CN116060124B - Oil-soluble organic metal salt composition and preparation method and application thereof - Google Patents
Oil-soluble organic metal salt composition and preparation method and application thereof Download PDFInfo
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- CN116060124B CN116060124B CN202111278243.8A CN202111278243A CN116060124B CN 116060124 B CN116060124 B CN 116060124B CN 202111278243 A CN202111278243 A CN 202111278243A CN 116060124 B CN116060124 B CN 116060124B
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- salt composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 163
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 82
- 239000002184 metal Substances 0.000 title claims abstract description 82
- 150000003839 salts Chemical class 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 62
- 239000011733 molybdenum Substances 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 49
- 150000007524 organic acids Chemical class 0.000 claims abstract description 49
- 238000002156 mixing Methods 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 41
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 31
- 239000010941 cobalt Substances 0.000 claims abstract description 31
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003960 organic solvent Substances 0.000 claims abstract description 25
- 239000004793 Polystyrene Substances 0.000 claims abstract description 23
- 239000004005 microsphere Substances 0.000 claims abstract description 23
- 229920002223 polystyrene Polymers 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 13
- 125000002524 organometallic group Chemical group 0.000 claims description 67
- 239000000295 fuel oil Substances 0.000 claims description 25
- -1 molybdenum ions Chemical class 0.000 claims description 20
- OVBFMEVBMNZIBR-UHFFFAOYSA-N 2-methylvaleric acid Chemical compound CCCC(C)C(O)=O OVBFMEVBMNZIBR-UHFFFAOYSA-N 0.000 claims description 18
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims description 17
- NKBWMBRPILTCRD-UHFFFAOYSA-N 2-Methylheptanoic acid Chemical compound CCCCCC(C)C(O)=O NKBWMBRPILTCRD-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 14
- 239000003921 oil Substances 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 11
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- 235000012431 wafers Nutrition 0.000 claims description 9
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 claims description 8
- CWYNKKGQJYAHQG-UHFFFAOYSA-N 4-pentylbenzoic acid Chemical compound CCCCCC1=CC=C(C(O)=O)C=C1 CWYNKKGQJYAHQG-UHFFFAOYSA-N 0.000 claims description 8
- OBKXEAXTFZPCHS-UHFFFAOYSA-N 4-phenylbutyric acid Chemical compound OC(=O)CCCC1=CC=CC=C1 OBKXEAXTFZPCHS-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- WSWMGHRLUYADNA-UHFFFAOYSA-N 7-nitro-1,2,3,4-tetrahydroquinoline Chemical compound C1CCNC2=CC([N+](=O)[O-])=CC=C21 WSWMGHRLUYADNA-UHFFFAOYSA-N 0.000 claims description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 7
- 150000002891 organic anions Chemical class 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- GMQQCOYAGZTOEF-UHFFFAOYSA-N 2,5-dimethyloctanoic acid Chemical compound CCCC(C)CCC(C)C(O)=O GMQQCOYAGZTOEF-UHFFFAOYSA-N 0.000 claims description 6
- JFKUBRAOUZEZSL-UHFFFAOYSA-N 4-butylbenzoic acid Chemical compound CCCCC1=CC=C(C(O)=O)C=C1 JFKUBRAOUZEZSL-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 6
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 6
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 claims description 5
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 5
- RCVXVULZIOSNEI-UHFFFAOYSA-N 4-ethylheptanoic acid Chemical compound CCCC(CC)CCC(O)=O RCVXVULZIOSNEI-UHFFFAOYSA-N 0.000 claims description 5
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000002356 single layer Substances 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
- ZTEHOZMYMCEYRM-UHFFFAOYSA-N 1-chlorodecane Chemical compound CCCCCCCCCCCl ZTEHOZMYMCEYRM-UHFFFAOYSA-N 0.000 claims description 4
- OVBFMEVBMNZIBR-UHFFFAOYSA-M 2-methylvalerate Chemical compound CCCC(C)C([O-])=O OVBFMEVBMNZIBR-UHFFFAOYSA-M 0.000 claims description 4
- CEUINTRVKVNPRT-UHFFFAOYSA-N 2-phenyloctanoic acid Chemical compound CCCCCCC(C(O)=O)C1=CC=CC=C1 CEUINTRVKVNPRT-UHFFFAOYSA-N 0.000 claims description 4
- MCLMZMISZCYBBG-UHFFFAOYSA-N 3-ethylheptanoic acid Chemical compound CCCCC(CC)CC(O)=O MCLMZMISZCYBBG-UHFFFAOYSA-N 0.000 claims description 4
- PWKJMPFEQOHBAC-UHFFFAOYSA-N 4-Ethyloctanoic acid Chemical compound CCCCC(CC)CCC(O)=O PWKJMPFEQOHBAC-UHFFFAOYSA-N 0.000 claims description 4
- JFKUBRAOUZEZSL-UHFFFAOYSA-M 4-butylbenzoate Chemical compound CCCCC1=CC=C(C([O-])=O)C=C1 JFKUBRAOUZEZSL-UHFFFAOYSA-M 0.000 claims description 4
- VSUKEWPHURLYTK-UHFFFAOYSA-N 4-heptylbenzoic acid Chemical compound CCCCCCCC1=CC=C(C(O)=O)C=C1 VSUKEWPHURLYTK-UHFFFAOYSA-N 0.000 claims description 4
- FLRVNGMVEBEPQG-UHFFFAOYSA-N 4-nonylbenzoic acid Chemical compound CCCCCCCCCC1=CC=C(C(O)=O)C=C1 FLRVNGMVEBEPQG-UHFFFAOYSA-N 0.000 claims description 4
- CWYNKKGQJYAHQG-UHFFFAOYSA-M 4-pentylbenzoate Chemical compound CCCCCC1=CC=C(C([O-])=O)C=C1 CWYNKKGQJYAHQG-UHFFFAOYSA-M 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- XSIFPSYPOVKYCO-UHFFFAOYSA-N benzoic acid butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 4
- 239000010779 crude oil Substances 0.000 claims description 4
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004914 cyclooctane Substances 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 4
- 229940094933 n-dodecane Drugs 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229950009215 phenylbutanoic acid Drugs 0.000 claims description 4
- DYWSVUBJGFTOQC-UHFFFAOYSA-N xi-2-Ethylheptanoic acid Chemical compound CCCCCC(CC)C(O)=O DYWSVUBJGFTOQC-UHFFFAOYSA-N 0.000 claims description 4
- KZDTZHQLABJVLE-UHFFFAOYSA-N 1,8-diiodooctane Chemical compound ICCCCCCCCI KZDTZHQLABJVLE-UHFFFAOYSA-N 0.000 claims description 3
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 claims description 3
- AYMUQTNXKPEMLM-UHFFFAOYSA-N 1-bromononane Chemical compound CCCCCCCCCBr AYMUQTNXKPEMLM-UHFFFAOYSA-N 0.000 claims description 3
- COYMEIBAQDZJCT-UHFFFAOYSA-N 2-phenylnonanoic acid Chemical compound CCCCCCCC(C(O)=O)C1=CC=CC=C1 COYMEIBAQDZJCT-UHFFFAOYSA-N 0.000 claims description 3
- HWXRWNDOEKHFTL-UHFFFAOYSA-N 2-propylhexanoic acid Chemical compound CCCCC(C(O)=O)CCC HWXRWNDOEKHFTL-UHFFFAOYSA-N 0.000 claims description 3
- YCYMCMYLORLIJX-UHFFFAOYSA-N 2-propyloctanoic acid Chemical compound CCCCCCC(C(O)=O)CCC YCYMCMYLORLIJX-UHFFFAOYSA-N 0.000 claims description 3
- CPEPWESLFZVUEP-UHFFFAOYSA-N 4-hexylbenzoic acid Chemical compound CCCCCCC1=CC=C(C(O)=O)C=C1 CPEPWESLFZVUEP-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- VSOYJNRFGMJBAV-UHFFFAOYSA-N N.[Mo+4] Chemical class N.[Mo+4] VSOYJNRFGMJBAV-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 claims description 3
- BZMHWDRSBWYALX-UHFFFAOYSA-L dichlorocobalt tetrahydrate Chemical compound O.O.O.O.Cl[Co]Cl BZMHWDRSBWYALX-UHFFFAOYSA-L 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 3
- 229940078552 o-xylene Drugs 0.000 claims description 3
- ZBZSVGXZAPNCSY-UHFFFAOYSA-N phenyl octanoate Chemical compound CCCCCCCC(=O)OC1=CC=CC=C1 ZBZSVGXZAPNCSY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 230000004580 weight loss Effects 0.000 claims description 3
- RBBNTRDPSVZESY-UHFFFAOYSA-N 1,10-dichlorodecane Chemical compound ClCCCCCCCCCCCl RBBNTRDPSVZESY-UHFFFAOYSA-N 0.000 claims description 2
- CKJCTZAIDVFHCX-UHFFFAOYSA-N 1,10-diiododecane Chemical compound ICCCCCCCCCCI CKJCTZAIDVFHCX-UHFFFAOYSA-N 0.000 claims description 2
- JMGRNJZUQCEJDB-UHFFFAOYSA-N 1,9-dichlorononane Chemical compound ClCCCCCCCCCCl JMGRNJZUQCEJDB-UHFFFAOYSA-N 0.000 claims description 2
- IKPSIIAXIDAQLG-UHFFFAOYSA-N 1-bromoundecane Chemical compound CCCCCCCCCCCBr IKPSIIAXIDAQLG-UHFFFAOYSA-N 0.000 claims description 2
- RKAMCQVGHFRILV-UHFFFAOYSA-N 1-chlorononane Chemical compound CCCCCCCCCCl RKAMCQVGHFRILV-UHFFFAOYSA-N 0.000 claims description 2
- SKIDNYUZJPMKFC-UHFFFAOYSA-N 1-iododecane Chemical compound CCCCCCCCCCI SKIDNYUZJPMKFC-UHFFFAOYSA-N 0.000 claims description 2
- UWLHSHAHTBJTBA-UHFFFAOYSA-N 1-iodooctane Chemical compound CCCCCCCCI UWLHSHAHTBJTBA-UHFFFAOYSA-N 0.000 claims description 2
- FKUQOQPBCHJHAP-UHFFFAOYSA-N 1-iodoundecane Chemical compound CCCCCCCCCCCI FKUQOQPBCHJHAP-UHFFFAOYSA-N 0.000 claims description 2
- DYWSVUBJGFTOQC-UHFFFAOYSA-M 2-ethylheptanoate Chemical compound CCCCCC(CC)C([O-])=O DYWSVUBJGFTOQC-UHFFFAOYSA-M 0.000 claims description 2
- CVKMFSAVYPAZTQ-UHFFFAOYSA-M 2-methylhexanoate Chemical compound CCCCC(C)C([O-])=O CVKMFSAVYPAZTQ-UHFFFAOYSA-M 0.000 claims description 2
- CVKMFSAVYPAZTQ-UHFFFAOYSA-N 2-methylhexanoic acid Chemical compound CCCCC(C)C(O)=O CVKMFSAVYPAZTQ-UHFFFAOYSA-N 0.000 claims description 2
- CPEPWESLFZVUEP-UHFFFAOYSA-M 4-hexylbenzoate Chemical compound CCCCCCC1=CC=C(C([O-])=O)C=C1 CPEPWESLFZVUEP-UHFFFAOYSA-M 0.000 claims description 2
- ZQLDNJKHLQOJGE-UHFFFAOYSA-M 4-octylbenzoate Chemical compound CCCCCCCCC1=CC=C(C([O-])=O)C=C1 ZQLDNJKHLQOJGE-UHFFFAOYSA-M 0.000 claims description 2
- ZQLDNJKHLQOJGE-UHFFFAOYSA-N 4-octylbenzoic acid Chemical compound CCCCCCCCC1=CC=C(C(O)=O)C=C1 ZQLDNJKHLQOJGE-UHFFFAOYSA-N 0.000 claims description 2
- YLCGEXHMSVRUFA-UHFFFAOYSA-N 5-chloroundecane Chemical compound CCCCCCC(Cl)CCCC YLCGEXHMSVRUFA-UHFFFAOYSA-N 0.000 claims description 2
- ZVSXKFNTWOIGJI-UHFFFAOYSA-N 7-phenyl heptanoic acid Chemical compound OC(=O)CCCCCCC1=CC=CC=C1 ZVSXKFNTWOIGJI-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 claims description 2
- 239000011280 coal tar Substances 0.000 claims description 2
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- USVUMWSMZMQXIZ-UHFFFAOYSA-N phenyl heptanoate Chemical compound CCCCCCC(=O)OC1=CC=CC=C1 USVUMWSMZMQXIZ-UHFFFAOYSA-N 0.000 claims description 2
- UHGWBEXBBNLGCZ-UHFFFAOYSA-N phenyl nonanoate Chemical compound CCCCCCCCC(=O)OC1=CC=CC=C1 UHGWBEXBBNLGCZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical group 0.000 claims 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 claims 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 208000012839 conversion disease Diseases 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 150000002751 molybdenum Chemical class 0.000 description 20
- 150000001868 cobalt Chemical class 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 238000004821 distillation Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 239000007790 solid phase Substances 0.000 description 10
- 238000000967 suction filtration Methods 0.000 description 10
- 239000000725 suspension Substances 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000013110 organic ligand Substances 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 1
- YCYMCMYLORLIJX-UHFFFAOYSA-M 2-propyloctanoate Chemical compound CCCCCCC(C([O-])=O)CCC YCYMCMYLORLIJX-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an oil-soluble organic metal salt composition, a preparation method and application thereof. The preparation method of the oil-soluble organic metal salt composition comprises the steps of firstly mixing a cobalt source, inorganic acid and an organic solvent to prepare a first material flow; then reacting with the first organic acid to obtain a second material flow; uniformly mixing a molybdenum source, an organic solvent and polystyrene microspheres to obtain a third material flow; uniformly mixing the third material flow, the first organic acid and the second organic acid, adding a reaction accelerator, and completing the reaction to obtain a fourth material flow; finally, the second material flow and the fourth material flow are uniformly mixed, and the organic metal salt composition is obtained after further separation. The preparation method of the organic metal salt composition has the characteristics of simple and convenient process, high reaction conversion rate, safe and environment-friendly production process, and is beneficial to industrial production and application.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and relates to an oil-soluble organic metal salt composition, a preparation method and application thereof.
Background
At the same time, the trend of inferior and heavy crude oil resources is becoming more and more remarkable. Along with the increase of the shortage of high-quality crude oil, the production of light component products by high-efficiency hydrogenation using inferior heavy oil, residual oil and vacuum residual oil as raw materials is becoming an important means for producing light oil products. Heavy oil hydrogenation processes currently developed are fixed bed, moving bed, ebullated bed and slurry bed (also known as suspended bed) processes. When heavy oil is processed by a fixed bed, the supported catalyst is easy to deactivate due to coking and has short service life, so that poor heavy oil with high colloid, asphaltene and heavy metal content is difficult to treat efficiently. The catalyst utilization rate of the moving bed and ebullated bed process technology is high, the running period of the device is long, and the application range of the raw oil can be widened. The slurry bed hydrogenation process makes the finely dispersed catalyst or additive, the raw oil and hydrogen pass through the reactor together, so that the slurry bed hydrogenation process has strong adaptability and can process various inferior residual oil. Therefore, slurry bed hydrogenation has the characteristics of strong raw material adaptability and remarkable economic benefit, and the related technology also becomes a hot spot in the processing of inferior heavy oil.
In the prior art, various patents report the preparation and application of oil-soluble dispersed organic metal salt catalysts. Patent CN 107867993A discloses a preparation method of an organic metal salt composition, the active metal component of the organic metal salt prepared by the method is up to 15.8%, and molybdenum has +3, +4, +5 mixed valence state, and after presulfiding, the molybdenum exists in a highly dispersed single-layer structure in residual oil, and has good catalytic activity. In addition, patent CN 110237866A discloses a preparation method of an oil-soluble sulfur catalyst, which comprises the steps of firstly reacting a benzene compound with sulfide to produce an organic ligand, then mixing active metal with the organic ligand, and forming the oil-soluble sulfur catalyst under the promotion of halogenated salts such as sodium chloride and the like, wherein the obtained catalyst has the characteristics of small addition and high activity, and can be used for efficiently converting and removing impurities from colloidal asphalt under the condition of small addition (less than or equal to 350 ppm).
Disclosure of Invention
Aiming at the defects existing in the prior art, the main purpose of the invention is to provide an oil-soluble organic metal salt composition, a preparation method and application thereof, and the provided organic metal salt composition has the characteristics of high content of active metal components, good dispersibility, fluidity and thermal stability, wherein the total metal content in the organic metal salt composition is higher than 20%.
In order to achieve the above object, the present invention provides in a first aspect an oil-soluble organometallic salt composition comprising molybdenum ions, cobalt ions, and an organic anion bonded to both metal ions; the organic anions are one or more of organic carboxylate radicals with carbon atoms of C6-C11 and containing branched chains, and one or more of organic carboxylate radicals with benzene rings and total carbon atoms of C10-C16.
Further, in the oil-soluble organic metal salt composition, the total metal content in the composition is more than or equal to 20wt% based on elements, wherein the cobalt content is more than or equal to 2wt% and the main active metal molybdenum content is more than or equal to 18wt%; wherein, on the valence distribution of molybdenum, 10.8 percent is more than or equal to 2.4 percent of Mo 4+≥3.6%,7.2%≥Mo5+≥3.6%,7.2%≥Mo6+.
Further, in the oil-soluble organic metal salt composition, the organic anion may be specifically selected from one or more of 2-methylpentanoate, 2-methylheptanoate, 2-ethylheptanoate, 3-ethylheptanoate, 4-ethylheptanoate, 2-methylhexanoate, 2-ethylhexyl ate, 2, 5-dimethyloctanoate, 7-dimethyloctanoate, 4-ethyloctanoate, 2-propyloctanoate, 4-butylbenzoate, 4-pentylbenzoate, 4-hexylbenzoate, 4-heptylbenzoate, 4-octylbenzoate, 4-nonylbenzoate, phenylbutyrate, phenylpentanoate, phenylheptanoate, phenyloctanoate, phenylnonanoate, preferably one or more of 2-methylpentanoate, 2-ethylhexyl ate, 4-butylbenzoate, 4-pentylbenzoate, phenylbutyrate and phenyloctanoate.
Further, in the oil-soluble organic metal salt composition, the dynamic viscosity mu 40 of the organic metal salt composition is 75-150 mPa.s at 40 ℃; the weight loss 50% temperature T 50 is not lower than 280 ℃; the proportion of single-layer MoS 2 wafers in the as-sulfided MoS 2 wafers in the sulfide formation is > 90%.
In order to achieve the above object, a second aspect of the present invention provides a method for producing an oil-soluble organometallic salt composition, comprising the steps of:
(1) Under the contact condition, uniformly mixing a cobalt source, inorganic acid and an organic solvent to obtain a first material flow;
(2) Under the contact condition, mixing the first material flow and the first organic acid uniformly, and obtaining a second material flow after reaction;
(3) Uniformly mixing a molybdenum source, an organic solvent and polystyrene microspheres under a contact condition to obtain a third material flow;
(4) Uniformly mixing the third material flow, the first organic acid and the second organic acid, then adding a reaction promoter, and reacting to obtain a fourth material flow;
(5) The second stream and the fourth stream are mixed uniformly and further separated to obtain the organic metal salt composition.
Further, in the above-mentioned method for preparing the organometallic salt composition, the cobalt source may be selected from one or more of cobalt oxide, hydroxide, nitrate, sulfate, hydrochloride and basic carbonate, preferably cobalt hydroxide and/or nitrate. Further, the cobalt source may be specifically selected from one or more of cobaltosic oxide, cobalt hydroxide, cobalt nitrate, cobalt sulfate, anhydrous cobalt chloride, tetrahydrate cobalt chloride, hexahydrate cobalt chloride, and basic cobalt carbonate.
Further, in the above-mentioned method for producing an organometallic salt composition, the organic solvent may be one or more of C1-C3 alkylbenzene, C6-C12 linear alkane, and C6-C12 cycloalkane. Wherein, the C1-C3 alkylbenzene can be one or more of toluene, ethylbenzene, o-xylene, m-xylene, p-xylene and isopropylbenzene, and is preferably p-xylene and/or isopropylbenzene; the C6-C12 linear alkane can be selected from one or more of n-heptane, n-octane, n-decane, n-nonane and n-dodecane, and is preferably n-octane and/or n-dodecane; the C6-C12 cycloalkane may be one or more selected from cyclohexane, cyclooctane and cyclododecane, preferably cyclohexane and/or cyclooctane.
Further, in the above-mentioned method for producing an organometallic salt composition, the first organic acid is an organic carboxylic acid having a carbon number of from C6 to C11 and containing a branched chain, and specifically may be at least one selected from 2-methylpentanoic acid, 2-methylheptanoic acid, 2-ethylheptanoic acid, 3-ethylheptanoic acid, 4-ethylheptanoic acid, 2-methylhexanoic acid, 2-ethylhexanoic acid, 2-propylhexanoic acid, 2, 5-dimethyloctanoic acid, 7-dimethyloctanoic acid, 4-ethyloctanoic acid, 2-propyloctanoic acid, preferably 2-methylpentanoic acid and/or 2-ethylhexanoic acid.
Further, in the above-mentioned method for producing an organometallic salt composition, the molybdenum source may be selected from one or more of molybdenum halides, molybdenum oxides, molybdenum alkali metal salts, molybdenum ammonium salts, and molybdic acids, and preferably molybdenum ammonium salts and/or molybdic acids. Further, the molybdenum source may be specifically selected from one or more of molybdenum hexafluoride, molybdenum trioxide, potassium molybdate, sodium molybdate, calcium molybdate, ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate, and molybdic acid.
Further, in the preparation method of the organic metal salt composition, the second organic acid is an organic carboxylic acid containing a benzene ring and having a total carbon number of 10 to 16, wherein the carboxyl group may be directly connected to the benzene ring or may not be directly connected to the benzene ring; when the carboxyl group is on the benzene ring, the second organic acid may be at least one selected from 4-butylbenzoic acid, 4-pentylbenzoic acid, 4-hexylbenzoic acid, 4-heptylbenzoic acid, 4-octylbenzoic acid, 4-nonylbenzoic acid, preferably 4-butylbenzoic acid and/or 4-pentylbenzoic acid; when the carboxyl group is not directly connected with the benzene ring, the second organic acid is phenylalkyl carboxylic acid, and specifically can be at least one of phenylbutyric acid, phenylvaleric acid, phenylheptanoic acid, phenyloctanoic acid and phenylnonanoic acid, and preferably phenylbutyric acid and/or phenyloctanoic acid.
Further, in the preparation method of the organometallic salt composition, the inorganic acid in the step (1) is one or more of sulfuric acid, nitric acid and hydrochloric acid.
Further, in the preparation method of the organometallic salt composition, in the step (4), the reaction promoter is halogenated alkane, and the halogenated alkane has 6 to 15 carbon atoms, preferably Cl, br and I; specifically, the solvent may be at least one selected from chlorooctane, bromooctane, iodooctane, 1, 8-diiodooctane, chlorononane, 1, 9-dichlorononane, 1-trichlorononane, bromononane, chlorodecane, 1, 10-dichlorodecane, bromodecane, iododecane, 1, 10-diiododecane, chloroundecane, bromoundecane and iodoundecane, preferably at least one selected from chlorooctane, bromooctane and chlorodecane.
Further, in the preparation method of the organometallic salt composition, the dosages of the molybdenum source, the cobalt source, the inorganic acid, the organic solvent, the first organic acid, the second organic acid, the reaction accelerator and the polystyrene microsphere are respectively as follows in parts by weight: 100 parts of molybdenum source, 10-30 parts of cobalt source, 0.5-6 parts of inorganic acid, 100-1000 parts of organic solvent, 225-900 parts of first organic acid, 25-100 parts of second organic acid, 0.02-2.5 parts of reaction accelerator and 1-10 parts of polystyrene microsphere; preferably 100 parts of molybdenum source, 12-20 parts of cobalt source, 0.6-4 parts of inorganic acid, 275-750 parts of organic solvent, 337.5-675 parts of first organic acid, 37.5-75 parts of second organic acid, 0.2-2 parts of reaction accelerator and 2-6 parts of polystyrene microsphere.
Further, in the preparation method of the organic metal salt composition, the organic solvent in the step (1) is used in an amount of 50 to 200 parts by weight, preferably 75 to 150 parts by weight, and the organic solvent in the step (3) is used in an amount of 50 to 800 parts by weight, preferably 200 to 600 parts by weight.
Further, in the preparation method of the organic metal salt composition, the amount of the first organic acid used in the step (2) is 50 to 200 parts by weight, preferably 75 to 150 parts by weight, and the amount of the first organic acid used in the step (4) is 175 to 700 parts by weight, preferably 262.5 to 525 parts by weight.
Further, in the above-mentioned method for producing an organometallic salt composition, the mixing temperature in the step (1) is 40 to 120 ℃, preferably 60 to 100 ℃.
Further, in the above-mentioned method for producing an organometallic salt composition, the reaction temperature in the step (2) is 100 to 250 ℃, preferably 120 to 200 ℃, and the reaction time is 2 to 10 hours, preferably 4 to 8 hours.
Further, in the above-mentioned method for producing an organometallic salt composition, the mixing temperature in the step (3) is 40 to 120 ℃, preferably 60 to 100 ℃.
Further, in the preparation method of the organometallic salt composition, the reaction temperature in the step (4) is 120 to 300 ℃, preferably 150 to 250 ℃; the reaction time is 4 to 24 hours, preferably 8 to 20 hours.
Further, in the above-mentioned method for producing an organometallic salt composition, the mixing temperature in the step (5) is 100 to 160 ℃, preferably 120 to 150 ℃.
Further, in the preparation method of the organic metal salt composition, water generated by the reaction is removed in a reflux manner in the reaction process in the step (2) and the step (4).
Further, in the above-mentioned method for preparing an organometallic salt composition, the separation process in the step (5) generally comprises two operations of suction filtration and distillation, typically, suction filtration is performed to remove the solid phase first, and then distillation is further performed to remove the solvent, wherein the distillation is preferably performed by vacuum distillation, the operation pressure of the vacuum distillation is 1.3-2.0 KPa, the operation temperature is 120-180 ℃, and the distillation end point can be determined according to the total amount of the remaining materials being 250-300 parts.
In a third aspect, the present invention provides a method for hydrogenating inferior heavy oil, comprising contacting the inferior heavy oil with the above-mentioned organometallic salt composition in the presence of hydrogen and carrying out hydrogenation reaction.
Further, in the above-mentioned inferior heavy oil hydrogenation method, the inferior heavy oil may be one or more of heavy distillate oil, atmospheric residuum, vacuum residuum, coal tar, catalytic slurry oil, crude oil, and other raw materials.
Further, in the above-mentioned inferior heavy oil hydrogenation method, the reaction conditions are generally as follows: the reaction pressure is 14-20 MPa, the reaction temperature is 380-420 ℃, and the reaction time is 1-20 h.
Further, in the inferior heavy oil hydrogenation method, the concentration of the organic metal salt composition in the inferior heavy oil is 200-2000mg/kg.
Furthermore, in the above-mentioned inferior heavy oil hydrogenation method, the organometallic salt composition generally needs to be vulcanized before use, and a person skilled in the art can select a proper vulcanization mode according to actual situations and needs.
Further, in the above-mentioned inferior heavy oil hydrogenation method, the reactor used in the hydrogenation reaction may be a slurry bed reactor and/or a suspended bed reactor.
Compared with the prior art, the oil-soluble organic metal salt composition and the preparation method and application thereof have the following advantages:
(1) The oil-soluble organic metal salt composition provided by the invention has the characteristics of high content of active metal components, good dispersibility, good fluidity and good thermal stability, wherein the total metal content in the organic metal salt composition is higher than 20%, the molybdenum content of the active metal components is higher than 18%, and the maximum value of the molybdenum content in the organic metal salt composition prepared by the prior art is generally lower than 16%, so that the method provided by the invention obviously improves the molybdenum content in the product, and can improve the catalytic activity of the material when the catalyst is used for poor heavy oil hydrogenation catalytic materials. Meanwhile, the organic metal salt composition prepared by the method has good fluidity, can greatly promote dilution and dispersion in inferior heavy oil, has good thermal stability, is favorable for keeping stable structure before presulfiding, and avoids active metal components from gathering and reducing activity due to premature decomposition in a heating stage of a hydrogenation device in the use process. Solves the technical problems that when the existing oil-soluble organic metal salt product is used, the product is decomposed in advance in the heating stage so as to generate aggregation in the reaction stage, and the hydrogenation activity of the nano-scale catalyst particles is seriously affected.
(2) According to the preparation method of the organic metal salt composition, nano-scale polystyrene microspheres with the particle size of monodisperse distribution are introduced, the nano-scale polystyrene microspheres are adsorbed at an inorganic molybdenum particle/organic solvent interface to form a Pickering emulsion, the Pickering emulsion has strong stability, the inorganic molybdenum particles are highly dispersed in the organic solvent, active sites are fully exposed, the reaction efficiency of an organic ligand and molybdenum is greatly improved under the further promotion of halogenated alkane, the molybdenum content in the molybdenum salt composition is improved, and meanwhile, the molybdenum salt composition with the molybdenum in a highly dispersed state can be obtained.
(3) In the preparation method of the organic metal salt composition, the auxiliary catalytic metal cobalt is introduced as the second metal component, and the stability and the dispersibility of the active metal component molybdenum are improved by introducing cobalt. Meanwhile, two 4s orbitals exist in the arrangement of the cobalt electronic layer, compared with 5s 1 and 34 d orbitals of molybdenum, the attraction capacity to sulfur is stronger, so that the presulfiding process of the cobalt-molybdenum bimetallic organic salt composition is more sufficient compared with that of the single-metal organic salt composition, and the catalytic activity of MoS 2 after presulfiding is higher.
(4) In the preparation method of the organic metal salt composition, the first organic acid and the second organic acid are used together as the composite organic ligand of molybdenum, the aromatic ring structure in the second organic acid provides larger steric hindrance, the generation of low-valence molybdenum, especially tetravalent molybdenum, is promoted, and the relative content of molybdenum is improved. Meanwhile, the interaction between the aromatic ring structure in the second organic acid and the inferior heavy oil raw material promotes the miscibility of the organic metal salt composition and the inferior heavy oil raw material. In addition, under the coordination of the two ligands, especially the use of the second organic acid obviously improves the heat stability of the organic metal salt composition, avoids the severe decomposition of the organic metal salt composition before the presulfiding reaction, leads to the aggregation of active metal components and reduces the catalytic efficiency
(5) The preparation method of the organic metal salt composition has the characteristics of simple and convenient process, high reaction conversion rate, safe and environment-friendly production process, and is beneficial to industrial production and application.
Drawings
FIG. 1 is a graph of the microscopic morphology of MoS 2 after vulcanization of the sample prepared in example 1 of the present invention.
FIG. 2 is a graph of the microscopic morphology of MoS 2 after vulcanization of the comparative example 2 preparation of the present invention.
Detailed Description
The following describes the preparation and use of the organometallic salt compositions of the present invention by way of specific examples, but is not intended to limit the invention.
The molybdenum content of the organic metal salt composition in the embodiment and the comparative example is measured by using an inductively coupled plasma emission spectrometer of the Shimadzu corporation ICPE-9000 full spectrum type; the metal valence state of molybdenum is analyzed by adopting an X-ray photoelectric energy spectrum of Siemens Feishul ESCALAB-250Xi, and the peak area is calculated after the peak separation treatment of the obtained XPS spectrogram to obtain the proportion of molybdenum in different valence states; the dynamic viscosity of the organometallic salt composition product is measured according to ASTM D5018-2018; the thermal stability of the organometallic salt composition product was analyzed using a mertler TGA-2 thermogravimetric analyzer. The morphology of the MoS2 wafer was characterized using a JEM-2200FS type 200kV energy filtered field emission transmission electron microscope (JEOL) from Japanese electronics Co.
The organometal salt composition of the examples and comparative examples of the present invention had a dynamic viscosity of mu 40 at 40 ℃; the temperature corresponding to the weight loss of the organic metal salt composition reaching 50% is T 50; the statistical proportion of single-layer MoS 2 wafers in the transmission electron microscope photo is N 1%
The ratios of materials appearing in all examples and comparative examples below are generally ratios of parts by weight of materials without special emphasis.
The polystyrene microspheres described in the examples and comparative examples of the present invention may be prepared using methods known in the art, such as those described in CN 109988333A.
Example 1
15.4 Parts of cobalt nitrate, 1.4 parts of hydrochloric acid and 94 parts of isopropylbenzene are fully and uniformly mixed at 92 ℃, 82 parts of 2-methyl valeric acid is added, the temperature is raised to 188 ℃ after the fully and uniformly mixed, and the organic cobalt salt composition is obtained after the reaction for 6.5 hours at the same temperature. 100 parts of molybdenum hexafluoride, 352 parts of n-decane, 5.8 parts of polystyrene microspheres (average particle diameter 433 nm) were thoroughly mixed at 87.5℃to form a homogeneous suspension. Then 282.5 parts of 2-methylheptanoic acid and 44.5 parts of 4-amyl benzoic acid are added and uniformly mixed at the same temperature. Adding 1.5 parts of bromooctane into the system, fully and uniformly mixing, heating to 238 ℃, reacting at the temperature for 18.5 hours, and stopping the reaction to obtain the organic molybdenum salt composition. The organic molybdenum salt composition and the organic cobalt salt composition are fully and uniformly mixed at 144 ℃, then the solid phase is removed by suction filtration, reduced pressure distillation is carried out at 1.53KPa and 151 ℃, and the total amount of the residual materials is 272 parts, so as to obtain the organic metal salt composition. The total metal content of the organometallic salt composition was 21.6wt%, wherein the cobalt content was 2.2wt%, the molybdenum content was 19.4wt%, and the Mo 4+、Mo5+、Mo6+ content was 10.6wt%, 5.2wt%, 3.6wt%, μ 40=99mPa·s,T50=320℃,N1% = 94.5%, respectively.
Example 2
Uniformly mixing 10 parts of cobaltosic oxide, 0.5 part of nitric acid and 50 parts of n-heptane at 40 ℃, adding 50 parts of 4-ethylheptanoic acid, uniformly mixing, heating to 100 ℃, and reacting for 2 hours at the same temperature to obtain an organic cobalt salt composition; 100 parts of potassium molybdate, 50 parts of cyclohexane and 1 part of polystyrene microspheres (average particle diameter 185 nm) were thoroughly mixed at 60℃to form a uniform suspension system. Then 700 parts of 2-ethylheptanoic acid and 100 parts of 4-amyl benzoic acid are added and uniformly mixed at the same temperature. Adding 0.02 part of chlorooctane into the system, fully and uniformly mixing, heating to 150 ℃, reacting for 20 hours at the temperature, and obtaining the organic molybdenum salt composition after the reaction. And fully and uniformly mixing the organic molybdenum salt composition and the organic cobalt salt composition at 100 ℃, filtering to remove solid phase by suction, and carrying out reduced pressure distillation at 1.3KPa and 120 ℃ to obtain the organic metal salt composition, wherein the total amount of the residual materials is 250 parts. The total metal content of the organometallic salt composition was 20.5wt%, wherein the cobalt content was 2.3wt%, the molybdenum content was 18.2wt%, and the Mo 4+、Mo5+、Mo6+ content was 10.8wt%, 5.0wt%, 2.4wt%, and μ 40=150mPa·s,T50=308℃,N1% = 92.3%, respectively.
Example 3
Mixing 30 parts of cobalt hydroxide, 6 parts of sulfuric acid and 200 parts of paraxylene uniformly at 120 ℃, adding 200 parts of 2-methylheptanoic acid, heating to 200 ℃ after fully mixing, and reacting for 10 hours at the same temperature to obtain the organic cobalt salt composition. 100 parts of molybdenum hexafluoride, 800 parts of o-xylene, 10 parts of polystyrene microspheres (average particle size 323 nm) were thoroughly mixed at 40℃to form a homogeneous suspension. Then 525 parts of 2-methyl valeric acid and 75 parts of phenyl nonanoic acid are added and mixed uniformly at the same temperature. 2.5 parts of bromooctane is added into the system, after fully and uniformly mixing, the temperature is raised to 250 ℃, the reaction is carried out for 8 hours at the temperature, and the organic molybdenum salt composition is obtained after the reaction. The organic molybdenum salt composition and the organic cobalt salt composition are fully and uniformly mixed at the temperature of 126 ℃, and then the solid phase is removed by suction filtration. The distillation under reduced pressure was carried out at 1.66KPa and 174℃to give a total of 300 parts of the remaining materials, to give an organometallic salt composition. The total metal content of the organic metal salt composition is 22.8wt%, wherein the cobalt content is 2.1wt%, the molybdenum content is 20.7wt%, and the Mo 4+、Mo5+、Mo6+ content is 6.3wt%, 7.2wt%, and mu 40=75mPa·s,T50=315℃,N1% = 94.2%, respectively.
Example 4
Mixing 12 parts of cobalt sulfate, 0.6 part of hydrochloric acid and 75 parts of m-xylene uniformly at 60 ℃, adding 75 parts of 2, 5-dimethyl octanoic acid, heating to 120 ℃ after fully mixing uniformly, and reacting for 4 hours at the same temperature to obtain the organic cobalt salt composition. 100 parts of ammonium heptamolybdate, 220 parts of cumene and 2 parts of polystyrene microspheres (average particle size: 143 nm) were thoroughly mixed at 100℃to form a uniform suspension system. Then 262.5 parts of 7, 7-dimethyl octanoic acid and 25 parts of 4-hexyl benzoic acid are added and uniformly mixed at the same temperature. Adding 0.2 part of bromodecane into the system, fully and uniformly mixing, heating to 120 ℃, reacting for 24 hours at the temperature, and obtaining the organic molybdenum salt composition after the reaction. The organic molybdenum salt composition and the organic cobalt salt composition are fully and uniformly mixed at 120 ℃, and then the solid phase is removed by suction filtration. And (3) carrying out reduced pressure distillation at the temperature of 2KPa and 180 ℃, wherein the total amount of the residual materials is 271 parts, and obtaining the organic metal salt composition. The total metal content of the organometallic salt composition was 21.7wt%, wherein the cobalt content was 2.6wt%, the molybdenum content was 19.1wt%, and the Mo 4+、Mo5+、Mo6+ content was 9.6wt%, 3.6wt%, 5.9wt%, μ 40=101mPa·s,T50=298℃,N1% = 96.6%, respectively.
Example 5
Uniformly mixing 20 parts of basic cobalt carbonate, 4 parts of nitric acid and 150 parts of n-nonane at 100 ℃, then adding 75 parts of 7, 7-dimethyl octanoic acid, fully and uniformly mixing, heating to 250 ℃, and reacting for 8 hours at the same temperature to obtain the organic cobalt salt composition. 100 parts of calcium molybdate, 600 parts of n-decane and 6 parts of polystyrene microspheres (average particle diameter 266 nm) were thoroughly mixed at 120℃to form a uniform suspension system. Then 175 parts of 2, 5-dimethyl octanoic acid and 37.5 parts of 4-butyl benzoic acid are added and uniformly mixed at the same temperature. Adding 2 parts of bromononane into the system, fully and uniformly mixing, heating to 300 ℃, reacting for 4 hours at the temperature, and obtaining the organic molybdenum salt composition after the reaction. The organic molybdenum salt composition and the organic cobalt salt composition are fully and uniformly mixed at 160 ℃, and then the solid phase is removed by suction filtration. Vacuum distillation was carried out at 1.38KPa and 162℃with the total amount of the remaining material being 263 parts, to obtain an organometallic salt composition. The total metal content of the organometallic salt composition was 23.0wt%, wherein the cobalt content was 2.3wt%, the molybdenum content was 20.7wt%, and the Mo 4+、Mo5+、Mo6+ content was 7.8wt%, 6.4wt%, 6.5wt%, μ 40=105mPa·s,T50=292℃,N1% = 92.5%, respectively.
Example 6
Mixing 16.5 parts of cobalt chloride tetrahydrate, 3.5 parts of sulfuric acid and 125 parts of n-heptane uniformly at 82 ℃, adding 92 parts of 2-ethylheptanoic acid, heating to 185 ℃ after fully mixing uniformly, and reacting for 5.5 hours at the same temperature to obtain the organic cobalt salt composition. 100 parts of sodium molybdate, 200 parts of n-octane and 3.3 parts of polystyrene microspheres (average particle size 312 nm) were thoroughly mixed at 112℃to form a uniform suspension system. Then 192 parts of 2-propylhexanoic acid and 66 parts of 4-butylbenzoic acid are added and mixed uniformly at the same temperature. Adding 0.65 part of 1, 8-diiodooctane into the system, fully and uniformly mixing, heating to 244 ℃, reacting at the temperature for 11 hours, and obtaining the organic molybdenum salt composition after the reaction. The organic molybdenum salt composition and the organic cobalt salt composition are fully and uniformly mixed at 133 ℃, and then the solid phase is removed by suction filtration. The distillation was carried out under reduced pressure at 1.57KPa and 187℃with the total amount of the remaining materials being 291 parts, to obtain an organometallic salt composition. The total metal content of the organometallic salt composition was 21.6wt%, wherein the cobalt content was 2.6wt%, the molybdenum content was 19.0wt%, and the Mo 4+、Mo5+、Mo6+ content was 8.3wt%, 6.2wt%, 4.5wt%, μ 40=122mPa·s,T50=314℃,N1% = 96.8%, respectively.
Comparative example 1
15.4 Parts of cobalt nitrate, 1.4 parts of hydrochloric acid and 94 parts of isopropylbenzene are fully and uniformly mixed at 92 ℃, 82 parts of 2-methyl valeric acid is added, the temperature is raised to 188 ℃ after the fully and uniformly mixed, and the organic cobalt salt composition is obtained after the reaction for 6.5 hours at the same temperature. 100 parts of molybdenum hexafluoride, 352 parts of n-decane, 5.8 parts of polystyrene microspheres (average particle diameter 433 nm) were thoroughly mixed at 87.5℃to form a homogeneous suspension. Then 282.5 parts of 2-methylheptanoic acid and 44.5 parts of 4-amyl benzoic acid are added, uniformly mixed at the same temperature, then the temperature is raised to 238 ℃, and the reaction is stopped after 18.5 hours of reaction at the temperature, thus obtaining the organic molybdenum salt composition. The organic molybdenum salt composition and the organic cobalt salt composition are fully and uniformly mixed at 144 ℃, then the solid phase is removed by suction filtration, reduced pressure distillation is carried out at 1.53KPa and 151 ℃, and the total amount of the residual materials is 272 parts, so as to obtain the organic metal salt composition. The total metal content of the organometallic salt composition was 15.9wt%, wherein the cobalt content was 2.2wt%, the molybdenum content was 13.7wt%, and the Mo 4+、Mo5+、Mo6+ content was 8.2wt%, 3.2wt%, 2.3wt%, μ 40=62mPa·s,T50=259℃,N1% = 18.2%, respectively.
Comparative example 2
15.4 Parts of cobalt nitrate, 1.4 parts of hydrochloric acid and 94 parts of isopropylbenzene are fully and uniformly mixed at 92 ℃, 82 parts of 2-methyl valeric acid is added, the temperature is raised to 188 ℃ after the fully and uniformly mixed, and the organic cobalt salt composition is obtained after the reaction for 6.5 hours at the same temperature. 100 parts of molybdenum hexafluoride and 352 parts of n-decane are thoroughly mixed at 87.5℃to form a homogeneous suspension. Then 282.5 parts of 2-methylheptanoic acid and 44.5 parts of 4-amyl benzoic acid are added and uniformly mixed at the same temperature. Adding 1.5 parts of bromooctane into the system, fully and uniformly mixing, heating to 238 ℃, reacting at the temperature for 18.5 hours, and stopping the reaction to obtain the organic molybdenum salt composition. The organic molybdenum salt composition and the organic cobalt salt composition are fully and uniformly mixed at 144 ℃, then the solid phase is removed by suction filtration, reduced pressure distillation is carried out at 1.53KPa and 151 ℃, and the total amount of the residual materials is 272 parts, so as to obtain the organic metal salt composition. The total metal content of the organometallic salt composition was 15.6wt%, wherein the cobalt content was 2.2wt%, the molybdenum content was 13.4wt%, and the Mo 4+、Mo5+、Mo6+ content was 8.2wt%, 2.9wt%, 2.3wt%, and μ 40=64mPa·s,T50=252℃,N1% = 8.4%, respectively.
Comparative example 3
15.4 Parts of cobalt nitrate, 1.4 parts of hydrochloric acid and 94 parts of isopropylbenzene are fully and uniformly mixed at 92 ℃, 82 parts of 2-methyl valeric acid is added, the temperature is raised to 188 ℃ after the fully and uniformly mixed, and the organic cobalt salt composition is obtained after the reaction for 6.5 hours at the same temperature. 100 parts of molybdenum hexafluoride, 352 parts of n-decane, 5.8 parts of polystyrene microspheres (average particle diameter 433 nm) were thoroughly mixed at 87.5℃to form a homogeneous suspension. Then 327 parts of 2-methylheptanoic acid are added and mixed uniformly at the same temperature. Adding 1.5 parts of bromooctane into the system, fully and uniformly mixing, heating to 238 ℃, reacting at the temperature for 18.5 hours, and stopping the reaction to obtain the organic molybdenum salt composition. The organic molybdenum salt composition and the organic cobalt salt composition are fully and uniformly mixed at 144 ℃, then the solid phase is removed by suction filtration, reduced pressure distillation is carried out at 1.53KPa and 151 ℃, and the total amount of the residual materials is 272 parts, so as to obtain the organic metal salt composition. The total metal content of the organometallic salt composition was 16.6wt%, wherein the cobalt content was 2.2wt%, the molybdenum content was 14.2wt%, and the Mo 4+、Mo5+、Mo6+ content was 3.2wt%, 3.5wt%, 7.5wt%, and μ 40=41mPa·s,T50=242℃,N1% = 25.6%, respectively.
Evaluation of Performance
The performance of the organic molybdenum catalyst of the examples and the comparative examples is evaluated by using straight-run vacuum residuum of a certain factory as a raw material and using a high-pressure reactor. The process conditions are as follows: the reaction pressure is 16MPa, the reaction temperature is 420 ℃, the reaction time is 2.5h, the adding amount of the organic metal salt composition is 650mg/kg, and the organic metal salt composition can be presulfided in a reactor in the heating process without separate presulfiding operation because the sulfur content in raw oil is higher (3.25 wt%).
The properties of the raw materials for reducing slag and the produced oil are shown in Table 1. As can be seen from the table, when the organic molybdenum catalyst described in examples 1-6 is used for processing the straight-run slag reduction raw material, compared with the raw material density and carbon residue value, the obtained product oil is reduced, meanwhile, the saturated component content in the product composition is generally improved, the saturated component content is improved by 23.7% at most, and the asphaltene content is obviously reduced. The catalyst shows that the organic molybdenum catalyst with high dispersion and good thermal stability has high catalytic activity and strong coke inhibition capability, and is beneficial to the generation of light components. When the organic molybdenum catalyst in comparative examples 1-3 is used for processing the straight-run slag reduction raw material, the saturation fraction in the product is 8.5% lower than that in examples 1-6, and the asphaltene yield is obviously improved. This indicates that the comparative sample has poor dispersibility and thermal stability, resulting in lower catalytic activity, lower hydrocracking efficiency of the feedstock, and severe coking during thermal cracking.
TABLE 1 raw materials for straight run slag reduction and oil-forming properties
As shown in the micro-morphology pairs of the catalysts of the example 1 and the comparative example 2, such as fig. 1 and fig. 2, the MoS 2 wafers formed in the sulfur-containing residual oil by the organomolybdenum catalyst prepared by the method of the example 1 are almost all single-layer wafers, the dispersibility is good, and the active sites are fully exposed; the MoS 2 wafer formed by the organic molybdenum catalyst prepared by the method of comparative example 2 is in a multi-layer stacked shape, has serious aggregation and poor dispersibility, and seriously affects the hydrogenation catalytic activity.
Claims (41)
1. An oil-soluble organic metal salt composition, which comprises molybdenum ions, cobalt ions and organic anions combined with the two metal ions, wherein the organic anions are one or more of organic carboxylate radicals with carbon atoms of C6-C11 and containing branched chains, and one or more of organic carboxylate radicals with benzene rings and total carbon atoms of C10-C16; the total metal content in the oil-soluble organic metal salt composition is more than or equal to 20wt% based on the element, wherein the cobalt content is more than or equal to 2wt% and the molybdenum content is more than or equal to 18wt%; wherein, in the valence distribution of molybdenum, 10.8 percent is more than or equal to 2.4 percent of Mo 4+≥3.6%,7.2%≥Mo5+≥3.6%,7.2%≥Mo6+;
The preparation method of the oil-soluble organic metal salt composition comprises the following steps:
(1) Under the contact condition, uniformly mixing a cobalt source, inorganic acid and an organic solvent to obtain a first material flow;
(2) Under the contact condition, mixing the first material flow and the first organic acid uniformly, and obtaining a second material flow after reaction;
(3) Uniformly mixing a molybdenum source, an organic solvent and polystyrene microspheres under a contact condition to obtain a third material flow;
(4) Uniformly mixing the third material flow, the first organic acid and the second organic acid, then adding a reaction promoter, and reacting to obtain a fourth material flow;
(5) Uniformly mixing the second material flow and the fourth material flow, and further separating to obtain an organic metal salt composition;
wherein the first organic acid is C6-C11 organic carboxylic acid containing branched chains, the second organic acid is C10-C16 organic carboxylic acid containing benzene rings, and the carboxyl is directly connected to the benzene rings or is not directly connected to the benzene rings;
The reaction promoter is halogenated alkane, and the carbon number of the halogenated alkane is 6-15;
The dosages of the molybdenum source, the cobalt source, the inorganic acid, the organic solvent, the first organic acid, the second organic acid, the reaction accelerator and the polystyrene microsphere are respectively as follows: 100 parts of molybdenum source, 10-30 parts of cobalt source, 0.5-6 parts of inorganic acid, 100-1000 parts of organic solvent, 225-900 parts of first organic acid, 25-100 parts of second organic acid, 0.02-2.5 parts of reaction accelerator and 1-10 parts of polystyrene microsphere;
The first organic acid in the step (2) is used in an amount of 50-200 parts by weight, and the first organic acid in the step (4) is used in an amount of 125-700 parts by weight.
2. The oil-soluble organometallic salt composition according to claim 1, wherein the organic anion is selected from one or more of 2-methylpentanoate, 2-methylheptanoate, 2-ethylheptanoate, 3-ethylheptanoate, 4-ethylheptanoate, 2-methylhexanoate, 2-ethylhexyl ate, 2, 5-dimethyloctanate, 7-dimethyloctanate, 4-ethyloctanate, 2-propyloctanate, 4-butylbenzoate, 4-pentylbenzoate, 4-hexylbenzoate, 4-heptylbenzoate, 4-octylbenzoate, 4-nonylbenzoate, phenylbutyrate, phenylpentanoate, phenylheptanoate, phenyloctanate, phenylnonanoate.
3. The oil-soluble organometallic salt composition according to claim 1 or 2, wherein the organic anion is selected from one or more of 2-methylpentanoate, 2-ethylhexanoate, 4-butylbenzoate, 4-pentylbenzoate, phenylbutyrate, phenyloctoate.
4. The oil-soluble organometallic salt composition according to claim 1, wherein the oil-soluble organometallic salt composition has a dynamic viscosity μ 40 of 75 to 150 mPa-s at 40 ℃; the weight loss 50% temperature T 50 is not lower than 280 ℃.
5. The oil-soluble organometallic salt composition according to claim 1, wherein the oil-soluble organometallic salt composition is sulfided to form a single layer MoS 2 wafer fraction of the sulfide state MoS 2 wafers in sulfide of greater than 90%.
6. A process for preparing the oil-soluble organometallic salt composition of any one of claims 1-5, comprising the steps of:
(1) Under the contact condition, uniformly mixing a cobalt source, inorganic acid and an organic solvent to obtain a first material flow;
(2) Under the contact condition, mixing the first material flow and the first organic acid uniformly, and obtaining a second material flow after reaction;
(3) Uniformly mixing a molybdenum source, an organic solvent and polystyrene microspheres under a contact condition to obtain a third material flow;
(4) Uniformly mixing the third material flow, the first organic acid and the second organic acid, then adding a reaction promoter, and reacting to obtain a fourth material flow;
(5) The second stream and the fourth stream are mixed uniformly and further separated to obtain the organic metal salt composition.
7. The method for preparing an oil-soluble organic metal salt composition according to claim 6, wherein the cobalt source is selected from one or more of cobalt oxide, hydroxide, nitrate, sulfate, hydrochloride and basic carbonate.
8. The method for preparing an oil-soluble organometallic salt composition according to claim 6 or 7, wherein the cobalt source is selected from hydroxide and/or nitrate of cobalt.
9. The method for preparing an oil-soluble organometallic salt composition according to claim 6 or 7, wherein the cobalt source is selected from one or more of cobaltosic oxide, cobalt hydroxide, cobalt nitrate, cobalt sulfate, anhydrous cobalt chloride, cobalt chloride tetrahydrate, cobalt chloride hexahydrate, basic cobalt carbonate.
10. The process for producing an oil-soluble organometallic salt composition according to claim 6, wherein the organic solvent is one or more of C1-C3 alkylbenzene, C6-C12 linear alkane, and C6-C12 cycloalkane.
11. The method for producing an oil-soluble organometallic salt composition according to claim 10, wherein the C1 to C3 alkylbenzene is one or more of toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, cumene; the C6-C12 straight-chain alkane is selected from one or more of n-heptane, n-octane, n-decane, n-nonane and n-dodecane; the C6-C12 cycloalkane is selected from one or more of cyclohexane, cyclooctane and cyclododecane.
12. The process for producing an oil-soluble organometallic salt composition according to claim 11, wherein the C1 to C3 alkylbenzene is para-xylene and/or cumene; the straight-chain alkane of C6-C12 is n-octane and/or n-dodecane; the C6-C12 cycloalkane is cyclohexane and/or cyclooctane.
13. The method for preparing an oil-soluble organometallic salt composition according to claim 6, wherein the first organic acid is at least one selected from the group consisting of 2-methylpentanoic acid, 2-methylheptanoic acid, 2-ethylheptanoic acid, 3-ethylheptanoic acid, 4-ethylheptanoic acid, 2-methylhexanoic acid, 2-ethylhexanoic acid, 2-propylhexanoic acid, 2, 5-dimethyloctanoic acid, 7-dimethyloctanoic acid, 4-ethyloctanoic acid, and 2-propyloctanoic acid.
14. The method for preparing an oil-soluble organometallic salt composition according to claim 6 or 13, wherein the first organic acid is 2-methylpentanoic acid and/or 2-ethylhexanoic acid.
15. The method for preparing an oil-soluble organic metal salt composition according to claim 6, wherein the molybdenum source is one or more selected from the group consisting of molybdenum halides, molybdenum oxides, molybdenum alkali metal salts, molybdenum ammonium salts, and molybdic acid.
16. The method for preparing an oil-soluble organometallic salt composition according to claim 6 or 15, wherein the molybdenum source is selected from ammonium salts of molybdenum and/or molybdic acid.
17. The method for preparing an oil-soluble organic metal salt composition according to claim 6 or 15, wherein the molybdenum source is one or more selected from molybdenum hexafluoride, molybdenum trioxide, potassium molybdate, sodium molybdate, ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate, and molybdic acid.
18. The method for preparing an oil-soluble organometallic salt composition according to claim 6, wherein the second organic acid is selected from at least one of 4-butylbenzoic acid, 4-pentylbenzoic acid, 4-hexylbenzoic acid, 4-heptylbenzoic acid, 4-octylbenzoic acid, 4-nonylbenzoic acid when the carboxyl group is on the benzene ring; when the carboxyl is not directly connected with the benzene ring, the second organic acid is phenylalkyl carboxylic acid, and is at least one selected from phenylbutyric acid, phenylvaleric acid, phenylheptanoic acid, phenyloctanoic acid and phenylnonanoic acid.
19. The method for preparing an oil-soluble organometallic salt composition according to claim 6 or 18, wherein the second organic acid is 4-butylbenzoic acid and/or 4-pentylbenzoic acid when the carboxyl group is on the benzene ring; when the carboxyl group is not directly connected with the benzene ring, the second organic acid is phenylbutyric acid and/or phenyloctanoic acid.
20. The method for producing an oil-soluble organometallic salt composition according to claim 6, wherein the inorganic acid in the step (1) is one or more of sulfuric acid, nitric acid, and hydrochloric acid.
21. The process for producing an oil-soluble organometallic salt composition according to claim 6, wherein the polystyrene microspheres in the step (3) have a median particle diameter D 50 of 300 to 600nm.
22. The process for preparing an oil-soluble organometallic salt composition according to claim 6, wherein the reaction promoter in the step (4) is a halogenated alkane of Cl, br, I; at least one selected from chlorooctane, bromooctane, iodooctane, 1, 8-diiodooctane, chlorononane, 1, 9-dichlorononane, 1-trichlorononane, bromononane, chlorodecane, 1, 10-dichlorodecane, bromodecane, iododecane, 1, 10-diiododecane, chloroundecane, bromoundecane and iodoundecane.
23. The process for producing an oil-soluble organometallic salt composition according to claim 6, wherein the reaction accelerator in the step (4) is at least one of chlorooctane, bromooctane and chlorodecane.
24. The method for preparing an oil-soluble organic metal salt composition according to claim 6, wherein the amounts of the molybdenum source, the cobalt source, the inorganic acid, the organic solvent, the first organic acid, the second organic acid, the reaction accelerator, and the polystyrene microspheres are respectively as follows in parts by weight: 100 parts of molybdenum source, 12-20 parts of cobalt source, 0.6-4 parts of inorganic acid, 275-750 parts of organic solvent, 337.5-675 parts of first organic acid, 37.5-75 parts of second organic acid, 0.2-2 parts of reaction accelerator and 2-6 parts of polystyrene microsphere.
25. The method for producing an oil-soluble organometallic salt composition according to claim 6, wherein the amount of the organic solvent used in the step (1) is 50 to 200 parts by weight and the amount of the organic solvent used in the step (3) is 50 to 800 parts by weight.
26. The method for producing an oil-soluble organometallic salt composition according to claim 6 or 25, wherein the amount of the organic solvent used in the step (1) is 75 to 150 parts by weight and the amount of the organic solvent used in the step (3) is 200 to 600 parts by weight.
27. The method for producing an oil-soluble organometallic salt composition according to claim 6, wherein the amount of the first organic acid used in the step (2) is 75 to 150 parts by weight, and the amount of the first organic acid used in the step (4) is 262.5 to 525 parts by weight.
28. The process for producing an oil-soluble organometallic salt composition according to claim 6, wherein the mixing temperature in the step (1) is 40 to 120 ℃.
29. The process for producing an oil-soluble organometallic salt composition according to claim 28, wherein the mixing temperature in the step (1) is 60 to 100 ℃.
30. The process for producing an oil-soluble organometallic salt composition according to claim 6, wherein the reaction temperature in the step (2) is 100 to 250 ℃ and the reaction time is 2 to 10 hours.
31. The process for preparing an oil-soluble organometallic salt composition according to claim 30, wherein the reaction temperature in the step (2) is 120 to 200 ℃ and the reaction time is 4 to 8 hours.
32. The process for producing an oil-soluble organometallic salt composition according to claim 6, wherein the mixing temperature in the step (3) is 40 to 120 ℃.
33. The process for producing an oil-soluble organometallic salt composition according to claim 32, wherein the mixing temperature in the step (3) is 60 to 100 ℃.
34. The process for producing an oil-soluble organometallic salt composition according to claim 6, wherein the reaction temperature in the step (4) is 120 to 300 ℃ and the reaction time is 4 to 24 hours.
35. The method for preparing an oil-soluble organometallic salt composition according to claim 34, wherein the reaction temperature in the step (4) is 150 to 250 ℃; the reaction time is 8-20 h.
36. The process for producing an oil-soluble organometallic salt composition according to claim 6, wherein the mixing temperature in the step (5) is 100 to 160 ℃.
37. The process for preparing an oil-soluble organometallic salt composition according to claim 36, wherein the mixing temperature in the step (5) is 120 to 150 ℃.
38. A process for hydrogenating a heavy oil of poor quality comprising contacting the heavy oil of poor quality with the oil-soluble organometallic salt composition of any one of claims 1 to 5 in the presence of hydrogen and performing hydrogenation.
39. The process for hydrogenating poor heavy oil according to claim 38, wherein the poor heavy oil is one or more of heavy distillate, atmospheric residue, vacuum residue, coal tar, catalytic slurry, and crude oil.
40. The process for hydrogenating a heavy oil of poor quality according to claim 38 wherein the reaction conditions are as follows: the reaction pressure is 14-20 MPa, the reaction temperature is 380-420 ℃, and the reaction time is 1-20 h.
41. The process for hydrogenating a low grade heavy oil according to claim 38 wherein the oil soluble organometallic salt composition has a concentration of 200 to 2000mg/kg in the low grade heavy oil.
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