CN103906755B - 纯化方法 - Google Patents
纯化方法 Download PDFInfo
- Publication number
- CN103906755B CN103906755B CN201280044051.3A CN201280044051A CN103906755B CN 103906755 B CN103906755 B CN 103906755B CN 201280044051 A CN201280044051 A CN 201280044051A CN 103906755 B CN103906755 B CN 103906755B
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- CN
- China
- Prior art keywords
- acid
- solvent
- ethylenediamine
- contaminant metals
- complexing agent
- Prior art date
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- 238000000746 purification Methods 0.000 title description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 150000002739 metals Chemical class 0.000 claims abstract description 24
- 239000000356 contaminant Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims description 55
- 239000008139 complexing agent Substances 0.000 claims description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 16
- 229960001484 edetic acid Drugs 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 238000007037 hydroformylation reaction Methods 0.000 claims description 11
- -1 aryl phosphine Chemical compound 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 claims description 2
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- TYFSYONDMQEGJK-UHFFFAOYSA-N 2-(2,2-dihydroxyethylamino)acetic acid Chemical compound OC(O)CNCC(O)=O TYFSYONDMQEGJK-UHFFFAOYSA-N 0.000 claims description 2
- SZUZWFXRVSNBOZ-UHFFFAOYSA-N 3-[2-(2-carboxyethylamino)ethylamino]propanoic acid Chemical compound OC(=O)CCNCCNCCC(O)=O SZUZWFXRVSNBOZ-UHFFFAOYSA-N 0.000 claims description 2
- KWYJDIUEHHCHCZ-UHFFFAOYSA-N 3-[2-[bis(2-carboxyethyl)amino]ethyl-(2-carboxyethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CCC(O)=O)CCN(CCC(O)=O)CCC(O)=O KWYJDIUEHHCHCZ-UHFFFAOYSA-N 0.000 claims description 2
- VVXLFFIFNVKFBD-UHFFFAOYSA-N 4,4,4-trifluoro-1-phenylbutane-1,3-dione Chemical compound FC(F)(F)C(=O)CC(=O)C1=CC=CC=C1 VVXLFFIFNVKFBD-UHFFFAOYSA-N 0.000 claims description 2
- QQEQHUHZBMUJET-UHFFFAOYSA-N 5-phenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC2=CC=CN=C2C2=NC=CC=C12 QQEQHUHZBMUJET-UHFFFAOYSA-N 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 2
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims description 2
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 claims description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 2
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 claims description 2
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 2
- VYTBPJNGNGMRFH-UHFFFAOYSA-N acetic acid;azane Chemical compound N.N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O VYTBPJNGNGMRFH-UHFFFAOYSA-N 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- HLVXFWDLRHCZEI-UHFFFAOYSA-N chromotropic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(O)=CC(S(O)(=O)=O)=CC2=C1 HLVXFWDLRHCZEI-UHFFFAOYSA-N 0.000 claims description 2
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 2
- 235000018417 cysteine Nutrition 0.000 claims description 2
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229930182817 methionine Natural products 0.000 claims description 2
- 229910052759 nickel Inorganic materials 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
- 229960003330 pentetic acid Drugs 0.000 claims description 2
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000004474 valine Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 4
- 230000037396 body weight Effects 0.000 claims 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- 235000019253 formic acid Nutrition 0.000 claims 2
- TWSRVQVEYJNFKQ-UHFFFAOYSA-N pentyl propanoate Chemical compound CCCCCOC(=O)CC TWSRVQVEYJNFKQ-UHFFFAOYSA-N 0.000 claims 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 2
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 claims 1
- JHRMQHFRVPVGHL-UHFFFAOYSA-N 2-chloro-1,10-phenanthroline Chemical compound C1=CN=C2C3=NC(Cl)=CC=C3C=CC2=C1 JHRMQHFRVPVGHL-UHFFFAOYSA-N 0.000 claims 1
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 claims 1
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 claims 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims 1
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 claims 1
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 claims 1
- 240000000203 Salix gracilistyla Species 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 235000009582 asparagine Nutrition 0.000 claims 1
- 229960001230 asparagine Drugs 0.000 claims 1
- OUDSFQBUEBFSPS-UHFFFAOYSA-N ethylenediaminetriacetic acid Chemical compound OC(=O)CNCCN(CC(O)=O)CC(O)=O OUDSFQBUEBFSPS-UHFFFAOYSA-N 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 239000007791 liquid phase Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 229960003540 oxyquinoline Drugs 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims 1
- KVGSJGNWRDPVKA-UHFFFAOYSA-N quinoline-5-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=N1 KVGSJGNWRDPVKA-UHFFFAOYSA-N 0.000 claims 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 13
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- 239000002738 chelating agent Substances 0.000 description 5
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- 239000000463 material Substances 0.000 description 5
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- 238000002474 experimental method Methods 0.000 description 4
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 150000003222 pyridines Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
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- 239000010931 gold Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229920001600 hydrophobic polymer Polymers 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
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Abstract
公开了一种降低在催化剂制备中使用的配体中的污染物金属水平的方法。
Description
相关申请的交叉引用
本申请要求2011年9月30日提交的临时申请第61/541,291号的优先权，该申请全部内容通过引用并入本文中。
背景技术
本发明涉及可用于制备催化剂的配体的纯化。
金属络合物催化剂为一类常见的催化剂且被用于例如工业规模的加氢甲酰化反应、氢氰化反应、烯烃异构化反应、环丙烷化反应和氢化反应。加氢甲酰化体系中某些金属(主要为过渡金属，例如铁)的存在是不利的，因为这些污染物金属可促进较重物质的形成或其他副反应。
三价磷配体中污染物金属例如铁的来源可来自多种来源，例如在磷与侧基偶合过程中用于制备侧基的试剂，或在生产过程中设备的腐蚀。这些金属来源之一为供应到加氢甲酰化反应器的配体(例如三苯基膦和双亚磷酸酯)中的杂质。几乎所有制备方法均包含如下所示的R-M物质与卤素-磷化合物P-X的偶合反应作为最后的步骤：
nR-M+XnP(R’)x(OR”)y→RnP(R’)x(OR”)y+nMX
其中n+x+y＝3(假设不含多齿配体部分)。通常用水洗涤以除去MX盐(通常，M＝Na、K、Li或Mg；X＝Cl、Br)。例如，将RnP(R’)x(OR”)y溶解于非水性溶剂例如甲苯中，并通过水洗来除去盐，直至所溶解的卤化物(通常为氯化物)的浓度足够低，表明残余MX含量低。倾析出有机层，并根据需要对所得产物进行重结晶或蒸馏。
由于加氢甲酰化反应中所用的配体易于与金属络合，这使得难以自加氢甲酰化反应器中除去铁时，不将昂贵的催化金属例如铑也除去。US4,143,075公开了一种用于除去铁的方法，但其包括停止工业生产以进行处理。
期望获得一种不需要停止生产过程来降低反应器中的铁的含量的加氢甲酰化方法。
发明概述
本发明为这样的方法，其包括：
(A)使三价磷配体、污染物金属、第一溶剂、极性络合剂和第二溶剂接触以形成混合物，
(B)获得包含配体和第一溶剂的第一相，和
(C)获得包含第二溶剂以及至少一种污染物金属与极性络合剂的络合物的第二相，
(D)分离两相。
令人惊讶的是，极少量的极性络合剂可以从包含极大过量配体的体系中基本上除去不希望的污染物金属，所述配体已知为极好的金属络合剂。
发明详述
本发明的方法采用配体、第一溶剂、第二溶剂和极性络合剂来除去污染物金属。在本发明的一个实施方式中，所述金属是通过自第一溶剂萃取至第二溶剂中的方法除去。
如本文中所用，无数量词修饰(a，an，the)、以“至少一种”修饰和以“一种或多种”修饰可互换使用。术语“包含”、“包括”及其变化形式在说明书与权利要求书中出现时不具有限制性含义。因此，例如，包括疏水聚合物的颗粒的水性组合物可解释为指该组合物包括“一种或多种”疏水聚合物的颗粒。
另外，在本文中以端点叙述的数值范围包括该范围内所包含的所有数值(例如，1-5包括1、1.5、2、2.75、3、3.80、4、5等)。
另外，在本文中数值范围和/或数值的叙述，包括权利要求书中的此类叙述，可被视为包括术语“约”。在该情况下，术语“约”指与本文所述的数值范围和/或数值基本上相同的数值范围和/或数值。
为了本发明的目的，应理解，与本领域技术人员所理解的一致，数值范围意欲包括并支持该范围中所包括的所有可能的子范围。例如，1-100的范围表示1.01-100、1-99.99、1.01-99.99、40-60、1-55等。
如本文中所用，术语“ppmw”是指以重量计的百万分率。
如本文中所用，术语“水溶性”是指在第二溶剂(通常为水)中具有大于0.1wt％的溶解度(在25℃下)。
在本发明的一个实施方式中，该方法包括使所述配体在第一溶剂中的溶液与所述极性络合剂在第二溶剂中的溶液相接触，并且使得相分离以将污染物金属及其盐同时移至第二溶剂中，并与第一溶剂中所需配体产物分离。优选地，极性络合剂在第一溶剂中几乎不溶解，使得将污染物金属自第一溶剂中除去，从而在后续纯化步骤之前有效地除去该污染物金属。可以使用该方法以重新处理不合格的物质。
在本发明的一个实施方式中，第一溶剂中的三价磷配体与固态极性络合剂(例如EDTA)接触足以除去污染物金属至所需程度的时间，随后滤除固态极性络合剂。在此实施方式中，固态极性络合剂包含吸附的水，后者充当第二溶剂。
该配体可以是将与加氢甲酰化或羰化反应中所用的、例如通过加氢甲酰化方法制备醛(其中α-烯烃在铑催化剂存在下用一氧化碳和氢进行加氢甲酰化)时所用的催化金属形成络合物的任何化合物。配体有利地为含磷配体。在本发明的一个实施方式中，所述含磷配体为三价磷配体。优选地，配体不溶于水，亦即在25℃下以重量计在水中小于0.1％的溶解性。合适配体的例子公开在美国专利4,283,562；4,400,548；4,599,206；4,668,651；4,748,261；4,789,753；5,235,113；5,710,344；6,265,620及美国专利申请公布2009/0171121中。
第一溶剂的功能为至少部分地溶解配体并且使第二溶剂能接触污染物金属。第一溶剂有利地基本上不混溶于第二溶剂中。在本文中，术语“基本上不混溶”是指在进行萃取的温度下，第一溶剂在第二溶剂中的溶解度不超过10wt.％。第一溶剂的例子包括芳族烃类(苯、甲苯、二甲苯、乙苯)、饱和烷烃类(己烷、辛烷)、超临界CO2、较高分子量的酯类(例如丙酸戊酯、乙酸丁酯和邻苯二甲酸二辛酯)、丙酮衍生物(例如二丁酮和异佛尔酮)，其中优选甲苯。可采用第一溶剂的混合物。第一溶剂的用量足以在萃取温度下溶解大部分或所有的配体。有利地，萃取温度为20℃至第一和第二溶剂中的最低沸点溶剂的最低沸点。有利地，第一溶剂的量足以溶解配体。
第二溶剂的功能为溶解络合剂以使其能够接触污染物金属且形成将优先保留于第二溶剂中的极性金属-螯合剂络合物。第二溶剂有利地基本上不混溶于第一溶剂中。在本文中，术语“基本上不混溶”意指在进行萃取的温度下，第二溶剂在第一溶剂中的溶解度不超过10wt.％。第二溶剂的例子包括水、甲醇、二甲亚砜、二甲基甲酰胺、六甲基磷酰胺及其混合物，其中优选水。第二溶剂的用量应足以(1)当与第一溶剂/配体混合物混合时形成分离层以及(2)溶解所述螯合剂。通常，极性螯合剂的量极小，因此第(2)项通常不是限制性的。一般说来，第二溶剂的量等于第一溶剂或低至第一溶剂的10％(主要由工业操作中分离各层的能力所限定)。
污染物金属为离子性/带电荷金属，其为用于醛醇缩合的路易斯酸催化剂。可存在超过一种污染物金属。这些金属的例子包括但不限于铁、镍、铬、钨、锌、锆、钛和钒。污染物金属可以化合物形式存在。在本发明的一个实施方式中，以配体的重量计，配体中污染物金属的初始浓度为100ppmw至10,000ppmw。有利地，以配体的重量计，该浓度减小至小于25ppmw，并且优选小于10ppmw。
极性络合剂可以是除三价磷化合物以外的、与污染物金属形成水溶性螯合络合物的任何物质。极性络合剂为一种螯合剂，其属于称为螯合物的一般类别的化合物。螯合物为具有两个或更多个与金属离子配位的位点的多官能配体。极性络合剂的例子包括但不限于乙二胺四乙酸(EDTA)及其盐。所用极性络合剂的量有利地较小，例如为所存在的污染物金属的量的1至500倍(摩尔当量)。优选地，极性络合剂在第二溶剂中的溶解度相比于第一溶剂更高。有利地，极性络合剂在第二溶剂中的溶解度与极性络合剂在第一溶剂中的溶解度的比率为至少10∶1，优选1000∶1，并且更优选至少10,000∶1。在本发明的一个实施方式中，极性络合剂基本上不溶于第一溶剂。
极性络合剂的例子包括：乙二胺四乙酸(“EDTA”)和相关的氨基多羧酸的钠盐(例如次氮基三乙酸二钠)；草酸；丙二酸；半胱氨酸(2-氨基-B-巯基丙酸)；酒石酸；乙酰丙酮；柠檬酸；葡萄糖酸；次氮基三乙酸；N-2-羟乙基亚氨基二乙酸；乙二胺-N，N-二乙酸；2’-羟基-吡啶并(3’：4’-2：3)吡嗪；8-羟基噌啉；8-羟基-1，7-萘啶；乙二胺-N，N’-二丙酸；8-羟基喹啉；8-羟基喹啉-5-磺酸；2-羟基环己基亚氨基二乙酸；2，6-二(2-吡啶基)吡啶；乙二胺；二亚乙基三胺；三亚乙基四胺；B，B’，B”-三氨基三乙胺；联吡啶；1，10-菲咯啉；5-氯-1，10-菲咯啉；5-硝基-1，10-菲咯啉；5-甲基-1，10-菲咯啉；5-苯基-1，10-菲咯啉；丙氨酸；天冬酰胺；甘氨酸；甲硫氨酸；苯丙氨酸；丝氨酸；色氨酸；缬氨酸；乙二胺四丙酸；水杨酸；5-磺基水杨酸；水杨醛；苯甲酰丙酮；苯甲酰三氟丙酮；二苯甲酰甲烷；2-糠酰基-苯甲酰甲烷；3，6-二磺基-1，8-二羟基萘(变色酸)；3，5-二磺基邻苯二酚；1，2-二氨基环己烷；N，N，N’-四乙酸；Versene Fe-3(商品名)；甲胺二乙酸；二亚乙基三胺五乙酸；乙二醇-双-(B-氨基乙醚)-N，N’-四乙酸；乙醚二胺四乙酸；N-羟基乙二胺三乙酸；1-甲基乙二胺四乙酸(或1，2-丙二胺四乙酸)；N，N-二羟基乙基甘氨酸；乙二胺-N，N，N’，N’-四丙酸。对于以质子化形式描述的许多上述配体，优选碱金属盐用于本发明的目的。
包含第二溶剂的第二相中的极性络合剂的浓度并不是关键的。为了污染物金属的全部络合，每摩尔污染物金属使用1摩尔或多于1摩尔的极性络合剂。
包含第二溶剂的第二相的pH值可在不会不利地影响金属萃取的情况下在宽范围内变化。由于强酸性或碱性条件增加了配体(尤其是亚磷酸酯)的分解，因此在某些情形中将溶液pH值调节到约3.5至10的范围是有利的。
本发明的具体实施方式
给出以下实施例以说明本发明，且这些实施例不应被视为限制本发明的范围。除非另作说明，否则所有份数及百分比皆以重量计。
对比实验1(不是本发明的实施方式)
制备6，6’-(3，3’，5，5’-四叔丁基联苯-2，2’-二基)双(氧基)-二-二苯并[d，f][1，3，2]-二氧杂磷杂环庚二烯(dioxaphosphepine)：
如US4,769,498和WO2009/120210(A1)中所述制备双亚磷酸酯粗品。使用623份2，2’-双酚、700份在2000份甲苯中的PCl3和8份吡啶，制备单次氯酸酯(monochloridite)。在除去过量PCl3后，添加785份吡啶和680份在3400份甲苯中的3，3’，5，5’-四叔丁基-2，2’-双酚(ISO-BHT，一种桥联二醇)。将得自所得混合物的样品用1500份去离子水萃取，以除去吡啶盐酸盐。所得粗产物接着用乙酸乙酯重结晶。由原子吸光度分析所得重结晶产物中的残余铁。使用仅用水萃取的方法产生含有47.2ppm铁的产物。
实施例2
除使用1500份在去离子水中的0.00875M EDTA-Na2(以提供每当量铁2当量的EDTA)进行萃取以除去吡啶盐酸盐以外，重复对比实验1。使用以EDTA水溶液萃取的方法产生含有6.7ppm铁的产物。
对比实验3和5与实施例4、6和7：
除采用不同浓度的EDTA以外，根据对比实验1和实施例2的方法制备另两批双亚磷酸酯粗品并评估。结果显示如下。
(BDL＝低于检测限，约1ppm)
*并非本发明的实施方式
实施例8：
如上所述，使用7当量在水中的EDTA处理全部工业规模批次的双亚磷酸酯。用于制备双亚磷酸酯的双酚含有25ppm铁。双亚磷酸酯粗品的处理得到仅具有7ppm残余铁的重结晶产物。在加氢甲酰化反应中测试所得物质，且就烯烃转化率而言，其性能与常规非EDTA处理的物质难以区分。通过衰减式全反射(ATR)红外光谱法分析双亚磷酸酯产物的样品。比较所得光谱发现没有可检测量的EDTA(根据在约1620cm-1处不存在EDTA特征峰)。通过用计数方法自EDTA处理的样品的光谱减去未经处理的参考光谱来确认此观测结果。所得差示光谱仅含有干扰噪音。基于此分析，确定EDTA并不以红外光谱法可检测的含量存在于经处理的样品中。
Claims (6)
1.一种用于纯化可用于制备加氢甲酰化工艺的铑络合物催化剂的三价磷配体的方法，其包括：
(A)使非水溶性三价磷配体、污染物金属、第一溶剂、水溶性极性络合剂和第二溶剂接触，以形成两相混合物，其中第一相包含所述配体和所述第一溶剂，和
第二相包含所述第二溶剂和至少一种所述污染物金属与所述极性络合剂的络合物；和
(B)在制备用于加氢甲酰化反应器的铑络合物催化剂之前，分离所述两个相；
其中在步骤(A)之前在所述配体存在下基于所述配体重量的污染物金属的浓度高于在步骤(B)后第一相中在所述配体存在下基于所述配体重量的污染物金属的浓度；
其中所述三价磷配体包含至少一种双亚磷酸酯或者至少一种芳基膦或烷基膦；
其中所述第一溶剂包括芳族烃类、饱和烷烃类、超临界CO2、丙酸戊酯、乙酸丁酯、邻苯二甲酸二辛酯、丙酮衍生物及其混合物；
其中所述第二溶剂包含水、甲醇、二甲亚砜、二甲基甲酰胺、六甲基磷酰胺及其混合物；
其中所述污染物金属包含铁、镍、铬、钨、锌、锆、钛和钒中的至少一种；和
其中在步骤(B)后第一相中在所述配体中基于所述配体重量的各污染物金属的浓度小于25ppmw。
2.根据权利要求1的方法，其中所述两个相主要呈液相。
3.根据权利要求1的方法，其中所述第二溶剂包含水。
4.根据权利要求1的方法，其中所述污染物金属包含铁。
5.根据权利要求1的方法，其中所述极性络合剂包含乙二胺四乙酸和其碱金属盐。
6.根据权利要求1的方法，其中所述三价磷配体包含至少一种双亚磷酸酯、芳基膦或烷基膦；
其中所述第一溶剂包括芳族烃类、饱和烷烃类、超临界CO2、丙酸戊酯、乙酸丁酯、邻苯二甲酸二辛酯、丙酮衍生物及其混合物；
其中所述第二溶剂包含水；和
其中所述极性络合剂包含以下的至少一种：乙二胺四乙酸；乙二胺四乙酸的钠盐；次氮基三乙酸二钠；草酸；丙二酸；半胱氨酸(2-氨基-B-巯基丙酸)；酒石酸；乙酰丙酮；柠檬酸；葡萄糖酸；次氮基三乙酸；N-2-羟乙基亚氨基二乙酸；乙二胺-N，N-二乙酸；2’-羟基-吡啶并(3’:4’-2:3)吡嗪；8-羟基噌啉；8-羟基-1,7-萘啶；乙二胺-N,N’-二丙酸；8-羟基喹啉；8-羟基喹啉-5-磺酸；2-羟基环己基亚氨基二乙酸；2,6-二(2-吡啶基)吡啶；乙二胺；二亚乙基三胺；三亚乙基四胺；B,B’,B”-三氨基三乙胺；联吡啶；1,10-菲咯啉；5-氯-1,10-菲咯啉；5-硝基-1,10-菲咯啉；5-甲基-1,10-菲咯啉；5-苯基-1,10-菲咯啉；丙氨酸；天冬酰胺；甘氨酸；甲硫氨酸；苯丙氨酸；丝氨酸；色氨酸；缬氨酸；乙二胺四丙酸；水杨酸；5-磺基水杨酸；水杨醛；苯甲酰丙酮；苯甲酰三氟丙酮；二苯甲酰甲烷；2-糠酰基-苯甲酰甲烷；3,6-二磺基-1,8-二羟基萘(变色酸)；3,5-二磺基邻苯二酚；1,2-二氨基环己烷；N,N,N’-四乙酸；甲胺二乙酸；二亚乙基三胺五乙酸；乙二醇-双-(B-氨基乙醚)-N,N’-四乙酸；乙醚二胺四乙酸；N-羟基乙二胺三乙酸；1-甲基乙二胺四乙酸或1,2-丙二胺四乙酸；N,N-二羟基乙基甘氨酸；和乙二胺-N,N,N’,N’-四丙酸。
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| PCT/US2012/054197 WO2013048701A1 (en) | 2011-09-30 | 2012-09-07 | Purification process |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3706822A (en) * | 1969-10-02 | 1972-12-19 | James E Caldwell | Method of refining esters of organophosphorus |
| US4143075A (en) * | 1976-08-12 | 1979-03-06 | Union Carbide Corporation | Control of condensation products in hydroformylation process |
| US4276235A (en) * | 1980-04-24 | 1981-06-30 | The United States Of America As Represented By The United States Department Of Energy | Method for purifying bidentate organophosphorous compounds |
| CN101307072A (zh) * | 2001-02-08 | 2008-11-19 | 旭瑞达有限公司 | 提纯磷酸酯的方法 |
| CN101981041A (zh) * | 2008-03-28 | 2011-02-23 | 陶氏环球技术公司 | 用于单次氯酸化膦合成的等温方法 |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3527809A (en) * | 1967-08-03 | 1970-09-08 | Union Carbide Corp | Hydroformylation process |
| US4283562A (en) | 1979-10-26 | 1981-08-11 | Union Carbide Corporation | Hydroformylation process using stable rhodium catalyst |
| US4400548A (en) | 1981-08-17 | 1983-08-23 | Union Carbide Corporation | Hydroformylation process using bisphosphine monooxide ligands |
| US4599206A (en) | 1984-02-17 | 1986-07-08 | Union Carbide Corporation | Transition metal complex catalyzed reactions |
| US4789753A (en) | 1984-02-17 | 1988-12-06 | Union Carbide Corporation | Phosphite ligands |
| US4668651A (en) | 1985-09-05 | 1987-05-26 | Union Carbide Corporation | Transition metal complex catalyzed processes |
| US4748261A (en) | 1985-09-05 | 1988-05-31 | Union Carbide Corporation | Bis-phosphite compounds |
| US4716250A (en) * | 1986-07-10 | 1987-12-29 | Union Carbide Corporation | Hydroformylation using low volatile/organic soluble phosphine ligands |
| US4845306A (en) * | 1987-04-24 | 1989-07-04 | Eastman Kodak Company | Catalyst material recovery or concentration process |
| TW213465B (zh) | 1991-06-11 | 1993-09-21 | Mitsubishi Chemicals Co Ltd | |
| KR960007736B1 (ko) * | 1993-07-27 | 1996-06-11 | 한국과학기술연구원 | 원료 가스 중에 함유된 철 카르보닐 화합물의 제거 방법 |
| US5710344A (en) | 1996-11-08 | 1998-01-20 | E. I. Du Pont De Nemours And Company | Process to prepare a linear aldehyde |
| AU6518398A (en) | 1997-03-27 | 1998-10-22 | Mitsubishi Chemical Corporation | Process for producing aldehydes |
| US6548708B1 (en) * | 1998-08-05 | 2003-04-15 | Sri International | Preparation of biphosphine ligands for incorporation into catalytic complexes |
| DE10005084C1 (de) * | 2000-02-04 | 2001-09-13 | Celanese Chem Europe Gmbh | Verfahren zur Wiedergewinnung von Rhodium aus Reaktionsprodukten der Oxosynthese |
| US7872156B2 (en) | 2007-12-26 | 2011-01-18 | Eastman Chemical Company | Fluorophosphite containing catalysts for hydroformylation processes |
| CN102177171B (zh) * | 2008-10-08 | 2014-02-12 | 陶氏技术投资有限公司 | 合成二亚磷酸酯的淤浆方法 |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3706822A (en) * | 1969-10-02 | 1972-12-19 | James E Caldwell | Method of refining esters of organophosphorus |
| US4143075A (en) * | 1976-08-12 | 1979-03-06 | Union Carbide Corporation | Control of condensation products in hydroformylation process |
| US4276235A (en) * | 1980-04-24 | 1981-06-30 | The United States Of America As Represented By The United States Department Of Energy | Method for purifying bidentate organophosphorous compounds |
| CN101307072A (zh) * | 2001-02-08 | 2008-11-19 | 旭瑞达有限公司 | 提纯磷酸酯的方法 |
| CN101981041A (zh) * | 2008-03-28 | 2011-02-23 | 陶氏环球技术公司 | 用于单次氯酸化膦合成的等温方法 |
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| WO2013048701A1 (en) | 2013-04-04 |
| IN2014CN02246A (zh) | 2015-06-12 |
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| EP2751122A1 (en) | 2014-07-09 |
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| TWI628001B (zh) | 2018-07-01 |
| KR101987513B1 (ko) | 2019-06-10 |
| ZA201401261B (en) | 2015-05-27 |
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