CN102352265B - Method for producing catalytic reforming raw material - Google Patents
Method for producing catalytic reforming raw material Download PDFInfo
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- CN102352265B CN102352265B CN201110191281.XA CN201110191281A CN102352265B CN 102352265 B CN102352265 B CN 102352265B CN 201110191281 A CN201110191281 A CN 201110191281A CN 102352265 B CN102352265 B CN 102352265B
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- raw material
- catalytic reforming
- reforming raw
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- 238000001833 catalytic reforming Methods 0.000 title claims abstract description 43
- 239000002994 raw material Substances 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 74
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- 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
- 239000003921 oil Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 13
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 claims description 72
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 70
- 239000002002 slurry Substances 0.000 claims description 66
- 239000000243 solution Substances 0.000 claims description 35
- 239000004033 plastic Substances 0.000 claims description 31
- 230000032683 aging Effects 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910001868 water Inorganic materials 0.000 claims description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 238000000465 moulding Methods 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 150000003818 basic metals Chemical class 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 17
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 16
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 15
- 229910052728 basic metal Inorganic materials 0.000 claims description 15
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 239000010937 tungsten Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 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
- 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
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical group [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 239000004480 active ingredient Substances 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 230000029087 digestion Effects 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 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
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- 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 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 38
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 19
- 150000001336 alkenes Chemical class 0.000 abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 38
- 239000005864 Sulphur Substances 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004073 vulcanization Methods 0.000 description 11
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 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
- 239000000047 product Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 235000011089 carbon dioxide Nutrition 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000004115 Sodium Silicate Substances 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
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 229940078494 nickel acetate Drugs 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-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
- 239000004411 aluminium Substances 0.000 description 2
- -1 aluminum ion Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229940071264 lithium citrate Drugs 0.000 description 2
- 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 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910001415 sodium ion Inorganic materials 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 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
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 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
- 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
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption 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
- 229910052742 iron Inorganic materials 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
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- DBJYYRBULROVQT-UHFFFAOYSA-N platinum rhenium Chemical compound [Re].[Pt] DBJYYRBULROVQT-UHFFFAOYSA-N 0.000 description 1
- HWLDNSXPUQTBOD-UHFFFAOYSA-N platinum-iridium alloy Chemical compound [Ir].[Pt] HWLDNSXPUQTBOD-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000007670 refining Methods 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
- 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
- 238000010998 test method Methods 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention provides a method for producing catalytic reforming raw materials, which carries out primary hydrogenation treatment on the raw materials. The hydrotreating process conditions are as follows: the reaction inlet temperature is 200-320 ℃, the operation pressure is more than 2.4MPa, and the volume space velocity of fresh raw oil is 4-12 h-1The volume ratio of hydrogen to oil is 50-300; the hydrotreating catalyst has silicon-containing alumina as carrier, Ni and W as active components and P and alkali metal and/or alkali earth metal as assistant. The method can process the catalytic reforming raw material with high sulfur and nitrogen contents and high olefin content under the condition of low pressure, and provides qualified raw materials with the sulfur and nitrogen contents of less than 0.5 mu g/g for the catalytic reforming device.
Description
Technical field
The present invention relates to a kind of method of producing catalytic reforming raw material, be specially adapted to the hydrotreatment of catalytic reforming unit charging.
Background technology
Catalytic reforming process is one of important technique of oil refining and petrochemical complex, and it is with C
6～C
11naphtha fraction is raw material, is reacted and is produced the reformation be rich in aromatic hydrocarbons and produce oil, simultaneously by-product hydrogen by catalytic hydroprocessing.Catalytic reforming process adopts two (many) noble metal catalysts such as platinum-rhenium and platinum-iridium conventionally, for preventing poisoning of catalyst, requires sulphur, nitrogen content in its charging to be all less than 0.5 μ g/g.Therefore, need raw material before entering reformer, first to carry out pre-hydrotreating, to remove impurity harmful to catalytic reforming catalyst in stock oil, comprising sulphur, nitrogen, alkene and arsenic, lead, copper and moisture etc.
In recent years, 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 hydrotreating catalyst.For example, when coker gas oil is carried out to hydrotreatment, 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 hydrotreating 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 hydrotreating catalyst preparation process, be 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 hydrotreating 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.
CN100448951C discloses a kind of method of producing catalytic reforming raw material, mainly middle matter gasoline fraction and virgin naphtha after the cutting of secondary processing of gasoline raw material are carried out to twice hydrofining, the first Hydrobon catalyst: take aluminum oxide as carrier, nickel, molybdenum and/or tungsten are active ingredient, and basic metal is auxiliary agent; The second Hydrobon catalyst: a kind of metal load type catalyst, take aluminum oxide as carrier, nickel, cobalt, tungsten are active ingredient, promotor is the arbitrary element in magnesium, zinc, iron, calcium.
Summary of the invention
The object of the present invention is to provide a kind of method of producing catalytic reforming raw material, particularly a kind of hydroprocessing process for raw materials for catalytic reforming device.The method only need be carried out a hydrotreatment, invests lowly, and catalyst hydrogenation activity and good stability, can operational condition wide ranges.
The method of production catalytic reforming raw material of the present invention comprises: catalytic reforming raw material enters the reactor that hydrotreating catalyst is housed under hydrogen atmosphere, hydroprocessing technique condition is: reaction temperature in is 200～320 ℃ (preferably 220～300 ℃), working pressure is greater than 2.4MPa (preferably 2.4～3.0MPa), and fresh feed oil volume air speed is 4～12h
-1(preferred 6～10h
-1), hydrogen to oil volume ratio is 50～300 (preferably 60～200); Described hydrotreating catalyst is tungsten nickel catalyst, take silicon-containing alumina as carrier, nickel, tungsten are active ingredient, and phosphorus and basic metal and/or alkaline-earth metal are as auxiliary agent, in catalyst weight, contain Tungsten oxide 99.999 20～30wt%, nickel oxide 1～6wt%, phosphorous oxides 0.5～5wt%, basic metal and/or alkaline earth metal oxide 1～4wt%, silicon oxide 5～28wt%, specific surface area of catalyst 200～300m
2/ g, pore volume 0.5～0.75ml/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, denitrogenation and olefin saturation.Reactor insulation fix bed reactor preferably in the present invention.
Catalytic reforming raw material comprises virgin naphtha, catalytically cracked gasoline or both mixtures.The weight ratio of described catalytically cracked gasoline and virgin naphtha is 10: 90～50: 50.
The present invention also provides a kind of hydrotreating catalyst that is applicable to produce catalytic reforming raw material, uses this catalyzer can obtain excellent especially desulfurization, denitrogenation 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 in 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.
Hydrotreating catalyst can adopt the preparation method that the present invention recommends to obtain: nickeliferous and aqueous solution tungsten soluble salt be impregnated on carrier, dry after at 300～500 ℃ roasting 3～6h.
Basic metal and/or alkaline-earth metal and auxiliary agent phosphorus all can add when preparing carrier, also can be after carrier moulding, before nickel, tungsten add, be added in advance in carrier, again the aqueous solution nickeliferous, tungsten soluble salt be impregnated on silicon-containing alumina carrier, after dry at 300～500 ℃ roasting 3～6h, make catalyzer.Can also be when dipping nickel, tungsten, add with nickel, tungsten simultaneously, be about to basic metal, alkaline-earth metal and/or phosphoric and be added to the aqueous solution nickeliferous, tungsten 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 of tungstenic, nickel soluble salt, dry after at 300～500 ℃ roasting 3～6h, make catalyzer.
The present invention produces the most outstanding feature of hydrotreating catalyst that the method for catalytic reforming raw material used and 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.
Hydrotreating 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 method of production catalytic reforming raw material of the present invention has the following advantages:
1, the inventive method analoging industrial device, adopts insulation fix bed reactor, is conducive to the popularization to full scale plant.
2, the inventive method only need be carried out a hydrotreatment, and energy consumption is low, simple to operate and turndown ratio is large.
While 3, using the inventive method, adopt specific hydrotreating catalyst, hydrogenation activity and desulfurization, nitrogen removal performance are high, chemical stability and Heat stability is good, the strong and long service life of anti-coking performance.
4, use and the invention provides method, can under low pressure condition, process the raw materials for catalytic reforming device that high sulfur-bearing is nitrogenous and olefin(e) centent is high, for catalytic reforming unit provides sulphur, nitrogen content, be all less than the acceptable material of 0.5 μ g/g.
Embodiment
Kaolinite Preparation of Catalyst agents useful for same source:
Ammonium metawolframate: the Kunshan tungsten technology company limited that makes the country prosperous
Nickelous nitrate: Xi'an chemical reagent factory
Industry amorphous aluminum silicide: Zibo safe photoinitiator chemical company limited, SiO
2content 45%.
Industry pseudo-boehmite: Zibo Wanlin Chemical Technology Co., Ltd.
Analytical procedure:
Oil distillation: adopt petroleum products test method SYB-2110-60 to measure;
Arsenic: adopt DV-4300 Atomic Emission SpectrometerAES to measure;
Sulphur: adopt WK-2B Microcoulomb instrument to measure;
Nitrogen: adopt KY-3000N chemoluminescence azotometer 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 40 ℃ of plastic cans temperature, 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 18min 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 35 ℃ 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 10min obtains amorphous aluminum silicide slurries.
Under the condition constantly stirring, 2L amorphous aluminum silicide slurries are joined in 1L pseudo-boehmite slurries, 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, nitric acid, water mixer kneader, after extruded moulding, 120 ℃ of oven dry, 500 ℃ of roasting 3h, then use the saturated impregnated carrier of Lithium Citrate de solution, 120 ℃ of oven dry, 520 ℃ of roasting 4h, obtain the alumina supporter of siliceous, phosphorus and lithium.Nickelous nitrate and ammonium metawolframate are jointly dissolved in the water and make steeping fluid, be impregnated on 100g carrier, 120 ℃ of oven dry, 460 ℃ of roasting 4h, obtain containing NiO 4.0wt%, WO
323.5wt%, SiO
217wt%, P
2o
52.0wt%, Li
2the catalyzer 1 of O 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, magnesium nitrate, 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 and ammonium tungstate are jointly dissolved in the water and make steeping fluid, be impregnated on 100g carrier, 120 ℃ of oven dry, 400 ℃ of roasting 5h, obtain containing NiO 2.0wt%, WO
326wt%, SiO
220.4wt%, P
2o
5the catalyzer 2 of 2.0wt%, MgO 3.0wt%.
The preparation of catalyzer 3:
Configuration 2L concentration is 100gAl
2o
3the sodium aluminate solution of/L is placed in plastic cans, controls 40 ℃ of plastic cans temperature, under agitation condition, passes into 60v%CO
2the mixed gas of+40v% air, in gas mixture, the flow of carbonic acid gas is 5Nm
3/ h.When pH value reaches 10.0, stop passing into mixed gas, then 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, controls 20 ℃ of temperature of reaction, passes into 50v%CO
2the mixed gas of+50v% air, CO in mixed gas
2flow be 6Nm
3/ h, controlling endpoint pH is 9.5, aging 18min 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 40 ℃ of mixing temperatures, aging 15min, 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, 460 ℃ of roasting 4h, then use the saturated impregnated carrier of liquor kalii acetici, 120 ℃ of oven dry, 600 ℃ of roasting 4h, obtain the alumina supporter of siliceous, phosphorus and potassium.Nickel acetate and ammonium tungstate are jointly dissolved in the water and make steeping fluid, be impregnated on 100g carrier, 120 ℃ of oven dry, 450 ℃ of roasting 4h, obtain containing NiO 1.5wt%, WO
329wt%, SiO
218.9wt%, P
2o
52.5wt%, K
2the catalyzer 3 of O 1.5wt%.
The preparation of catalyzer 4:
The preparation method of amorphous aluminum silicide slurries and pseudo-boehmite slurries is with catalyzer 3.
Under the condition constantly stirring, 1.5L pseudo-boehmite slurries and 1.6L amorphous aluminum silicide slurries stream are joined in plastic cans, control 45 ℃ of mixing temperatures, aging 20min, 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 4h, then use the saturated impregnated carrier of strontium nitrate solution, 120 ℃ of oven dry, 550 ℃ of roasting 4h, obtain the alumina supporter of siliceous, phosphorus and strontium.Nickelous nitrate and ammonium metawolframate are jointly dissolved in the water and make steeping fluid, be impregnated on 100g carrier, 120 ℃ of oven dry, 500 ℃ of roasting 3h, obtain containing NiO 6.0wt%, WO
320wt%, SiO
214wt%, P
2o
5the catalyzer 4 of 1.5wt%, SrO 2.5wt%.
The preparation of catalyzer 5:
Configuration 2L concentration is 100gAl
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 80gSiO
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 18min 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 60 ℃ 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, nitric acid, water mixer kneader, after extruded moulding, 120 ℃ of oven dry, 500 ℃ of roasting 4h, obtain siliceous and phosphorus oxidation alumina supporter.Nickel acetate, ammonium tungstate, saltpetre and magnesium nitrate are jointly dissolved in the water and make steeping fluid, be impregnated on 100g carrier, 120 ℃ of oven dry, 400 ℃ of roasting 4h, obtain containing NiO 4.5wt%, WO
327.5wt%, SiO
26.8wt%, P
2o
54.0wt%, K
2the catalyzer 5 of O 0.5wt%, MgO 1.5wt%.
The preparation of catalyzer 6:
The preparation method of amorphous aluminum silicide slurries and pseudo-boehmite slurries is with catalyzer 3.
Under the condition constantly stirring, 1L pseudo-boehmite slurries and 1L amorphous aluminum silicide slurries stream are joined in plastic cans, control 45 ℃ of mixing temperatures, aging 15min, 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, 450 ℃ of roasting 4h, then use the saturated impregnated carrier of magnesium acetate solution, 120 ℃ of oven dry, 600 ℃ of roasting 4h, obtain the alumina supporter of siliceous, phosphorus and magnesium.Nickel acetate and ammonium tungstate are jointly dissolved in the water and make steeping fluid, be impregnated on 100g carrier, 120 ℃ of oven dry, 450 ℃ of roasting 4h, obtain containing NiO 5.5wt%, WO
326wt%, SiO
212.5wt%, P
2o
5the catalyzer 6 of 2.0wt%, MgO 2.5wt%.
The preparation of catalyzer 7:
The preparation method of amorphous aluminum silicide slurries and pseudo-boehmite slurries is with catalyzer 1.
Under the condition constantly stirring, L amorphous aluminum silicide slurries are joined in 1.5L pseudo-boehmite slurries, 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, nitric acid, water mixer kneader, after extruded moulding, 120 ℃ of oven dry, 500 ℃ of roasting 3h, then use the saturated impregnated carrier of Lithium Citrate de solution, 120 ℃ of oven dry, 550 ℃ of roasting 4h, obtain the alumina supporter of siliceous, phosphorus and lithium.Nickelous nitrate and ammonium paratungstate are jointly dissolved in the water and make steeping fluid, be impregnated on 100g carrier, 120 ℃ of oven dry, 450 ℃ of roasting 4h, obtain containing NiO 4.5wt%, WO
324wt%, SiO
29.9wt%, P
2o
51.0wt%, Li
2the catalyzer 7 of O 1.5wt%.
Embodiment is as shown in table 1 with the physico-chemical property of catalyzer 1～7.
Stock oil character is in Table 2.
The physico-chemical property of catalyzer 1～7 for table 1 embodiment
Table 2 stock oil character
| Project | Stock oil 1 | Stock oil 2 | Stock oil 3 | Stock oil 4 |
| Density (g/ml) | 0.722 | 0.724 | 0.734 | 0.740 |
| Boiling range (℃) | 60～180 | 62～180 | 60～178 | 60～182 |
| Bromine valency * 10 -2(g/g) | 2.02 | 2.10 | 15.4 | 17.8 |
| Sulphur content (μ g/g) | 178 | 180 | 240 | 285 |
| Nitrogen content (μ g/g) | 3.26 | 3.88 | 7.21 | 9.56 |
| Arsenic content (ng/g) | 13 | 14 | 17 | 19 |
Note: raw material 1,2 is virgin naphtha; Raw material 3 is catalytically cracked gasoline and virgin naphtha mixture, and wherein the weight ratio of catalytically cracked gasoline and virgin naphtha is 15: 85; Raw material 4 is catalytically cracked gasoline and virgin naphtha mixture, and wherein the weight ratio of catalytically cracked gasoline and virgin naphtha is 30: 70.
Embodiment 1
Hydrotreating reactor adopts heat-insulating fixed bed, uses catalyzer 1.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, switch to stock oil 1,240 ℃ of temperature of reaction, reaction pressure 2.4MPa, liquid air speed 11h
-1, hydrogen to oil volume ratio 80, running 200h, sulphur, nitrogen content in every 24h sampling analysis product, the results are shown in Table 3.
Embodiment 2
Hydrotreating reactor adopts heat-insulating fixed bed, uses catalyzer 2.Catalyst vulcanization treatment process is with embodiment 1.
After sulfidizing finishes, switch to stock oil 2,250 ℃ of temperature of reaction, reaction pressure 2.6MPa, liquid air speed 10h
-1, hydrogen to oil volume ratio 100, running 200h, sulphur, nitrogen content in every 24h sampling analysis product, the results are shown in Table 3.
Embodiment 3
Hydrotreating reactor adopts heat-insulating fixed bed, uses catalyzer 3.Catalyst vulcanization treatment process is with embodiment 1.
After sulfidizing finishes, switch to stock oil 3,270 ℃ of temperature of reaction, reaction pressure 2.8MPa, liquid air speed 8h
-1, hydrogen to oil volume ratio 120, running 200h, sulphur, nitrogen content in every 24h sampling analysis product, the results are shown in Table 3.
Embodiment 4
Hydrotreating reactor adopts heat-insulating fixed bed, uses catalyzer 4.Catalyst vulcanization treatment process is with embodiment 1.
After sulfidizing finishes, switch to stock oil 4,300 ℃ of temperature of reaction, reaction pressure 2.8MPa, liquid air speed 8h
-1, hydrogen to oil volume ratio 150, running 200h, sulphur, nitrogen content in every 24h sampling analysis product, the results are shown in Table 3.
Embodiment 5
Hydrotreating reactor adopts heat-insulating fixed bed, uses catalyzer 5.Catalyst vulcanization treatment process is with embodiment 1.
After sulfidizing finishes, switch to stock oil 2,240 ℃ of temperature of reaction, reaction pressure 2.6MPa, liquid air speed 10h
-1, hydrogen to oil volume ratio 80, running 200h, sulphur, nitrogen content in every 24h sampling analysis product, the results are shown in Table 3.
Embodiment 6
Hydrotreating reactor adopts heat-insulating fixed bed, uses catalyzer 6.Catalyst vulcanization treatment process is with embodiment 1.
After sulfidizing finishes, switch to stock oil 4,280 ℃ of temperature of reaction, reaction pressure 2.6MPa, liquid air speed 7h
-1, hydrogen oil volume 150, running 200h, sulphur, nitrogen content in every 24h sampling analysis product, the results are shown in Table 3.
Embodiment 7
Hydrotreating reactor adopts heat-insulating fixed bed, uses catalyzer 7.Catalyst vulcanization treatment process is with embodiment 1.
After sulfidizing finishes, switch to stock oil 2,260 ℃ of temperature of reaction, reaction pressure 2.5MPa, liquid air speed 10h
-1, hydrogen oil volume 80, running 200h, sulphur, nitrogen 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.
Hydrotreating reactor adopts heat-insulating fixed bed, and catalyst vulcanization treatment process is with embodiment 1; Hydrotreatment, 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.
Hydrotreating reactor adopts heat-insulating fixed bed, and catalyst vulcanization treatment process is with embodiment 1; Hydrotreatment, 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.
Hydrotreating reactor adopts heat-insulating fixed bed, and catalyst vulcanization treatment process is with embodiment 1; Hydrotreatment, 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 1 for embodiment.Catalyzer consists of: NiO 4.0wt%, WO
323.5wt%, SiO
230.6wt%, P
2o
52.0wt%, Li
2o 2.5wt%.
Hydrotreating reactor adopts heat-insulating fixed bed, and catalyst vulcanization processing and hydrotreatment are with embodiment 1, and running 200h, 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.
Hydrotreating reactor adopts heat-insulating fixed bed, and catalyst vulcanization treatment process is with embodiment 1; Hydrotreatment is with embodiment 1, and running 200h, the results are shown in Table 3.
As shown in Table 3, the present invention contains hydrogenation catalyst prepared by the pseudo-boehmite of amorphous aluminum silicide by employing reformer feed is carried out to hydrotreatment, sulphur content < 0.5 μ g/g in hydrogenated products, nitrogen content < 0.5 μ g/g, meets catalytic reforming unit charging requirement; For processing the reformer feed that high sulfur-bearing is nitrogenous and olefin(e) centent is high, can all be less than the acceptable material of 0.5 μ g/g for catalytic reforming unit provides sulphur, nitrogen content equally simultaneously.
Table 3 embodiment 1～7 and comparative example 1～6 hydrotreatment data
Claims (17)
1. a method of producing catalytic reforming raw material, it is characterized in that the method comprises: catalytic reforming raw material enters the reactor that hydrotreating catalyst is housed under hydrogen atmosphere, hydroprocessing technique condition is: reaction temperature in is 200～320 ℃, working pressure is greater than 2.4MPa, and fresh feed oil volume air speed is 4～12h
-1, hydrogen to oil volume ratio is 50～300; Described hydrotreating catalyst is tungsten nickel catalyst, take silicon-containing alumina as carrier, nickel, tungsten are active ingredient, and phosphorus and basic metal and/or alkaline-earth metal are as auxiliary agent, in catalyst weight, contain Tungsten oxide 99.999 20～30wt%, nickel oxide 1～6wt%, phosphorous oxides 0.5～5wt%, basic metal and/or alkaline earth metal oxide 1～4wt%, silicon oxide 5～28wt%, specific surface area of catalyst 200～300m
2/ g, pore volume 0.5～0.75ml/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 the pseudo-boehmite containing amorphous aluminum silicide.
2. production catalytic reforming raw material method according to claim 1, it is characterized in that reacting temperature in is 220～300 ℃.
3. production catalytic reforming raw material method according to claim 1, is characterized in that working pressure is 2.4～3.0MPa.
4. production catalytic reforming raw material method according to claim 1, is characterized in that fresh feed oil volume air speed is 6～10h
-1.
5. production catalytic reforming raw material method according to claim 1, is characterized in that hydrogen to oil volume ratio is 60～200.
6. production catalytic reforming raw material method according to claim 1, is characterized in that: described catalytic reforming raw material is virgin naphtha, catalytically cracked gasoline or both mixtures.
7. production catalytic reforming raw material method according to claim 6, is characterized in that: described catalytic reforming raw material is virgin naphtha, both mixtures of catalytically cracked gasoline, and the weight ratio of catalytically cracked gasoline and virgin naphtha is 10:90～50:50.
8. production catalytic reforming raw material method 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.
9. according to the production catalytic reforming raw material method described in claim 1 or 8, it is characterized in that when aging that temperature is 20～65 ℃.
10. according to the production catalytic reforming raw material method described in claim 1 or 8, 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 under the condition that temperature is 25～40 ℃ (c) 5～20min, obtains amorphous aluminum silicide slurries.
11. according to the production catalytic reforming raw material method described in claim 1 or 8, 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 1～10Nm
3/ 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.
12. production catalytic reforming raw material methods according to claim 1, is characterized in that tungsten nickel catalyst is by the aqueous solution of tungstenic, nickel soluble salt be impregnated on silicon-containing alumina carrier, what after being dried, at 300～500 ℃, roasting 3～6h made.
13. production catalytic reforming raw material methods according to claim 12, 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.
14. production catalytic reforming raw material methods according to claim 12, 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.
15. production catalytic reforming raw material methods according to claim 12, it is characterized in that tungsten nickel catalyst is by basic metal, alkaline-earth metal and/or phosphoric were added in advance in silicon-containing alumina carrier before tungsten, nickel add, impregnated in again the aqueous solution of tungstenic, nickel soluble salt, what after being dried, at 300～500 ℃, roasting 3～6h made.
16. production catalytic reforming raw material methods according to claim 12, it is characterized in that tungsten nickel catalyst is to impregnated on silicon-containing alumina carrier by basic metal, alkaline-earth metal and/or phosphoric being added to the aqueous solution of tungstenic, nickel soluble salt, what after being dried, at 300～500 ℃, roasting 3～6h made.
17. production catalytic reforming raw material methods according to claim 15, it is characterized in that tungsten 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 of tungstenic, nickel soluble salt, what after being dried, at 300～500 ℃, roasting 3～6h made.
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| CN102746878B (en) * | 2012-08-02 | 2015-07-15 | 吴峰 | Catalytic reforming method |
| CN103254927B (en) * | 2013-05-24 | 2015-05-27 | 中国海洋石油总公司 | Treatment method for catalytic reformation and prehydrogenation of gasoline |
| CN104419451A (en) * | 2013-09-04 | 2015-03-18 | 中国石油天然气股份有限公司 | Method for producing reforming raw material by hydrofining blended inferior gasoline |
| CN107365600B (en) * | 2016-05-13 | 2020-04-21 | 神华集团有限责任公司 | Method for producing catalytic reforming raw material by hydrofining non-petrochemical naphtha and reaction device thereof |
| CN106732749B (en) * | 2016-11-17 | 2022-03-29 | 中国海洋石油集团有限公司 | One-step synthesis preparation method of hydrocracking catalyst |
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