CN114790136A - Preparation method and application of active trivalent organic chromium compound - Google Patents
Preparation method and application of active trivalent organic chromium compound Download PDFInfo
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- CN114790136A CN114790136A CN202210221163.7A CN202210221163A CN114790136A CN 114790136 A CN114790136 A CN 114790136A CN 202210221163 A CN202210221163 A CN 202210221163A CN 114790136 A CN114790136 A CN 114790136A
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- Prior art keywords
- acid
- chromium
- organic
- active
- reagent
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- 150000001845 chromium compounds Chemical class 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000011651 chromium Substances 0.000 claims abstract description 122
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 99
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 77
- -1 organic acid salt Chemical class 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000010438 heat treatment Methods 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 33
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000005977 Ethylene Substances 0.000 claims abstract description 23
- 238000007670 refining Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 9
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 8
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 43
- 239000002253 acid Substances 0.000 claims description 24
- 150000007529 inorganic bases Chemical class 0.000 claims description 22
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 16
- 239000012442 inert solvent Substances 0.000 claims description 16
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 14
- LJOODBDWMQKMFB-UHFFFAOYSA-N cyclohexylacetic acid Chemical compound OC(=O)CC1CCCCC1 LJOODBDWMQKMFB-UHFFFAOYSA-N 0.000 claims description 12
- MHPUGCYGQWGLJL-UHFFFAOYSA-N 5-methyl-hexanoic acid Chemical compound CC(C)CCCC(O)=O MHPUGCYGQWGLJL-UHFFFAOYSA-N 0.000 claims description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 10
- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical compound ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 claims description 10
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 8
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- JBDSSBMEKXHSJF-UHFFFAOYSA-N cyclopentanecarboxylic acid Chemical compound OC(=O)C1CCCC1 JBDSSBMEKXHSJF-UHFFFAOYSA-N 0.000 claims description 8
- FGKJLKRYENPLQH-UHFFFAOYSA-N isocaproic acid Chemical compound CC(C)CCC(O)=O FGKJLKRYENPLQH-UHFFFAOYSA-N 0.000 claims description 8
- SIOLDWZBFABPJU-UHFFFAOYSA-N isotridecanoic acid Chemical compound CC(C)CCCCCCCCCC(O)=O SIOLDWZBFABPJU-UHFFFAOYSA-N 0.000 claims description 8
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- CVKMFSAVYPAZTQ-UHFFFAOYSA-N 2-methylhexanoic acid Chemical compound CCCCC(C)C(O)=O CVKMFSAVYPAZTQ-UHFFFAOYSA-N 0.000 claims description 6
- UMVOQQDNEYOJOK-UHFFFAOYSA-N 3,5-dimethylbenzoic acid Chemical compound CC1=CC(C)=CC(C(O)=O)=C1 UMVOQQDNEYOJOK-UHFFFAOYSA-N 0.000 claims description 6
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 6
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 6
- YPGCWEMNNLXISK-UHFFFAOYSA-N hydratropic acid Chemical compound OC(=O)C(C)C1=CC=CC=C1 YPGCWEMNNLXISK-UHFFFAOYSA-N 0.000 claims description 6
- RIZUCYSQUWMQLX-UHFFFAOYSA-N 2,3-dimethylbenzoic acid Chemical compound CC1=CC=CC(C(O)=O)=C1C RIZUCYSQUWMQLX-UHFFFAOYSA-N 0.000 claims description 5
- RZWGTXHSYZGXKF-UHFFFAOYSA-N 2-(2-methylphenyl)acetic acid Chemical compound CC1=CC=CC=C1CC(O)=O RZWGTXHSYZGXKF-UHFFFAOYSA-N 0.000 claims description 5
- 239000005711 Benzoic acid Substances 0.000 claims description 5
- 235000010233 benzoic acid Nutrition 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000005649 metathesis reaction Methods 0.000 claims description 5
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 5
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 4
- BEVYUARQHKRBMH-UHFFFAOYSA-N 1-(4-methylphenyl)cyclohexane-1-carboxylic acid Chemical compound C1=CC(C)=CC=C1C1(C(O)=O)CCCCC1 BEVYUARQHKRBMH-UHFFFAOYSA-N 0.000 claims description 4
- YKDWTRWSHHGVII-UHFFFAOYSA-N 1-(4-methylphenyl)cyclopentane-1-carboxylic acid Chemical compound C1=CC(C)=CC=C1C1(C(O)=O)CCCC1 YKDWTRWSHHGVII-UHFFFAOYSA-N 0.000 claims description 4
- QJRRBVNPIKYRQJ-UHFFFAOYSA-N 10-methylundecanoic acid Chemical compound CC(C)CCCCCCCCC(O)=O QJRRBVNPIKYRQJ-UHFFFAOYSA-N 0.000 claims description 4
- ZONJATNKKGGVSU-UHFFFAOYSA-N 14-methylpentadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCC(O)=O ZONJATNKKGGVSU-UHFFFAOYSA-N 0.000 claims description 4
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 claims description 4
- BKYWPNROPGQIFZ-UHFFFAOYSA-N 2,4-dimethylbenzoic acid Chemical compound CC1=CC=C(C(O)=O)C(C)=C1 BKYWPNROPGQIFZ-UHFFFAOYSA-N 0.000 claims description 4
- HCBHQDKBSKYGCK-UHFFFAOYSA-N 2,6-dimethylbenzoic acid Chemical compound CC1=CC=CC(C)=C1C(O)=O HCBHQDKBSKYGCK-UHFFFAOYSA-N 0.000 claims description 4
- RUSCTNYOPQOXDJ-UHFFFAOYSA-N 2-(2,5-dimethylphenyl)acetic acid Chemical compound CC1=CC=C(C)C(CC(O)=O)=C1 RUSCTNYOPQOXDJ-UHFFFAOYSA-N 0.000 claims description 4
- GPLBEAZWBXIBCQ-UHFFFAOYSA-N 2-(4-cyclopropylphenyl)acetic acid Chemical compound C1=CC(CC(=O)O)=CC=C1C1CC1 GPLBEAZWBXIBCQ-UHFFFAOYSA-N 0.000 claims description 4
- QMBLXRHXCGJOGU-UHFFFAOYSA-N 2-(4-ethylphenyl)acetic acid Chemical compound CCC1=CC=C(CC(O)=O)C=C1 QMBLXRHXCGJOGU-UHFFFAOYSA-N 0.000 claims description 4
- VGMCZELQCNPMQV-UHFFFAOYSA-N 2-(4-ethylphenyl)propanoic acid Chemical compound CCC1=CC=C(C(C)C(O)=O)C=C1 VGMCZELQCNPMQV-UHFFFAOYSA-N 0.000 claims description 4
- RERBQXVRXYCGLT-UHFFFAOYSA-N 2-(4-propan-2-ylphenyl)acetic acid Chemical compound CC(C)C1=CC=C(CC(O)=O)C=C1 RERBQXVRXYCGLT-UHFFFAOYSA-N 0.000 claims description 4
- MAUWNTOYRZRVLG-UHFFFAOYSA-N 2-(4-propylphenyl)butanoic acid Chemical compound CCCC1=CC=C(C(CC)C(O)=O)C=C1 MAUWNTOYRZRVLG-UHFFFAOYSA-N 0.000 claims description 4
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 claims description 4
- PGIOANNVJQQCDT-UHFFFAOYSA-N 2-phenylhexanoic acid Chemical compound CCCCC(C(O)=O)C1=CC=CC=C1 PGIOANNVJQQCDT-UHFFFAOYSA-N 0.000 claims description 4
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 claims description 4
- KAWUBNUJMFOOOE-UHFFFAOYSA-N 3-amino-3-(3,5-dibromo-4-hydroxyphenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC(Br)=C(O)C(Br)=C1 KAWUBNUJMFOOOE-UHFFFAOYSA-N 0.000 claims description 4
- ZRPLANDPDWYOMZ-UHFFFAOYSA-N 3-cyclopentylpropionic acid Chemical compound OC(=O)CCC1CCCC1 ZRPLANDPDWYOMZ-UHFFFAOYSA-N 0.000 claims description 4
- NQVALZRLGIRTKX-UHFFFAOYSA-N 3-methyl-2-phenylpentanoic acid Chemical compound CCC(C)C(C(O)=O)C1=CC=CC=C1 NQVALZRLGIRTKX-UHFFFAOYSA-N 0.000 claims description 4
- GJMPSRSMBJLKKB-UHFFFAOYSA-N 3-methylphenylacetic acid Chemical compound CC1=CC=CC(CC(O)=O)=C1 GJMPSRSMBJLKKB-UHFFFAOYSA-N 0.000 claims description 4
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 claims description 4
- OBKXEAXTFZPCHS-UHFFFAOYSA-N 4-phenylbutyric acid Chemical compound OC(=O)CCCC1=CC=CC=C1 OBKXEAXTFZPCHS-UHFFFAOYSA-N 0.000 claims description 4
- YRQKWRUZZCBSIG-UHFFFAOYSA-N 4-propan-2-ylcyclohexane-1-carboxylic acid Chemical compound CC(C)C1CCC(C(O)=O)CC1 YRQKWRUZZCBSIG-UHFFFAOYSA-N 0.000 claims description 4
- BYHDDXPKOZIZRV-UHFFFAOYSA-N 5-phenylpentanoic acid Chemical compound OC(=O)CCCCC1=CC=CC=C1 BYHDDXPKOZIZRV-UHFFFAOYSA-N 0.000 claims description 4
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 claims description 4
- JIPTZBYHWFNYFB-UHFFFAOYSA-N Anteisomyristic acid Chemical compound CCC(C)CCCCCCCCCC(O)=O JIPTZBYHWFNYFB-UHFFFAOYSA-N 0.000 claims description 4
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 4
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 4
- OOUMMVQQCICTGF-UHFFFAOYSA-K chromium(3+);dihydrogen phosphate Chemical compound [Cr+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O OOUMMVQQCICTGF-UHFFFAOYSA-K 0.000 claims description 4
- AWECJTDFTJYSGZ-UHFFFAOYSA-K chromium(3+);triperchlorate;hexahydrate Chemical compound O.O.O.O.O.O.[Cr+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O AWECJTDFTJYSGZ-UHFFFAOYSA-K 0.000 claims description 4
- HJZLEGIHUQOJBA-UHFFFAOYSA-N cyclohexane propionic acid Chemical compound OC(=O)CCC1CCCCC1 HJZLEGIHUQOJBA-UHFFFAOYSA-N 0.000 claims description 4
- ZHYZQXUYZJNEHD-VQHVLOKHSA-N geranic acid Chemical compound CC(C)=CCC\C(C)=C\C(O)=O ZHYZQXUYZJNEHD-VQHVLOKHSA-N 0.000 claims description 4
- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 4
- AXVMPIXXTHEJOH-UHFFFAOYSA-N 2-(4-ethylphenyl)butanoic acid Chemical compound CCC(C(O)=O)C1=CC=C(CC)C=C1 AXVMPIXXTHEJOH-UHFFFAOYSA-N 0.000 claims description 3
- CNMLOXDIFVZRNO-UHFFFAOYSA-N 2-(4-propylphenyl)acetic acid Chemical compound CCCC1=CC=C(CC(O)=O)C=C1 CNMLOXDIFVZRNO-UHFFFAOYSA-N 0.000 claims description 3
- IDZLDUPVMGWZLD-UHFFFAOYSA-N 2-methyl-2-phenylbutanoic acid Chemical compound CCC(C)(C(O)=O)C1=CC=CC=C1 IDZLDUPVMGWZLD-UHFFFAOYSA-N 0.000 claims description 3
- OFJWFSNDPCAWDK-UHFFFAOYSA-N 2-phenylbutyric acid Chemical compound CCC(C(O)=O)C1=CC=CC=C1 OFJWFSNDPCAWDK-UHFFFAOYSA-N 0.000 claims description 3
- QTDXSEZXAPHVBI-UHFFFAOYSA-N 4-methylcyclohexane-1-carboxylic acid Chemical compound CC1CCC(C(O)=O)CC1 QTDXSEZXAPHVBI-UHFFFAOYSA-N 0.000 claims description 3
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 3
- PPUZYFWVBLIDMP-UHFFFAOYSA-K chromium(3+);triiodide Chemical compound I[Cr](I)I PPUZYFWVBLIDMP-UHFFFAOYSA-K 0.000 claims description 3
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 claims description 3
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 3
- XZQOHYZUWTWZBL-UHFFFAOYSA-L chromium(ii) bromide Chemical compound [Cr+2].[Br-].[Br-] XZQOHYZUWTWZBL-UHFFFAOYSA-L 0.000 claims description 3
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 claims description 3
- IIUXHTGBZYEGHI-UHFFFAOYSA-N isoheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCC(O)=O IIUXHTGBZYEGHI-UHFFFAOYSA-N 0.000 claims description 3
- RGWUYUDLSVKMDI-UHFFFAOYSA-N 2-(1-ethylcyclohexyl)acetic acid Chemical compound OC(=O)CC1(CC)CCCCC1 RGWUYUDLSVKMDI-UHFFFAOYSA-N 0.000 claims description 2
- LTBPRPATSZONGJ-UHFFFAOYSA-N 2-(1-methylcyclohexyl)acetic acid Chemical compound OC(=O)CC1(C)CCCCC1 LTBPRPATSZONGJ-UHFFFAOYSA-N 0.000 claims description 2
- GXXXUZIRGXYDFP-UHFFFAOYSA-N 2-(4-methylphenyl)acetic acid Chemical compound CC1=CC=C(CC(O)=O)C=C1 GXXXUZIRGXYDFP-UHFFFAOYSA-N 0.000 claims description 2
- XMKDPSQQDXTCCK-UHFFFAOYSA-N 2,4-dimethylpentanoic acid Chemical compound CC(C)CC(C)C(O)=O XMKDPSQQDXTCCK-UHFFFAOYSA-N 0.000 claims 1
- ATZHGRNFEFVDDJ-UHFFFAOYSA-N 4-propylbenzoic acid Chemical compound CCCC1=CC=C(C(O)=O)C=C1 ATZHGRNFEFVDDJ-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 36
- 150000007524 organic acids Chemical class 0.000 abstract description 32
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 64
- 239000008367 deionised water Substances 0.000 description 43
- 229910021641 deionized water Inorganic materials 0.000 description 43
- 239000007788 liquid Substances 0.000 description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 238000007599 discharging Methods 0.000 description 26
- 239000000243 solution Substances 0.000 description 24
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 22
- 239000010410 layer Substances 0.000 description 19
- 238000001816 cooling Methods 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- FRBFQWMZETVGKX-UHFFFAOYSA-K chromium(3+);6-methylheptanoate Chemical compound [Cr+3].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O FRBFQWMZETVGKX-UHFFFAOYSA-K 0.000 description 15
- 239000007791 liquid phase Substances 0.000 description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 13
- 238000005829 trimerization reaction Methods 0.000 description 13
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 10
- 239000003446 ligand Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 8
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 7
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- VLTQUJCOJRMZJV-UHFFFAOYSA-K chromium(3+) 2-methylpropanoate Chemical compound [Cr+3].CC(C)C([O-])=O.CC(C)C([O-])=O.CC(C)C([O-])=O VLTQUJCOJRMZJV-UHFFFAOYSA-K 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- PAPNRQCYSFBWDI-UHFFFAOYSA-N 2,5-Dimethyl-1H-pyrrole Chemical compound CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 description 4
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 4
- OXMLCJOPQGRRKV-UHFFFAOYSA-K chromium(3+);tribenzoate Chemical compound [Cr+3].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 OXMLCJOPQGRRKV-UHFFFAOYSA-K 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 4
- CVKMFSAVYPAZTQ-UHFFFAOYSA-M 2-methylhexanoate Chemical compound CCCCC(C)C([O-])=O CVKMFSAVYPAZTQ-UHFFFAOYSA-M 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 description 3
- CWPINIPJCSBFEB-UHFFFAOYSA-K chromium(3+);hexadecanoate Chemical compound [Cr+3].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O CWPINIPJCSBFEB-UHFFFAOYSA-K 0.000 description 3
- SVBJDMIHJDNGRL-UHFFFAOYSA-K chromium(3+);triacetate;hexahydrate Chemical compound O.O.O.O.O.O.[Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVBJDMIHJDNGRL-UHFFFAOYSA-K 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- IAWWAVGUKRSONG-UHFFFAOYSA-N 2,4-dimethyl-2-phenylpentanoic acid Chemical compound CC(C)CC(C)(C(O)=O)C1=CC=CC=C1 IAWWAVGUKRSONG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YVHAIVPPUIZFBA-UHFFFAOYSA-N Cyclopentylacetic acid Chemical compound OC(=O)CC1CCCC1 YVHAIVPPUIZFBA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- NPCUWXDZFXSRLT-UHFFFAOYSA-N chromium;2-ethylhexanoic acid Chemical compound [Cr].CCCCC(CC)C(O)=O NPCUWXDZFXSRLT-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- JLYXXMFPNIAWKQ-GNIYUCBRSA-N gamma-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H]1Cl JLYXXMFPNIAWKQ-GNIYUCBRSA-N 0.000 description 2
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N gamma-hexachlorocyclohexane Natural products ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 229940038384 octadecane Drugs 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- RHRYVHICRLKJDI-UHFFFAOYSA-N 1-propylcyclohexa-2,4-diene-1-carboxylic acid Chemical compound CCCC1(C(O)=O)CC=CC=C1 RHRYVHICRLKJDI-UHFFFAOYSA-N 0.000 description 1
- FPGFBEGEJLJJJZ-UHFFFAOYSA-N 2-(1-methylcyclohexa-2,4-dien-1-yl)acetic acid Chemical compound OC(=O)CC1(C)CC=CC=C1 FPGFBEGEJLJJJZ-UHFFFAOYSA-N 0.000 description 1
- RPXFDOOFVNTCQA-UHFFFAOYSA-N 2-cyclohexylbutanoic acid Chemical compound CCC(C(O)=O)C1CCCCC1 RPXFDOOFVNTCQA-UHFFFAOYSA-N 0.000 description 1
- VRLUSLNMNQAPOH-UHFFFAOYSA-N 2-cyclohexylpropanoic acid Chemical compound OC(=O)C(C)C1CCCCC1 VRLUSLNMNQAPOH-UHFFFAOYSA-N 0.000 description 1
- YYEROYLAYAVZNW-UHFFFAOYSA-N 2-methyl-2-phenylpropanoic acid Chemical compound OC(=O)C(C)(C)C1=CC=CC=C1 YYEROYLAYAVZNW-UHFFFAOYSA-N 0.000 description 1
- UBJNPHAYKBNFOC-UHFFFAOYSA-N 2-phenylbut-2-enoic acid Chemical compound CC=C(C(O)=O)C1=CC=CC=C1 UBJNPHAYKBNFOC-UHFFFAOYSA-N 0.000 description 1
- UVZMNGNFERVGRC-UHFFFAOYSA-N 4-cyclohexylbutanoic acid Chemical compound OC(=O)CCCC1CCCCC1 UVZMNGNFERVGRC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000501667 Etroplus Species 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-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
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- WFOOTRPLCMPWIP-UHFFFAOYSA-K chromium(3+) pentanoate Chemical compound [Cr+3].CCCCC([O-])=O.CCCCC([O-])=O.CCCCC([O-])=O WFOOTRPLCMPWIP-UHFFFAOYSA-K 0.000 description 1
- RPBPCPJJHKASGQ-UHFFFAOYSA-K chromium(3+);octanoate Chemical compound [Cr+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O RPBPCPJJHKASGQ-UHFFFAOYSA-K 0.000 description 1
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 1
- ANNXSSGQVXBUEI-UHFFFAOYSA-H chromium(3+);trisulfate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ANNXSSGQVXBUEI-UHFFFAOYSA-H 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229960001680 ibuprofen Drugs 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ZOCYQVNGROEVLU-UHFFFAOYSA-N isopentadecanoic acid Chemical compound CC(C)CCCCCCCCCCCC(O)=O ZOCYQVNGROEVLU-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
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- C07C2531/22—Organic complexes
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Abstract
The invention provides a preparation method and application of an active trivalent organic chromium compound, wherein the preparation method comprises the following steps: step 1, carrying out double decomposition reaction on an organic acid salt and a chromium reagent; step 2, washing the mixture after reaction with water, heating to 150-300 ℃, and refining to obtain an active trivalent organic chromium compound; wherein the chromium reagent is a water-soluble chromium compound, and the chromium in the chromium reagent is trivalent. The method realizes the preparation of the organic acid chromium compound with three empty coordination, has high chromium raw material conversion rate, high yield of active trivalent organic acid chromium of a target product and good stability, and can be used for ethylene oligomerization.
Description
Technical Field
The invention relates to a preparation method of an active trivalent organic chromium compound, in particular to a preparation method of active trivalent organic acid chromium with three empty coordination, wherein the active trivalent organic acid chromium is used for ethylene oligomerization.
Background
Trivalent chromium (iii) is the most stable and important oxidation state in the element, and has six coordination sites arranged in an octahedral configuration around a central ion. Trivalent chromium has a strong ability to form a complex, normally in a fully coordinated state, i.e., readily co-ordinated to H 2 O、NH 3 、Cl - Ligand such as CN, etc. with a coordination number of 6 2 sp 3 Type of complex having octahedral configuration, Cr 3 + Located in the center of the octahedron.
The trivalent chromium organic acid is an important chromium salt, and usually three coordination sites are occupied by carboxylate anions and the other three coordination sites are occupied by H 2 O、NH 3 、Cl - And small molecular ligands such as CN. However, the trivalent chromium organic acid complex with complete coordination generally has no activity, while the organic acid complex with three empty coordination has high solubility and high dissolution speed in a nonpolar solvent, coordination sites are released for participating in a catalytic reaction, and the complex has an active function and is often used as a catalyst for ethylene oligomerization and epoxidation reaction, and the like, Cr (RCOO) 3 Is based on the short-lived occupation of available chromium III coordination sites by ethylene or epoxide or imide molecules or the like, and can be regenerated to participate in further reactions.
The organic acid chromium (III) used as the catalyst needs to vacate three coordination sites, namely a small molecule ligand needs to be removed from coordination during the preparation process of the organic acid chromium (III) so as to form an organic acid chromium (III) compound with three unoccupied coordination sites and catalytic activity. However, the removal of the above ligands from the chromium (III) compounds or the replacement of these ligands by other ligands is a relatively difficult and slow process.
U.S. Pat. Nos. 3968135 and 3962182 disclose a process for preparing chromium 2-ethylhexanoate by converting organic acid into sodium organic acid, reacting with aqueous solution of inorganic chromium compound, washing with alkali and water to obtain crude product, drying, decompressing, crystallizing to obtain solid hydrated trivalent chromium compound, adding acidic dehydration assistant, and heating to 140 deg.C or higher to obtain organic acid chromium with catalytic activity. The method has the advantages of high toxicity of chloroform and other reagents, long process and poor economy. Chinese patent CN01140236.9 also discloses a preparation method of active chromium organic acid, which comprises mixing trivalent chromium compound with organic carboxylic acid, heating to 140 deg.C under stirring, heating to 190 deg.C and 210 deg.C after the chromium compound solid is completely dissolved, and maintaining for a certain time. In the method, the yield of the target product, namely the organic acid chromium is limited, and in addition, volatile components evaporated by heating are acidic compounds such as hydrochloric acid, acetic acid and the like, so that the problem of corrosion resistance of device materials needs to be considered in large-scale preparation.
Disclosure of Invention
The invention mainly aims to provide a preparation method and application of an active trivalent organic chromium compound, the preparation method is simple in process and free of corrosion influence on equipment, the preparation of the chromium compound with three vacant coordination is realized, the conversion rate of raw material chromium is high, and the target product active trivalent organic acid chromium is high in yield and good in stability.
In order to achieve the above object, the present invention provides a method for preparing an active trivalent organic chromium compound, the method comprising the steps of:
step 1, carrying out double decomposition reaction on an organic acid salt and a chromium reagent;
step 2, washing the reacted mixture with water, heating to 150-300 ℃, and refining to obtain an active trivalent organic chromium compound;
wherein the chromium reagent is a water-soluble chromium compound, and the chromium in the chromium reagent is trivalent.
The preparation method of the active trivalent organic chromium compound comprises the following steps of reacting organic carboxylic acid and inorganic base to obtain the organic acid salt, wherein the organic carboxylic acid is alkanyl monocarboxylic acid, naphthenic monocarboxylic acid or aralkyl monocarboxylic acid at least containing 4 carbon atoms, and the inorganic base is alkali metal hydroxide or alkaline earth metal hydroxide; the inorganic base is calculated by hydroxide ions, and the molar ratio of the organic carboxylic acid to the inorganic base is more than 1: 1.
The preparation method of the active trivalent organic chromium compound comprises the step of carrying out double decomposition reaction on an organic acid salt and a chromium reagent in the presence of water and an inert solvent, wherein the inert solvent at least comprises a solvent with a boiling point of not lower than 150-300 ℃.
The preparation method of the active trivalent organic chromium compound comprises the steps of calculating the inorganic alkali by hydroxide ions, and calculating the chromium reagent by Cr 3+ The molar ratio of the inorganic base to the chromium reagent is at least 3: 1.
The preparation method of the active trivalent organic chromium compound comprises the following step of preparing a chromium reagent, wherein the chromium reagent is one or more of hydrated chromium acetate, hydrated chromium nitrate, hydrated chromium perchlorate, hydrated chromium phosphate, hydrated chromium dihydrogen phosphate, hydrated chromium sulfate, hydrated chromium chloride, hydrated chromium bromide and hydrated chromium iodide.
The preparation method of the active trivalent organic chromium compound comprises the following steps of 6 ～C 18 One or more of (a).
Wherein C 6 ～C 18 The alkane of (2) may be an alkane or a cycloalkane. The inert solvent may be a normal paraffin or a multi-fraction isoparaffin, or a mixture of several paraffins, optionally with the addition of at least one C 10 ～ C 18 C is an alkane of 10 ～C 18 The adding amount of alkane accounts for 20-100% of the total volume of the inert solvent.
The preparation method of the active trivalent organic chromium compound, disclosed by the invention, has the advantages that the temperature range is controlled according to different organic acid radicals in the product, and the double decomposition reaction temperature in the step 1 is 50-200 ℃; and 2, gradually heating the refining treatment to 150-300 ℃, and keeping the temperature for 0.5-5 hours.
The active trivalent organic chromium compound of the present invention is prepared by a process comprising reacting an organic carboxylic acid selected from the group consisting of n/isobutyric acid, n/isovaleric acid, n/isocaproic acid, n/isoheptanoic acid, n/isooctanoic acid, n/isononanoic acid, n/isodecanoic acid, n/isoundecanoic acid, n/isododecanoic acid, n/isotridecanoic acid, n/isotetradecanoic acid, n/isotentadecanoic acid, n/isohexadecanoic acid, n/isoheptanoic acid, n/isostearic acid, 3-methylcyclobutyric acid, cyclopentanecarboxylic acid, cyclopenteacetic acid, cyclopentanepropionic acid, cyclohexanecarboxylic acid, cyclohexaneacetic acid, cyclohexanepropionic acid, p-methylcyclohexanecarboxylic acid, isopropylcyclohexanecarboxylic acid, methylcyclohexaneacetic acid, ethylcyclohexaneacetic acid, benzoic acid, phenylacetic acid, cyclohexanecarboxylic acid, and cyclohexanecarboxylic acid, Phenylpropionic acid, 2-phenylpropionic acid, phenylbutyric acid, 2-phenylisobutyric acid, phenylpentanoic acid, 3-methyl-2-phenylpentanoic acid, phenylhexanoic acid, p-methylbenzoic acid, m-methylbenzoic acid, 2, 3-dimethylbenzoic acid, 2, 4-dimethylbenzoic acid, 2, 6-dimethylbenzoic acid, 3, 5-dimethylbenzoic acid, o-methylphenylacetic acid, m-methylphenylacetic acid, 2, 5-dimethylphenylacetic acid, methamphetac acid, α -methylphenylbutyric acid, p-ethylphenylacetic acid, p-ethylphenylpropionic acid, 4-propylbenzoic acid, 4-propylphenylacetic acid, 4-isopropylphenylacetic acid, 4-cyclopropylphenylacetic acid, ibuprofen, 4-propylphenylbutyric acid, 1- (4-methylphenyl) -1-cyclopentanecarboxylic acid, 1-propylbenzoic acid, 1-methylphenylacetic acid, 2-methylphenylacetic acid, p-methylbenzoacetic acid, p-methylphenylacetic acid, p-methylben-methyle, and a-methylben-methyle, 1- (p-tolyl) -cyclohexanecarboxylic acid, 2-ethylhexanoic acid, and 2, 2-methyl-hexanoic acid.
The preparation method of the active trivalent organic chromium compound provided by the invention is characterized in that the active trivalent organic chromium compound is active trivalent organic acid chromium and has three empty coordination.
In order to achieve the above object, the present invention provides a method for oligomerization of ethylene, wherein the catalyst used in the method is the active trivalent organic chromium compound obtained by the above method for preparing the active trivalent organic chromium compound.
The active trivalent chromium organic acid obtained by the method can judge whether the obtained chromium organic acid really removes micromolecular ligands to form the active trivalent chromium organic acid through the product color and the infrared spectrum.
The active trivalent chromium organic acid obtained by the method can be used for measuring the content of chromium metal by using an atomic absorption spectrometry, a plasma emission spectrometry, a spectrophotometry and the like, so that the yield of the chromium organic acid is obtained by calculation.
The yield of the organic acid chromium product is calculated by the formula: yield of product (in terms of Cr) as actual product quantity 3+ Compound)/theoretical product amount 100%. Wherein the theoretical product amount is calculated according to all reactions of the raw material chromide.
The invention has the beneficial effects that:
the active trivalent organic acid chromium of the target product obtained by the method has high yield and good stability; the obtained active trivalent chromium organic acid can be directly used as an active component of a catalyst for ethylene oligomerization, particularly for catalyzing the reaction of ethylene trimerization to prepare 1-hexene, and has high catalytic activity.
Drawings
FIG. 1 is an infrared spectrum of inactive chromium isooctanoate;
FIG. 2 is an infrared spectrum of active chromium isooctanoate.
Detailed Description
The following examples of the present invention are described in detail, and the present invention is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and procedures are given, but the scope of the present invention is not limited to the following examples, and the following examples are experimental methods without specific conditions noted, and generally follow conventional conditions.
The invention provides a preparation method of an active trivalent organic chromium compound, which comprises the following steps:
step 1, carrying out double decomposition reaction on an organic acid salt and a chromium reagent;
step 2, washing the mixture after reaction with water, heating to 150-300 ℃, and refining to obtain an active trivalent organic chromium compound;
wherein the chromium reagent is a water-soluble chromium compound, and the chromium in the chromium reagent is trivalent.
The method of the invention is that the organic acid salt and the chromium reagent are subjected to double decomposition reaction to prepare the organic acid chromium hydrate, then the water-soluble ionic compound is washed out by water, and then the active trivalent organic acid chromium is prepared by refining treatment, high temperature impurity removal and coordination water dissociation. The active trivalent chromium organic acid prepared by the method has high conversion rate of the raw material chromium and high and stable yield of the target product. The active trivalent chromium organic acid prepared by the method can be used as an active component of a catalyst for synthesizing alpha-olefin by ethylene oligomerization, and has high catalytic activity.
In one embodiment, the organic acid salt of the present invention is obtained by reacting an organic carboxylic acid, which is an alkanyl monocarboxylic acid, a cycloalkyl monocarboxylic acid or an aralkyl monocarboxylic acid having at least 4 carbon atoms, with an inorganic base, which is an alkali metal hydroxide or an alkaline earth metal hydroxide.
The neutralization reaction of the organic acid and the inorganic base determines whether to heat for reaction and the reaction time according to the properties of reactants.
In one embodiment, the chromium reagent is a trivalent water soluble chromium compound; in another embodiment, the chromium reagent of the present invention is one or more of hydrated chromium acetate, hydrated chromium nitrate, hydrated chromium perchlorate, hydrated chromium phosphate, hydrated chromium dihydrogen phosphate, hydrated chromium sulfate, hydrated chromium chloride, hydrated chromium bromide and hydrated chromium iodide, or an aqueous solution having a ratio of these chromium salts, and the ratio is not particularly limited in the present invention.
The chromium (III) compound is stable in an acidic solution and is not easily oxidized. Thus, the reactive trivalent organic chromium compound of the present invention is prepared by considering the molar amount of the acid to be larger than the molar amount of the base (as OH) - In one embodiment, the inorganic base is present in a molar ratio of organic carboxylic acid to inorganic base greater than 1:1, calculated as hydroxide ions. In another embodiment, the organic carboxylic acid and the inorganic base are present in a molar ratio of 1:0.5 to 1, and in yet another embodiment, the organic carboxylic acid and the inorganic base are present in a molar ratio of 1:0.7 to 0.9. Inorganic alkali is calculated by hydroxide ions, and chromium reagent is calculated by Cr 3+ The molar ratio of inorganic base to chromium reagent is at least 3: 1. In yet another embodiment, the molar ratio of the inorganic base to the chromium reagent of the present invention is 3 to 6:1, from an economic point of view, to maximize the conversion of the chromium reagent and the organic carboxylic acid, and the presence of acid during the refining process; in yet another embodiment, the molar ratio of the inorganic base to the chromium reagent of the present invention is 3 to 4: 1.
In another embodiment, the organic acid salt of the present invention can be a commercially available organic acid salt, and the organic acid salt is reacted with a chromium reagent in the presence of water and an organic solvent. After the reaction, the obtained mixture can be subjected to layering treatment firstly and then the organic layer is subjected to washing treatment, or the mixture after the reaction can be directly subjected to washing treatment, so that the target product active trivalent organic chromium compound is easily dissolved in an organic solvent. In addition, since the active trivalent organic chromium compound is stable in an acidic solution and is not easily oxidized, a small amount of organic acid needs to be added in the subsequent high-temperature refining process in this embodiment, so that the refining process is performed in the presence of the organic acid, and the active trivalent chromium compound of the product can stably exist.
In one embodiment, the active trivalent organic acids chromium cr (rcoo) of the present invention 3 The preparation method comprises the following steps: stirring and mixing organic acid and inorganic base with a stoichiometric proportion, adding a trivalent water-soluble chromium compound, adding an inert organic solvent, heating for reaction, washing with deionized water after the reaction is finished, heating to 150-300 ℃, refining under the conditions of reduced pressure or normal pressure or pressure, and keeping for 0.5-5 hours to obtain a green homogeneous phase viscous liquid, namely an active trivalent organic acid chromium compound Cr (RCOO) 3 . The above reaction of the present invention may be carried out under the condition of inert gas pressure holding or without pressure holding.
In another embodiment, the organic carboxylic acid of the invention is selected from n/isobutyric acid, n/isovaleric acid, n/isocaproic acid, n/isoheptanoic acid, n/isooctanoic acid, n/isononanoic acid, n/isodecanoic acid, n/isoundecanoic acid, n/isododecanoic acid, n/isotridecanoic acid, n/isotetradecanoic acid, n/isopentadecanoic acid, n/isohexadecanoic acid, n/isoheptadecanoic acid, n/isooctadecanoic acid, 3-methylcyclobutyric acid, cyclopentanecarboxylic acid, cyclopentaneacetic acid, cyclopentanepropionic acid, cyclohexanecarboxylic acid, cyclohexaneacetic acid, cyclohexanepropionic acid, cyclohexanecarboxylic acid, phenylacetic acid, phenylpropanoic acid, 2-phenylpropanoic acid, phenylbutyric acid, 2-phenylbutyric acid, phenylpentanoic acid, 3-methyl-2-phenylpentanoic acid, phenylhexanoic acid, p-methylbenzoic acid, m-methylbenzoic acid, 2, 3-dimethylbenzoic acid, 2, 4-dimethylbenzoic acid, 2, 6-dimethylbenzoic acid, 3, 5-dimethylbenzoic acid, o-methylphenylacetic acid, m-methylphenylacetic acid, 2, 5-dimethylphenylacetic acid, methylphenylacetic acid, alpha-methylphenylbutyric acid, p-ethylphenylacetic acid, p-ethylphenylpropionic acid, p-ethylphenylbutyric acid, 4-propylbenzoic acid, 4-isopropylphenylacetic acid, 4-cyclopropylphenylacetic acid, isobutylphenylpropionic acid, 4-propylphenylbutyric acid, 1- (4-methylphenyl) -1-cyclopentanecarboxylic acid, 1- (p-tolyl) -cyclohexanecarboxylic acid, One or more of 2-ethyl hexanoic acid and 2, 2-methyl-hexanoic acid. In a further embodiment, the organic carboxylic acid of the invention is selected from isobutyric acid, pentanoic acid, 2-ethylhexanoic acid, n-octanoic acid, cyclohexaneacetic acid, benzoic acid, 3, 5-dimethylbenzoic acid, 2-methyl-hexanoic acid.
The inorganic base of the present invention is sodium hydroxide, potassium hydroxide, barium hydroxide, etc., and in one embodiment, the inorganic base of the present invention is dissolved in a solvent and then mixed with an organic acid.
The active trivalent organic chromium compound as the target product of the invention is easy to dissolve in organic solvent, and the solvent can reduce the viscosity of the reaction product, thus being beneficial to the forward speed of the reaction and improving the yield of the product. Preferably, the appropriate solvent is added at an appropriate time, and a gradient temperature rise effect is realized during the refining treatment process, so that the bound water is sufficiently dissociated, and the yield of the active organic acid chromium with three coordination spaces is maximized, therefore, the double decomposition reaction and the refining treatment process are carried out in the presence of the inert solvent.
In one embodiment, the inert solvent of the present invention is an organic solvent, and the inert solvent at least comprises a solvent with a boiling point of not less than 150-300 ℃. In another embodiment, the inert solvent of the present invention comprises C 6 ～C 18 Aliphatic alkanes of, i.e. including C 6 ～C 18 Straight-chain aliphatic alkane of (1), C 6 ～C 18 Branched aliphatic hydrocarbons and C 6 ～C 18 The alicyclic hydrocarbon of (2). In another embodiment, the inert solvent of the present invention is a normal paraffin, or a multi-distillate isoparaffin, or a mixture of paraffins, optionally with the addition of at least one C 6 ～ C 18 (or C) 10 ～C 18 ) A C to C 6 ～C 18 (or C) 10 ～C 18 ) The adding amount of alkane accounts for 20-100% of the total volume of the inert solvent.
The inert solvent may be added in a variety of ways, including during the addition of the chromium reagent, or during the metathesis, or at the end of the metathesis reaction, or during the washing with water, or during the high temperature refining process, either in batch or in one portion, but at least to ensure that the metathesis reaction is carried out in the inert solvent.
After the double decomposition reaction is finished, water is washed to remove impurities, and deionized water is used as washing liquid in the water washing process. And (3) washing with water to remove metal ions, acid radical ions and other water-soluble compounds dissolved in the water. After the reaction is finished, the temperature is reduced and the washing is carried out, wherein the washing temperature is determined according to the properties of the solvent, and the washing can be carried out at normal temperature or under the condition of the temperature.
In one embodiment, the temperature of the refining treatment after water washing is 150-300 ℃ and is kept for 0.5-5 hours, preferably the temperature of the refining treatment is 170-230 ℃ and is kept for 1-3 hours according to the difference of organic acid radicals in the product; alternatively, the purification treatment temperature is preferably 230 to 300 ℃ and the temperature is maintained for 1 to 3 hours. The high-temperature refining treatment is carried out under the condition of reduced pressure or normal pressure or inert gas pressure maintaining. The free water, partial solvent, excessive organic acid, small molecular ligand on organic acid chromium and the like can be removed through the refining treatment.
The active trivalent organic chromium compound prepared by the invention is trivalent organic acid chromium with three empty coordination Cr (RCOO) 3 An aliphatic chromium carboxylate compound, a chromium naphthenate compound or a chromium aralkanoate compound having at least 4 carbon atoms, wherein the acid corresponding to the RCOO group is a monocarboxylic acid, including but not limited to n/isobutyric acid, n/isovaleric acid, n/isocaproic acid, n/isoheptanoic acid, n/isooctanoic acid, n/isononanoic acid, n/isodecanoic acid, n/isoundecanoic acid, n/isododecanoic acid, n/isotridecanoic acid, n/isotetradecanoic acid, n/isotentadecanoic acid, n/isohexadecanoic acid, n/isoheptadecanoic acid, n/isostearic acid, 3-methylcyclobutyric acid, cyclopentanecarboxylic acid, cyclopenteacetic acid, cyclopentylpropionic acid, cyclohexanecarboxylic acid, cyclohexaneacetic acid, cyclohexanepropionic acid, cyclohexanepropanecarboxylic acid, p-methylcyclohexanecarboxylic acid, isopropylcyclohexanecarboxylic acid, cyclohexanecarboxylic acid, 3-methylcyclobutyric acid, cyclohexanecarboxylic acid, and a, Methyl cyclohexylacetic acid, ethyl cyclohexylacetic acid, benzoic acid, phenylacetic acid, phenylpropionic acid, 2-phenylpropionic acid, phenylbutyric acid, 2-phenylbutyric acid, phenylpentanoic acid, 3-Methyl-2-phenylpentanoic acid, phenylhexanoic acid, p-methylbenzoic acid, m-methylbenzoic acid, 2, 3-dimethylbenzoic acid, 2, 4-dimethylbenzoic acid, 2, 6-dimethylbenzoic acid, 3, 5-dimethylbenzoic acid, o-methylphenylacetic acid, m-methylphenylacetic acid, 2, 5-dimethylphenylacetic acid, methylphenylacrylic acid, alpha-methylphenylacetic acid, p-ethylphenylacetic acid, p-ethylphenylpropionic acid, p-ethylphenylbutyric acid, 4-propylbenzoic acid, 4-propylphenylacetic acid, 4-isopropylphenylacetic acid, 4-cyclopropylphenylacetic acid, isobutylphenylpropionic acid, 4-propylphenylbutyric acid, 1- (4-methylphenyl) -1-cyclopentanecarboxylic acid, 1- (p-tolyl) -cyclohexanecarboxylic acid.
In one embodiment, the active trivalent chromium organic acids of the present invention include, but are not limited to, chromium isobutyrate, chromium valerate, chromium 2-ethylhexanoate, chromium n-octanoate, chromium cyclohexylacetate, chromium benzoate, chromium 3, 5-dimethylbenzoate, chromium 2, 2-methyl-hexanoate.
The active trivalent chromium organic acid obtained by the invention can be stored for more than 12 months or even several years without deterioration under the conventional storage, namely, the state that three empty coordination sites are not occupied by other small molecules is maintained. The method for judging whether the active trivalent chromium organic acid is deteriorated is to observe color change, wherein the deterioration of the active trivalent chromium organic acid is to absorb water oxygen micromolecules in the environment, and the empty coordination is occupied by the micromolecules to cause a color change phenomenon; the active trivalent chromium organic acid may also be oxidized, and the color change may also occur.
The active trivalent chromium organic acid obtained by the method can be used for measuring the content of chromium metal by using an atomic absorption spectrometry, a plasma emission spectrometry, a spectrophotometry and the like, so that the amount of the active trivalent chromium organic acid is obtained, and the yield of the active trivalent chromium organic acid is obtained by calculation. The yield of the organic acid chromium product is calculated by the formula: product yield-actual product quantity (in terms of active trivalent chromium organic acid)/theoretical product quantity 100%. Wherein the theoretical product amount is calculated according to the total reaction of the raw material chromium reagent.
The method can judge whether the obtained organic chromium acid really removes the micromolecular ligand to form the active trivalent organic chromium acid by the product color and the infrared spectrum. Taking chromium isooctanoate as an example, the color of inactive chromium isooctanoate is blue or bluish purple, and the chromium isooctanoate is removedThe color of the active chromium isooctanoate obtained after water treatment is green; in addition, inactive chromium isooctanoate (i.e. before dehydration) was 1530cm on the IR spectrum -1 Near the peak of the sharp carboxylic acid carbonyl group, the peak becomes smaller gradually as the dehydration proceeds, or becomes a small shoulder, and 1607cm in the infrared spectrum as the dehydration proceeds -1 Becomes stronger (as in fig. 1 and 2).
Therefore, the preparation method of the active trivalent organic acid chromium provided by the invention is simple in process, has no corrosion influence on equipment, realizes the preparation of the chromium compound with three empty coordination, and has the advantages of high conversion rate of the chromium compound, high yield of the active trivalent organic acid chromium of a target product and good stability. The active trivalent organic acid chromium of the present invention is mainly used for ethylene oligomerization, and provides a method for producing a chromium compound of an aliphatic carboxylic acid, a cycloalkane carboxylic acid or an aralkane carboxylic acid having at least 4 carbon atoms, considering that the alkyl side chain of a carboxylate anion can be adjusted to achieve necessary solubility, stability and the like in various reaction media required for effective catalysis.
The invention does not particularly limit the specific process of the active trivalent organic chromium compound used for the trimerization of ethylene to synthesize 1-hexene, and the specific process is as follows: taking 0.001mol (calculated as chromium) of organic acid chromium, and diluting the organic acid chromium to 100ml by cyclohexane to obtain an organic acid chromium solution with the concentration of 0.01 mmol/ml. Similarly, cyclohexane solutions of 2, 5-dimethylpyrrole, triethylaluminum and gamma-hexachlorocyclohexane were prepared at concentrations of 0.03mmol/ml, 1mmol/ml and 0.1mmol/ml, respectively, and were used. The reaction was carried out in a 1L stirred tank reactor. Before the reaction, the reactor was boiled and washed with cyclohexane and purged with nitrogen. Adding 200ml of cyclohexane into a reaction kettle, sequentially adding 1ml of each of triethyl aluminum (cocatalyst), 2, 5-dimethylpyrrole (catalyst ligand), gamma-hexachlorocyclohexane (electron donor) and organic acid chromium solution, stirring and heating to 90 ℃, introducing ethylene to the pressure of 5MPa, maintaining the temperature at 110-120 ℃, reacting for 30min, cooling and reducing the pressure, discharging materials, weighing, and calculating the catalytic activity, wherein the calculation method comprises the following steps:
catalyst activity ═ total mass of product/mass of chromium ions × 100% (in kg product/gCr · h)
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1:
A1L flask was charged with 6.0g of sodium hydroxide dissolved in 50ml of deionized water, and 20.4g of n-pentanoic acid was added to start stirring. 16.85g of chromium acetate hexahydrate is weighed, quickly dropped into a flask, 40ml of hexane is added, and the temperature is raised to 80 ℃ for reaction for 2 hours. And after the reaction is finished, stopping heating, cooling to room temperature, pouring into a separating funnel, layering, and discharging a bottom liquid phase. Adding 50ml of decane and 80ml of deionized water into the separating funnel, shaking, standing, and discharging the bottom liquid after layering; repeatedly washing with deionized water for 4 times to obtain upper layer liquid, pouring into flask, gradually heating to 150 deg.C, maintaining at 150 deg.C for 3 hr, and introducing nitrogen gas to make distillation system have micro-positive pressure. The heating was stopped and the mixture was cooled to room temperature to obtain 21.1g of a green viscous liquid. Cr is obtained by measuring the obtained product chromium n-valerate 3+ The content was 118840. mu.g/g. The product yield was calculated to be 96%.
The prepared chromium n-valerate is used for catalyzing the trimerization of ethylene to synthesize 1-hexene, and the catalytic activity of the chromium n-valerate is 75kg of product/gCr.h -1 。
Example 2:
A1L flask was charged with 6.0g of sodium hydroxide dissolved in 50ml of deionized water, and 26.0g of isooctanoic acid was added to start stirring. 12.8g of chromium chloride hexahydrate is added into a flask, 40ml of heptane is added, and the temperature is raised to 100 ℃ for reaction for 1 h. And after the reaction is finished, stopping heating, cooling to room temperature, pouring into a separating funnel, layering, and discharging a bottom liquid phase. Adding 90ml of deionized water into the separating funnel, shaking, standing, and discharging bottom liquid after layering; the solution was washed repeatedly with deionized water for 4 times to obtain the upper layer, and the upper layer was poured into a flask, and 60ml of dodecane was added and stirred, gradually heated to 210 ℃ and kept at about 210 ℃ for 2 hours. The heating was stopped and the temperature was cooled to room temperature to obtain 29.2g of a green viscous liquid. Cr is obtained by measuring the obtained product chromium isooctanoate 3+ The content is 84025 mu g/g. The product yield was calculated to be 98%.
The prepared chromium isooctanoate is used for catalyzing the trimerization of ethylene to synthesize 1-hexene, and the catalytic activity is 755kg of product/gCr.h -1 。
Example 3:
8.4g of potassium hydroxide was weighed out and dissolved in 50ml of deionized water, and the resulting solution was put into a 1-liter flask, followed by addition of 23.0g of isooctanoic acid and stirring was started. Adding 15.5g of chromium acetate hexahydrate into a flask, heating to 100 ℃ for reaction, adding 60ml of decane when the reaction is carried out for 10min, stopping heating after the reaction is carried out for 1h, cooling to room temperature, pouring into a separating funnel, layering, and discharging a bottom liquid phase. Adding 80ml of deionized water into the separating funnel, shaking, standing, and discharging bottom liquid after layering; the solution was washed repeatedly with deionized water for 4 times to obtain an upper layer liquid, which was poured into a flask and stirred, gradually warmed to 220 ℃ and kept at about 220 ℃ for 1.5 hours. The heating was stopped and the temperature was cooled to room temperature to obtain 26.6g of a green viscous liquid. Cr is obtained by measuring the obtained product chromium isooctanoate 3+ The content was 87620. mu.g/g. The product yield was calculated to be 97%.
The prepared chromium isooctanoate is used for catalyzing ethylene trimerization reaction, and the obtained catalytic activity is 778kg of product/gCr.h -1 。
Example 4:
6.0g of sodium hydroxide was dissolved in 50ml of deionized water, and the solution was charged into a 1-liter flask, followed by addition of 35.2g of isooctanoic acid and stirring. Adding 15.2g of chromium nitrate nonahydrate into a flask, heating to 90 ℃ for reaction, adding 60ml of cyclohexane when reacting for 30min, stopping heating after reacting for 3h, cooling to room temperature, pouring into a separating funnel, layering, and discharging a bottom liquid phase. Adding 80ml of deionized water into the separating funnel, shaking, standing, and discharging bottom liquid after layering; the solution was washed repeatedly with deionized water for 4 times to obtain the upper layer liquid, which was poured into a flask and stirred, and 30ml of dodecane was added during the gradual temperature rise, and the temperature was raised to 220 ℃ and maintained at about 220 ℃ for 5 hours. Stopping heating and cooling to room temperature gave 20.7g of a green viscous liquid. Cr is obtained by measuring the obtained product chromium isooctanoate 3+ The content was 94860. mu.g/g. The product yield was calculated to be 99%.
The prepared chromium isooctanoate is used for catalyzing ethylene trimerization reaction, and the obtained catalytic activity is 878kg of product/gCr.h -1 。
Example 5:
8.4g of potassium hydroxide was weighed out and dissolved in 50ml of deionized water, and the solution was charged into a 1L flask, and 23.7g of cyclohexylacetic acid was further added thereto, and stirring was started. 17.2g of aqueous solution containing 50% chromium acetate is weighed and added into a flaskThe temperature was raised to 90 ℃ to effect reaction, and 50ml of cyclohexane was added thereto during 10min of the reaction. After reacting for 1h, the heating was stopped, 30ml tetradecane was added, cooled to room temperature, poured into a separatory funnel, and the bottom liquid phase was discharged after layering. Adding 80ml of deionized water into the separating funnel, shaking, standing, and discharging bottom liquid after layering; the solution was washed repeatedly with deionized water for 4 times to obtain an upper layer liquid, which was poured into a flask, gradually warmed to 240 ℃ and kept at about 240 ℃ for 4 hours. The heating was stopped and the temperature was cooled to room temperature to obtain 22.3g of a green viscous liquid. Cr is obtained by measuring the obtained product of chromium cyclohexylacetate 3+ Content 85630 mu g/g, Cr 3+ The content was not detected. The product yield was calculated to be 98%.
The prepared cyclohexyl chromium acetate is used for catalyzing the trimerization of ethylene to synthesize 1-hexene, and the catalytic activity of the prepared cyclohexyl chromium acetate is 133kg of product/gCr.h -1 。
Example 6:
6.0g of sodium hydroxide was weighed and dissolved in 50ml of deionized water, and the solution was charged into a 1L flask, and 28.6g of 3, 5-dimethylbenzoic acid was further charged into the flask, and the temperature was raised to 170 ℃ with stirring. Adding 14.0g of chromium sulfate dodecahydrate into a flask, reacting at 170 ℃, adding 80ml of mixed hexadecane when reacting for 30min, stopping heating after reacting for 3h, cooling to room temperature, pouring into a separating funnel, layering, and discharging a bottom layer liquid phase. Adding 80ml of deionized water into the separating funnel, shaking, standing, and discharging bottom liquid after layering; the solution is repeatedly washed with deionized water for 4 times to obtain upper layer liquid, which is poured into a flask to be stirred, gradually heated to 280 ℃, and kept at about 280 ℃ for 2 hours. The heating was stopped and the temperature was cooled to room temperature to obtain 28.8g of a green viscous liquid. Cr is obtained by measuring the obtained product of 3, 5-chromium dimethylbenzoate 3+ The content was 79340. mu.g/g. The product yield was calculated to be 95%.
Example 7:
6.0g of sodium hydroxide was weighed out and dissolved in 50ml of deionized water, and the solution was charged into a 1-liter flask, and 33.0g of benzoic acid was further charged into the flask, and the temperature was raised to 128 ℃ with stirring. Adding 9.0g of chromium chloride hexahydrate into a flask, adding 50ml of decane, reacting at 130 ℃ for 4 hours, stopping heating, adding 30ml of mixed tetradecane, cooling to about 50 ℃, pouring into a separating funnel, layering, and discharging a bottom liquid phase. Adding 80ml of deionized water into the separating funnel, shaking, standing, and layeringDischarging the bottom layer liquid; the solution was washed repeatedly with deionized water for 4 times to obtain an upper layer, which was poured into a flask and stirred, gradually heated to 255 ℃ and kept at about 255 ℃ for 1.5 hours. Cooling to room temperature was stopped to give a green viscous liquid, which was diluted with 10ml of cyclohexane to give 24.7 g. Cr is obtained by measuring the obtained product chromium benzoate 3+ The content is 66505. mu.g/g. The product yield was calculated to be 94%.
The prepared chromium benzoate is used for catalyzing the trimerization of ethylene to synthesize 1-hexene, and the catalytic activity of the chromium benzoate is 37kg of product/gCr.h -1 。
Example 8:
6.0g of sodium hydroxide is weighed, dissolved in 50ml of deionized water, added into a 1L flask, then 45.0g of hexadecanoic acid is added, stirred and heated to 100 ℃. Adding 17.0g of aqueous solution containing 50% chromium acetate into a flask, adding 40ml of n-octane, continuing to react for 4 hours at 100 ℃, stopping heating, cooling to 50 ℃, pouring into a separating funnel, and discharging a bottom layer liquid phase after layering. Adding 100ml of deionized water into the separating funnel, shaking, standing, and discharging bottom liquid after layering; the solution was washed repeatedly with deionized water for 4 times to obtain an upper layer liquid, which was poured into a flask and stirred, 40ml of octadecane was added, the vacuum pump was turned on, the temperature was gradually raised to 270 ℃ under a pressure of 13.3kpa, and the temperature was maintained at about 270 ℃ for 2.0 hours. The heating was stopped and the temperature was cooled to room temperature to obtain 30.6g of a green viscous liquid. Cr is obtained by measuring the obtained product of chromium hexadecanoate 3+ The content was 58445. mu.g/g. The product yield was calculated to be 93%.
The prepared chromium hexadecanoate is used for catalyzing the trimerization of ethylene to synthesize 1-hexene, and the catalytic activity of the chromium hexadecanoate is 12kg of product/gCr.h -1 。
Example 9:
potassium hydroxide (12.0 g) was weighed out and dissolved in 50ml of deionized water, and charged into a 1-liter flask, and isobutyric acid (19.0 g) was further added to the flask to start stirring. Adding 18.0g of chromium chloride hexahydrate into a flask, heating to 80 ℃ for 30 minutes, adding 40ml of cyclohexane, continuing to react for 1 hour, stopping heating, cooling to room temperature, pouring into a separating funnel, layering, and discharging a bottom liquid phase. Adding 100ml of deionized water into the separating funnel, shaking, standing, and discharging the bottom liquid after layering; repeatedly washing with deionized water for 4 times to obtain upper layer liquid, and pouring into flaskStirring, heating to 80 deg.C, adding 60ml nonane, gradually heating to 150 deg.C, maintaining at the temperature for 1.0h, and introducing nitrogen gas to make distillation system have slight positive pressure. The heating was stopped and the mixture was cooled to room temperature to obtain a green viscous liquid, which was diluted with 10ml of cyclohexane to obtain 31.3 g. Cr is obtained by measuring the obtained product chromium isobutyrate 3+ The content was 107740. mu.g/g. The product yield was calculated to be 96%.
Example 10:
potassium hydroxide (12.0 g) was weighed out and dissolved in 50ml of deionized water, and the resulting solution was charged into a 1-liter flask, followed by addition of isobutyric acid (21.0 g) and stirring was started. Adding 17.0g of chromium perchlorate hexahydrate into a flask, introducing nitrogen to keep the pressure at 0-0.2 MPa, heating to 90 ℃ for 40 minutes, adding 80ml of decane, continuing to react for 1.5 hours, stopping heating, cooling to room temperature, pouring into a separating funnel, layering, and discharging a bottom liquid phase. Adding 70ml of deionized water into the separating funnel, shaking, standing, and discharging the bottom liquid after layering; the solution was washed repeatedly with deionized water 4 times to obtain an upper layer liquid, which was poured into a flask and stirred, gradually warmed to 160 ℃ and kept at this temperature for 2.0 hours. Cooling to room temperature was stopped to give a green viscous liquid, which was diluted with 10ml of cyclohexane to give 20.8 g. Cr is obtained by measuring the obtained product chromium isobutyrate 3+ The content was 90668. mu.g/g. The product yield was calculated to be 98%.
The prepared chromium isobutyrate is used for catalyzing the reaction of synthesizing 1-hexene by ethylene trimerization, and the catalytic activity of the chromium isobutyrate is 29kg of product/gCr.h -1 。
Example 11:
10.0g of sodium hydroxide was weighed, dissolved in 50ml of deionized water, and added to a 1-liter flask, 46.0g of isopropyl cyclohexanecarboxylic acid was added thereto, and the mixture was stirred and warmed to 100 ℃. Adding 20.0g of chromium acetate hexahydrate into a flask, adding 60ml of nonane, continuously reacting for 5 hours at 150 ℃, stopping heating, cooling to 60 ℃, pouring into a separating funnel, layering, and discharging a bottom liquid phase. Adding 100ml of deionized water into the separating funnel, shaking, standing, and discharging bottom liquid after layering; the solution was washed repeatedly with deionized water for 4 times to obtain an upper layer liquid, which was poured into a flask and stirred, 100ml of octadecane was added, a vacuum pump was started, and the temperature was gradually raised to 300 ℃ under a pressure of 13.3kpa, and maintained at about 300 ℃ for 0.5 hour. Stopping heating and coolingA green viscous liquid was obtained at room temperature, which was diluted with 5ml of cyclohexane to obtain 38.7 g. Cr is obtained by measuring the obtained product of chromium isopropyl cyclohexanecarboxylate 3+ The content is 69852 μ g/g. The product yield was calculated to be 88%.
The prepared chromium isopropylcyclohexanecarboxylate is used for catalyzing the reaction of synthesizing 1-hexene by ethylene trimerization, and the catalytic activity of the chromium isopropylcyclohexanecarboxylate is 160kg of product/gCr.h -1 。
Example 12:
sodium hydroxide 10.0g was weighed out and dissolved in 50ml of deionized water, and charged into a 1L flask, and then 46.0g of 2, 2-methylhexanoic acid was added thereto, and stirring was started. Adding 22.0g of water solution containing 42% of chromium dihydrogen phosphate into a flask, introducing nitrogen to keep the pressure at 0-0.2 MPa, heating to 90 ℃ for 10 minutes, adding 50ml of cyclohexane, continuing to react for 1.5 hours, stopping heating, cooling to room temperature, pouring into a separating funnel, layering, and discharging a bottom layer liquid phase. Adding 100ml of deionized water into the separating funnel, shaking, standing, and discharging the bottom liquid after layering; the solution was washed repeatedly with deionized water 4 times to obtain the upper layer liquid, which was poured into a flask and stirred, heated to 80 deg.C, added with 60ml dodecane, gradually heated to 220 deg.C, and kept at this temperature for 2.0 h. The heating was stopped and the mixture was cooled to room temperature to obtain 36.0g of a green viscous liquid. Cr is obtained by measuring the obtained product of chromium 2, 2-methylhexanoate 3+ The content was 84906. mu.g/g. The product yield was calculated to be 95%.
Example 13:
10.0g of sodium hydroxide was dissolved in 50ml of deionized water, and the solution was charged into a 1-liter flask, followed by addition of 45.0g of 2, 2-methylhexanoic acid and stirring. Adding 20.0g of the mixture into a flask, adding 100ml of dodecane, heating to 90 ℃, reacting for 2 hours, stopping heating, cooling to room temperature, pouring into a separating funnel, layering, and discharging a bottom liquid phase. Adding 100ml of deionized water into the separating funnel, shaking, standing, and discharging the bottom liquid after layering; the solution was washed repeatedly with deionized water 4 times to obtain an upper layer liquid, which was poured into a flask and stirred, gradually warmed to 220 ℃ and kept at this temperature for 2.0 hours. The heating was stopped and the temperature was cooled to room temperature to obtain 42.4g of a green viscous liquid. Cr is obtained by measuring the obtained product of chromium 2, 2-methylhexanoate 3+ The content was 86070. mu.g/g. The product yield was calculated to be 94%.
To obtain 2, 2-methylThe chromium caproate is used for catalyzing the reaction of synthesizing 1-hexene by ethylene trimerization, and the catalytic activity of the chromium caproate is 286kg of product/gCr.h -1 。
Example 14:
52g of sodium isooctanoate was weighed into a 1L flask, and 30g of a 50% aqueous solution of chromium acetate was added thereto to start stirring. 50ml of cyclohexane were added. Heating to 130 ℃ for reaction for 2.5 hours, stopping heating, cooling to room temperature, pouring into a separating funnel, layering, and discharging a bottom liquid phase. Adding 50ml of dodecane, stirring uniformly, adding 100ml of deionized water into a separating funnel, shaking, standing, and layering to discharge bottom liquid; the solution was washed repeatedly with deionized water 4 times to obtain an upper layer liquid, which was poured into a flask and stirred, gradually warmed to 240 ℃ and kept at this temperature for 3.0 hours. The heating was stopped and the temperature was cooled to room temperature to obtain 46.2g of a green viscous liquid. Cr is obtained by measuring the obtained product chromium isooctanoate 3+ The content was 68580. mu.g/g. The product yield was calculated to be 93%.
The prepared chromium isooctanoate is used for catalyzing the trimerization of ethylene to synthesize 1-hexene, and the catalytic activity is 586kg of product/gCr.h -1 。
The present invention is capable of other embodiments, and various changes and modifications can be made by one skilled in the art without departing from the spirit and scope of the invention.
Claims (11)
1. A preparation method of an active trivalent organic chromium compound is characterized by comprising the following steps:
step 1, carrying out double decomposition reaction on an organic acid salt and a chromium reagent;
step 2, washing the reacted mixture with water, heating to 150-300 ℃, and refining to obtain an active trivalent organic chromium compound;
wherein the chromium reagent is a water-soluble chromium compound, and the chromium in the chromium reagent is trivalent.
2. The method for producing an active trivalent organic chromium compound according to claim 1, wherein the organic acid salt is obtained by reacting an organic carboxylic acid which is an alkanyl monocarboxylic acid, a cycloalkyl monocarboxylic acid or an aralkyl monocarboxylic acid having at least 4 carbon atoms with an inorganic base which is an alkali metal hydroxide or an alkaline earth metal hydroxide; the inorganic base is calculated by hydroxide ions, and the molar ratio of the organic carboxylic acid to the inorganic base is more than 1: 1.
3. The method for producing an active trivalent organic chromium compound according to claim 1, wherein the organic acid salt and the chromium reagent are subjected to a metathesis reaction in the presence of water and an inert solvent, and the inert solvent contains at least a solvent having a boiling point of not less than 150 to 300 ℃.
4. The method of claim 2, wherein the inorganic base is in the form of hydroxide ion and the chromium reagent is Cr 3+ The molar ratio of the inorganic base to the chromium reagent is at least 3: 1.
5. The method of claim 4, wherein the chromium reagent is one or more selected from the group consisting of hydrated chromium acetate, hydrated chromium nitrate, hydrated chromium perchlorate, hydrated chromium phosphate, hydrated chromium dihydrogen phosphate, hydrated chromium sulfate, hydrated chromium chloride, hydrated chromium bromide and hydrated chromium iodide.
6. The method of claim 3, wherein the inert solvent comprises at least C 6 ～C 18 One or more of (a) an alkane.
7. The method of claim 6, wherein the inert solvent comprises at least C 10 ～C 18 One or more of alkanes of (1), C 10 ～C 18 The alkane is used in an amount based on the inert solvent20-100% of the total volume.
8. The method for preparing an active trivalent organic chromium compound according to claim 1, wherein the metathesis reaction temperature in the step 1 is 50 to 200 ℃; and step 2, the refining treatment is to gradually raise the temperature to 150-300 ℃ and keep the temperature for 0.5-5 hours.
9. The method for preparing an active trivalent organic chromium compound according to claim 2, wherein the organic carboxylic acid is selected from the group consisting of n/isobutyric acid, n/isovaleric acid, n/isocaproic acid, n/isoheptanoic acid, n/isooctanoic acid, n/isononanoic acid, n/isodecanoic acid, n/isoundecanoic acid, n/isododecanoic acid, n/isotridecanoic acid, n/isotetradecanoic acid, n/isotadecanoic acid, n/isohexadecanoic acid, n/isoheptadecanoic acid, 3-methylcyclobutyric acid, cyclopentanecarboxylic acid, cyclopentanepropionic acid, cyclohexanecarboxylic acid, cyclohexaneacetic acid, cyclohexanepropanoic acid, p-methylcyclohexanecarboxylic acid, isopropylcyclohexanecarboxylic acid, methylcyclohexaneacetic acid, ethylcyclohexaneacetic acid, cyclohexanecarboxylic acid, and mixtures thereof, Benzoic acid, phenylacetic acid, phenylpropionic acid, 2-phenylpropionic acid, phenylbutyric acid, 2-phenylbutyric acid, phenylpentanoic acid, 3-methyl-2-phenylpentanoic acid, phenylhexanoic acid, p-methylbenzoic acid, m-methylbenzoic acid, 2, 3-dimethylbenzoic acid, 2, 4-dimethylbenzoic acid, 2, 6-dimethylbenzoic acid, 3, 5-dimethylbenzoic acid, o-methylphenylacetic acid, m-methylphenylacetic acid, 2, 5-dimethylphenylacetic acid, methamphetanic acid, alpha-methylphenylbutyric acid, p-ethylphenylacetic acid, p-ethylphenylpropionic acid, p-ethylphenylbutyric acid, 4-propylbenzoic acid, 4-isopropylphenylacetic acid, 4-cyclopropylphenylacetic acid, isobutylpropionic acid, 4-propylphenylbutyric acid, 1- (4-methylphenyl) -1-cyclopentanecarboxylic acid, 1-propylphenylbutyric acid, 4-methylphenylacetic acid, p-methylacetic acid, p-propylphenylacetic acid, p-propylpropionic acid, p-propylbenzoic acid, 1- (p-tolyl) -cyclohexanecarboxylic acid, 2-ethylhexanoic acid, and 2, 2-methyl-hexanoic acid.
10. The method of claim 1, wherein the active trivalent organic chromium compound is active trivalent chromium organic acid with three vacant coordinates.
11. A process for the oligomerization of ethylene, wherein the catalyst used in the process is an active trivalent organic chromium compound obtained by the process for the preparation of active trivalent organic chromium compounds according to any one of claims 1 to 10.
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|---|---|---|---|---|
| US3932285A (en) * | 1973-10-03 | 1976-01-13 | Tenneco Chemicals, Inc. | Chromium salt compositions and a process for their production |
| US3968135A (en) * | 1970-01-19 | 1976-07-06 | Aerojet-General Corporation | Chromium salt catalysts |
| CN1422839A (en) * | 2001-12-07 | 2003-06-11 | 北京燕山石油化工公司研究院 | Preparation method for active chromium of organic acid |
| KR101482962B1 (en) * | 2014-03-05 | 2015-01-15 | 아주대학교산학협력단 | Chromium compound, catalyst system comprising the same, and method for polymerization of olefin using the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3968135A (en) * | 1970-01-19 | 1976-07-06 | Aerojet-General Corporation | Chromium salt catalysts |
| US3932285A (en) * | 1973-10-03 | 1976-01-13 | Tenneco Chemicals, Inc. | Chromium salt compositions and a process for their production |
| CN1422839A (en) * | 2001-12-07 | 2003-06-11 | 北京燕山石油化工公司研究院 | Preparation method for active chromium of organic acid |
| KR101482962B1 (en) * | 2014-03-05 | 2015-01-15 | 아주대학교산학협력단 | Chromium compound, catalyst system comprising the same, and method for polymerization of olefin using the same |
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