CN1357628A - Two-step microbial fermentation process of producing propylene glycol - Google Patents
Two-step microbial fermentation process of producing propylene glycol Download PDFInfo
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- CN1357628A CN1357628A CN 01138769 CN01138769A CN1357628A CN 1357628 A CN1357628 A CN 1357628A CN 01138769 CN01138769 CN 01138769 CN 01138769 A CN01138769 A CN 01138769A CN 1357628 A CN1357628 A CN 1357628A
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- fermentation
- ammediol
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- glucose
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- 238000000855 fermentation Methods 0.000 title claims abstract description 50
- 230000004151 fermentation Effects 0.000 title claims abstract description 50
- 230000000813 microbial effect Effects 0.000 title claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 title abstract description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 87
- 235000011187 glycerol Nutrition 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 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 claims abstract description 25
- 239000008103 glucose Substances 0.000 claims abstract description 24
- 229920002472 Starch Polymers 0.000 claims abstract description 11
- 235000019698 starch Nutrition 0.000 claims abstract description 11
- 239000008107 starch Substances 0.000 claims abstract description 11
- 239000001913 cellulose Substances 0.000 claims abstract description 4
- 229920002678 cellulose Polymers 0.000 claims abstract description 4
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 3
- 235000014633 carbohydrates Nutrition 0.000 claims abstract description 3
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 22
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims description 12
- 235000014680 Saccharomyces cerevisiae Nutrition 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 241000894006 Bacteria Species 0.000 claims description 8
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 claims description 6
- 241000193830 Bacillus <bacterium> Species 0.000 claims description 6
- 241000235648 Pichia Species 0.000 claims description 6
- 239000011573 trace mineral Substances 0.000 claims description 6
- 235000013619 trace mineral Nutrition 0.000 claims description 6
- 230000001580 bacterial effect Effects 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 241000228212 Aspergillus Species 0.000 claims description 4
- 241000235649 Kluyveromyces Species 0.000 claims description 4
- 241000235395 Mucor Species 0.000 claims description 4
- 241000235017 Zygosaccharomyces Species 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000001954 sterilising effect Effects 0.000 claims description 4
- 238000004659 sterilization and disinfection Methods 0.000 claims description 4
- 108010059892 Cellulase Proteins 0.000 claims description 3
- 241000588748 Klebsiella Species 0.000 claims description 3
- 229940041514 candida albicans extract Drugs 0.000 claims description 3
- 229940106157 cellulase Drugs 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 239000002054 inoculum Substances 0.000 claims description 3
- 239000012138 yeast extract Substances 0.000 claims description 3
- 241000222120 Candida <Saccharomycetales> Species 0.000 claims description 2
- 241000588923 Citrobacter Species 0.000 claims description 2
- 235000005979 Citrus limon Nutrition 0.000 claims description 2
- 244000131522 Citrus pyriformis Species 0.000 claims description 2
- 241001112696 Clostridia Species 0.000 claims description 2
- 241000193403 Clostridium Species 0.000 claims description 2
- 241000235036 Debaryomyces hansenii Species 0.000 claims description 2
- 241001030162 Debaryomyces sp. Species 0.000 claims description 2
- 229930003779 Vitamin B12 Natural products 0.000 claims description 2
- 241001148470 aerobic bacillus Species 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
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- 239000011715 vitamin B12 Substances 0.000 claims description 2
- 235000019163 vitamin B12 Nutrition 0.000 claims description 2
- FDJOLVPMNUYSCM-WZHZPDAFSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+3].N#[C-].N([C@@H]([C@]1(C)[N-]\C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C(\C)/C1=N/C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C\C1=N\C([C@H](C1(C)C)CCC(N)=O)=C/1C)[C@@H]2CC(N)=O)=C\1[C@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]1[C@@H](O)[C@@H](N2C3=CC(C)=C(C)C=C3N=C2)O[C@@H]1CO FDJOLVPMNUYSCM-WZHZPDAFSA-L 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 238000005516 engineering process Methods 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000011218 seed culture Methods 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 244000005700 microbiome Species 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- -1 and 1 Substances 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 241000235645 Pichia kudriavzevii Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000001963 growth medium Substances 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
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- AKXKFZDCRYJKTF-UHFFFAOYSA-N 3-Hydroxypropionaldehyde Chemical compound OCCC=O AKXKFZDCRYJKTF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
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- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
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- 229910052750 molybdenum Inorganic materials 0.000 description 2
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- 239000000178 monomer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000588747 Klebsiella pneumoniae Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000010564 aerobic fermentation Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000007664 blowing Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- AGVAZMGAQJOSFJ-WZHZPDAFSA-M cobalt(2+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+2].N#[C-].[N-]([C@@H]1[C@H](CC(N)=O)[C@@]2(C)CCC(=O)NC[C@@H](C)OP(O)(=O)O[C@H]3[C@H]([C@H](O[C@@H]3CO)N3C4=CC(C)=C(C)C=C4N=C3)O)\C2=C(C)/C([C@H](C\2(C)C)CCC(N)=O)=N/C/2=C\C([C@H]([C@@]/2(CC(N)=O)C)CCC(N)=O)=N\C\2=C(C)/C2=N[C@]1(C)[C@@](C)(CC(N)=O)[C@@H]2CCC(N)=O AGVAZMGAQJOSFJ-WZHZPDAFSA-M 0.000 description 1
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- 238000007323 disproportionation reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
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- 238000005984 hydrogenation reaction Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
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Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The present invention relates to bioengineering technology. The present invention features that one kind of aerobiota is first used to ferment glucose, saccharified starch liquid, enzymolyzed cellulose liquid and other carbohydrate to produce glycerin, and one other kind of anerobic microbe is then used to convert glycerin into propylene glycol. The fermented liquid in the first step may be centrifugalized and filtered or sterilized to eliminate aerobiota, the clear liquid is fed to second step of fermentation directly or after concentration, and partial aerobiota may be reused in continuous fermentation. The present invention has low production cost and short production period.
Description
Technical field
The invention belongs to technical field of bioengineering, specially refer to two-step microbial fermentation and produce 1, the method for ammediol.
Background technology
As everyone knows, 1, ammediol is a kind of important chemical material, can be used as organic solvent and is applied to industries such as printing ink, printing and dyeing, coating, lubricant, antifreezing agent, goes back the useful as drug synthetic intermediate.1, the topmost purposes of ammediol will be the macromolecular material as the synthetic excellent performance of polymer monomer.1, ammediol can substitute ethylene glycol, 1, the 2-propylene glycol, and 1, intermediates such as 4-butyleneglycol and neopentyl glycol are used to produce how pure polyester and extend agent as carbochain.With 1, ammediol and terephthalic acid synthetic polyester PTT (polytrimethylene terephthalate) are that monomer synthetic polymer P ET (polyethylene terephthalate), PBT (polybutylene terephthalate) have better performance than with ethylene glycol, butyleneglycol, good continuous printing and dyeing that present as need not to add any speciality chemical in the tint permanence of recovery of elasticity, uvioresistant, ozone and the oxynitride of nylon sample, low static, low water absorption, the panchromatic scope and biodegradable etc.PTT is considered to the new polyester material of the workability of the high-performance of a kind of PET of having concurrently and PBT, have broad application prospects, but expensive at present price has hindered its widespread use.
Present 1, the production method of ammediol mainly is a chemical synthesis, is raw material with ethene as Shell Co. Ltd, under high temperature (280 ℃), become oxyethane as catalyst oxidation with silver, hydrogenation and carbon monoxide change into the 3-hydroxy propanal then, are hydrogenated to product 1 at last, ammediol; Degussa company then is raw material with the propylene, is propenal with molybdenum as catalyst oxidation under 350 ℃, 0.2Mpa, and rehydration is the 3-hydroxy propanal, is hydrogenated to 1 then, ammediol (USP5008473).These two kinds of methods all need be carried out under high temperature and valuable catalyst action, and product removes 1, and ammediol also has 1 outward, 2-propylene glycol and the close by product of character such as dimer, tripolymer thereof, and it is difficult to cause product separation to be purified, and production cost is corresponding higher.
The microbial method glycerine converting is 1, and the research of ammediol starts from 1881, but just causes people's attention gradually up to the eighties in 20th century.Compare with chemical synthesis, it has mild condition, easy and simple to handle, characteristics such as by product is few, non-environmental-pollution.Present 1, the microorganisms producing method of ammediol is broadly divided into three classes: the one, and be 1 with intestinal bacteria with the glycerine disproportionation, (USP 5254467 for ammediol; EP 0373230 A1); The 2nd, be that substrate produces 1 with genetic engineering bacterium, ammediol (PCT/US96/06705 with glucose; USP5599689; USP6025184; WO96/35796; WO9821340; WO9821339; ZL96195288); The 3rd, with production glycerine and production 1, two strain bacterium mixed culture (USP5599689) of ammediol.These methods respectively have relative merits, and the transformation efficiency of first method and production concentration are all higher, but glycerine is on the high side, influence 1, the cost of ammediol; Second method can reduce raw materials cost, but the throughput of genetic engineering bacterium and stability thereof are also not ideal; The third method helps to reduce the time of two-step fermentation, but because the growth conditions of two kinds of bacterium is not quite similar, as produce glycerol stock (as yeast saccharomyces cerevisiae (Saccharomyces cerevisiae), zygosaccharomyces (Zygosaccharomyces), pichia spp (Pichia), candiyeast (Candida), debaryomyces hansenii (Hansenula), Dbaly yeast (Debaryomyces sp.), kluyveromyces (Kluyveromyces), aspergillus (Aspergillus), genus bacillus (Bacillus), Mucor (Mucor) etc.) under aerobic condition, grow usually, and produce 1, the ammediol bacterium is (as klebsiella (Klebsiella), lemon bacterium (Citrobacter) and clostridium (Clostridia) etc.) growth under anaerobic usually, therefore be difficult to obtain comparatively ideal effect.
Summary of the invention
The objective of the invention is to utilize cheap starch, Mierocrystalline cellulose to make raw material, after enzymolysis obtains glucose solution, produce 1 by two-step fermentation again, ammediol, i.e. the first step employing aerobic fermentation is a glycerine with conversion of glucose, it is 1 with transformation of glycerol that second step was adopted anaerobically fermenting, ammediol, be Production by Microorganism Fermentation 1, ammediol provides a kind of practicable technology, and fermentation period is long, transformation efficiency is low and a production cost high-technology difficult problem to solve.
Technical scheme
The invention provides a kind of two-step microbial fermentation and produce 1, the method of ammediol, at first use a kind of aerobic microbiological cell that carbohydrate such as glucose, starch saccharificating liquid, cellulase hydrolysis liquid are converted into glycerine, the glycerine that to go up in the step fermented liquid by another kind of anaerobion cell further is converted into 1, ammediol again.The resulting fermented liquid of the first step glycerol fermentation is removed or the recycle thalline with centrifugal or filtering method, batch formula stream liquid feeding that centrifuged supernatant or filtering filtrate directly enter the fermentation of second step or ferments as second step after evaporation concentration; The first step fermented liquid also can not centrifugally carry out the fermentation of second step again after sterilization, and does not need to add yeast powder, yeast extract or vitamin B12.
The step that realizes the inventive method is as follows:
1) preparation of saccharification liquid: in starch and 1: 2.5 ratio of water preparation starch fluid, add an amount of high temperature resistant liquefaction enzyme (α-Dian Fenmei) (4~6u/g starch),, be cooled to 60 ℃ then, transfer pH4.0~4.5 in 90~100 ℃ of stirring liquefaction 60min; The amount of pressing 200u/g starch adds saccharifying enzyme (B-amylase), and saccharification was filtered after 24 hours under 60 ℃ of constant temperature, got saccharification liquid.
2) preparation of substratum: must possess the required nutritive ingredient of microorganism growth in the substratum, as carbon sources such as glucose or glycerine, nitrogenous source and phosphoric acid salt (phosphorus source) and vitriol (sulphur source) etc. such as urea, ammonium salt, yeast extract or yeast powder.Also need positively charged ion and trace elements such as zinc, iron, manganese, copper, cobalt, boron and molybdenum such as sodium, potassium, magnesium, calcium in addition, every kind of content of elements is greatly in the scope of 0.01mg/L~50mg/L.Substratum must be sterilized down at 121 ℃ and can be used in 15~20 minutes.
3) seed culture: carry out in shaking bottle, shaking speed is 100~300 rev/mins, and temperature is 27~40 ℃, and incubation time is 9~30 hours.
4) fermentation culture: can carry out in fermentor tank, the fermentor tank inoculum size is 5%~20%, and rotating speed of agitator is 100~400 rev/mins, and temperature is 27~40 ℃.Can lead to nitrogen or air in the fermenting process in fermentor tank, air flow is 0.2~4vvm.Fermentation mode can be that batch fermentation, batch formula stream add fermentation or continuously ferments, the time that intermittence or batch formula stream add fermentation is 10~200 hours, advanced person's fermentation of in the ranks having a rest when continuously fermenting, when treating in the fermented liquid that thalline reaches certain density (is 2~5 as optical density(OD) under the 650nm), stream adds fermention medium (containing glucose or glycerol concentration is 40%~99%) and carries out the perseverance cultivation again.The first step glycerol fermentation glucose concn can be in 10%~50% scope, and pH is controlled in 3.5~5.5 scopes, and the rate of consumption of glucose can reach 80%~95%, and the concentration of product glycerine can reach 5%~30%; In second step 1, ammediol ferment glycerin starting point concentration is 2%~15%, and pH is 6~8, product 1, and the concentration of ammediol can reach 10~85g/L.
Advantage of the inventive method and beneficial effect have been to give full play to the characteristics of each step fermentation, aerobic bacteria and anerobe can both be grown under optimum separately condition, thereby improve glycerine and 1, the productive rate of ammediol, and saved the isolating expense of glycerine, reduced production cost, shortened whole fermentation time, improved production efficiency, be Production by Microorganism Fermentation 1, the industrialization of ammediol is laid a good foundation.It is the production of raw material that this technology both had been suitable for glucose, and being suitable for starch or Mierocrystalline cellulose again is the production of raw material; Can in a bio-reactor, operate, also can operate with two reactors in series; Also can be applicable to glycerine and 1 in addition, the coproduction of ammediol.
Embodiment
Below be described in detail most preferred embodiment of the present invention:
1) bacterial classification: the first step used bacterial classification that ferments is candida krusei (Candida krusei) in the embodiment of the invention, is a kind of aerobic osmophilic yeast; The bacterial classification of second step fermentation is Cray Bai Shi bacillus (Klebsiella pneumoniae), is a kind of anerobe.They are all available from Chinese common micro-organisms DSMZ (CGMCC), and culture presevation number is respectively AS2.1708 and AS1.1736.
2) substratum: divide two kinds of seed culture medium and fermention mediums, division is as follows:
2.1 candida krusei
A. seed culture medium:
Glucose: 10%, corn steep liquor: 3 ‰, urea: 3 ‰, pH4.0~4.5
B. fermention medium:
Glucose: 25%, corn steep liquor: 2.5 ‰, urea: 2.5 ‰, pH4.0~4.5
2.2 Cray Bai Shi bacillus:
A. seed culture medium: (1000ml):
Glycerine: 20g K
2HPO
43H
2O:4.56g
KH
2PO
4:1.3g (NH
4)
2SO
4:2.0g
MgSO
47H
2O:2g yeast powder: 1g
CaCO
3: 2g trace element TE1:2ml
0.5%FeSO
4Solution: 1ml 2%CaCl
2Solution: 1ml
Trace element TE1 forms (1000ml):
Saturated hydrochloric acid: 0.9ml ZnCl
2: 70mg
MnCl
2·4H
2O:100mg H
3BO
3:60mg
CoCl
2·6H
2O:200mg NiCl
2·6H
2O:25mg
NaMoO
4·2H
2O:35mg CuCl
2·2H
2O:20mg
B. fermention medium is formed (1000ml):
(NH
4)SO
4:6.61g KH
2PO
4:1.36g
MgCl
26H
2O:0.26 citric acid: 0.42g
Yeast powder: 1g trace element TE2:5ml
Trace element TE2 forms (1000ml):
Saturated hydrochloric acid: 10ml ZnCl
26H
2O:0.68g
FeCl
3·6H
2O:5.4g MnCl
2·4H
2O:0.17g
CoCl
2·6H
2O:0.47g H
3BO
3:0.06g
NaMoO
4·2H
2O:0.005g CuCl
2·2H
2O:0.47g
It is 7.0 that seed and fermention medium all need to regulate pH before sterilization.
3) fermenting process: divide two kinds of seed culture and fermentation culture, wherein seed culture is carried out in the triangular flask of a 500mL, and liquid amount is 200mL, and shaking speed is 200 commentaries on classics/min; Fermentation culture can be carried out in automatic fermenter, and working volume is 5L, and actual liquid amount is 3L, and inoculum size is 10%, and rotating speed is controlled to be 300 commentaries on classics/min, and the air flow 0.4vvm of air or nitrogen regulates pH with 2mol/L sodium hydroxide.
A. the first step fermentation: the seed culture temperature is 35 ℃, and incubation time is 24hr; When batch fermentation is cultivated in pure glucose or the W-Gum saccharification liquid concentration of glucose be 25%, pH and temperature are controlled to be 4.0 and 35 ℃ respectively, in the fermenting process in fermentor tank blowing air stop fermentation when remaining sugar concentration is 1% left and right sides to keep aerobic condition.
B. second step fermentation: the seed culture temperature is 37 ℃, and incubation time is 12hr; Batch fermentation is cultivated preceding with the centrifugal thalline of removing of the first step fermented liquid, in clear liquid, add the cultivation composition, regulating the pH value is 7.0, sterilization cooling back inoculation, the glycerine starting point concentration is adjusted to 7%, pH and temperature are respectively 7.0 and 37 ℃, and logical nitrogen is to keep anaerobic condition in fermentor tank in the fermenting process, and fermentation proceeds to till the glycerine consumption fully.
Resulting result is as follows for most preferred embodiment of the present invention:
Pure glucose solution with 25% is that raw material carries out two-step fermentation, and when the first step fermentation proceeded to 70 hours, remaining glucose concn was 0.76g/L, contains 69.3g/L glycerine and 1.26g/L ethanol in the fermented liquid, and the molar yield of glycerine is 54.2%; The second step fermentation has been carried out 15 hours, and in the fermented liquid 1, the concentration of ammediol is 24.39g/L, the concentration of ethanol and acetate respectively 8.56 and 3.74g/L, 1, and the ammediol molar yield is 42.2%.
With the W-Gum saccharification liquid that contains 25% glucose is that raw material carries out two-step fermentation, and the first step fermentation has been carried out 54 hours, and remaining glucose concn is 11.6g/L, contains 49.9g/L glycerine and 7.35g/L ethanol in the fermented liquid, and the molar yield of glycerine is 39.1%; The second step fermentation has been carried out 31 hours, and in the fermented liquid 1, the concentration of ammediol is 13.18g/L, the concentration of ethanol and acetate respectively 10.95 and 4.14g/L, 1, and the ammediol molar yield is 22.8%.
Claims (1)
1. one kind is utilized the grape sugar and starch, enzymolysis solutions such as Mierocrystalline cellulose produce 1 through two-step microbial fermentation, the method of ammediol, in temperature, under pH and the mixing speed constant condition, carry out intermittence, batch formula stream adds or continuously ferments, at first use yeast saccharomyces cerevisiae (Saccharomyces cerevisiae), zygosaccharomyces (Zygosaccharomyces), pichia spp (Pichia), candiyeast (Candida), debaryomyces hansenii (Hansenula), Dbaly yeast (Debaryomyces sp.), kluyveromyces (Kluyveromyces), aspergillus (Aspergillus), genus bacillus (Bacillus), Mucor aerobic bacterias such as (Mucor) is a glycerine with conversion of glucose, then use Cray Bai Shi bacillus (Klebsiella), lemon bacterium (Citrobacter) and clostridium anerobes such as (Clostridia) further are converted into 1 with glycerine, ammediol, the inoculum size of bacterial classification is 5%~20% in the fermenting process, the fermentor tank rotating speed of agitator is 100~400 rev/mins, temperature is 27~40 ℃, the air flow of nitrogen or air is 0.2~4vvm, pH is controlled between 3.5~5.5 in the first step glycerol fermentation, the rate of consumption of glucose reaches 80%~95%, and the concentration of product glycerine reaches 5%~30%; In second step 1, the glycerine starting point concentration is 2%~15% in the ammediol fermentation, and pH is 6.0~8.0, product 1, and the concentration of ammediol reaches 10~85g/L;
This inventive method is characterised in that:
A) the resulting fermented liquid of the first step glycerol fermentation needn't be removed thalline, adds for second step 1 after the direct heating sterilization, the ammediol needed trace element that ferments, and the fermentation of second step is carried out in inoculation, and does not need to add yeast powder, yeast extract or vitamin B12;
B) the first step glycerol fermented broth is removed thalline with centrifugal or filtering method, adds the second step needed nutritive ingredient of fermentation and bacterial classification and proceed the fermentation of second step in clear liquid;
C) criticizing formula stream adds when fermenting, the used stream liquid feeding of the first step glycerol fermentation is dense glucose solution or spissated starch saccharificating liquid, cellulase hydrolysis liquid, wherein the concentration of glucose is 40%~90%, second step 1, the stream liquid feeding of ammediol fermentation is the glycerol fermented broth through evaporation concentration, and wherein the concentration of glycerine is 40%~90%;
When d) continuously fermenting, the first step glycerol fermentation and second step 1, the thalline concentrated solution of the fermented liquid of ammediol fermentation after with centrifugal or filter method separation is with 10%~90% ratio recycle;
E) the used raw material of two-step fermentation is carbohydrate such as glucose, starch saccharificating liquid, cellulase hydrolysis liquid, and wherein glucose content is between 10%~50%.
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