CN102268284B - Hydrorefining method of medium-low distillate oil - Google Patents
Hydrorefining method of medium-low distillate oil Download PDFInfo
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- CN102268284B CN102268284B CN201110191283.9A CN201110191283A CN102268284B CN 102268284 B CN102268284 B CN 102268284B CN 201110191283 A CN201110191283 A CN 201110191283A CN 102268284 B CN102268284 B CN 102268284B
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- pseudo
- boehmite
- slurries
- medium
- molybdenum
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- 238000000034 method Methods 0.000 title claims abstract description 72
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 70
- 239000002002 slurry Substances 0.000 claims abstract description 69
- 239000003054 catalyst Substances 0.000 claims abstract description 68
- 239000003921 oil Substances 0.000 claims abstract description 52
- 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 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000032683 aging Effects 0.000 claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 15
- 239000011733 molybdenum Substances 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical group [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims abstract description 10
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 claims description 70
- 239000000243 solution Substances 0.000 claims description 37
- 239000004033 plastic Substances 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910001868 water Inorganic materials 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 19
- 238000000465 moulding Methods 0.000 claims description 18
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 16
- 150000003818 basic metals Chemical class 0.000 claims description 16
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 229910052728 basic metal Inorganic materials 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 13
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 12
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 10
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 10
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 10
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000002210 silicon-based material Substances 0.000 claims description 6
- 230000029087 digestion Effects 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 229910001038 basic metal oxide Inorganic materials 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 15
- 238000002156 mixing Methods 0.000 abstract description 14
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052794 bromium Inorganic materials 0.000 abstract description 12
- 238000000197 pyrolysis Methods 0.000 abstract description 8
- 239000002243 precursor Substances 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 239000011959 amorphous silica alumina Substances 0.000 abstract 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 239000000306 component Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 19
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- 239000005864 Sulphur Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004073 vulcanization Methods 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 8
- 239000011609 ammonium molybdate Substances 0.000 description 8
- 235000018660 ammonium molybdate Nutrition 0.000 description 8
- 229940010552 ammonium molybdate Drugs 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 230000000694 effects Effects 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
- 238000005070 sampling Methods 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 235000011089 carbon dioxide Nutrition 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229940078494 nickel acetate Drugs 0.000 description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 4
- 229910001950 potassium oxide Inorganic materials 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- -1 aluminum ion Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium 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
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001648 diaspore Inorganic materials 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
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229940071264 lithium citrate Drugs 0.000 description 1
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000009183 running Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention provides a medium-low distillate oil hydrofining method. The catalyst is a molybdenum-nickel hydrogenation catalyst, and the hydrogenation process conditions are as follows: the inlet temperature is 200-300 ℃, the operating pressure is more than or equal to 2.4MPa, the liquid volume airspeed is 1-5 h < -1 >, and the volume ratio of hydrogen to oil is 100-500; the molybdenum-nickel catalyst takes silicon-containing alumina as a carrier, molybdenum and nickel as active components, and phosphorus and alkali metal are added as auxiliaries; the precursor of the silicon-containing alumina carrier is pseudo-boehmite containing amorphous silica-alumina, which is obtained by firstly preparing amorphous silica-alumina slurry and pseudo-boehmite slurry, mixing and aging the two slurries, and then carrying out post-treatment processes including filtering, washing and drying. The method is adopted to hydrofining the first-stage hydrogenation product of the middle-low fraction pyrolysis gasoline, and the bromine number in the hydrogenation product is less than 1.0 multiplied by 10-2g/g, sulfur content < 1.0 mu g/g, crack-meetingThe gasoline two-stage hydrogenation requirement is solved.
Description
Technical field
The present invention relates to a kind of hydrofinishing process of medium-low distillate oil, the hydrofining of two sections of low cut fraction pyrolysis gasoline during the method is specially adapted to.
Background technology
Pyrolysis gasoline is the byproduct in ethylene production, its output is the more than 50%～80% of ethylene production capacity, wherein aromaticity content is up to more than 50%, it is important aromatic hydrocarbon resource, wherein contain height unsaturated hydrocarbons, as: diolefin, vinylbenzene etc., the general raw material as Aromatics Extractive Project after two-stage hydrogenation.In recent years, ethylene industry has obtained unprecedented development, and ethylene production capacity improves year by year, as the output of the pyrolysis gasoline of the important by-product of ethene, will have significantly and increase.And take the hydrogen addition technology that pyrolysis gasoline hydrogenation catalyst is core, be an important branch in field of hydrogenation, in the aftertreatment of preparing ethylene by steam cracking technology, occupy very important position.
Along with the increasingly stringent of environmental legislation, more and more harsher to the requirement of Sulfur Content in Petroleum Products and nitrogen content; Simultaneously due to crude quality worse and worse, the foreign matter contents such as sulphur, nitrogen are more and more higher, therefore also more and more higher to the requirement of Hydrobon catalyst.For example, when coker gas oil is carried out to hydrofining, the nitrogen compound of high level especially basic nitrogen compound can be adsorbed on the acidic site of catalyzer, cause catalyst desulfurizing denitrification activity to decline, and the emphasis of raising Hydrobon catalyst imurity-removal ability is a kind of novel carriers material of exploitation or improve catalyst activity component concentration.People are when being optimized alumina supporter specific surface area, pore volume and aperture, by introducing the modifying elements such as silicon, titanium, phosphorus, come modulation alumina supporter surface acidity, improve the strong interaction between active ingredient and alumina supporter or occur new synergistic effect.The amorphous aluminum silicide specific surface area with divergence hole distribution is high, and anti-sintering property is good, and has certain surface acidity, therefore in Hydrobon catalyst preparation process, often used, but amorphous aluminosilicate exists the poor defect of formability.At present, the preparation method of silicon-containing alumina is a lot, is summed up and is mainly two kinds, and a kind of is in silico-aluminate, to add a small amount of aluminum oxide (2～10wt%) as structural promoter; Another kind is in aluminum oxide, to add a small amount of silico-aluminate, comes modulation alumina surface acid, improves its specific surface area.
US4721696 discloses a kind of method that the pH of employing swing method is prepared silicon-containing alumina, mainly be used as the carrier of sulfur-bearing and metallic impurity material hydrotreating catalyst, silicone content is generally no more than 15wt%, and silicon oxide is mainly as structural stabilizing agent rather than take the acid sites that provides more is object.
CN1267187C discloses a kind of silica-alumina containing structure of similar to thin diaspore, described carrier silica content is high, and be by silicon-containing compound solution directly or and stream be incorporated in pseudo-boehmite slurries, object is that the aluminium content that increases four-coordination improves aluminum oxide strength of acid and sour amount, the silicon-containing alumina of preparation has very high cracking activity, but higher cracking activity, as catalyst carrier for hydrgenating, has reduced liquid yield.
CN1074303C has proposed the manufacture method of a kind of aluminum oxide and monox composite oxides, it first mixes the solution in the solution in salic source and silicon oxide-containing source, then in mixing solutions, add hydrochloric acid to obtain colloidal sol, in colloidal sol, add sodium hydroxide to obtain gel again, finally make alumina source and silica source in gel react and obtain powdery silico-aluminate under high temperature, high pressure.But composite oxides prepared by the method have a large amount of micropores, be unsuitable for the carrier as medium-low distillate oil Hydrobon catalyst.
CN1048957C discloses and has prepared method amorphous, catalytic activity silica-alumina, adopt tetraalkylammonium hydroxide, tri-alkoxy aluminium and positive silicic acid tetraalkyl ester hydrolysis gel to obtain, this gel has the hole dimension that can control, and its specific surface area is at least 500m
2/ g, the mol ratio of silicon-dioxide and aluminium sesquioxide is at least 30: 1.This silica-alumina gel is mainly used in lighter hydrocarbons isomery and oligomerizing.
CN1306977C discloses a kind of silica-alumina and preparation method thereof, concrete steps are to adopt coprecipitation method first to prepare a kind of salic water mixed liquid, introduce again a kind of solution of silicon-containing compound, be a kind of mother liquor of synthesis of molecular sieve, through aging, the dry silica-alumina that makes.This carrier is mainly used in the preparation of catalytic cracking catalyst.
Summary of the invention
The object of the present invention is to provide a kind of medium-low distillate oil hydrofinishing process, particularly a kind of hydrofinishing process for two sections of low cut fraction pyrolysis gasoline.
Medium-low distillate oil hydrofinishing process provided by the invention, use molybdenum nickel catalyst, it is characterized in that hydrogenation technique condition is: 200～300 ℃ of temperature ins (preferably 220～280 ℃), working pressure>=2.4MPa (preferably 2.4～3.0Mpa), liquid volume air speed 1～5h
-1(preferred 2～4h
-1), hydrogen to oil volume ratio 100～500 (preferably 200～400); Molybdenum nickel catalyst be take silicon-containing alumina as carrier, take molybdenum, nickel is active ingredient, add phosphorus and basic metal as auxiliary agent, in catalyst weight, contain molybdenum oxide 20～30wt%, nickel oxide 2～10wt%, phosphorous oxides 0.8～5wt%, basic metal and/or alkaline earth metal oxide 1～5wt%, silicon oxide 2.5～25wt%, specific surface area of catalyst 200～300m
2/ g, pore volume 0.5～0.8ml/g; Wherein the presoma of silicon-containing alumina carrier is the pseudo-boehmite containing amorphous aluminum silicide, it is by first preparing amorphous aluminum silicide slurries and pseudo-boehmite slurries, by above-mentioned amorphous aluminum silicide slurries and pseudo-boehmite slurries according to the ratio of silica content 5～40wt% mix, aging, digestion time is 10～30min, then through comprising filtration, washing, dry last handling process, obtains.If silicon-containing alumina carrier prepared by other method can not reach effect of the present invention even if same catalyzer forms.
In reactor, mainly carry out hydrogenating desulfurization and olefin saturation.Reactor insulation fix bed reactor preferably in the present invention.
The present invention also provides a kind of hydrorefined catalyzer of medium-low distillate oil that is applicable to, and uses this catalyzer can obtain excellent especially desulfurization and olefin saturated effect.
Support of the catalyst can add one or more in phosphorus, basic metal, alkaline-earth metal before extruded moulding.The method of recommend adoption one of the following obtains:
Method one: by containing the pseudo-boehmite of amorphous aluminum silicide and nitric acid, water mixer kneader, extruded moulding, 80～140 ℃ of oven dry, 400～700 ℃ of roasting 3～6h, obtain support of the catalyst.
Method two: silicon-containing alumina carrier is by add one or more acquisitions of basic metal, alkaline-earth metal, phosphoric before extruded moulding.As contained the pseudo-boehmite of amorphous aluminum silicide and the precursor of basic metal, alkaline-earth metal and/or phosphoric, nitric acid, water mixer kneader, extruded moulding, 80～140 ℃ of oven dry, 400～700 ℃ of roasting 3～6h, obtain support of the catalyst.
Method three: after adding nitric acid, water to mediate in containing the pseudo-boehmite of amorphous aluminum silicide, extruded moulding, 80～120 ℃ of oven dry, 300～600 ℃ of roasting 3～6h, then flood the precursor solutions such as soluble salt of basic metal, alkaline-earth metal and/or phosphoric, 80～140 ℃ of oven dry, 400～700 ℃ of roasting 3～6h, make support of the catalyst.
Hydrobon catalyst can adopt the preparation method that the present invention recommends to obtain: the aqueous solution containing molybdenum and nickel soluble salt be impregnated on carrier, and after being dried, at 300～500 ℃, roasting 3～6h makes catalyzer.
Basic metal and/or alkaline-earth metal and auxiliary agent phosphorus all can add when preparing carrier, also can be after carrier moulding, before molybdenum, nickel add, be added in advance in carrier, the aqueous solution containing molybdenum, nickel soluble salt be impregnated on silicon-containing alumina carrier, after being dried, at 300～500 ℃, roasting 3～6h makes catalyzer again.Can also be when dipping molybdenum, nickel, add with molybdenum, nickel simultaneously, be about to the aqueous solution that basic metal, alkaline-earth metal and/or phosphoric be added to containing molybdenum, nickel soluble salt and impregnated on silicon-containing alumina carrier, dry after at 300～500 ℃ roasting 3～6h, make catalyzer.
Can be to add nitric acid, water to carry out mixer kneader containing in the pseudo-boehmite of amorphous aluminum silicide more specifically, extruded moulding, 80～120 ℃ of oven dry, 300～600 ℃ of roasting 3～6h, then flood the soluble salt solution of basic metal, alkaline-earth metal and/or phosphoric, 80～120 ℃ of oven dry, 400～700 ℃ of roasting 4～6h, again with the aqueous solution dipping containing molybdenum, nickel soluble salt, dry after at 300～500 ℃ roasting 3～6h, make catalyzer.
The most outstanding feature of Hydrobon catalyst that the hydrorefined method of medium-low distillate oil of the present invention is used is that the presoma of the silicon-containing alumina carrier that catalytic amount is used is the pseudo-boehmite containing amorphous aluminum silicide, having selected it is to mix with first preparing amorphous aluminum silicide slurries and pseudo-boehmite slurries, aging, and include filtration, dry last handling process obtains, the mixing process of these amorphous aluminum silicide slurries and pseudo-boehmite slurries, both be different from simple and mechanical mixing of two kinds of powders of amorphous aluminum silicide and pseudo-boehmite, it not again the structure of amorphous aluminum silicide coated alumina type.By two bursts of mixing of materials, one side amorphous aluminum silicide and pseudo-boehmite interaction; On the other hand, be also accompanied by a small amount of free aluminum ion and the reaction between silicate ion.
The present invention also provides a kind of preparation method of the pseudo-boehmite containing amorphous aluminum silicide, it is characterized in that amorphous aluminum silicide slurries and pseudo-boehmite slurries stream mix or a kind of material is joined in another kind of material and mixed, after mixing, aging 10～30min, filter, wash to sodium ions content and be less than 0.5wt%, at 80～120 ℃, dry 2～20h, obtains the pseudo-boehmite containing amorphous aluminum silicide.Its specific surface area is preferably 250～400m
2/ g, pore volume is preferably 0.7～1.4ml/g, and infrared acidity is preferably 0.28～0.55mmol/g, so that the catalyzer finally making meets requirement of the present invention.
Preparation process of pseudoboehmite containing amorphous aluminum silicide provided by the invention comprises the preparation of amorphous aluminum silicide slurries and the preparation of pseudo-boehmite slurries, and these two kinds of slurries are mixed, the mixing of two kinds of slurries can adopt and flow and mixes or a kind of slurries are joined in another kind of slurries and mixed, then aging, more after filtration, washing, the last handling process such as dry obtain the pseudo-boehmite containing amorphous aluminum silicide.When aging, pH value of solution is preferably 9.0～10.5, and temperature is preferably 20～65 ℃, and the time is preferably 10～25min.Drying temperature is preferably 80～120 ℃.
The present invention is not particularly limited the preparation method of amorphous aluminum silicide slurries and pseudo-boehmite slurries, adopts current techique, as the preparation of pseudo-boehmite slurries can adopt existing nitrate method or carborization.
The present invention provides a kind of preparation method of amorphous aluminum silicide slurries simultaneously, comprising:
(a) compound concentration is 10～150gAl
2o
3the sodium metaaluminate of/L or sodium aluminate solution, be added in plastic cans, controls 15～50 ℃ of plastic cans temperature.
(b) compound concentration is 50～200gSiO
2the silicon-containing compound solution of/L, joins silicon-containing compound solution in the solution of (a), controls pH value 11.5～13.
(c) low whipping speed is greater than under the condition of 250r/min, passes into continuously the carbon dioxide that concentration is greater than 20v%, controls the flow of carbon dioxide at 1～10Nm
3/ h, with time 20～40min, controls endpoint pH 7.5～9.5 in control, and neutralization finishes.
(d), in pH value 7.5～9.5, solution 5～20min prepared by aging under the condition that temperature is 25～40 ℃ (c), obtains amorphous aluminum silicide slurries.
Amorphous aluminum silicide slurries of the present invention are preferably with carbon dioxide process preparation, and silicon-containing compound can be water glass, silicon sol, water glass preferably, and concentration of sodium silicate is counted 50～200gSiO with silicon oxide
2/ L, is preferably 80～120gSiO
2/ L; The concentration of sodium metaaluminate or sodium aluminate solution is counted 10～150gAl with aluminum oxide
2o
3/ L, is preferably 35～110gAl
2o
3/ L; Digestion time is preferably controlled at 5～15min; In final amorphous aluminum silicide, control silica alumina ratio 40～60wt%.
The present invention also provides a kind of preparation method of pseudo-boehmite slurries.Sodium metaaluminate or sodium aluminate solution are added in plastic cans, intermittence or continuous mode to pass into carbon dioxide through plastic, the aging pseudo-boehmite slurries that obtain.The concentration of sodium metaaluminate or sodium aluminate solution is 20～150gAl
2o
3/ L; The concentration of carbonic acid gas is greater than 20v%, is preferably between 40～100v%, and the flow of carbon dioxide is 1～10Nm
3/ h; 20～65 ℃ of plastic temperature, best 30～45 ℃; Plastic endpoint pH 9.0～10.5; Plastic and digestion time are preferably no more than 40min altogether, with 25～35min, are advisable.
In the preparation process of pseudo-boehmite slurries of the present invention, plastic terminal pH is preferably controlled at 9.0～10.5, pH value was lower than 9.0 o'clock, the pseudo-boehmite forming easily and reaction of sodium bicarbonate generate a sodium stone structure, the silk sodium stone generating is a kind of insoluble salt, hinder the washing of sodium ion, likely affected aluminum oxide as the use properties of carrier.
Pseudo-boehmite best surfaces acidic site containing amorphous aluminum silicide prepared by the present invention be take weak acid position as main.
The pseudo-boehmite containing amorphous aluminum silicide that the present invention selects, has the high acidity of amorphous aluminum silicide, the characteristic of high-specific surface area, contains the advantage of pseudo-boehmite simultaneously, has overcome the poor problem of amorphous aluminum silicide moulding.The aluminum oxide containing amorphous aluminum silicide of preparation is specially adapted to do the carrier of hydrogenation catalyst.
Hydrobon catalyst provided by the invention contains basic metal and/or alkaline-earth metal, can change the acid-basicity on support of the catalyst surface, is conducive to reduce the deposition of carbonaceous in hydrogenation process, colloid, thus the work-ing life of extending catalyst.Adding of auxiliary agent phosphorus can effectively regulate alumina supporter physico-chemical property, makes pore distribution concentration; Improve the weak acid of carrier, reduce strong acid; Improve the thermostability of carrier.
The hydrogenation that method of the present invention is applicable to alkene in medium-low distillate oil product is saturated, and compared with prior art, it is high that this method of hydrotreating has reactive system hydrogenation activity, and stability and anti-coking performance are strong, can operational condition wide ranges etc. advantage.While using medium-low distillate oil hydrofinishing process of the present invention, adopt specific Hydrobon catalyst, hydrogenation activity and desulfurization performance are high, chemical stability and Heat stability is good, the strong and long service life of anti-coking performance.
Embodiment
Kaolinite Preparation of Catalyst agents useful for same source:
Ammonium molybdate: Shanghai gelatinizing factory
Nickelous nitrate: Xi'an chemical reagent factory
Analytical procedure:
Oil distillation: adopt petroleum products test method SYB-2110-60 to measure;
Bromine valency: adopt ICl method to measure, show with a gram bromine/100 gram oil meter;
Diene: adopt apple acid anhydrides method to measure, show with a gram iodine/100 gram oil meter;
Arsenic: adopt DV-4300 Atomic Emission SpectrometerAES to measure;
Sulphur: adopt WK-2B Microcoulomb instrument to measure;
Colloid: adopt petroleum products test method SYB-2103-60 to measure;
Catalyst crystalline phases: adopt BRUKER D
8aDVERCE type X-ray diffractometer is measured;
Infrared acidity: adopt pyridine-infrared mensuration;
Specific surface area, pore volume: adopt low temperature N
2the method of adsorption-desorption is measured.
The preparation of catalyzer 1～7 for embodiment:
The preparation of catalyzer 1:
Configuration 2L concentration is 120gAl
2o
3the sodium aluminate solution of/L is placed in plastic cans, controls plastic cans temperature 45 C, under agitation condition, passes into 65v%CO
2the mixed gas of+35v% air, in gas mixture, the flow of carbonic acid gas is 3Nm
3/ h.When pH value reaches 10.0, stop passing into mixed gas, then aging 20min obtains pseudo-boehmite slurries.
Configuration 2L concentration is 120gAl
2o
3the sodium aluminate solution of/L is placed in plastic cans, then adds 2L 80gSiO
2the sodium silicate solution of/L, controls 30 ℃ of plastic cans temperature, passes into 60v%CO
2the mixed gas of+40v% air, CO in gas mixture
2flow be 3Nm
3/ h, controlling endpoint pH is 10.0, aging 15min obtains amorphous aluminum silicide slurries.
Under the condition constantly stirring, 2L amorphous aluminum silicide slurries are joined in 1L pseudo-boehmite slurries, control 45 ℃ of mixing temperatures, aging 15min, filtration washing is to Na
+content is less than 0.5%, 120 ℃ of dry 10h, obtains the pseudo-boehmite containing amorphous aluminum silicide.
By containing the pseudo-boehmite of amorphous aluminum silicide and phosphoric acid, nitric acid, water mixer kneader, after extruded moulding, 120 ℃ of oven dry, 480 ℃ of roasting 4h, then use the saturated impregnated carrier of Lithium Citrate de solution, 120 ℃ of oven dry, 600 ℃ of roasting 4h, obtain the alumina supporter of siliceous, phosphorus and lithium.Nickel acetate, ammonium molybdate are jointly dissolved in the water and make steeping fluid, be impregnated on 100g carrier, 120 ℃ of oven dry, 480 ℃ of roasting 3h, obtain the catalyzer 1 containing molybdenum oxide 23.5wt%, nickel oxide 6.5wt%, Vanadium Pentoxide in FLAKES 1.5wt%, silicon oxide 16.5wt%, Lithium Oxide 98min 2.5wt%.
The preparation of catalyzer 2:
The preparation of amorphous aluminum silicide slurries is with catalyzer 1.Configuration 2L concentration is 95gAl
2o
3the sodium aluminate solution of/L is placed in plastic cans, controls plastic cans temperature 45 C, under agitation condition, passes into 65v%CO
2the mixed gas of+35v% air, in gas mixture, the flow of carbonic acid gas is 3Nm
3/ h.When pH value reaches 10.0, stop passing into mixed gas, then aging 20min obtains pseudo-boehmite slurries.
Under the condition constantly stirring, 3L amorphous aluminum silicide slurries are joined in 1L pseudo-boehmite slurries, control 40 ℃ of mixing temperatures, aging 20min, filtration washing is to Na
+content is less than 0.5%, 120 ℃ of dry 12h, obtains the pseudo-boehmite containing amorphous aluminum silicide.
By containing the pseudo-boehmite of amorphous aluminum silicide and phosphoric acid, nitric acid, water mixer kneader, after extruded moulding, 120 ℃ of oven dry, 580 ℃ of roasting 4h, obtain alumina supporter siliceous, phosphorus.Nickel acetate, ammonium molybdate, saltpetre are jointly dissolved in the water and make steeping fluid, be impregnated on 100g carrier, 120 ℃ of oven dry, 400 ℃ of roasting 5h, obtain the catalyzer 2 containing molybdenum oxide 20wt%, nickel oxide 6.0wt%, silicon oxide 21.4wt%, Vanadium Pentoxide in FLAKES 2.5wt%, potassium oxide 1.0wt%.
The preparation of catalyzer 3:
Configuration 2L concentration is 100gAl
2o
3the sodium aluminate solution of/L, is placed in the plastic cans of a 8L, and the temperature of controlling plastic cans is 35 ℃, and under the condition constantly stirring, passing into concentration is 60v%CO
2the mixed gas of+40v% air, in gas mixture, the flow of carbonic acid gas is 2Nm
3/ h stops passing into carbonic acid gas when pH value reaches 10.5, and aging 25min obtains pseudo-boehmite slurries.
Configuration 2L concentration is 130gAl
2o
3the sodium aluminate solution of/L is placed in plastic cans, then adds 2L 80gSiO
2the sodium silicate solution of/L, controlling temperature of reaction is 25 ℃, passes into 50v%CO
2the mixed gas of+50v% air, CO
2flow be 5Nm
3/ h, the pH value of controlling terminal is 10.0, aging 10min obtains amorphous aluminum silicide slurries.
Under the condition constantly stirring, 1L pseudo-boehmite slurries and 3L amorphous aluminum silicide slurries stream are joined in plastic cans, control mixing temperature at 45 ℃, aging 15min, filtration washing are to Na
+ion content is less than till 0.5%, and 120 ℃ of dry 12h obtain the pseudo-boehmite containing amorphous aluminum silicide.
By containing the pseudo-boehmite of amorphous aluminum silicide and phosphoric acid, nitric acid, water mixer kneader, after extruded moulding, 120 ℃ of oven dry, 500 ℃ of roasting 4h, then use the saturated impregnated carrier of saltpetre and strontium nitrate solution, 120 ℃ of oven dry, 650 ℃ of roasting 4h, obtain the alumina supporter of siliceous, phosphorus, potassium and strontium.Nickelous nitrate, ammonium molybdate are jointly dissolved in the water and make steeping fluid, be impregnated on 100g carrier, 120 ℃ of oven dry, 480 ℃ of roasting 3h, obtain the catalyzer 3 containing molybdenum oxide 28wt%, nickel oxide 3.5wt%, Vanadium Pentoxide in FLAKES 1.5wt%, silicon oxide 18.8wt%, potassium oxide 0.5wt%, strontium oxide 1.5wt%.
The preparation of catalyzer 4:
The preparation method of pseudo-boehmite slurries is with catalyzer 3.Configuration 2L concentration is 132gAl
2o
3the sodium aluminate solution of/L is placed in plastic cans, then adds 2L 80gSiO
2the sodium silicate solution of/L, controlling temperature of reaction is 25 ℃, passes into 50v%CO
2the mixed gas of+50v% air, CO
2flow be 5Nm
3/ h, the pH value of controlling terminal is 9.5, aging 20min obtains amorphous aluminum silicide slurries.
Under the condition constantly stirring, 1.5L pseudo-boehmite slurries and 1.6L amorphous aluminum silicide slurries stream are joined in plastic cans, control 50 ℃ of mixing temperatures, aging 10min, filtration washing is to Na
+content is less than 0.5%, 110 ℃ of dry 15h, obtains the pseudo-boehmite containing amorphous aluminum silicide.
By containing the pseudo-boehmite of amorphous aluminum silicide and phosphoric acid, nitric acid, water mixer kneader, after extruded moulding, 120 ℃ of oven dry, 500 ℃ of roasting 3h, then use the saturated impregnated carrier of magnesium nitrate solution, 120 ℃ of oven dry, 700 ℃ of roasting 4h, obtain the alumina supporter of siliceous, phosphorus and magnesium.Nickelous nitrate, ammonium molybdate are jointly dissolved in the water and make steeping fluid, be impregnated on 100g carrier 120 ℃ of oven dry, 420 ℃ of roasting 4h, obtain containing molybdenum oxide 26wt%, nickel oxide 6wt%, silicon oxide 12.4wt%, Vanadium Pentoxide in FLAKES 2.5wt%, the catalyzer 4 of magnesium oxide 3.5wt%.
The preparation of catalyzer 5:
Configuration 2L concentration is 85gAl
2o
3the sodium aluminate solution of/L, is placed in plastic cans, and controlling plastic cans temperature is 50 ℃, and under the condition constantly stirring, passing into concentration is 80v%CO
2the mixed gas of+20v% air, in gas mixture, the flow of carbonic acid gas is 4Nm
3/ h stops passing into mixed gas when pH value reaches 10.0, and aging 20min obtains pseudo-boehmite slurries.
Configuration 3L concentration is 100gAl
2o
3the sodium aluminate solution of/L is placed in plastic cans, then adds 2L 60gSiO
2the sodium silicate solution of/L, controls 30 ℃ of temperature of reaction, passes into 60v%CO
2the mixed gas of+40v% air, CO in gas mixture
2flow be 5Nm
3/ h, controlling endpoint pH is 9.5, aging 20min obtains amorphous aluminum silicide slurries.
Under the condition constantly stirring, 2L pseudo-boehmite slurries and 1L amorphous aluminum silicide slurries stream are joined in plastic cans, control 50 ℃ of mixing temperatures, aging 15min, filtration washing is to Na
+content is less than 0.5%, 120 ℃ of dry 10h, obtains the pseudo-boehmite containing amorphous aluminum silicide.
By containing the pseudo-boehmite of amorphous aluminum silicide and phosphoric acid, Lithium Acetate, nitric acid, water mixer kneader, after extruded moulding, 120 ℃ of oven dry, 550 ℃ of roasting 4h, obtain the alumina supporter of siliceous, phosphorus and lithium.Nickel acetate, ammonium molybdate are jointly dissolved in the water and make steeping fluid, be impregnated on 100g carrier, 120 ℃ of oven dry, 460 ℃ of roasting 4h, obtain the catalyzer 5 containing molybdenum oxide 25wt%, nickel oxide 7.0wt%, silicon oxide 5.8wt%, Vanadium Pentoxide in FLAKES 4.0wt%, Lithium Oxide 98min 2.0wt%.
The preparation of catalyzer 6:
The preparation of pseudo-boehmite slurries and amorphous aluminum silicide slurries is with catalyzer 3.
Under the condition constantly stirring, 2L pseudo-boehmite slurries and 2L amorphous aluminum silicide slurries stream are joined in plastic cans, control mixing temperature at 45 ℃, aging 15min, filtration washing are to Na
+ion content is less than till 0.5%, and 120 ℃ of dry 12h obtain the pseudo-boehmite containing amorphous aluminum silicide.
By containing the pseudo-boehmite of amorphous aluminum silicide and phosphoric acid, nitric acid, water mixer kneader, after extruded moulding, 120 ℃ of oven dry, 500 ℃ of roasting 4h, then use the saturated impregnated carrier of potassium nitrate solution, 120 ℃ of oven dry, 600 ℃ of roasting 4h, obtain the alumina supporter of siliceous, phosphorus and potassium.Nickelous nitrate, ammonium molybdate are jointly dissolved in the water and make steeping fluid, be impregnated on 100g carrier, 120 ℃ of oven dry, 480 ℃ of roasting 3h, obtain the catalyzer 6 containing molybdenum oxide 26wt%, nickel oxide 4.0wt%, Vanadium Pentoxide in FLAKES 2.5wt%, silicon oxide 12.8wt%, potassium oxide 2.0wt%.
The preparation of catalyzer 7:
The preparation of pseudo-boehmite slurries and amorphous aluminum silicide slurries is with catalyzer 5.
Under the condition constantly stirring, 2L pseudo-boehmite slurries and 2L amorphous aluminum silicide slurries stream are joined in plastic cans, control 55 ℃ of mixing temperatures, aging 10min, filtration washing is to Na
+content is less than 0.5%, 120 ℃ of dry 10h, obtains the pseudo-boehmite containing amorphous aluminum silicide.
By containing the pseudo-boehmite of amorphous aluminum silicide and phosphoric acid, magnesium acetate, nitric acid, water mixer kneader, after extruded moulding, 120 ℃ of oven dry, 550 ℃ of roasting 4h, obtain the alumina supporter of siliceous, phosphorus and magnesium.Nickel acetate, ammonium molybdate are jointly dissolved in the water and make steeping fluid, be impregnated on 100g carrier, 120 ℃ of oven dry, 450 ℃ of roasting 4h, obtain the catalyzer 7 containing molybdenum oxide 24wt%, nickel oxide 6.0wt%, silicon oxide 9.2wt%, Vanadium Pentoxide in FLAKES 4.0wt%, magnesium oxide 1.0wt%.
Embodiment is as shown in table 1 with the physico-chemical property of catalyzer 1～7.
Testing raw materials used is Lanzhou Petrochemical Company cracking C
6～C
8middle runnings and C
5～C
9full-fraction one-stage hydrogenated products, its character is in Table 2.
The physico-chemical property of catalyzer 1～7 for table 1 embodiment
Table 2 hydrogenating materials oil nature
Embodiment 1
Live catalyst 1 is packed in 100ml adiabatic reactor reaction unit, first carry out the sulfuration of catalyzer: dithiocarbonic anhydride is joined to the vulcanized oil that is made into sulphur content 1000 μ g/g left and right in hexanaphthene, reactor is warmed up to 240 ℃ to start into vulcanized oil, pressure 2.5Mpa, vulcanized oil volume space velocity 3.0h
-1, hydrogen/vulcanized oil volume ratio 300: 1, then the temperature rise rate with 10 ℃/h is warmed up to 350 ℃, maintains 25h, completes the sulfidizing to catalyzer.
After sulfidizing finishes, take stock oil 1 as raw material, in 220 ℃ of temperature ins, reaction pressure 2.4MPa, liquid volume air speed: 4h
-1, hydrogen with oil volume than the 200h that turns round under 300 conditions.Bromine valency and sulphur content in every 24h sampling analysis product, the results are shown in Table 3.
Embodiment 2
Live catalyst 2 is packed in 100ml adiabatic reactor reaction unit, and catalyst vulcanization treatment process is with embodiment 1.
After sulfidizing finishes, take stock oil 2 as raw material, in 240 ℃ of temperature ins, reaction pressure 2.6MPa, liquid volume air speed: 4.5h
-1, hydrogen with oil volume than the 200h that turns round under 350 conditions.Bromine valency and sulphur content in every 24h sampling analysis product, the results are shown in Table 3.
Embodiment 3
Live catalyst 3 is packed in 100ml adiabatic reactor reaction unit, and catalyst vulcanization treatment process is with embodiment 1.
After sulfidizing finishes, take stock oil 3 as raw material, in 280 ℃ of temperature ins, reaction pressure 3.0MPa, liquid volume air speed: 2h
-1, hydrogen with oil volume than the 200h that turns round under 450 conditions.Bromine valency and sulphur content in every 24h sampling analysis product, the results are shown in Table 3.
Embodiment 4
Live catalyst 4 is packed in 100ml adiabatic reactor reaction unit, and catalyst vulcanization treatment process is with embodiment 1.
After sulfidizing finishes, take stock oil 4 as raw material, in 250 ℃ of temperature ins, reaction pressure 2.6MPa, liquid volume air speed: 3.5h
-1, hydrogen with oil volume than the 200h that turns round under 400 conditions.Bromine valency and sulphur content in every 24h sampling analysis product, the results are shown in Table 3.
Embodiment 5
Live catalyst 5 is packed in 100ml adiabatic reactor reaction unit, and catalyst vulcanization treatment process is with embodiment 1.
After sulfidizing finishes, take stock oil 4 as raw material, in 250 ℃ of temperature ins, reaction pressure 2.8MPa, liquid volume air speed: 3.5h
-1, hydrogen with oil volume than the 200h that turns round under 300 conditions.Bromine valency and sulphur content in every 24h sampling analysis product, the results are shown in Table 3.
Embodiment 6
Live catalyst 6 is packed in 100ml adiabatic reactor reaction unit, and catalyst vulcanization treatment process is with embodiment 1.
After sulfidizing finishes, take stock oil 2 as raw material, in 260 ℃ of temperature ins, reaction pressure 2.6MPa, liquid volume air speed: 4.0h
-1, hydrogen with oil volume than the 200h that turns round under 300 conditions.Bromine valency and sulphur content in every 24h sampling analysis product, the results are shown in Table 3.
Embodiment 7
Live catalyst 7 is packed in 100ml adiabatic reactor reaction unit, and catalyst vulcanization treatment process is with embodiment 1.
After sulfidizing finishes, take stock oil 4 as raw material, at temperature in 250C, reaction pressure 2.8MPa, liquid volume air speed: 3.0h
-1, hydrogen with oil volume than the 200h that turns round under 400 conditions.Bromine valency and sulphur content in every 24h sampling analysis product, the results are shown in Table 3.
Comparative example 1
It is silica-alumina powder that this comparative example is used the presoma of support of the catalyst, according to the method preparation described in embodiment in CN1267187C 3; The preparation method of catalyzer and composition are with catalyzer 3 for embodiment.
Catalyst vulcanization treatment process is with embodiment 1; Evaluating catalyst condition, with embodiment 3, the results are shown in Table 3.
Comparative example 2
This comparative example is used the presoma of support of the catalyst according to the method preparation described in embodiment in CN1074303C 1; The preparation method of catalyzer and composition are with catalyzer 4 for embodiment.
Catalyst vulcanization treatment process is with embodiment 1; Evaluating catalyst condition, with embodiment 4, the results are shown in Table 3.
Comparative example 3
This comparative example is used the presoma of support of the catalyst according to the method preparation described in embodiment in CN1306977C 4; The preparation method of catalyzer and composition are with catalyzer 2 for embodiment.
Catalyst vulcanization treatment process is with embodiment 1; Evaluating catalyst condition, with embodiment 2, the results are shown in Table 3.
Comparative example 4
It is industrial amorphous aluminum silicide (SiO that this comparative example is used the presoma of support of the catalyst
2content 45%); The preparation method of catalyzer is with catalyzer 2 for embodiment.Catalyzer consists of: molybdenum oxide 20wt%, nickel oxide 6wt%, silicon oxide 31.7wt%, Vanadium Pentoxide in FLAKES 2.5wt%, potassium oxide 1.0wt%.
Catalyst vulcanization treatment process is with embodiment 1; Evaluating catalyst condition, with embodiment 2, the results are shown in Table 3.
Comparative example 5
It is industrial pseudo-boehmite that this comparative example is used the presoma of support of the catalyst; The preparation method of catalyzer is with catalyzer 1 for embodiment, the oxygen-free SiClx of this catalyzer, and all the other form with catalyzer 1.
Catalyst vulcanization treatment process and evaluating catalyst condition are with embodiment 1, and bromine valency and sulphur content in every 24h sampling analysis product, the results are shown in Table 3.
As shown in Table 3, the present invention contains the low cut fraction pyrolysis gasoline one-stage hydrogenation of hydrogenation catalyst centering product prepared by the pseudo-boehmite of amorphous aluminum silicide by employing and carries out hydrofining, bromine valency < 1.0 * 10 in hydrogenated products
-2g/g, sulphur content < 1.0 μ g/g, meet the requirement of pyrolysis gasoline secondary hydrogenation.
Table 3 embodiment 1～7 and comparative example 1～5 hydrogenation result
Claims (15)
1. a medium-low distillate oil hydrofinishing process, used catalyst is molybdenum nickel series hydrogenating catalyst, it is characterized in that hydrogenation technique condition is: 200～300 ℃ of temperature ins, working pressure>=2.4MPa, liquid volume air speed 1～5h
-1, hydrogen to oil volume ratio 100～500; Molybdenum nickel catalyst be take silicon-containing alumina as carrier, take molybdenum, nickel is active ingredient, add phosphorus and basic metal as auxiliary agent, in catalyst weight, contain molybdenum oxide 20～30wt%, nickel oxide 2～10wt%, phosphorous oxides 0.8～5wt%, basic metal and/or alkaline earth metal oxide 1～5wt%, silicon oxide 2.5～25wt%, specific surface area of catalyst 200～300m
2/ g, pore volume 0.5～0.8ml/g; Wherein the presoma of silicon-containing alumina carrier is the pseudo-boehmite containing amorphous aluminum silicide, it is by first preparing amorphous aluminum silicide slurries and pseudo-boehmite slurries, by above-mentioned amorphous aluminum silicide slurries and pseudo-boehmite slurries according to the ratio of silica content 5～40wt% mix, aging, digestion time is 10～30min, then through comprising filtration, washing, dry last handling process, obtains.
2. medium-low distillate oil hydrofinishing process according to claim 1, is characterized in that in hydrogenation technique condition, and temperature in is 220～280 ℃.
3. medium-low distillate oil hydrofinishing process according to claim 1, is characterized in that in hydrogenation technique condition, and working pressure is 2.4～3.0MPa.
4. medium-low distillate oil hydrofinishing process according to claim 1, is characterized in that in hydrogenation technique condition, and liquid volume air speed is 2～4h
-1.
5. medium-low distillate oil hydrofinishing process according to claim 1, is characterized in that in hydrogenation technique condition, and hydrogen to oil volume ratio is 200～400.
6. medium-low distillate oil hydrofinishing process according to claim 1, it is characterized in that the pseudo-boehmite containing amorphous aluminum silicide is by amorphous aluminum silicide slurries and pseudo-boehmite slurries are also flowed and mix or a kind of slurries are joined in another kind of slurries and mixed, after having mixed, when aging, pH value of solution is 9.0～10.5.
7. according to the medium-low distillate oil hydrofinishing process described in claim 1 or 6, it is characterized in that when aging that temperature is 20～65 ℃.
8. according to the medium-low distillate oil hydrofinishing process described in claim 1 or 6, it is characterized in that amorphous aluminum silicide slurries obtain by following method:
(a) compound concentration is 10～150gAl
2o
3the sodium metaaluminate of/L or sodium aluminate solution, join in plastic cans, controls 15～50 ℃ of plastic cans temperature;
(b) compound concentration is 50～200gSiO
2the silicon-containing compound solution of/L, joins in the sodium metaaluminate or sodium aluminate solution of (a), controls pH value 11.5～13;
(c) low whipping speed is greater than under the condition of 250r/min, passes into continuously the carbon dioxide that concentration is greater than 20v%, controls the flow of carbon dioxide at 1～10Nm
3/ h, in and time 20～40min, endpoint pH 7.5～9.5, neutralization finishes;
(d), in pH value 7.5～9.5, aging 5～20min under the condition that temperature is 25～40 ℃, obtains amorphous aluminum silicide slurries.
9. according to the medium-low distillate oil hydrofinishing process described in claim 1 or 6, it is characterized in that pseudo-boehmite slurries obtain by following method: sodium metaaluminate or sodium aluminate solution are placed in to plastic cans, intermittence or continuous mode to pass into carbon dioxide plastic, the aging pseudo-boehmite slurries that obtain; The concentration of sodium metaaluminate or sodium aluminate solution is 20～150gAl
2o
3/ L; Gas concentration lwevel is greater than 20v%, flow 1～10Nm3/h; 20～65 ℃ of plastic temperature; Plastic endpoint pH 9.0～10.5, is less than 40min with time and digestion time sum in plastic.
10. medium-low distillate oil hydrofinishing process according to claim 1, is characterized in that molybdenum nickel catalyst is by the aqueous solution containing molybdenum, nickel soluble salt be impregnated on silicon-containing alumina carrier, what after being dried, at 300～500 ℃, roasting 3～6h made.
11. medium-low distillate oil hydrofinishing process according to claim 10, it is characterized in that silicon-containing alumina carrier is by by containing the pseudo-boehmite of amorphous aluminum silicide and nitric acid, water mixer kneader, extruded moulding, 80～140 ℃ of oven dry, 400～700 ℃ of roasting 3～6h make.
12. medium-low distillate oil hydrofinishing process according to claim 10, it is characterized in that silicon-containing alumina carrier is by by containing the pseudo-boehmite of amorphous aluminum silicide and nitric acid, water mixer kneader, add one or more in basic metal, alkaline-earth metal, phosphoric, then extruded moulding, 80～140 ℃ of oven dry, 400～700 ℃ of roasting 3～6h make.
13. medium-low distillate oil hydrofinishing process according to claim 10, it is characterized in that molybdenum nickel catalyst is by basic metal, alkaline-earth metal and/or phosphoric were added in advance in silicon-containing alumina carrier before molybdenum, nickel add, impregnated in again the aqueous solution containing molybdenum, nickel soluble salt, what after being dried, at 300～500 ℃, roasting 3～6h made.
14. medium-low distillate oil hydrofinishing process according to claim 10, it is characterized in that molybdenum nickel catalyst is that the aqueous solution by basic metal, alkaline-earth metal and/or phosphoric being added to containing molybdenum, nickel soluble salt impregnated on silicon-containing alumina carrier, what at 300～500 ℃, roasting 3～6h made after dry.
15. medium-low distillate oil hydrofinishing process according to claim 13, it is characterized in that molybdenum nickel catalyst is by adding nitric acid, water to carry out mixer kneader containing in the pseudo-boehmite of amorphous aluminum silicide, extruded moulding, 80～120 ℃ of oven dry, 300～600 ℃ of roasting 3～6h, then flood the soluble salt solution of basic metal, alkaline-earth metal and/or phosphoric, 80～120 ℃ of oven dry, 400～700 ℃ of roasting 4～6h, impregnated in again the aqueous solution containing molybdenum, nickel soluble salt, what after being dried, at 300～500 ℃, roasting 3～6h made.
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| CN1250746A (en) * | 1998-10-13 | 2000-04-19 | 中国石油化工集团公司 | Process for preparing artificial diasporite and gamma-alumina |
| CN1597093A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Method of preparing amorphous silica-alumina using carbonization |
| CN101037614A (en) * | 2006-03-17 | 2007-09-19 | 中国石油天然气股份有限公司 | Hydrofining catalyst, preparation method and application |
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| CN1218089A (en) * | 1997-11-24 | 1999-06-02 | 中国石油化工总公司 | Catalyst carrier containing difunctional amorphous aluminum silicide and preparation thereof |
| CN1250746A (en) * | 1998-10-13 | 2000-04-19 | 中国石油化工集团公司 | Process for preparing artificial diasporite and gamma-alumina |
| CN1597093A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Method of preparing amorphous silica-alumina using carbonization |
| CN101037614A (en) * | 2006-03-17 | 2007-09-19 | 中国石油天然气股份有限公司 | Hydrofining catalyst, preparation method and application |
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