CN1778872A - Hydrogenation desulfurized catalyst containing molecular screen - Google Patents
Hydrogenation desulfurized catalyst containing molecular screen Download PDFInfo
- Publication number
- CN1778872A CN1778872A CN 200410091490 CN200410091490A CN1778872A CN 1778872 A CN1778872 A CN 1778872A CN 200410091490 CN200410091490 CN 200410091490 CN 200410091490 A CN200410091490 A CN 200410091490A CN 1778872 A CN1778872 A CN 1778872A
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- Prior art keywords
- ets
- metal
- catalyzer
- molecular sieve
- hts
- Prior art date
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 239000002808 molecular sieve Substances 0.000 claims abstract description 40
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 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 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 239000003921 oil Substances 0.000 claims description 16
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 11
- 239000000470 constituent Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 239000002283 diesel fuel Substances 0.000 claims description 8
- 238000005987 sulfurization reaction Methods 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 238000006477 desulfuration reaction Methods 0.000 claims description 7
- 230000023556 desulfurization Effects 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 239000004480 active ingredient Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 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 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 14
- 239000002253 acid Substances 0.000 abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 7
- 102000040350 B family Human genes 0.000 abstract 1
- 108091072128 B family Proteins 0.000 abstract 1
- 230000003009 desulfurizing effect Effects 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 25
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 20
- 239000000843 powder Substances 0.000 description 16
- 229960005196 titanium dioxide Drugs 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 206010013786 Dry skin Diseases 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 229910001648 diaspore Inorganic materials 0.000 description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000005864 Sulphur Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 9
- 235000010215 titanium dioxide Nutrition 0.000 description 9
- 239000004411 aluminium Substances 0.000 description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 235000015165 citric acid Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- -1 Xiao Suangu Chemical compound 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 241000219782 Sesbania Species 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000001935 peptisation Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 239000001166 ammonium sulphate Substances 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 101100065719 Drosophila melanogaster Ets98B gene Proteins 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-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
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940024548 aluminum oxide Drugs 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
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- 229940078494 nickel acetate Drugs 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 239000010742 number 1 fuel oil Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006250 specific catalysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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Abstract
A hydrogenation desulfurizing catalyst containing molecular sieve consists of alumina 20.0~80.0wt% and silicon titanate molecular sieve of ETS 0.5~50.0wt%. It takes at least one Fe, Co and Ni metal of VIII family and Mo and W metal of VI B family as active component. It has controllable acid distribution and can improve metal component dispersity on carrier and hydrogenation catalyst activity.
Description
Technical field
The present invention relates to a kind of Hydrobon catalyst that contains molecular sieve in the chemical field.
Technical background
Typical catalyst for hydrodesulfurizationfraction fraction oil is to be carrier with the aluminum oxide, and VIII family and group vib element are that metal active constituent constitutes.As everyone knows, the physico-chemical property of carrier often produces material impact to the performance of catalyzer, therefore, the selection of carrier is very crucial, and it requires the pore volume of carrier unit volume and specific surface area bigger, pore distribution concentration, can load suitable active metal component, and can improve active metal component and carrier interactions, and it is uniformly dispersed, form more II class active reaction center (II class active centre and carrier combine a little less than, MoS
2Or WS
2The dispersity of agglomerate is relatively poor, often is formed by stacking by bigger sheet, and its advantage is to be made each active centre inherent activity have very high activity by more tight cure).The design of high-activity hydrofining catalyst is exactly to make II class active centre many as far as possible, and good dispersiveness and accessibility are arranged, thereby improves the catalytic activity of catalyst for hydrodesulfurizationfraction fraction oil greatly.For this reason, people attempt and have explored different additive or the auxiliary agents of introducing in the hydrogenation catalyst system.
TiO
2Sulphur there is stronger adsorptive power, and TiO
2Vattability and and the metal active constituent of load between stronger interaction, make TiO
2The catalyst system of base often shows some outstanding characteristic in the hydrogenation catalyst reaction.
CNO0136874.5 discloses a kind of selection catalyst carrier for hydrgenating and its production and use.It is combined with each other by aluminum oxide and titanium oxide and forms, and wherein the weight percent content of aluminum oxide is 1～99%.This invention complex carrier adopts chemical coprecipitation preparation, then load active component and make the selection hydrogenation catalyst.When the catalyzer that makes of invention carrier is used to select hydrogenation thus, not only active high, selectivity is high, and can resist sulphur and arseniasis, life cycle and life-span are long.
CN01127448.4 provides a kind of hydrogenation catalyst and preparation method thereof, and this catalyzer is made up of metal active constituent and carrier, and the metal active constituent of catalyzer is metal oxide MoO
3, among CoO and the NiO any two kinds or three kinds, in total catalyst weight, metal active constituent accounts for 2.0～35.0%; In total weight of carrier, carrier is made up of 5.0%～80.0% titanium dioxide, 10.0%～80.0% modified zsm-5 zeolite and 10.0%～85.0% tackiness agent.Use this invention catalyzer, can reduce the content of sulphur and alkene in the inferior patrol, and increase gasoline octane rating.
CN01116022.5 has related to a kind of catalyst carrier for hydrgenating and preparation method thereof, this support of the catalyst is the complex body of titanium dioxide or titanium dioxide and silicon-dioxide or titanium dioxide and aluminum oxide, the particle diameter of its basic granules is 2～40nm, preparing this catalyst carrier for hydrgenating comprises from the sol system to the gelling system, and through supercritical technology exsiccant process, all bigger with this invention support of the catalyst dipping active ingredient or active ingredient with specific surface area of catalyst and the pore volume that this carrier while nanometer makes, acidity is strong, can satisfy the needs of the hydrofining and the hydrocracking of different petroleum fractionss.
CN00110018.1 provides a kind of hydrogenation catalyst and preparation method thereof, this catalyzer is supported on a kind of aluminum oxide by the special methods preparation by W, Ni and prepares, the aluminum oxide of special methods preparation is by adding the fluorine modification, adds one or more oxide compound preparation of boron, silicon, phosphorus, magnesium, titanium, zirconium, gallium simultaneously.Contain Tungsten oxide 99.999 18.0～30.0% in the catalyzer.Contain nickel oxide 3.0～8.0%, fluorine-containing 3.0～10.0%, the oxide compound 1.0～5.0% of boracic, silicon, phosphorus, magnesium, titanium, zirconium, gallium.Be applicable to the hydrotreatment of heavy distillate, be specially adapted to the hydrotreatment of diesel oil and vacuum gas oil.
CN00123151.0 discloses alumina supporter of a kind of wide aperture titaniferous and silicon composite assistant and preparation method thereof.Silicon-containing compound and titanium-containing compound are introduced in this invention in the process of preparation aluminium hydroxide.This preparation process technology is simple, and cost is low.Simultaneous oxidation titanium and silicon-dioxide are uniformly dispersed at alumina surface, the aluminum oxide of this invention titaniferous, silicon has good peptization, eliminated the shortcoming of siliceous routinely alumina pore distribution disperse, peptization difference, the carrier that this invention titaniferous silicon oxidation aluminum is equipped with has big aperture, average pore diameter is 10～15nm, has stronger surface acid property simultaneously.Support of the catalyst or catalyzer with this invention preparation when having big average pore diameter, have stronger acid matter, can be used for the preparation of wide aperture hydrotreating catalyst or hydrogenation conversion catalyst.
CN03126138.8 discloses a kind of production method and used catalyzer of this method of kerosene type solvent naphtha.In the method, stock oil is 130～300 ℃ virgin kerosene or hydrocracking kerosene(oil)fraction, adopts hydrogenation method to produce fat coal oil type solvent oil, and hydrogenation catalyst used therein is Ni/TiO
2-Al
2O
3Or W-Mo-Ni/TiO
2-Al
2O
3, the required hydrogen dividing potential drop of hydrogenation is 6.0～15.0MPa, and temperature of reaction is 220～360 ℃, and volume space velocity is 0.3～2.0h
-1, hydrogen to oil volume ratio is 300～800; 1.With the product that this method is produced, not only color water-white, nontoxic tasteless, and sulphur, nitrogen content are all less than 1 μ g/g, and aromaticity content is less than 200 μ g/g.
CN02116267.0 relates to a kind of gasoline hydrogenation catalyst and method for making and its application in desulfurating and reducing olefinic hydrocarbon.The catalyzer of this invention is by the weight percent meter to catalyzer, and its component comprises: containing consumption is the TiO that comprises of 20～90wt%
2The carrier of component; The A active ingredient: the content of VIII family metal oxide is 0.1～8wt%; The B active ingredient: the content of group vib metal oxide is 1～13wt%; Surplus is a binding agent.This invention catalyzer under than the demulcent hydroconversion condition, is handled the FCC gasoline of sulfur-bearing, alkene after prevulcanized, show very high hydrodesulfurization activity and selectivity.Compare with traditional hydrogenation catalyst, under the horizontal situation of identical hydrogenating desulfurization, the loss of octane number that shows gasoline is smaller, and the liquid of product is received than higher, reaches 99wt%.
CN88106099.2 has related to a kind of Hydrodevulcanizing catalyst for hydro-carbons, to be loaded with the γ-Al of titanium oxide
2O
3Be carrier, activeconstituents is molybdenum, cobalt, nickel.Make with pickling process.This catalyzer does not need prevulcanize to use, and keeps high stability hydrodesulfurization activity.Sulphur content is less than or equal to 1ppm in the hydrocarbon of this catalyst treatment, and the bromine valency is less than or equal to 0.10 gram bromine/100 gram oil.
USP4128505, USP4186080 provides a kind of hydrotreating catalyst, mixture with titanium oxide and zirconia composite or titanium oxide, zirconium white and aluminum oxide is a carrier, supported V IB and VIII family metal, after the sulfuration, in the hydrogenation of hydrogenating desulfurization, hydrodenitrification and the aromatic hydrocarbons of oil product is saturated, demonstrate good effect.
USP5229347 has described a kind of hydrogenation catalyst with weak hydrogenation cracking activity, it is a carrier with titanium oxide and alumina compound, supported V IB and VIII family metal, after sulfuration, to oil product after the cracking, especially diesel oil had the saturated selectivity of hydrogenation of good hydrogenating desulfurization, hydrodenitrification and aromatic hydrocarbons.
From above situation as can be seen, titanium introduced the catalyst system modification after, make hydrogenation catalyst demonstrate good hydrogenation activity and unique hydrogenation catalyst performance, still, the main at present TiO that adopts
2Sneak into conventional carriers Al
2O
3And SiO
2In, and pure TiO
2The specific surface area of carrier own is less relatively, bad mechanical strength and active anatase octahedrite unstable at high temperature, cause surface-area to descend rapidly, thereby losing of its active sites makes its application be subjected to certain restriction (Applied Catalysis A:1997,165:1-13; Chemical industry and engineering, 1996,17 (4): 5-9).
In order to improve the activity of hydrogenation catalyst, people have introduced molecular sieve in the conventional oxidation alumina supporter, as: Y, ZSM-5, β, mordenite, L zeolite, MCM-41 or Al-MCM-41 etc.For example, CN01130973.3 has described a kind of method of hydrotreating of distillate, has wherein related to a kind of hydrogenation catalyst, is active ingredient with the metal of VIII family, group vib in the periodic table of elements, is carrier with the mixture of aluminum oxide and zeolite (preferred y-type zeolite).This method can be processed light cycle oil and/or the heavy cycle oil that comes catalytic cracking, and its cetane value increases substantially, and density, sulphur content all reduce significantly, but diesel yield has only about 96%.
The disclosed aluminum oxide mixed carrier that contains molecular sieve because molecular sieve has stronger acidity, can cause the cracking catalyst activity higher at present, and product yield descends.
Summary of the invention
Purpose of the present invention is exactly a kind of highly active, Hydrobon catalyst of containing molecular sieve of exploitation, is applicable to that the hydrogenating desulfurization of fraction oil of petroleum is refining, is specially adapted to the deep hydrodesulfurizationof of diesel oil.The most outstanding a kind of hydrogenation catalyst of research and design that is characterised in that of the present invention, it makes full use of advantages such as industrial its high strength of traditional alumina supporter, Heat stability is good and pore size distribution suit, and introduce the micropore ETS HTS (preferred code name be the HTS of ETS-10) of a class appropriate acid first, increase specific surface area, make pore distribution more concentrated simultaneously, and it is acid adjustable, after suitable modification, further optimize the structure and the surface acid property of catalyzer, substantially improve the dispersity of metal active phase, strengthen the hydrogenation performance of catalyzer.
The present invention is achieved in that
Hydrobon catalyst described in the invention, it is characterized in that comparing with titanium dioxide, the code name of introducing is that (reference literature is synthetic: Microporous and MesoporousMaterials for the HTS of ETS-10,2001,46:1-11), the skeleton of this molecular sieve has thermostability and higher specific surface area (about 300～500m preferably based on silicon oxide and titanium oxide
2/ g), overcome weakness such as traditional titanium dioxide specific surface area is low, poor heat stability.And at present existing open report does not relate to titanium silicon molecular sieve ETS-4-10 and is applied in the Hydrobon catalyst, especially in the deep hydrodesulfurizationof of diesel oil.
We think that the titanium on this titanium silicon molecular sieve ETS-4 skeleton is not only the adsorption activity position of desulfurization, and the silicon on titanium and the skeleton all helps improving, and intensive interacts between metal and the carrier (especially aluminum oxide), and be used for the sodium and the potassium of the unnecessary negative charge of balance skeleton on its skeleton, also can gather materials on the spot, as the electronics auxiliary agent, promote the formation of metal active phase precursor and neutralize a small amount of strong acid center of crossing, suppress coking deactivation (Journal of Catalysis, 2000,194:393-400; Energy﹠amp; Fuels, 1997,11:119-1126).In addition, sodium and potassium on the skeleton have ion exchangeable, can be according to concrete reaction properties requirement, and ammonium or other different metal ion (iron, copper, zinc, lanthanum etc.) in the ion-exchange, its acidity of modulation and catalytic performance.Also can adopt methods such as dipping or co-precipitation to introduce and have the metal (platinum, palladium, rubidium, ruthenium, zinc etc.) of specific catalysis its modification.Also but original position is synthesized the HTS of metal heteroatom (aluminium, zirconium, cobalt etc.), thereby satisfies the requirement of different hydrogenation catalysts reactions.
Hydrobon catalyst described in the invention is characterized in that the ETS HTS introduced, preferably the ETS-10 HTS.HTS is 0.5%～50.0% with respect to the weight content of the gross weight of catalyzer, preferably 5.0%～45.0%.
Hydrobon catalyst described in the invention, it is characterized in that the usage quantity of aluminum oxide in catalyzer account for catalyzer gross weight 20.0%～80.0%, 30.0%～50.0% (weight percentage) preferably.It can select for use commercially available plan win diaspore dry powder (for example: the rich diaspore powder of the plan that Shandong Aluminium Industry Co., Ltd produces), also can be through special processing the commercial alumina carrier with certain pore distribution (for example: the high purity aluminium oxide carrier series that Jiangyan City, Jiangsu Province auxiliary chemicals factory produces).
Hydrobon catalyst described in the invention, it is characterized in that by in aluminum oxide, introducing a class ETS micropore titanium silicon molecular sieve (preferred ETS-10 HTS), improved the specific surface area (seeing Table) of complex carrier, it is relatively low to have overcome conventional oxidation alumina supporter specific surface, the limitation that content of metal is limited provides prerequisite for further improving high active of hydrogenation catalysis.
Hydrobon catalyst described in the invention, it is characterized in that titanium silicon molecular sieve ETS-4-10 dry powder (or the titanium silicon molecular sieve ETS-4 of crystallization certain hour-10 colloidal sol), intend rich diaspore dry powder (or the rich diaspore gel of the plan behind the sour peptization or other commercially available alumina supporter), mineral acid, organic acid and extrusion aid, mix by a certain percentage, extrusion moulding obtains the said support of the catalyst of the present invention.
Hydrobon catalyst described in the invention is characterized in that mineral acid is selected from phosphoric acid, nitric acid, hydrochloric acid and sulfuric acid; Organic acid is selected from polycarboxylic acids such as citric acid, tartrate, ethylenediamine tetraacetic acid (EDTA) and trinitro-nitrilotriacetic; Extrusion aid is selected from dry starch, sesbania powder etc.
Hydrobon catalyst described in the invention is characterized in that catalyst appearance can be bar shaped, and trifolium-shaped also can be a particulate state or spherical.
Hydrobon catalyst described in the invention, it is characterized in that the complex carrier that obtains after complex carrier extrusion moulding, drying, the roasting, by suitable modification, its surface acidity distributes controlled, thereby can improve the interaction between metal component and the carrier, thereby improve the dispersity of metal component on carrier, and then improve its high active of hydrogenation catalysis.
Hydrobon catalyst described in the invention, other metal ion of titanium silicon molecular sieve ETS-4-10 modification indication, it is characterized in that preferred IIB family and/or IIIA family element, the best is zinc and/or lanthanum, wherein with respect to the gross weight of catalyzer, the weight percentage scope of metallic zinc and/or lanthanum is 0.0～3.0%.The used lanthanoid metal of titanium silicon molecular sieve ETS-4-10 modification is selected from lanthanum nitrate, Lanthanum trichloride etc., preferred lanthanum nitrate.The used metallic zinc of titanium silicon molecular sieve ETS-4-10 modification is selected from zinc nitrate, zinc acetate, zinc chloride etc., preferred zinc nitrate.
Hydrobon catalyst described in the invention is characterized in that metal active constituent is selected from the Mo and the W of group vib metal, preferred W, and wherein with respect to the gross weight of catalyzer, the weight percentage scope of group vib metal is 5.0～40.0%.
Hydrobon catalyst described in the invention is characterized in that the group vib metallic compound is selected from ammonium molybdate or ammonium metawolframate, ethyl metatungstic acid, metatungstic acid nickel etc.
Hydrobon catalyst described in the invention is characterized in that metal active constituent is selected from the Fe of VIII family metal, Co and Ni, preferred Ni, and wherein with respect to the gross weight of catalyzer, the weight percentage scope of VIII family metal is 1.0～10.0%.
Hydrobon catalyst described in the invention is characterized in that VIII family metallic compound is selected from nickelous nitrate, nickel acetate, Xiao Suangu, Cobaltous diacetate or iron nitrate etc.
The carrying method of said metal active constituent can be after being two kinds of forming materials of HTS of ETS-10 with aluminum oxide and code name, together the above-mentioned metal active constituent of load.Also can be to be that the HTS of ETS-10 is carrier load respectively with aluminum oxide or code name respectively, and then two kinds of carriers behind the supported active metal are carried out composite molding by method noted earlier.Also can be, and another carrier supported active metal component not carries out composite molding by method noted earlier then with one of them carrier elder generation supported active metal component, the active metal component of load 0.0%～35.0% as required more afterwards.Hydrobon catalyst described in the invention is characterized in that this catalyzer before use, in hydrogen atmosphere, catalyzer is converted into sulphided state with sulfide (as dithiocarbonic anhydride, thioether etc.) after, just can carry out effective catalyzed reaction.
Description of drawings
Fig. 1 is the XRD spectra of sodium potassium type HTS;
Fig. 2 is that sodium potassium type HTS is at (A) 550 ℃ of roasting 5h; (B) 600 ℃ of roasting 5h;
(C) XRD spectra of not roasting sample contrast;
Fig. 3 for (A) ammonium exchange behind the 25wt% sodium potassium XRD spectra (not roasting);
(B) XRD spectra behind 550 ℃ of roasting 5h;
Fig. 4 is (A) pure alumina carrier; (B) complex carrier is at 550 ℃ of roasting 5h;
(C) XRD spectra of complex carrier behind 600 ℃ of roasting 5h
Embodiment
The following examples will give further instruction to Hydrobon catalyst provided by the invention, but not thereby limiting the invention.
Embodiment one
Synthesize that (its XRD spectra is seen figure one at 100 ℃ of dried sodium potassium type titanium silicon molecular sieve ETS-4s-10 then with 50 grams are own, figure two), win diaspore powder with the plan that 30 gram Shandong Aluminium Industry Co., Ltd produce, 10 gram sesbania powder, behind the mixing, be added dropwise to 10 the gram concentrated nitric acids, 10 the gram citric acids and 50 the gram water mixing solutions, extrusion becomes the 1mm cylinder shape, after 100 ℃ of dryings then at 550 ℃ of roasting 5h.Be dissolved in the solution impregnation 4h of 50 gram water again with 20 gram nickelous nitrates, 44 gram ammonium metawolframates, 100 ℃ of dryings are behind 550 ℃ of roasting 5h.By specific requirement, broken or be cut to required particle diameter or length, can carry out hydrogenation reaction after the sulfuration.
Embodiment two
Own synthetic (its XRD composes and sees figure one at 100 ℃ of dried sodium potassium type titanium silicon molecular sieve ETS-4s-10 then with 50 grams, figure two), win diaspore powder with the plan that 30 gram Shandong Aluminium Industry Co., Ltd produce, 10 gram sesbania powder, behind the mixing, be added dropwise to the mixing solutions of 10 gram concentrated nitric acids, 10 gram citric acids and 50 gram water, extrusion becomes the 1mm cylinder shape, after 100 ℃ of dryings, behind 550 ℃ of roasting 5h.Be dissolved in 50 gram water retting 4h with 20 gram nickelous nitrates earlier, 100 ℃ of dryings behind 550 ℃ of roasting 5h, are dissolved in the solution impregnation 4h of 50 gram water again with 44 gram ammonium metawolframates, and 100 ℃ of dryings are behind 550 ℃ of roasting 5h.By specific requirement, broken or be cut to required particle diameter or length, can carry out hydrogenation reaction after the sulfuration.
Embodiment three
With the sodium potassium type titanium silicon molecular sieve ETS-4s-10 of 50 grams among the embodiment one, be changed to 50 grams and exchange ammonium modifying titanium-silicon molecular sieve ETS-10 (its XRD spectrum is seen figure three) behind the 25% sodium potassium by the 0.1M ammoniumsulphate soln, below preparation is with embodiment one.
Embodiment four
With the sodium potassium type titanium silicon molecular sieve ETS-4s-10 of 50 grams among the embodiment one, be changed to 50 grams by containing the titanium silicon molecular sieve ETS-4-10 (XRD spectra and ammonium type are similar, and be not attached) of 4.0% lanthanum with the ion-exchange of 0.05M lanthanum nitrate hexahydrate, below prepare with embodiment one.
Embodiment five
With the sodium potassium type titanium silicon molecular sieve ETS-4s-10 of 50 grams among the embodiment one, be changed to 50 grams by containing the titanium silicon molecular sieve ETS-4-10 (XRD spectra and ammonium type are similar, and be not attached) of 3.0% zinc with the ion-exchange of 0.05M zinc nitrate solution, below prepare with embodiment one.
Embodiment six
40 grams oneself are synthetic, 100 ℃ of dried sodium potassium type titanium silicon molecular sieve ETS-4s-10, after the exchange of 0.1M ammoniumsulphate soln, washing and filtering, redispersion make the 100 gram water-sols.Win the diaspore mixing with the plan that 90 gram 10wt% nitric acid and 60 gram Shandong Aluminium Industry Co., Ltd produce, behind the peptization 6h, with above-mentioned titanium silicon molecular sieve ETS-4-10 water-sol, the vigorous stirring mixing, 100 ℃ of dryings, (its XRD spectrum is seen figure four to get complex carrier, identify that through XRD complex carrier has the characteristic peak and the crystal phase structure of titanium silicon molecular sieve ETS-4-10) broken again 200 mesh sieves of crossing, add 10 gram dry starch, behind the mixing, be added dropwise to the mixing solutions of 10 gram concentrated nitric acids, 10 gram citric acids and 50 gram water, extrusion becomes the cylinder shape of 1mm, behind 100 ℃ of dryings, the 550 ℃ of roasting 5h.Be dissolved in the solution impregnation 4h of 50 gram water again with 18 gram nickelous nitrates, 48 gram ammonium metawolframates, 100 ℃ of dryings are behind 550 ℃ of roasting 5h.By specific requirement, broken or be cut to required particle diameter or length, can carry out hydrogenation reaction after the sulfuration.
Embodiment seven
Restrain through 100 ℃ of dried sodium potassium type titanium silicon molecular sieve ETS-4s-10 40, after the exchange of 0.1M ammoniumsulphate soln, washing and filtering, after 100 ℃ of dryings, add 60 gram GA one 383 aluminum oxide powders (production of Jiangyan City, Jiangsu Province auxiliary chemicals factory) and 10 gram dry starch, behind the mixing, be added dropwise to the mixing solutions of 10 gram concentrated nitric acids, 10 gram citric acids and 50 gram water, extrusion becomes the cylinder shape of 1mm, behind 100 ℃ of dryings, the 550 ℃ of roasting 5h.Be dissolved in the solution impregnation 4h of 50 gram water again with 18 gram nickelous nitrates, 48 gram ammonium metawolframates, 100 ℃ of dryings are behind 550 ℃ of roasting 5h.By specific requirement, broken or be cut to required particle diameter or length, can carry out hydrogenation reaction after the sulfuration.
Embodiment eight
With cylindrical catalyst made among the embodiment six, broken, sieve, get the 40-60 order, filling 1.2ml is a model compound in the n-decane solution that is dissolved with dibenzothiophene (with sulphur 1000 μ g/g), respectively at 553K, 573K, 593K, 4.0MPa, LHSV=10h
-1Hydrogen/oil volume is than being under 400 the operational condition, estimate its hydrodesulfurization activity, and with pure alumina, aluminum oxide and titanium dioxide (Detitanium-ore-type, titanium content is identical with complex carrier among the embodiment six) mixed oxide be that the catalyzer of carrier is compared, the result shows, the hydrogenating desulfurization rate of the catalyzer described in the embodiment six is the highest under the same conditions, has shown good hydrodesulfurization activity (seeing figure five).
Embodiment nine
With cylindrical catalyst made among the embodiment six, be cut into the segment of 1.5mm, filling 15ml is a raw material with the grand celebration catalytic cracking diesel oil, after sulfuration is stable, at pressure 8.0MPa, 360 ℃ of temperature, air speed 2.0h
-1, hydrogen/oil volume ratio is under 500: 1 the operational condition, sulphur content is less than 15 μ g/g in the product diesel oil behind the hydrogenation, and oil-collecting ratio is not less than 100.0%.And the catalyzer of pure alumina and aluminum oxide and titanium dioxide (Detitanium-ore-type, titanium content is identical with complex carrier among the embodiment six) preparation, the sulphur content behind the hydrogenation in the product diesel oil also has 25 μ g/g and 37 μ g/g respectively.
Embodiment ten
The rich diaspore powder of plan that the rich diaspore powder of plan, the 40 own synthetic ETS-10 powder of gram and the 60 gram Shandong Aluminium Industry Co., Ltd that the rich diaspore powder of plan, the 20 own synthetic ETS-10 powder of gram and the 80 gram Shandong Aluminium Industry Co., Ltd that 100 gram Shandong Aluminium Industry Co., Ltd are produced produce produce, respectively with 10 gram sesbania powder, behind the mixing, be added dropwise to the mixing solutions of 10 gram concentrated nitric acids, 10 gram citric acids and 50 gram water, extrusion becomes the 1mm cylinder shape, after 100 ℃ of dryings, behind 550 ℃ of roasting 5h, the shaping carrier that obtains, be labeled as carrier A successively, carrier B, support C; As can be seen, along with the increase of molecular sieve content in carrier, the specific surface area of shaping carrier constantly increases (seeing Table one).
By the XRD spectra of Fig. 1～Fig. 4, proved that further described new titanium-silicone molecular sieve of this patent and complex carrier thereof have good thermostability.
Table a part sieve add-on is to the influence of carrier specific surface area
| Bearer number | Molecular sieve add-on w% | Specific surface area m 2/g |
| Carrier A carrier B support C | 0 20 40 | 273.4 316.7 348.8 |
Claims (8)
1. Hydrobon catalyst that contains molecular sieve, it is characterized in that: this catalyzer is that the HTS with aluminum oxide and ETS is that carrier is composited, with at least a VIII Fe of family, Co, Ni metal and at least a group vib Mo, W metal is active ingredient, the usage quantity of the HTS of ETS in catalyzer is 0.5%～50.0% weight percentage with respect to the gross weight of catalyzer, and the usage quantity of described aluminum oxide in catalyzer is 20.0%～80.0% weight percentage with respect to the gross weight of catalyzer.
2. a kind of Hydrobon catalyst that contains molecular sieve according to claim 1 is characterized in that: contain titanium and element silicon in the HTS of ETS, preferred ETS HTS is that code name is the HTS of ETS-10.
3. a kind of Hydrobon catalyst that contains molecular sieve according to claim 2, it is characterized in that: the HTS of ETS is sodium, potassium type, or be Hydrogen by ammonium ion exchange, roasting, or in modes such as dipping, co-precipitation or ion-exchanges, introduce the HTS that other metal ion carries out the modification ETS after the modification, or the original position synthetic contains the heteroatoms ETS HTS of different metal atom.
4. a kind of Hydrobon catalyst that contains molecular sieve according to claim 1 is characterized in that: alumina supporter is commercially available pseudo-boehmite, or the commercial alumina carrier with pore distribution of process special processing.
5. a kind of Hydrobon catalyst that contains molecular sieve according to claim 1, it is characterized in that: the HTS of described modification ETS is chosen IIB family or IIIA family metallic salt, salt as modified metal cerium, lanthanum or zinc, platinum, palladium, rubidium, ruthenium metal carries out as said modification in the claim 3 the ETS-10 HTS, and wherein modified metal is 0.0%～3.0% with respect to the overall weight percent scope of catalyzer.
6. a kind of Hydrobon catalyst that contains molecular sieve according to claim 1, it is characterized in that: VIII family metal active constituent is selected from Fe, Co and Ni, preferred Ni, wherein with respect to the gross weight of catalyzer, the weight percentage scope of VIII family metal is 1.0%～10.0%.
7. a kind of Hydrobon catalyst that contains molecular sieve according to claim 1, it is characterized in that: the group vib metal active constituent is selected from Mo and W, preferred W, wherein with respect to the gross weight of catalyzer, the weight percentage scope of group vib metal is 5.0%～40.0%.
8. a kind of Hydrobon catalyst that contains molecular sieve according to claim 1 is characterized in that: this catalyzer can be used for the hydrogenating desulfurization of fraction oil of petroleum after sulfuration makes with extra care, and is specially adapted to the deep hydrodesulfurizationof of diesel oil.
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| US4853202A (en) * | 1987-09-08 | 1989-08-01 | Engelhard Corporation | Large-pored crystalline titanium molecular sieve zeolites |
| US5453263A (en) * | 1994-05-24 | 1995-09-26 | Engelhard Corporation | Halide-free process for the synthesis of ETS-10 |
| CN1064988C (en) * | 1995-11-22 | 2001-04-25 | 中国石油化工总公司 | Diesel oil fraction hydrogenation converting process |
| CN1234814C (en) * | 2001-08-29 | 2006-01-04 | 中国石油化工股份有限公司 | Hydrogenation of distilled oil |
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2004
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