CA2735637C - Method of producing diol or triol - Google Patents
Method of producing diol or triol Download PDFInfo
- Publication number
- CA2735637C CA2735637C CA2735637A CA2735637A CA2735637C CA 2735637 C CA2735637 C CA 2735637C CA 2735637 A CA2735637 A CA 2735637A CA 2735637 A CA2735637 A CA 2735637A CA 2735637 C CA2735637 C CA 2735637C
- Authority
- CA
- Canada
- Prior art keywords
- membrane
- butanediol
- nanofiltration
- diol
- triol
- 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.)
- Active
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- 150000002009 diols Chemical class 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 37
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 title abstract description 73
- 239000012528 membrane Substances 0.000 claims abstract description 215
- 238000001728 nano-filtration Methods 0.000 claims abstract description 126
- 239000004952 Polyamide Substances 0.000 claims abstract description 59
- 229920002647 polyamide Polymers 0.000 claims abstract description 59
- 239000012466 permeate Substances 0.000 claims abstract description 44
- 239000002346 layers by function Substances 0.000 claims abstract description 25
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 36
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 36
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 36
- 238000001223 reverse osmosis Methods 0.000 claims description 35
- 238000001914 filtration Methods 0.000 claims description 33
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 15
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 46
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 44
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 40
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 26
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 26
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 26
- 238000004821 distillation Methods 0.000 description 25
- 235000011187 glycerol Nutrition 0.000 description 20
- 229920002301 cellulose acetate Polymers 0.000 description 18
- 235000000346 sugar Nutrition 0.000 description 16
- 238000000746 purification Methods 0.000 description 15
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 11
- 230000004907 flux Effects 0.000 description 11
- 238000000855 fermentation Methods 0.000 description 10
- 230000004151 fermentation Effects 0.000 description 10
- 150000008163 sugars Chemical class 0.000 description 10
- 150000004072 triols Chemical class 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000012527 feed solution Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 7
- 235000019341 magnesium sulphate Nutrition 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- -1 aromatic carboxylic acids Chemical class 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000005374 membrane filtration Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-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
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-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
- 230000007423 decrease Effects 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 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
- 239000010410 layer Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000012465 retentate Substances 0.000 description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 239000001963 growth medium Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 235000013772 propylene glycol Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 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
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-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
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 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
- 230000009467 reduction Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000000638 solvent extraction Methods 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
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 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
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-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
- BTVWZWFKMIUSGS-UHFFFAOYSA-N 2-methylpropane-1,2-diol Chemical compound CC(C)(O)CO BTVWZWFKMIUSGS-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
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 241000235343 Saccharomycetales Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-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
- 238000002835 absorbance Methods 0.000 description 1
- YTDMXCVMQCKOPF-UHFFFAOYSA-N acetic acid;butane-1,3-diol Chemical compound CC(O)=O.CC(O)CCO YTDMXCVMQCKOPF-UHFFFAOYSA-N 0.000 description 1
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920001727 cellulose butyrate Polymers 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000012228 culture supernatant Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- HZZOEADXZLYIHG-UHFFFAOYSA-N magnesiomagnesium Chemical compound [Mg][Mg] HZZOEADXZLYIHG-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 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
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- FVGBHSIHHXTYTH-UHFFFAOYSA-N pentane-1,1,1-triol Chemical compound CCCCC(O)(O)O FVGBHSIHHXTYTH-UHFFFAOYSA-N 0.000 description 1
- 239000008177 pharmaceutical agent Substances 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- JNLTYWDDGFTRSX-UHFFFAOYSA-N prop-1-ene-1,1-diol Chemical compound CC=C(O)O JNLTYWDDGFTRSX-UHFFFAOYSA-N 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
- 229940079877 pyrogallol Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- CBXWGGFGZDVPNV-UHFFFAOYSA-N so4-so4 Chemical compound OS(O)(=O)=O.OS(O)(=O)=O CBXWGGFGZDVPNV-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 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
Classifications
-
- 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
-
- 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
- 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
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 for producing a diol or triol, which has a step of removing impurities contained in a diol- or triol-containing solution, is provided. In the method, a diol-or triol-containing solution is filtered through a nanofiltration membrane having a polyamide-containing functional layer. The diol-or triol-containing solution is then collected from the permeate flow of the nanofiltration membrane.
Description
Method of Producing Diol or Triol Background of the Invention Field of the Invention [0001]
The present invention relates to a method for producing a diol or triol, which method comprises a step of removing impurities from a diol- or triol-containing solution.
Description of the Related Art
The present invention relates to a method for producing a diol or triol, which method comprises a step of removing impurities from a diol- or triol-containing solution.
Description of the Related Art
[0002]
Diols and triols are compounds which are industrially very important as raw materials of polymers and as raw materials of pharmaceutical agents. Diols such as butanediol and ethylene glycol produce polyesters when they are copolymerized with dicarboxylic acids such as terephthalic acid and adipic acid. Further, glycerin, which is a triol, is used as a raw material of cosmetics and the like. It is well known that these diols and triols can be produced by chemical synthesis, but, in recent years, since they can be produced by biochemical methods such as fermentation methods and enzymatic methods, they are drawing attention as nonpetroleum biopolymer materials. Therefore, technologies by which such diols and triols can be produced at high purity and at high efficiency have been demanded.
Diols and triols are compounds which are industrially very important as raw materials of polymers and as raw materials of pharmaceutical agents. Diols such as butanediol and ethylene glycol produce polyesters when they are copolymerized with dicarboxylic acids such as terephthalic acid and adipic acid. Further, glycerin, which is a triol, is used as a raw material of cosmetics and the like. It is well known that these diols and triols can be produced by chemical synthesis, but, in recent years, since they can be produced by biochemical methods such as fermentation methods and enzymatic methods, they are drawing attention as nonpetroleum biopolymer materials. Therefore, technologies by which such diols and triols can be produced at high purity and at high efficiency have been demanded.
[0003]
In general, as the method for purifying diols and triols, 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, leading to increase in the cost (Patent Document 1). Further, in purification by distillation, if impurities are contained, distillation residues are generated, leading to decrease in the yield.
Further, diol-and triol-containing liquids prepared by the fermentation method contain sugars, which are nutrient sources of microorganisms, and organic acids and proteins, which are metabolites, and these are reported to yield colored impurities by heating (Non-patent Document 1). Therefore, in order to carry out purification of highly pure diol or triol and highly efficient production thereof, removal of impurities in the fermentation broth is very important.
In general, as the method for purifying diols and triols, 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, leading to increase in the cost (Patent Document 1). Further, in purification by distillation, if impurities are contained, distillation residues are generated, leading to decrease in the yield.
Further, diol-and triol-containing liquids prepared by the fermentation method contain sugars, which are nutrient sources of microorganisms, and organic acids and proteins, which are metabolites, and these are reported to yield colored impurities by heating (Non-patent Document 1). Therefore, in order to carry out purification of highly pure diol or triol and highly efficient production thereof, removal of impurities in the fermentation broth is very important.
[0004]
As methods for producing highly pure diol or triol, a method for producing 1,3-propanediol wherein distillation purification is carried out in combination with microfiltration, ultrafiltration, nanofiltration or ion exchange (Patent Document 2);
and a method for separating diol using a reverse osmosis membrane or a nanofiltration membrane (Patent Document 3) are disclosed. However, they do not disclose the effect of difference in the material of the nanofiltration membrane on the permeation selectivity and on purity of the diol or triol after the purification.
Prior Art References Patent Documents
As methods for producing highly pure diol or triol, a method for producing 1,3-propanediol wherein distillation purification is carried out in combination with microfiltration, ultrafiltration, nanofiltration or ion exchange (Patent Document 2);
and a method for separating diol using a reverse osmosis membrane or a nanofiltration membrane (Patent Document 3) are disclosed. However, they do not disclose the effect of difference in the material of the nanofiltration membrane on the permeation selectivity and on purity of the diol or triol after the purification.
Prior Art References Patent Documents
[0005]
Patent Document 1 US 2007/193960 A
Patent Document 2 US2005/069997 A
Patent Document 3 US2006/065600 A
Non-patent Documents
Patent Document 1 US 2007/193960 A
Patent Document 2 US2005/069997 A
Patent Document 3 US2006/065600 A
Non-patent Documents
[0006]
Non-patent Document I Yoshiyuki MATSUO, Determination of Residual Glucose: Journal of Fermentation Technology, 39, 5,256-262 (1961) Summary of the Invention
Non-patent Document I Yoshiyuki MATSUO, Determination of Residual Glucose: Journal of Fermentation Technology, 39, 5,256-262 (1961) Summary of the Invention
[0007]
In view of the above-mentioned purpose, that is, purification of a diol or triol, the present invention aims to provide a method by which a diol or triol can be separated and recoverd more efficiently at higher purity than by the conventional methods.
In view of the above-mentioned purpose, that is, purification of a diol or triol, the present invention aims to provide a method by which a diol or triol can be separated and recoverd more efficiently at higher purity than by the conventional methods.
[0008]
The present inventors intensively studied to solve the above problems and discovered that a high-purity diol or triol can be obtained by filtering a diol- or triol-containing solution through a nanofiltration membrane having a functional layer containing a polyamide, and that the distillation yield can be effectively increased by this process, thereby completing the present invention.
The present inventors intensively studied to solve the above problems and discovered that a high-purity diol or triol can be obtained by filtering a diol- or triol-containing solution through a nanofiltration membrane having a functional layer containing a polyamide, and that the distillation yield can be effectively increased by this process, thereby completing the present invention.
[0009]
That is, the present invention is constituted by the following (1) to (7).
That is, the present invention is constituted by the following (1) to (7).
[0010]
(1) A method of producing at least one type of diols or at least one type of triols, said method comprising the steps of: filtering a solution containing said at least one type of diols or at least one type of triols solution through a nanofiltration membrane having a polyamide-containing functional layer; and collecting the diol- or triol-containing solution from the permeate flow of said nanofiltration membrane.
(2) The method according to (1), wherein said diol is ethylene glycol, 1,3-propanediol, 2,3-butanediol, 1,4-butanediol or 1,3-butanediol.
(3) The method according to (1), wherein said triol is glycerin or butanetriol.
(4) The method according to (1), wherein said polyamide comprises a cross-linked piperazine polyamide as a major component, and a constituting component represented by Formula [I]:
-Ni CH2CN-n [1]
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 diol-or triol-containing solution through a reverse osmosis membrane to increase the diol or trio!
concentration.
(6) The method according to (1), further comprising the step of distilling the collected diol or triol-containing solution under a pressure of not less than 1 Pa and not more than atmospheric pressure, at a temperature of not less than 25 C and not more than 200 C.
(7) The method according to (1), further comprising the step of distilling the concentrated diol or triol solution after filtration through said reverse osmosis membrane under a pressure of not less than 1 Pa and not more than atmospheric pressure, at a temperature of not less than 25 C
and not more than 200 C.
The present invention further provides a method of producing at least one butanediol, said method comprising: filtering a solution containing said at least one butanediol through a nanofiltration membrane having a polyamide-containing functional layer; and collecting butanediol-containing solution from the permeate flow of said nanofiltration membrane; wherein said butanediol is 2,3-butanediol, 1,4-butanediol or 1,3-butanediol.
(1) A method of producing at least one type of diols or at least one type of triols, said method comprising the steps of: filtering a solution containing said at least one type of diols or at least one type of triols solution through a nanofiltration membrane having a polyamide-containing functional layer; and collecting the diol- or triol-containing solution from the permeate flow of said nanofiltration membrane.
(2) The method according to (1), wherein said diol is ethylene glycol, 1,3-propanediol, 2,3-butanediol, 1,4-butanediol or 1,3-butanediol.
(3) The method according to (1), wherein said triol is glycerin or butanetriol.
(4) The method according to (1), wherein said polyamide comprises a cross-linked piperazine polyamide as a major component, and a constituting component represented by Formula [I]:
-Ni CH2CN-n [1]
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 diol-or triol-containing solution through a reverse osmosis membrane to increase the diol or trio!
concentration.
(6) The method according to (1), further comprising the step of distilling the collected diol or triol-containing solution under a pressure of not less than 1 Pa and not more than atmospheric pressure, at a temperature of not less than 25 C and not more than 200 C.
(7) The method according to (1), further comprising the step of distilling the concentrated diol or triol solution after filtration through said reverse osmosis membrane under a pressure of not less than 1 Pa and not more than atmospheric pressure, at a temperature of not less than 25 C
and not more than 200 C.
The present invention further provides a method of producing at least one butanediol, said method comprising: filtering a solution containing said at least one butanediol through a nanofiltration membrane having a polyamide-containing functional layer; and collecting butanediol-containing solution from the permeate flow of said nanofiltration membrane; wherein said butanediol is 2,3-butanediol, 1,4-butanediol or 1,3-butanediol.
[0011]
By the present invention, metal catalysts, inorganic salts, sugars and/or proteins existing in a diol- or triol-containing chemically synthesized reaction solution or fermentation broth can be removed by a simple process, and therefore the distillation yield can be increased, so that a highly pure diol or triol can be produced highly efficiently.
Brief Description of the Drawings
By the present invention, metal catalysts, inorganic salts, sugars and/or proteins existing in a diol- or triol-containing chemically synthesized reaction solution or fermentation broth can be removed by a simple process, and therefore the distillation yield can be increased, so that a highly pure diol or triol can be produced highly efficiently.
Brief Description of the Drawings
[0012]
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.
4a 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.
4a 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
[0013]
1 Feed tank 2 Cell equipped with nanofiltration membrane or reverse osmosis 5 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 7 904) 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.
In the method of the present invention for producing a diol or triol, the diol or trio' is separated from a diol- or triol-containing solution, and the present invention relates to a method for producing a diol or triol, comprising a step of allowing the diol- or triol-containing solution to pass through a nanofiltration membrane to remove metal catalysts, inorganic salts, sugars, proteins and/or the like to obtain a diol or triol solution, and a step of allowing the diol or triol solution obtained by the above step to be fed into a reverse osmosis membrane to concentrate the solution, followed by distilling the resulting concentrate.
[0015]
In the present invention, the term "diol" means a compound having two hydroxyl groups (OH groups) in the molecule and having no other functional groups, and the "diol" is not restricted as long as the molecule is within this scope.
In the present invention, a diol may comprise a single type of diol or may be a mixture of plural types of diols. The diol in the present invention is preferably a diol having 1 to 6 carbon atoms, and particular examples thereof include linear aliphatic compbunds such as methylene glycol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol and 1,5-pentanediol, branched aliphatic saturated compounds such as isobutylene glycol;
aromatic compounds such as catechol and resorcinol; and unsaturated compounds such as propenediol and butenediol.
[0016]
In the present invention, the term "triol" means a compound having three hydroxyl groups (01-1 groups) in the molecule and having no other functional groups, and the "triol" is not restricted as long as the molecule is within this scope. In the present invention, a triol may comprise a single type of triol or may be a mixture of plural types of triols. The triol in the present invention is preferably a triol having 1 to 6 carbon atoms, and particular examples thereof include aliphatic compounds such as glycerin, butanetriol, pentanetriol, hexanetriol, trimethylol propane; and aromatic compounds such as pyrogallol, hydroxyhydroquinone and phloroglucinol; among which glycerin is more preferred.
[0017]
The method for producing a diol- or triol-containing solution used in the present invention is not restricted as long as it is known to those skilled in the art, and, in cases where a chemical synthesis method is used, examples of the method include synthesis of 1,2-propanediol by asymmetric reduction as described in JP 63-A, and a method for producing glycerin via an allyl alcohol or acrolein using propylene as a starting material. Further, in cases where fermentation culture of a microorganism is employed, examples of the method include the method for producing glycerin as described in JP 5-153982 A, and the method for producing 1,2-propanediol as described in JP 6-30790 A. The method used in the present invention for producing a diol- or triol-containing solution is preferably fermentation culture of a microorganism, and, in such a case, the fermentation broth itself containing a diol or triol can be used as the diol- or triol-containing solution to be applied to the nanofiltration membrane.
[0018]
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.
[0019]
By filtering a diol- or triol-containing solution is filtered through a nanofiltration membrane, impurities (substances other than diols and triols) are removed at the feed flow and the diol- or triol-containing solution is collected from the permeate flow.
[0020]
Examples of known materials constituting the functional layer of nanofiltration membranes generally include polymer materials such as cellulose acetate polymers; polyamides; polyesters; polyimides; and vinyl polymers; and, in the present invention, a nanofiltration membrane having a functional layer comprising a polyamide is used since a high purification efficiency can be attained therewith.
Other plural membrane materials may also be contained in the functional layer comprising a polyamide, but the functional layer preferably comprises a polyamide as a major component. In the present specification, in cases where the nanofiltration membrane is specified by a material, the nanofiltration membrane has a functional layer comprising the material unless otherwise specified.
[0021]
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-containing functional layer was placed on a support membrane made of a polysulfone membrane material.
[0022]
The nanofiltration membrane having a polyamide-containing functional layer (hereinafter also referred to as polyamide nanofiltration membrane) used in the present invention is preferably a composite membrane having a high pressure resistance, a high permeability and a high solute removal 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 structure wherein the polyamide-containing functional layer is held by a support made of a porous membrane ancUor a non-woven fabric.
[0023]
In the polyamide nanofiltration membrane, preferred examples of the carboxylic acid 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.
[0024]
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-triaminobiphenyl 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-aminobenzoy1)-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 piperidinc and derivatives thereof; and, in particular, a nanofiltration membrane having a functional layer composed of a cross-linked polyamide containing piperazine or piperidine as monomers has a high pressure resistance and durability as well as heat resistance and chemical resistance, and is therefore preferably used. The polyamide 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]; 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 having a functional layer comprising a cross-linked piperazine polyamide as a major component and further comprising 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., which has a functional layer 2 5 comprising a cross-linked piperazine polyamide as a major component and further comprising a constituting component represented by the Formula [I] wherein n--3.
[0025]
The polyamide nanofiltration membrane used in the present invention may be in an appropriate form such as a spiral-wound membrane, flat membrane or hollow fiber membrane module, and is preferably used as a spiral-wound membrane module.
Particular examples of the nanofiltration membrane which may be used include SU-5 210, SU-220, SU-600 and SU-610, which are nanofiltration modules manufactured by TORAY INDUSTRIES, INC. containing UTC60 manufactured by the same manufacturer, which nanofiltration modules have a polyamide fimetional layer comprising a cross-linked piperazine polyamide as a major component and further a constituting component represented by the Formula [I]. Further particular examples 10 of the membrane include flat membranes, such as 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, and membrane modules using these membrane materials.
[0026]
In the present invention, the filtration of a diol- or triol-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, 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 the diol- or triol-containing solution can be allowed to pass through the membrane efficiently with less possibility of causing damage to the membrane, which is more preferred. A filtration pressure of 1 MPa to 6 MPa is especially preferred.
[0027]
In the present invention, in the filtration of a diol- or triol-containing solution through a nanofiltration membrane, the recovery of the diol or triol can be increased by returning the retentate to the feed solution and repeating the filtration.
The recovery of the diol or triol can be calculated by measuring the total amount of the diol or triol contained before the nanofiltration and the total amount of the diol or triol permeated through the nanofiltration membrane, followed by calculation by Equation 1.
[0028]
Recovery of diol or triol (%) = (total amount of diol or triol which has permeated through nanofiltration membrane / total amount of diol or triol contained before nanofiltration) x 100 ... (Equation 1).
[0029]
In terms of the membrane separation performance of the nanofiltration membrane used in the present invention, the membrane preferably shows a salt removal 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 removal rate can be calculated by measuring the salt concentration of the permeated aqueous sodium chloride solution, followed by calculation by Equation 2.
[0030]
Salt removal rate = 100 x (1-(salt concentration of permeate / salt concentration of feed solution ... (Equation 2).
[00311 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 an 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.
[0032]
Membrane permeation flux (m3/(m2. day)) = amount of permeant /
(membrane area x collection time) ... (Equation 3).
[0033]
In the present invention, examples of the impurities separated from the diol-or triol-containing solution into the retentate 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.
[0034]
The permeability of the nanofiltration membrane to a diol- or triol-containing solution in the present invention can be evaluated by calculating the permeation rate of the diol or triol. The permeation rate of the diol or triol can be calculated by measuring the concentration of the diot or triol (diol or triol concentration of feed solution) contained in the feed solution (diol- or triol-containing liquid) and the concentration of the diol or triol (diol or triol concentration of permeate) contained in the permeate (diol or triol solution) by analysis represented by high performance liquid chromatography and gas chromatography, followed by calculation by Equation 4.
[0035]
Permeation rate of diol or triol (%) = (diol or trial concentration of permeate /
diol or triol concentration of feed solution) x 100 ... (Equation 4).
[0036]
The permeate from the nanofiltration membrane is preferably concentrated in cases where the concentration of the substance of interest is low, since, in such cases, the later-mentioned distillation step requires a large amount of energy to remove water, which has a lower boiling point than diols and triols. 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.
[0037]
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 liquid to be treated as the driving force, 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 are successfully 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.
1 Feed tank 2 Cell equipped with nanofiltration membrane or reverse osmosis 5 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 7 904) 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.
In the method of the present invention for producing a diol or triol, the diol or trio' is separated from a diol- or triol-containing solution, and the present invention relates to a method for producing a diol or triol, comprising a step of allowing the diol- or triol-containing solution to pass through a nanofiltration membrane to remove metal catalysts, inorganic salts, sugars, proteins and/or the like to obtain a diol or triol solution, and a step of allowing the diol or triol solution obtained by the above step to be fed into a reverse osmosis membrane to concentrate the solution, followed by distilling the resulting concentrate.
[0015]
In the present invention, the term "diol" means a compound having two hydroxyl groups (OH groups) in the molecule and having no other functional groups, and the "diol" is not restricted as long as the molecule is within this scope.
In the present invention, a diol may comprise a single type of diol or may be a mixture of plural types of diols. The diol in the present invention is preferably a diol having 1 to 6 carbon atoms, and particular examples thereof include linear aliphatic compbunds such as methylene glycol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol and 1,5-pentanediol, branched aliphatic saturated compounds such as isobutylene glycol;
aromatic compounds such as catechol and resorcinol; and unsaturated compounds such as propenediol and butenediol.
[0016]
In the present invention, the term "triol" means a compound having three hydroxyl groups (01-1 groups) in the molecule and having no other functional groups, and the "triol" is not restricted as long as the molecule is within this scope. In the present invention, a triol may comprise a single type of triol or may be a mixture of plural types of triols. The triol in the present invention is preferably a triol having 1 to 6 carbon atoms, and particular examples thereof include aliphatic compounds such as glycerin, butanetriol, pentanetriol, hexanetriol, trimethylol propane; and aromatic compounds such as pyrogallol, hydroxyhydroquinone and phloroglucinol; among which glycerin is more preferred.
[0017]
The method for producing a diol- or triol-containing solution used in the present invention is not restricted as long as it is known to those skilled in the art, and, in cases where a chemical synthesis method is used, examples of the method include synthesis of 1,2-propanediol by asymmetric reduction as described in JP 63-A, and a method for producing glycerin via an allyl alcohol or acrolein using propylene as a starting material. Further, in cases where fermentation culture of a microorganism is employed, examples of the method include the method for producing glycerin as described in JP 5-153982 A, and the method for producing 1,2-propanediol as described in JP 6-30790 A. The method used in the present invention for producing a diol- or triol-containing solution is preferably fermentation culture of a microorganism, and, in such a case, the fermentation broth itself containing a diol or triol can be used as the diol- or triol-containing solution to be applied to the nanofiltration membrane.
[0018]
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.
[0019]
By filtering a diol- or triol-containing solution is filtered through a nanofiltration membrane, impurities (substances other than diols and triols) are removed at the feed flow and the diol- or triol-containing solution is collected from the permeate flow.
[0020]
Examples of known materials constituting the functional layer of nanofiltration membranes generally include polymer materials such as cellulose acetate polymers; polyamides; polyesters; polyimides; and vinyl polymers; and, in the present invention, a nanofiltration membrane having a functional layer comprising a polyamide is used since a high purification efficiency can be attained therewith.
Other plural membrane materials may also be contained in the functional layer comprising a polyamide, but the functional layer preferably comprises a polyamide as a major component. In the present specification, in cases where the nanofiltration membrane is specified by a material, the nanofiltration membrane has a functional layer comprising the material unless otherwise specified.
[0021]
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-containing functional layer was placed on a support membrane made of a polysulfone membrane material.
[0022]
The nanofiltration membrane having a polyamide-containing functional layer (hereinafter also referred to as polyamide nanofiltration membrane) used in the present invention is preferably a composite membrane having a high pressure resistance, a high permeability and a high solute removal 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 structure wherein the polyamide-containing functional layer is held by a support made of a porous membrane ancUor a non-woven fabric.
[0023]
In the polyamide nanofiltration membrane, preferred examples of the carboxylic acid 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.
[0024]
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-triaminobiphenyl 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-aminobenzoy1)-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 piperidinc and derivatives thereof; and, in particular, a nanofiltration membrane having a functional layer composed of a cross-linked polyamide containing piperazine or piperidine as monomers has a high pressure resistance and durability as well as heat resistance and chemical resistance, and is therefore preferably used. The polyamide 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]; 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 having a functional layer comprising a cross-linked piperazine polyamide as a major component and further comprising 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., which has a functional layer 2 5 comprising a cross-linked piperazine polyamide as a major component and further comprising a constituting component represented by the Formula [I] wherein n--3.
[0025]
The polyamide nanofiltration membrane used in the present invention may be in an appropriate form such as a spiral-wound membrane, flat membrane or hollow fiber membrane module, and is preferably used as a spiral-wound membrane module.
Particular examples of the nanofiltration membrane which may be used include SU-5 210, SU-220, SU-600 and SU-610, which are nanofiltration modules manufactured by TORAY INDUSTRIES, INC. containing UTC60 manufactured by the same manufacturer, which nanofiltration modules have a polyamide fimetional layer comprising a cross-linked piperazine polyamide as a major component and further a constituting component represented by the Formula [I]. Further particular examples 10 of the membrane include flat membranes, such as 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, and membrane modules using these membrane materials.
[0026]
In the present invention, the filtration of a diol- or triol-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, 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 the diol- or triol-containing solution can be allowed to pass through the membrane efficiently with less possibility of causing damage to the membrane, which is more preferred. A filtration pressure of 1 MPa to 6 MPa is especially preferred.
[0027]
In the present invention, in the filtration of a diol- or triol-containing solution through a nanofiltration membrane, the recovery of the diol or triol can be increased by returning the retentate to the feed solution and repeating the filtration.
The recovery of the diol or triol can be calculated by measuring the total amount of the diol or triol contained before the nanofiltration and the total amount of the diol or triol permeated through the nanofiltration membrane, followed by calculation by Equation 1.
[0028]
Recovery of diol or triol (%) = (total amount of diol or triol which has permeated through nanofiltration membrane / total amount of diol or triol contained before nanofiltration) x 100 ... (Equation 1).
[0029]
In terms of the membrane separation performance of the nanofiltration membrane used in the present invention, the membrane preferably shows a salt removal 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 removal rate can be calculated by measuring the salt concentration of the permeated aqueous sodium chloride solution, followed by calculation by Equation 2.
[0030]
Salt removal rate = 100 x (1-(salt concentration of permeate / salt concentration of feed solution ... (Equation 2).
[00311 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 an 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.
[0032]
Membrane permeation flux (m3/(m2. day)) = amount of permeant /
(membrane area x collection time) ... (Equation 3).
[0033]
In the present invention, examples of the impurities separated from the diol-or triol-containing solution into the retentate 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.
[0034]
The permeability of the nanofiltration membrane to a diol- or triol-containing solution in the present invention can be evaluated by calculating the permeation rate of the diol or triol. The permeation rate of the diol or triol can be calculated by measuring the concentration of the diot or triol (diol or triol concentration of feed solution) contained in the feed solution (diol- or triol-containing liquid) and the concentration of the diol or triol (diol or triol concentration of permeate) contained in the permeate (diol or triol solution) by analysis represented by high performance liquid chromatography and gas chromatography, followed by calculation by Equation 4.
[0035]
Permeation rate of diol or triol (%) = (diol or trial concentration of permeate /
diol or triol concentration of feed solution) x 100 ... (Equation 4).
[0036]
The permeate from the nanofiltration membrane is preferably concentrated in cases where the concentration of the substance of interest is low, since, in such cases, the later-mentioned distillation step requires a large amount of energy to remove water, which has a lower boiling point than diols and triols. 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.
[0037]
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 liquid to be treated as the driving force, 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 are successfully 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.
14 [0038]
Further, the term "filtering through the reverse osmosis membrane" means that the diol- or triol-containing solution which has permeated through the nanofiltration membrane is concentrated by being allowed to pass through the reverse osmosis membrane, followed by collecting the resulting solution containing a diol or triol in the retentate flow.
[0039]
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.
[0040]
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-710P 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-Li OUR, SC-L200R, 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, ES15-D, ES15-U and LF10-D manufactured by Nitto Denko Corporation; R098pHt, R099, HR98PP and CE4040C-30D manufactured by Alfa-Laval; GE Sepa manufactured by 5 GE; and BW30-4040, TW30-4040, XLE-4040, LP-4040, LE-4040, SW30-4040 and SW3OHRLE-4040 manufactured by FilmTec Corporation.
[0041]
In the present invention, filtration of the permeate from the nanofiltration membrane with the reverse osmosis membrane is carried out under pressure, and the 10 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 diol or triol solution can be efficiently concentrated.
Further, the term "filtering through the reverse osmosis membrane" means that the diol- or triol-containing solution which has permeated through the nanofiltration membrane is concentrated by being allowed to pass through the reverse osmosis membrane, followed by collecting the resulting solution containing a diol or triol in the retentate flow.
[0039]
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.
[0040]
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-710P 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-Li OUR, SC-L200R, 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, ES15-D, ES15-U and LF10-D manufactured by Nitto Denko Corporation; R098pHt, R099, HR98PP and CE4040C-30D manufactured by Alfa-Laval; GE Sepa manufactured by 5 GE; and BW30-4040, TW30-4040, XLE-4040, LP-4040, LE-4040, SW30-4040 and SW3OHRLE-4040 manufactured by FilmTec Corporation.
[0041]
In the present invention, filtration of the permeate from the nanofiltration membrane with the reverse osmosis membrane is carried out under pressure, and the 10 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 diol or triol solution can be efficiently concentrated.
15 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.
[0042]
Further, in the present invention, by subjecting the concentrate of the permeate from the nanofiltration membrane to the step of distillation, a highly pure diol or triol can 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 50 C to 150 C.
Examples [0043]
[0042]
Further, in the present invention, by subjecting the concentrate of the permeate from the nanofiltration membrane to the step of distillation, a highly pure diol or triol can 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 50 C to 150 C.
Examples [0043]
16 The present invention will now be described more concretely by way of Examples, but the present invention is not restricted to the Examples below. -[0044]
(Reference Example 1) Evaluation of Permeability of Nanofiltration Membrane to Diol and Triol To 10 L of ultrapure water, 10 g of ethylene glycol, 1,3-propanediol, 2,3-butanediol, glycerin, 1,3-butanediol or 1,4-butanediol (all of which were manufactured from Wako Pure Chemical Industries, Ltd.) was added, and the resulting mixture was stirred at 25 C for 1 hour, thereby preparing 1000 ppm aqueous diol or trio! solution. Subsequently, 10 L of the thus prepared aqueous diol or triol solution was fed to a feed tank 1 of the membrane filtration apparatus shown in Fig. 1. As the 909 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 cross-linked piperazine polyamide nanofiltration membrane "NF-400" (nanofiltration membrane 3; manufactured by FilmTec Corporation), a cellulose acetate nanofiltration membrane "GE Sepa"
(nanofiltration membrane 4; manufactured by GE Osmonics) and a polyamide nanofiltration membrane "NF99HF" (nanofiltration membrane 5; manufactured by Alfa-Laval) was placed in a cell 2 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 diol 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 the diol.
[0045]
(Reference Example 1) Evaluation of Permeability of Nanofiltration Membrane to Diol and Triol To 10 L of ultrapure water, 10 g of ethylene glycol, 1,3-propanediol, 2,3-butanediol, glycerin, 1,3-butanediol or 1,4-butanediol (all of which were manufactured from Wako Pure Chemical Industries, Ltd.) was added, and the resulting mixture was stirred at 25 C for 1 hour, thereby preparing 1000 ppm aqueous diol or trio! solution. Subsequently, 10 L of the thus prepared aqueous diol or triol solution was fed to a feed tank 1 of the membrane filtration apparatus shown in Fig. 1. As the 909 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 cross-linked piperazine polyamide nanofiltration membrane "NF-400" (nanofiltration membrane 3; manufactured by FilmTec Corporation), a cellulose acetate nanofiltration membrane "GE Sepa"
(nanofiltration membrane 4; manufactured by GE Osmonics) and a polyamide nanofiltration membrane "NF99HF" (nanofiltration membrane 5; manufactured by Alfa-Laval) was placed in a cell 2 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 diol 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 the diol.
[0045]
17 Column: TC-1, 0.53 mm I.D. x 15 m, df=1.5 pm (GL Science); Mobile phase:
helium gas (7.9 mL/min., 50 to 100 C: 5 C/min.); Detection: FID 250 C.
[0046]
Further, the glycerin concentration was calculated using "F-kit Glycerin"
(manufactured by J. K. International Inc.) based on the amount of change in the absorbance at UV 340 run, to calculate the permeation rate of glycerin. The results are shown in Table 1.
[0047]
helium gas (7.9 mL/min., 50 to 100 C: 5 C/min.); Detection: FID 250 C.
[0046]
Further, the glycerin concentration was calculated using "F-kit Glycerin"
(manufactured by J. K. International Inc.) based on the amount of change in the absorbance at UV 340 run, to calculate the permeation rate of glycerin. The results are shown in Table 1.
[0047]
18 [Table 1]
Product name Feed Permeate Permeation (manufacturer name) Diol or trio!
(ppm) (ppm) rate (%) /membrane material Ethylene glycol 1000 721 72.1 UTC60 (TORAY 1,3-Propanediol 1000 298 29.8 Nanofiltration INDUSTRIES, INC.)! 2,3-Butanediol 1000 388 38.8 membrane 1 Cross-linked Glycerin 1000 321 32.1 piperazine polyamide 1,3-Butanediol 1000 355 35.5 1,4-Butanediol 1000 564 56.4 Ethylene glycol 1000 733 73.3 1,3-Propanediol 1000 263 26.3 Nanofiltration NF99 (Alfa-Laval)! 2,3-Butanediol 1000 394 39.4 membrane 2 Polyamide Glycerin 1000 436 = 43.6 1,3-Butanediol 1000 315 31.5 1,4-Butanediol 1000 463 46.3 Ethylene glycol 1000 702 70.2 NF-400 (FilmTec 1,3-Propanediol 1000 321 32.1 Nanofiltration Corporation)/ 2,3-Butanediol 1000 355 35.5 membrane 3 Cross-linked Glycerin 1000 421 42.1 piperazine polyamide 1,3-Butanediol 1000 410 41.0 1,4-Butanediol 1000 544 54.4 Ethylene glycol 1000 696 69.6 _ 1,3-Propanediol , 1000 208 20.8 GE Sepa (GE
Nanofiltration 2,3-Butanediol 1000 423 42.3 Osmonics)/
membrane 4 Glycerin 1000 369 36.9 Cellulose acetate 1,3-Butanediol 1000 390 39.0 1,4-Butanediol 1000_ 583 58.3 Ethylene glycol 1000 802 80.2 1,3-Propanediol 1000 348 34.8 Nanofiltration NF99HF (Alfa-Laval)/ 2,3-Butanediol 1000 413 41.3 membrane 5 Polyamide Glycerin 1000 466 46.6 1,3-Butanediol 1000 397 39.7 1,4-Butanediol 1000 515 51.5
Product name Feed Permeate Permeation (manufacturer name) Diol or trio!
(ppm) (ppm) rate (%) /membrane material Ethylene glycol 1000 721 72.1 UTC60 (TORAY 1,3-Propanediol 1000 298 29.8 Nanofiltration INDUSTRIES, INC.)! 2,3-Butanediol 1000 388 38.8 membrane 1 Cross-linked Glycerin 1000 321 32.1 piperazine polyamide 1,3-Butanediol 1000 355 35.5 1,4-Butanediol 1000 564 56.4 Ethylene glycol 1000 733 73.3 1,3-Propanediol 1000 263 26.3 Nanofiltration NF99 (Alfa-Laval)! 2,3-Butanediol 1000 394 39.4 membrane 2 Polyamide Glycerin 1000 436 = 43.6 1,3-Butanediol 1000 315 31.5 1,4-Butanediol 1000 463 46.3 Ethylene glycol 1000 702 70.2 NF-400 (FilmTec 1,3-Propanediol 1000 321 32.1 Nanofiltration Corporation)/ 2,3-Butanediol 1000 355 35.5 membrane 3 Cross-linked Glycerin 1000 421 42.1 piperazine polyamide 1,3-Butanediol 1000 410 41.0 1,4-Butanediol 1000 544 54.4 Ethylene glycol 1000 696 69.6 _ 1,3-Propanediol , 1000 208 20.8 GE Sepa (GE
Nanofiltration 2,3-Butanediol 1000 423 42.3 Osmonics)/
membrane 4 Glycerin 1000 369 36.9 Cellulose acetate 1,3-Butanediol 1000 390 39.0 1,4-Butanediol 1000_ 583 58.3 Ethylene glycol 1000 802 80.2 1,3-Propanediol 1000 348 34.8 Nanofiltration NF99HF (Alfa-Laval)/ 2,3-Butanediol 1000 413 41.3 membrane 5 Polyamide Glycerin 1000 466 46.6 1,3-Butanediol 1000 397 39.7 1,4-Butanediol 1000 515 51.5
19 [0048]
As shown by the results in Table 1, the diols and triol permeated through any of the nanofiltration membranes. Further, the permeation rate varied among the compounds, and ethylene glycol showed the highest permeation rate. In terms of the other compounds, the effect of difference in the membrane material contained in the functional layer was small.
[0049]
(Reference Example 2) Evaluation of Rejection Rate of Nanofiltration Membrane against Inorganic Salt (Magnesium Sulfate) To 10 L of ultrapure water, 10 g of magnesium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the resulting mixture was stirred at 25 C for 1 hour, to prepare 1000 ppm aqueous magnesium sulfate solution.
Subsequently 10 L of the prepared aqueous magnesium sulfate solution was fed to the feed tank 1, followed by collecting the permeate from each of the nanofiltration membranes 1 to 4 under the same conditions as in Reference Example 1. The concentration of magnesium sulfate in each of the feed tank 1 and the permeate 4 was analyzed with an ion chromatography (manufactured by Dionex Corporation) under the following conditions, thereby calculating the rejection rate of the magnesium sulfate.
[0050]
Anion; column (AS4A-SC (manufactured by Dionex Corporation)), eluent (1.8 mM sodium carbonate/1.7 mM sodium hydrogen carbonate), temperature (35 C).
[0051]
Cation; column (CS12A (manufactured by Dionex Corporation)), eluent (20 mM methanesulfonic acid), temperature (35 C).
[0052]
The results are shown in Table 2.
[0053]
Table 2 Magnesium Product name Magnesium Magnesium Filtration sulfate (manufacturer sulfate sulfate pressure concentration name) concentration rejection /membrane material (MPa) in feed (ppm) in permeate rate (%) (ppm) UTC60 (TORAY
INDUSTRIES, Nanofiltration INC.)!
1 1000 2 99.8 membrane 1 Cross-linked piperazine polyamide Nanofiltration NF99 (Alfa-Laval)!
1 1000 20 98.0 membrane 2 Polyamide NF-400 (FilmTec Corporation)/
Nanofiltration Cross-linked 1 1000 20 98.0 membrane 3 piperazine polyamide GE Sepa (GE
Nanofiltration Osmonics)/ 1 1000 30 97.0 membrane 4 Cellulose acetate NF99IIF (Alfa-Nanofiltration Laval)/ 1 1000 20 98.0 membrane 5 Polyamide [0054]
5 From the results in Table 2, it was shown that UTC60 (nanofiltration membrane 1: manufactured by TORAY INDUSTRIES, [NC.) shows the highest rejection rate against the inorganic salt, and that, compared to the polyamide nanofiltration membranes (nanofiltration membranes 1 to 3), the cellulose acetate nanofiltration membrane GE Sepa (nanofiltration membrane 4) shows a lower 10 removal rate of magnesium sulfate. Thus, it was suggested that diols and triols can be purified at higher efficiency when a polyamide nanofiltration membrane is used.
[0055]
(Examples 1 to 9) Purification of 1,3-Propanediol from Fermentation Broth Using Nanofiltration Membrane <Preparation of 1,3-Propanediol-containing Broth >
A budding yeast strain NBRC10505 was cultured as follows. In terms of the culture medium, 2 L of a culture medium containing 60 g/L Yutosei (manufactured by MUSO Co., Ltd.) and 1.5 g/L ammonium sulfate was prepared and then autoclaved (121 C, 15 minutes).
[0056]
First, the yeast NBRC10505 strain was cultured overnight with shaking in a test tube containing 5 ml of the culture medium (pre-preculture). The pre-preculture broth was inoculated to 100 ml of a fresh lot of the medium, and culture was carried out in a 500-ml Sakaguchi flask for 24 hours with shaking (preeulture).
Culture was carried out while adjusting temperature and pH. The operating conditions of the jar fermenter were as shown below.
[0057]
Reaction vessel volume (amount of 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. After 24 hours of the culture, the broth was centrifuged to remove the yeast cells, and the supernatant was collected. To this broth, 1,3-propanediol was 2C added to 20 g/L.
[0058]
<Purification with Nanofiltration 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(p 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 for the respective pressures.
The concentration of 1,3-proopanediol contained in each of the liquid 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 sulfate ion concentration was analyzed with an ion chromatography (manufactured by Dionex Corporation) under the same conditions as in Reference Example 2.
Further, the sugar concentration (glucose, fructose and sucrose) was analyzed with a high performance liquid chromatography (manufactured by Shimadzu Corporation) under the following conditions.
Column: Luna 5u NH2 1 00A (manufactured by Phenomenex, Inc.), 30 C
Mobile phase: wateracetonitrile ¨ 1:3, 0.6 mUmin.
Detector: RI.
[0059]
The results are shown in Table 3.
[0060]
, ..
[Table 3]
_______________________________________________________________________________ ________________ , Sulfate ion concentration 1,3-Propanediol concentration Total sugar concentration Filtration Nanofiltration Flux Rejection Permeation Rejection pressure, Feed Permeate Feed Permeate Feed Permeate membrane (tn'im2 /day) rate rate rate o (MPa) (loPm) (PPnl) (WI-) (S5-,) (g/L) (g/L) (%) (%) (%) 0 N.) , Example 1 1 1.62 873 11 98.7 20 5.8 29.0 15 0.8 95.0 w Nanofiltration , Example 2 3 4.83 873 5 99.4 20 5.3 26.3 15 0.6 96.0 j w membrane 1 NJ ...1 Example 3 5 7.29 873 3 99.7 20 4.8 24.1 15 , 0.5 97.0 I I
1-`
Example 4 1 2.03 958 20 97.9 20 5.3 26.3 17 0.7 96.0 I
Nanofiltration Example 5 3 5.83 958 19 ' 98.0 20 4.8 24.0 17 0.5 97.0 w membrane 2 N.) Example 6 5 8.54 958 15 98.4 20 4.7 .
23.5 17 0.5 97.0 l0 I
Example 7 1 2A2 905 , 24 , 97.3 20 5.6 , 28.0 17 0.7 96.0 Nanofiltration Example 8 3 5.42 4 905 21 97.7 20 4.8 24.0 17 0.5 97.0 membrane 3 1 I
Example 9 5 8.23 , 905 i 17 98.1 i 20 4.2 21.0 17 0.5 97.0 [0061]
As shown in Table 3, with all the nanofiltration membranes and under all the filtration pressures, sulfate ion and the sugars were removed and a 1,3-propanediol solution was obtained. Further, the other impurities were also mostly removed from the brown-colored broth, and a colorless transparent solution was obtained.
Further, compared to the separation properties of the nanofiltration membrane disclosed in Table 7 of US2005/069997, Examples 1 to 9 showed remarkably superior removal capacities for sulfate ion and sugars.
[0062]
Further, 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 four times in order to increase the recovery of 1,3-propanediol. As a result, not less than 55% of 1,3-propanediol in the broth could be recovered.
[0063]
<Distillation from Solution Concentrated Using Reverse Osmosis Membrane >
Among the clean 1,3-propanediol 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, 5.5 L of the solution was fed. As the 90(p 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 3 MPa and the temperature of the feed solution to 35 C, thereby removing 5.4 L of the permeate 4 from the reverse osmosis membrane.
One hundred milliliters of the thus obtained concentrate was subjected to distillation under reduced pressure (5 mmHg). The results of the distillation are shown in Table 4.
[0064]
Table 4 1,3-Propanediol concentration Nanofiltration (g/L) Distillation GC
purity membrane yield (1)/0) Before After (%) concentration concentration Nanofiltration Example 2 5.0 274 95 99,7 membrane 1 Nanofiltration Example 5 4.5 248 92 99.5 membrane 2 _______________ Nanofiltration Example 8 4.5 248 90 99.5 membrane 3 [0065]
From these results, it was shown that the present method allows efficient 5 production of high-purity 1,3-propanediol.
[0066]
(Comparative Example 1) Purification of 1,3-Propanediol by Using Active Carbon and Ion-exchange hi the same manner as in Example 1, 2 L of a 1,3-propanediol-containing 10 broth was prepared. The broth was treated with 20 g of active carbon, and allowed to pass through an ion-exchange resin (IRA-140:IR-120=2:1) to desalt the solution.
The 1,3-propanediol-containing solution was concentrated using a reverse osmosis membrane, and then subjected to distillation under reduced pressure (5 mmHg), in the same manner as in the above Example 1. As a result, the distillation yield was 5 76%, and the GC purity was 94.5%. The decrease in the distillation yield was considered to be due to a large amount the remaining residue. Further, since 4.2 g/L
of glucose was detected in the concentrate, it was assumed that impurities derived from sugars decreased the GC purity.
[0067]
As shown by the results in Table 1, the diols and triol permeated through any of the nanofiltration membranes. Further, the permeation rate varied among the compounds, and ethylene glycol showed the highest permeation rate. In terms of the other compounds, the effect of difference in the membrane material contained in the functional layer was small.
[0049]
(Reference Example 2) Evaluation of Rejection Rate of Nanofiltration Membrane against Inorganic Salt (Magnesium Sulfate) To 10 L of ultrapure water, 10 g of magnesium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the resulting mixture was stirred at 25 C for 1 hour, to prepare 1000 ppm aqueous magnesium sulfate solution.
Subsequently 10 L of the prepared aqueous magnesium sulfate solution was fed to the feed tank 1, followed by collecting the permeate from each of the nanofiltration membranes 1 to 4 under the same conditions as in Reference Example 1. The concentration of magnesium sulfate in each of the feed tank 1 and the permeate 4 was analyzed with an ion chromatography (manufactured by Dionex Corporation) under the following conditions, thereby calculating the rejection rate of the magnesium sulfate.
[0050]
Anion; column (AS4A-SC (manufactured by Dionex Corporation)), eluent (1.8 mM sodium carbonate/1.7 mM sodium hydrogen carbonate), temperature (35 C).
[0051]
Cation; column (CS12A (manufactured by Dionex Corporation)), eluent (20 mM methanesulfonic acid), temperature (35 C).
[0052]
The results are shown in Table 2.
[0053]
Table 2 Magnesium Product name Magnesium Magnesium Filtration sulfate (manufacturer sulfate sulfate pressure concentration name) concentration rejection /membrane material (MPa) in feed (ppm) in permeate rate (%) (ppm) UTC60 (TORAY
INDUSTRIES, Nanofiltration INC.)!
1 1000 2 99.8 membrane 1 Cross-linked piperazine polyamide Nanofiltration NF99 (Alfa-Laval)!
1 1000 20 98.0 membrane 2 Polyamide NF-400 (FilmTec Corporation)/
Nanofiltration Cross-linked 1 1000 20 98.0 membrane 3 piperazine polyamide GE Sepa (GE
Nanofiltration Osmonics)/ 1 1000 30 97.0 membrane 4 Cellulose acetate NF99IIF (Alfa-Nanofiltration Laval)/ 1 1000 20 98.0 membrane 5 Polyamide [0054]
5 From the results in Table 2, it was shown that UTC60 (nanofiltration membrane 1: manufactured by TORAY INDUSTRIES, [NC.) shows the highest rejection rate against the inorganic salt, and that, compared to the polyamide nanofiltration membranes (nanofiltration membranes 1 to 3), the cellulose acetate nanofiltration membrane GE Sepa (nanofiltration membrane 4) shows a lower 10 removal rate of magnesium sulfate. Thus, it was suggested that diols and triols can be purified at higher efficiency when a polyamide nanofiltration membrane is used.
[0055]
(Examples 1 to 9) Purification of 1,3-Propanediol from Fermentation Broth Using Nanofiltration Membrane <Preparation of 1,3-Propanediol-containing Broth >
A budding yeast strain NBRC10505 was cultured as follows. In terms of the culture medium, 2 L of a culture medium containing 60 g/L Yutosei (manufactured by MUSO Co., Ltd.) and 1.5 g/L ammonium sulfate was prepared and then autoclaved (121 C, 15 minutes).
[0056]
First, the yeast NBRC10505 strain was cultured overnight with shaking in a test tube containing 5 ml of the culture medium (pre-preculture). The pre-preculture broth was inoculated to 100 ml of a fresh lot of the medium, and culture was carried out in a 500-ml Sakaguchi flask for 24 hours with shaking (preeulture).
Culture was carried out while adjusting temperature and pH. The operating conditions of the jar fermenter were as shown below.
[0057]
Reaction vessel volume (amount of 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. After 24 hours of the culture, the broth was centrifuged to remove the yeast cells, and the supernatant was collected. To this broth, 1,3-propanediol was 2C added to 20 g/L.
[0058]
<Purification with Nanofiltration 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(p 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 for the respective pressures.
The concentration of 1,3-proopanediol contained in each of the liquid 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 sulfate ion concentration was analyzed with an ion chromatography (manufactured by Dionex Corporation) under the same conditions as in Reference Example 2.
Further, the sugar concentration (glucose, fructose and sucrose) was analyzed with a high performance liquid chromatography (manufactured by Shimadzu Corporation) under the following conditions.
Column: Luna 5u NH2 1 00A (manufactured by Phenomenex, Inc.), 30 C
Mobile phase: wateracetonitrile ¨ 1:3, 0.6 mUmin.
Detector: RI.
[0059]
The results are shown in Table 3.
[0060]
, ..
[Table 3]
_______________________________________________________________________________ ________________ , Sulfate ion concentration 1,3-Propanediol concentration Total sugar concentration Filtration Nanofiltration Flux Rejection Permeation Rejection pressure, Feed Permeate Feed Permeate Feed Permeate membrane (tn'im2 /day) rate rate rate o (MPa) (loPm) (PPnl) (WI-) (S5-,) (g/L) (g/L) (%) (%) (%) 0 N.) , Example 1 1 1.62 873 11 98.7 20 5.8 29.0 15 0.8 95.0 w Nanofiltration , Example 2 3 4.83 873 5 99.4 20 5.3 26.3 15 0.6 96.0 j w membrane 1 NJ ...1 Example 3 5 7.29 873 3 99.7 20 4.8 24.1 15 , 0.5 97.0 I I
1-`
Example 4 1 2.03 958 20 97.9 20 5.3 26.3 17 0.7 96.0 I
Nanofiltration Example 5 3 5.83 958 19 ' 98.0 20 4.8 24.0 17 0.5 97.0 w membrane 2 N.) Example 6 5 8.54 958 15 98.4 20 4.7 .
23.5 17 0.5 97.0 l0 I
Example 7 1 2A2 905 , 24 , 97.3 20 5.6 , 28.0 17 0.7 96.0 Nanofiltration Example 8 3 5.42 4 905 21 97.7 20 4.8 24.0 17 0.5 97.0 membrane 3 1 I
Example 9 5 8.23 , 905 i 17 98.1 i 20 4.2 21.0 17 0.5 97.0 [0061]
As shown in Table 3, with all the nanofiltration membranes and under all the filtration pressures, sulfate ion and the sugars were removed and a 1,3-propanediol solution was obtained. Further, the other impurities were also mostly removed from the brown-colored broth, and a colorless transparent solution was obtained.
Further, compared to the separation properties of the nanofiltration membrane disclosed in Table 7 of US2005/069997, Examples 1 to 9 showed remarkably superior removal capacities for sulfate ion and sugars.
[0062]
Further, 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 four times in order to increase the recovery of 1,3-propanediol. As a result, not less than 55% of 1,3-propanediol in the broth could be recovered.
[0063]
<Distillation from Solution Concentrated Using Reverse Osmosis Membrane >
Among the clean 1,3-propanediol 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, 5.5 L of the solution was fed. As the 90(p 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 3 MPa and the temperature of the feed solution to 35 C, thereby removing 5.4 L of the permeate 4 from the reverse osmosis membrane.
One hundred milliliters of the thus obtained concentrate was subjected to distillation under reduced pressure (5 mmHg). The results of the distillation are shown in Table 4.
[0064]
Table 4 1,3-Propanediol concentration Nanofiltration (g/L) Distillation GC
purity membrane yield (1)/0) Before After (%) concentration concentration Nanofiltration Example 2 5.0 274 95 99,7 membrane 1 Nanofiltration Example 5 4.5 248 92 99.5 membrane 2 _______________ Nanofiltration Example 8 4.5 248 90 99.5 membrane 3 [0065]
From these results, it was shown that the present method allows efficient 5 production of high-purity 1,3-propanediol.
[0066]
(Comparative Example 1) Purification of 1,3-Propanediol by Using Active Carbon and Ion-exchange hi the same manner as in Example 1, 2 L of a 1,3-propanediol-containing 10 broth was prepared. The broth was treated with 20 g of active carbon, and allowed to pass through an ion-exchange resin (IRA-140:IR-120=2:1) to desalt the solution.
The 1,3-propanediol-containing solution was concentrated using a reverse osmosis membrane, and then subjected to distillation under reduced pressure (5 mmHg), in the same manner as in the above Example 1. As a result, the distillation yield was 5 76%, and the GC purity was 94.5%. The decrease in the distillation yield was considered to be due to a large amount the remaining residue. Further, since 4.2 g/L
of glucose was detected in the concentrate, it was assumed that impurities derived from sugars decreased the GC purity.
[0067]
20 (Comparative Examples 2 to 4) Purification of 1,3-Propanediol with Cellulose Acetate Nanofiltration Membrane In the same manner as in Example 1, 2 L of a 1,3-propanediol-containing broth was prepared. Subsequently, a cellulose acetate nanofiltration membrane "GE
Sepa" (nanofiltration membrane 4) was placed in a cell made of stainless steel, and the permeate 4 under a pressure of 1 MPa, 3 MPa or 5 MPa was collected as in the above Examples, followed by filtration. The results of analysis of the permeates are shown in Table 5.
[0068]
[Table 5]
r) Sulfate ion concentration 1,3-Propanediol concentration Total sugar concentration Filtration0 Nanofiltration Flux 1 Rejection Feed Permeation Rejection n.) ...3 pressure Feed Permeate Permeate Feed Permeate w membrane (m3/m2/day) rate rate rate cri (MPa) (PPm) (PPIn) (%) (g/L) (g/1-) (g/L) 01 w (%) Comparative 1 1.19 916 30 96.7 20 4.2 20.8 15 0.9 94.0 I-.
I
Example 2 w Comparative Nanofiltration n.) 3 3,75 916 25 97.3 20 3.7 18.4 15 0.8 95.0 tO
Example 3 membrane 4 , Comparative 4.64 916 19 97.9 20 2.9 14.3 15 0.5 97.0 Example 4 [0069]
Thus, the cellulose acetate nanofiltration membrane showed a lower permeation rate of 1,3-propanediol as well as lower removal rates of sulfate ion/sugars compared to polyamide nanofiltration membranes. Further, when the permeate obtained in Comparative Examples 3 was subjected to concentration with a reverse osmosis membrane and distillation under reduced pressure in the same manner as in the above Example 1, the distillation yield was 88% and the GC
purity was 99.0%, indicating that a cellulose acetate nanofiltration membrane shows a lower purification efficiency than a polyamide nanofiltration membrane.
[0070]
(Examples 10 to 14) Purification of Ethylene Glycol, 2,3-Butanediol, Glycerin, 1,3-Butanediol or 1,4-Butanediol from Fermentation Broth Using Nanofiltration Membrane In the same manner as in Example 1, 2 L each of 20 g/L ethylene glycol-containing broth, 2,3-butanediol-containing broth, glycerin-containing broth, 1,3-butanediol-containing broth and 1,4-butanediol-containing broth was prepared.
Each of these was fed to the feed tank 1 of the membrane filtration apparatus.
As the 909 nanofiltration membrane indicated by Symbol 7 in Fig. 2, the nanofiltration =
membrane 1 (UTC60) was placed in a cell made of stainless steel (SUS316), and the pressure of the high-pressure pump 3 was adjusted to 3 MPa, followed by collecting the permeate 4. The concentration of ethylene glycol, 2,3-butanediol, 1,3-butanediol or 1,4-butanediol in each of the feed solution and the permeate was measured by gas chromatography in the same manner as in the above Example 1.
The glycerin concentration was measured using F-kit in the same manner as in Reference Example 1. The inorganic salt concentration and sugar concentration were measured by high performance liquid chromatography in the same manner as in the method described in Example 1. The results are shown in Table 6.
..
--.1 .--.
[Table 6]
.
Sulfate ion concentration Concentration of desired compound Total sugar concentration Filtration -Nanofiltration Flux Rejection Permeation Rejecton pressure Target Feed Permeate Feed Permeate Feed Permeate membrane (m3/m2/day) rate rate rate o (MPa) (PPin) (PPIT) (.8/1-) (13/1-) (SP (g/L) 5:g N
N(0/0 0 .
N.) -.1 Example Nanofiltration Ethylene UJ
3 4.99 923 4 99.6 20 13.1 65.7 15 0.8 95.0 01 membrane 1 glycol ol U) . .
.
--I
Example Nanofiltration 2,3-3 4.83 896 5 99.4 20 7.0 35.1 18 0.7 96.0 ,z) o 11 membrane 1 Butanediol- 1-`
-I-.
O
Example Nanofiltration 3 Glycerin 4.62 914 3 99.7 20 6.8 34.2 14 0.4 97.0 w 12 membrane 1.
_ , _ _ _ N.) l0 Example Nanofiltration 3 1,3-3.16 832 2 99.8 20 5.0 25.1 15 0.7 95.5 13 membrane 1 Butanediol Example Nanofiltration 3 1,4-3 44 844 3 99.6 20 6.2 30.8 14 0.6 95.8 14 membrane 1 Butanediol , [0072]
As shown in Table 6, with any of the compounds, sulfate ion and sugars were removed, and a clean diol- or triol-containing solution was obtained.
[0073]
5 Subsequently, the diol- or triol-containing solution was concentrated using a reverse osmosis membrane, and then subjected to distillation under reduced pressure (5 mmHg), in the same manner as in the above Example 1. The results are shown in Table 7.
[0074]
Concentration of desired GC
compound (g/1_,) Distillation Target purity Before After yield (%) concentration concentration (%) Example 10 Ethylene glycol 12.4 679 96 99.5 Example 11 2,3-Butanediol 6.6 363 91 99.5 Example 12 Glycerin 6.4 354 88 99.8 Example 13 1,3-Butanediol 4.7 259 94 99.8 Example 14 1,4-Butanediol 5.8 321 96 99.8 10 [0075]
As shown in Table 7, in any of the cases, a highly pure diol or trial was obtained at high yield. Therefore, it was shown that the present invention may increase the yield of the diol or trial.
[0076]
15 (Comparative Examples 5 and 6) Purification of 1,3-Butanediol or 1,4-Butanediol with Cellulose Acetate Nanofiltration Membrane In the same manner as in Example 1,2 Leach of a 1,3-butanediol-containing broth and 1,4-butanediol-containing broth was prepared. Subsequently, a cellulose 20 acetate nanofiltration membrane "GE Sepa" (nanofiltration membrane 4) was placed in a cell made of stainless steel, and the permeate 4 was collected at 3 MPa in the same manner as in the above Examples, thereby carrying out filtration. This V, .9 9 CD
DI
DO
[Table 8]
'.
.
fD
fa.
,.....
ig Concentration of desired Sulfate ion concentration Total sugar concentration , Filtration compound a.
cn Nanofiltration Flux ¨ ¨
o pressure Target 1 Rejection Permeation Rejection -.1 membrane (m3/m2/day) Feed Permeate Feed Permeate Feed Permeate co w (MPa) rate rate rate (Ppm) (PPtn) (84,) (gII-) (PA) (8/1-) ol (%) (%) (%) g w ...1 -N.) Comparative 1,3-'.'1 .... o 3 2.21 832 30 96.4 20 5.6 28.1 15 0.9 94.0 Example 5 Nanofiltration ButanediolI-.
.
. H
Comparative membrane 4 1,4-co w 3 2.41 844 25 97.0 20 7.9 39.7 14 0.7 95.0 '1 I
Example 6 Butanediol v)(1) N.) ko a N
CD
rn g H
P
*CT
[0078]
Thus, it was revealed that, compared to the case of purification with the polyamide nanofiltration membrane shown in Examples 13 and 14, the cellulose acetate nanofiltration membrane shows a higher permeation rate of 1,3-butanediol and 1,4-butanediol but lower removal rates of sulfate ion/sugars. Therefore, these permeates were subjected to concentration with a reverse osmosis membrane and distillation under reduced pressure as in the above Example 1. As a result, 1,3-butanediol showed a distillation yield of 85% and GC purity of 98.4%, and 1,4-butanediol showed a distillation yield of 87% and GC purity of 98.9%. Thus, it was shown that the cellulose acetate nanofiltration membrane shows lower purification efficiencies than the polyamide nanofiltration membrane.
Sepa" (nanofiltration membrane 4) was placed in a cell made of stainless steel, and the permeate 4 under a pressure of 1 MPa, 3 MPa or 5 MPa was collected as in the above Examples, followed by filtration. The results of analysis of the permeates are shown in Table 5.
[0068]
[Table 5]
r) Sulfate ion concentration 1,3-Propanediol concentration Total sugar concentration Filtration0 Nanofiltration Flux 1 Rejection Feed Permeation Rejection n.) ...3 pressure Feed Permeate Permeate Feed Permeate w membrane (m3/m2/day) rate rate rate cri (MPa) (PPm) (PPIn) (%) (g/L) (g/1-) (g/L) 01 w (%) Comparative 1 1.19 916 30 96.7 20 4.2 20.8 15 0.9 94.0 I-.
I
Example 2 w Comparative Nanofiltration n.) 3 3,75 916 25 97.3 20 3.7 18.4 15 0.8 95.0 tO
Example 3 membrane 4 , Comparative 4.64 916 19 97.9 20 2.9 14.3 15 0.5 97.0 Example 4 [0069]
Thus, the cellulose acetate nanofiltration membrane showed a lower permeation rate of 1,3-propanediol as well as lower removal rates of sulfate ion/sugars compared to polyamide nanofiltration membranes. Further, when the permeate obtained in Comparative Examples 3 was subjected to concentration with a reverse osmosis membrane and distillation under reduced pressure in the same manner as in the above Example 1, the distillation yield was 88% and the GC
purity was 99.0%, indicating that a cellulose acetate nanofiltration membrane shows a lower purification efficiency than a polyamide nanofiltration membrane.
[0070]
(Examples 10 to 14) Purification of Ethylene Glycol, 2,3-Butanediol, Glycerin, 1,3-Butanediol or 1,4-Butanediol from Fermentation Broth Using Nanofiltration Membrane In the same manner as in Example 1, 2 L each of 20 g/L ethylene glycol-containing broth, 2,3-butanediol-containing broth, glycerin-containing broth, 1,3-butanediol-containing broth and 1,4-butanediol-containing broth was prepared.
Each of these was fed to the feed tank 1 of the membrane filtration apparatus.
As the 909 nanofiltration membrane indicated by Symbol 7 in Fig. 2, the nanofiltration =
membrane 1 (UTC60) was placed in a cell made of stainless steel (SUS316), and the pressure of the high-pressure pump 3 was adjusted to 3 MPa, followed by collecting the permeate 4. The concentration of ethylene glycol, 2,3-butanediol, 1,3-butanediol or 1,4-butanediol in each of the feed solution and the permeate was measured by gas chromatography in the same manner as in the above Example 1.
The glycerin concentration was measured using F-kit in the same manner as in Reference Example 1. The inorganic salt concentration and sugar concentration were measured by high performance liquid chromatography in the same manner as in the method described in Example 1. The results are shown in Table 6.
..
--.1 .--.
[Table 6]
.
Sulfate ion concentration Concentration of desired compound Total sugar concentration Filtration -Nanofiltration Flux Rejection Permeation Rejecton pressure Target Feed Permeate Feed Permeate Feed Permeate membrane (m3/m2/day) rate rate rate o (MPa) (PPin) (PPIT) (.8/1-) (13/1-) (SP (g/L) 5:g N
N(0/0 0 .
N.) -.1 Example Nanofiltration Ethylene UJ
3 4.99 923 4 99.6 20 13.1 65.7 15 0.8 95.0 01 membrane 1 glycol ol U) . .
.
--I
Example Nanofiltration 2,3-3 4.83 896 5 99.4 20 7.0 35.1 18 0.7 96.0 ,z) o 11 membrane 1 Butanediol- 1-`
-I-.
O
Example Nanofiltration 3 Glycerin 4.62 914 3 99.7 20 6.8 34.2 14 0.4 97.0 w 12 membrane 1.
_ , _ _ _ N.) l0 Example Nanofiltration 3 1,3-3.16 832 2 99.8 20 5.0 25.1 15 0.7 95.5 13 membrane 1 Butanediol Example Nanofiltration 3 1,4-3 44 844 3 99.6 20 6.2 30.8 14 0.6 95.8 14 membrane 1 Butanediol , [0072]
As shown in Table 6, with any of the compounds, sulfate ion and sugars were removed, and a clean diol- or triol-containing solution was obtained.
[0073]
5 Subsequently, the diol- or triol-containing solution was concentrated using a reverse osmosis membrane, and then subjected to distillation under reduced pressure (5 mmHg), in the same manner as in the above Example 1. The results are shown in Table 7.
[0074]
Concentration of desired GC
compound (g/1_,) Distillation Target purity Before After yield (%) concentration concentration (%) Example 10 Ethylene glycol 12.4 679 96 99.5 Example 11 2,3-Butanediol 6.6 363 91 99.5 Example 12 Glycerin 6.4 354 88 99.8 Example 13 1,3-Butanediol 4.7 259 94 99.8 Example 14 1,4-Butanediol 5.8 321 96 99.8 10 [0075]
As shown in Table 7, in any of the cases, a highly pure diol or trial was obtained at high yield. Therefore, it was shown that the present invention may increase the yield of the diol or trial.
[0076]
15 (Comparative Examples 5 and 6) Purification of 1,3-Butanediol or 1,4-Butanediol with Cellulose Acetate Nanofiltration Membrane In the same manner as in Example 1,2 Leach of a 1,3-butanediol-containing broth and 1,4-butanediol-containing broth was prepared. Subsequently, a cellulose 20 acetate nanofiltration membrane "GE Sepa" (nanofiltration membrane 4) was placed in a cell made of stainless steel, and the permeate 4 was collected at 3 MPa in the same manner as in the above Examples, thereby carrying out filtration. This V, .9 9 CD
DI
DO
[Table 8]
'.
.
fD
fa.
,.....
ig Concentration of desired Sulfate ion concentration Total sugar concentration , Filtration compound a.
cn Nanofiltration Flux ¨ ¨
o pressure Target 1 Rejection Permeation Rejection -.1 membrane (m3/m2/day) Feed Permeate Feed Permeate Feed Permeate co w (MPa) rate rate rate (Ppm) (PPtn) (84,) (gII-) (PA) (8/1-) ol (%) (%) (%) g w ...1 -N.) Comparative 1,3-'.'1 .... o 3 2.21 832 30 96.4 20 5.6 28.1 15 0.9 94.0 Example 5 Nanofiltration ButanediolI-.
.
. H
Comparative membrane 4 1,4-co w 3 2.41 844 25 97.0 20 7.9 39.7 14 0.7 95.0 '1 I
Example 6 Butanediol v)(1) N.) ko a N
CD
rn g H
P
*CT
[0078]
Thus, it was revealed that, compared to the case of purification with the polyamide nanofiltration membrane shown in Examples 13 and 14, the cellulose acetate nanofiltration membrane shows a higher permeation rate of 1,3-butanediol and 1,4-butanediol but lower removal rates of sulfate ion/sugars. Therefore, these permeates were subjected to concentration with a reverse osmosis membrane and distillation under reduced pressure as in the above Example 1. As a result, 1,3-butanediol showed a distillation yield of 85% and GC purity of 98.4%, and 1,4-butanediol showed a distillation yield of 87% and GC purity of 98.9%. Thus, it was shown that the cellulose acetate nanofiltration membrane shows lower purification efficiencies than the polyamide nanofiltration membrane.
Claims (5)
1. A method of producing at least one butanediol, said method comprising:
filtering a solution containing said at least one butanediol through a nanofiltration membrane having a polyamide-containing functional layer; and collecting butanediol-containing solution from the permeate flow of said nanofiltration membrane; wherein said butanediol is 2,3-butanediol, 1,4-butanediol or 1,3-butanediol.
filtering a solution containing said at least one butanediol through a nanofiltration membrane having a polyamide-containing functional layer; and collecting butanediol-containing solution from the permeate flow of said nanofiltration membrane; wherein said butanediol is 2,3-butanediol, 1,4-butanediol or 1,3-butanediol.
2. The method according to claim 1, wherein said polyamide comprises a cross-linked piperazine polyamide as a major component, and said piperazine polyamide is formed from 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.
3. The method according to claim 1, further comprising filtering the collected butanediol-containing solution through a reverse osmosis membrane to increase the diol concentration.
4. The method according to claim 1, further comprising distilling the collected butanediol-containing solution under a pressure of not less than 1 Pa and not more than atmospheric pressure, and at a temperature of not less than 25°C and not more than 200°C.
5. The method according to claim 3, further comprising distilling the concentrated butanediol solution after filtration through said reverse osmosis membrane under a pressure of not less than 1 Pa and not more than atmospheric pressure, and at a temperature of not less than 25°C and not more than 200°C.
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| CA2735637A CA2735637C (en) | 2011-03-29 | 2011-03-29 | Method of producing diol or triol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA2735637A CA2735637C (en) | 2011-03-29 | 2011-03-29 | Method of producing diol or triol |
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| CA2735637C true CA2735637C (en) | 2018-07-17 |
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