DE60124229T2 - Verfahren zur gewinnung von organischen säuren aus wässrigen lösungen - Google Patents
Verfahren zur gewinnung von organischen säuren aus wässrigen lösungen Download PDFInfo
- Publication number
- DE60124229T2 DE60124229T2 DE60124229T DE60124229T DE60124229T2 DE 60124229 T2 DE60124229 T2 DE 60124229T2 DE 60124229 T DE60124229 T DE 60124229T DE 60124229 T DE60124229 T DE 60124229T DE 60124229 T2 DE60124229 T2 DE 60124229T2
- Authority
- DE
- Germany
- Prior art keywords
- acid
- stock solution
- klg
- grams
- broth
- 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.)
- Expired - Fee Related
Links
- 150000007524 organic acids Chemical class 0.000 title claims abstract description 146
- 238000000034 method Methods 0.000 title claims abstract description 109
- 239000007864 aqueous solution Substances 0.000 title abstract description 24
- 235000005985 organic acids Nutrition 0.000 title abstract description 22
- VBUYCZFBVCCYFD-UHFFFAOYSA-N D-arabino-2-Hexulosonic acid Natural products OCC(O)C(O)C(O)C(=O)C(O)=O VBUYCZFBVCCYFD-UHFFFAOYSA-N 0.000 claims abstract description 313
- VBUYCZFBVCCYFD-NUNKFHFFSA-N 2-dehydro-L-idonic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)C(=O)C(O)=O VBUYCZFBVCCYFD-NUNKFHFFSA-N 0.000 claims abstract description 312
- 239000000203 mixture Substances 0.000 claims abstract description 126
- 238000011084 recovery Methods 0.000 claims abstract description 123
- 239000002253 acid Substances 0.000 claims abstract description 110
- 150000001450 anions Chemical class 0.000 claims abstract description 53
- 238000000855 fermentation Methods 0.000 claims abstract description 15
- 230000004151 fermentation Effects 0.000 claims abstract description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 82
- 238000000354 decomposition reaction Methods 0.000 claims description 43
- 235000010323 ascorbic acid Nutrition 0.000 claims description 41
- 229960005070 ascorbic acid Drugs 0.000 claims description 41
- 239000011668 ascorbic acid Substances 0.000 claims description 41
- 238000001914 filtration Methods 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 18
- 238000004448 titration Methods 0.000 claims description 17
- 150000001768 cations Chemical class 0.000 claims description 14
- 239000003957 anion exchange resin Substances 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000010908 decantation Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- VBUYCZFBVCCYFD-JJYYJPOSSA-N 2-dehydro-D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C(=O)C(O)=O VBUYCZFBVCCYFD-JJYYJPOSSA-N 0.000 claims 3
- 238000004064 recycling Methods 0.000 claims 1
- 238000004611 spectroscopical analysis Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 59
- 239000008346 aqueous phase Substances 0.000 abstract description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011550 stock solution Substances 0.000 description 329
- 235000010633 broth Nutrition 0.000 description 188
- 238000002425 crystallisation Methods 0.000 description 160
- 230000008025 crystallization Effects 0.000 description 160
- 230000001965 increasing effect Effects 0.000 description 141
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 130
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 99
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 81
- 239000000047 product Substances 0.000 description 80
- 239000000706 filtrate Substances 0.000 description 73
- 229910052698 phosphorus Inorganic materials 0.000 description 70
- 238000003828 vacuum filtration Methods 0.000 description 69
- 238000001035 drying Methods 0.000 description 64
- 239000011734 sodium Substances 0.000 description 59
- 239000000126 substance Substances 0.000 description 59
- 229910052708 sodium Inorganic materials 0.000 description 58
- 238000001704 evaporation Methods 0.000 description 44
- 230000008020 evaporation Effects 0.000 description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 42
- 229910052799 carbon Inorganic materials 0.000 description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 39
- 230000005588 protonation Effects 0.000 description 38
- 229910052700 potassium Inorganic materials 0.000 description 37
- 238000005341 cation exchange Methods 0.000 description 36
- 239000011777 magnesium Substances 0.000 description 35
- 229910052749 magnesium Inorganic materials 0.000 description 34
- 230000020477 pH reduction Effects 0.000 description 34
- 239000002585 base Substances 0.000 description 28
- 239000000460 chlorine Substances 0.000 description 26
- 239000003729 cation exchange resin Substances 0.000 description 25
- 239000007787 solid Substances 0.000 description 24
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical class C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 23
- 238000001471 micro-filtration Methods 0.000 description 23
- 238000011282 treatment Methods 0.000 description 23
- 229910052801 chlorine Inorganic materials 0.000 description 22
- 229940093915 gynecological organic acid Drugs 0.000 description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 19
- 150000007513 acids Chemical class 0.000 description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 15
- 238000005349 anion exchange Methods 0.000 description 15
- 239000011574 phosphorus Substances 0.000 description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 14
- 229910052717 sulfur Inorganic materials 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 239000011575 calcium Substances 0.000 description 11
- -1 alkali metal salt Chemical class 0.000 description 10
- 230000007423 decrease Effects 0.000 description 10
- 239000012452 mother liquor Substances 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 150000007942 carboxylates Chemical class 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 241000894007 species Species 0.000 description 7
- 206010020601 Hyperchlorhydria Diseases 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 150000001767 cationic compounds Chemical class 0.000 description 5
- 238000010494 dissociation reaction Methods 0.000 description 5
- 230000005593 dissociations Effects 0.000 description 5
- 229910001411 inorganic cation Inorganic materials 0.000 description 5
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 4
- 229910001626 barium chloride Inorganic materials 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 2
- 229930192627 Naphthoquinone Natural products 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
- 229960005261 aspartic acid Drugs 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229940023913 cation exchange resins Drugs 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001412 inorganic anion Inorganic materials 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 150000003893 lactate salts Chemical class 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 150000002791 naphthoquinones Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- JMSVCTWVEWCHDZ-UHFFFAOYSA-N syringic acid Chemical compound COC1=CC(C(O)=O)=CC(OC)=C1O JMSVCTWVEWCHDZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- XWSGEVNYFYKXCP-UHFFFAOYSA-N 2-[carboxymethyl(methyl)amino]acetic acid Chemical compound OC(=O)CN(C)CC(O)=O XWSGEVNYFYKXCP-UHFFFAOYSA-N 0.000 description 1
- RMZNXRYIFGTWPF-UHFFFAOYSA-N 2-nitrosoacetic acid Chemical compound OC(=O)CN=O RMZNXRYIFGTWPF-UHFFFAOYSA-N 0.000 description 1
- XSDMYDIROCZZIK-UHFFFAOYSA-N 6-[[4-(5-carboxypentylcarbamoyl)benzoyl]amino]hexanoic acid Chemical compound OC(=O)CCCCCNC(=O)C1=CC=C(C(=O)NCCCCCC(O)=O)C=C1 XSDMYDIROCZZIK-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 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 1
- 239000005715 Fructose Substances 0.000 description 1
- 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 1
- 241000257303 Hymenoptera Species 0.000 description 1
- DGABKXLVXPYZII-UHFFFAOYSA-N Hyodeoxycholic acid Natural products C1C(O)C2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)CC2 DGABKXLVXPYZII-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- SKCKOFZKJLZSFA-UHFFFAOYSA-N L-Gulomethylit Natural products CC(O)C(O)C(O)C(O)CO SKCKOFZKJLZSFA-UHFFFAOYSA-N 0.000 description 1
- 235000011430 Malus pumila Nutrition 0.000 description 1
- 235000015103 Malus silvestris Nutrition 0.000 description 1
- 101100345589 Mus musculus Mical1 gene Proteins 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 108020004511 Recombinant DNA Proteins 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000010564 aerobic fermentation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 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 1
- 210000000941 bile Anatomy 0.000 description 1
- 239000003613 bile acid Substances 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical group S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- HUBANNPOLNYSAD-UHFFFAOYSA-N clopyralid Chemical compound OC(=O)C1=NC(Cl)=CC=C1Cl HUBANNPOLNYSAD-UHFFFAOYSA-N 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- DGABKXLVXPYZII-SIBKNCMHSA-N hyodeoxycholic acid Chemical compound C([C@H]1[C@@H](O)C2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)CC1 DGABKXLVXPYZII-SIBKNCMHSA-N 0.000 description 1
- 229910001504 inorganic chloride Inorganic materials 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- YIBXWXOYFGZLRU-UHFFFAOYSA-N syringic aldehyde Natural products CC12CCC(C3(CCC(=O)C(C)(C)C3CC=3)C)C=3C1(C)CCC2C1COC(C)(C)C(O)C(O)C1 YIBXWXOYFGZLRU-UHFFFAOYSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 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
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S435/00—Chemistry: molecular biology and microbiology
- Y10S435/803—Physical recovery methods, e.g. chromatography, grinding
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S435/00—Chemistry: molecular biology and microbiology
- Y10S435/8215—Microorganisms
- Y10S435/822—Microorganisms using bacteria or actinomycetales
- Y10S435/874—Pseudomonas
- Y10S435/876—Pseudomonas fluorescens
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S435/00—Chemistry: molecular biology and microbiology
- Y10S435/8215—Microorganisms
- Y10S435/822—Microorganisms using bacteria or actinomycetales
- Y10S435/886—Streptomyces
- Y10S435/896—Streptomyces fradiae
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US519936 | 2000-03-07 | ||
| US09/519,936 US6670505B1 (en) | 2000-03-07 | 2000-03-07 | Process for the recovery of organic acids from aqueous solutions |
| PCT/US2001/007140 WO2001066508A2 (en) | 2000-03-07 | 2001-03-06 | Process for the recovery of organic acids from aqueous solutions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE60124229D1 DE60124229D1 (de) | 2006-12-14 |
| DE60124229T2 true DE60124229T2 (de) | 2007-02-15 |
Family
ID=24070463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE60124229T Expired - Fee Related DE60124229T2 (de) | 2000-03-07 | 2001-03-06 | Verfahren zur gewinnung von organischen säuren aus wässrigen lösungen |
Country Status (8)
| Country | Link |
|---|---|
| US (2) | US6670505B1 (enExample) |
| EP (1) | EP1261574B1 (enExample) |
| JP (1) | JP2003525923A (enExample) |
| CN (1) | CN100413839C (enExample) |
| AT (1) | ATE344225T1 (enExample) |
| BR (1) | BR0109005A (enExample) |
| DE (1) | DE60124229T2 (enExample) |
| WO (1) | WO2001066508A2 (enExample) |
Families Citing this family (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10007702A1 (de) | 2000-02-19 | 2001-08-23 | Sueddeutsche Kalkstickstoff | Verfahren zur Herstellung von N-(Phosphonomethyl)glycin |
| AU6293001A (en) | 2000-05-22 | 2001-12-11 | Monsanto Technology Llc | Reaction systems for making n-(phosphonomethyl)glycine compounds |
| US20060149084A1 (en) * | 2002-12-19 | 2006-07-06 | Thomas Domschke | Method for extracting 2-ketone-l-gulonic acid from a polar, preferably aqueous solvent |
| DE10308045B3 (de) * | 2003-02-26 | 2004-06-17 | Lurgi Ag | Verfahren und Vorrichtung zur kontinuierlichen Gewinnung freier Weinsäure aus Kaliumhydrogentartrat enthaltenden Rohstoffen |
| JP4469568B2 (ja) | 2003-07-09 | 2010-05-26 | 三菱化学株式会社 | 有機酸の製造方法 |
| BRPI0413403A (pt) | 2003-08-28 | 2006-10-17 | Mitsubishi Chem Corp | método para produzir ácido succìnico |
| WO2005026349A1 (ja) | 2003-09-17 | 2005-03-24 | Mitsubishi Chemical Corporation | 非アミノ有機酸の製造方法 |
| WO2005030973A1 (ja) | 2003-09-30 | 2005-04-07 | Ajinomoto Co., Inc. | 発酵液からのコハク酸の精製方法 |
| CN1989238B (zh) | 2004-05-20 | 2010-05-26 | 味之素株式会社 | 生产琥珀酸的细菌和生产琥珀酸的方法 |
| CN100389075C (zh) * | 2004-08-10 | 2008-05-21 | 株式会社神钢环境舒立净 | 排水处理方法和排水处理装置 |
| AU2005292735A1 (en) * | 2004-10-01 | 2006-04-13 | Ge Healthcare As | Method for producing pyruvic acid |
| BRPI0617491B1 (pt) | 2005-10-18 | 2021-04-27 | Ajinomoto Co., Inc | Processo para produção de ácido succínico |
| BRPI0707674A2 (pt) | 2006-02-24 | 2011-05-10 | Mitsubishi Chem Corp | bactÉria capaz de produzir Ácido orgÂnico e processo para produÇço do mesmo |
| CN101906032A (zh) * | 2010-07-14 | 2010-12-08 | 华东理工大学 | 回收和循环使用l-(+)-酒石酸的方法 |
| US9376364B2 (en) * | 2011-08-16 | 2016-06-28 | Purac Biochem B.V. | Acid/salt separation |
| MY179474A (en) * | 2011-08-16 | 2020-11-07 | Purac Biochem Bv | Recovery of carboxylic acid from their magnesium salts by precipitation using hydrochloric acid, useful for fermentation broth work-up |
| US9061986B2 (en) * | 2011-08-16 | 2015-06-23 | Purac Biochem B.V. | Acid/salt separation |
| EP2744747B1 (en) | 2011-08-16 | 2020-11-18 | Purac Biochem B.V. | Recovery of carboxylic acid from their magnesium salts by precipitation using hydrochloric acid, useful for fermentation broth work-up |
| US9480574B2 (en) | 2013-03-14 | 2016-11-01 | Benvenue Medical, Inc. | Spinal fusion implants and devices and methods for deploying such implants |
| CN103450007B (zh) * | 2013-09-02 | 2015-06-17 | 西安通鑫半导体辅料有限公司 | 一种从硅片脱胶工序产生的废乳酸中回收乳酸的方法 |
| US9422398B2 (en) | 2014-05-30 | 2016-08-23 | Industrial Technology Research Institute | Copolymer, and method for preparing a monomer used to form the copolymer |
| US10314605B2 (en) | 2014-07-08 | 2019-06-11 | Benvenue Medical, Inc. | Apparatus and methods for disrupting intervertebral disc tissue |
| CN104447529B (zh) * | 2014-11-25 | 2017-05-24 | 利尔化学股份有限公司 | 3,6‑二氯吡啶甲酸的提取纯化方法 |
| CN104672078B (zh) * | 2015-02-02 | 2017-05-24 | 江苏索普(集团)有限公司 | 一种羰基合成醋酸副产物提纯制丙酸的工艺 |
| US10022243B2 (en) | 2015-02-06 | 2018-07-17 | Benvenue Medical, Inc. | Graft material injector system and method |
| US10758286B2 (en) | 2017-03-22 | 2020-09-01 | Benvenue Medical, Inc. | Minimal impact access system to disc space |
| WO2019148083A1 (en) | 2018-01-29 | 2019-08-01 | Benvenue Medical, Inc. | Minimally invasive interbody fusion |
| WO2019178575A1 (en) | 2018-03-16 | 2019-09-19 | Benvenue Medical, Inc. | Articulated instrumentation and methods of using the same |
| CN108314164B (zh) * | 2018-03-27 | 2020-06-19 | 浙江大学 | 回收废水中钡的方法 |
| CN108947066A (zh) * | 2018-07-13 | 2018-12-07 | 宁波永顺精细化工有限公司 | 羧酸钡废水中羧酸及钡盐的回收方法 |
| CA3122178A1 (en) * | 2018-12-19 | 2020-06-25 | Basf Se | Method for separating biomass from a solution comprising biomass and at least one oligosaccaride |
| KR102520535B1 (ko) * | 2018-12-24 | 2023-04-11 | 안형일 | 미네랄을 포함하는 사료 첨가 조성물 |
| CN111943836A (zh) * | 2019-05-16 | 2020-11-17 | 帝斯曼知识产权资产管理有限公司 | 回收2-酮-l-古洛糖酸的改进方法 |
| CN111978202B (zh) * | 2020-08-12 | 2022-08-05 | 浙江理工大学上虞工业技术研究院有限公司 | 可碱洗分散染料水解产物的回收方法 |
| CN112552164B (zh) * | 2020-12-08 | 2022-12-09 | 日照金禾博源生化有限公司 | 一种从不合格柠檬酸钠母液中提取苹果酸的工艺方法 |
| US20240391861A1 (en) * | 2021-10-29 | 2024-11-28 | Alliance For Sustainable Energy, Llc | Process for the recovery of monopotassium glucarate and glucaric acid |
Family Cites Families (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2318500A (en) * | 1935-10-21 | 1943-05-04 | Parke Davis & Co | Preparation of ascorbic acid and 1-gulosone |
| US2421612A (en) | 1945-05-04 | 1947-06-03 | Byron E Gray | Preparation of 2-keto gulonic acid and its salts |
| US2421611A (en) * | 1945-05-04 | 1947-06-03 | Byron E Gray | Preparation of 2-keto gulonic acid and its salts |
| US2462251A (en) | 1945-05-16 | 1949-02-22 | Merck & Co Inc | Process for preparing ascorbic acids |
| US2918492A (en) * | 1956-08-24 | 1959-12-22 | Miles Lab | Method of preparing methyl 2-ketogluconate |
| US3043749A (en) * | 1960-07-28 | 1962-07-10 | Pfizer & Co C | Preparation of 2-keto-l-gulonic acid |
| US3234105A (en) * | 1962-09-20 | 1966-02-08 | Takeda Chemical Industries Ltd | Method for producing 2-keto-lgulonic acid |
| US3381027A (en) * | 1964-04-22 | 1968-04-30 | Hoffmann La Roche | Preparation and recovery of methyl 2-ketogluconate |
| US4113771A (en) | 1971-04-07 | 1978-09-12 | Ethyl Corporation | Process for the purification of citric acid |
| US4202828A (en) | 1978-01-10 | 1980-05-13 | Kawasaki Kasei Chemicals Limited | Process for separation of naphthoquinone and phthalic acid |
| FR2421864A1 (fr) | 1978-04-05 | 1979-11-02 | Hoechst France | Procede de fabrication de l'acide hydroxy-4, dimethoxy-3,5 benzoique a partir de l'acide trimethoxy-3,4,5 benzoique |
| US4334074A (en) | 1981-02-02 | 1982-06-08 | The Dow Chemical Company | Method of recovering 3,6-dichloropicolinic acid from basic aqueous solutions of salts thereof |
| DE3345411A1 (de) | 1983-12-15 | 1985-06-27 | Dynamit Nobel Ag, 5210 Troisdorf | Verfahren zur reindarstellung von carbonsaeuren |
| US4771001A (en) | 1986-03-27 | 1988-09-13 | Neurex Corp. | Production of lactic acid by continuous fermentation using an inexpensive raw material and a simplified method of lactic acid purification |
| US5168055A (en) | 1986-06-11 | 1992-12-01 | Rathin Datta | Fermentation and purification process for succinic acid |
| US5202476A (en) * | 1988-04-29 | 1993-04-13 | Takeda Chemical Industries, Ltd. | Purification of 2-keto-L-gulonic acid |
| FR2636343B1 (enExample) | 1988-09-13 | 1994-11-25 | Rhone Poulenc Sante | |
| FR2648136B1 (fr) | 1989-06-12 | 1994-06-17 | Rhone Poulenc Sante | Procede de preparation de l'acide ascorbique |
| CH678057A5 (de) | 1989-06-26 | 1991-07-31 | Enco Eng Ag | Verfahren zur herstellung von natrium- oder kalium-l-ascorbat. |
| US5202475A (en) | 1990-09-27 | 1993-04-13 | Eastman Kodak Company | Process for preparation of cyclohexanedicarboxylic acid |
| EP0483831B1 (en) | 1990-11-02 | 1995-09-06 | Mitsubishi Chemical Corporation | Process for separating an organic acid or acids from an organic acid-containing solution |
| US5210296A (en) | 1990-11-19 | 1993-05-11 | E. I. Du Pont De Nemours And Company | Recovery of lactate esters and lactic acid from fermentation broth |
| US5159110A (en) | 1991-05-16 | 1992-10-27 | W. R. Grace & Co.-Conn. | Process for recovering n-methyliminodiacetic acid from sodium sulfate |
| IT1254254B (it) | 1992-03-11 | 1995-09-14 | Erregierre Ind Chim | Procedimento per la preparazione di acido iodesossicolico ad elevata purezza per impiego farmaceutico |
| US5352825A (en) | 1993-07-06 | 1994-10-04 | Hoarmann & Reimer Corp. | Recovery of organic acid salts from impure process streams by addition of bases |
| CA2126365C (en) | 1993-07-06 | 1999-08-24 | Steven W. Felman | Recovery of citric acid from impure process streams by addition of strong acids and salts thereof |
| US5426219A (en) | 1993-07-26 | 1995-06-20 | A.E. Staley Manufacturing Co. | Process for recovering organic acids |
| US5410076A (en) | 1993-11-12 | 1995-04-25 | Lever Brothers Company, Division Of Conopco, Inc. | Process for the preparation of bis(amidocarboxylic acid) |
| KR960023076A (ko) | 1994-12-09 | 1996-07-18 | 미우라 아끼라 | L-아스파르트산의 제조 방법 |
| US5522995A (en) | 1995-02-28 | 1996-06-04 | Cockrem; Michael C. M. | Process for recovering organic acids from aqueous salt solutions |
| JP3976832B2 (ja) | 1996-04-30 | 2007-09-19 | ディーエスエム アイピー アセッツ ビー.ブイ. | 2−ケト−l−グロン酸の単離方法 |
-
2000
- 2000-03-07 US US09/519,936 patent/US6670505B1/en not_active Expired - Fee Related
-
2001
- 2001-03-06 DE DE60124229T patent/DE60124229T2/de not_active Expired - Fee Related
- 2001-03-06 WO PCT/US2001/007140 patent/WO2001066508A2/en not_active Ceased
- 2001-03-06 CN CNB018090400A patent/CN100413839C/zh not_active Expired - Fee Related
- 2001-03-06 JP JP2001565329A patent/JP2003525923A/ja not_active Withdrawn
- 2001-03-06 EP EP01918380A patent/EP1261574B1/en not_active Expired - Lifetime
- 2001-03-06 AT AT01918380T patent/ATE344225T1/de not_active IP Right Cessation
- 2001-03-06 BR BR0109005-4A patent/BR0109005A/pt not_active IP Right Cessation
- 2001-08-03 US US09/921,946 patent/US20020026077A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| BR0109005A (pt) | 2003-06-03 |
| JP2003525923A (ja) | 2003-09-02 |
| WO2001066508A3 (en) | 2002-05-02 |
| US6670505B1 (en) | 2003-12-30 |
| EP1261574A2 (en) | 2002-12-04 |
| WO2001066508A2 (en) | 2001-09-13 |
| EP1261574B1 (en) | 2006-11-02 |
| CN100413839C (zh) | 2008-08-27 |
| ATE344225T1 (de) | 2006-11-15 |
| DE60124229D1 (de) | 2006-12-14 |
| CN1427813A (zh) | 2003-07-02 |
| US20020026077A1 (en) | 2002-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE60124229T2 (de) | Verfahren zur gewinnung von organischen säuren aus wässrigen lösungen | |
| DE2803019A1 (de) | Verfahren zum reinigen fluorid enthaltendenm wassers | |
| DE69405127T2 (de) | Extraktion von Zitronensäuren | |
| DE69122402T2 (de) | Verfahren zur Herstellung von Sauerstoffsäuren aus Kohlenhydraten | |
| DE2627111C2 (de) | Verfahren zur chemischen oder enzymatischen Isomerisierung einer Aldose oder eines Aldosederivates zur entsprechenden Ketose oder zum entsprechenden Ketosederivat | |
| DE69704711T2 (de) | Ein verfahren zur herstellung des kondensationsproduktes einer carbonsäure | |
| DE1542249A1 (de) | Verfahren zum Herstellen eines Metallsalzes aus einem Metallchlorid und einer Saeure | |
| DE2634126A1 (de) | Zubereitungen auf der basis von basischen aluminiumchloriden | |
| DE69112770T2 (de) | Verfahren zur Abscheidung der organischen Säure oder Säuren aus einer organische Säuren enthaltenden Lösung. | |
| DE2131753A1 (de) | Verfahren zum Umwandeln der Carboxylgruppen von Carbonsaeuren in Hydroxymethylgruppen durch Hydrogenolyse | |
| DE2431483B2 (de) | Verfahren zur Herstellung von Alkalioder Ammoniumsalzen von Insulin | |
| DE69519799T2 (de) | Verfahren zur herstellung von [s,s]-ethylendiamin-n,n'-dibernsteinsäure | |
| EP0417604A2 (de) | Verfahren zur Herstellung von Riboflavin-5'-phosphat bzw. dessen Natriumsalz | |
| CH638464A5 (de) | Verfahren zur herstellung von natriumpercarbonat aus einer sodaloesung bzw. -suspension. | |
| DE69805780T2 (de) | Verfahren zur gewinnung von milchsäure | |
| DE69710212T2 (de) | Verfahren zur gewinnung von ascorbinsäure | |
| DE2644148B2 (de) | Kontinuierliches Verfahren zur Herstellung eines kompakten, grobkörnigen Natriumpercarbonats | |
| DE69720904T2 (de) | Verfahren zur Herstellung einer Zusammensetzung zum Besprühen von Pflanzenblättern und Früchten | |
| DE69614108T2 (de) | Verfahren zur gewinnung von ascorbinsäure | |
| DE68906097T2 (de) | Verfahren zur herstellung von ethercarbonsaeuren. | |
| DE69423744T2 (de) | VERFAHREN ZUR HERSTELLUNG VON cis-EPOXYBERNSTEINSÄURESALZEN | |
| EP0278107B1 (de) | Verfahren zur Herstellung von Aldonsäuren oder deren Salze | |
| WO2000026398A1 (de) | Verfahren zur herstellung von asparaginsäurederivaten | |
| EP0015478B2 (de) | Alterungsbeständige Chromgerbstoffe | |
| DE864874C (de) | Verfahren zur Herstellung eines Mehrstoff-Duengemittels aus einer sauren fluorhaltigen, Calcium und Phosphorsaeure enthaltenden Loesung |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8364 | No opposition during term of opposition | ||
| 8339 | Ceased/non-payment of the annual fee |