CN1609171A - Hydroprocessing catalyst and its prepn process - Google Patents
Hydroprocessing catalyst and its prepn process Download PDFInfo
- Publication number
- CN1609171A CN1609171A CN 200310104917 CN200310104917A CN1609171A CN 1609171 A CN1609171 A CN 1609171A CN 200310104917 CN200310104917 CN 200310104917 CN 200310104917 A CN200310104917 A CN 200310104917A CN 1609171 A CN1609171 A CN 1609171A
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- China
- Prior art keywords
- catalyst
- molybdenum
- nickel
- roasting
- tungsten
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- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 68
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000002360 preparation method Methods 0.000 claims abstract description 39
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 36
- 239000011148 porous material Substances 0.000 claims abstract description 31
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 50
- 238000007598 dipping method Methods 0.000 claims description 50
- 239000007864 aqueous solution Substances 0.000 claims description 34
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 32
- 239000011733 molybdenum Substances 0.000 claims description 32
- 229910052721 tungsten Inorganic materials 0.000 claims description 23
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 21
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 21
- 239000010937 tungsten Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000005470 impregnation Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 11
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- 229910052728 basic metal Inorganic materials 0.000 claims description 10
- 150000003818 basic metals Chemical group 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 150000002816 nickel compounds Chemical class 0.000 claims description 8
- -1 vitriol Chemical compound 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 150000001869 cobalt compounds Chemical class 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052790 beryllium Inorganic materials 0.000 claims description 4
- 230000010354 integration Effects 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims 1
- 238000005554 pickling Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 8
- 239000003513 alkali Substances 0.000 abstract description 4
- 238000009738 saturating Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 36
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000012530 fluid Substances 0.000 description 14
- 239000003921 oil Substances 0.000 description 13
- 229920006395 saturated elastomer Polymers 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 238000007670 refining Methods 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 10
- 238000012805 post-processing Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 206010013786 Dry skin Diseases 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 241000219793 Trifolium Species 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- VYQMZUUUGRXQHR-UHFFFAOYSA-N magnesium;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Mg+2].[Ti+4] VYQMZUUUGRXQHR-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 150000003658 tungsten compounds Chemical class 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002198 cosolvency Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The present invention is one kind of hydroprocessing catalyst and its preparation process. The catalyst contains alkali assistant and active components including Ni and Mo and/or W, with the atom number of Ni accounting for 0.3-0.9 of the total atom number of Ni and Mo and/or W; and the pore volume of 2-6 nm pores accounts for 70-90 % of total pore volume. The catalyst is prepared through mixing different pore structures of alumina to form carrier, soaking the alumina carrier first with alkali assistant aqua and then Mo and/or W compounds aqua and Ni compound aqua. Compared with available technology, the catalyst of the present invention has high Ni content in active components, more middle and small sized holes, high hydrogenation mercaptol-eliminating and olefin-saturating activity, and is especially suitable for mercaptol-eliminating process after hydrogenation.
Description
Technical field
The present invention relates to a kind of hydrotreating catalyst and preparation method thereof, especially a kind of hydrocracking post-processing catalyst and preparation method thereof.
Background technology
Hydrocracking is a kind of petroleum refining process that high-boiling hydrocarbons is formed small molecules, lower boiling purpose product by the C-C bond rupture.Because hydrocracking raw materials such as heavy oil contain impurity such as sulphur, oxygen, nitrogen usually, raw material can carry out hydrocracking after need removing impurity through hydrocracking pre-refining process (HDS, HDN, HDO) usually.High-boiling hydrocarbons can form the small molecules hydro carbons by the fracture of C-C key in the hydrocracking reaction process, and can obtain H/C than higher purpose product by hydrogenation.Organic sulfide in the raw material generates H after hydrofining
2S enters in the gas phase and generates mercaptan with olefine reaction that cracking produces.A spot of mercaptan can make product generation stench and make oil quality and stability decline in the product.In the bottom of hydrocracking reactor, it is more obvious that higher temperature of reaction makes that mercaptan generates trend.And the enhancing of the increase of high-sulfur crude oil refining amount and environmental protection standard makes the handling problem of mercaptan seem more outstanding.
Industrial, because raw material and complete processing difference, the removal methods of mercaptan is not quite similar.Usually can comprise soda acid electrochemical treating technology, oxidation deodorizing technology, hydrofining technology and hydrocracking aftertreatment technology.
Hydrofining is a kind of comparatively effectively mercaptan removing process, and this method (as illuminating kerosene, aviation kerosene, FCC gasoline) when handling intermediate oil and light-end products is used comparatively general.Because this method needs independent reactor to carry out hydrofining (reaction conditions restriction), thereby be used for hydrocracking process meeting increase facility investment and energy consumption.
Hydrocracking aftertreatment technology (post-treatment) is the method that the minimizing mercaptan that generally adopts on the industrial hydroeracking unit generates.Promptly add that at the hydrocracking reactor back segment a small amount of hydrocracking post-processing catalyst generates and satisfies product index and environmental requirement with saturation of olefins, inhibition mercaptan.The hydrocracking aftertreatment is carried out under higher relatively temperature of reaction usually, and is higher about 15 ℃ even higher than common hydrofining temperature.The hydrocracking post-processing catalyst that adopts on the industrialized unit is common Hydrobon catalyst mostly.Common Hydrobon catalyst is unsatisfactory owing to being subjected to nickel/(nickel+molybdenum and/or tungsten) atomic ratio effect low and that the higher restriction of hydrocracking aftertreatment temperature of reaction generates inhibition mercaptan.
Chinese patent CN 1229835A discloses a kind of light-end products that are used for and has contained Tungsten oxide 99.999 and/or molybdenum oxide, nickel oxide, cobalt oxide hydrotreating catalyst, and this catalyst metal content is low, has higher low temperature active.Chinese patent CN 1229838A improves on this basis, makes the hydrofining mercaptan removal not only can carry out under 150～260 ℃ of lower temperature of reaction, has lower hydrogen-oil ratio (5～30) simultaneously.U.S. Pat 6231753 adopts two sections vapor-phase hydrodesulfurizations (HDS) technology, after first section HDS reaction, removes most of H
2S is with H
2S separates with raw material, carries out second section HDS again.Adopt this method can obviously reduce the generation of alkene and mercaptan.The method reaction conditions that heats up in a steamer alcohol comparatively relaxes, the mercaptan removal effect is preferable though above-mentioned relevant fraction oil hydrogenation refining takes off, and often still has certain limitation because of can not directly mating with hydrocracking process.
U.S. Pat 3338819 is one piece of patent that relate to the hydrocracking aftertreatment early, this patent disclosure at the interval H of hydrocracking reaction
2S can generate mercaptan with alkene.The existence of mercaptan has reduced the oil quality of respective regions, and this patent adopts the mode of further aftertreatment to address the above problem, with a spot of hydrotreating catalyst (Ni-Mo/Al
2O
3) be loaded on the hydrocracking reactor bottom, reduce the mercaptan in the light benzine (final boiling point is 230 promptly 110 ℃), but the effect of not mentioned other fractional oil desulfurizing alcohol.
Since mercaptan during with the sulfocompound desulfurization required desulfurization depth different, being specifically designed to the hydrocracking post-processing catalyst has higher (nickel+cobalt)/(nickel+molybdenum and/or tungsten+cobalt) atomic ratio usually.Foregoing Chinese patent CN 1229835A, CN 1229838A and U.S. Pat 6231753 all have comparatively detailed description.But the unifining process that above-mentioned three patents adopted all with usually adopt under the hydrocracking post-treatment condition different, and the extra facility investment of need, thereby the disclosed method of above-mentioned patent is used for hydrocracking process certain limitation is all arranged.In addition, it is an important parameters that catalyst pores distributes, and has only the aperture major part of catalyzer to concentrate in the scope that is suitable for reactant and resultant diffusion, its due katalysis of competence exertion, and catalyzer just can show good activity.The situation that the above-mentioned three pieces of all not mentioned catalyzer of patent apertures distribute, those of ordinary skill in the art thinks it should is the pore size distribution of common catalyst for refining, and the pore size distribution of common catalyst for refining is dispersed in 4～10nm scope mostly, medium and small hole number is few, is not suitable for the hydro-sweetening reaction of low-molecular-weight fraction oil.
Summary of the invention
The catalyzer that is used for the hydrocracking aftertreatment provided by the invention contains aluminum oxide in the carrier, active ingredient is the base metal of group vib and group VIII.Described base metal comprises the nickel of group vib molybdenum and/or tungsten and group VIII.Described alkaline assistant is basic metal (IA family) and/or alkaline-earth metal (IIA family), and wherein basic metal is Li, Na, K, Rh and/or Cs, and alkaline-earth metal is Be, Mg, Ca, Sr and/or Ba.With the catalyst weight is benchmark, and molybdenum oxide and/or tungsten oxide content are 5.0%～30.0%, and nickel oxide content is 1.0%～15.0%; Alkaline assistant content is 0.05%～5.00%; The nickle atom number is 0.3～0.9 with the ratio of the total atom number of nickel, molybdenum and/or tungsten, is preferably 0.4～0.9, and the specific surface area of above-mentioned catalyzer is 100～500m
2/ g is preferably 150～350m
2/ g, pore volume is 0.30～0.55ml/g, is preferably 0.35～0.50ml/g, accounts for 70%～90% of total pore volume at the pore volume integration rate of 2～6nm, is preferably 75%～85%.Also can contain cobalt in the catalyzer, be benchmark with the catalyst weight, and cobalt oxide content is 0.1%～5.0%, and the cobalt atom number is 0.005～0.300 with the ratio of the total atom number of nickel, cobalt, molybdenum and/or tungsten.Also can contain auxiliary agent phosphorus in the catalyzer, be benchmark with the catalyst weight, and its content is 0.5%～10.0%.The B acid amount of described catalyzer is 0.001～0.250mmol/g, is preferably 0.005～0.150mmol/g.L acid amount is 0.010～0.700mmol/g, is preferably 0.010～0.500mmol/g.The B acid amount of the catalyzer that the present invention mentioned and L acid amount are measured by infrared acidity method, promptly measure on Nicloet 560F-IR instrument.
The aluminum oxide that is used for the carrier of hydrocracking post-processing catalyst provided by the invention, preferred gama-alumina, η-aluminum oxide or its mixture, its specific surface area 150～500m
2/ g, pore volume are 0.40～0.70ml/g, account for 70%～90% of total pore volume at the pore volume integration rate of 2～6nm.
The preparation method of hydrocracking post-processing catalyst of the present invention comprises the steps:
(1), macroporous aluminium oxide, aperture aluminum oxide are mixed, add to mix behind the tackiness agent and pinch, roll, make support of the catalyst after the moulding, drying, roasting; Described drying temperature is 40～180 ℃, is preferably 100～150 ℃, and be 0.5～24 hour time of drying, is preferably 1～8 hour; Described maturing temperature is 350～900 ℃, is preferably 400～800 ℃, and roasting time is 0.5～24 hour, is preferably 1～8 hour.
(2), flood the alumina supporter of above-mentioned preparation, the support of the catalyst that contains auxiliary agent of the present invention is made in dipping back drying, roasting with the aqueous solution of alkali metal containing and/or alkaline-earth metal.Described drying temperature is generally 40～180 ℃, preferably 100～150 ℃.Be generally time of drying 0.5～24 hour, and be preferably 1～8 hour.Described maturing temperature is generally 350～1200 ℃, preferably 400～1000 ℃.Roasting time was generally 0.5～24 hour, was preferably 1～8 hour.
(3) with comprising the aqueous solution dipping said catalyst carrier that contains molybdenum and/or Tungstenic compound, nickel compound containing, catalyzer of the present invention is made in dipping back drying, roasting; Wherein said drying temperature is 60～180 ℃, is preferably 100～150 ℃, and be 0.5～24 hour time of drying, is preferably 1～8 hour; Described maturing temperature is 300～700 ℃, is preferably 350～600 ℃, and roasting time is 0.5～24 hour, is preferably 1～8 hour.
Among the above-mentioned preparation method, the pore volume of the described macroporous aluminium oxide of step (1) is 0.85～1.25ml/g, and specific surface is 300～550m
2/ g; The pore volume of little porous aluminum oxide is 0.30～0.60ml/g, and specific surface is 180～450m
2/ g.The weight ratio of little porous aluminum oxide and macroporous aluminium oxide is 0.25～9.0.Macroporous aluminium oxide and little porous aluminum oxide can adopt wherein one or more.
The described tackiness agent of step (1) comprises aluminum oxide and peptizing agent, weight with carrier after the roasting is benchmark, the aluminum oxide solid content is 5%～30%, and peptizing agent/alumina molar ratio is 0.10～0.35, and peptizing agent is one or more in Tai-Ace S 150, citric acid, nitric acid, acetic acid and the oxalic acid.Also can add clay, silicon oxide, sial, zirconium white, titanium oxide-magnesium oxide and their mixture in the described binder ingredients.
The described aqueous solution dipping that contains molybdenum and/or tungsten compound and nickel compound containing both can adopt and soak method altogether and also can adopt step impregnation method.This soaks method altogether and step impregnation method can adopt method of the prior art.Soak legal system altogether when being equipped with when adopting, will add P contained compound in the steeping fluid.When adopting step impregnation method to prepare, can add P contained compound in the steeping fluid, also can not add P contained compound.When adopting step impregnation, all need dry, roasting behind each dipping, its condition and the required drying of catalyzer, roasting condition are identical.
The present invention contains among the preparation method of support of the catalyst of alkaline assistant, and the compound of alkali metal containing described in the step (2) (as Li, Na, K, Rh, Cs) and/or alkaline-earth metal (as Be, Mg, Ca, Sr, Ba) is one or more in its water soluble chloride, carbonate, vitriol, nitrate, oxalate and the subcarbonate.
In the Preparation of catalysts method of the present invention, the impregnation catalyst agent carrier process described in the step (3) is one of following method:
A, employing contain the solution impregnating catalyst carrier of molybdenum and/or tungsten, nickel and phosphorus;
B, elder generation, flood with the nickeliferous aqueous solution after drying, the roasting with the solution impregnating catalyst carrier that contains molybdenum and/or tungsten again;
C, elder generation's solution impregnating catalyst carrier that contains molybdenum and/or tungsten are after drying, the roasting, again with containing molybdenum, nickel, phosphorus aqueous solution dipping;
D, elder generation, with nickeliferous aqueous solution dipping, after drying, the roasting, flood with the nickeliferous aqueous solution after drying, the roasting with the solution impregnating catalyst carrier that contains molybdenum and/or tungsten more again; Also cobalt compound can be arranged in the nickeliferous aqueous solution in above-mentioned four kinds of methods.
Above-mentioned nickel compound containing and cobalt compound are one or more in its water soluble chloride, carbonate, vitriol, nitrate, oxalate and the subcarbonate, Tungstenic compound is an ammonium metawolframate, molybdate compound is ammonium molybdate and/or molybdenum oxide, and P contained compound is one or more in phosphoric acid, ammonium hydrogen phosphate, biphosphate phosphoric acid and the ammonium phosphate.
The carrier of catalyzer of the present invention also can use and be clay, silicon oxide, sial, zirconium white, titanium oxide-magnesium oxide or its mixture.Can also sneak into the acidic components or the inorganic oxide component of other type in the carrier, acidic components can be unformed metal oxide, crystalline molecular sieve and their mixture.Metal oxide comprises amorphous silicon aluminium, SiO
2-MgO, SiO
2-TiO
2, SiO
2-Al
2O
3-TiO
2, SiO
2-TiO
2-ZrO
2, be dispersed in sial, Al on the aluminum oxide
2O
3-B
2O
3And other acidic mixed oxide.The crystalline molecular sieve structure type comprises FAU, EMT, MOR, LTL, MAZ, MTW, OFF, BOG, AET, AFI, AFR, AFS, AFY, ATS, VFI and CLO.Also comprise the big mesoporous aluminosilicate of crystallization such as MCM-41, MCM-48 etc. in addition.
Support shapes after the described moulding can be sheet, spherical, cylinder bar and special-shaped bar (trifolium, Herba Galii Bungei), preferably cylinder bar and special-shaped bar (trifolium, Herba Galii Bungei).The diameter of carrier can be 0.8～2.0mm slice and＞the thick bar of 2.5mm.
Compared with prior art, nickel in the catalyst activity component of the present invention/(nickel+molybdenum and/or tungsten) total atom is than higher, the content that nickel accounts for (nickel+molybdenum and/or tungsten) is 0.3～0.9, be about about 0.25-0.30 and common catalyst for refining nickel accounts for the content of (nickel+molybdenum and/or tungsten), can directly apply in the hydrocracking aftertreatment mercaptan removal sulphur process.Catalyzer of the present invention is in addition compared with common catalyst for refining, medium and small hole number in the support of the catalyst obviously increases and distributes to be concentrated, 70%～90% pore volume concentrates on 2～6nm (common catalyst for refining pore size distribution is dispersed in 4～10nm scope mostly) in the pore size distribution, thereby this will be more suitable for generating the reactive behavior that improves catalyzer that contacts oily and catalyzer in lower molecular weight.
Catalyzer provided by the invention is applicable to that the boiling range scope is the hydrofining of 70～380 ℃ fraction oil of petroleum, be specially adapted to hydrocracking and generate oily mercaptan removal process, this process comprises refining desulfurization alcohol process behind the hydrogenation at least, also can comprise one or several other hydrofinings and hydrocracking process, be preferably used in the hydrocracking aftertreatment and produce low thioalcohol product process.
Embodiment
According to Preparation of catalysts method provided by the invention, its concrete steps are as follows respectively:
(1) preparation of support of the catalyst
A, be that raw material mixes with macroporous aluminium oxide and little porous aluminum oxide.
Add tackiness agent (preferred aluminum oxide in b, the raw material after mixed, with vehicle weight after the roasting is benchmark, the aluminum oxide solid content is 5%～30%, the mol ratio of peptizing agent and aluminum oxide is 0.10～0.35) and add extrusion aid (optimization citric acid, sesbania powder, with vehicle weight after the roasting is benchmark, and extrusion aid content is 0.5%～10%) back is mixed and is pinched, rolls, extruded moulding.
C, will extrude bar and under room temperature, dry naturally, and pulverize after 1～24 hour in 100～150 ℃ of dryings and obtain the dried strip that length is 3～8mm.
D, with 450～700 ℃ of roastings 0.5～24 hour in retort furnace of above-mentioned dried strip, obtain support of the catalyst.
(2) contain the preparation of the support of the catalyst of alkaline assistant
The interpolation of alkaline assistant can be adopted single component alkaline assistant and polycomponent alkaline assistant, is mainly used to prepare the support of the catalyst that contains alkaline assistant.When adopting the polycomponent alkaline assistant to add, can be divided into a step again soaks altogether and adds or the multistep dipping adds, and when the alkaline assistant component adopts a step to soak altogether to add, can be undertaken by the method for being prepared as follows.
A, the prepared alumina supporter of employing the present invention, as steeping fluid, adopt saturated or excessive impregnation method to flood with the aqueous solution that contains one or more basic cu nitrates (nitrate of Li, Na, K, Rh, Cs, Be, Mg, Ca, Sr and/or Ba) 1～6 hour.Dipping back leaches steeping fluid with funnel, will flood bar and dry naturally under room temperature, in 100～150 ℃ of dryings 1～48 hour, 400～600 ℃ of roastings in retort furnace of above-mentioned dried strip must be contained the support of the catalyst of alkaline assistant in 0.5～24 hour.
When the alkaline assistant component adopts multistep to add, can be undertaken by the method for being prepared as follows.
A, adopt the prepared alumina supporter of the present invention, earlier with a kind of and/or multiple soluble alkali and/or the alkaline-earth metal of containing as steeping fluid, adopt saturated or excessive impregnation method to flood 1～6 hour.The dipping back leaches steeping fluid with funnel, to flood bar dries under room temperature naturally, in 100～150 ℃ of dryings 1～48 hour, 400～600 ℃ of roastings in retort furnace of above-mentioned dried strip must be contained a kind of and/or multiple support of the catalyst that contains alkaline assistant in 0.5～24 hour.
B, again with another kind of and/or multiple soluble alkali and/or the alkaline-earth metal of containing as steeping fluid, adopt saturated or excessive impregnation method to flood 1～6 hour.Dipping back leaches steeping fluid with funnel, will flood bar and dry naturally under room temperature, in 100～150 ℃ of dryings 1～48 hour, 400～600 ℃ of roastings in retort furnace of above-mentioned dried strip must be contained the support of the catalyst of multiple alkaline assistant in 0.5～24 hour.
The solubility solution of two kinds of alkali metal containings and/or alkaline-earth metal can adopt different acid ions, as flooding calcium ion with nitrocalcite earlier, is flooding potassium ion with salt of wormwood.The addition sequence of alkaline assistant can change as required.
(3) Preparation of catalysts
Supporting of catalyst metal components can be adopted step impregnation method and co-impregnation.
When catalyst metal components adopted step impregnation method to load on the catalyzer, method for preparing catalyst can carry out as follows:
A, the prepared carrier that contains alkaline assistant of employing the present invention as steeping fluid, adopt saturated or excessive impregnation method to flood with the aqueous solution that contains molybdenum and/or Tungstenic compound (preferred ammonium metawolframate and/or ammonium molybdate) 1～6 hour.Dipping back leaches steeping fluid with funnel, will flood bar and dry naturally under room temperature, in 100～150 ℃ of dryings 1～24 hour, with 400～700 ℃ of roastings 0.5～24 hour in retort furnace of above-mentioned dried strip.
B, with the aqueous solution of nickel compound containing (preferred nickelous nitrate, basic nickel carbonate) as steeping fluid or with the aqueous solution of nickel compound containing and cobalt compound (preferred Xiao Suangu) as steeping fluid, the saturated or excessive impregnation method of getting after the step a roasting of carrier employing flooded 1～6 hour.Dipping back leaches steeping fluid with funnel, and will flood bar and under room temperature, dry naturally, in 100～150 ℃ of dryings 1～24 hour, must the catalyst soakage bar.
C, dipping bar after 0.5～24 hour, can obtain the catalyzer finished product in 400～700 ℃ of roastings.
When catalyst metal components adopted co-impregnation to load on the catalyzer, method for preparing catalyst can carry out as follows:
A, with nickel compound containing (preferred nickelous nitrate, basic nickel carbonate), to contain molybdenum and/or tungsten compound (preferred ammonium molybdate and/or ammonium metawolframate), be with or without cobalt compound (preferred Xiao Suangu) be raw material adding distilled water and P contained compound (preferably phosphoric acid), stirred 0.25～24 hour at 70～99 ℃ of following azeotropic, solution transfers deep green to by initial yellow-green colour and forms nickeliferous, (cobalt), molybdenum of while and/or the cosolvency aqueous solution of tungsten, phosphorus.
B, adopt the prepared support of the catalyst that contains alkaline assistant of the present invention, with the solution impregnation of above-mentioned configuration 1～6 hour.Dipping back leaches steeping fluid with funnel, will flood bar and dry naturally under room temperature, in 100～150 ℃ of dryings 1～24 hour.
C, 400～700 ℃ of roastings in retort furnace of dipping bar can obtain the catalyzer finished product after 0.5～24 hour.
The invention will be further described below by specific embodiment.
The used various macropores and the character of little porous aluminum oxide see Table 1 in the various embodiments of the present invention.The acidity of catalyst of being mentioned in the embodiment of the invention is to adopt infrared acidity method to measure, and promptly measures on Nicloet 560F-IR instrument.
Comparative Examples 1
Comparative catalyst of the present invention is a kind of common industrialized external hydrocracking post-processing catalyst at present, catalyzer numbering C-0, and its physico-chemical property sees table 2.
The used various macropores and the character of little porous aluminum oxide among table 1 embodiment
| Raw material | The industry macroporous aluminium oxide | The little porous aluminum oxide of industry | Germany PURAL SB-Al 2O 3 |
| Specific surface area, m 2/g | ????480 | ????301 | ??357 |
| Pore volume, ml/g | ????1.02 | ????0.37 | ??0.48 |
| Butt, wt% | ????0.72 | ????0.72 | ??0.72 |
Embodiment 1
Embodiment 1 is the preparation of carrier provided by the invention.
Get industrial macroporous aluminium oxide 128.5g, industrial aperture aluminum oxide 150g, moral home-made PURALSB-Al
2O
341.7g, citric acid 5g, industrial sesbania powder 8g mixed 45 minutes, (Germany produces PURAL SB-Al to add the 240g tackiness agent
2O
3With volumetric concentration be that the making beating of 65% nitric acid is prepared from tackiness agent solid content 25wt%, nitric acid/SB-Al
2O
3Mol ratio is 0.25) to mix to pinch after 30 minutes and rolled 5 minutes, extrusion gets diameter 1.5mm trifolium bar, 110 ℃ of dryings 2 hours, 550 ℃ of roastings 24 hours.Obtain carrier Z-A.
Embodiment 2-5 is the preparation that contains basic metal auxiliary agent support of the catalyst provided by the invention.
Embodiment 2
Get 0.8g nitrate of baryta Ba (NO
3)
2The adding distil water dissolving is diluted to 250ml with volumetric flask, is made into the baric aqueous solution.Get the carrier Z-A 100g that above-mentioned preparation method obtains, carry out saturated dipping with the aqueous solution of the baric of 70ml method for preparing, dipping time 6 hours dries behind the dipping and spends the night, and in 110 ℃ dry 24 hours down, then 550 ℃ of following roastings 3 hours.Get the carrier Z-B of alkali metal containing barium.
Embodiment 3
Get 25g magnesium nitrate (Mg (NO
3)
26H
2O) adding distil water dissolving is diluted to 250ml with volumetric flask, is made into Mg-bearing water solution.Get the carrier Z-A 100g that above-mentioned preparation method obtains, carry out saturated dipping with the magniferous aqueous solution of 70ml method for preparing, dipping time 6 hours dries behind the dipping and spends the night, and in 110 ℃ dry 24 hours down, then 550 ℃ of following roastings 3 hours.Get the carrier Z-C of alkali metal containing magnesium.
Embodiment 4
Get 82.5g magnesium chloride Mg Cl
2The adding distil water dissolving is diluted to 250ml with volumetric flask, is made into Mg-bearing water solution.Get the carrier Z-A 100g that above-mentioned preparation method obtains, carry out saturated dipping with the magniferous aqueous solution of 70ml method for preparing, dipping time 6 hours dries behind the dipping and spends the night, and in 110 ℃ dry 24 hours down, then 550 ℃ of following roastings 3 hours.Get the carrier Z-D of alkali metal containing magnesium.
Embodiment 5
Get 9g saltpetre KNO
3, 7.2g nitrocalcite (Ca (NO
3)
24H
2O) adding distil water dissolving is diluted to 250ml with volumetric flask, is made into the aqueous solution that contains potassium and calcium.Get the carrier Z-A 100g that above-mentioned preparation method obtains, carry out saturated dipping with the aqueous solution that contains potassium and calcium of 70ml method for preparing, dipping time 6 hours dries behind the dipping and spends the night, and in 110 ℃ dry 24 hours down, then 550 ℃ of following roastings 3 hours.The carrier Z-E that must contain alkaline assistant potassium and calcium.
Embodiment 6-7 is a Preparation of Catalyst provided by the invention.
Embodiment 6
Get 94g ammonium metawolframate ((NH
4)
6W
7O
246H
2O) adding distil water dissolving is diluted to 250ml with volumetric flask, is made into the tungstenic aqueous solution.Get the Z-A that above-mentioned preparation method obtains, each 100g of Z-B carrier, the tungstenic aqueous solution with the above-mentioned preparation of 75ml carries out saturated dipping respectively, and dipping time 6 hours dries behind the dipping and spends the night, and in 110 ℃ times dry 24 hours, then 600 ℃ of following roastings 8 hours.Get 40g nickelous nitrate (Ni (NO
3)
26H
2O) adding distil water dissolving is diluted to 250ml with volumetric flask, is made into the nickeliferous aqueous solution.The roasting bar of getting the tungstenic that above-mentioned preparation method obtains is 100g altogether, the nickeliferous aqueous solution with the 70ml method for preparing carries out the saturated dipping of secondary respectively, and dipping time 6 hours dries behind the dipping and spends the night, and in 110 ℃ times dry 24 hours, then 550 ℃ of following roastings 3 hours.Get catalyzer C-1 and C-3.
Embodiment 7
In the 1000ml four-hole boiling flask, add 200g molybdic oxide, 215g basic nickel carbonate (NiCO
32Ni (OH)
24H
2O), 35g Xiao Suangu (Co (NO
3)
26H
2O) and add 300ml distilled water and stir, it is 85% phosphoric acid that the back that stirs adds the 50ml volumetric concentration, and 75 ℃ of following backflow heated and stirred 8 hours, solution faded to green by yellow, filters nickeliferously, the aqueous solution of cobalt, molybdenum, phosphorus, and it is standby to be diluted to 1000ml.Get Z-A, Z-C, Z-D, each 100g of Z-E carrier that above-mentioned preparation method obtains, nickeliferous, cobalt, molybdenum, phosphorus solution with the 150ml method for preparing carries out excessive dipping respectively, dipping time 6 hours, dry behind the dipping and spend the night, and in 110 ℃ times dry 12 hours, then 450 ℃ of following roastings 6 hours.Obtain corresponding catalyzer C-2, C-4 and C-5 respectively.
Embodiment 8
Add the 25g ammonium molybdate and add 100ml distilled water in the 1000ml four-hole boiling flask and stir, PH=9 is regulated with strong aqua in the back that stirs, stirring and dissolving at room temperature, and the solution water white transparency, it is standby to be diluted to 250ml.The aqueous solution that contains molybdenum with the above-mentioned preparation of 75ml carries out saturated dipping, and dipping time 6 hours dries behind the dipping and spends the night, and in 110 ℃ times dry 24 hours, then 600 ℃ of following roastings 8 hours.
Get 200g nickelous nitrate (Ni (NO
3)
26H
2O), 65g Xiao Suangu (Co (NO
3)
26H
2O) be dissolved in water, be diluted to 250ML.That gets that above-mentioned preparation method obtains contains molybdenum carrier 100g, carries out saturated dipping with the aqueous solution of the nickel and cobalt containing of the above-mentioned preparation of 75ml, and dipping time 6 hours dries behind the dipping and spends the night, and in 110 ℃ dry 24 hours down, then 600 ℃ of following roastings 8 hours.
The physico-chemical property of table 2 C-0～C-6 catalyzer
| The catalyzer numbering | ??C-0 | ??C-1 | ??C-2 | ??C-3 | ??C-4 | ??C-5 | ??C-6 |
| ?NiO，wt％ | ??3.05 | ??2.29 | ??6.05 | ??2.85 | ??6.25 | ??5.89 | ??14.20 |
| ?CoO，wt％ | ??— | ??— | ??0.41 | ??— | ??0.52 | ??0.52 | ??0.41 |
| ?MoO 3，wt％ | ??15.28 | ??— | ??13.20 | ??— | ??12.42 | ??12.93 | ??5.17 |
| ?WO 3，wt％ | ??— | ??22.25 | ??— | ??22.45 | ??— | ??— | ??— |
| ?P，wt％ | ??2.79 | ??— | ??1.94 | ??— | ??2.18 | ??1.69 | ??— |
| The basic metal kind | ??— | ??— | ??— | ??Ba | ??Mg | ??Mg | ??K、Ca |
| Basic metal, wt% | ??0 | ??0 | ??0 | ??0.13 | ??0.47 | ??4.63 | ??1.05 |
| Ni/ (Ni+Mo or W) atomic ratio | ??0.28 | ??0.31 | ??0.45 | ??0.32 | ??0.47 | ??0.47 | ??0.84 |
| Co/ (Ni+Co+Mo or W) atomic ratio | ??0 | ??0 | ??0.03 | ??0 | ??0.04 | ??0.04 | ??0.03 |
| Specific surface, m 2/g | ??219 | ??217 | ??254 | ??205 | ??198 | ??152 | ??171 |
| B acid amount, m mol/g | ??0.082 | ??0.145 | ??0.053 | ??0.111 | ??0.028 | ??0.005 | ??0.037 |
| L acid amount, m mol/g | ??0.525 | ??0.537 | ??0.465 | ??0.382 | ??0.067 | ??0.106 | ??0.332 |
| Pore volume, ml/g | ??0.366 | ??0.411 | ??0.407 | ??0.401 | ??0.397 | ??0.395 | ??0.382 |
| Pore size distribution | |||||||
| ?2～4nm，％ | ??5.8 | ??16.6 | ??20.3 | ??17.5 | ??18.2 | ??18.6 | ??19.9 |
| ?4-6nm，％ | ??32.6 | ??61.3 | ??61.4 | ??60.9 | ??63.7 | ??60.9 | ??61.9 |
| ?6-8nm，％ | ??39.3 | ??16.6 | ??10.6 | ??17.2 | ??10.7 | ??13.6 | ??13.2 |
| ?＞8nm，％ | ??22.3 | ??5.5 | ??5.0 | ??4.4 | ??7.4 | ??6.9 | ??5.0 |
Embodiment 9
Present embodiment is that hydrocracking post-processing catalyst hydrogenation and mercaptan remove performance evaluation.
For high hydrogenation activity and the high mercaptan that further specifies catalyzer of the present invention removes ability, adopt C-0, C-1, C-2, C-3, C-4, C-5 and C-6 catalyzer, generating oil with the hydrocracking of allocating is that raw material carries out activity rating.Stock oil character sees Table 3, and evaluation result sees table 4.
Table 3 stock oil character
| Stock oil character | |
| Density, g/cm 3(20℃) | ????0.8240 |
| Boiling range, ℃ (ASTM-D1160) | |
| IBP/10％ | ????73.6/135.3 |
| 50％/EP | ????311.7/355.1 |
| S，μg/g | ????3300 |
| N，μg/g | ????58.6 |
| The bromine valency, gBr/100ml | ????1.62 |
| Mercaptan sulfur, μ g/g | ????46.1 |
| Alkene, v% | ????23.8 |
Catalyst for refining catalytic perfomance evaluation result after table 4 hydrocracking
| Catalyzer | ??C-0 | ??C-1 | ??C-2 | ??C-3 | ??C-4 | ??C-5 | ??C-6 |
| Reaction conditions hydrogen dividing potential drop, MPa volume space velocity, h -1Hydrogen-oil ratio (v) temperature of reaction, ℃ | ??14.7 ??10 ??1500 ??385 | ??14.7 ??10 ??1500 ??385 | ??14.7 ??10 ??1500 ??385 | ??14.7 ??10 ??1500 ??385 | ??14.7 ??10 ??1500 ??385 | ??14.7 ??10 ??1500 ??385 | ??14.7 ??10 ??1500 ??385 |
| Generate oily S, μ g/g mercaptan sulfur, μ g/g alkene, v% bromine valency, gBr/100ml | ??99 ??8.8 ??7.7 ??0.74 | ??65 ??4.9 ??5.7 ??0.52 | ??77 ??5.3 ??3.9 ??0.36 | ??60 ??4.5 ??4.8 ??0.45 | ??59 ??3.3 ??2.1 ??0.25 | ??69 ??4.9 ??3.2 ??0.33 | ??64 ??4.2 ??2.6 ??0.30 |
The hydrogenation of hydrocracking post-processing catalyst and mercaptan removal activity are represented by the decreasing ratio of the bromine valency in the product and olefin conversion, sulphur and mercaptan sulfur respectively.Catalyzer physico-chemical property data see Table 2, the activity rating data see Table 4.Adopt the C-3～C-6 catalyzer of the inventive method preparation to compare in the table 2, have more concentrated middle aperture pore size distribution with reference catalyst C-0, the aperture in 2～6nm ratio up to more than 70%.Adopt the C-3 that contains alkaline assistant, C-4, C-5, the C-6 catalyzer of the inventive method preparation to compare with the C-2 catalyzer with the C-1 of corresponding alkali-free auxiliary agent respectively, similar in pore structure and active metal component.Under identical reaction conditions, total sulfur, mercaptan sulfur, olefin(e) centent all are lower than the catalyzer that adopts the alkali-free metal in the product.Because after adding basic metal, the part acid sites is capped, and has not only reduced cracked trend under the high temperature; Simultaneously, alkali-metal adding has reduced the L acid of catalyzer, has reduced the possibility of isomerization reaction, thereby makes its parallel reactor---and hydrogenation reaction has bigger selectivity, thereby the hydrogenation effect is more obvious.The increase of hydrogenation performance also makes the generation of mercaptan obtain inhibition, generates thereby show as lower mercaptan sulfur in product.In addition, catalyst surface dipping basic metal may make catalyzer that the absorption property of acid product mercaptan is strengthened, thereby help mercaptan removing on the surface.Thereby show as overall mercaptans content and reduce.
Adopt present method preparation have high Ni/ (Ni and/or Co+Mo and/or W) atomic ratio, pore size distribution Ni (Co) Mo (W) that concentrate and that contain the basic metal auxiliary agent (P) catalyzer be a kind of comparatively good hydrocracking post-processing catalyst, can be used for the hydrocracking reactor back segment as aftertreatment and behind the coal that is used to navigate in the middle of the similar reaction such as refining desulfurization alcohol.
Claims (14)
1, a kind of hydrotreating catalyst, with group vib and VIII family metal is active ingredient, contain aluminum oxide in the carrier, it is characterized in that active ingredient comprises molybdenum and/or tungsten and nickel, alkaline assistant is basic metal and/or alkaline-earth metal, with the catalyst weight is benchmark, molybdenum oxide and/or tungsten oxide content are 5.0%～30.0%, nickel oxide content is 1.0%～15.0%, alkaline assistant content is 0.05%～5.00%, the nickle atom number is 0.3～0.9 with the ratio of the total atom number of nickel, molybdenum and/or tungsten, accounts for 70%～90% of total pore volume at the pore volume integration rate of 2～6nm.
2, according to the described catalyzer of claim 1, it is characterized in that the ratio of nickle atom number and the total atom number of nickel, molybdenum and/or tungsten is 0.4～0.9 in the described catalyzer, account for 75%～85% of total pore volume at the pore volume integration rate of 2～6nm.
3, according to the described catalyzer of claim 1, the specific surface area that it is characterized in that described catalyzer is 100～500m
2/ g, pore volume are 0.30～0.55ml/g, and B acid amount is 0.001～0.250mmol/g, and L acid amount is 0.010-0.700mmol/g.
4, according to the described catalyzer of claim 1, it is characterized in that described basic metal is Li, Na, K, Rh and/or Cs, alkaline-earth metal is Be, Mg, Ca, Sr and/or Ba.
5, according to the described catalyzer of claim 1, it is characterized in that containing cobalt in the described catalyzer, with the catalyst weight benchmark, cobalt oxide content is 0.1%～5.0%, the cobalt atom number is 0.005～0.300 with the ratio of the total atom number of nickel, cobalt, molybdenum and/or tungsten.
6, according to the described catalyzer of claim 1, it is characterized in that containing phosphorus in the described catalyzer, with the catalyst weight benchmark, phosphorus content is 0.5%～10.0%.
7, the described Preparation of catalysts method of claim 1 may further comprise the steps:
(1) macroporous aluminium oxide, aperture aluminum oxide are mixed, add to mix behind the tackiness agent and pinch, roll, make alumina supporter after the moulding, drying, roasting;
(2) flood the alumina supporter of above-mentioned preparation with the aqueous solution of alkali metal containing and/or alkaline-earth metal, the support of the catalyst that contains alkaline assistant is made in dipping back drying, roasting;
(3) with comprising the above-mentioned support of the catalyst that contains alkaline assistant of aqueous solution dipping that contains molybdenum and/or Tungstenic compound, nickel compound containing, catalyzer is made in dipping back drying, roasting.
8, according to the described Preparation of catalysts method of claim 7, it is characterized in that the pore volume of the described macroporous aluminium oxide of step (1) is 0.85～1.25ml/g, specific surface is 300～550m
2/ g; The pore volume of little porous aluminum oxide is 0.30～0.60ml/g, and specific surface is 180～450m
2/ g.
9, Preparation of catalysts method according to claim 7, the weight ratio that it is characterized in that medium and small porous aluminum oxide of step (1) and macroporous aluminium oxide is 0.25～9.00.
10,, it is characterized in that the method with the aqueous solution oxide impregnation alumina supporter of alkali metal containing and/or alkaline-earth metal described in the step (2) can adopt a step pickling process or a step impregnation method according to the described Preparation of catalysts method of claim 7.
11,, it is characterized in that the support of the catalyst process that the dipping described in the step (3) contains alkaline assistant is one of following method according to the described Preparation of catalysts method of claim 7:
A, employing contain the solution impregnating catalyst carrier of molybdenum and/or tungsten, nickel and phosphorus;
B, elder generation, flood with the nickeliferous aqueous solution after drying, the roasting with the solution impregnating catalyst carrier that contains molybdenum and/or tungsten again;
C, elder generation's solution impregnating catalyst carrier that contains molybdenum and/or tungsten are after drying, the roasting, again with containing molybdenum, nickel, phosphorus aqueous solution dipping;
D, elder generation, with nickeliferous aqueous solution dipping, after drying, the roasting, flood with the nickeliferous aqueous solution after drying, the roasting with the solution impregnating catalyst carrier that contains molybdenum and/or tungsten more again.
12, according to the described Preparation of catalysts method of claim 11, it is characterized in that also having cobalt compound in the nickeliferous aqueous solution, cobalt compound is one or more in its water soluble chloride, carbonate, vitriol, nitrate, oxalate and the subcarbonate.
13,, it is characterized in that alkali metal containing described in the step (2) and/or alkaline earth metal compounds are one or more in its water soluble chloride, carbonate, vitriol, nitrate, oxalate and the subcarbonate according to the described Preparation of catalysts method of claim 7; Nickel compound containing described in the step (3) is one or more in its water soluble chloride, carbonate, vitriol, nitrate, oxalate and the subcarbonate, and Tungstenic compound is an ammonium metawolframate, and molybdate compound is ammonium molybdate and/or molybdenum oxide.
14, according to the described Preparation of catalysts method of claim 7, it is characterized in that the drying conditions described in the step (1) is to descend dry 0.5～24 hour at 40～180 ℃, roasting condition is 350～900 ℃ of following roastings 0.5～24 hour; Drying conditions described in the step (2) is to descend dry 0.5～24 hour at 40～180 ℃, and roasting condition is 350～1200 ℃ of following roastings 0.5～24 hour; Drying conditions described in the step (3) is to descend dry 0.5～24 hour at 60～180 ℃, and roasting condition is 300～700 ℃ of following roastings 0.5～24 hour.
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