CN1672791A - Double active species catalyst and its application - Google Patents
Double active species catalyst and its application Download PDFInfo
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- CN1672791A CN1672791A CN 200410032271 CN200410032271A CN1672791A CN 1672791 A CN1672791 A CN 1672791A CN 200410032271 CN200410032271 CN 200410032271 CN 200410032271 A CN200410032271 A CN 200410032271A CN 1672791 A CN1672791 A CN 1672791A
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- Prior art keywords
- catalyst
- acetate
- acid
- reaction
- organic
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- 239000003054 catalyst Substances 0.000 title claims abstract description 109
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 169
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000010948 rhodium Substances 0.000 claims abstract description 54
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 39
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 32
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000002500 ions Chemical class 0.000 claims abstract description 23
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 13
- 230000006315 carbonylation Effects 0.000 claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 12
- 150000001875 compounds Chemical group 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 11
- -1 carboxylic acid compound Chemical class 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 86
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 50
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 150000003839 salts Chemical class 0.000 claims description 25
- 229920001577 copolymer Polymers 0.000 claims description 24
- 150000001768 cations Chemical class 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 20
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 20
- 125000004429 atom Chemical group 0.000 claims description 18
- 150000001450 anions Chemical class 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 16
- 239000000376 reactant Substances 0.000 claims description 16
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 15
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 claims description 14
- 150000007524 organic acids Chemical class 0.000 claims description 13
- 229940081066 picolinic acid Drugs 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 12
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 11
- 150000004696 coordination complex Chemical class 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 230000001052 transient effect Effects 0.000 claims description 11
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- 239000003426 co-catalyst Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 150000001413 amino acids Chemical class 0.000 claims description 8
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 150000007529 inorganic bases Chemical class 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 125000004989 dicarbonyl group Chemical group 0.000 claims description 4
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims description 4
- 125000002743 phosphorus functional group Chemical group 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 125000004354 sulfur functional group Chemical group 0.000 claims description 4
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- PAEXAIBDCHBNDC-UHFFFAOYSA-N 2-pyridin-4-ylacetic acid Chemical compound OC(=O)CC1=CC=NC=C1 PAEXAIBDCHBNDC-UHFFFAOYSA-N 0.000 claims description 2
- BPSNETAIJADFTO-UHFFFAOYSA-N 2-pyridinylacetic acid Chemical compound OC(=O)CC1=CC=CC=N1 BPSNETAIJADFTO-UHFFFAOYSA-N 0.000 claims description 2
- AJHPGXZOIAYYDW-UHFFFAOYSA-N 3-(2-cyanophenyl)-2-[(2-methylpropan-2-yl)oxycarbonylamino]propanoic acid Chemical compound CC(C)(C)OC(=O)NC(C(O)=O)CC1=CC=CC=C1C#N AJHPGXZOIAYYDW-UHFFFAOYSA-N 0.000 claims description 2
- WGNUNYPERJMVRM-UHFFFAOYSA-N 3-pyridylacetic acid Chemical compound OC(=O)CC1=CC=CN=C1 WGNUNYPERJMVRM-UHFFFAOYSA-N 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 229960003692 gamma aminobutyric acid Drugs 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 abstract description 19
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000013461 design Methods 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 230000035484 reaction time Effects 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- 238000010792 warming Methods 0.000 description 13
- 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 8
- 239000010949 copper Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 241000894007 species Species 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000007868 Raney catalyst Substances 0.000 description 4
- 229910000564 Raney nickel Inorganic materials 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 150000007824 aliphatic compounds Chemical class 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- 239000012327 Ruthenium complex Substances 0.000 description 2
- 239000004280 Sodium formate Substances 0.000 description 2
- RDMKPWSKRFNJIZ-UHFFFAOYSA-N carbamic acid;nickel Chemical compound [Ni].NC(O)=O RDMKPWSKRFNJIZ-UHFFFAOYSA-N 0.000 description 2
- 230000002079 cooperative effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004247 glycine and its sodium salt Substances 0.000 description 2
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229940071870 hydroiodic acid Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- FPBMTPLRBAEUMV-UHFFFAOYSA-N nickel sodium Chemical compound [Na][Ni] FPBMTPLRBAEUMV-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 229940029258 sodium glycinate Drugs 0.000 description 2
- WUWHFEHKUQVYLF-UHFFFAOYSA-M sodium;2-aminoacetate Chemical compound [Na+].NCC([O-])=O WUWHFEHKUQVYLF-UHFFFAOYSA-M 0.000 description 2
- JWYUFVNJZUSCSM-UHFFFAOYSA-N 2-aminobenzimidazole Chemical compound C1=CC=C2NC(N)=NC2=C1 JWYUFVNJZUSCSM-UHFFFAOYSA-N 0.000 description 1
- JMUIJVIDHXYLQP-UHFFFAOYSA-N 2-ethenylpyridine;methyl prop-2-enoate Chemical compound COC(=O)C=C.C=CC1=CC=CC=N1 JMUIJVIDHXYLQP-UHFFFAOYSA-N 0.000 description 1
- JJSHLLDJXDKNKJ-UHFFFAOYSA-N 4-aminobutanoic acid;sodium Chemical compound [Na].NCCCC(O)=O JJSHLLDJXDKNKJ-UHFFFAOYSA-N 0.000 description 1
- AEJCOUPTIZZZSK-UHFFFAOYSA-N 4-ethenylpyridine methyl prop-2-enoate Chemical compound COC(=O)C=C.C=CC1=CC=NC=C1 AEJCOUPTIZZZSK-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- IUDZOQNYWQZEIC-UHFFFAOYSA-N C(=C)C1=NC=CC=C1.C(=C)C(=O)C Chemical compound C(=C)C1=NC=CC=C1.C(=C)C(=O)C IUDZOQNYWQZEIC-UHFFFAOYSA-N 0.000 description 1
- CRGHYXMPIUBNGC-UHFFFAOYSA-N CC(C=C)=O.C(=C)C1=CC=NC=C1 Chemical compound CC(C=C)=O.C(=C)C1=CC=NC=C1 CRGHYXMPIUBNGC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- PGLPFSFFKDRZMD-UHFFFAOYSA-N NC(C(=O)O)CC.[Rh] Chemical compound NC(C(=O)O)CC.[Rh] PGLPFSFFKDRZMD-UHFFFAOYSA-N 0.000 description 1
- NZDFSUOXHVEUKV-DKWTVANSSA-N N[C@@H](C)C(=O)O.[Rh] Chemical compound N[C@@H](C)C(=O)O.[Rh] NZDFSUOXHVEUKV-DKWTVANSSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DPOPAJRDYZGTIR-UHFFFAOYSA-N Tetrazine Chemical compound C1=CN=NN=N1 DPOPAJRDYZGTIR-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- RUHQXWYJJWNMOJ-JIZZDEOASA-N [Cu].N[C@@H](C)C(=O)O.[Rh] Chemical compound [Cu].N[C@@H](C)C(=O)O.[Rh] RUHQXWYJJWNMOJ-JIZZDEOASA-N 0.000 description 1
- GDQKEZPXXHZHTJ-UHFFFAOYSA-N [Rh].NC1=C(C(=O)O)C=CC=C1 Chemical compound [Rh].NC1=C(C(=O)O)C=CC=C1 GDQKEZPXXHZHTJ-UHFFFAOYSA-N 0.000 description 1
- LOZXWYYLTOAFRQ-UHFFFAOYSA-N [Ru].NC(C(=O)O)CC.[Rh] Chemical compound [Ru].NC(C(=O)O)CC.[Rh] LOZXWYYLTOAFRQ-UHFFFAOYSA-N 0.000 description 1
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 description 1
- SPDCFZAAMSXKTK-UHFFFAOYSA-N acetic acid;ruthenium Chemical compound [Ru].CC(O)=O SPDCFZAAMSXKTK-UHFFFAOYSA-N 0.000 description 1
- LEKJTGQWLAUGQA-UHFFFAOYSA-N acetyl iodide Chemical compound CC(I)=O LEKJTGQWLAUGQA-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- FSRXIRGQJIHEFB-UHFFFAOYSA-N diphenylphosphane;ethane Chemical compound CC.C=1C=CC=CC=1PC1=CC=CC=C1 FSRXIRGQJIHEFB-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000005054 naphthyridines Chemical class 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- CKKFIFWNJHNWFE-UHFFFAOYSA-N nickel;pyridine-2-carboxylic acid Chemical compound [Ni].OC(=O)C1=CC=CC=N1 CKKFIFWNJHNWFE-UHFFFAOYSA-N 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- CQDAMYNQINDRQC-UHFFFAOYSA-N oxatriazole Chemical compound C1=NN=NO1 CQDAMYNQINDRQC-UHFFFAOYSA-N 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
The present invention is catalyst capable of catalyzing the carbonylation of methanol into acetic acid and the carbonylation of methyl acetate into acetic anhydride in high speed, high selectivity and relatively mild condition. By means of design of catalyst molecule structure, non-rhodium metal with certain catalytic activity or obvious catalysis assisting activity on carbonylation reaction is introduced into catalyst with rhodium as active component to form new double active component catalyst. Of the catalyst, the positive ion active component may be square planar cis-bicarbonyl structure formed with organic compound or polymer containing N and O donor atom and Rh(I); and the negative ion active component may be coordination compound structure formed with organic carboxylic acid compound containing N and O donor atom and transition metal salt.
Description
Technical field
The present invention proposes a kind of new catalyst, it is characterized in that this catalyst is the catalyst of the negative ions type of dual-active species.The catalyst of the negative ions type of these dual-active species can be the catalyst that is applied to methanol carbonylation to synthesize acetic acid, acetic anhydride.
Background technology
The humans such as Paulik of twentieth century Monsanto at beginning of the seventies company have been opened up new enforcement approach in the invention (US 3 769 329) that methanol carbonyl is combined to homogeneous rhodium catalyst for carbonylic synthesis technology.Process is updated and is perfect, and low pressure carbonyl synthetic technology has become most important technology path in present acetate, the acetic anhydride industry.
In the research of catalyst, the square plane negative ion type structural coordination compound of rhodium successfully is applied to industrial production.This class complex structure pattern has high catalytic activity and good selectivity, but exists the weakness that easily is converted into the trivalent rhodium and precipitates inactivation simultaneously.This phenomenon more mostly occurs under the lower situation of catalyst separation circulation time carbon monoxide pressure of tension.In order to address this problem, at present in acetic acid production process, higher water and hydroiodic acid content are to reach the dissolubility that increases catalyst, the purpose that improves catalyst activity in the need maintenance reaction system, but when improving catalytic rate, water gas reaction is quickened, consumed the raw material carbon monoxide.Because the severe corrosive of reaction medium has improved the requirement to equipment material, also increased the investment of equipment simultaneously.
The improvement of carbonyl synthesis of acetic acid, acetic anhydride Study of Catalyst and reaction system thereof and perfect is the problem that people pay close attention to all the time.In numerous research work, there are a lot of researchs to obtain obvious progress, (CN1 00 750 as the part of catalyst for example to adopt high polymer, US5 281 359, US 6 458 996), the so-called polymer catalyst of this class not only still has advantages of high catalytic activity, and the heat endurance and the reaction stability of proportioning, the especially catalyst of some performance such as optimizing reaction system medium are improved simultaneously.With rhodium as site catalyst by big quantity research in, adopt non-rhodium System Catalyst (GB 20000419), and in reaction system, add aspect the research of different types of promotion catalyst (US 5 922 911), good progress is all arranged.Wherein the commercial Application of iridium series catalysts is exactly the example of a success.
The objective of the invention is to, by the catalyst molecule structure Design, to have certain catalytic activity or have the non-rhodium metal of obvious promoting catalysis methanol carbonylation, being incorporated into the rhodium is in the catalyst molecule of active specy, obtain can be under gentle relatively condition can be high-speed, highly selective catalysis methanol carbonyl turns to the new catalyst that acetate, acetate carbonyl turn to acetic anhydride.
Summary of the invention
The present invention proposes the novel catalyst structure pattern of a class, also promptly: the catalyst of the negative ions type of dual-active species.
From appended examples of the present invention, as can be seen, adopt no matter dual-active species catalyst is catalysis methanol carbonylation system acetate, or acetate carbonyl system acetic anhydride, all demonstrate high activity.These characteristics are that the special construction pattern by catalyst is determined, promptly the conjugation nitrogen of the strong coordination ability of tool forms N → Rh key on the rhodium atom in cation activated centre and the pyridine ring, and form O → Rh key with the more weak ketonic oxygen of coordination ability.O in course of reaction → Rh key easy fracture makes rhodium be in the coordination undersaturated condition, thereby helps the addition of co-catalyst iodomethane, makes the synthetic middle species acetyl iodide (CH of carbonyl
3COI) be easy to generate the carrying out that has quickened catalytic process.In addition, anion part list of coordination units has played common promoter effect.Owing to be in together in the molecular structure with the activity unit of rhodium, its cooperative effect makes it promote the effect of catalysis to be improved.
Specific embodiments
The form of the catalyst of the negative ions type of the concrete described dual-active species of implementing can be as mentioned below:
Described catalyst can be a class dual-active species negative ions type oxo catalyst, it is characterized in that:
The part alternative condition of the cation architectural feature of described catalyst is: contain 2 or above nitrogen, phosphorus, oxygen, sulphur functional group or functional unit in the compound molecule, and wherein have nitrogen or phosphorus functional group at least;
The part alternative condition of the anion architectural feature of described catalyst is: the organic acid that contains nitrogen, sulphur, phosphorus donor atom.
The part that a large amount of multiple tooth organic and macromolecular compound well known in the art all can be used as catalyst cation architectural feature of the present invention is selected, as long as contain 2 or above nitrogen, phosphorus, oxygen, sulphur functional group or functional unit in these compound molecules, and wherein have nitrogen or phosphorus functional group at least.With regard to organic molecule, following three compounds all can be used as the part of the cation part of dual-active species catalyst of the present invention:
1. the fragrant heterocycle and the aliphatic compounds that contain two or more nitrogen-atoms, as imidazoles, triazole, tetrazolium, bipyridyl, compound and derivatives thereof such as naphthyridines, pyrimidine, pyrazine, tetrazine, purine, diamines and the many ammonia of many ethene.
2. one or above nitrogen-atoms arranged and contain the fragrant heterocycle or the aliphatic compounds of one or above oxygen, sulphur atom again, as oxadiazole, oxatriazole, two oxazoles, two oxadiazoles, trioazole, 2-mercaptopyridine, 2-mercaptobenzothiazole, the amino benzimidazole of 2-, pyrrolidones, two-2-pyridine-glyoxal and several amino acids and derivative thereof.
3. contain one or above phosphorus atoms and aromatic series and the aliphatic compound that contains or above nitrogen, oxygen, sulphur atom arranged, as: 2-diphenylphosphine yl pyridines and 1, two (diphenylphosphine) ethane of 2-etc.For high molecular polymer, alternative part is more, not only comprises the synthetic high polymer that meets aforementioned condition, and a large amount of natural polymer for example polypeptide class large biological molecule etc. also can be used as part and uses.
Equally, the numerous well knownly organic acid that contains nitrogen, sulphur, phosphorus donor atom can be used as the selection of anion part in the catalyst structure of the present invention.
An embodiment in concrete the application is:
The cation of described catalyst partly adopts cation that the compound that contains N, O donor atom or high polymer and Rh (I) form along dicarbonyl structure;
The salt that anion partly forms after the alkali effect for the organic acid that contains N, O donor atom and the complex of transition metal reactant salt formation.For example:
The main body catalytic active species be with part in the chelating type square plane of rhodium of N, N or N, O donor Atomic coordinate along dicarbonyl structure, this active specy is a cation version, its anion then be with part in the transient metal complex of N, O donor Atomic coordinate.The non-rhodium metal that the present invention relates to self has certain catalytic action because and rhodium metal be in in a part, its cooperative effect and promoting catalysis are embodied fully, be that the catalytic performance of the active specy at center is improved significantly so make with the rhodium.
The version of this class catalyst is:
Ligand L in the formula
1Be respectively picolinic acid or 2-vinylpyridine, 4-vinylpyridine and with the copolymer of butenone, methyl acrylate, acrylonitrile;
Ligand L
2Be picolinic acid, amino acids;
M is Co, Cu, Ni, Fe, Ru, n=2 or 3.
Technology of the present invention is used and is also comprised and be used for carbonyl synthetic dual-active species catalyst structure pattern and its preparation method, and the reaction system of the carbonyl synthesis of acetic acid that adapts therewith, acetic anhydride is formed and using method.
Use catalyst of the present invention and when the catalysis methanol carbonylation, have good performance.Table 1 is to be cation active specy, amion acetic acid and NiCl after 2-vinylpyridine/methyl acrylate copolymer and the rhodium coordination
2Complex be the reaction result of the formed negative ions type of anion active specy dual-active species catalyst carbonylation of methanol.
Table 1 Rh-Ni dual-active species catalyst methanol carbonylation product is formed data
| Name of material | Product/wt% | Weight/g | Mole/mol |
| ?CH 3I ?AcOMe | ????29.28 ????15.11 | ????129.7 ????68.4 | ????0.92 ????0.92 |
| ?CH 3OH ?AcOH ?H 2O ?Me 2O ?CO 2?(AcO) 2O | ????0 ????48.22 ????3.88 ????0.76 ????0 ????2.1 | ????0 ????218.2 ????17.5 ????3.4 ????0 ????16.2 | ????0 ????3.64 ????0.98 ????0.07 ????0 ????0.16 |
Reaction condition: CH
3OH 192.1g, CH
3I 142.1g, catalyst 8g (Rh=3%), reaction time 90min, 140 ℃ of reaction temperatures, reaction pressure 4MPa
From the data of table 1 as can be seen this class catalyst have remarkable advantages in the following aspects:
1. need not in the reaction system to add water again, even there is water to generate in the course of reaction, the water gas reaction that itself and carbon monoxide take place is also extremely micro-, and this point can not detect CO from table
2Obtain proof (part experiment has＜CO of 0.03mol%
2Generate).
2. reaction temperature is low, and reaction temperature remains on below 140 ℃, can obtain The above results.
3. catalysis high activity, from the data of table 1 as can be seen, in the reaction time, methyl alcohol all transforms, and can directly obtain a small amount of acetic anhydride.
Dual-active species catalyst of the present invention is when the catalysis methanol carbonylation prepares acetate, and the co-catalyst of adding is an iodomethane, and its content is in overall reaction liquid between 1～5mol/L scope.Reactant is a methyl alcohol, makes solvent as adding acetate, can improve reaction speed, and the acetate consumption is between 3～97% (Wt) of methyl alcohol and acetate total amount.When having hydroiodic acid and water to exist in the reaction system, reaction speed is improved.Catalyst consumption in the reaction system is counted 400～2000ppm scope with rhodium, 140～180 ℃ of reaction temperatures, and carbon monoxide pressure is 3～5MPa.
When such catalyst acetate carbonylization prepared acetic anhydride, co-catalyst iodomethane content was 1～5mol/L scope in reaction system.In addition, promoter lithium iodide or lithium acetate content in reaction system is 50～300 scopes with lithium atom and rhodium atom mol ratio, 150～200 ℃ of reaction temperatures.Keep certain hydrogen content to help the generation of acetic anhydride in the reaction system, when in the closed reactor, reacting usually in the reactor hydrogen content remain between 0.1～0.5MPa, on continuous reacting device, adopt CO and H
2The mist charging, wherein hydrogen content is within 1～10% scope.For the reaction system that acetate carbonyl is combined to acetic anhydride, acetate is a kind of excellent solvent, it can not only make in the reaction system performance that mixes of the chemistry between each main component better, and carbonylation also had significantly induce and facilitation, help the raising of rate of catalysis reaction.On the other hand, because the existence of acetate can increase the solubility of catalyst in reaction medium in the reaction system, improve the space-time yield of acetic anhydride, in the reaction system of the synthetic acetic anhydride of the catalyst acetate carbonyl that the present invention relates to, acetic acid content is between 40～70% (Wt) of reaction medium.
Embodiment
Following examples are showed the invention effect with illustrative ground, only do not constitute the restriction to the scope of application of the present invention.
Embodiment 1
Catalyst anion part transient metal complex preparation method is an example with the nickel complex of Nicotinicum Acidum sodium.
Take by weighing the Nicotinicum Acidum that is 0.02mol and NaOH and be dissolved in and be heated to 70 ℃ of reaction 1h in the 2mol water, the cooling back obtains Nicotinicum Acidum sodium with the excessive propanone precipitation after the drying.
Take by weighing 0.01mol Nicotinicum Acidum sodium and be dissolved in the mixed liquor of 1mol methyl alcohol and 0.5mol water, add the NiCl of 0.01mol
2, under agitation heating reflux reaction 1h after the cooling, uses acetone precipitation, obtains Nicotinicum Acidum sodium nickel complex after the drying.
Obtain iron, copper, cobalt and the ruthenium complex of Nicotinicum Acidum sodium, pyridine-2-sodium formate, pyridine-4-sodium formate, pyridine-3-sodium acetate, pyridine-2-sodium acetate, pyridine-4-sodium acetate as stated above.Adopt nickel, iron, copper, cobalt and the ruthenium complex of method for preparing Sodium Glycinate, 3-alanine sodium, 4-aminobutyric acid sodium, ortho-aminobenzoic acid sodium, gavaculine sodium, ortho-aminobenzoic acid sodium.
Embodiment 2
Dual-active species Preparation of catalysts is an example with Nicotinicum Acidum rhodium-Nicotinicum Acidum nickel dual-active species catalyst.
Take by weighing the Nicotinicum Acidum of 0.02mol and the [Rh (CO) of 0.01mol
2Cl]
2Be dissolved in the 3mol methyl alcohol,, add the methanol-water mixed liquor (mol ratio of methyl alcohol and water is 2: 1) of the Nicotinicum Acidum sodium nickel complex that contains 0.01mol then, continue at 70 ℃ of following stirring reaction 1h at 70 ℃ of following stirring reaction 1h.Cooling back ether sedimentation filters.(2: 1mol) the mixed solution washing is 2 times, and drying at room temperature obtains brown Nicotinicum Acidum rhodium-Nicotinicum Acidum nickel dual-active species catalyst to constant weight with 0 ℃ methanol-water.
Adopt method for preparing to go out the dual-active species catalyst of cobalt, iron, copper and the ruthenium of listed picolinic acid among the embodiment 1 and amino carboxylic acid nickel, cobalt, iron, copper.
Adopt method for preparing to go out 2-vinylpyridine-methyl acrylate, 2-vinylpyridine-butenone, 4-vinylpyridine-methyl acrylate, 4-vinylpyridine-butenone (2-vinylpyridine in the copolymer, 4-vinylpyridine content is 20-30mol%), with the dual-active species catalyst of picolinic acid nickel, iron, copper, cobalt, ruthenium and amino carboxylic acid nickel, iron, copper, cobalt, ruthenium.
All copolymer ligand catalyst rhodium content are 3-5%.
Embodiment 3
In 250ml zirconium matter autoclave pressure, add pyridine-2-formic acid rhodium-Nicotinicum Acidum Raney nickel 0.3g, methyl alcohol 1.24mol, acetate 0.87mol, iodomethane 0.24mol is warming up to 150 ℃ behind the feeding CO, keeps reaction pressure 4.0MPa, 500 rev/mins of mixing speeds, reaction time 30min.Methanol conversion 100%, methyl acetate content are 0.02mol, and the acetate increment is 1.19mol, and the acetate space-time yield is 20.7mol AcOH/Lh.
Embodiment 4
In autoclave pressure, add pyridine-4-formic acid rhodium-Nicotinicum Acidum iron catalyst 0.32g, methyl alcohol 1.24mol, acetate 0.87mol, iodomethane 0.24mol, be warming up to 160 ℃ after feeding CO, keep reaction pressure 4.0MPa, 500 rev/mins of mixing speeds, reaction time 30min, methanol conversion 100%, methyl acetate content is 0.08mol, and the acetate increment is 1.1mol, and the acetate space-time yield is 19.2mol AcOH/Lh.
Embodiment 5
In autoclave pressure, add Nicotinicum Acidum rhodium-amion acetic acid ruthenium catalyst 0.33g, methyl alcohol 1.24mol, acetate 0.87mol, iodomethane 0.24mol.Be warming up to 160 ℃ after feeding CO, keep reaction pressure 4.0MPa, 500 rev/mins of mixing speeds, reaction time 25min, methanol conversion 100%, methyl acetate content are 0, and the acetate increment is 1.20mol, and the acetate space-time yield is 25.1mol AcOH/Lh.
Embodiment 6
In autoclave pressure, add Nicotinicum Acidum rhodium-Nicotinicum Acidum ketone catalyst 0.3g, methyl acetate 0.52mol, acetate 0.53mol, iodomethane 0.24mol, lithium iodide 0.037mol.Feed CO after feeding hydrogen 0.3MPa, be warming up to 140 ℃, keep reaction pressure 4.0MPa, 500 rev/mins of mixing speeds, reaction 20min, the methyl acetate conversion ratio is that 61.2% acetate increment is 0.15mol, obtain acetic anhydride 0.15mol, its space-time yield is 5.2mol/Lh.
Embodiment 7
In autoclave pressure, add poly-2-vinylpyridine/methyl acrylate (2-vinylpyridine content is 29.7%) rhodium-alanine Co catalysts 3g (rhodium content 3%), methyl alcohol 2.48mol, iodomethane 0.34mol.Be warming up to 135 ℃ after feeding CO, keep reaction pressure 4.0MPa, 500 rev/mins of mixing speeds, reaction time 60min, methanol conversion 100% obtains methyl acetate 0.7mol, obtains acetate 1.67mol, and the acetate space-time yield is 13.9mol AcOH/Lh.
Embodiment 8
In autoclave pressure, add poly-2-vinylpyridine/butenone (2-vinylpyridine content is 28.9%) rhodium-aminobutyric acid ruthenium catalyst 3g (rhodium content 3.2%), methyl alcohol 2.48mol, iodomethane 0.34mol.Be warming up to 140 ℃ after feeding CO, keep reaction pressure 4.0MPa, 500 rev/mins of mixing speeds, reaction time 60min, methanol conversion 100% obtains methyl acetate 0.8mol, obtains acetate 1.52mol, and the acetate space-time yield is 12mol AcOH/Lh.
Embodiment 9
In autoclave pressure, add poly-4-vinylpyridine/methyl acrylate (4-vinylpyridine content is 26.1%) rhodium-Nicotinicum Acidum Raney nickel 3g (rhodium content 3.1%), methyl alcohol 2.48mol, iodomethane 0.34mol is warming up to 150 ℃ behind the feeding CO, keeps reaction pressure 4.0MPa, 500 rev/mins of mixing speeds, reaction time 60min, methanol conversion 100% obtains methyl acetate 0.6mol, obtain acetate 1.75mol, the acetate space-time yield is 14.5molAcOH/Lh.
Embodiment 10
In autoclave pressure, add poly-4-vinylpyridine/butenone (4-vinylpyridine content is 29.1%) rhodium-Nicotinicum Acidum Co catalysts 4g (rhodium content is 3.6%), methyl alcohol 2.48mol, iodomethane 0.34mol.Be warming up to 140 ℃ after feeding CO, keep reaction pressure 4.0MPa, 500 rev/mins of mixing speeds, reaction time 60min, methanol conversion 100% obtains methyl acetate 0.6mol, obtains acetate 1.58mol, and the acetate space-time yield is 13.1mol AcOH/Lh.
Embodiment 11
In autoclave pressure, add Nicotinicum Acidum rhodium-alanine copper catalyst 0.4g, methyl alcohol 1.24mol, acetate 0.87mol, iodomethane 0.24mol.Feed CO, be warming up to 180 ℃ and keep reaction pressure 4.0MPa, 500 rev/mins of mixing speeds, reaction time 15min, methanol conversion 100% obtains methyl acetate 0.03mol, and the acetate increment is 1.19mol, and the acetate space-time yield is 41.4mol AcOH/Lh.
Embodiment 12
In autoclave pressure, add pyridine-2-formic acid rhodium-Nicotinicum Acidum Co catalysts 0.3g, methyl acetate 0.52mol, acetate 0.53mol, iodomethane 0.24mol, lithium iodide 0.037mol.Feed CO after feeding hydrogen 0.4MPa, be warming up to 170 ℃ and keep reaction pressure 4.0MPa, 500 rev/mins of mixing speeds, reaction time 17min, methyl acetate conversion ratio are 70%, and the acetate increment is 0.11mol, obtain acetic anhydride 0.23mol, its space-time yield is 7.0mol/Lh.
Embodiment 13
In autoclave pressure, add pyridine-3-rhodium acetate-amion acetic acid copper catalyst 0.3g, methyl acetate 0.52mol, acetate 0.53mol, iodomethane 0.24mol, lithium iodide 0.037mol.Feed CO after feeding hydrogen 0.3MPa, be warming up to 180 ℃, keep reaction pressure 4.0MPa, 500 rev/mins of mixing speeds, reaction time 12min.The methyl acetate conversion ratio is 79%, and the acetate increment is 0.12mol, obtains acetic anhydride 0.27mol, and the acetic anhydride space-time yield is 11.7mol/Lh.
Embodiment 14
In autoclave pressure, add Nicotinicum Acidum rhodium-ortho-aminobenzoic acid Raney nickel 0.4g, methyl acetate 0.52mol, acetate 0.53mol, iodomethane 0.24mol, lithium iodide 0.037mol.Feed CO after feeding hydrogen 0.3MPa, be warming up to 185 ℃, keep reaction pressure 4.0MPa, 500 rev/mins of mixing speeds, reaction time 10min.The methyl acetate conversion ratio is 72%, and the acetate increment is 0.11mol, obtains acetic anhydride 0.24mol, and the acetic anhydride space-time yield is 12.5mol/Lh.
Embodiment 15
In autoclave pressure, add Nicotinicum Acidum rhodium-aminobutyric acid Raney nickel 0.32g, methyl acetate 0.52mol, acetate 0.53mol, iodomethane 0.24mol, lithium iodide 0.037mol.Feed CO after feeding hydrogen 0.4MPa, be warming up to 190 ℃, keep reaction pressure 4.0MPa, 500 rev/mins of mixing speeds, reaction time 10min.The methyl acetate conversion ratio is 79%, and the acetate increment is 0.12mol, obtains acetic anhydride 0.27mol, and the acetic anhydride space-time yield is 14.1mol/Lh.
Embodiment 16
With 2-vinylpyridine-methyl acrylate copolymer, amion acetic acid, dichloride copper, dichloro four carbonyls two rhodiums is example, and the dual-active species Preparation of catalysts method of the present invention of demonstration:
1. the part amion acetic acid of 1 molar part and the NaOH of 1 molar part are dissolved in 50～200 molar part water,, obtain the amion acetic acid sodium salt in 70 ℃ of following stirring reaction 1h.
2. the Glycinates of 1 molar part and the copper chloride of 1 molar part are dissolved in 50～200 molar part methanol-waters (methyl alcohol and water mol ratio are 2: the 1) solution,, obtain Sodium Glycinate and copper chloride complex in 70 ℃ of stirring reaction 1～2h.
3. part 2-vinylpyridine-methyl acrylate copolymer and four carbonyl dichloros, two rhodiums are dissolved in the methanol solution (volume of methyl alcohol is 10～20 times of copolymer), under 70 ℃ of stirrings, react 1h, obtain the copolymer of monodentate coordination and the complex solution of rhodium, the mol ratio of copolymer ligand N atom and Rh atom is 3: 1～10: 1.
4. the copolymer rhodium complex solution with the monodentate coordination under agitation mixes (mol ratio of transition metal M and Rh atom is 1: 1) with organic salt transient metal complex solution, under agitation continue the 1～2h that refluxes, use excessive ether sedimentation, obtain dual-active species catalyst.
In sum, the invention provides a kind of catalyst, it is characterized in that this catalyst is the catalyst of the negative ions type of dual-active species.
A kind of embodiment is that wherein said catalyst is a class dual-active species negative ions type oxo catalyst, it is characterized in that
The part alternative condition of the cation architectural feature of described catalyst is: contain 2 or above nitrogen, phosphorus, oxygen, sulphur functional group or functional unit in the compound molecule, and wherein have nitrogen or phosphorus functional group at least;
The part alternative condition of the anion architectural feature of described catalyst is: the organic acid that contains nitrogen, sulphur, phosphorus donor atom.
A kind of embodiment is that the cation of wherein said catalyst partly adopts cation that the compound that contains N, O donor atom or high polymer and Rh (I) form along dicarbonyl structure;
The salt that anion partly forms after the alkali effect for the organic acid that contains N, O donor atom and the complex of transition metal reactant salt formation.
A kind of embodiment is that wherein said catalyst can have following structural formula:
In the formula
Ligand L
1Be respectively picolinic acid or 2-vinylpyridine, 4-vinylpyridine homopolymers and with the copolymer of butenone, methyl acrylate, acrylonitrile;
Ligand L
2Be picolinic acid, amino acids;
M is Co, Cu, Ni, Fe, Ru;
N=2 or 3.
A kind of embodiment is wherein
In the part of cation part:
Picolinic acid is pyridine-2-formic acid, Nicotinicum Acidum, pyridine-4-formic acid, pyridine-2-acetate, pyridine-3-acetate, pyridine-4-acetate,
Copolymer ligand is the copolymer of 2-vinylpyridine, 4-vinylpyridine and methyl acrylate, butenone, acrylonitrile.
A kind of embodiment is wherein
The organic acid that anion partly contains N, O donor atom is described picolinic acid of claim 5 and amino acid.
A kind of embodiment is that wherein said amino acid is selected from:
Amion acetic acid, 3-alanine, 4-aminobutyric acid, 2-amino benzoic Acid, 3-amino benzoic Acid and 4-amino benzoic Acid.
A kind of embodiment is that wherein Rh (I) is: [Rh (CO)
2Cl]
2, [Rh (CO)
2Br]
2, [Rh (CO)
2I]
2
A kind of embodiment is that wherein said alkali is: the inorganic base that is selected from NaOH and KOH.
A kind of embodiment is that wherein anion part coordination transition metal salt is selected from NiCl
2, CuCl
2, FeCl
3, CoCl
2And RuCl
3
The present invention also provides described dual-active species negative ions type Preparation of catalysts method, and this method is characterised in that:
Cation structure division solution is mixed with anion structure division solution.
A kind of embodiment is that wherein this method may further comprise the steps:
Organic acid and inorganic base reaction obtain the organic salt part;
Organic salt part and transition metal reactant salt obtain organic metal salt transient metal complex solution;
Add above-mentioned organic salt transient metal complex solution to cation structure division solution, obtain dual-active species negative ions type catalyst.
A kind of embodiment is that wherein this method may further comprise the steps:
1. above-mentioned organic acid of 1 molar part and the above-mentioned inorganic base of 1 molar part are dissolved in 50～200 molar part water, in 70 ℃ of stirring reaction 1～2h, obtain the organic salt part;
2. the organic salt part and the above-mentioned transition metal salt of 1 molar part that obtain in 1. of 1 molar part is dissolved in 50～200 molar part methanol aqueous solutions, in 70 ℃ of stirring reaction 1～2h, obtains organic metal salt transient metal complex solution; Wherein said methyl alcohol and water mol ratio are 2: 1;
3. the Rh of above-mentioned cation part of 2 molar part and 1 molar part
2(CO)
4X
2Be dissolved in the solvent of 50～200 molar part, the mol ratio of copolymer ligand N atom and Rh atom is 3: 1～10: 1;
Wherein, picolinic acid is dissolved in methanol aqueous solution, and copolymer is dissolved in the methanol solution; Wherein methyl alcohol and water mol ratio are 2: 1; The volume that copolymer is dissolved in methyl alcohol in the methanol solution is 10～20 times of copolymer;
Under agitation reflux behind 1～2h, adding is dissolved with aforesaid organic salt transient metal complex methanol aqueous solution, and wherein the mol ratio of transition metal M and Rh atom is 1: 1;
Under agitation continue reaction 1～2h, excessive ether sedimentation is used in the cooling back, obtains dual-active species negative ions type catalyst.
The method that the present invention also provides a kind of carbonylation of methanol to prepare acetate is characterized in that using above-mentioned dual-active species negative ions type catalyst.
A kind of embodiment is wherein
Reactant is that methyl alcohol or adding acetate are made solvent in the reaction system, and the acetate addition is 3～97 weight % of methyl alcohol and acetate total amount;
Co-catalyst iodomethane content in reactant liquor is the 1-5mol/L scope;
Catalyst amount is rhodium content 200-2000ppm scope in reactant liquor in the reaction system;
Reaction temperature 140-180 ℃;
Carbon monoxide pressure is 3.0-5.0MPa.
The invention still further relates to a kind of catalysis acetate carbonylization and prepare the method for acetic anhydride, it is characterized in that:
Used above-mentioned dual-active species negative ions type catalyst.
A kind of embodiment is wherein
Catalyst content is counted the 400-1200ppm scope with rhodium in the reaction system;
The co-catalyst iodomethane is the 1-5mol/L scope in reactant liquor;
Content is in the ratio of lithium metal with rhodium atom in reactant liquor for promoter lithium iodide or lithium acetate, and it is worth in the 50-300 scope;
Reaction temperature is 150-200 ℃;
The reaction gross pressure is 3.0-6.0Mpa;
Wherein, keep certain hydrogen to help reaction in the reaction system and carry out, its pressure is the 1-10% of carbon monoxide pressure.
Claims (17)
1. a catalyst is characterized in that this catalyst is the catalyst of the negative ions type of dual-active species.
2. catalyst as claimed in claim 1, wherein said catalyst are class dual-active species negative ions type oxo catalysts, it is characterized in that
The part alternative condition of the cation architectural feature of described catalyst is: contain 2 or above nitrogen, phosphorus, oxygen, sulphur functional group or functional unit in the compound molecule, and wherein have nitrogen or phosphorus functional group at least;
The part alternative condition of the anion architectural feature of described catalyst is: the organic acid that contains nitrogen, sulphur, phosphorus donor atom.
3. catalyst as claimed in claim 2, wherein
The cation of described catalyst partly adopts cation that the compound that contains N, O donor atom or high polymer and Rh (I) form along dicarbonyl structure;
The salt that anion partly forms after the alkali effect for the organic acid that contains N, O donor atom and the complex of transition metal reactant salt formation.
4. catalyst as claimed in claim 3, wherein said catalyst can have following structural formula:
In the formula
Ligand L
1Be respectively picolinic acid or 2-vinylpyridine, 4-vinylpyridine homopolymers and with the copolymer of butenone, methyl acrylate, acrylonitrile;
Ligand L
2Be picolinic acid, amino acids;
M is Co, Cu, Ni, Fe, Ru;
N=2 or 3.
5. catalyst as claimed in claim 4, wherein:
In the part of cation part:
Picolinic acid is pyridine-2-formic acid, Nicotinicum Acidum, pyridine-4-formic acid, pyridine-2-acetate, pyridine-3-acetate, pyridine-4-acetate,
Copolymer ligand is the copolymer of 2-vinylpyridine, 4-vinylpyridine and methyl acrylate, butenone, acrylonitrile.
6. catalyst as claimed in claim 4, wherein
The organic acid that anion partly contains N, O donor atom is described picolinic acid of claim 5 and amino acid.
7. catalyst as claimed in claim 6, wherein said amino acid is selected from:
Amion acetic acid, 3-alanine, 4-aminobutyric acid, 2-amino benzoic Acid, 3-amino benzoic Acid and 4-amino benzoic Acid.
8. catalyst as claimed in claim 4, wherein
Rh (I) is: [Rh (CO)
2Cl]
2, [Rh (CO)
2Br]
2, [Rh (CO)
2I]
2
9. catalyst as claimed in claim 3, wherein
Described alkali is: the inorganic base that is selected from NaOH and KOH.
10. catalyst as claimed in claim 6, wherein
Anion part coordination transition metal salt is selected from NiCl
2, CuCl
2, FeCl
3, CoCl
2And RuCl
3
11. each dual-active species negative ions type Preparation of catalysts method among the claim 1-3, this method is characterised in that:
Cation structure division solution is mixed with anion structure division solution.
12. each preparation method among the claim 4-10, this method may further comprise the steps:
Organic acid and inorganic base reaction obtain the organic salt part;
Organic salt part and transition metal reactant salt obtain organic metal salt transient metal complex solution;
Add above-mentioned organic salt transient metal complex solution to cation structure division solution, obtain dual-active species negative ions type catalyst.
13. the preparation method of claim 12, this method may further comprise the steps:
1. 1 molar part claim 6 or 7 described organic acids and the described inorganic base of 1 molar part claim 9 are dissolved in 50～200 molar part water, in 70 ℃ of stirring reaction 1～2h, obtain the organic salt part;
2. the organic salt part and the described transition metal salt of 1 molar part claim 10 that obtain in 1. of 1 molar part is dissolved in 50～200 molar part methanol aqueous solutions, in 70 ℃ of stirring reaction 1～2h, obtains organic metal salt transient metal complex solution; Wherein said methyl alcohol and water mol ratio are 2: 1;
3. the Rh of described cation part of 2 molar part claims 5 and 1 molar part
2(CO)
4X
2Be dissolved in the solvent of 50～200 molar part, the mol ratio of copolymer ligand N atom and Rh atom is 3: 1～10: 1;
Wherein, picolinic acid is dissolved in methanol aqueous solution, and copolymer is dissolved in the methanol solution; Wherein methyl alcohol and water mol ratio are 2: 1; The volume that copolymer is dissolved in methyl alcohol in the methanol solution is 10～20 times of copolymer;
Under agitation reflux behind 1～2h, adding is dissolved with aforesaid organic salt transient metal complex methanol aqueous solution, and wherein the mol ratio of transition metal M and Rh atom is 1: 1;
Under agitation continue reaction 1～2h, excessive ether sedimentation is used in the cooling back, obtains dual-active species negative ions type catalyst.
14. a carbonylation of methanol prepares the method for acetate, it is characterized in that having used claim 4 or 10 described dual-active species negative ions type catalyst.
15. the method as claim 14 is characterized in that:
Reactant is that methyl alcohol or adding acetate are made solvent in the reaction system, and the acetate addition is 3～97 weight % of methyl alcohol and acetate total amount;
Co-catalyst iodomethane content in reactant liquor is the 1-5mol/L scope;
Catalyst amount is rhodium content 200-2000ppm scope in reactant liquor in the reaction system;
Reaction temperature 140-180 ℃;
Carbon monoxide pressure is 3.0-5.0MPa.
16. a catalysis acetate carbonylization prepares the method for acetic anhydride, it is characterized in that:
Claim 4 or 10 described dual-active species negative ions type catalyst have been used.
17. as the method for claim 16, wherein
Catalyst content is counted the 400-1200ppm scope with rhodium in the reaction system;
The co-catalyst iodomethane is the 1-5mol/L scope in reactant liquor;
Content is in the ratio of lithium metal with rhodium atom in reactant liquor for promoter lithium iodide or lithium acetate, and it is worth in the 50-300 scope;
Reaction temperature is 150-200 ℃;
The reaction gross pressure is 3.0-6.0Mpa;
Wherein, keep certain hydrogen to help reaction in the reaction system and carry out, its pressure is the 1-10% of carbon monoxide pressure.
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| CN112778535A (en) * | 2021-01-12 | 2021-05-11 | 青岛科技大学 | Preparation method and application of multi-element heterogeneous metal organic framework material |
| CN112778535B (en) * | 2021-01-12 | 2022-04-08 | 青岛科技大学 | Preparation method and application of multi-element heterogeneous metal organic framework material |
| CN114515605A (en) * | 2022-02-16 | 2022-05-20 | 江苏索普（集团）有限公司 | Preparation and application of ruthenium-palladium double-active-center catalyst for synthesizing acetic acid or acetic anhydride through carbonylation |
| CN114558619A (en) * | 2022-02-16 | 2022-05-31 | 江苏索普化工股份有限公司 | Preparation method of polymer ligand multi-metal cage catalyst and application of catalyst in carbonylation synthesis of acetic acid or acetic anhydride |
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