CA2735505C - Method of producing butanol - Google Patents
Method of producing butanol Download PDFInfo
- Publication number
- CA2735505C CA2735505C CA2735505A CA2735505A CA2735505C CA 2735505 C CA2735505 C CA 2735505C CA 2735505 A CA2735505 A CA 2735505A CA 2735505 A CA2735505 A CA 2735505A CA 2735505 C CA2735505 C CA 2735505C
- Authority
- CA
- Canada
- Prior art keywords
- butanol
- membrane
- nanofiltration membrane
- polyamide
- containing solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 title claims abstract description 221
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000012528 membrane Substances 0.000 claims abstract description 168
- 238000001728 nano-filtration Methods 0.000 claims abstract description 81
- 239000012466 permeate Substances 0.000 claims abstract description 21
- 239000004952 Polyamide Substances 0.000 claims description 42
- 229920002647 polyamide Polymers 0.000 claims description 42
- 238000001223 reverse osmosis Methods 0.000 claims description 31
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 25
- 238000000855 fermentation Methods 0.000 claims description 20
- 230000004151 fermentation Effects 0.000 claims description 20
- 239000002346 layers by function Substances 0.000 claims description 20
- 230000000813 microbial effect Effects 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 41
- 235000002639 sodium chloride Nutrition 0.000 description 15
- 239000000306 component Substances 0.000 description 14
- 238000004821 distillation Methods 0.000 description 13
- 238000000746 purification Methods 0.000 description 11
- 235000000346 sugar Nutrition 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 10
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 9
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 9
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 229920002301 cellulose acetate Polymers 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910001868 water Inorganic materials 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 7
- 239000012527 feed solution Substances 0.000 description 7
- 230000004907 flux Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000002609 medium Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 150000008163 sugars Chemical class 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- -1 aromatic carboxylic acids Chemical class 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000005374 membrane filtration Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- DNZWLJIKNWYXJP-UHFFFAOYSA-N butan-1-ol;propan-2-one Chemical compound CC(C)=O.CCCCO DNZWLJIKNWYXJP-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 241000193403 Clostridium Species 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- 239000005715 Fructose Substances 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920004482 WACKER® Polymers 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000012228 culture supernatant Substances 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000002054 inoculum Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 238000005373 pervaporation Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000012465 retentate Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 description 1
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical compound C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- WKRCOZSCENDENK-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=CC=C2S1 WKRCOZSCENDENK-UHFFFAOYSA-N 0.000 description 1
- XZYQBYQGHHGXBC-UHFFFAOYSA-N 4-(1,3-benzoxazol-2-yl)aniline Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=CC=C2O1 XZYQBYQGHHGXBC-UHFFFAOYSA-N 0.000 description 1
- VQFBXSRZSUJGOF-UHFFFAOYSA-N 4-(1h-benzimidazol-2-yl)aniline Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=CC=C2N1 VQFBXSRZSUJGOF-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920001747 Cellulose diacetate Polymers 0.000 description 1
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 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
- 239000007836 KH2PO4 Substances 0.000 description 1
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
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- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
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- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
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- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
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- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
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- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
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- 239000001384 succinic acid Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 210000005253 yeast cell Anatomy 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/58—Multistep processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/26—Further operations combined with membrane separation processes
- B01D2311/2669—Distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method of producing butanol, which has a step of removing impurities contained in a butanol-containing solution, is provided. In the method, a butanol--containing solution is filtered through a nanofiltration membrane. Then the butanol-containing solution is collected from the permeate flow of the nanofiltration membrane.
Description
I
Method of Producing Butanol Background of the Invention Field of the Invention [0001]
The present invention relates to a method of producing butanol by separating butanol from a butanol-containing solution. More particularly, the present invention relates to a method for producing butanol, which method comprises a step of removing inorganic salts, sugars, proteins, catalytic components and/or the like remaining in a butanol-containing solution with a nanofiltration membrane.
Description of the Related Art
Method of Producing Butanol Background of the Invention Field of the Invention [0001]
The present invention relates to a method of producing butanol by separating butanol from a butanol-containing solution. More particularly, the present invention relates to a method for producing butanol, which method comprises a step of removing inorganic salts, sugars, proteins, catalytic components and/or the like remaining in a butanol-containing solution with a nanofiltration membrane.
Description of the Related Art
[0002]
Butanol is a compound which is industrially very important as a raw material of chemicals and pharmaceutical agents, as a solvent, and as a fuel material.
It is well known that butanol can be industrially synthesized from acetaldehyde by the Wacker process, or from propylene, carbon monoxide and water by the Reppe process, and it also has long been known that these can be produced by acetone-butanol fermentation. Production of butanol by acetone-butanol fermentation have problems in that the cost of the substrate to be used as the nutrient source for microorganisms and the cost of purification of the product are high, so that production of butanol has become dependent on chemical synthesis. However, because of the recent decrease in the crude oil resource and substantial rise in its price, production methods of butanol using biomass have been expected to be useful as alternatives to chemical synthesis, and therefore reduction of the production cost in acetone-butanol fermentation is demanded.
Butanol is a compound which is industrially very important as a raw material of chemicals and pharmaceutical agents, as a solvent, and as a fuel material.
It is well known that butanol can be industrially synthesized from acetaldehyde by the Wacker process, or from propylene, carbon monoxide and water by the Reppe process, and it also has long been known that these can be produced by acetone-butanol fermentation. Production of butanol by acetone-butanol fermentation have problems in that the cost of the substrate to be used as the nutrient source for microorganisms and the cost of purification of the product are high, so that production of butanol has become dependent on chemical synthesis. However, because of the recent decrease in the crude oil resource and substantial rise in its price, production methods of butanol using biomass have been expected to be useful as alternatives to chemical synthesis, and therefore reduction of the production cost in acetone-butanol fermentation is demanded.
[0003]
In general, as the method for purifying butanol, solvent extraction or distillation is employed. In solvent extraction, in cases where the desired product is a lower alcohol, which is highly soluble in water, distribution of the lower alcohol into the organic phase is difficult, so that use of a special extraction solvent or multistep extraction may be required, which leads to increase in the cost (Patent Document 1). Further, in purification by distillation, since the concentration of butanol in the fermentation broth is low, water, whose boiling point is lower than that of butanol, needs to be distilled off in a large amount, so that a method that enables efficient concentration of butanol is demanded. As a solution to solve the problem, a method for concentrating a fermentation alcohol using a separation membrane has been devised. In Patent Document 2, a method for concentrating an alcohol by the pervaporation separation method using a silicone rubber membrane is disclosed.
However, this method is the so called batch filtration concentration wherein purified fermentation broth is recovered from a fermenter and then treated in a pervaporation apparatus under specific conditions, which is not rational in view of device configuration.
In general, as the method for purifying butanol, solvent extraction or distillation is employed. In solvent extraction, in cases where the desired product is a lower alcohol, which is highly soluble in water, distribution of the lower alcohol into the organic phase is difficult, so that use of a special extraction solvent or multistep extraction may be required, which leads to increase in the cost (Patent Document 1). Further, in purification by distillation, since the concentration of butanol in the fermentation broth is low, water, whose boiling point is lower than that of butanol, needs to be distilled off in a large amount, so that a method that enables efficient concentration of butanol is demanded. As a solution to solve the problem, a method for concentrating a fermentation alcohol using a separation membrane has been devised. In Patent Document 2, a method for concentrating an alcohol by the pervaporation separation method using a silicone rubber membrane is disclosed.
However, this method is the so called batch filtration concentration wherein purified fermentation broth is recovered from a fermenter and then treated in a pervaporation apparatus under specific conditions, which is not rational in view of device configuration.
[0004]
Examples of the continuous method for alcohol concentration as an alternative to the batch process include the method using a silicalite membrane coated with silicone rubber, which is disclosed in Patent Document 3. In cases where the operation of concentration is carried out by introducing a silicalite membrane into a fermenter, fouling occurs with time due to organic acids such as succinic acid and malic acid produced as by-products. By coating the surface of the silicalite membrane with the silicone rubber to make the membrane surface hydrophobic, this fouling is suppressed. However, since fouling substances accumulate with time also on the surface of the silicone rubber, the performance of the separation membrane may decrease with time.
Examples of the continuous method for alcohol concentration as an alternative to the batch process include the method using a silicalite membrane coated with silicone rubber, which is disclosed in Patent Document 3. In cases where the operation of concentration is carried out by introducing a silicalite membrane into a fermenter, fouling occurs with time due to organic acids such as succinic acid and malic acid produced as by-products. By coating the surface of the silicalite membrane with the silicone rubber to make the membrane surface hydrophobic, this fouling is suppressed. However, since fouling substances accumulate with time also on the surface of the silicone rubber, the performance of the separation membrane may decrease with time.
[0005]
Further, in case where an alcohol is distilled from a fermentation broth, sugars, amino acids, side metabolites such as organic acids, and the like remaining in the fermentation broth are heated to yield by-products, which are then contaminated in the distillate fraction as impurities, which is problematic. Therefore, purification of the fermentation broth is also an important problem. As methods for purifying an alcohol, a method for purifying 1,3-propanediol wherein distillation is carried out in combination with microfiltration, ultrafiltration, nanofiltration or ion exchange (Patent Document 4); and a method for separating diol using a reverse osmosis membrane or a nanofiltration membrane (Patent Document 5) are disclosed.
However, these prior arts do not disclose the effect of difference in the material of the nanofiltration membrane on the permeation selectivity and on purification of butanol.
Prior Art References Patent Documents
Further, in case where an alcohol is distilled from a fermentation broth, sugars, amino acids, side metabolites such as organic acids, and the like remaining in the fermentation broth are heated to yield by-products, which are then contaminated in the distillate fraction as impurities, which is problematic. Therefore, purification of the fermentation broth is also an important problem. As methods for purifying an alcohol, a method for purifying 1,3-propanediol wherein distillation is carried out in combination with microfiltration, ultrafiltration, nanofiltration or ion exchange (Patent Document 4); and a method for separating diol using a reverse osmosis membrane or a nanofiltration membrane (Patent Document 5) are disclosed.
However, these prior arts do not disclose the effect of difference in the material of the nanofiltration membrane on the permeation selectivity and on purification of butanol.
Prior Art References Patent Documents
[0006]
Patent Document 1 US 2007/193960 A
Patent Document 2 JP 57-136905 A
Patent Document 3 JP 2003-135090 A
Patent Document 4 US 2005/069997 A
Patent Document 5 US 2006/065600 A
Summary of the Invention
Patent Document 1 US 2007/193960 A
Patent Document 2 JP 57-136905 A
Patent Document 3 JP 2003-135090 A
Patent Document 4 US 2005/069997 A
Patent Document 5 US 2006/065600 A
Summary of the Invention
[0007]
In view of the above-mentioned purpose, that is, purification of butanol, the present invention aims to provide a method by which butanol can be separated and collected at higher purity and at lower cost than by the conventional methods.
In view of the above-mentioned purpose, that is, purification of butanol, the present invention aims to provide a method by which butanol can be separated and collected at higher purity and at lower cost than by the conventional methods.
[0008]
The present inventors intensively studied to solve the above problems and discovered that high-purity butanol can be obtained by filtering a butanol-containing solution through a nanofiltration membrane having a functional layer containing a polyamide, and that the cost of distillation can be effectively reduced by this process, thereby completing the present invention.
The present inventors intensively studied to solve the above problems and discovered that high-purity butanol can be obtained by filtering a butanol-containing solution through a nanofiltration membrane having a functional layer containing a polyamide, and that the cost of distillation can be effectively reduced by this process, thereby completing the present invention.
[0009]
That is, the present invention provides the following (1) to (7):
(1) A method of producing butanol, the method comprising the steps of:
filtering a butanol-containing solution through a nanofiltration membrane; and collecting butanol-containing solution from the permeate flow of the nanofiltration membrane.
(2) The method according to (1), wherein the butanol-containing solution is a fermentation broth obtained by microbial fermentation.
(3) The method according to (1), wherein the nanofiltration membrane has a functional layer comprising a polyamide.
(4) The method according to (3), wherein the polyamide comprises a cross-linked piperazine polyamide as a major component, and a constituting component represented by Formula [I]:
N\-CH2 JN-R R
[I]
wherein R represents -H or -CH3, and n represents an integer of 0 to 3.
(5) The method according to (1), further comprising the step of filtering the collected butanol-containing solution through a reverse osmosis membrane to increase the butanol concentration.
(6) The method according to (1), further comprising the step of distilling the collected butanol-containing solution under a pressure of not less than I Pa and not more than atmospheric pressure, at 25 C to 200 C.
(7) The method according to (5), further comprising the step of distilling the butanol-containing solution after concentration through the reverse osmosis membrane under a pressure of not less than 1 Pa and not more than atmospheric pressure, at 25 C to 200 C.
That is, the present invention provides the following (1) to (7):
(1) A method of producing butanol, the method comprising the steps of:
filtering a butanol-containing solution through a nanofiltration membrane; and collecting butanol-containing solution from the permeate flow of the nanofiltration membrane.
(2) The method according to (1), wherein the butanol-containing solution is a fermentation broth obtained by microbial fermentation.
(3) The method according to (1), wherein the nanofiltration membrane has a functional layer comprising a polyamide.
(4) The method according to (3), wherein the polyamide comprises a cross-linked piperazine polyamide as a major component, and a constituting component represented by Formula [I]:
N\-CH2 JN-R R
[I]
wherein R represents -H or -CH3, and n represents an integer of 0 to 3.
(5) The method according to (1), further comprising the step of filtering the collected butanol-containing solution through a reverse osmosis membrane to increase the butanol concentration.
(6) The method according to (1), further comprising the step of distilling the collected butanol-containing solution under a pressure of not less than I Pa and not more than atmospheric pressure, at 25 C to 200 C.
(7) The method according to (5), further comprising the step of distilling the butanol-containing solution after concentration through the reverse osmosis membrane under a pressure of not less than 1 Pa and not more than atmospheric pressure, at 25 C to 200 C.
[0010]
By the present invention, metal catalysts, inorganic salts and/or sugars 5 existing in a butanol-containing chemically synthesized reaction solution or fermentation broth can be removed by a simple process, and therefore the distillation efficiency can be increased and the cost can be reduced, so that highly pure butanol can be produced at low cost.
Brief Description of the Drawings
By the present invention, metal catalysts, inorganic salts and/or sugars 5 existing in a butanol-containing chemically synthesized reaction solution or fermentation broth can be removed by a simple process, and therefore the distillation efficiency can be increased and the cost can be reduced, so that highly pure butanol can be produced at low cost.
Brief Description of the Drawings
[0011]
Fig. 1 is a schematic view showing an embodiment of the separation apparatus used in the present invention having a nanofiltration membrane and a reverse osmosis membrane.
Fig. 2 is a schematic view showing an embodiment of a cross-sectional view of a cell in the separation apparatus used in the present invention having a nanofiltration membrane and a reverse osmosis membrane, which cell has the reverse osmosis membrane attached thereto.
Description of Symbols in Drawings
Fig. 1 is a schematic view showing an embodiment of the separation apparatus used in the present invention having a nanofiltration membrane and a reverse osmosis membrane.
Fig. 2 is a schematic view showing an embodiment of a cross-sectional view of a cell in the separation apparatus used in the present invention having a nanofiltration membrane and a reverse osmosis membrane, which cell has the reverse osmosis membrane attached thereto.
Description of Symbols in Drawings
[0012]
1 Feed tank 2 Cell equipped with nanofiltration membrane or reverse osmosis membrane 3 High-pressure pump 4 Permeate flow which has pass through membrane 5 Retentate flow which has been concentrated with membrane 6 Feed flow sent by high-pressure pump 7 Nanofiltration membrane or reverse osmosis membrane 8 Supporting plate Best Mode for Carrying out the Invention
1 Feed tank 2 Cell equipped with nanofiltration membrane or reverse osmosis membrane 3 High-pressure pump 4 Permeate flow which has pass through membrane 5 Retentate flow which has been concentrated with membrane 6 Feed flow sent by high-pressure pump 7 Nanofiltration membrane or reverse osmosis membrane 8 Supporting plate Best Mode for Carrying out the Invention
[0013]
The present invention will now be described more concretely.
The method of the present invention for producing butanol is a method for producing butanol by separating butanol from a butanol-containing solution, and relates to a method for producing butanol, comprising a step of allowing the butanol-containing solution to pass through a nanofiltration membrane to remove metal catalysts, inorganic salts, sugars and/or the like.
The present invention will now be described more concretely.
The method of the present invention for producing butanol is a method for producing butanol by separating butanol from a butanol-containing solution, and relates to a method for producing butanol, comprising a step of allowing the butanol-containing solution to pass through a nanofiltration membrane to remove metal catalysts, inorganic salts, sugars and/or the like.
[0014]
In the present invention, butanol means a collective name of compounds having a hydroxyl group and four carbon atoms, and examples thereof include n-butanol, isobutanol, 2-butanol and 2-methyl-2-propanol. In the present invention, a butanol may comprise a single type of butanol or may be a mixture of plural types of butanols.
In the present invention, butanol means a collective name of compounds having a hydroxyl group and four carbon atoms, and examples thereof include n-butanol, isobutanol, 2-butanol and 2-methyl-2-propanol. In the present invention, a butanol may comprise a single type of butanol or may be a mixture of plural types of butanols.
[0015]
The method used in the present invention for producing a butanol-containing solution is not restricted as long as it is known to those skilled in the art, and examples of the method include a method wherein the solution is prepared by the Wacker process from acetaldehyde and a method wherein the solution is prepared by Reppe process from propylene, carbon monoxide and water, as mentioned above, in cases where a chemical synthesis method is used. In terms of fermentation culture, the solution is produced by anaerobic culture of Clostridium butylicum. A
preferred method for the butanol-containing solution used in the present invention is the method by fermentation culture of a microorganism, and, in this case, the fermentation broth itself containing butanol can be used as the butanol-containing solution to be applied to the nanofiltration membrane.
The method used in the present invention for producing a butanol-containing solution is not restricted as long as it is known to those skilled in the art, and examples of the method include a method wherein the solution is prepared by the Wacker process from acetaldehyde and a method wherein the solution is prepared by Reppe process from propylene, carbon monoxide and water, as mentioned above, in cases where a chemical synthesis method is used. In terms of fermentation culture, the solution is produced by anaerobic culture of Clostridium butylicum. A
preferred method for the butanol-containing solution used in the present invention is the method by fermentation culture of a microorganism, and, in this case, the fermentation broth itself containing butanol can be used as the butanol-containing solution to be applied to the nanofiltration membrane.
[0016]
The nanofiltration membrane used in the present invention is also called NF
membrane, and generally defined as a "membrane that allows permeation of monovalent ions but blocks divalent ions". The membrane is considered to have voids of as small as several nanometers, and mainly used for rejection microparticles, molecules, ions, salts and/or the like in water.
The nanofiltration membrane used in the present invention is also called NF
membrane, and generally defined as a "membrane that allows permeation of monovalent ions but blocks divalent ions". The membrane is considered to have voids of as small as several nanometers, and mainly used for rejection microparticles, molecules, ions, salts and/or the like in water.
[0017]
By filtering the butanol-containing solution through the nanofiltration membrane, impurities (substances other than butanol) are removed at the feed flow of the nanofiltration membrane and the butanol-containing solution is collected from the permeate flow of the nanofiltration membrane.
By filtering the butanol-containing solution through the nanofiltration membrane, impurities (substances other than butanol) are removed at the feed flow of the nanofiltration membrane and the butanol-containing solution is collected from the permeate flow of the nanofiltration membrane.
[0018]
Examples of known materials of nano filtration membranes generally include polymer materials such as cellulose acetate polymers; polyamides; polyesters;
polyimides; vinyl polymers including polyvinyl alcohols; and polysulfones, which can be used in the present invention. Among these, a nanofiltration membrane having a polyamide in its functional layer is preferably used in the present invention since high purification efficiency can be attained therewith. Other plural membrane materials may also be contained in the membrane as long as the functional layer contains a polyamide. In terms of the membrane structure, either an asymmetric membrane wherein at least one side of the membrane has a dense layer, which membrane has micropores having a diameter that gradually increases from the dense layer to the inside of the membrane or to the other side of the membrane, or a composite membrane having on the dense layer of an asymmetric membrane a very thin functional layer formed by another material can be used. Examples of the composite membrane which may be used include the composite membrane described in JP 62-201606 A, wherein a nanofiltration membrane having a polyamide functional layer was placed on a support membrane made of a polysulfone membrane material.
Examples of known materials of nano filtration membranes generally include polymer materials such as cellulose acetate polymers; polyamides; polyesters;
polyimides; vinyl polymers including polyvinyl alcohols; and polysulfones, which can be used in the present invention. Among these, a nanofiltration membrane having a polyamide in its functional layer is preferably used in the present invention since high purification efficiency can be attained therewith. Other plural membrane materials may also be contained in the membrane as long as the functional layer contains a polyamide. In terms of the membrane structure, either an asymmetric membrane wherein at least one side of the membrane has a dense layer, which membrane has micropores having a diameter that gradually increases from the dense layer to the inside of the membrane or to the other side of the membrane, or a composite membrane having on the dense layer of an asymmetric membrane a very thin functional layer formed by another material can be used. Examples of the composite membrane which may be used include the composite membrane described in JP 62-201606 A, wherein a nanofiltration membrane having a polyamide functional layer was placed on a support membrane made of a polysulfone membrane material.
[0019]
The nanofiltration membrane having a polyamide functional layer preferably used in the present invention is preferably a composite membrane having a high pressure resistance, a high permeability and a high solute rejection performance.
Further, in order to allow maintenance of durability against the operation pressure, a high permeability and a high rejection performance, the membrane preferably has a polyamide functional layer which is retained by a support made of a porous membrane and/or a non-woven fabric. In a nanofiltration membrane having a polyamide functional layer, preferred examples of the carboxylic component, expressed in terms of monomers, constituting the polyamide include aromatic carboxylic acids such as trimesic acid, benzophenone tetracarboxylic acid, trimellitic acid, pyromellitic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, diphenylcarboxylic acid and pyridinecarboxylic acid, and, in view of solubility to the film-forming solvent, trimesic acid, isophthalic acid or terephthalic acid, or a mixture thereof is more preferred.
The nanofiltration membrane having a polyamide functional layer preferably used in the present invention is preferably a composite membrane having a high pressure resistance, a high permeability and a high solute rejection performance.
Further, in order to allow maintenance of durability against the operation pressure, a high permeability and a high rejection performance, the membrane preferably has a polyamide functional layer which is retained by a support made of a porous membrane and/or a non-woven fabric. In a nanofiltration membrane having a polyamide functional layer, preferred examples of the carboxylic component, expressed in terms of monomers, constituting the polyamide include aromatic carboxylic acids such as trimesic acid, benzophenone tetracarboxylic acid, trimellitic acid, pyromellitic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, diphenylcarboxylic acid and pyridinecarboxylic acid, and, in view of solubility to the film-forming solvent, trimesic acid, isophthalic acid or terephthalic acid, or a mixture thereof is more preferred.
[0020]
Preferred examples of the amine component, expressed in terms of monomers, constituting the polyamide include primary diamines having an aromatic ring(s), such as m-phenylenediamine, p-phenylenediamine, benzidine, methylenebisdianiline, 4,4'-diaminobiphenyl ether, dianisidine, 3,3',4-tiaminobiphenyl ether, 3,3',4,4'-tetraaminobiphenyl ether, 3,3'-dioxybenzidine, 1,8-naphthalenediamine, m(p)-monomethylphenylenediamine, 3,3'-monomethylamino-4,4'-diaminobiphenyl ether, 4,N,N'-(4-aminobenzoyl)-p(m)-phenylenediamine-2,2'-bis(4-aminophenyl benzimidazol), 2,2'-bis(4-aminophenyl benzoxazol), 2,2'-bis(4-aminophenyl benzothiazole); and secondary diamines such as piperazine and piperidine and derivatives thereof; and, in particular, a nanofiltration membrane having a functional layer composed of a cross-linked polyamide containing piperazine or piperidine, expressed in terms of monomers, has a high pressure resistance and durability as well as heat resistance and chemical resistance, and is therefore preferably used.
The functional layer of the nanofiltration membrane more preferably comprises a cross-linked piperazine polyamide or a cross-linked piperidine polyamide as a major component; the polyamide still more preferably comprises a cross-linked piperazine polyamide or a cross-linked piperidine polyamide as a major component and further comprises a constituting component represented by the Formula [I]; and the polyamide still more preferably comprises a cross-linked piperazine polyamide as a major component and further comprises a constituting component represented by the Formula [I]. Further, preferably, in the Formula [I], n=3. Examples of the nanofiltration membrane comprising a cross-linked piperazine polyamide as a major component and further comprises a constituting component represented by the Formula [I] include the one described in JP 62-201606 A, and particular examples of the nanofiltration membrane include a cross-linked piperazine polyamide nanofiltration membrane UTC60 manufactured by TORAY INDUSTRIES, INC.
Preferred examples of the amine component, expressed in terms of monomers, constituting the polyamide include primary diamines having an aromatic ring(s), such as m-phenylenediamine, p-phenylenediamine, benzidine, methylenebisdianiline, 4,4'-diaminobiphenyl ether, dianisidine, 3,3',4-tiaminobiphenyl ether, 3,3',4,4'-tetraaminobiphenyl ether, 3,3'-dioxybenzidine, 1,8-naphthalenediamine, m(p)-monomethylphenylenediamine, 3,3'-monomethylamino-4,4'-diaminobiphenyl ether, 4,N,N'-(4-aminobenzoyl)-p(m)-phenylenediamine-2,2'-bis(4-aminophenyl benzimidazol), 2,2'-bis(4-aminophenyl benzoxazol), 2,2'-bis(4-aminophenyl benzothiazole); and secondary diamines such as piperazine and piperidine and derivatives thereof; and, in particular, a nanofiltration membrane having a functional layer composed of a cross-linked polyamide containing piperazine or piperidine, expressed in terms of monomers, has a high pressure resistance and durability as well as heat resistance and chemical resistance, and is therefore preferably used.
The functional layer of the nanofiltration membrane more preferably comprises a cross-linked piperazine polyamide or a cross-linked piperidine polyamide as a major component; the polyamide still more preferably comprises a cross-linked piperazine polyamide or a cross-linked piperidine polyamide as a major component and further comprises a constituting component represented by the Formula [I]; and the polyamide still more preferably comprises a cross-linked piperazine polyamide as a major component and further comprises a constituting component represented by the Formula [I]. Further, preferably, in the Formula [I], n=3. Examples of the nanofiltration membrane comprising a cross-linked piperazine polyamide as a major component and further comprises a constituting component represented by the Formula [I] include the one described in JP 62-201606 A, and particular examples of the nanofiltration membrane include a cross-linked piperazine polyamide nanofiltration membrane UTC60 manufactured by TORAY INDUSTRIES, INC.
[0021]
A nanofiltration membrane is generally used as a spiral-wound membrane element, and the nanofiltration membrane used in the present invention can also be preferably used a spiral-wound membrane element. Particular examples of a preferred nanofiltration membrane which may be used include SU-2 10, SU-220, SU-600 and SU-6 10, which are nanofiltration modules manufactured by TORAY
INDUSTRIES, INC. using UTC60 manufactured by the same manufacturer, which nanofiltration modules have a polyamide functional layer comprising a cross-linked piperazine polyamide as a major component and further a constituting component represented by the Formula [I]. Further particular examples of the membrane include nanofiltration membranes NF-45, NF-90, NF-200 and NF-400 manufactured by FilmTec Corporation, which have a functional layer made of a cross-linked piperazine polyamide, and nanofiltration membranes NF99, NF97 and NF99HF
manufactured by Alfa-Laval, which have a polyamide functional layer.
5 [0022]
In the present invention, the filtration of the butanol-containing solution through a nanofiltration membrane may be carried out under pressure. With a filtration pressure lower than 0.1 MPa, the membrane permeation flux decreases, and with a filtration pressure higher than 8 MPa, the membrane is damaged.
Therefore, 10 the filtration pressure is preferably within the range of 0.1 MPa to 8 MPa, and, in cases where it is within the range of 0.5 MPa to 7 MPa, the membrane permeation flux is high, so that butanol can be allowed to pass through the membrane efficiently with less possibility of causing damage to the membrane. A filtration pressure of 1 MPa to 6 MPa is especially preferred.
[0023]
In the present invention, in the filtration of a butanol-containing solution through a nanofiltration membrane, the recovery of butanol can be increased by returning the retentate to the feed solution and repeating the filtration. The recovery of butanol can be calculated by measuring the total amount of butanol contained before the nanofiltration and the total amount of butanol permeated through the nanofiltration membrane, followed by calculation by Equation 1.
[0024]
Recovery of butanol (%) = (total amount of butanol permeated through nanofiltration membrane / total amount of butanol contained before nanofiltration) x 100 ... (Equation 1).
[0025]
In terms of the membrane separation performance of the nanofiltration membrane used in the present invention, the membrane preferably shows a salt rejection rate of not less than 45% when an aqueous sodium chloride solution (500 mg/L) at 25 C, pH 6.5 is filtered under a filtration pressure of 0.75 MPa.
Here, the salt rejection rate can be calculated by measuring the salt concentration of the permeated aqueous sodium chloride solution, followed by calculation by Equation 2.
[0026]
Salt rejection rate = 100 x { 1-(salt concentration of permeate / salt concentration of feed solution} ... (Equation 2).
[0027]
Further, in terms of the permeation performance of the nanofiltration membrane, the membrane preferably shows a membrane permeation flux (m3/(m2 day)) of not less than 0.3 with aqueous sodium chloride solution (500 mg/L) under a filtration pressure of 0.3 MPa. The membrane permeation flux can be calculated by measuring the amount of the permeant, the length of time required for collecting this amount of the permeant, and the membrane area, followed by calculation by Equation 3.
[0028]
Membrane permeation flux (m3/(m2 = day)) = amount of permeant /
(membrane area x collection time) ... (Equation 3).
[0029]
In the present invention, examples of the impurities separated from the butanol-containing solution into the feed flow by the nanofiltration membrane include inorganic substances such as calcium, sodium, sulfuric acid, nitric acid and phosphoric acid; sugars such as glucose, fructose, xylose, sucrose, galactose and starch; and proteins; and mixtures thereof can also be preferably separated.
[0030]
The permeability of the nanofiltration membrane to butanol in the present invention can be evaluated by calculating the permeation rate of butanol. The permeation rate of butanol can be calculated by measuring the concentration of butanol (butanol concentration of feed solution) contained in the feed solution (butanol-containing solution) and the concentration of butanol (butanol concentration of permeate) contained in the permeate (butanol solution) by analysis represented by high performance liquid chromatography and gas chromatography, followed by calculation by Equation 4.
[0031]
Permeation rate of butanol (butanol concentration of permeate / butanol concentration of feed solution) x 100 ... (Equation 4).
[0032]
The permeate from the nanofiltration membrane is preferably concentrated in cases where the concentration of the substance of interest is low. In terms of the method for concentrating the permeate from the nanofiltration membrane, methods using a concentrator represented by an evaporator are commonly employed and also applicable to the present invention, but, since the heat capacity of water is much larger than those of organic solvents, enormous energy and time are required for the concentration. On the other hand, concentration by a reverse osmosis membrane is superior to concentration using an evaporator in view of reduction in the energy/cost, and therefore preferably applied to the present invention.
[0033]
The reverse osmosis membrane in the present invention is a filter for removing ions and/or low molecular-weight molecules using a pressure difference larger than the osmotic pressure of the solution to be treated, and examples thereof which can be used include cellulose membranes such as those made of cellulose acetate and membranes wherein a multifunctional amine compound and a multifunctional acid halide were polycondensed to provide a separation functional layer made of a polyamide on a microporous support membrane. In order to suppress dirt, that is, fouling, on the surface of the reverse osmosis membrane, a low-fouling reverse osmosis membrane, which is mainly for sewage treatment, can also be preferably employed, which reverse osmosis membrane is prepared by covering the surface of a separation functional layer made of a polyamide with an aqueous solution of a compound having at least one reactive group reactive with an acid halide group, thereby allowing acid halide groups remaining on the surface the separation functional layer to form covalent bonds with the reactive groups.
Since most of the divalent ions have been removed in the step of filtering through the nanofiltration membrane of the present invention, stable membrane concentration can be carried out without formation of scale on the surface of the reverse osmosis membrane.
[0034]
Further, the term "filtering through the reverse osmosis membrane" means that the butanol-containing solution permeated through the nanofiltration membrane is concentrated by being allowed to pass through the reverse osmosis membrane, followed by collecting the resulting solution containing butanol in the concentrate flow.
[0035]
Examples of the reverse osmosis membrane preferably used in the present invention include composite membranes having a cellulose acetate polymer as a functional layer (hereinafter referred to as cellulose acetate reverse osmosis membranes) and composite membranes having a polyamide functional layer (hereinafter referred to as polyamide reverse osmosis membranes). Here, examples of the cellulose acetate polymer include polymers prepared with organic acid esters of cellulose such as cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose propionate and cellulose butyrate, which may be used solely, as a mixture, or as a mixed ester. Examples of the polyamide include linear polymers and cross-linked polymers constituted by aliphatic and/or aromatic diamine monomers.
Examples of the form of the membrane which may be used as appropriate include the flat membrane, spiral-wound membrane and hollow fiber membrane.
[0036]
Particular examples of the reverse osmosis membrane used in the present invention include polyamide reverse osmosis membrane modules manufactured by TORAY INDUSTRIES, INC., such as low-pressure type modules SU-710, SU-720, SU-720F, SU-710L, SU-720L, SU-720LF, SU-720R, SU-71 OP and SU-720P, as well as high-pressure type modules SU-810, SU-820, SU-820L and SU-820FA containing UTC70 as the reverse osmosis membrane; cellulose acetate reverse osmosis membranes manufactured by the same manufacturer SC-L100R, SC-1,200R, SC-1100, SC-1200, SC-2100, SC-2200, SC-3100, SC-3200, SC-8100 and SC-8200;
NTR-759HR, NTR-729HF, NTR-70SWC, ES10-D, ES20-D, ES20-U, ESI5-D, ES 15-U and LF10-D manufactured by Nitto Denko Corporation; RO98pHt, R099, HR98PP and CE404OC-30D manufactured by Alfa-Laval; GE Sepa manufactured by GE; and BW30-4040, TW30-4040, XLE-4040, LP-4040, LE-4040, SW30-4040 and SW30HRLE-4040 manufactured by FilmTec Corporation.
[0037]
In the present invention, filtration of the permeate from the nanofiltration membrane with the reverse osmosis membrane is carried out under pressure, and the filtration pressure is preferably within the range of 1 MPa to 8 MPa since, with a filtration pressure lower than 1 MPa, the membrane permeation flux decreases, and with a filtration pressure higher than 8 MPa, the membrane is damaged.
Further, since, with a filtration pressure within the range of 1 MPa to 7 MPa, the membrane permeation flux is high, the butanol solution can be efficiently concentrated.
The filtration pressure is most preferably within the range of 2 MPa to 6 MPa since there is less possibility of causing damage to the membrane in this case.
[0038]
Further, in the present invention, by subjecting the permeate from the nanofiltration membrane to a step of distilling the permeate, highly pure butanol can 5 be obtained. The distillation step is carried out preferably under a reduced pressure of not less than 1 Pa and not more than atmospheric pressure (normal pressure, about 101 kPa), more preferably under a reduced pressure of not less than 100 Pa and not more than 15 kPa. In cases where the distillation is carried out under reduced pressure, the distillation temperature is preferably 20 C to 200 C, more preferably 10 50 C to 150 C.
Examples [0039]
The present invention will now be described more concretely by way of Examples, but the present invention is not restricted to the Examples below.
15 [0040]
Reference Example 1 Evaluation of Permeability of Nanofiltration Membrane to Butanol To 20 L of ultrapure water, 20 g of n-butanol (both of which were manufactured from Wako Pure Chemical Industries, Ltd.) was added, and the resulting mixture was stirred at 25 C for 30 minutes, thereby preparing l Og/L
butanol solution. Subsequently, 20 L of the thus prepared aqueous butanol solution was fed to a feed tank 1 of the membrane filtration apparatus shown in Fig. 1. As the nanofiltration membrane indicated by Symbol 7 in Fig. 2, each of a cross-linked piperazine polyamide nanofiltration membrane "UTC60" (nanofiltration membrane 1; manufactured by TORAY INDUSTRIES, INC.), a polyamide nanofiltration membrane "NF99" (nanofiltration membrane 2, manufactured by Alfa-Laval), a cellulose acetate nanofiltration membrane "GE Sepa" (nanofiltration membrane 3;
manufactured by GE Osmonics) , and a cross-linked piperazine polyamide nanofiltration membrane "NF-400" (nanofiltration membrane 4; manufactured by FilmTec Corporation) was placed in a cell made of stainless steel (SUS316), and the temperature of the feed solution was adjusted to 25 C and the pressure of a high-pressure pump 3 was adjusted to 1 MPa, followed by collecting the permeate 4.
The concentration of butanol contained in each of the feed tank 1 and the permeate 4 was analyzed with a gas chromatography: GC-2010 (manufactured by Shimadzu Corporation) under the following conditions, thereby calculating the permeation rate of butanol.
Column: TC-1, 0.53 mm I.D. x 15 m, df l.5 pm (GL Science) Mobile phase: helium gas (7.9 mL/min., 50 to 100 C: 5 C/min.) Detection: FID 250 C.
[0041]
The results are shown in Table 1.
[0042]
0) 00 0 N rn 00 y rn v .-~ 00 0 00 t~ 0; 00 ~ O O O O
U U
U
a) c U
171 0 o 0 c oll p, H
w H Q
N O M O
0 cr-O g, o O E, o o z z z [0043]
As shown by the results in Table 1, butanol permeated through any of the nanofiltration membranes. Further, since the permeation rates of butanol were high, a possibility that butanol can be purified from nonorganic salts and sugars at high efficiency was suggested. The differences in the permeation rate of butanol among the different types of the membrane materials were small, but the cross-linked piperazine polyamide nanofiltration membranes showed higher permeation rates of butanol, and the polyamide nanofiltration membrane showed a somewhat lower permeation rate.
[0044]
(Examples 1 to 9) Purification of Butanol from Fermentation Broth Using Nanofiltration Membrane <n-Butanol Fermentation>
Two liters of the medium shown in Table 2 was prepared and adjusted to pH
6.5. The resulting medium was autoclaved (121 C, 15 minutes) and then allowed to cool to 37 C, followed by addition of 25 mL of inoculum thereto to carry out main culture. The inoculum used was prepared by culturing Clostridium butylicum at 37 C for 24 hours in the same medium as that shown in Table 2 except that the glucose concentration was 50 g/L. The main culture was carried out by anaerobic culture under stirring at 100 rpm at 37 C for 72 hours. After the culture, the bacterial cells were precipitated by centrifugation, and the culture supernatant was collected as an n-butanol-containing solution.
[0045]
Table 2 Medium component Concentration [g/L]
Glucose 150 KH2PO4 0.8 K2HPO4 0.8 MgSO4 2 MnSO4 = H2O 0.01 FeSO4.7H2O 0.01 NaCl 1 Cysteine 0.5 Asparagine 2 Yeast extract 5 [0046]
<Purification of n-Butanol with Nano filtration Membrane>
Thereafter, 2 L of the culture supernatant obtained as described above was fed to the feed tank 1 of the membrane filtration apparatus shown in Fig. 1. As the 90~ nanofiltration membrane indicated by Symbol 7 in Fig. 2, each of the above nanofiltration membranes 1 to 3 was placed in a cell made of stainless steel (SUS316), and the pressure by the high-pressure pump 3 was adjusted to 1 MPa, MPa or 5 MPa, followed by collecting the permeate 4 under the respective pressures.
The concentration of n-butanol contained in each of the feed tank 1 and the permeate 4 was analyzed under the same conditions as those in Reference Example 1 using a gas chromatography (manufactured by Shimadzu Corporation). Further, the sugar concentrations (glucose, fructose and sucrose) were analyzed with a high performance liquid chromatography (manufactured by Shimadzu Corporation) under the following conditions.
Column: Luna 5u NH2 100A (manufactured by Phenomenex, Inc.), 30 C
Mobile phase: water:acetonitrile = 1:3, 0.6 mL/min.
Detector: RI.
[0047]
The results are shown in Table 3.
[0048]
o 0 O O O O O O O O tn c:) O O
o =N ON ON ON O, C ON rn ON C, Q, O1 C
=~ al H
cd C." a) CO O fl N v v~ N O ao r k L
~D~D 0 0 0 0 0 O O O O O
cn c E i v) vn vn N N N N N- N N- N N
a) a) o ..
o a N 00 -, \O N CO N Q, N
o, N ~r 00 \~O d ri Co tf 4 00 00 00 tN ID lD O, 00 00 00 00 00 a) H
w a) o O 00 of Q\ \IR N & ct 00 O V7 O\ 00 00 N ,0 "0 0, Co 00 00 00 00 W a c:) C) O O o 0 C) 0 O o o O
a) a) ~C b N M 0 M M 'd' N N M 1r 't O
N oo N O CO ' '-1 ~t N v 1 ,0 O
Gi -, ~t N N cn 00 N vi 00 '-+ N
C
O r~
N z Q Q C C C
o o D N o o ai ^ a) ,~ a) cd :, a) o z N M ct cn ,O N Co Q, O N
sc x x x sc k k X
F' W W W W W W W W W W W W
A nanofiltration membrane is generally used as a spiral-wound membrane element, and the nanofiltration membrane used in the present invention can also be preferably used a spiral-wound membrane element. Particular examples of a preferred nanofiltration membrane which may be used include SU-2 10, SU-220, SU-600 and SU-6 10, which are nanofiltration modules manufactured by TORAY
INDUSTRIES, INC. using UTC60 manufactured by the same manufacturer, which nanofiltration modules have a polyamide functional layer comprising a cross-linked piperazine polyamide as a major component and further a constituting component represented by the Formula [I]. Further particular examples of the membrane include nanofiltration membranes NF-45, NF-90, NF-200 and NF-400 manufactured by FilmTec Corporation, which have a functional layer made of a cross-linked piperazine polyamide, and nanofiltration membranes NF99, NF97 and NF99HF
manufactured by Alfa-Laval, which have a polyamide functional layer.
5 [0022]
In the present invention, the filtration of the butanol-containing solution through a nanofiltration membrane may be carried out under pressure. With a filtration pressure lower than 0.1 MPa, the membrane permeation flux decreases, and with a filtration pressure higher than 8 MPa, the membrane is damaged.
Therefore, 10 the filtration pressure is preferably within the range of 0.1 MPa to 8 MPa, and, in cases where it is within the range of 0.5 MPa to 7 MPa, the membrane permeation flux is high, so that butanol can be allowed to pass through the membrane efficiently with less possibility of causing damage to the membrane. A filtration pressure of 1 MPa to 6 MPa is especially preferred.
[0023]
In the present invention, in the filtration of a butanol-containing solution through a nanofiltration membrane, the recovery of butanol can be increased by returning the retentate to the feed solution and repeating the filtration. The recovery of butanol can be calculated by measuring the total amount of butanol contained before the nanofiltration and the total amount of butanol permeated through the nanofiltration membrane, followed by calculation by Equation 1.
[0024]
Recovery of butanol (%) = (total amount of butanol permeated through nanofiltration membrane / total amount of butanol contained before nanofiltration) x 100 ... (Equation 1).
[0025]
In terms of the membrane separation performance of the nanofiltration membrane used in the present invention, the membrane preferably shows a salt rejection rate of not less than 45% when an aqueous sodium chloride solution (500 mg/L) at 25 C, pH 6.5 is filtered under a filtration pressure of 0.75 MPa.
Here, the salt rejection rate can be calculated by measuring the salt concentration of the permeated aqueous sodium chloride solution, followed by calculation by Equation 2.
[0026]
Salt rejection rate = 100 x { 1-(salt concentration of permeate / salt concentration of feed solution} ... (Equation 2).
[0027]
Further, in terms of the permeation performance of the nanofiltration membrane, the membrane preferably shows a membrane permeation flux (m3/(m2 day)) of not less than 0.3 with aqueous sodium chloride solution (500 mg/L) under a filtration pressure of 0.3 MPa. The membrane permeation flux can be calculated by measuring the amount of the permeant, the length of time required for collecting this amount of the permeant, and the membrane area, followed by calculation by Equation 3.
[0028]
Membrane permeation flux (m3/(m2 = day)) = amount of permeant /
(membrane area x collection time) ... (Equation 3).
[0029]
In the present invention, examples of the impurities separated from the butanol-containing solution into the feed flow by the nanofiltration membrane include inorganic substances such as calcium, sodium, sulfuric acid, nitric acid and phosphoric acid; sugars such as glucose, fructose, xylose, sucrose, galactose and starch; and proteins; and mixtures thereof can also be preferably separated.
[0030]
The permeability of the nanofiltration membrane to butanol in the present invention can be evaluated by calculating the permeation rate of butanol. The permeation rate of butanol can be calculated by measuring the concentration of butanol (butanol concentration of feed solution) contained in the feed solution (butanol-containing solution) and the concentration of butanol (butanol concentration of permeate) contained in the permeate (butanol solution) by analysis represented by high performance liquid chromatography and gas chromatography, followed by calculation by Equation 4.
[0031]
Permeation rate of butanol (butanol concentration of permeate / butanol concentration of feed solution) x 100 ... (Equation 4).
[0032]
The permeate from the nanofiltration membrane is preferably concentrated in cases where the concentration of the substance of interest is low. In terms of the method for concentrating the permeate from the nanofiltration membrane, methods using a concentrator represented by an evaporator are commonly employed and also applicable to the present invention, but, since the heat capacity of water is much larger than those of organic solvents, enormous energy and time are required for the concentration. On the other hand, concentration by a reverse osmosis membrane is superior to concentration using an evaporator in view of reduction in the energy/cost, and therefore preferably applied to the present invention.
[0033]
The reverse osmosis membrane in the present invention is a filter for removing ions and/or low molecular-weight molecules using a pressure difference larger than the osmotic pressure of the solution to be treated, and examples thereof which can be used include cellulose membranes such as those made of cellulose acetate and membranes wherein a multifunctional amine compound and a multifunctional acid halide were polycondensed to provide a separation functional layer made of a polyamide on a microporous support membrane. In order to suppress dirt, that is, fouling, on the surface of the reverse osmosis membrane, a low-fouling reverse osmosis membrane, which is mainly for sewage treatment, can also be preferably employed, which reverse osmosis membrane is prepared by covering the surface of a separation functional layer made of a polyamide with an aqueous solution of a compound having at least one reactive group reactive with an acid halide group, thereby allowing acid halide groups remaining on the surface the separation functional layer to form covalent bonds with the reactive groups.
Since most of the divalent ions have been removed in the step of filtering through the nanofiltration membrane of the present invention, stable membrane concentration can be carried out without formation of scale on the surface of the reverse osmosis membrane.
[0034]
Further, the term "filtering through the reverse osmosis membrane" means that the butanol-containing solution permeated through the nanofiltration membrane is concentrated by being allowed to pass through the reverse osmosis membrane, followed by collecting the resulting solution containing butanol in the concentrate flow.
[0035]
Examples of the reverse osmosis membrane preferably used in the present invention include composite membranes having a cellulose acetate polymer as a functional layer (hereinafter referred to as cellulose acetate reverse osmosis membranes) and composite membranes having a polyamide functional layer (hereinafter referred to as polyamide reverse osmosis membranes). Here, examples of the cellulose acetate polymer include polymers prepared with organic acid esters of cellulose such as cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose propionate and cellulose butyrate, which may be used solely, as a mixture, or as a mixed ester. Examples of the polyamide include linear polymers and cross-linked polymers constituted by aliphatic and/or aromatic diamine monomers.
Examples of the form of the membrane which may be used as appropriate include the flat membrane, spiral-wound membrane and hollow fiber membrane.
[0036]
Particular examples of the reverse osmosis membrane used in the present invention include polyamide reverse osmosis membrane modules manufactured by TORAY INDUSTRIES, INC., such as low-pressure type modules SU-710, SU-720, SU-720F, SU-710L, SU-720L, SU-720LF, SU-720R, SU-71 OP and SU-720P, as well as high-pressure type modules SU-810, SU-820, SU-820L and SU-820FA containing UTC70 as the reverse osmosis membrane; cellulose acetate reverse osmosis membranes manufactured by the same manufacturer SC-L100R, SC-1,200R, SC-1100, SC-1200, SC-2100, SC-2200, SC-3100, SC-3200, SC-8100 and SC-8200;
NTR-759HR, NTR-729HF, NTR-70SWC, ES10-D, ES20-D, ES20-U, ESI5-D, ES 15-U and LF10-D manufactured by Nitto Denko Corporation; RO98pHt, R099, HR98PP and CE404OC-30D manufactured by Alfa-Laval; GE Sepa manufactured by GE; and BW30-4040, TW30-4040, XLE-4040, LP-4040, LE-4040, SW30-4040 and SW30HRLE-4040 manufactured by FilmTec Corporation.
[0037]
In the present invention, filtration of the permeate from the nanofiltration membrane with the reverse osmosis membrane is carried out under pressure, and the filtration pressure is preferably within the range of 1 MPa to 8 MPa since, with a filtration pressure lower than 1 MPa, the membrane permeation flux decreases, and with a filtration pressure higher than 8 MPa, the membrane is damaged.
Further, since, with a filtration pressure within the range of 1 MPa to 7 MPa, the membrane permeation flux is high, the butanol solution can be efficiently concentrated.
The filtration pressure is most preferably within the range of 2 MPa to 6 MPa since there is less possibility of causing damage to the membrane in this case.
[0038]
Further, in the present invention, by subjecting the permeate from the nanofiltration membrane to a step of distilling the permeate, highly pure butanol can 5 be obtained. The distillation step is carried out preferably under a reduced pressure of not less than 1 Pa and not more than atmospheric pressure (normal pressure, about 101 kPa), more preferably under a reduced pressure of not less than 100 Pa and not more than 15 kPa. In cases where the distillation is carried out under reduced pressure, the distillation temperature is preferably 20 C to 200 C, more preferably 10 50 C to 150 C.
Examples [0039]
The present invention will now be described more concretely by way of Examples, but the present invention is not restricted to the Examples below.
15 [0040]
Reference Example 1 Evaluation of Permeability of Nanofiltration Membrane to Butanol To 20 L of ultrapure water, 20 g of n-butanol (both of which were manufactured from Wako Pure Chemical Industries, Ltd.) was added, and the resulting mixture was stirred at 25 C for 30 minutes, thereby preparing l Og/L
butanol solution. Subsequently, 20 L of the thus prepared aqueous butanol solution was fed to a feed tank 1 of the membrane filtration apparatus shown in Fig. 1. As the nanofiltration membrane indicated by Symbol 7 in Fig. 2, each of a cross-linked piperazine polyamide nanofiltration membrane "UTC60" (nanofiltration membrane 1; manufactured by TORAY INDUSTRIES, INC.), a polyamide nanofiltration membrane "NF99" (nanofiltration membrane 2, manufactured by Alfa-Laval), a cellulose acetate nanofiltration membrane "GE Sepa" (nanofiltration membrane 3;
manufactured by GE Osmonics) , and a cross-linked piperazine polyamide nanofiltration membrane "NF-400" (nanofiltration membrane 4; manufactured by FilmTec Corporation) was placed in a cell made of stainless steel (SUS316), and the temperature of the feed solution was adjusted to 25 C and the pressure of a high-pressure pump 3 was adjusted to 1 MPa, followed by collecting the permeate 4.
The concentration of butanol contained in each of the feed tank 1 and the permeate 4 was analyzed with a gas chromatography: GC-2010 (manufactured by Shimadzu Corporation) under the following conditions, thereby calculating the permeation rate of butanol.
Column: TC-1, 0.53 mm I.D. x 15 m, df l.5 pm (GL Science) Mobile phase: helium gas (7.9 mL/min., 50 to 100 C: 5 C/min.) Detection: FID 250 C.
[0041]
The results are shown in Table 1.
[0042]
0) 00 0 N rn 00 y rn v .-~ 00 0 00 t~ 0; 00 ~ O O O O
U U
U
a) c U
171 0 o 0 c oll p, H
w H Q
N O M O
0 cr-O g, o O E, o o z z z [0043]
As shown by the results in Table 1, butanol permeated through any of the nanofiltration membranes. Further, since the permeation rates of butanol were high, a possibility that butanol can be purified from nonorganic salts and sugars at high efficiency was suggested. The differences in the permeation rate of butanol among the different types of the membrane materials were small, but the cross-linked piperazine polyamide nanofiltration membranes showed higher permeation rates of butanol, and the polyamide nanofiltration membrane showed a somewhat lower permeation rate.
[0044]
(Examples 1 to 9) Purification of Butanol from Fermentation Broth Using Nanofiltration Membrane <n-Butanol Fermentation>
Two liters of the medium shown in Table 2 was prepared and adjusted to pH
6.5. The resulting medium was autoclaved (121 C, 15 minutes) and then allowed to cool to 37 C, followed by addition of 25 mL of inoculum thereto to carry out main culture. The inoculum used was prepared by culturing Clostridium butylicum at 37 C for 24 hours in the same medium as that shown in Table 2 except that the glucose concentration was 50 g/L. The main culture was carried out by anaerobic culture under stirring at 100 rpm at 37 C for 72 hours. After the culture, the bacterial cells were precipitated by centrifugation, and the culture supernatant was collected as an n-butanol-containing solution.
[0045]
Table 2 Medium component Concentration [g/L]
Glucose 150 KH2PO4 0.8 K2HPO4 0.8 MgSO4 2 MnSO4 = H2O 0.01 FeSO4.7H2O 0.01 NaCl 1 Cysteine 0.5 Asparagine 2 Yeast extract 5 [0046]
<Purification of n-Butanol with Nano filtration Membrane>
Thereafter, 2 L of the culture supernatant obtained as described above was fed to the feed tank 1 of the membrane filtration apparatus shown in Fig. 1. As the 90~ nanofiltration membrane indicated by Symbol 7 in Fig. 2, each of the above nanofiltration membranes 1 to 3 was placed in a cell made of stainless steel (SUS316), and the pressure by the high-pressure pump 3 was adjusted to 1 MPa, MPa or 5 MPa, followed by collecting the permeate 4 under the respective pressures.
The concentration of n-butanol contained in each of the feed tank 1 and the permeate 4 was analyzed under the same conditions as those in Reference Example 1 using a gas chromatography (manufactured by Shimadzu Corporation). Further, the sugar concentrations (glucose, fructose and sucrose) were analyzed with a high performance liquid chromatography (manufactured by Shimadzu Corporation) under the following conditions.
Column: Luna 5u NH2 100A (manufactured by Phenomenex, Inc.), 30 C
Mobile phase: water:acetonitrile = 1:3, 0.6 mL/min.
Detector: RI.
[0047]
The results are shown in Table 3.
[0048]
o 0 O O O O O O O O tn c:) O O
o =N ON ON ON O, C ON rn ON C, Q, O1 C
=~ al H
cd C." a) CO O fl N v v~ N O ao r k L
~D~D 0 0 0 0 0 O O O O O
cn c E i v) vn vn N N N N N- N N- N N
a) a) o ..
o a N 00 -, \O N CO N Q, N
o, N ~r 00 \~O d ri Co tf 4 00 00 00 tN ID lD O, 00 00 00 00 00 a) H
w a) o O 00 of Q\ \IR N & ct 00 O V7 O\ 00 00 N ,0 "0 0, Co 00 00 00 00 W a c:) C) O O o 0 C) 0 O o o O
a) a) ~C b N M 0 M M 'd' N N M 1r 't O
N oo N O CO ' '-1 ~t N v 1 ,0 O
Gi -, ~t N N cn 00 N vi 00 '-+ N
C
O r~
N z Q Q C C C
o o D N o o ai ^ a) ,~ a) cd :, a) o z N M ct cn ,O N Co Q, O N
sc x x x sc k k X
F' W W W W W W W W W W W W
22 [0049]
As shown in Table 3, with all the nanofiltration membranes and under all the filtration pressures, the sugars were removed and n-butanol solutions were obtained.
Further, since a colorless transparent solution was obtained from the brown-colored broth, it was assumed that the other impurities were also mostly removed.
Further, when an operation in which 1.5 L of the permeate was collected and 1.5 L of distilled water was added thereto, followed by collecting the permeate again was repeated three times in order to increase the recovery of n-butanol shown by (Equation 1), the recovery became 94%.
[0050]
<Distillation from Solution Concentrated Using Reverse Osmosis Membrane >
Among the n-butanol solutions obtained as described above, those of Example 2, Example 5, Example 8 and Example 11 were subjected to the study. To the feed tank 1 of the membrane filtration apparatus shown in Fig. 1, 4.5 L of the solution was fed. As the 904 reverse osmosis membrane indicated by Symbol 7 in Fig. 2, a polyamide reverse osmosis membrane (UTC-70, manufactured by TORAY
INDUSTRIES, INC.) was attached to a cell made of stainless steel (SUS316), and membrane filtration was carried out by adjusting the pressure by the high-pressure pump 3 to 5 MPa and the temperature of the feed solution to 35 C, thereby removing 4.4 L of the permeate 4 from the reverse osmosis membrane. One hundred milliliter of the thus obtained concentrate was subjected to atmospheric distillation at 117 C.
The results of the distillation are shown in Table 4.
[0051]
As shown in Table 3, with all the nanofiltration membranes and under all the filtration pressures, the sugars were removed and n-butanol solutions were obtained.
Further, since a colorless transparent solution was obtained from the brown-colored broth, it was assumed that the other impurities were also mostly removed.
Further, when an operation in which 1.5 L of the permeate was collected and 1.5 L of distilled water was added thereto, followed by collecting the permeate again was repeated three times in order to increase the recovery of n-butanol shown by (Equation 1), the recovery became 94%.
[0050]
<Distillation from Solution Concentrated Using Reverse Osmosis Membrane >
Among the n-butanol solutions obtained as described above, those of Example 2, Example 5, Example 8 and Example 11 were subjected to the study. To the feed tank 1 of the membrane filtration apparatus shown in Fig. 1, 4.5 L of the solution was fed. As the 904 reverse osmosis membrane indicated by Symbol 7 in Fig. 2, a polyamide reverse osmosis membrane (UTC-70, manufactured by TORAY
INDUSTRIES, INC.) was attached to a cell made of stainless steel (SUS316), and membrane filtration was carried out by adjusting the pressure by the high-pressure pump 3 to 5 MPa and the temperature of the feed solution to 35 C, thereby removing 4.4 L of the permeate 4 from the reverse osmosis membrane. One hundred milliliter of the thus obtained concentrate was subjected to atmospheric distillation at 117 C.
The results of the distillation are shown in Table 4.
[0051]
23 rn Oo Iq O, C O: o; of rn o. rn ON
U
-ts rn rn rn C
.~
'.o M 00 V U O1 .-+ 00 00 ~. M M M M
o U
O
O
00 0\ ' O
U
N
c2 p p p p o o o o z z El z 02 z E
N yr 00 W W W W
U
-ts rn rn rn C
.~
'.o M 00 V U O1 .-+ 00 00 ~. M M M M
o U
O
O
00 0\ ' O
U
N
c2 p p p p o o o o z z El z 02 z E
N yr 00 W W W W
24 [0052]
From these results, it was shown that the present invention allows highly efficient production of high-purity n-butanol at low cost.
[0053]
(Comparative Example 1) Purification of 1,3-Propanediol with Nanofiltration Membrane A model broth containing 1,3-propanediol was filtered through a nanofiltration membrane as follows.
[0054]
In terms of the culture medium, 2.5 L of a culture medium containing 60 g/L
of Yutosei (MUSO Co., Ltd.) and 1.5 g/L of ammonium sulfate was prepared and then autoclaved (121 C, 15 minutes). First, an yeast strain NBRC 10505 was cultured in 5 ml of the above raw material sugar medium in a test tube overnight with shaking (pre-preculture). The pre-preculture broth was inoculated to 100 ml of a fresh lot of the above raw material sugar medium, and culture was carried out in a 500-m1 Sakaguchi flask for 24 hours with shaking (preculture). The preculture broth was added to 2L of the above raw material sugar medium, and culture was carried out while adjusting temperature and pH in ajar fermenter. The operating conditions of the jar fermenter were as shown below.
[0055]
Reaction vessel volume (amount of lactic acid fermentation medium), 2 (L);
temperature adjustment, 30 ( C); ventilation volume for the reaction vessel, 0.2 (L/min.); stirring rate of the reaction vessel, 400 rpm; pH adjustment, adjusted to pH
5 with 1 N calcium hydroxide.
[0056]
After 24 hours of the culture, the fermentation broth was centrifuged to remove the yeast cells, and the supernatant was collected. To this broth, 1,3-propanediol was added to 10 g/L. This broth was subjected to treatment with the nanofiltration membrane in the same manner as in the above Example 2. The resultant was further concentrated using the reverse osmosis membrane in the same manner as in the above Example 2, followed by distillation under reduced pressure (5 5 mmHg) at 97 C.
[0057]
As a result, the distillation yield of 1,3-propanediol was 95%, and the GC
purity was 99.7%. Thus, it was suggested that usage of the nanofiltration membrane allows purification of high-purity 1,3-propanediol. However, since the membrane 10 permeability of 1,3-propanediol with respect to the nano filtration membrane I
(UTC60) was as low as 26%, the yield of 1,3-propanediol was lower than that of butanol. Thus, it was shown that, although 1,3-propanediol and butanol described in Example 2 have almost the same molecular weights, n-butanol shows a higher permeation rate with respect to the nanofiltration membrane, so that butanol is a 15 compound more suitable for purification with the nanofiltration membrane.
From these results, it was shown that the present invention allows highly efficient production of high-purity n-butanol at low cost.
[0053]
(Comparative Example 1) Purification of 1,3-Propanediol with Nanofiltration Membrane A model broth containing 1,3-propanediol was filtered through a nanofiltration membrane as follows.
[0054]
In terms of the culture medium, 2.5 L of a culture medium containing 60 g/L
of Yutosei (MUSO Co., Ltd.) and 1.5 g/L of ammonium sulfate was prepared and then autoclaved (121 C, 15 minutes). First, an yeast strain NBRC 10505 was cultured in 5 ml of the above raw material sugar medium in a test tube overnight with shaking (pre-preculture). The pre-preculture broth was inoculated to 100 ml of a fresh lot of the above raw material sugar medium, and culture was carried out in a 500-m1 Sakaguchi flask for 24 hours with shaking (preculture). The preculture broth was added to 2L of the above raw material sugar medium, and culture was carried out while adjusting temperature and pH in ajar fermenter. The operating conditions of the jar fermenter were as shown below.
[0055]
Reaction vessel volume (amount of lactic acid fermentation medium), 2 (L);
temperature adjustment, 30 ( C); ventilation volume for the reaction vessel, 0.2 (L/min.); stirring rate of the reaction vessel, 400 rpm; pH adjustment, adjusted to pH
5 with 1 N calcium hydroxide.
[0056]
After 24 hours of the culture, the fermentation broth was centrifuged to remove the yeast cells, and the supernatant was collected. To this broth, 1,3-propanediol was added to 10 g/L. This broth was subjected to treatment with the nanofiltration membrane in the same manner as in the above Example 2. The resultant was further concentrated using the reverse osmosis membrane in the same manner as in the above Example 2, followed by distillation under reduced pressure (5 5 mmHg) at 97 C.
[0057]
As a result, the distillation yield of 1,3-propanediol was 95%, and the GC
purity was 99.7%. Thus, it was suggested that usage of the nanofiltration membrane allows purification of high-purity 1,3-propanediol. However, since the membrane 10 permeability of 1,3-propanediol with respect to the nano filtration membrane I
(UTC60) was as low as 26%, the yield of 1,3-propanediol was lower than that of butanol. Thus, it was shown that, although 1,3-propanediol and butanol described in Example 2 have almost the same molecular weights, n-butanol shows a higher permeation rate with respect to the nanofiltration membrane, so that butanol is a 15 compound more suitable for purification with the nanofiltration membrane.
Claims (7)
1. A method of producing butanol, said method comprising the steps of:
filtering a butanol-containing solution through a nanofiltration membrane;
and collecting butanol-containing solution from the permeate flow of said nanofiltration membrane.
filtering a butanol-containing solution through a nanofiltration membrane;
and collecting butanol-containing solution from the permeate flow of said nanofiltration membrane.
2. The method according to claim 1, wherein said butanol-containing solution is a fermentation broth obtained by microbial fermentation.
3. The method according to claim 1, wherein said nanofiltration membrane has a functional layer comprising a polyamide.
4. The method according to claim 3, wherein said polyamide comprises a cross-linked piperazine polyamide as a major component, and a constituting component represented by Formula [I]:
wherein R represents -H or -CH3, and n represents an integer of 0 to 3.
wherein R represents -H or -CH3, and n represents an integer of 0 to 3.
5. The method according to claim 1, further comprising the step of filtering the collected butanol-containing solution through a reverse osmosis membrane to increase the butanol concentration.
6. The method according to claim 1, further comprising the step of distilling the collected butanol-containing solution under a pressure of not less than 1 Pa and not more than atmospheric pressure, at 25°C to 200°C.
7. The method according to claim 5, further comprising the step of distilling the butanol-containing solution after concentration through said reverse osmosis membrane under a pressure of not less than 1 Pa and not more than atmospheric pressure, at 25°C to 200°C.
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