EP2788310A1 - Procédé de purification d'acides carboxyliques issus de bouillons de fermentation - Google Patents
Procédé de purification d'acides carboxyliques issus de bouillons de fermentationInfo
- Publication number
- EP2788310A1 EP2788310A1 EP12794869.3A EP12794869A EP2788310A1 EP 2788310 A1 EP2788310 A1 EP 2788310A1 EP 12794869 A EP12794869 A EP 12794869A EP 2788310 A1 EP2788310 A1 EP 2788310A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- separation
- biomass
- fermentation
- lactic acid
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 81
- 238000000855 fermentation Methods 0.000 title claims abstract description 50
- 230000004151 fermentation Effects 0.000 title claims abstract description 50
- 235000010633 broth Nutrition 0.000 title claims abstract description 30
- 150000001735 carboxylic acids Chemical class 0.000 title claims abstract description 17
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- 239000002028 Biomass Substances 0.000 claims abstract description 22
- 238000000746 purification Methods 0.000 claims abstract description 18
- 238000001728 nano-filtration Methods 0.000 claims abstract description 15
- 239000007790 solid phase Substances 0.000 claims abstract description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 11
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 120
- 239000004310 lactic acid Substances 0.000 claims description 60
- 235000014655 lactic acid Nutrition 0.000 claims description 60
- 238000000926 separation method Methods 0.000 claims description 21
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 239000001384 succinic acid Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001471 micro-filtration Methods 0.000 claims description 5
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001223 reverse osmosis Methods 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 claims description 2
- KJTLQQUUPVSXIM-ZCFIWIBFSA-N (R)-mevalonic acid Chemical compound OCC[C@](O)(C)CC(O)=O KJTLQQUUPVSXIM-ZCFIWIBFSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- ODBLHEXUDAPZAU-ZAFYKAAXSA-N D-threo-isocitric acid Chemical compound OC(=O)[C@H](O)[C@@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-ZAFYKAAXSA-N 0.000 claims description 2
- KJTLQQUUPVSXIM-UHFFFAOYSA-N DL-mevalonic acid Natural products OCCC(O)(C)CC(O)=O KJTLQQUUPVSXIM-UHFFFAOYSA-N 0.000 claims description 2
- ODBLHEXUDAPZAU-FONMRSAGSA-N Isocitric acid Natural products OC(=O)[C@@H](O)[C@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-FONMRSAGSA-N 0.000 claims description 2
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 229960002510 mandelic acid Drugs 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 claims description 2
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- ODBLHEXUDAPZAU-UHFFFAOYSA-N threo-D-isocitric acid Natural products OC(=O)C(O)C(C(O)=O)CC(O)=O ODBLHEXUDAPZAU-UHFFFAOYSA-N 0.000 claims description 2
- 238000000108 ultra-filtration Methods 0.000 claims description 2
- 230000002779 inactivation Effects 0.000 claims 1
- 239000011343 solid material Substances 0.000 abstract 1
- 238000003795 desorption Methods 0.000 description 28
- 239000011347 resin Substances 0.000 description 22
- 229920005989 resin Polymers 0.000 description 22
- 239000003463 adsorbent Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000012535 impurity Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 238000002336 sorption--desorption measurement Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000001720 carbohydrates Chemical class 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 235000011044 succinic acid Nutrition 0.000 description 6
- 238000002955 isolation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 235000014633 carbohydrates Nutrition 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 235000000346 sugar Nutrition 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- -1 for example Chemical class 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 229920000747 poly(lactic acid) Polymers 0.000 description 3
- 239000004626 polylactic acid Substances 0.000 description 3
- 102000004196 processed proteins & peptides Human genes 0.000 description 3
- 108090000765 processed proteins & peptides Proteins 0.000 description 3
- 150000008163 sugars Chemical class 0.000 description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000012465 retentate Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004251 Ammonium lactate Substances 0.000 description 1
- 208000035404 Autolysis Diseases 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 206010057248 Cell death Diseases 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000000159 acid neutralizing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 229940059265 ammonium lactate Drugs 0.000 description 1
- 235000019286 ammonium lactate Nutrition 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000009089 cytolysis Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940001447 lactate Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000004094 preconcentration Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000028043 self proteolysis Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine group Chemical class C(CCC)N(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- 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
- B01D61/08—Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
Definitions
- the invention relates to a process for the purification of carboxylic acids from fermentation broths, and to a device for carrying out the method according to the invention.
- the isolation of carboxylic acids, which can not be separated or only with difficulty by distillation, is very complicated.
- succinic acid for example.
- the qualities of the succinic acid produced can be differentiated by the subdivision into a technical grade with a succinic acid content of at least 97% by mass and a succinic acid (polymer grade or 1,4 butanediol grade) especially suitable for use for the polymerization with a content of at least 99% , 5 Mao / o.
- Extractive processes using extraction agents such as tributylamines, trialkylamines, olefins, various alcohols and aromatic
- Membrane processes such as, for example, reverse osmosis and other filtration processes, wherein also couplings of these processes and supplementation by further prior art corresponding steps are discussed.
- Such methods are described inter alia in the patents DE 69821951 T2; DE 69015233 T2; DE 69015019 T2; DE 69006555 T2; DE 69015019; DE 60028958T2; DE 10 2004 026152 A1.
- lactic acid can be isolated, for example, from a fermentation broth acidified with sulfuric acid, which in addition to free lactic acid still contains ammonium and sulfate ions, can be isolated by means of chromatographic methods.
- DE 69815369 T2 describes, inter alia, the separation of lactic acid from aqueous mixtures by adsorption on a solid adsorbent, preferably a solid adsorbent is used here, which adsorbs lactic acid versus lactate.
- weak anion exchangers for lactic acid isolation come into question.
- DE 10 2009 019 248 A1 further describes chromatographic Methods for purifying organic acids, in particular lactic acid, by performing Simulated Moving Bed Chromatography.
- WO 2006/124633 A1 describes a process for the production of ammonium lactate by fermentation.
- the ammonium salt of lactic acid formed from the fermentation solution e.g. can be separated by extraction.
- the ammonium salt can be easily split in a subsequent step with weak acids or carbon dioxide. This gives you the free lactic acid, which can then be purified by distillation, for example.
- WO99 / 19290 describes a lactic acid fermentation with subsequent filtration and extraction, wherein the extraction may be an adsorption.
- the type of interaction with the solid phase of adsorption is not disclosed.
- a similar process is disclosed in WO93 / 06226, in which case the solid phase of the adsorption is provided with tertiary amino groups and thereby the production rate of free acid is increased.
- EP0135728 also teaches the isolation of enzymatically produced carboxylic acids via adsorbers which are provided with tertiary amino groups. The fermentation takes place via cells immobilized on columns.
- DE19939630C2 discloses a process for the fine purification of aqueous solutions containing fermentatively produced organic acids, such as, for example, citric acid, lactic acid, succinic acid or tartaric acid.
- the solution coming from the fermentation is first filtered and then the resulting solution is passed through an anion exchanger and a subsequent Adsorberharzbett.
- the adsorbent resin bed used for the fine cleaning is initially loaded with OH " ions and binds the product acid, and there is no mention of further purification of the filtered solution downstream of the filtration to remove impurities contained, such as cell debris, carbohydrates, nutrients, amino acids and sugars.
- the solid adsorbent may here be a poly-4-vinylpyridine resin or a tertiary polystyrene-bivinylbenzene-amine resin. Again, an intermediate step to remove other contaminants is not taught.
- the object of the invention is to provide a process for the separation and purification of carboxylic acids from fermentation broths which has a high product purity of> 80% by mass and avoids known disadvantages of other processes.
- the object is achieved by the use of a process for the separation and purification of carboxylic acids from fermentation broths, the process comprising the following steps,
- the advantage of this method is that is greatly reduced by the arranged before the adsorption fine cleaning, the content of impurities in the fermentation broth from step a), which is then sent through the solid phase of adsorption, whereby the production rate of carboxylic acid on can be increased and the equipment cost is reduced, creating a cheaper method, as disclosed for example in EP0135728, created.
- EP0135728 proposes to strongly adsorb the carboxylic acids and to carry out a circulation process in highly contaminated fermentation solutions, which is very expensive.
- Another advantage of the inventive method is that is not neutralized during the fermentation and the separation and purification with the free acid and not with its salt, as is often the case in the prior art.
- the process is simplified in that no acidification step is necessary and thus no further substances added during the fermentation must be separated off, which are normally used in the prior art for neutralization.
- microorganisms for the fermentation itself, a variety of microorganisms can be used, including bacteria, yeasts and fungi.
- the fermentation broth may also contain various recycle streams from the overall process.
- the fermentation broth containing the carboxylic acid, biomass and constituents of the substrate is continuously fed to precoat filtration and / or microfiltration and / or ultrafiltration.
- the resulting separated biomass is optionally returned to the fermenter.
- temperature and pH correspond to the values of the fermentation, since it was found that by inactivating the biomass by increasing the temperature and lowering the pH by adding acid autolysis of the biomass is accelerated and more lysis products be discharged into the fermentation broth.
- the time between completion of the fermentation and separation of the biomass should be kept as short as possible and should not be more than 2 hours, preferably less than 1-2 hours.
- the biomass concentration in the filtrate should not exceed 1 g / l. This process management positively influences the end product quality.
- step b In order to produce the production of carboxylic acids in a high-purity quality, a fine cleaning is performed due to still existing residues of dyes and impurities in step b), which is preferably configured as nanofiltration.
- membranes of a separation size of 100 to 400 Da are used. It was shown that nanofiltration with a cut-off of 200 Da gives good quality results.
- the process is conducted so that the retentate of the nanofiltration is not more than 10% of the total throughput.
- the permeate is fed to the further process step c).
- a reverse osmosis is carried out between the process steps b) and c). This step will serve as an exemplary further way of concentrating before
- tertiary amino groups are preferably used, which are pryridine, which are preferably selected from the group comprising polyvinylpyridine and poly-2 or poly-4-vinylpyridine.
- the one or more solid phase used for adsorption in process step c) is a polymer which is crosslinked with divinylbenzene.
- the one or more solid phase used for adsorption in process step c) is formed from one or more different polymer materials.
- Further suitable polymers having tertiary amino groups which selectively adsorb carboxylic acids and permit their desorption with polar solvents are described, for example, in DE 1274128 and DE 3043766.
- the adsorbed carboxylic acids are desorbed in process step c) preferably by treatment with a polar solvent from the group of aliphatic alcohols, aliphatic ketones and aliphatic carboxylic acid esters.
- Desorption is particularly preferably carried out by means of methyl acetate or ethyl acetate, acetone or methyl ethyl ketone and in particular with lower alcohols such as ethanol and particularly advantageously with methanol.
- the desorption with water which is advantageously heated to a temperature of 20 ° C to 60 ° C, is possible.
- the solvent is optionally then separated via a distillation of the carboxylic acid and / or the product is crystallized out.
- further purification steps such as activated carbon filtration and / or anion and / or cation exchange can be provided.
- the carboxylic acid to be separated off and to be purified is preferably selected from the group comprising hydroxycarboxylic acids and dicarboxylic acids.
- the hydroxycarboxylic acid is selected from the group comprising
- Malic acid glycolic acid, isocitric acid, mandelic acid, lactic acid, tartronic acid, tartaric acid, citric acid, ⁇ -hydroxybutyric acid, mevalonic acid and salicylic acid, and is preferably lactic acid.
- the dicarboxylic acid is selected from the group comprising oxalic acid, maleic acid, succinic acid, glutaric acid, Adipic acid, pimelic acid, suberic acid, fumaric acid and itaconic acid, and is preferably succinic acid.
- the present invention claims an apparatus for carrying out the method set forth in claim 1.
- Embodiment 1 is a diagrammatic representation of Embodiment 1:
- a fermentation broth containing exemplarily lactic acid, biomass and constituent parts of the substrate was continuously separated from the biomass by precoat filtration and microfiltration.
- the resulting broth contained 2% lactic acid.
- the lactic acid-containing permeate containing 2% is used in an adsorption-desorption experiment.
- An adsorbent resin which carries poly-4-vinylpyridine as active component and is crosslinked with divinylbenzene and polymerized into a spherical structure is used here.
- the lactic acid is to be seen here as an exemplary representative of a carboxylic acid. With the aid of the adsorber resin, the lactic acid is bound to the resin from the lactic acid solution. In a subsequent desorption step, the lactic acid is recovered. For desorption, 40 ° C. warm water was used here. The results can be found in the following Tab. 1.
- Tab. 1 Adsorption and desorption of lactic acid to an amino group-bearing adsorbent resin, wherein the desorption was carried out with water, having a temperature of 40 ° C:
- Table 1 shows a 6-fold adsorption-desorption cycle. 10 g of an adsorbent resin were used. It could be shown that a desorption of almost 100% is possible.
- the loading capacity is 0.54 g of lactic acid per 10 g of polymer when 40 ° C warm water is used for desorption. % Desorption is calculated to be 95% over the last 5 cycles.
- the first charge / discharge cycle shows a higher adsorption of 1.13 g of lactic acid and a reduced desorption. This can be explained by the fact that the resin must first be charged with a basic load.
- the impurities still contained interfere with a subsequent processing of the lactic acid, e.g. to polylactic acid.
- a subsequent processing of the lactic acid e.g. to polylactic acid.
- even more adsorption desorption cycles are necessary to achieve a desired product quality, since the other impurities partially adsorb to the column material.
- a larger number of adsorption columns would be necessary.
- Embodiment 2 is a diagrammatic representation of Embodiment 1:
- a process chain including nanofiltration as a fine cleaning is shown.
- a fermentation broth containing carboxylic acids such as lactic acid was produced by fermentation of microorganisms. At this time, the pH became between 6.0 and 7.3 held constant, without neutralization agent, such as NaOH, were added. This was achieved by continuously withdrawing fermentation broth and purifying it. For this purpose, it is necessary for an average productivity of lactic acid during the fermentation of 4 g / l / h and the specified pH range, the subsequent microfiltration of the process step a) and the nanofiltration of the process step b) be interpreted such that the volume of the permeate from the nanofiltration corresponds to 2 times the working volume of the fermenter.
- the fermentation broth exemplified by lactic acid, biomass and constituents of the substrate, was continuously separated from the biomass by precoat filtration and microfiltration.
- the resulting broth contained 2% lactic acid. It was ensured that the temperature and the pH correspond to the values in the fermentation carried out.
- the subsequent fine cleaning was carried out as nanofiltration. A membrane with a separation size of 200 Da was used. Care was taken that nanofiltration was carried out at a temperature equal to that of the fermentation, with a temperature difference of ⁇ 5 ° C being tolerated. It was worked here in a temperature range of 48 ° C to 52 ° C. Also, the pH of the fermentation, which ranges from 6 to 7.3, has been maintained.
- the retentate stream, at The nanofiltration obtained and containing the impurities can be returned to the fermentation again.
- the lactic acid-containing permeate containing 2% was used in an adsorption-desorption experiment.
- An adsorbent resin which carries poly-4-vinylpyridine as the active component and is crosslinked with divinylbenzene and polymerized into a spherical structure was used.
- the lactic acid is to be seen here as an exemplary representative of a carboxylic acid.
- the adsorber resin With the aid of the adsorber resin, the lactic acid is bound to the resin from the lactic acid solution.
- the lactic acid is recovered. For desorption, 40 ° C. warm water was used here. The results can be found in the following Tab. 1.
- Tab. 2 Adsorption and desorption of lactic acid to an amino group-bearing adsorbent resin, wherein the desorption was carried out with water, having a temperature of 40 ° C:
- Table 1 shows a 6-fold adsorption-desorption cycle. 10 g of an adsorbent resin were used. It could be shown that a desorption of almost 100% is possible. In summary it can be said that the loading capacity is 0.59 g of lactic acid per 10 g of polymer when 40 ° C warm water is used for desorption. The desorption in% is calculated over the last 5 cycles at 97%. The first charge / discharge cycle shows a higher adsorption of 1, 26 g lactic acid and a reduced desorption. This can be explained by the fact that the resin must first be charged with a basic load.
- Embodiment 3 is
- Embodiment 3 differs from Embodiment 2 in the choice of the desorbent.
- Embodiment 3 methanol was used as an example of an aliphatic alcohol. The results can be found in the following Tab. 3.
- Table 3 shows a 6-fold adsorption-desorption cycle.
- the loading capacity of the adsorber resin is 0.78 g of lactic acid per 10 g of polymer when methanol is used for desorption.
- The% desorption is calculated to be at least 100% over the last 5 cycles.
- the first loading / unloading cycle shows a higher adsorption of 1, 14 g of lactic acid and a reduced desorption. This can also be explained by the fact that the resin must first be charged with a basic load.
- Impurities that permanently damage the resin Possible components are including sugars, dyes and peptides.
- Embodiment 4 is a diagrammatic representation of Embodiment 4:
- Embodiment 4 differs from Embodiment 2 by an additional method step.
- a reverse osmosis (UO) was additionally applied to the NF. The results can be found in FIG. 1.
- Fig. 1 loading capacity after preconcentration of lactic acid
- Fig. 1 the amount of lactic acid adsorbed in g on 10 g of polymer is plotted against the concentration of lactic acid solution in g / L used to charge the column. From this graph it can be seen that the loading capacity increases with the lactic acid concentration. A concentration by a factor of 4.5 leads to an increase in loading to 2.5 times. Further concentration by other known from the prior art measures or a
- the additional process step requires much less resin for adsorption. Furthermore, the concentration of lactic acid after desorption is higher and thus the cost of further concentration lower.
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Abstract
Procédé de séparation et de purification d'acides carboxyliques à partir de bouillons de fermentation, ledit procédé comprenant les étapes suivantes : a) séparation de la biomasse et des matières solides éventuellement présentes du bouillon de fermentation, b) purification du bouillon de fermentation obtenu à l'étape a) par nanofiltration, c) séparation de l'acide carboxylique par adsorption sur une ou plusieurs phase(s) solide(s) comportant des groupes amino tertiaires.
Applications Claiming Priority (2)
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DE102011120632A DE102011120632A1 (de) | 2011-12-09 | 2011-12-09 | Verfahren zur Aufreinigung von Carbonsäuren aus Fermentationsbrühen |
PCT/EP2012/004741 WO2013083229A1 (fr) | 2011-12-09 | 2012-11-15 | Procédé de purification d'acides carboxyliques issus de bouillons de fermentation |
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EP2788310A1 true EP2788310A1 (fr) | 2014-10-15 |
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EP12794869.3A Withdrawn EP2788310A1 (fr) | 2011-12-09 | 2012-11-15 | Procédé de purification d'acides carboxyliques issus de bouillons de fermentation |
Country Status (5)
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US (1) | US9272976B2 (fr) |
EP (1) | EP2788310A1 (fr) |
BR (1) | BR112014013798A2 (fr) |
DE (1) | DE102011120632A1 (fr) |
WO (1) | WO2013083229A1 (fr) |
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DE102016001070A1 (de) | 2015-02-06 | 2016-08-11 | Rwth Aachen | Verfahren zur Trennung organischer Dicarbonsäuren durch Adsorption hydrophober poröser Materialien |
EP3268099A1 (fr) * | 2015-03-12 | 2018-01-17 | Novasep Process SAS | Procédé de purification d'un acide organique comprenant une étape de traitement par électrodialyse |
EP3290101A1 (fr) * | 2016-09-05 | 2018-03-07 | Nanoscience for life GmbH & Co. KG | Procede de fabrication de membranes separatrices a selection de matiere et son utilisation |
KR20220052965A (ko) | 2019-08-28 | 2022-04-28 | 다니스코 유에스 인크. | 메발로노락톤을 포함하는 스킨 케어 조성물 |
EP3822356A1 (fr) * | 2019-11-18 | 2021-05-19 | Corvay Bioproducts GmbH | Procédé de production d'un acide dicarboxylique |
CN111138273A (zh) * | 2019-12-24 | 2020-05-12 | 上海凯赛生物技术股份有限公司 | 一种长链二元酸的精制工艺及系统 |
US12017182B2 (en) | 2019-12-24 | 2024-06-25 | Cathay Biotech Inc. | Method and system for refining long chain dicarboxylic acid |
CN113880710B (zh) * | 2021-10-22 | 2023-10-20 | 万华化学集团股份有限公司 | 一种乳酸的纯化方法 |
US20230248677A1 (en) * | 2022-02-08 | 2023-08-10 | Visolis Technologies, Inc. | Novel highly sustainable compositions for modulation of gene expression in human skin, and methods of production thereof |
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JPS5125232B1 (fr) | 1965-02-24 | 1976-07-29 | ||
JPS5675451A (en) | 1979-11-21 | 1981-06-22 | Koei Chem Co Ltd | Method for treating composition containing carboxylic acid |
DE3328093A1 (de) | 1983-08-04 | 1985-02-21 | Hoechst Ag, 6230 Frankfurt | Isolierung von durch fermentation erzeugten carbonsaeuren |
US5168055A (en) | 1986-06-11 | 1992-12-01 | Rathin Datta | Fermentation and purification process for succinic acid |
US5143834A (en) | 1986-06-11 | 1992-09-01 | Glassner David A | Process for the production and purification of succinic acid |
US5034105A (en) | 1989-07-27 | 1991-07-23 | Michigan Biotechnology Institute | Carboxylic acid purification and crystallization process |
US6137004A (en) * | 1991-03-14 | 2000-10-24 | Reilly Industries, Inc. | Processes for recovering citric acid |
EP0603321A1 (fr) | 1991-09-13 | 1994-06-29 | Purdue Research Foundation | Procede de fermentation servant a produire de l'acide lactique |
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BE1011197A3 (fr) | 1997-06-06 | 1999-06-01 | Brussels Biotech En Abrege Bb | Procede de purification d'acide lactique. |
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DE102004026152A1 (de) | 2004-05-28 | 2005-12-15 | Basf Ag | Fermentative Herstellung von Feinchemikalien |
WO2006124633A1 (fr) | 2005-05-13 | 2006-11-23 | Cargill, Incorporated | Production d'acide lactique |
DE102007045701B3 (de) | 2007-09-24 | 2009-05-14 | Uhde Gmbh | Gewinnung von Milchsäure durch Fermentation und Extraktion mit Aminen |
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- 2011-12-09 DE DE102011120632A patent/DE102011120632A1/de not_active Ceased
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2012
- 2012-11-15 EP EP12794869.3A patent/EP2788310A1/fr not_active Withdrawn
- 2012-11-15 WO PCT/EP2012/004741 patent/WO2013083229A1/fr active Application Filing
- 2012-11-15 BR BR112014013798A patent/BR112014013798A2/pt not_active Application Discontinuation
- 2012-11-15 US US14/363,844 patent/US9272976B2/en not_active Expired - Fee Related
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US9272976B2 (en) | 2016-03-01 |
BR112014013798A8 (pt) | 2017-06-13 |
WO2013083229A1 (fr) | 2013-06-13 |
US20140371486A1 (en) | 2014-12-18 |
DE102011120632A1 (de) | 2013-06-13 |
BR112014013798A2 (pt) | 2017-06-13 |
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