CN116060130B - Organic molybdenum salt composition and preparation method and application thereof - Google Patents
Organic molybdenum salt composition and preparation method and application thereof Download PDFInfo
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- CN116060130B CN116060130B CN202111278236.8A CN202111278236A CN116060130B CN 116060130 B CN116060130 B CN 116060130B CN 202111278236 A CN202111278236 A CN 202111278236A CN 116060130 B CN116060130 B CN 116060130B
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- organic
- acid
- salt composition
- molybdenum
- organomolybdenum
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- 239000000203 mixture Substances 0.000 title claims abstract description 92
- 150000002751 molybdenum Chemical class 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 87
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000011733 molybdenum Substances 0.000 claims abstract description 85
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 150000007524 organic acids Chemical class 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 36
- 229920000620 organic polymer Polymers 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 18
- -1 molybdenum ions Chemical class 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 150000002891 organic anions Chemical class 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 39
- 150000003839 salts Chemical class 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000295 fuel oil Substances 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 19
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 18
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
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- 239000003999 initiator Substances 0.000 claims description 13
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- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 13
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 10
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 10
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 8
- OVBFMEVBMNZIBR-UHFFFAOYSA-N 2-methylvaleric acid Chemical compound CCCC(C)C(O)=O OVBFMEVBMNZIBR-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- NKBWMBRPILTCRD-UHFFFAOYSA-N 2-Methylheptanoic acid Chemical compound CCCCCC(C)C(O)=O NKBWMBRPILTCRD-UHFFFAOYSA-N 0.000 claims description 7
- CWYNKKGQJYAHQG-UHFFFAOYSA-N 4-pentylbenzoic acid Chemical compound CCCCCC1=CC=C(C(O)=O)C=C1 CWYNKKGQJYAHQG-UHFFFAOYSA-N 0.000 claims description 7
- OBKXEAXTFZPCHS-UHFFFAOYSA-N 4-phenylbutyric acid Chemical compound OC(=O)CCCC1=CC=CC=C1 OBKXEAXTFZPCHS-UHFFFAOYSA-N 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000010779 crude oil Substances 0.000 claims description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 6
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 claims description 5
- RKAMCQVGHFRILV-UHFFFAOYSA-N 1-chlorononane Chemical compound CCCCCCCCCCl RKAMCQVGHFRILV-UHFFFAOYSA-N 0.000 claims description 5
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 claims description 5
- JFKUBRAOUZEZSL-UHFFFAOYSA-N 4-butylbenzoic acid Chemical compound CCCCC1=CC=C(C(O)=O)C=C1 JFKUBRAOUZEZSL-UHFFFAOYSA-N 0.000 claims description 5
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 5
- ZTEHOZMYMCEYRM-UHFFFAOYSA-N 1-chlorodecane Chemical compound CCCCCCCCCCCl ZTEHOZMYMCEYRM-UHFFFAOYSA-N 0.000 claims description 4
- GMQQCOYAGZTOEF-UHFFFAOYSA-N 2,5-dimethyloctanoic acid Chemical compound CCCC(C)CCC(C)C(O)=O GMQQCOYAGZTOEF-UHFFFAOYSA-N 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
- CPEPWESLFZVUEP-UHFFFAOYSA-N 4-hexylbenzoic acid Chemical compound CCCCCCC1=CC=C(C(O)=O)C=C1 CPEPWESLFZVUEP-UHFFFAOYSA-N 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 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
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 229940094933 n-dodecane Drugs 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002002 slurry Substances 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
- 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
- MCLMZMISZCYBBG-UHFFFAOYSA-N 3-ethylheptanoic acid Chemical compound CCCCC(CC)CC(O)=O MCLMZMISZCYBBG-UHFFFAOYSA-N 0.000 claims description 3
- RCVXVULZIOSNEI-UHFFFAOYSA-N 4-ethylheptanoic acid Chemical compound CCCC(CC)CCC(O)=O RCVXVULZIOSNEI-UHFFFAOYSA-N 0.000 claims description 3
- VSUKEWPHURLYTK-UHFFFAOYSA-N 4-heptylbenzoic acid Chemical compound CCCCCCCC1=CC=C(C(O)=O)C=C1 VSUKEWPHURLYTK-UHFFFAOYSA-N 0.000 claims description 3
- FLRVNGMVEBEPQG-UHFFFAOYSA-N 4-nonylbenzoic acid Chemical compound CCCCCCCCCC1=CC=C(C(O)=O)C=C1 FLRVNGMVEBEPQG-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- ZVSXKFNTWOIGJI-UHFFFAOYSA-N 7-phenyl heptanoic acid Chemical compound OC(=O)CCCCCCC1=CC=CC=C1 ZVSXKFNTWOIGJI-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
- 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
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-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
- DYWSVUBJGFTOQC-UHFFFAOYSA-N xi-2-Ethylheptanoic acid Chemical compound CCCCCC(CC)C(O)=O DYWSVUBJGFTOQC-UHFFFAOYSA-N 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
- 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
- CVKMFSAVYPAZTQ-UHFFFAOYSA-N 2-methylhexanoic acid Chemical compound CCCCC(C)C(O)=O CVKMFSAVYPAZTQ-UHFFFAOYSA-N 0.000 claims description 2
- COYMEIBAQDZJCT-UHFFFAOYSA-N 2-phenylnonanoic acid Chemical compound CCCCCCCC(C(O)=O)C1=CC=CC=C1 COYMEIBAQDZJCT-UHFFFAOYSA-N 0.000 claims description 2
- PWKJMPFEQOHBAC-UHFFFAOYSA-N 4-Ethyloctanoic acid Chemical compound CCCCC(CC)CCC(O)=O PWKJMPFEQOHBAC-UHFFFAOYSA-N 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
- BYHDDXPKOZIZRV-UHFFFAOYSA-N 5-phenylpentanoic acid Chemical compound OC(=O)CCCCC1=CC=CC=C1 BYHDDXPKOZIZRV-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
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- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
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- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- 150000001350 alkyl halides Chemical group 0.000 claims 1
- 150000003863 ammonium salts Chemical group 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
- 239000002994 raw material Substances 0.000 abstract description 12
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- CWYNKKGQJYAHQG-UHFFFAOYSA-M 4-pentylbenzoate Chemical compound CCCCCC1=CC=C(C([O-])=O)C=C1 CWYNKKGQJYAHQG-UHFFFAOYSA-M 0.000 description 2
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- XSIFPSYPOVKYCO-UHFFFAOYSA-N benzoic acid butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
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- ZBZSVGXZAPNCSY-UHFFFAOYSA-N phenyl octanoate Chemical compound CCCCCCCC(=O)OC1=CC=CC=C1 ZBZSVGXZAPNCSY-UHFFFAOYSA-N 0.000 description 2
- 229950009215 phenylbutanoic acid Drugs 0.000 description 2
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- 238000001228 spectrum Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
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- 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
- DYWSVUBJGFTOQC-UHFFFAOYSA-M 2-ethylheptanoate Chemical compound CCCCCC(CC)C([O-])=O DYWSVUBJGFTOQC-UHFFFAOYSA-M 0.000 description 1
- CVKMFSAVYPAZTQ-UHFFFAOYSA-M 2-methylhexanoate Chemical compound CCCCC(C)C([O-])=O CVKMFSAVYPAZTQ-UHFFFAOYSA-M 0.000 description 1
- KJYXVWHRKCNYKU-UHFFFAOYSA-N 4-ethyl-hexanoic acid Chemical compound CCC(CC)CCC(O)=O KJYXVWHRKCNYKU-UHFFFAOYSA-N 0.000 description 1
- CPEPWESLFZVUEP-UHFFFAOYSA-M 4-hexylbenzoate Chemical compound CCCCCCC1=CC=C(C([O-])=O)C=C1 CPEPWESLFZVUEP-UHFFFAOYSA-M 0.000 description 1
- ZQLDNJKHLQOJGE-UHFFFAOYSA-M 4-octylbenzoate Chemical compound CCCCCCCCC1=CC=C(C([O-])=O)C=C1 ZQLDNJKHLQOJGE-UHFFFAOYSA-M 0.000 description 1
- BUIZICPOJVBQGZ-UHFFFAOYSA-N 5-methylhexyl prop-2-enoate Chemical compound CC(C)CCCCOC(=O)C=C BUIZICPOJVBQGZ-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition 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
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- USVUMWSMZMQXIZ-UHFFFAOYSA-N phenyl heptanoate Chemical compound CCCCCCC(=O)OC1=CC=CC=C1 USVUMWSMZMQXIZ-UHFFFAOYSA-N 0.000 description 1
- UHGWBEXBBNLGCZ-UHFFFAOYSA-N phenyl nonanoate Chemical compound CCCCCCCCC(=O)OC1=CC=CC=C1 UHGWBEXBBNLGCZ-UHFFFAOYSA-N 0.000 description 1
- MVIMPQVBUPCHEV-UHFFFAOYSA-N phenyl pentanoate Chemical compound CCCCC(=O)OC1=CC=CC=C1 MVIMPQVBUPCHEV-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J31/16—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
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- 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
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1077—Vacuum residues
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
- C10G2300/206—Asphaltenes
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- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an organic molybdenum salt composition, a preparation method and application thereof, wherein the organic molybdenum salt composition comprises molybdenum ions and organic anions combined with the molybdenum ions, and the content of molybdenum is more than or equal to 18wt% in terms of elements. The preparation method comprises the steps of firstly, uniformly mixing a molybdenum source, an organic solvent and an organic polymer to obtain a first material flow; then introducing a first organic acid, a second organic acid and a reaction promoter for reaction, and separating to obtain the organic molybdenum salt composition after the reaction is completed. The organic molybdenum salt composition has high molybdenum content, strong thermal stability, good dispersibility, high hydrogenation catalytic activity on inferior hydrocarbon-containing raw materials and good coke inhibition performance.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and relates to a molybdenum-containing organic matter, a preparation method and application thereof.
Background
At present, the demand for light oil products has a trend of rising year by year, and at the same time, the trend of poor quality and heavy quality of crude oil resources is gradually increased. In order to solve the problem of shortage of high-quality crude oil, how to efficiently convert inferior heavy oil into light oil becomes a research hotspot in the current field. In poor-quality raw material compositions represented by poor-quality heavy oil, residual oil and vacuum residual oil, the asphaltene content is high, and the conversion of the high-boiling complex fraction is difficult. When a fixed bed reactor and a conventional supported catalyst are adopted to process inferior crude oil, asphaltene and the like are easy to generate Jiao Zu minutes in the hydrogenation process, coking and carbon deposition are easy to occur on the surface of the conventional supported catalyst, so that a catalyst pore canal and an active site are blocked and deactivated, and bed pressure drop is caused.
In contrast, the slurry bed reactor and the oil-soluble dispersion type catalyst can obtain better effect when being used for processing inferior crude oil, because the oil-soluble dispersion type catalyst can be uniformly dispersed in the raw oil in nano-size or molecular scale, the hydrogenation reaction activity is high, the coke yield is low, and the product quality is better. But also the performance of the catalyst is a central factor affecting the use effect of this technology.
Patent US7,842,635B2 discloses a preparation method of a bimetallic oil-soluble catalyst, wherein organic nickel/cobalt/iron and organic molybdenum are mixed, and molybdenum is stably dispersed in an oil phase in a hydrogenation catalysis process by introducing a second transition metal, wherein the total metal amount of the bimetallic oil-soluble catalyst is more than 14wt%. Patent CN 107867993A discloses a preparation method of an organic molybdenum salt composition, the active metal component of the organic molybdenum salt prepared by the method is up to 15.8%, and molybdenum has +3, +4, +5 mixed valence state, and after presulfiding, the organic molybdenum salt exists in a highly dispersed single-layer structure in residual oil, and has good catalytic activity. Patent CN 110237866A discloses a preparation method of oil-soluble sulfurized catalyst, firstly, the benzene compound is reacted with sulfide to produce organic ligand, then the active metal is mixed with the organic ligand, and the oil-soluble sulfurized catalyst is formed under the promotion of halide salt of sodium chloride, etc., and the obtained catalyst has the characteristics of small dosage and high activity, and can make colloid asphalt implement high-efficiency conversion and impurity-removing under the condition of less dosage (less than or equal to 350 ppm).
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide an oil-soluble organic molybdenum salt composition with high molybdenum content, strong thermal stability, good dispersibility, high hydrogenation catalytic activity on inferior hydrocarbon-containing raw materials and good coke inhibition performance, and a preparation method and application thereof.
The first aspect of the present invention provides an organic molybdenum salt composition comprising molybdenum ions, and an organic anion associated with the molybdenum ions; the content of molybdenum is more than or equal to 18 weight percent based on the element, wherein 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 molybdenum salt composition, the organic anion is an organic acid ion, and specifically may be selected from one or more of 2-methylpentanoate, 2-methylheptanoate, 2-ethylheptanoate, 3-ethylheptanoate, 4-ethylheptanoate, 2-methylhexanoate, 2-ethylhexanoate, 2, 5-dimethyloctanate, 7-dimethyloctanate, 4-ethyloctanate, 2-propyloctanate, 4-butylbenzoate, 4-pentylbenzoate, 4-hexylbenzoate, 4-heptylbenzoate, 4-octylbenzoate, 4-nonylbenzoate, phenylbutyrate, phenylvalerate, phenylheptanoate, phenyloctanate, phenylnonanoate, and preferably one or more of 2-methylpentanoate, 2-ethylhexanoate, 4-butylbenzoate, 4-pentylbenzoate, phenylbutyrate and phenyloctanate.
Further, in the molybdenum salt composition, the dynamic viscosity (mu 40) of the organic molybdenum salt composition at 40 ℃ is 60 to 120 mPas; the weight loss temperature (T 50) is not lower than 280 ℃;
Further, in the molybdenum salt composition, the proportion of single-layer MoS 2 wafers in the sulfurized MoS 2 wafers formed by sulfurizing the organic molybdenum salt composition is more than 90%.
In a second aspect, the present invention provides a process for preparing an organomolybdenum salt composition, the process comprising the steps of:
(1) Mixing a molybdenum source, an organic solvent and an organic polymer uniformly to obtain a first material flow;
(2) Introducing a first organic acid and a second organic acid into the first material flow obtained in the step (1), uniformly mixing, adding a reaction promoter, reacting, and separating to obtain the organic molybdenum salt composition.
Further, in the above-mentioned method for preparing an organic molybdenum salt composition, the molybdenum source may be one or more selected from molybdenum halides, molybdenum oxides, molybdenum alkali metal salts, molybdenum ammonium salts, and molybdic acid, and preferably molybdenum ammonium salts and/or molybdic acid. 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 molybdenum salt composition, the organic solvent in the step (1) can 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 preparation method of the organic molybdenum salt composition, the organic polymer is an amphiphilic polymer prepared by adopting precipitation polymerization and free radical initiation, and the structural formula is shown as formula (1):
(1)
Wherein a, b, c, d is an integer between 20 and 120, and 400 is more than or equal to a+b+c+d is more than or equal to 100;
Further, the preparation method of the organic polymer comprises the following steps: adding acrylamide, sodium styrenesulfonate, methyl methacrylate and isooctyl acrylate into a solvent, uniformly mixing to obtain a material A, heating to a reaction temperature, adding an initiator into the material A for reaction, and finally separating, washing and drying to obtain a polymer.
In the preparation method of the organic polymer, the molar ratio of the four monomers of acrylamide, sodium styrene sulfonate, methyl methacrylate and isooctyl acrylate is (2-6): (1-2): (2-4): (1-2).
In the preparation method of the organic polymer, the solvent is a mixed solution of alcohol and water, and the mass ratio of the alcohol to the water is 4: 6-6: 4, the alcohol can be one or more of methanol, ethanol, propanol and isopropanol, and is preferably ethanol.
In the preparation method of the organic polymer, the total mass fraction of four monomers of acrylamide, sodium styrenesulfonate, methyl methacrylate and isooctyl acrylate in the material A is 4-16%.
In the above method for producing an organic polymer, the reaction temperature is 50 to 75 ℃.
In the preparation method of the organic polymer, the initiator is one or more of 2,2' -azobisisobutylaminidine dihydrochloride (AIBA), azobisisobutyronitrile (AIBN) and dibenzoyl peroxide (BPO), preferably azobisisobutyronitrile, and the use amount of the initiator is 0.2-3% of the total mass of the monomer.
In the above method for producing an organic polymer, the separation may be performed by any of centrifugation, filtration, and the like, the washing may be performed several times, generally 1 to 6 times, with deionized water, and the drying may be performed at 45 to 105 ℃ for 4 to 24 hours.
In the preparation method of the organic polymer, the organic polymer is white or light yellow amphiphilic polymer powder, and the number average molecular weight M n of the amphiphilic polymer is 13000-62000 measured by Gel Permeation Chromatography (GPC).
Further, in the above-mentioned method for producing an organomolybdenum 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-ethylhexanoic acid, 2-propyloctanoic acid, preferably 2-methylpentanoic acid and/or 2-ethylhexanoic acid.
Further, in the preparation method of the organic molybdenum salt composition, the second organic acid is an organic carboxylic acid containing benzene rings and having a total carbon number of 10-16, wherein the carboxyl group can be directly connected to the benzene rings or can be not directly connected to the benzene rings; 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 organic molybdenum salt composition, the reaction promoter is halogenated alkane, and the halogenated alkane has 6-15 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 organic molybdenum salt composition, the dosages of the molybdenum source, the organic solvent, the first organic acid, the second organic acid, the organic polymer and the reaction promoter are respectively as follows in parts by weight: 100 parts of molybdenum source, 50-800 parts of organic solvent, 175-700 parts of first organic acid, 25-100 parts of second organic acid, 0.1-10 parts of organic polymer and 0.02-2.5 parts of reaction promoter; preferably 100 parts of molybdenum source, 200-600 parts of organic solvent, 262.5-525 parts of first organic acid, 37.5-75 parts of second organic acid, 1-6 parts of organic polymer and 0.2-2 parts of reaction promoter.
Further, in the above-mentioned method for producing an organomolybdenum salt composition, the mixing temperature in the step (1) is 40 to 120 ℃, preferably 60 to 100 ℃.
Further, in the preparation method of the organic molybdenum salt composition, the reaction temperature in the step (2) is 120-300 ℃, preferably 150-250 ℃; the reaction time is 4 to 24 hours, preferably 8 to 20 hours.
Further, in the preparation method of the organic molybdenum salt composition, water generated by the reaction is removed in a reflux manner in the reaction process in the step (2).
Further, in the above-mentioned preparation method of the organic molybdenum salt composition, the separation process in the step (2) is generally that the solid phase is removed by suction filtration, and then the solvent is further distilled off, and the distillation generally includes two steps of suction filtration and distillation, wherein the distillation preferably adopts a reduced pressure distillation mode, the operation pressure of the reduced pressure distillation is 1.3-2.0 KPa, the operation temperature is 120-180 ℃, and the distillation end point can be judged according to the total amount of the residual materials being 250-300 parts.
The third aspect of the invention provides a hydrogenation method for inferior heavy oil, which comprises the steps of contacting the inferior heavy oil with the organic molybdenum salt composition under the condition 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 above-mentioned inferior heavy oil hydrogenation method, the concentration of the organic molybdenum salt composition in the inferior heavy oil is 200-2000 mg/kg
Furthermore, in the above-mentioned inferior heavy oil hydrogenation method, the organic molybdenum 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 organic molybdenum salt composition and the preparation method and application thereof have the following advantages:
(1) The organic molybdenum salt composition has the characteristics of high molybdenum content of an active metal component, good dispersibility, good fluidity and good thermal stability. The molybdenum content in the organic molybdenum salt composition obtained by the preparation method is higher than 18%, and the molybdenum content in the organic molybdenum salt composition prepared by the prior art is generally lower than 16%, so that the molybdenum content in the product is obviously improved by the method, and the catalytic activity of the material can be improved when the catalyst is used for the poor heavy oil hydrogenation catalytic material. Meanwhile, the organic molybdenum 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 organic molybdenum 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) In the preparation method of the organic molybdenum salt composition, an amphiphilic quaternary copolymer is introduced, wherein acrylamide, sodium styrenesulfonate, methyl methacrylate and isoheptyl acrylate are taken as monomers, and the amphiphilic quaternary copolymer is obtained through precipitation polymerization and free radical initiation. Hydrophilic groups in the copolymer can be adsorbed on the surfaces of molybdenum source particles and are tightly combined with molybdenum, so that the copolymer is highly dispersed in an organic solvent by virtue of an oleophilic organic carbon chain, and thus, the molybdenum is wrapped and fully dispersed in the organic solvent by virtue of an organic polymer, active sites are fully exposed, and under the further promotion of halogenated alkane, the reaction efficiency of an organic ligand and the molybdenum is greatly improved, the molybdenum content in the molybdenum salt composition is improved, and meanwhile, the molybdenum salt composition in a highly dispersed state of molybdenum can be obtained.
(3) In the preparation method of the organic molybdenum 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 molybdenum salt composition and the inferior heavy oil raw material. In addition, under the coordination effect of the two ligands, especially the use of the second organic acid obviously improves the heat stability of the organic molybdenum salt composition, and avoids the severe decomposition of the organic molybdenum salt composition before the pre-vulcanization reaction, thereby causing the aggregation of active metal components and the reduction of the catalytic efficiency.
(4) The preparation method of the organic molybdenum salt composition has the characteristics of simple process, high reaction conversion rate, safe and environment-friendly production process, and is beneficial to industrial production and application.
Drawings
FIG. 1 is a TEM image of a sample prepared according to example 7 of the invention after vulcanization.
FIG. 2 is a TEM image of a sample prepared according to comparative example 2 of the present invention after vulcanization.
Detailed Description
The following is a further description of the preparation and use of the organomolybdenum salt composition of the invention by way of specific examples, which are not intended to limit the invention.
The molybdenum content of the organic molybdenum 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 organomolybdenum salt composition product was measured according to ASTM D5018-2018; the thermal stability of the organomolybdenum salt composition product was analyzed using a mertler TGA-2 thermogravimetric analyzer. The morphology of the MoS 2 wafer was characterized by means of a JEM-2200FS type 200kV energy filtered field emission transmission electron microscope (JEOL) from japan electronics corporation.
The dynamic viscosity of the organic molybdenum salt composition in the embodiment and the comparative example is mu 40 at 40 ℃; the temperature corresponding to the weight loss of the organic molybdenum 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.
Example 1
Preparation of organic Polymer A: adding acrylamide, sodium styrene sulfonate, methyl methacrylate and isooctyl acrylate into an ethanol/water solution (the mass ratio of ethanol to water is 13:11) according to the monomer ratio a:b:c:d=6:1:2:2 to obtain a material A, adding an initiator AIBN (the AIBN dosage is 1.5% of the total mass of the four monomers) into the material A, reacting for 8 hours at 60 ℃, and further carrying out centrifugal separation, washing for 2 times and drying for 22 hours at 55 ℃ to obtain the amphiphilic polymer A, wherein the number average molecular weight M n =17500.
Example 2
Preparation of organic Polymer B: adding acrylamide, sodium styrenesulfonate, methyl methacrylate and isooctyl acrylate into a methanol/water solution (the mass ratio of methanol to water is 4:6) according to a monomer ratio a: B: c: d=2:2:4:1 to obtain a material A, adding an initiator AIBA (the AIBA dosage is 0.2% of the total mass of the four monomers) into the material A, reacting for 24 hours at 50 ℃, and further carrying out centrifugal separation, washing for 3 times and drying for 24 hours at 45 ℃ to obtain an amphiphilic polymer B, wherein the number average molecular weight M n =13000.
Example 3
Preparation of organic Polymer C
Adding acrylamide, sodium styrenesulfonate, methyl methacrylate and isooctyl acrylate into an isopropanol/water solution (the mass ratio of the isopropanol to the water is 6:4) according to a monomer ratio a: b: C: d=2:1:3:2 to obtain a material A, adding an initiator BPO (the using amount of the BPO is 4.5% of the total mass of the four monomers) into the material A, reacting for 4 hours at 75 ℃, and further carrying out centrifugal separation, washing for 1 time and drying for 4 hours at 105 ℃ to obtain an amphiphilic polymer C, wherein the number average molecular weight M n =62000.
Example 4
Preparation of organic Polymer D
Adding acrylamide, sodium styrene sulfonate, methyl methacrylate and isooctyl acrylate into a propanol/water solution (the mass ratio of propanol to water is 1:1) according to a monomer ratio a: b: c: d=5:1:3:1 to obtain a material A, adding an initiator AIBN (the AIBN dosage is 1% of the total mass of the four monomers) into the material A, reacting for 20h at 65 ℃, further centrifugally separating, washing for 4 times, and drying for 8h at 75 ℃ to obtain the amphiphilic polymer D, wherein the number average molecular weight M n =28500.
Example 5
Preparation of organic Polymer E
Adding acrylamide, sodium styrenesulfonate, methyl methacrylate and isooctyl acrylate into an ethanol/water solution (the mass ratio of ethanol to water is 13:12) according to a monomer ratio a:b:c:d=5:2:2 to obtain a material A, adding an initiator AIBA (the AIBA dosage is 2.2% of the total mass of the four monomers) into the material A, reacting at 60 ℃ for 13h, and further carrying out centrifugal separation, washing for 1 time and drying at 95 ℃ for 9.5h to obtain an amphiphilic polymer E, wherein the number average molecular weight M n =30300.
Example 6
Preparation of organic Polymer F
Adding acrylamide, sodium styrenesulfonate, methyl methacrylate and isooctyl acrylate into an ethanol/water solution (the mass ratio of ethanol to water is 12:13) according to a monomer ratio a: b: c: d=2:1:2:1 to obtain a material A, adding an initiator BPO (the using amount of the BPO is 0.8% of the total mass of the four monomers) into the material A, reacting for 15h at 70 ℃, further centrifugally separating, washing for 3 times, and drying for 5.5h at 100 ℃ to obtain an amphiphilic polymer F, wherein the number average molecular weight M n =42600.
Example 7
100 Parts of molybdenum trioxide, 325 parts of n-heptane, 7.5 parts of organic polymer A were thoroughly mixed at 95℃to form a homogeneous suspension. 288 parts of 2-ethylhexanoic acid and 48 parts of 4-amyl benzoic acid are then added and uniformly mixed at the same temperature. Adding 1.8 parts of chlorononane into the system, fully and uniformly mixing, heating to 245 ℃, reacting at the temperature for 12.5 hours, stopping the reaction, filtering to remove solid phase, and carrying out reduced pressure distillation at 1.44KPa and 152 ℃ to obtain 273 parts of the total amount of the residual materials, thereby obtaining the oil-soluble organic molybdenum catalyst. The molybdenum content of the organic molybdenum catalyst is 19.8%, wherein the Mo 4+、Mo5+、Mo6+ content is 7.9%, 6.2%, 5.7%, μ 40=90mPa·s,T50=308℃,N1% = 98.2%, respectively.
Example 8
100 Parts of molybdenum hexafluoride, 50 parts of cyclohexane and 0.1 part of the amphiphilic copolymer B are thoroughly mixed at 60℃to form a homogeneous suspension. Then 700 parts of 2-methylheptanoic acid and 75 parts of phenylbutyric 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 at the temperature for 8 hours, stopping the reaction, filtering to remove solid phase, and carrying out reduced pressure distillation at the temperature of 1.3KPa and 120 ℃, wherein the total amount of the rest materials is 250 parts, thus obtaining the oil-soluble organic molybdenum catalyst. The molybdenum content of the organic molybdenum catalyst is 19.6%, wherein the Mo 4+、Mo5+、Mo6+ content is 9.2%, 4.6%, 5.8%, μ 40=105mPa·s,T50=292℃,N1% = 95.6%, respectively.
Example 9
100 Parts of potassium molybdate, 800 parts of toluene and 10 parts of the amphiphilic copolymer C are thoroughly mixed at 40 ℃ to form a uniform suspension system. Then 525 parts of 2-ethylheptanoic acid and 100 parts of phenylheptanoic acid are added and uniformly mixed at the same temperature. Adding 2.5 parts of bromooctane into the system, fully and uniformly mixing, heating to 250 ℃, reacting for 20 hours at the temperature, stopping the reaction, filtering to remove solid phase by suction, and carrying out reduced pressure distillation at 1.6KPa and 146 ℃, wherein the total amount of the rest materials is 300 parts, thus obtaining the oil-soluble organic molybdenum catalyst. The molybdenum content of the organic molybdenum catalyst is 20.4%, wherein the Mo 4+、Mo5+、Mo6+ content is 10.8%, 7.2%, 2.4%, μ 40=120mPa·s,T50=302℃,N1% = 92.9%, respectively.
Example 10
100 Parts of sodium molybdate, 200 parts of n-octane and 1 part of amphiphilic copolymer D are thoroughly mixed at 100 ℃ to form a uniform suspension system. Then 262.5 parts of 2-propylhexanoic 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, stopping the reaction, filtering to remove solid phase by suction, and carrying out reduced pressure distillation at 2KPa and 180 ℃, wherein the total amount of the rest materials is 285 parts, thus obtaining the oil-soluble organic molybdenum catalyst. The molybdenum content of the organic molybdenum catalyst is 19.2%, wherein the Mo 4+、Mo5+、Mo6+ content is 7.4%, 4.6%, 7.2%, μ 40=60mPa·s,T50=285℃,N1% = 92.5%, respectively.
Example 11
100 Parts of calcium molybdate, 600 parts of n-decane and 6 parts of amphiphilic copolymer E are thoroughly mixed at 120℃to form a homogeneous suspension. Then 175 parts of 2, 5-dimethyl octanoic acid and 37.5 parts of 4-hexyl benzoic acid are added and uniformly mixed at the same temperature. Adding 2 parts of 1, 8-diiodooctane into the system, fully and uniformly mixing, heating to 300 ℃, reacting at the temperature for 4 hours, stopping the reaction, carrying out reduced pressure distillation at 1.4KPa and 162 ℃, and removing solid phase by suction filtration, thereby obtaining the oil-soluble organic molybdenum catalyst. The molybdenum content of the organic molybdenum catalyst is 18.6%, wherein the Mo 4+、Mo5+、Mo6+ content is 7.8%, 3.6%, 7.2%, μ 40=72mPa·s,T50=294℃,N1% = 96.1%, respectively.
Example 12
100 Parts of ammonium heptamolybdate, 220 parts of cumene and 5.5 parts of amphiphilic copolymer F are thoroughly mixed at 112℃to form a homogeneous suspension. Then 182 parts of 7, 7-dimethyl octanoic acid and 72 parts of 4-butyl benzoic acid are added and mixed uniformly at the same temperature. Adding 0.8 part of bromononane into the system, fully and uniformly mixing, heating to 265 ℃, reacting at the temperature for 10 hours, stopping the reaction, filtering to remove solid phase, and carrying out reduced pressure distillation at 1.55KPa and 174 ℃, wherein the total amount of the rest materials is 269 parts, thus obtaining the oil-soluble organic molybdenum catalyst. The molybdenum content of the organic molybdenum catalyst is 19.2%, wherein the Mo 4+、Mo5+、Mo6+ content is 9.9%, 6.9%, 2.4%, μ 40=74mPa·s,T50=299℃,N1% = 95.3%, respectively.
Comparative example 1
100 Parts of molybdenum trioxide, 325 parts of n-heptane and 7.5 parts of the amphiphilic copolymer A were thoroughly mixed at 95℃to form a homogeneous suspension. Then 288 parts of 2-ethylhexanoic acid and 48 parts of 4-amyl benzoic acid are added, uniformly mixed at the same temperature, then the temperature is raised to 245 ℃, the reaction is stopped after the reaction is carried out for 12.5 hours at the temperature, the reduced pressure distillation is carried out at 1.44KPa and 135 ℃, the total amount of the residual materials is 273 parts, and the solid phase is removed by suction filtration, thus obtaining the oil-soluble organic molybdenum catalyst. The molybdenum content of the organic molybdenum catalyst is 13.8%, wherein the Mo 4 +、Mo5+、Mo6+ content is 6.2%, 4.0%, 3.6%, μ 40=49mPa·s,T50=242℃,N1% = 28.2%, respectively.
Comparative example 2
100 Parts of molybdenum trioxide and 325 parts of n-heptane were thoroughly mixed at 95℃to form a homogeneous suspension. 288 parts of 2-ethylhexanoic acid and 48 parts of 4-amyl benzoic acid are then added and uniformly mixed at the same temperature. Adding 1.8 parts of chlorononane into the system, fully and uniformly mixing, heating to 245 ℃, reacting at the temperature for 12.5 hours, stopping the reaction, performing reduced pressure distillation at 1.44KPa and 135 ℃, and filtering to remove solid phase by suction filtration, thereby obtaining the oil-soluble organic molybdenum catalyst. The molybdenum content of the organic molybdenum catalyst is 13.1%, wherein the Mo 4+、Mo5+、Mo6+ content is 6.8%, 3.5%, 2.8%, μ 40=52mPa·s,T50=238℃,N1% = 6.8%, respectively.
Comparative example 3
100 Parts of molybdenum trioxide, 325 parts of n-heptane and 7.5 parts of the amphiphilic copolymer A were thoroughly mixed at 95℃to form a homogeneous suspension. Then 336 parts of 2-ethylhexanoic acid are added and mixed uniformly at the same temperature. Adding 1.8 parts of chlorononane into the system, fully and uniformly mixing, heating to 245 ℃, reacting at the temperature for 12.5 hours, stopping the reaction, performing reduced pressure distillation at 1.44KPa and 135 ℃, and filtering to remove solid phase by suction filtration, thereby obtaining the oil-soluble organic molybdenum catalyst. The molybdenum content of the organic molybdenum catalyst is 13.2%, wherein the Mo 4+、Mo5+、Mo6+ content is 3.6%, 3.8%, 5.8%, μ 40=39mPa·s,T50=236℃,N1% = 16.2%, 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 2.5 hours, the addition amount of the organic molybdenum salt composition is 650mg/kg, and the organic molybdenum salt composition can synchronously complete in-device presulfiding in the heating process due to the higher sulfur content (3.25 wt percent) in the raw oil, and the separate presulfiding operation is not needed.
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 7-12 is used for processing the raw material for reducing the residue of straight-run distillation, compared with the density and carbon residue value of the raw material, the obtained product oil has reduced 50%, 90% distillation temperature and end point, and simultaneously the saturated component content in the product composition is generally improved, the saturated component content is improved by about 23% at maximum, 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 oil density of the obtained product is higher, the 50% distillation temperature is higher than that of the products in examples 7-12 by nearly 100 ℃, the saturation fraction in the product is lower than that in examples 7-12 by more than 8%, 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 catalyst of example 7 and comparative example 2, such as fig. 1 and fig. 2, it can be seen that the MoS 2 wafers formed in the sulfur-containing residual oil by using the organomolybdenum catalyst prepared by the method of example 7 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 (35)
1. An organic molybdenum salt composition comprising molybdenum ions, and an organic anion associated with the molybdenum ions; the content of molybdenum is more than or equal to 18 weight percent based on the element, wherein 10.8 percent of Mo 4+≥3.6%,7.2%≥Mo5+≥3.6%,7.2%≥Mo6+ is more than or equal to 2.4 percent;
Wherein the preparation method of the organic molybdenum salt composition comprises the following steps:
(1) Mixing a molybdenum source, an organic solvent and an organic polymer uniformly to obtain a first material flow;
(2) Introducing a first organic acid and a second organic acid into the first material flow obtained in the step (1), uniformly mixing, adding a reaction promoter, reacting, and separating to obtain an organic molybdenum salt composition after the reaction is completed;
the first organic acid is an organic carboxylic acid with C6-C11 carbon atoms and containing branched chains;
the second organic acid is organic carboxylic acid containing benzene ring and having total carbon atoms of 10-16, wherein carboxyl is directly connected to the benzene ring or is not directly connected with the benzene ring;
The organic polymer has the structural formula:
Wherein a, b, c, d is an integer between 20 and 120, and 400 is more than or equal to a+b+c+d is more than or equal to 100;
The reaction promoter is halogenated alkane, and the carbon number of the halogenated alkane is 6-15;
The dosages of the molybdenum source, the organic solvent, the first organic acid, the second organic acid, the organic polymer and the reaction promoter in parts by weight are respectively as follows: 100 parts of molybdenum source, 50-800 parts of organic solvent, 175-700 parts of first organic acid, 25-100 parts of second organic acid, 0.1-10 parts of organic polymer and 0.02-2.5 parts of reaction accelerator.
2. The organomolybdenum salt composition of claim 1, wherein the organomolybdenum salt composition has a dynamic viscosity μ 40 of 60 to 120 mPa-s at 40 ℃.
3. The organomolybdenum salt composition of claim 1, wherein the organomolybdenum salt composition has a weight loss of 50% at a temperature T 50 of not less than 280 ℃.
4. The organomolybdenum salt composition of claim 1, wherein the organomolybdenum salt composition is sulfided to form a sulfided MoS 2 wafer having a single layer MoS 2 wafer fraction of greater than 90%.
5. The organomolybdenum salt composition of claim 1, wherein the first organic acid is selected from at least one 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, 2-propyloctanoic acid.
6. The organomolybdenum salt composition of claim 1 or 5, wherein the first organic acid is 2-methylpentanoic acid and/or 2-ethylhexanoic acid.
7. The organomolybdenum salt composition of claim 1, 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.
8. The organomolybdenum salt composition of claim 1 or 7, wherein the second organic acid is 4-butylbenzoic acid and/or 4-pentylbenzoic acid when the carboxyl group is on a 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.
9. A process for preparing the organomolybdenum salt composition of any of claims 1-8, said process comprising the steps of:
(1) Mixing a molybdenum source, an organic solvent and an organic polymer uniformly to obtain a first material flow;
(2) Introducing a first organic acid and a second organic acid into the first material flow obtained in the step (1), uniformly mixing, adding a reaction promoter, reacting, and separating to obtain the organic molybdenum salt composition.
10. The method for preparing an organic molybdenum salt composition according to claim 9, wherein the molybdenum source is selected from one or more of molybdenum halides, molybdenum oxides, molybdenum alkali metal salts, molybdenum ammonium salts, and molybdic acid.
11. The method for preparing an organomolybdenum salt composition according to claim 9 or 10, wherein the molybdenum source is selected from ammonium salts of molybdenum and/or molybdic acid.
12. The method for preparing an organic molybdenum salt composition according to claim 9 or 10, wherein the molybdenum source is selected from one or more of molybdenum hexafluoride, molybdenum trioxide, potassium molybdate, sodium molybdate, ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate, and molybdic acid.
13. The process for producing an organic molybdenum salt composition according to claim 9, wherein the organic solvent in the step (1) is one or more of C1-C3 alkylbenzene, C6-C12 linear alkane, and C6-C12 cycloalkane.
14. The method for producing an organomolybdenum salt composition according to claim 13, wherein the C1-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.
15. The process for preparing an organomolybdenum salt composition according to claim 14, wherein the C1-C3 alkylbenzene is para-xylene and/or cumene; the C6-C12 straight-chain alkane is selected from n-octane and/or n-dodecane; the C6-C12 cycloalkane is selected from cyclohexane and/or cyclooctane.
16. The method for preparing an organic molybdenum salt composition according to claim 9, wherein the method for preparing an organic polymer comprises the steps of: adding acrylamide, sodium styrenesulfonate, methyl methacrylate and isooctyl acrylate into a solvent, uniformly mixing to obtain a material A, heating to a reaction temperature, adding an initiator into the material A for reaction, and finally separating, washing and drying to obtain a polymer.
17. The method for preparing the organic molybdenum salt composition according to claim 16, wherein the molar ratio of the four monomers of acrylamide, sodium styrenesulfonate, methyl methacrylate and isooctyl acrylate is (2-6): (1-2): (2-4): (1-2).
18. The method for preparing an organomolybdenum salt composition according to claim 16, wherein the solvent is a mixed solution of alcohol and water, and the mass ratio of alcohol to water is 4: 6-6: and 4, the alcohol is one or more of methanol, ethanol, propanol and isopropanol.
19. The method for preparing the organic molybdenum salt composition according to claim 16, wherein the total mass fraction of four monomers in the material A, namely acrylamide, sodium styrene sulfonate, methyl methacrylate and isooctyl acrylate is 4-16%.
20. The process for preparing an organomolybdenum salt composition according to claim 16, wherein the reaction temperature is 50 to 75 ℃.
21. The method for preparing an organic molybdenum salt composition according to claim 16, wherein the initiator is one or more of 2,2' -azobisisobutylamino dihydrochloride, azobisisobutyronitrile and dibenzoyl peroxide, and the initiator is used in an amount of 0.2-3% of the total mass of the monomers.
22. The process for preparing an organomolybdenum salt composition as defined in claim 21, wherein the initiator is azobisisobutyronitrile.
23. The method for preparing an organic molybdenum salt composition according to claim 16, wherein the drying is a drying treatment at 45-105 ℃ for 4-24 hours.
24. The process for producing an organic molybdenum salt composition according to claim 9, wherein the organic polymer has a number average molecular weight M n of 5000 to 40000.
25. The method for preparing an organomolybdenum salt composition according to claim 9, wherein the reaction promoter is a haloalkane 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.
26. The method for preparing an organic molybdenum salt composition according to claim 25, wherein the reaction accelerator is at least one of chlorooctane, bromooctane, chlorodecane.
27. The method for preparing an organic molybdenum salt composition according to claim 9, wherein the amounts of the molybdenum source, the organic solvent, the first organic acid, the second organic acid, the organic polymer, and the reaction accelerator are respectively, in parts by weight: 100 parts of molybdenum source, 200-600 parts of organic solvent, 262.5-525 parts of first organic acid, 37.5-75 parts of second organic acid, 1-6 parts of organic polymer and 0.2-2 parts of reaction accelerator.
28. The process for preparing an organomolybdenum salt composition according to claim 9, wherein the mixing temperature in step (1) is 40 to 120 ℃.
29. The process for preparing an organomolybdenum salt composition according to claim 28, wherein the mixing temperature in step (1) is 60 to 100 ℃.
30. The process for preparing an organomolybdenum salt composition according to claim 9, wherein the reaction temperature in step (2) is 120 to 300 ℃ and the reaction time is 4 to 24 hours.
31. The method for preparing an organomolybdenum salt composition according to claim 30, wherein the reaction temperature in step (2) is 150 to 250 ℃; the reaction time is 8-20 h.
32. A process for hydrogenating a heavy oil of poor quality, comprising contacting the heavy oil of poor quality with the organomolybdenum salt composition of any of claims 1-8 in the presence of hydrogen and performing a hydrogenation reaction.
33. The process for hydrogenating poor heavy oil according to claim 32 wherein the poor heavy oil is one or more of heavy distillate, atmospheric residuum, vacuum residuum, coal tar, catalytic slurry oil, crude oil.
34. The process for hydrogenating poor heavy oil of claim 32, 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.
35. The process for hydrogenating a low grade heavy oil according to claim 32 wherein the concentration of the organomolybdenum salt composition in the low grade heavy oil is from 200 to 2000mg/kg.
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| CN101370913A (en) * | 2006-01-06 | 2009-02-18 | 上游技术革新有限公司 | Hydrocarbon-soluble molybdenum catalyst precursors and methods of making same |
| CN107866278A (en) * | 2016-09-28 | 2018-04-03 | 中国石油化工股份有限公司 | A kind of hydrocracking heavy oil catalyst and preparation method thereof |
| CN107867993A (en) * | 2016-09-28 | 2018-04-03 | 中国石油化工股份有限公司 | A kind of organic-molybdenum salt composite and preparation method thereof |
| CN112742476A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Catalyst, preparation method thereof and method for producing low-sulfur petroleum coke |
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| US7842635B2 (en) * | 2006-01-06 | 2010-11-30 | Headwaters Technology Innovation, Llc | Hydrocarbon-soluble, bimetallic catalyst precursors and methods for making same |
| US9403153B2 (en) * | 2012-03-26 | 2016-08-02 | Headwaters Heavy Oil, Llc | Highly stable hydrocarbon-soluble molybdenum catalyst precursors and methods for making same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101370913A (en) * | 2006-01-06 | 2009-02-18 | 上游技术革新有限公司 | Hydrocarbon-soluble molybdenum catalyst precursors and methods of making same |
| CN107866278A (en) * | 2016-09-28 | 2018-04-03 | 中国石油化工股份有限公司 | A kind of hydrocracking heavy oil catalyst and preparation method thereof |
| CN107867993A (en) * | 2016-09-28 | 2018-04-03 | 中国石油化工股份有限公司 | A kind of organic-molybdenum salt composite and preparation method thereof |
| CN112742476A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Catalyst, preparation method thereof and method for producing low-sulfur petroleum coke |
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