as Carboxydothermus hydrogenoformans), production acetobacter (such as Acetogenium kivui), acetic acid
Bacillus (such as Acetobacterium woodii), anaerobism acetobacter (such as Acetoanaerobium noterae), butyric acid bar
Pseudomonas (such as Butyribaceterium methylotrophicum), Peptostreptococcus (such as Peptostreptococcus
) and Raul's formula Pseudomonas (such as Ralstonia eutropha) productus；
(6) pH value of fermentation culture is 6.0~8.0；With
(7) fermentation temperature is 25~75 DEG C.
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