CN1291787C - Hydrocarbon cracking catalyst containing molecular sieve and its preparing mehtod - Google Patents
Hydrocarbon cracking catalyst containing molecular sieve and its preparing mehtod Download PDFInfo
- Publication number
- CN1291787C CN1291787C CN 200410029863 CN200410029863A CN1291787C CN 1291787 C CN1291787 C CN 1291787C CN 200410029863 CN200410029863 CN 200410029863 CN 200410029863 A CN200410029863 A CN 200410029863A CN 1291787 C CN1291787 C CN 1291787C
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- Prior art keywords
- metal
- weight
- catalyst
- zeolite
- oxide
- Prior art date
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- Expired - Lifetime
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- 239000003054 catalyst Substances 0.000 title claims abstract description 220
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 104
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000005336 cracking Methods 0.000 title claims abstract description 44
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 23
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 22
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 181
- 239000002184 metal Substances 0.000 claims abstract description 181
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 132
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 131
- 239000010457 zeolite Substances 0.000 claims abstract description 131
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 109
- 239000000203 mixture Substances 0.000 claims abstract description 72
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 70
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 57
- 239000004927 clay Substances 0.000 claims abstract description 53
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 46
- 239000011148 porous material Substances 0.000 claims abstract description 39
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000002829 reductive effect Effects 0.000 claims abstract description 16
- 230000000737 periodic effect Effects 0.000 claims abstract description 12
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 86
- 239000005995 Aluminium silicate Substances 0.000 claims description 63
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 58
- -1 imvite Chemical compound 0.000 claims description 54
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 54
- 235000012211 aluminium silicate Nutrition 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 53
- 238000002360 preparation method Methods 0.000 claims description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 239000007789 gas Substances 0.000 claims description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims description 34
- 239000001257 hydrogen Substances 0.000 claims description 34
- 239000003921 oil Substances 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 25
- 229910052698 phosphorus Inorganic materials 0.000 claims description 25
- 239000011574 phosphorus Substances 0.000 claims description 25
- 230000009467 reduction Effects 0.000 claims description 24
- 230000003647 oxidation Effects 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 22
- 229910017052 cobalt Inorganic materials 0.000 claims description 20
- 239000010941 cobalt Substances 0.000 claims description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 239000011701 zinc Substances 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 229910052733 gallium Inorganic materials 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000011135 tin Substances 0.000 claims description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- 239000010953 base metal Substances 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- 239000011133 lead Substances 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 2
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052621 halloysite Inorganic materials 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 229910000275 saponite Inorganic materials 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 28
- 230000000694 effects Effects 0.000 abstract description 15
- 239000000295 fuel oil Substances 0.000 abstract description 8
- 238000006477 desulfuration reaction Methods 0.000 abstract description 4
- 230000023556 desulfurization Effects 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 description 38
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 37
- 239000002002 slurry Substances 0.000 description 34
- 239000007787 solid Substances 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 32
- 229910052717 sulfur Inorganic materials 0.000 description 32
- 239000011593 sulfur Substances 0.000 description 32
- 239000000047 product Substances 0.000 description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 27
- 238000004523 catalytic cracking Methods 0.000 description 25
- 238000006722 reduction reaction Methods 0.000 description 24
- 239000003502 gasoline Substances 0.000 description 23
- JGBBILLMZPWNFU-QGZVFWFLSA-N [(4r)-4-(3-hydroxyphenyl)-1,6-dimethyl-2-thioxo-1,2,3,4-tetrahydropyrimidin-5-yl](phenyl)methanone Chemical compound C=1([C@H](NC(=S)N(C=1C)C)C=1C=C(O)C=CC=1)C(=O)C1=CC=CC=C1 JGBBILLMZPWNFU-QGZVFWFLSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 16
- 239000008246 gaseous mixture Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 238000009826 distribution Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229910001593 boehmite Inorganic materials 0.000 description 13
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 13
- 239000002243 precursor Substances 0.000 description 12
- 102100028099 Thyroid receptor-interacting protein 6 Human genes 0.000 description 11
- 101710084345 Thyroid receptor-interacting protein 6 Proteins 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 11
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 11
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 238000013019 agitation Methods 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 229910001122 Mischmetal Inorganic materials 0.000 description 9
- 238000007598 dipping method Methods 0.000 description 9
- 239000002841 Lewis acid Substances 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 150000007517 lewis acids Chemical class 0.000 description 8
- 239000000395 magnesium oxide Substances 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
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- 230000032683 aging Effects 0.000 description 6
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- 239000002283 diesel fuel Substances 0.000 description 5
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- 150000002431 hydrogen Chemical class 0.000 description 5
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- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 4
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- 230000003197 catalytic effect Effects 0.000 description 4
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- 229910052746 lanthanum Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- 239000000654 additive Substances 0.000 description 3
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
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- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
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- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
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- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
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- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 description 1
- 229940001007 aluminium phosphate Drugs 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 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
- 238000003556 assay Methods 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- ZOIVSVWBENBHNT-UHFFFAOYSA-N dizinc;silicate Chemical compound [Zn+2].[Zn+2].[O-][Si]([O-])([O-])[O-] ZOIVSVWBENBHNT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 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
- 235000001055 magnesium Nutrition 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910001723 mesolite Inorganic materials 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a hydrocarbon cracking catalyst comprising a molecular sieve. The catalyst comprises a molecular sieve, a heat-resistant inorganic oxide substrate, clay and one metal component, wherein the metal component basically exists in a reductive valence state and is selected from one or several kinds of non-aluminum metal in group IIIA, metal in group IVA, group VA, group IB, group IIB, group VB, group VIB and group VIIB, and non-noble metal in group VIII in the periodic table. The catalyst also comprises rare earth metal existing outside a pore canal of the molecular sieve. The molecular sieve is selected from Y type zeolite, or a mixture of Y type zeolite and at least one of zeolite with an MFI structure, and beta zeolite. The content of the molecular sieve is from 1 to 90 wt%; the content of the heat-resisting inorganic oxides is from 2 to 80 wt%; the content of the clay is from 2 to 80 wt%; the content of the rare earth metal existing outside a pore canal of the molecular sieve is from 0.1 to 10 wt%; the content of the metal component is from 0.1 to 30 wt%. The catalyst has high desulfurization capability, high vanadium resistant capability and high heavy oil cracking activity.
Description
Technical field
The invention relates to a kind of hydrocarbon cracking catalyzer and preparation method thereof, more particularly, is about a kind of hydrocarbon cracking catalyzer that contains molecular sieve and preparation method thereof.
Background technology
Content of vanadium is higher in some heavy oil, as can be up to 20ppm even up to 60ppm, in catalytic cracking reaction, vanadium constantly is deposited on the Cracking catalyst, make that content of vanadium reaches 7000-11000ppm on the Cracking catalyst, high content of vanadium not only makes the structure of catalytic cracking catalyst be damaged, and increases the consumption of catalyst, and causes product quality and product distribution variation.The Cracking catalyst that therefore need have higher anti-vanadium ability.
Introducing alkaline earth oxide in Cracking catalyst is a kind of method that improves the anti-vanadium ability of Cracking catalyst, as US5, uses MgO and the kaolin bead anti-vanadium assistant as catalytic cracking catalyst in 300,469.US4 uses IIA in 485,184, IIIB, and IVB, the oxide of VB isofamily element is as anti-vanadium catalytic cracking catalyst auxiliary agent.US4, in 843,052 and US4,940,531 with the mixed oxide of tin, titanium as anti-vanadium component, anti-preferably vanadium effect is arranged.
Introducing the rare earth metal component in Cracking catalyst is to improve another method of the anti-vanadium ability of Cracking catalyst, as US4,900,428 and EP0,189, soluble ree compound solution impregnated catalyst or matrix such as the halide of use rare earth metal, nitrate are incorporated into rare earth in the catalyst in 267.US5, the catalyst that discloses in 248,642 and US5,304,299 are to be matrix as active component, aluminium colloidal sol as binding agent, kaolin and sour modified kaolin with rare earth oxide.US4,515,683 and ZL88100418 in be rare earth chloride to be deposited on the y-type zeolite with ammoniacal liquor, making with this y-type zeolite is that the catalytic cracking catalyst of active component has certain anti-vanadium performance.US5 uses the 5-10% bastnasite in 173,174, directly joins in the catalytic cracking catalyst, and this catalyst also has certain anti-vanadium effect.
CN1341697A discloses a kind of hydrocarbon cracking catalyzer and preparation method of anti-vanadium, this catalyst be by y-type zeolite or the y-type zeolite of 10-60 weight % and have the zeolite of MFI structure and/or two kinds of aluminium oxide of the clay of beta-molecular sieve, 10-75 weight %, 10-70 weight %, with P
2O
5The phosphorus of the 0.1-7.0 weight % of meter and in rare earth oxide, the rare earth of 0.1-22 weight % is formed, and wherein deposition of rare-earth accounts for 0.1-10 weight %.This catalyst is with the y-type zeolite after handling through phosphorus solution, with or not with the zeolite with MFI structure and/after beta-molecular sieve mixes, mixes with clay, double aluminium binder, rare-earth hydroxide precipitation suspension again, in 500 ℃ of roastings or spray-drying after the solution containing phosphate processing obtain.
In recent years, for the consideration of environmental protection, worldwide, the requirement of fuel oil standard is improved constantly.With China is example, and State Quality Supervision Bureau had formulated " motor petrol harmful substance control criterion " in 1999, and according to the requirement of this standard, the sulfur content of gasoline product should be less than 800ppm.In fact, the sulphur of gasoline product more than 90% comes from FCC gasoline.On the other hand, the proportion of middle-eastern crude in the shared crude oil in Chinese refinery with higher sulfur content is also increasing, therefore, need develop the Cracking catalyst with stronger desulfurization performance.
US6,036,847 and patent families EP0,798,362A2 discloses a kind of fluidized catalytic cracking of hydrocarbons method, wherein, and under the condition of described hydrocarbon feed hydrogenation outside not existing, by cracking, and all particles that comprise catalyst granules are constantly in cracking hydrocarbon district and a catalyst regeneration zones circulation a zone of cracking.Wherein, contain another particle in all particles, this particle has the activity of the cracking hydrocarbon ils lower than catalyst granules, and described activity is benchmark with the fresh granules.This particle is made up of the inorganic oxide of titanium oxide and a kind of non-oxide titanium basically.The inorganic oxide of described non-oxide titanium contains a kind of Lewis acid, this Lewis acid is selected from following element and compound composition thereof one group: nickel, copper, zinc, silver, cadmium, indium, tin, mercury, thallium, lead, bismuth, boron, aluminium (non-oxide aluminium) and germanium, described Lewis acid loads on the aluminium oxide.Because use this auxiliary agent that contains titanium oxide, crackate FCC sulfur in gasoline content is reduced.
US5,376,608 disclose a kind of cracking catalyst composition with desulfidation, said composition contains (A) and is dispersed in zeolite/molecular sieve in a kind of inorganic oxide matrix, (b) contain the alumina component of Lewis acid, this alumina component contains the Lewis acid of 1-50 weight %, and described Lewis acid is selected to load on and contains nickel, copper, zinc, silver, cadmium, indium, tin, mercury, thallium, lead, bismuth, boron, aluminium (non-oxide aluminium) and the element of gallium and a group of oxide on the aluminium oxide.
WO 99/49001A1 discloses a kind of composition that reduces sulfur content in the hydrocarbon component, and said composition contains a kind of houghite (Hydrotalcite) material, and this material can also contain a kind of FCC catalyst with a kind of Lewis acid dip in the said composition.Described Lewis acid comprises transition metal, particularly the element of zinc, copper, nickel, cobalt, iron and manganese and compound.
WO 01/21733A1 discloses a kind of in the presence of heat regeneration Cracking catalyst, contains the catalyst cracking method of organosulfur compound hydrocarbon raw material, and described catalyst contains a kind of component that reduces The product sulfur, this component contains a kind of oxidation state greater than zero metal component, and described metal component comprises the 3rd cycle of the periodic table of elements, VB family, VIIB family, VIII family, IIB family, the metallic compound of IVA family or complex compound, as vanadium, zinc, iron, cobalt, the metallic compound of manganese and gallium or complex compound.The component of described reduction The product sulfur comprises that pore structure contains the molecular sieve of above-mentioned metal component, also comprises being dispersed in the catalyst carrier optional position, as the above-mentioned metal component in the porous oxide carrier.
WO 01/21732A1 discloses a kind of method that reduces sulfur content in the cracking petroleum fraction, this method is included in the temperature of raising and a kind of Cracking catalyst and a kind of additive that reduces the product sulfur content and exists down, with the petroleum distillate catalytic cracking, obtain having liquid crackate than low sulfur content.Wherein, the additive of described reduction product sulfur content contains a kind of non-molecular sieve carrier of vanadium that contains, and described non-molecular sieve carrier can be the organic or inorganic carrier, preferred carrier is amorphous or the para-crystal inorganic oxide, as aluminium oxide, silica, clay or their mixture.
CN1281887A discloses a kind of method that reduces catalytic cracking gasoline cut sulfur content, and this method is included in high temperature and the product desulphurization catalyst exists down, catalytic cracking gasoline feedstock fraction, the liquid cracked product of preparation low sulfur content.This desulphurization catalyst contains the porous molecular screen that metal ingredient is contained in a kind of cavernous structure inside.Described porous molecular screen can be a large pore zeolite, and promptly orifice diameter is at least the zeolite of 0.7 nanometer, as y-type zeolite, rare earth Y type zeolite (REY), overstable gamma zeolite (USY), L zeolite, Beta zeolite, modenite, ZSM-18 zeolite.Described molecular sieve also can be a mesopore zeolite, be orifice diameter for greater than 0.56 zeolite, as Pentasil zeolite, ZSM-5 zeolite, ZSM-22, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite, MCM-56 zeolite less than 0.7 nanometer.Described molecular sieve can also be a non-zeolite molecular sieve, as has the silicate (as metal silicate metallosilicate, titan silicate titanosilicate) of Different Silicon aluminum ratio, metal aluminate metalloaluminates (as germanium aluminate Germaniumaluminates), metal phosphate metallophosphates, aluminate or phosphate aluminophosphates, metallic aluminium phosphate metalloaluminophosphates, the silicoaluminophosphate metal integrated silicoaluminophosphates (MeAPSO and ELAPSO) of metal combination, alumino-silicate silicoalumino-phosphates (SAPO), gallium germanate (gallogermanates) and their combination.
CN1261618A discloses a kind of sulfur method of catalytic cracking gasoline cut, this method is included under the existence of high temperature, Cracking catalyst and product desulphurization catalyst, to contain the petroleum cut catalytic cracking of organosulfur compound, produce the liquid crackate of low sulfur content.Described product desulphurization catalyst contains a kind of porous molecular screen, this molecular sieve contains first metal component and second metal component, first metal component is positioned at Molecular Sieve Pore inside and oxidation state greater than zero, and second metal component comprises at least a rare earth element that is positioned at Molecular Sieve Pore inside.Described first kind of metal component is selected from periodic table of elements period 4 and IIB, VB, IIIA, the metal, particularly vanadium of VIII family, zinc, iron, gallium.
Because above-mentioned catalyst all through super-dry, roasting and/or hydrothermal treatment consists, does not have reduction process in preparation process, metal component contained in the above-mentioned catalyst all exists with its highest oxidation state.
CN 1382199A discloses a kind of adsorbent composition, and said composition is made up of bimetallic promoter and pelleted substrate, and described bimetallic promoter is gone up substantially with the reduction valence state and existed, and the amount of its existence can remove sulphur from cracking gasoline under desulfurization condition.Described bimetallic promoter be selected from cobalt, nickel, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony and vanadium any two or more.Described carrier is by forming with the zinc oxide of any suitable inorganic and organic carrier combination.Described inorganic carrier comprises silica, silica gel, aluminium oxide, clay, alumina silicate, silica-alumina, titanium oxide, zirconia, zinc aluminate, zinc titanate, zinc silicate, calcium aluminate, calcium silicates, magnesium silicate, magnesium aluminate, magnesium titanate, synthetic zeolite and natural zeolite.Said composition is as the adsorbent that removes sulphur from cracking gasoline and diesel fuel, rather than Cracking catalyst.
The purpose of this invention is to provide a kind of new higher desulphurizing ability that has, have the Cracking catalyst that contains molecular sieve of higher anti-vanadium ability simultaneously.
The present inventor finds, goes back the metal component of ortho states if introduce in Cracking catalyst, and join with specific molecular sieve, the catalyst that obtains not only has higher desulphurizing ability, and has higher anti-vanadium ability.
Catalyst provided by the invention contains molecular sieve, heat-resistant inorganic oxide matrix, clay and a kind of metal component, wherein, described metal component exists with the reduction valence state basically, it is selected from the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, in the VIII family base metal one or more, described catalyst also contains and is present in the outer rare earth metal of molecular sieve pore passage, described molecular screening is from y-type zeolite or y-type zeolite and zeolite with MFI structure, at least a mixture in the β zeolite, with the catalyst total amount is benchmark, the content of molecular sieve is 1-90 weight %, the content of heat-resistant inorganic oxide is 2-80 weight %, the content of clay is 2-80 weight %, in oxide, the content that is present in the outer rare earth metal of molecular sieve pore passage is 0.1-10 weight %, in the metal oxide of highest price attitude, the content of metal component is 0.1-30 weight %.
Preparation of catalysts method provided by the invention comprises rare-earth oxide and/or the hydroxide that is present in outside the molecular sieve pore passage containing, the metal component compound, molecular sieve, the composition of heat-resistant inorganic oxide and clay contacts with the atmosphere that contains reducing gas, the temperature of contact is enough to make the average valence of described metal component to be lower than its highest oxidation state with the time that contacts, described metal component is selected from the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, in the VIII family base metal one or more, described molecular screening is from y-type zeolite or y-type zeolite and zeolite with MFI structure, at least a mixture in the β zeolite, each components contents makes in the final catalyst and contains in the composition, with the catalyst total amount is benchmark, the molecular sieve of 1-90 weight %, the heat-resistant inorganic oxide of 2-80 weight %, the clay of 2-80 weight %, in oxide, 0.1-10 weight % is present in the outer rare earth metal of molecular sieve pore passage, oxide in highest price attitude metal, 0.1-30 the metal component of weight %, the temperature of described contact is 100-900 ℃, and the time of contact is 0.1 second to 10 hours.
Compared with prior art, catalyst provided by the invention has higher desulphurizing ability, higher anti-vanadium ability and higher heavy oil cracking ability.For example, adopting MOY zeolite content provided by the invention is 32.8 weight %, and the content of aluminium oxide is 28.4 weight %, and kaolinic content is 35 weight %, and the content that is present in the outer rare earth metal of molecular sieve pore passage is 2.8 weight %, with Co
2O
3Meter, cobalt content is 1 weight %, the average valence of cobalt be 0 valency or+catalyst of 1.5 (ratio of the highest price attitude of the average valence of cobalt and cobalt is 0 or 0.5), be 500 ℃ in reaction temperature, weight (hourly) space velocity (WHSV) is 16 hours
-1, the agent weight of oil is 2.0 weight % than being under 4.0 the condition to sulfur content, and boiling range is that 329-550 ℃ decompressed wax oil carries out catalytic cracking, and conversion ratio is up to 71.2-73.8 weight %, and the sulfur content in the gasoline product has only the 426.9-453.6 mg/litre.And adopt zeolite content identical, the Cracking catalyst that does not contain cobalt is all identical with each constituent content, just the valence state of cobalt is the catalyst of its highest price attitude (+3 valency), under identical condition, identical feedstock oil is carried out catalytic cracking, conversion ratio has only 68.5-70.4 weight % respectively, and the sulfur content in the gasoline product is up to the 684.7-761.2 mg/litre.
Again for example, adopting the MOY zeolite content is 32.8 weight %, and the content of aluminium oxide is 28.4 weight %, and kaolinic content is 35 weight %, and the content that is present in the outer rare earth metal of molecular sieve pore passage is 2.8 weight %, with Co
2O
3Meter, cobalt content is 1 weight %, and the average valence of cobalt is+1.5 catalyst, is 480 ℃ in reaction temperature, and weight (hourly) space velocity (WHSV) is 20 hours
-1The agent weight of oil is than being under 6 the condition, to sulfur content is 3.2 weight %, content of vanadium carries out catalytic cracking up to the mixing reduced crude of 27.2ppm, after each reaction is finished, with flow is the nitrogen switching feedstock oil of 300 ml/min, purged 0.5 hour, and fed the air that flow is 500 ml/min again, be warming up to 600 ℃, burnt carbon 2 hours, and then be that the nitrogen replacement of 300 ml/min goes out air wherein with flow, be cooled to 400 ℃ of temperature, feeding flow is the hydrogen of 500 ml/min, make hydrogen contact 0.5 hour, wherein cobalt is reduced again with described solid.Compare during the first time with reaction, the conversion ratio and the product distribution of reacting after the 20th time do not change substantially, and the sulfur content in the gasoline is slightly reduction also.
The specific embodiment
According to catalyst provided by the invention, with the catalyst total amount is benchmark, the content of molecular sieve is 1-90 weight %, the content of heat-resistant inorganic oxide is 2-80 weight %, the content of clay is 2-80 weight %, and in oxide, the content that is present in the outer rare earth metal of molecular sieve pore passage is 0.1-10 weight %, in the metal oxide of highest price attitude, the content of metal component is 0.1-30 weight %.Under the preferable case, the content of described molecular sieve is 10-60 weight %, the content of heat-resistant inorganic oxide is 10-50 weight %, the content of clay is 20-60 weight %, in oxide, the content that is present in the outer rare earth metal of molecular sieve pore passage is 0.1-5 weight %, and in the oxide of highest price attitude metal, the content of described metal component is 0.5-20 weight %.
Described reduction valence state refers to that the average valence of described metal is zeroth order or is higher than zeroth order and is lower than its highest oxidation state.Under the preferable case, the ratio of the average valence of described metal and its highest price attitude is 0-0.95, and more preferably under the situation, this ratio is 0.1-0.7.
The highest price attitude of metal described here is meant after abundant oxidation, the highest oxidation state of metal described in the metal oxide of energy stable existence.For example, the highest oxidation state of the non-aluminum metal of periodic table of elements IIIA family is generally+3 valencys (as gallium); The highest oxidation state of IVA family metal is generally+4 valencys; The highest oxidation state of VA metal is generally+5 valencys; The highest oxidation state of IB family metal is generally+divalent (as copper) or+1 valency (as silver); The highest oxidation state of IIB family metal is generally+divalent; The highest oxidation state of VB family metal is generally+5 valencys; The highest oxidation state of group vib metal is generally+6 valencys; The highest oxidation state of VIIB family metal is generally+4 valencys (as manganese) or+7 valencys (as rhenium); The non-noble metal highest oxidation state of VIII family is generally+3 valencys (as iron or cobalt) or+divalent (as nickel).
The method of measuring described metal average valence is as follows:
Accurately take by weighing about 0.4 gram catalyst, put into the sample cell of TPD/R/O analysis tester, feeding hydrogen content is the hydrogen of 5 volume % and the gaseous mixture of nitrogen, the flow of hydrogen is 20 ml/min, with the speed of sample cell with 10 ℃/minute, be warming up to 1000 ℃ from room temperature, the catalyst in the sample cell is carried out temperature programmed reduction, measure before the reduction respectively and the reduction rear catalyst on the TPR characteristic peak of metal component, calculate the average valence of metal according to following formula:
β
M＝β
M′-2f(A
1-A)/N
Wherein: β
MBe the average valence of metal component M in the catalyst, β
M 'Highest price attitude for metal component M in the catalyst; The TPR characteristic peak area of metal M in the A catalyst that to be metal component M exist with the reduction valence state; A
1The TPR characteristic peak area of metal M in the catalyst that exists with highest oxidation state for metal component M; N is the content (unit is mole) of metal component M in the catalyst; F is a correction factor, and its assay method is as follows: accurately take by weighing the sample cell that about 6.5 milligrams of CuO put into above-mentioned TPD/R/O analysis tester, under these conditions, measure the TPR characteristic peak area K that CuO is reduced fully
2, calculate hydrogen-consuming volume (mole) K by the stoichiometric number of reduction reaction
1, f is the ratio of hydrogen-consuming volume and TPR characteristic peak area, i.e. f=K
1/ K
2, the unit of f is a mole/TPR characteristic peak area.
Because therefore the position difference of the TPR characteristic peak of each metal, even contain metal component more than 2 kinds in the catalyst, also can determine the TPR characteristic peak of each metal.
Described metal component is selected from one or more in the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, group vib metal, VIIB family metal, the VIII family base metal.The non-aluminum metal of described IIIA family comprises gallium, indium, thallium.Described IVA family metal comprises germanium, tin, lead.Described VA family metal comprises antimony, bismuth.Described IB family metal comprises copper, silver.Described IIB family metal comprises zinc, cadmium.Described VB family metal comprises vanadium, niobium, tantalum.Described group vib metal comprises chromium, molybdenum, tungsten.Described VIIB family metal comprises manganese, technetium, rhenium.Described VIII family base metal comprises iron, cobalt, nickel.Described metal component is preferably one or more in gallium, germanium, tin, antimony, bismuth, lead, copper, silver, zinc, cadmium, vanadium, molybdenum, tungsten, manganese, iron, cobalt, the nickel, more preferably one or more in gallium, tin, copper, silver, zinc, vanadium, molybdenum, manganese, iron, the cobalt.
Described metal component can be present in molecular sieve, heat-resistant inorganic oxide and the clay simultaneously, also may reside in molecular sieve, heat-resistant inorganic oxide and clay any two kinds, can also be present in any one of molecular sieve, heat-resistant inorganic oxide and clay.
Described molecular screening is from y-type zeolite or y-type zeolite and have the zeolite of MFI structure, at least a mixture in the β zeolite.
Described y-type zeolite is selected from one or more in the overstable gamma zeolite of the y-type zeolite, overstable gamma zeolite of HY, phosphorous and/or rare earth, phosphorous and/or rare earth.
The zeolite of the described MFI of having structure is preferably the zeolite with MFI structure of ZSM-5 zeolite, phosphorous and/or rare earth, as the zeolite with MFI structure of disclosed phosphorous and/or rare earth among CN1052290A, CN1058382A, CN1147420A, the CN1194181A.
According to embodiment preferred of the present invention, described molecular screening is from y-type zeolite and have the zeolite of MFI structure, at least a mixture in the β zeolite, at least a and weight ratio y-type zeolite that has in the zeolite, β zeolite of MFI structure is 0.01-0.8, is preferably 0.02-0.5.
The kind of described heat-resistant inorganic oxide is selected from as in the heat-resistant inorganic oxide of Cracking catalyst matrix and binder component one or more, as in aluminium oxide, silica, amorphous silicon aluminium, zirconia, titanium oxide, boron oxide, the alkaline earth oxide one or more.In preferred aluminium oxide, silica, amorphous silicon aluminium, zirconia, titanium oxide, magnesia, the calcium oxide one or more.These heat-resistant inorganic oxides are conventionally known to one of skill in the art.
Described clay is selected from as in the clay of active component of cracking catalyst one or more, as in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the bentonite one or more.Preferred clay is a kaolin.These clays are conventionally known to one of skill in the art.
In the catalyst provided by the present invention, the described outer rare earth metal of molecular sieve pore passage that is present in is with metal and/or compound, form as the salt of the oxide of rare earth metal, rare earth metal is present in molecular sieve surface, heat-resistant inorganic oxide and the clay, also may reside in molecular sieve surface, heat-resistant inorganic oxide and clay any two kinds, can also be present in any one of molecular sieve surface, heat-resistant inorganic oxide and clay.Be present in the outer rare earth metal of molecular sieve pore passage and be different from rare earth metal contained in the zeolite, contained rare earth metal is present in the cation-bit in the zeolite cavity in the zeolite, in catalyst regeneration process, because the inhibition in the duct of zeolite, be not easy and be deposited on the vanadium effect in the catalyst, and be present in the rare earth metal outside the molecular sieve pore passage owing to there is not this inhibition, have an effect with the vanadium that is deposited in the catalyst easily, form stable rare-earth vanadate, avoided the destruction of vanadium, thereby played the effect of anti-vanadium the catalyst activity component.Therefore, if molecular sieve contains rare earth metal described in the catalyst provided by the invention, then contained rare earth metal does not belong to and is present in the outer rare earth metal of molecular sieve pore passage in the molecular sieve, and the molecular sieve that contains rare earth metal is done as a whole, and promptly molecular sieve is treated.
Catalyst provided by the invention can also contain phosphorus component, and described phosphorus component is with the compound of phosphorus, as the oxide and/or the existence of phosphatic form of phosphorus.Described phosphorus component can be present in molecular sieve, heat-resistant inorganic oxide and the clay simultaneously, also may reside in molecular sieve, heat-resistant inorganic oxide and clay any two kinds, can also be present in any one of molecular sieve, heat-resistant inorganic oxide and clay.With the catalyst total amount is benchmark, and in element phosphor, the content of described phosphorus component is 0-15 weight %, is preferably 0-8 weight %.Because phosphorus component is very complicated in the form of molecular sieve, be difficult to molecular sieve and its phosphorus strictness that contains are made a distinction, therefore, in example of the present invention, if when phosphorus component was the preparation catalyst, used molecular sieve contained itself, the content of described molecular sieve is the content that contains the molecular sieve of phosphorus component, the content of phosphorus component does not calculate separately, does not provide separately yet.
According to the invention provides the Preparation of catalysts method, the described atmosphere that contains reducing gas refers to pure reducing gas or contains reducing gas and inert gas atmosphere.
The example of described pure reducing gas comprises hydrogen, carbon monoxide and contains in the hydro carbons of 1-5 carbon atom one or more, preferably includes in hydrogen, carbon monoxide, methane, ethane, propane, butane and various isomers thereof, pentane and the various isomers thereof one or more.
Described inert gas refers to not the gas with described composition or metallic compound generation chemical action, as periodic table of elements O family gas, one or more in nitrogen, the carbon dioxide.
The described example that contains reducing gas and inert gas atmosphere comprises hydrogen, carbon monoxide, contain in one or more and the inert gas in the hydro carbons of 1-5 carbon atom one or more mixture and the dry gas in the oil plant.
In the described atmosphere that contains reducing gas, the concentration of reducing gas is not particularly limited, as long as the amount of used reducing gas can be with described metallic reducing.Under the preferable case, in the described atmosphere that contains reducing gas, reducing gas content is at least 10 volume %, more preferably 50 volume %.
The temperature of described contact is enough to make the average valence of described metal component and the ratio of its highest price attitude to be reduced to 0-0.95 with the time that contacts, and is preferably 0.1-0.7.In general, the temperature of described contact can be 100-900 ℃, is preferably 400-700 ℃, and the time of contact is 0.1 second to 10 hours, is preferably 1 second to 5 hours.Described contact can be a Static Contact, and promptly in an airtight container, the atmosphere that will contain reducing gas contacts with described composition.Described contact can be dynamic contact also, is about to the described bed that contains the atmosphere of reducing gas by described composition.The pressure of described contact both can carry out under normal pressure without limits, also can carry out being higher or lower than under the normal pressure.The consumption that contains the atmosphere of reducing gas is that every gram catalyst per hour is not less than 5 milliliters of reducing gas, and preferred every gram catalyst per hour is not less than 10 milliliters of reducing gas, and more preferably every gram catalyst is 100-2000 milliliter reducing gas per hour.
Each components contents preferably makes in the final catalyst and contains in the composition, in the catalyst total amount, the molecular sieve of 10-60 weight %, the heat-resistant inorganic oxide of 10-50 weight %, the clay of 20-60 weight %, in oxide, 0.1-5 weight % is present in the outer rare earth metal of molecular sieve pore passage, in the oxide of highest price attitude metal, the metal component of 0.5-20 weight %.
According to the Preparation of catalysts method that this aspect provides, the described composition that is present in the outer rare-earth oxide of molecular sieve pore passage and/or hydroxide, metal component compound, molecular sieve, heat-resistant inorganic oxide and clay that contains can adopt at least a preparation in the following method:
One of method, at least a with in the precursor of the solution impregnation rare-earth oxide that contains described metal component compound and/or rare earth metal hydroxide, molecular sieve, heat-resistant inorganic oxide and/or heat-resistant inorganic oxide and the clay, dry or moist, mix making beating with remaining component and water again, being prepared into solid content is 10-60 weight %, be preferably the slurries of 20-50 weight %, with slurry dried, roasting or the not roasting that obtains;
Two of method, the solution and the precursor of rare-earth oxide and/or rare earth metal hydroxide, molecular sieve, heat-resistant inorganic oxide and/or heat-resistant inorganic oxide and at least a mixing the in the clay that will contain described metal component compound, dry or moist, mix making beating with all the other components and water again, being prepared into solid content is 10-60 weight %, be preferably the slurries of 20-50 weight %, with slurry dried, roasting or the not roasting that obtains;
Three of method, precursor and clay physical mixed with described metal component compound and rare-earth oxide and/or rare earth metal hydroxide, molecular sieve, heat-resistant inorganic oxide and/or heat-resistant inorganic oxide, mix making beating then with water, being prepared into solid content is 10-60 weight %, be preferably the slurries of 20-50 weight %, with slurry dried, roasting or the not roasting that obtains;
Four of method, solution and the rare-earth oxide and/or the rare earth metal hydroxide that will contain described metal component compound, molecular sieve, at least a mixing in the precursor of heat-resistant inorganic oxide and/or heat-resistant inorganic oxide and the clay, the precipitating reagent that adds described metal component compound, described metal component is deposited to rare-earth oxide and/or rare earth metal hydroxide, molecular sieve, on at least a in the precursor of heat-resistant inorganic oxide and/or heat-resistant inorganic oxide and the clay, dry or moist, mix making beating with all the other components and water again, being prepared into solid content is 10-60 weight %, be preferably the slurries of 20-50 weight %, with the slurry dried that obtains, roasting or not roasting;
Five of method, the solution and the precursor of rare-earth oxide and/or rare earth metal hydroxide, molecular sieve, heat-resistant inorganic oxide and/or heat-resistant inorganic oxide and at least a mixing the in the clay that will contain described metal component compound, the slurry preparation that obtains is become colloid, dry or moist, mix making beating with all the other components and water again, being prepared into solid content is 10-60 weight %, is preferably the slurries of 20-50 weight %, with slurry dried, roasting or the not roasting that obtains.
Six of method, precursor, clay and deionized water making beating with rare-earth oxide and/or hydroxide, molecular sieve, heat-resistant inorganic oxide and/or heat-resistant inorganic oxide, being prepared into solid content is 10-60 weight %, be preferably the slurries of 20-50 weight %, the slurries that drying obtains, roasting or not roasting, then, with the dried solid of the solution impregnation that contains described metal component compound, perhaps the solution with described metal component compound mixes with dried solid, then, drying, roasting or not roasting.
If also contain phosphorus component in the catalyst, can adopt top method separately or introduce phosphorus component when introducing above-mentioned metal component, just replace the compound of above-mentioned metal component to get final product with phosphorus compound.Described phosphorus component can also be (as phosphorous y-type zeolite or the overstable gamma zeolite) that commercially available molecular sieve itself is had.
Wherein, the drying behind the described introducing metal component compound and the drying means of slurries and condition are conventionally known to one of skill in the art, for example, dry method can be dry, oven dry, forced air drying, spray-drying.The method of the drying means preferably spray drying of slurries.Dry temperature can be a room temperature to 400 ℃, is preferably 100-350 ℃.Roasting condition behind roasting after the described slurry dried and the impregnating metal compound also is conventionally known to one of skill in the art, in general, sintering temperature behind roasting after the described slurry dried and the impregnating metal compound is 400-700 ℃, be preferably 450-650 ℃, roasting time was at least 0.5 hour, be preferably 0.5-100 hour, more preferably 0.5-10 hour.
The precursor of described heat-resistant inorganic oxide refers in described Cracking catalyst preparation process, can form in the material of described heat-resistant inorganic oxide one or more.Precursor as aluminium oxide can be selected from hydrated alumina (as boehmite) and/or aluminium colloidal sol.The precursor of silica can be selected from Ludox, one or more in silicon gel and the waterglass.The precursor of amorphous aluminum silicide can be selected from silicon-aluminum sol, the mixture of Ludox and aluminium colloidal sol, one or more in the silica-alumina gel.The precursor of other heat-resistant inorganic oxide can be selected from its hydroxide, as hydroxide, the boric acid of zirconium, titanium, alkaline-earth metal.
Described metal component compound can be water-soluble compound of described metal, also can be to be insoluble in water and/or water-fast compound, as the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, the non-noble metal nitrate of VIII family, chloride, hydroxide, in the oxide one or more, particularly gallium, tin, copper, silver, zinc, vanadium, molybdenum, manganese, iron, the nitrate of cobalt, chloride, hydroxide, in the oxide one or more.
Rare-earth oxide and/or rare earth metal hydroxide can replace with rare-earth oxide and/or rare earth metal hydroxide suspension.Described suspension can mix the aqueous solution of rare earth metal soluble-salt and obtain with alkali compounds.For example, the aqueous solution of the chloride of rare earth metal and/or nitrate mixes the rare-earth hydroxide suspension that obtains with alkali metal and/or ammoniacal liquor.
Described phosphorus compound can be water-soluble phosphorus compound, also can be to be insoluble in water and/or water-fast phosphorus compound, and as phosphoric acid, phosphorous acid, the oxide of the phosphate of ammonium, alkali-metal phosphate, phosphorus, in the aluminum phosphate one or more.
Catalyst provided by the invention can be used as the FCC catalyst and uses separately, also can be used as desulfurization and/or anti-vanadium assistant and mixes use with existing various Cracking catalyst.Content and the desired sulfur content of gasoline products according to sulphur, vanadium in the feedstock oil, determine the ratio of contained catalyst provided by the invention in the catalyst mixture, generally, catalyst provided by the invention accounts at least 0.1 weight % of catalyst mixture, be preferably at least 1 weight %, more preferably at least 5 weight %, preferably at least 10 weight %.In addition, as the cracking catalysis agent aid, catalyst provided by the invention also can with other auxiliary agent, mix use with existing Cracking catalyst together as combustion adjuvant, sulfur transfer catalyst, octane enhancing additive etc.
No matter catalyst provided by the invention is as major catalyst or auxiliary agent, and the condition of its use is the reaction condition of general cracking hydrocarbon process routine, is 400-700 ℃ as reaction temperature, is preferably 450-600 ℃, and the agent weight of oil is preferably 3-15 than for 1-20.
Catalyst provided by the invention can carry out catalytic cracking to the hydrocarbon ils of sulfur-bearing and/or vanadium, also can carry out catalytic cracking to the hydrocarbon ils of sulfur-bearing and/or vanadium not, is particularly suitable for the hydrocarbon ils of sulfur-bearing and/or vanadium is carried out catalytic cracking.These hydrocarbon ils are selected from oil and various cut thereof, as sulfur-bearing and/or vanadium, and the perhaps not reduced crude of sulfur-bearing and/or vanadium, decompression residuum, decompressed wax oil, the normal pressure wax oil, straight-run gas oil, propane is light/heavy one or more in de-oiling and the wax tailings.
The following examples will the present invention will be further described.
Unless stated otherwise, used kaolin is that Suzhou kaolin company produces in the example, and its solid content is 76 weight %; Used boehmite is that Shandong Zibo 501 factories produce, and its solid content is 62 weight %; Used aluminium colloidal sol is produced its Al for the Shandong catalyst plant
2O
3Content is 21 weight %; Used Ludox is produced its SiO for the Shandong catalyst plant
2Content is 27 weight %; The compound of metal component is chemical pure.
The cracking activity of fresh Cracking catalyst mesolite is very high, in the industrial production of reality, catalyst circulation is used, fresh catalyst is after reaction a period of time, its activity reaches a level relatively stably, therefore, the true activity of judging catalyst just should with the catalyst deactivation extremely with industrial poising agent corresponding horizontal, this can reach zeolite deactivation wherein by catalyst is carried out hydrothermal aging.In the example below the present invention, the step of an aging catalyst was arranged all before reduction, adding this step is for the ease of the judge activity of such catalysts, rather than says that Preparation of catalysts method provided by the invention needs this aging step.In fact, in industrial production, this aging step is unnecessary.
Embodiment 1
Present embodiment illustrates Catalysts and its preparation method provided by the invention.
(1) get in rare earth oxide, rare earth metal content be 228 grams per liters the cerium-rich mischmetal chloride (Inner Mongol Baotou rare earth factory product, wherein, CeO
2Account for 50 weight %, the La of rare earth oxide
2O
3Account for 21 weight %, the Pr of rare earth oxide
2O
3Account for 14 weight %, the Nd of rare earth oxide
2O
3Account for 13 weight % of rare earth oxide, all the other are other rare-earth oxide) solution, under agitation, slowly splash into the concentrated ammonia liquor that concentration is 28 weight %, until slurries pH value to 8.8, obtain rare earth oxygen oxide suspension.
(2) cobalt nitrate aqueous solution with kaolin, boehmite, concentration 30 weight % mixes, add deionized water, mix, slowly adding concentration under stirring fast is the hydrochloric acid of 36.5 volume %, regulate the pH value to 2.0 of slurries, (the industrial trade mark is MOY, and lattice constant is 24.59 dusts, Na to add the HY zeolite of phosphorous and rare earth
2O content is 1.5 weight %, in element phosphor, phosphorus content is 1.2 weight %, rare earth oxide content is 8.5 weight %, and wherein, lanthana content is 4.5 weight %, cerium oxide content is 1.1 weight %, other rare earth oxide content is 2.9 weight %, and the Shandong catalyst plant is produced) and rare-earth hydroxide suspension, mix.It is 25 weight % that the consumption of deionized water makes the solid content of the slurries that obtain.The consumption of kaolin, boehmite, MOY zeolite, rare-earth hydroxide suspension and cobalt nitrate aqueous solution makes kaolin butt weight, Al
2O
3, MOY zeolite butt weight, be present in molecular sieve pore passage outer rare-earth oxide and Co
2O
3The ratio of weight be 35.0: 28.4: 32.8: 2.8: 1.0.
(3),,, wore out 8 hours with 100% steam then at 800 ℃ 550 ℃ of following roastings 1 hour with the slurries spray-drying under 150 ℃ temperature that obtains.The catalyst 200 that obtains is restrained in the fixed bed reduction reactor of packing into, under 400 ℃ of temperature, feeding flow is the hydrogen of 1000 ml/min, make hydrogen contact 0.5 hour with described solid, the temperature of reactor is reduced to room temperature, unload the solid after the reduction, obtain catalyst C1 provided by the invention.The ratio of the composition of catalyst C1 and the kind of metal component, distribution, average valence and average valence and its highest price attitude is listed in the table 1.Catalyst is formed by calculating in the table 1, and the content of metal component is in the oxide of described metal component highest oxidation state.
Embodiment 2
Present embodiment illustrates Catalysts and its preparation method provided by the invention.
Method by example 1 prepares catalyst, and different is, the temperature that described solid contacts with hydrogen is 500 ℃, and be 3 hours time of contact, obtains catalyst C2 provided by the invention.The ratio of the composition of catalyst C2 and the kind of metal component, distribution, average valence and average valence and its highest price attitude is listed in the table 1.
Embodiment 3
Present embodiment illustrates Catalysts and its preparation method provided by the invention.
With 1.89 kilograms of concentration is 3.0 kilograms of (dry basis) kaolin of cobalt nitrate aqueous solution dipping of 10 weight %, 120 ℃ of oven dry, and 600 ℃ of roastings 1 hour obtain containing Co
2O
32.78 the kaolin of weight %.
Method by example 1 prepares catalyst, and different is with containing Co
2O
32.78 the kaolin of weight % replaces example 1 described kaolin, does not add cobalt nitrate aqueous solution, obtains catalyst C3 provided by the invention.The ratio of the composition of catalyst C3 and the kind of metal component, distribution, average valence and average valence and its highest price attitude is listed in the table 1.
Comparative Examples 1
This Comparative Examples illustrates reference catalyst of metallic components not and preparation method thereof.
Method by example 1 prepares catalyst, different is not add cobalt nitrate aqueous solution, the process that in fixed bed reactors, solid is not contacted with hydrogen, and the consumption of kaolin, boehmite, MOY zeolite, rare-earth hydroxide suspension makes kaolin butt weight, boehmite butt weight, MOY zeolite butt weight, the ratio that is present in molecular sieve pore passage rare-earth oxide outward is 35.0: 29.4: 32.8: 2.8.It is identical with kaolin content to obtain molecular sieve, not the reference catalyst CB1 of metallic components.The composition of CB1 is listed in the table 1.
Comparative Examples 2
The explanation of this Comparative Examples contains reference catalyst of highest oxidation state metal component and preparation method thereof.
Method by example 1 prepares catalyst, and different is that the process that in fixed bed reactors solid is not contacted with hydrogen obtains reference catalyst CB2.The composition of CB2 is listed in the table 1.
Comparative Examples 3
The explanation of this Comparative Examples contains reference catalyst of highest oxidation state metal component and preparation method thereof.
Method by example 3 prepares catalyst, and different is that the process that in fixed bed reactors solid is not contacted with hydrogen obtains reference catalyst CB3.The composition of CB3 is listed in the table 1.
Table 1
| Example number | 1 | 2 | 3 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| The catalyst numbering | C1 | C2 | C3 | CB1 | CB2 | CB3 |
| The molecular sieve kind | MOY | MOY | MOY | MOY | MOY | MOY |
| Molecular sieve content, weight % | 32.8 | 32.8 | 32.8 | 32.8 | 32.8 | 32.8 |
| The heat-resistant inorganic oxide kind | Al 2O 3 | Al 2O 3 | Al 2O 3 | Al 2O 3 | Al 2O 3 | Al 2O 3 |
| Heat-resistant inorganic oxide content, weight % | 28.4 | 28.4 | 28.4 | 29.4 | 28.4 | 28.4 |
| Be present in the outer rare-earth oxide content of molecular sieve pore passage, weight % | 2.8 | 2.8 | 2.8 | 2.8 | 2.8 | 2.8 |
| Clay types | Kaolin | Kaolin | Kaolin | Kaolin | Kaolin | Kaolin |
| Clay content, weight % | 35.0 | 35.0 | 35.0 | 35.0 | 35.0 | 35.0 |
| The metal component kind | Co | Co | Co | - | Co | Co |
| Metal oxide content, weight % | 1.0 | 1.0 | 1.0 | - | 1.0 | 1.0 |
| The metal component average valence | +1.5 | 0 | +1.5 | - | +3 | +3 |
| The ratio of metal component average valence and its highest price attitude | 0.5 | 0 | 0.5 | - | 1 | 1 |
| Metal component distributes | Be evenly distributed in the catalyst | Be evenly distributed in the catalyst | Be evenly distributed in the clay | - | Be evenly distributed in the catalyst | Be evenly distributed in the clay |
Embodiment 4
Present embodiment illustrates Catalysts and its preparation method provided by the invention.
(1) get in rare earth oxide, rare earth metal content be 279 grams per liters the lanthanum rich mischmetal chloride (Inner Mongol Baotou rare earth factory product, wherein, CeO
2Account for 20 weight %, the La of rare earth oxide
2O
3Account for 70 weight %, the Pr of rare earth oxide
2O
3Account for 5 weight %, the Nd of rare earth oxide
2O
3Account for 3 weight % of rare earth oxide, all the other are other rare-earth oxide) solution, under agitation, slowly splash into the concentrated ammonia liquor that concentration is 28 weight %, until slurries pH value to 9.2, obtain rare-earth hydroxide suspension.
(2) with 3.19 kilograms of concentration be 3.0 kilograms of (dry basis) kaolin of zinc nitrate aqueous solution dipping of 7.0 weight %, 120 ℃ of oven dry, 600 ℃ of roastings 1 hour obtain containing the kaolin of ZnO 3.1 weight %.
(3) with 500 gram NaY (Na
2O content 11 weight %, silica alumina ratio is 5.6, the Chang Ling catalyst plant is produced) with the aqueous ammonium chloride solution of 10 liter of 0.15 mol 60 ℃ of exchanges 1 hour down, the filter cake after the filtration was 550 ℃ of roastings 2 hours.Again by above-mentioned steps exchange and roasting twice, obtaining sodium oxide content is the HY zeolite of 0.3 weight % with it.
(4) method by (2) in the example 1 and (3) prepares catalyst, different is to replace example 1 described rare-earth hydroxide suspension with the rare-earth hydroxide suspension that this example (1) prepares, the kaolin that contains ZnO with this example (2) preparation replaces example 1 described kaolin, do not add cobalt nitrate, with the HY zeolite replacement MOY of this example (3) preparation; The consumption of the kaolin of the described ZnO of containing, boehmite, HY zeolite, rare-earth hydroxide suspension makes kaolin butt weight, Al
2O
3, HY zeolite butt weight, the ratio that is present in the weight of outer rare-earth oxide of molecular sieve pore passage and ZnO is 25.0: 17.2: 55.0: 2.0: 0.8; The atmosphere of reduction is hydrogen content 50 volume % and the hydrogen of carbon monoxide content 50 volume % and the gaseous mixture of carbon monoxide, the flow of gaseous mixture is 2000 ml/min, the temperature that described solid contacts with gaseous mixture is 800 ℃, and be 3 hours time of contact, obtains catalyst C4 provided by the invention.The ratio of the composition of catalyst C4 and the kind of metal component, distribution, average valence and average valence and its highest price attitude is listed in the table 2.
Embodiment 5
Present embodiment illustrates Catalysts and its preparation method provided by the invention.
(1) get in rare earth oxide, rare earth metal content be 258 grams per liters the cerium-rich mischmetal chloride (Inner Mongol Baotou rare earth factory product, wherein, CeO
2Account for 75 weight %, the La of rare earth oxide
2O
3Account for 15 weight %, the Pr of rare earth oxide
2O
3Account for 5 weight %, the Nd of rare earth oxide
2O
3Account for 3 weight % of rare earth oxide, all the other are other rare-earth oxide) solution, under agitation, slowly splash into the concentrated ammonia liquor that concentration is 28 weight %, until slurries pH value to 9.5, obtain rare-earth hydroxide suspension.
(2) with 2.90 kilograms of concentration be 3.0 kilograms of (dry basis) kaolin of iron nitrate aqueous solution dipping of 10 weight %, 120 ℃ of oven dry, 600 ℃ of roastings 2 hours obtain containing Fe
2O
33.1 the kaolin of weight %.
(3) method by (2) in the example 1 and (3) prepares catalyst, and different is to replace example 1 described rare-earth hydroxide suspension with the rare-earth hydroxide suspension that this example (1) prepares, with the Fe that contains of this example (2) preparation
2O
3Kaolin replace example 1 described kaolin, do not add cobalt nitrate, replace MOY with the HY zeolite of (3) preparation in the example 4; The described Fe that contains
2O
3Kaolin, boehmite, HY zeolite, the consumption of rare-earth hydroxide suspension make kaolin butt weight, Al
2O
3, HY zeolite butt weight, be present in molecular sieve pore passage outer rare-earth oxide and Fe
2O
3The ratio of weight be 25.0: 18.0: 55.0: 1.2: 0.8; The atmosphere of reduction is hydrogen content 50 volume % and the hydrogen of carbon monoxide content 50 volume % and the gaseous mixture of carbon monoxide, the flow of gaseous mixture is 1200 ml/min, the temperature that described solid contacts with gaseous mixture is 600 ℃, be 0.5 hour time of contact, obtains catalyst C5 provided by the invention.The ratio of the composition of catalyst C5 and the kind of metal component, distribution, average valence and average valence and its highest price attitude is listed in the table 2.
Embodiment 6
Present embodiment illustrates Catalysts and its preparation method provided by the invention.
(1) get in rare earth oxide, rare earth metal content be 240 grams per liters the lanthanum rich mischmetal chloride (Inner Mongol Baotou rare earth factory product, wherein, CeO
2Account for 18 weight %, the La of rare earth oxide
2O
3Account for 75 weight %, the Pr of rare earth oxide
2O
3Account for 2 weight %, the Nd of rare earth oxide
2O
3Account for 3 weight % of rare earth oxide, all the other are other rare-earth oxide) solution, under agitation, slowly splash into the concentrated ammonia liquor that concentration is 28 weight %, until slurries pH value to 9.2, obtain rare-earth hydroxide suspension.
(2) be 2.925 kilograms of (dry basis) kaolin of copper nitrate aqueous solution dipping of 20 weight % and the mixture of 0.075 kilogram of titanium dioxide with 3.36 kilograms of concentration, 120 ℃ of oven dry, 600 ℃ of roastings 2 hours obtain containing the kaolin of CuO 8.68 weight %.
(3) method by (2) in the example 1 and (3) prepares catalyst, different is to replace example 1 described rare-earth hydroxide suspension with the rare-earth hydroxide suspension that this example (1) prepares, the kaolin that contains CuO with this example (2) preparation replaces example 1 described kaolin, do not add cobalt nitrate, (the industrial trade mark is DASY0.0 with overstable gamma zeolite, lattice constant is 24.45 dusts, Na
2O content is 1.5 weight %, and the Shandong catalyst plant is produced) replacement MOY; Contain kaolin, boehmite, the overstable gamma zeolite of CuO, the consumption of rare-earth hydroxide suspension makes kaolin butt weight, TiO
2, Al
2O
3, overstable gamma zeolite butt weight, the ratio that is present in the weight of outer rare-earth oxide of molecular sieve pore passage and CuO is 39.0: 1.0: 23.0: 30.0: 3.2: 3.8; The atmosphere of reduction is hydrogen content 50 volume % and the hydrogen of carbon monoxide content 50 volume % and the gaseous mixture of carbon monoxide, the flow of gaseous mixture is 1000 ml/min, the temperature that described solid contacts with gaseous mixture is 400 ℃, be 0.5 hour time of contact, obtains catalyst C6 provided by the invention.The ratio of the composition of catalyst C6 and the kind of metal component, distribution, average valence and average valence and its highest price attitude is listed in the table 2.
Embodiment 7
Present embodiment illustrates Catalysts and its preparation method provided by the invention.
(1) get in rare earth oxide, rare earth metal content be 228 grams per liters the cerium-rich mischmetal chloride (Inner Mongol Baotou rare earth factory product, wherein, CeO
2Account for 50 weight %, the La of rare earth oxide
2O
3Account for 21 weight %, the Pr of rare earth oxide
2O
3Account for 14 weight %, the Nd of rare earth oxide
2O
3Account for 13 weight % of rare earth oxide, all the other are other rare-earth oxide) solution, under agitation, slowly splash into the concentrated ammonia liquor that concentration is 28 weight %, until slurries pH value to 9.1, obtain rare-earth hydroxide suspension.
(2) with 3.34 kilograms of concentration be 3.0 kilograms of (dry basis) kaolin of manganese nitrate aqueous solution dipping of 5.0 weight %, 120 ℃ of oven dry, 550 ℃ of roastings 2 hours obtain containing MnO
22.63 the kaolin of weight %.
(3) method by (2) in the example 1 and (3) prepares catalyst, and different is to replace example 1 described rare-earth hydroxide suspension with the rare-earth hydroxide suspension that this example (1) prepares, with the MnO that contains of this example (2) preparation
2Kaolin replace example 1 described kaolin, do not add cobalt nitrate; (the industrial trade mark is ZRP-1 with the zeolite with MFI structure of overstable gamma zeolite (specification is with example 6) and phosphorous and rare earth, in element phosphor, phosphorus content is 2.0 weight %, rare earth oxide content is 1.0 weight %, wherein, lanthana content is 0.53 weight %, and cerium oxide content is 0.13 weight %, other rare earth oxide content is 0.34 weight %, Na
2O content is less than 0.1 weight %, SiO
2With Al
2O
3Mol ratio be 60, the Shandong catalyst plant is produced) replace MOY; Contain MnO
2Kaolin, boehmite, overstable gamma zeolite, ZRP-1 zeolite, the consumption of rare-earth hydroxide suspension make kaolin butt weight, Al
2O
3, overstable gamma zeolite butt weight, ZRP-1 zeolite butt weight, be present in molecular sieve pore passage outer rare-earth oxide and MnO
2The ratio of weight be 37.0: 22.2: 30.0: 5.1: 4.7: 1.0.The atmosphere of reduction is hydrogen content 80 volume % and the hydrogen of propane content 20 volume % and the gaseous mixture of propane, the flow of gaseous mixture is 1500 ml/min, the temperature that described solid contacts with gaseous mixture is 500 ℃, and be 1 hour time of contact, obtains catalyst C7 provided by the invention.The ratio of the composition of catalyst C7 and the kind of metal component, distribution, average valence and average valence and its highest price attitude is listed in the table 2.
Table 2
| Example number | 4 | 5 | 6 | 7 |
| The catalyst numbering | C4 | C5 | C6 | C7 |
| The molecular sieve kind | HY | HY | DASY0.0 | DASY0.0+ ZRP-1 |
| Molecular sieve content, weight % | 55.0 | 55.0 | 30.0 | 35.1 |
| The heat-resistant inorganic oxide kind | Al 2O 3 | Al 2O 3 | Al 2O 3+TiO2 | Al 2O 3 |
| Heat-resistant inorganic oxide content, weight % | 17.2 | 18.0 | 24.0 | 22.2 |
| Be present in the outer rare-earth oxide content of molecular sieve pore passage, weight % | 2.0 | 1.2 | 3.2 | 4.7 |
| Clay types | Kaolin | Kaolin | Kaolin | Kaolin |
| Clay content, weight % | 25.0 | 25.0 | 39.0 | 37.0 |
| The metal component kind | Zn | Fe | Cu | Mn |
| Metal oxide content, weight % | 0.8 | 0.8 | 3.8 | 1.0 |
| The metal component average valence | 1.4 | 2.0 | 0.6 | 1.5 |
| The ratio of metal component average valence and its highest price attitude | 0.70 | 0.67 | 0.3 | 0.38 |
| Metal component distributes | Be evenly distributed in the clay | Be evenly distributed in the clay | Be distributed in clay and the heat-resistant inorganic oxide | Be evenly distributed in the clay |
Embodiment 8
Present embodiment illustrates Catalysts and its preparation method provided by the invention.
(1) get in rare earth oxide, rare earth metal content be 279 grams per liters the lanthanum rich mischmetal chloride (Inner Mongol Baotou rare earth factory product, wherein, CeO
2Account for 20 weight %, the La of rare earth oxide
2O
3Account for 70 weight %, the Pr of rare earth oxide
2O
3Account for 5 weight %, the Nd of rare earth oxide
2O
3Account for 3 weight % of rare earth oxide, all the other are other rare-earth oxide) solution, under agitation, slowly splash into the concentrated ammonia liquor that concentration is 28 weight %, until slurries pH value to 9.0, obtain rare-earth hydroxide suspension.
(2) with 3.22 kilograms of concentration be the ammonium molybdate ((NH of 5.0 weight %
4)
6Mo
7O
244H
2O) (solid content is 85.0 weight % for the aqueous solution 3.0 kilograms of (dry basis) kaolin of dipping and 0.5 kilogram of (dry basis) diatomite, Shengzhou, Zhejiang Province city China power diatomite factory product) mixture, 120 ℃ of oven dry, and then with the silver nitrate aqueous solution of 2.42 kilogram of 2.0 weight % dipping, 120 ℃ of oven dry, 600 ℃ of roastings 2 hours obtain containing MoO
33.58 weight % and Ag
2The kaolin of O 0.90 weight % and diatomaceous mixture.
(3) method by (2) in the example 1 and (3) prepares catalyst, and different is to replace example 1 described rare-earth hydroxide suspension with the rare-earth hydroxide suspension that this example (1) prepares, with the MoO that contains of this example (2) preparation
3And Ag
2The kaolin of O and diatomite replace example 1 described kaolin, do not add cobalt nitrate, contain MoO
3And Ag
2The consumption of the kaolin of O and diatomite, boehmite, MOY zeolite, rare-earth hydroxide suspension makes kaolin and diatomite butt weight, Al
2O
3, MOY zeolite butt weight, be present in molecular sieve pore passage outer rare-earth oxide, MoO
3And Ag
2The ratio of the weight of O is 32.0: 16.5: 49.2: 0.8: 1.2: 0.3.The atmosphere of reduction is the nitrogen of hydrogen content 50 volume % and mixing of hydrogen, and the flow of gaseous mixture is 2500 ml/min, and the temperature that described solid contacts with gaseous mixture is 650 ℃, and be 1 hour time of contact, obtains catalyst C8 provided by the invention.The ratio of the composition of catalyst C8 and the kind of metal component, distribution, average valence and average valence and its highest price attitude is listed in the table 3.
Embodiment 9
Present embodiment illustrates Catalysts and its preparation method provided by the invention.
(1) get in rare earth oxide, rare earth metal content be 258 grams per liters the cerium-rich mischmetal chloride (Inner Mongol Baotou rare earth factory product, wherein, CeO
2Account for 75 weight %, the La of rare earth oxide
2O
3Account for 15 weight %, the Pr of rare earth oxide
2O
3Account for 5 weight %, the Nd of rare earth oxide
2O
3Account for 3 weight % of rare earth oxide, all the other are other rare-earth oxide) solution, under agitation, slowly splash into the concentrated ammonia liquor that concentration is 28 weight %, until slurries pH value to 9.2, obtain rare-earth hydroxide suspension.
(2) under agitation, with 2.96 kilograms of concentration be the ammonium metavanadate (NH of 2.0 weight %
4VO
3) 3.0 kilograms of (dry basis) kaolin of aqueous solution dipping and 0.08 kilogram of magnesian mixture, 120 ℃ of slurries that oven dry obtains, 550 ℃ of roastings 2 hours obtain containing MgO 2.56 weight %, V
2O
51.47 the kaolin of weight %.
(3) method by (2) in the example 1 and (3) prepares catalyst, and different is replaces example 1 described rare-earth hydroxide suspension with the rare-earth hydroxide suspension of this example (1) preparation, contains MgO and V with what this example (2) prepared
2O
5Kaolin replace example 1 described kaolin, do not add cobalt nitrate, replace the MOY zeolite with overstable gamma zeolite (specification is with example 6); Contain MgO and V
2O
5Kaolin, boehmite, overstable gamma zeolite, the consumption of rare-earth hydroxide suspension make kaolinic butt weight, magnesia, Al
2O
3, overstable gamma zeolite butt weight, be present in molecular sieve pore passage outer rare-earth oxide and V
2O
5The ratio of weight be 39.0: 1.0: 21.0: 35.0: 3.4: 0.6; The temperature that described solid contacts with hydrogen is 550 ℃, and the flow of hydrogen is 1000 ml/min, and be 1 hour time of contact, obtains catalyst C9 provided by the invention.The ratio of the composition of catalyst C9 and the kind of metal component, distribution, average valence and average valence and its highest price attitude is listed in the table 3.
Embodiment 10
Present embodiment illustrates Catalysts and its preparation method provided by the invention.
(1) get in rare earth oxide, rare earth metal content be 258 grams per liters the lanthanum rich mischmetal chloride (Inner Mongol Baotou rare earth factory product, wherein, CeO
2Account for 18 weight %, the La of rare earth oxide
2O
3Account for 75 weight %, the Pr of rare earth oxide
2O
3Account for 2 weight %, the Nd of rare earth oxide
2O
3Account for 3 weight % of rare earth oxide, all the other are other rare-earth oxide) solution, under agitation, slowly splash into the concentrated ammonia liquor that concentration is 28 weight %, until slurries pH value to 9.4, obtain rare-earth hydroxide suspension.
(2) be 3.0 kilograms of (dry basis) kaolin of gallium chloride aqueous solution dipping of 40 weight % and the mixture of 0.86 kilogram of (dry basis) boehmite with 2.74 kilograms of concentration, 120 ℃ of oven dry, 600 ℃ of roastings 2 hours obtain containing Ga
2O
313.1 the kaolin of weight % and the mixture of aluminium oxide.
(3) with the Ga that contains of this example (2) preparation
2O
3Kaolin and mixture, Ludox and the deionized water of aluminium oxide mix, the rare-earth hydroxide suspension that adds overstable gamma zeolite (specification is with example 6), ZRP-1 zeolite (specification is with example 7) and this example (1) preparation again, mix, it is 25 weight % that the consumption of deionized water makes the solid content of the slurries that obtain, and contains Ga
2O
3Kaolin and mixture, Ludox, the overstable gamma zeolite of aluminium oxide and have the zeolite of MFI structure, the consumption of rare-earth hydroxide suspension makes kaolin butt weight, aluminium oxide, silica, overstable gamma zeolite butt weight, ZRP-1 zeolite butt weight, is present in molecular sieve pore passage outer rare-earth oxide and Ga
2O
3The ratio of weight be 35.0: 10.0: 10.0: 30.0: 5.1: 3.1: 6.8.With the slurries spray-drying under 150 ℃ temperature that obtains, 550 ℃ of following roastings 2 hours.
With the catalyst sample that obtains at 800 ℃, with aging 12 hours of 100% steam.The solid 200 that obtains is restrained in the fixed bed reduction reactor of packing into, and under 600 ℃ of temperature, feeding flow is the hydrogen of 3000 ml/min, make hydrogen contact 2 hours with described solid, make the temperature of reactor reduce to room temperature, unload the solid after the reduction, obtain catalyst C10 provided by the invention.The ratio of the composition of catalyst C10 and the kind of metal component, distribution, average valence and average valence and its highest price attitude is listed in the table 3.
Embodiment 11
Present embodiment illustrates Catalysts and its preparation method provided by the invention.
(1) get in rare earth oxide, rare earth metal content be 228 grams per liters the cerium-rich mischmetal chloride (Inner Mongol Baotou rare earth factory product, wherein, CeO
2Account for 50 weight %, the La of rare earth oxide
2O
3Account for 21 weight %, the Pr of rare earth oxide
2O
3Account for 14 weight %, the Nd of rare earth oxide
2O
3Account for 13 weight % of rare earth oxide, all the other are other rare-earth oxide) solution, under agitation, slowly splash into the concentrated ammonia liquor that concentration is 28 weight %, until slurries pH value to 9.0, obtain rare-earth hydroxide suspension.
(2) with 3.15 kilograms of concentration be the stannous chloride SnCl of 6.0 weight %
2The aqueous solution, 0.6 kilogram of (dry basis) Ludox and 3.0 kilograms of (dry basis) kaolin mix, 120 ℃ of oven dry, and 550 ℃ of roastings 3 hours obtain containing SnO
24.0 the kaolin of weight % and the mixture of silica.
(3) will contain SnO
2Kaolin and mixture, aluminium colloidal sol and the deionized water of silica mix, add overstable gamma zeolite (specification is with example 6), ZRP-1 zeolite (specification is with example 7) and rare-earth hydroxide suspension again, mix, it is 25 weight % that the consumption of deionized water makes the solid content of the slurries that obtain, and contains SnO
2Kaolin and the consumption of the mixture of silica, aluminium colloidal sol, overstable gamma zeolite, ZRP-1 zeolite, rare-earth hydroxide suspension make kaolin butt weight, aluminium oxide, silica, overstable gamma zeolite butt weight, ZRP-1 zeolite butt weight, be present in molecular sieve pore passage outer rare-earth oxide and SnO
2The ratio of weight be 40.0: 12.0: 8.0: 25.0: 5.1: 7.9: 2.0, wherein deposition of rare-earth is counted 7.9 weight % with rare earth oxide.With the slurries spray-drying under 150 ℃ temperature that obtains, 550 ℃ of following roastings 2 hours.
With the catalyst sample that obtains at 800 ℃, with aging 12 hours of 100% steam.The solid 200 that obtains is restrained in the fixed bed reduction reactor of packing into, and under 650 ℃ of temperature, feeding flow is the hydrogen of 1000 ml/min, make hydrogen contact 1 hour with described solid, make the temperature of reactor reduce to room temperature, unload the solid after the reduction, obtain catalyst C11 provided by the invention.The ratio of the composition of catalyst C11 and the kind of metal component, distribution, average valence and average valence and its highest price attitude is listed in the table 3.
Table 3
| Example number | 8 | 9 | 10 | 11 |
| The catalyst numbering | C8 | C9 | C10 | C11 |
| The molecular sieve kind | MOY | DASY0.0 | DASY0.0+ ZRP-1 | DASY0.0+ ZRP-1 |
| Molecular sieve content, weight % | 49.2 | 35.0 | 35.1 | 30.1 |
| The heat-resistant inorganic oxide kind | Al 2O 3 | Al 2O 3+ MgO | Al 2O 3+SiO 2 | Al 2O 3+SiO 2 |
| Heat-resistant inorganic oxide content, weight % | 16.5 | 22.0 | 20.0 | 20.0 |
| The content that is present in the outer rare-earth oxide of molecular sieve pore passage, weight % | 0.8 | 3.4 | 3.1 | 7.9 |
| Clay types | Kaolin+diatomite | Kaolin | Kaolin | Kaolin |
| Clay content, weight % | 32.0 | 39.0 | 35.0 | 40.0 |
| The metal component kind | Mo、Ag | V | Ga | Sn |
| Metal oxide content, weight % | Mo 1.2 Ag 0.3 | 0.6 | 6.8 | 2.0 |
| The metal component average valence | Mo 3.0 Ag 0 | 2.3 | 1.5 | 2.2 |
| The ratio of metal component average valence and its highest price attitude | Mo 0.5 Ag 0 | 0.46 | 0.5 | 0.55 |
| Metal component distributes | Be evenly distributed in the clay | Be evenly distributed in clay and the magnesia | Be distributed in clay and the aluminium oxide | Be distributed in clay and the silica |
Example 12-18
Following example illustrates the catalytic performance of catalyst provided by the invention.
On the small stationary bed reaction device, adopt catalyst C1-C7 provided by the invention, his-and-hers watches 4 listed boiling ranges are that 329-550 ℃ sulfur-bearing decompressed wax oil carries out catalytic cracking, catalyst loading amount 4.0 grams.Reaction condition and reaction result are listed among the table 5-6.The sulphur content determination method adopts gas-chromatography-atomic emission spectrometry in the crackate, measures on HP6890GC-G2350A AED gas-chromatography-Atomic Emission Spectrometer AES.Wherein, oil ratio refers to the weight ratio of catalyst and described feedstock oil.
Comparative Examples 4-6
The catalytic performance of following Comparative Examples explanation reference catalyst.
Method by example 12 is carried out catalytic cracking to identical feedstock oil, and different is that catalyst system therefor is respectively reference catalyst CB1, CB2 and CB3, and reaction condition and reaction result are listed in the table 5.
Table 4
| The feedstock oil title | Decompressed wax oil | Reduced crude | Mix reduced crude |
| Density (20 ℃), gram per centimeter 3 | 0.9154 | 0.8906 | 0.9043 |
| Viscosity, millimeter 2/ second | |||
| 50℃ | 34.14 | - | - |
| 100℃ | 6.96 | 24.84 | 14.72 |
| Asphalitine, weight % | 0.0 | 0.8 | 1.6 |
| Conradson carbon residue, weight % | 0.18 | 4.3 | 6.0 |
| Sulfur content, weight % | 2.0 | 0.13 | 3.2 |
| Content of vanadium (in V), ppm | 0 | 0 | 27.2 |
| Boiling range, ℃ | |||
| IBP | 329 | 282 | 245 |
| 10％ | 378 | 370 | 334 |
| 50％ | 436 | 553 | 476 |
| 90％ | 501 | - | 552(67％) |
| 95％ | 518 | - | - |
| FBP | 550 | - | - |
Table 5
| Example number | 12 | 13 | 14 | Comparative Examples 4 | Comparative Examples 5 | Comparative Examples 6 |
| The catalyst numbering | C1 | C2 | C3 | CB1 | CB2 | CB3 |
| Reaction temperature, ℃ | 500 | 500 | 500 | 500 | 500 | 500 |
| Weight (hourly) space velocity (WHSV), hour -1 | 16 | 16 | 16 | 16 | 16 | 16 |
| Oil ratio | 4 | 4 | 4 | 4 | 4 | 4 |
| Conversion ratio, weight % | 73.8 | 71.2 | 72.7 | 68.5 | 70.4 | 69.8 |
| Product yield, weight % | ||||||
| Dry gas | 2.3 | 2.0 | 2.2 | 1.8 | 2.0 | 1.9 |
| Liquefied gas | 12.7 | 12.1 | 12.4 | 11.6 | 12.0 | 11.9 |
| Gasoline | 51.8 | 50.4 | 51.2 | 48.2 | 48.9 | 48.7 |
| Diesel oil | 17.5 | 19.0 | 18.1 | 19.8 | 19.3 | 19.5 |
| Heavy oil | 8.8 | 9.8 | 9.2 | 11.7 | 10.3 | 10.7 |
| Coke | 7.0 | 6.7 | 6.9 | 6.9 | 7.5 | 7.3 |
| Gasoline sulfure content, mg/litre | 435.1 | 453.6 | 426.9 | 761.2 | 684.7 | 695.2 |
From the result of table 5 as can be seen, zeolite content is identical with adopting, the catalyst of metallic components and each constituent content are not identical, be that described metal component is compared with the catalyst that oxidation state exists, adopt catalyst provided by the invention that hydrocarbon oil containing surphur is carried out catalytic cracking, conversion ratio is higher, and the sulfur content in the gasoline reduces significantly, and this illustrates that catalyst provided by the invention has higher cracking activity and higher desulphurizing ability.
Table 6
| Example number | 15 | 16 | 17 | 18 |
| The catalyst numbering | C4 | C5 | C6 | C7 |
| Reaction temperature, ℃ | 480 | 480 | 480 | 520 |
| Weight (hourly) space velocity (WHSV), hour -1 | 16 | 16 | 16 | 16 |
| Oil ratio | 3 | 3 | 4 | 4 |
| Conversion ratio, weight % | 79.2 | 77.1 | 71.7 | 75.8 |
| Product yield, weight % | ||||
| Dry gas | 2.3 | 2.2 | 1.8 | 2.3 |
| Liquefied gas | 13.2 | 12.8 | 10.5 | 18.4 |
| Gasoline | 54.6 | 53.2 | 51.8 | 45.8 |
| Diesel oil | 14.3 | 15.7 | 18.7 | 17.4 |
| Heavy oil | 6.5 | 7.2 | 9.6 | 6.8 |
| Coke | 9.1 | 8.9 | 7.6 | 9.3 |
| Gasoline sulfure content, mg/litre | 514.6 | 536.4 | 406.8 | 424.9 |
Example 19-22
Following example illustrates the catalytic performance of catalyst provided by the invention.
On the small stationary bed reaction device, adopt catalyst C8-C11 provided by the invention, the decompressed wax oil content shown in the his-and-hers watches 4 is that 80 weight % and reduced crude content are that the miscella of 20 weight % carries out catalytic cracking, catalyst loading amount 4.0 grams.Reaction condition and reaction result are listed in the table 7.
Table 7
| Example number | 19 | 20 | 21 | 22 |
| The catalyst numbering | C8 | C9 | C10 | C11 |
| Reaction temperature, ℃ | 480 | 480 | 520 | 520 |
| Weight (hourly) space velocity (WHSV), hour -1 | 16 | 16 | 16 | 16 |
| Oil ratio | 3 | 4 | 4 | 6 |
| Conversion ratio, weight % | 78.7 | 75.5 | 71.4 | 73.5 |
| Product yield, weight % | ||||
| Dry gas | 2.2 | 2.3 | 1.9 | 2.2 |
| Liquefied gas | 12.6 | 11.8 | 17.6 | 18.2 |
| Gasoline | 54.6 | 53.2 | 43.5 | 44.5 |
| Diesel oil | 14.1 | 16.7 | 19.1 | 18.3 |
| Heavy oil | 7.2 | 7.8 | 9.5 | 8.2 |
| Coke | 9.3 | 8.2 | 8.4 | 8.6 |
| Gasoline sulfure content, mg/litre | 426.5 | 403.2 | 519.3 | 476.0 |
Example 23
Following example illustrates the catalytic performance of catalyst provided by the invention.
On medium-sized fixed-bed reactor, adopt catalyst C1, the sulfur-bearing that his-and-hers watches 4 are listed and the mixing reduced crude of vanadium carry out catalytic cracking, catalyst loading amount 100 grams, reaction temperature is 480 ℃, and agent weight of oil ratio is 6, and weight (hourly) space velocity (WHSV) is 20 hours
-1After reaction is finished, with flow is the nitrogen switching feedstock oil of 300 ml/min, purged 0.5 hour, feed the air that flow is 500 ml/min again, be warming up to 600 ℃, burnt carbon 2 hours, and then be that the nitrogen replacement of 300 ml/min goes out air wherein with flow, be cooled to 400 ℃ of temperature, feeding flow is the hydrogen of 500 ml/min, make hydrogen contact 0.5 hour with described solid, wherein cobalt is reduced again, the mixing reduced crude that feeds sulfur-bearing and vanadium once more carries out catalytic cracking reaction.React and the results are shown in Table 8 after the 1st time and the 20th time.
Table 8
| Reaction times | 1 | 20 |
| Conversion ratio, weight % | 72.7 | 72.7 |
| Product yield, weight % | ||
| Dry gas | 1.7 | 1.8 |
| Liquefied gas | 12.5 | 12.4 |
| Gasoline | 51.4 | 51.3 |
| Diesel oil | 18.4 | 18.2 |
| Heavy oil | 8.9 | 9.1 |
| Coke | 7.1 | 7.2 |
| Gasoline sulfure content, mg/litre | 587.3 | 579.7 |
From the result of table 8 as can be seen, adopt catalyst provided by the invention that content of vanadium is carried out catalytic cracking up to the feedstock oil of 27.2ppm, compare during the first time with reaction, the conversion ratio and the product distribution of reacting after the 20th time do not change substantially, and the sulfur content in the gasoline is slightly reduction also.This illustrates that catalyst provided by the invention not only has higher cracking activity and higher desulphurizing ability, and, have good anti-vanadium ability.
Claims (21)
1. hydrocarbon cracking catalyzer that contains molecular sieve, this catalyst contains molecular sieve, heat-resistant inorganic oxide matrix, clay and a kind of metal component, wherein, described metal component exists with the reduction valence state basically, it is selected from the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, in the VIII family base metal one or more, described catalyst also contains and is present in the outer rare earth metal of molecular sieve pore passage, described molecular screening is from y-type zeolite or y-type zeolite and zeolite with MFI structure, at least a mixture in the β zeolite, with the catalyst total amount is benchmark, the content of molecular sieve is 1-90 weight %, the content of heat-resistant inorganic oxide is 2-80 weight %, the content of clay is 2-80 weight %, in oxide, the content that is present in the outer rare earth metal of molecular sieve pore passage is 0.1-10 weight %, in the metal oxide of highest price attitude, the content of metal component is 0.1-30 weight %.
2. catalyst according to claim 1, it is characterized in that, with the catalyst total amount is benchmark, the content of described molecular sieve is 10-60 weight %, and the content of heat-resistant inorganic oxide is 10-50 weight %, and the content of clay is 20-60 weight %, in oxide, the content that is present in the outer rare earth metal of molecular sieve pore passage is 0.1-5 weight %, and in the oxide of highest price attitude metal, the content of described metal component is 0.5-20 weight %.
3. catalyst according to claim 1 is characterized in that, the ratio of the average valence of described metal and its highest price attitude is 0-0.95.
4. catalyst according to claim 3 is characterized in that, the ratio of the average valence of described metal and its highest price attitude is 0.1-0.7.
5. catalyst according to claim 1 is characterized in that described metal component is selected from one or more in gallium, germanium, tin, antimony, bismuth, lead, copper, silver, zinc, cadmium, vanadium, molybdenum, tungsten, manganese, iron, cobalt, the nickel.
6. catalyst according to claim 5 is characterized in that described metal component is selected from one or more in gallium, tin, copper, silver, zinc, vanadium, molybdenum, manganese, iron, the cobalt.
7. catalyst according to claim 1 is characterized in that, described y-type zeolite is selected from one or more in the overstable gamma zeolite of the y-type zeolite, overstable gamma zeolite of HY, phosphorous and/or rare earth, phosphorous and/or rare earth.
8. catalyst according to claim 1 is characterized in that, the zeolite of the described MFI of having structure is selected from the zeolite with MFI structure of ZSM-5 zeolite, phosphorous and/or rare earth.
9. catalyst according to claim 1, it is characterized in that, described molecular screening from y-type zeolite with have the zeolite of MFI structure, at least a mixture in the β zeolite, at least a and weight ratio y-type zeolite that has in the zeolite, β zeolite of MFI structure is 0.01-0.8.
10. catalyst according to claim 1 is characterized in that described heat-resistant inorganic oxide is selected from one or more in aluminium oxide, silica, amorphous silicon aluminium, zirconia, titanium oxide, boron oxide, the alkaline earth oxide.
11. catalyst according to claim 1 is characterized in that, described clay is selected from one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the bentonite.
12. catalyst according to claim 1 is characterized in that, described catalyst also contains phosphorus component, is benchmark with the catalyst total amount, and in element phosphor, the content of described phosphorus component is 0-15 weight %.
13. claim 1 Preparation of catalysts method, this method comprises rare-earth oxide and/or the hydroxide that is present in outside the molecular sieve pore passage containing, the metal component compound, molecular sieve, the composition of heat-resistant inorganic oxide and clay contacts with the atmosphere that contains reducing gas, the temperature of contact is enough to make the average valence of described metal component to be lower than its highest oxidation state with the time that contacts, described metal component is selected from the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, in the VIII family base metal one or more, described molecular screening is from y-type zeolite or y-type zeolite and zeolite with MFI structure, at least a mixture in the β zeolite, each components contents makes in the final catalyst and contains in the composition, with the catalyst total amount is benchmark, the molecular sieve of 1-90 weight %, the heat-resistant inorganic oxide of 2-80 weight %, the clay of 2-80 weight %, in oxide, 0.1-10 weight % is present in the outer rare earth metal of molecular sieve pore passage, oxide in highest price attitude metal, 0.1-30 the metal component of weight %, the temperature of described contact is 100-900 ℃, and the time of contact is 0.1 second to 10 hours.
14. method according to claim 13 is characterized in that, the described atmosphere that contains reducing gas refers to pure reducing gas or contains reducing gas and inert gas atmosphere.
15. method according to claim 14 is characterized in that, described pure reducing gas is selected from hydrogen, carbon monoxide and contains in the hydro carbons of 1-5 carbon atom one or more.
16. method according to claim 14, it is characterized in that, describedly contain reducing gas and inert gas atmosphere is selected from hydrogen, carbon monoxide, contains one or more the mixture in one or more and the inert gas in the hydro carbons of 1-5 carbon atom, the dry gas in the oil plant.
17. method according to claim 13 is characterized in that, the temperature of described contact is enough to make the average valence of described metal component and the ratio of its highest price attitude to be reduced to 0-0.95 with the time that contacts.
18. method according to claim 17 is characterized in that, the temperature of described contact is enough to make the average valence of described metal component and the ratio of its highest price attitude to be reduced to 0.1-0.7 with the time that contacts.
19. method according to claim 13 is characterized in that, the temperature of described contact is 400-700 ℃, and the time of contact is 1 second to 5 hours.
20. method according to claim 13, it is characterized in that, each components contents preferably makes in the final catalyst and contains, in the catalyst total amount, and the molecular sieve of 10-60 weight %, the heat-resistant inorganic oxide of 10-50 weight %, the clay of 20-60 weight %, in oxide, 0.1-5 weight % is present in the outer rare earth metal of molecular sieve pore passage, in the oxide of highest price attitude metal, the metal component of 0.5-20 weight %.
21. method according to claim 13, it is characterized in that described metal component compound is selected from one or more in the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, group vib metal, VIIB family metal, the non-noble metal nitrate of VIII family, chloride, hydroxide, the oxide.
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| CN 200410029863 Expired - Lifetime CN1291787C (en) | 2004-03-31 | 2004-03-31 | Hydrocarbon cracking catalyst containing molecular sieve and its preparing mehtod |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102000602B (en) * | 2010-11-05 | 2015-03-25 | 西安近代化学研究所 | Cyclamine catalyst |
| CN104212476B (en) * | 2013-05-31 | 2018-08-28 | 中国石油化工股份有限公司 | A kind of anti-vanadium assistant of catalyst for cracking heavy oil or contact agent |
| CN104511299B (en) * | 2013-09-30 | 2016-08-24 | 中国石油化工股份有限公司 | A kind of desulphurization catalyst and preparation method thereof and the method for desulfurization of hydrocarbon oil |
| CN104258903A (en) * | 2014-10-16 | 2015-01-07 | 中国科学院山西煤炭化学研究所 | Hydrocracking catalyst of polycyclic aromatic hydrocarbon compound as well as preparation method and application of hydrocracking catalyst |
| CN104307562B (en) * | 2014-11-12 | 2016-07-27 | 武汉科林精细化工有限公司 | A kind of preparing gasoline by methanol catalyst and preparation method thereof |
| CN109518067B (en) * | 2017-09-19 | 2021-01-22 | 北京中联电科技术有限公司 | Heavy oil catalytic cracking alloy and application thereof |
| CN112642395A (en) * | 2019-10-11 | 2021-04-13 | 中国石油化工股份有限公司 | Molecular sieve compound and composite material as well as preparation method and application thereof |
| CN111167510A (en) * | 2020-01-13 | 2020-05-19 | 杨涛 | Petroleum hydrocarbon cracking catalyst and its prepn |
| CN113578375B (en) * | 2020-04-30 | 2023-04-07 | 中国石油化工股份有限公司 | Modified ZSM-5 zeolite, catalytic cracking catalyst, and preparation method and application thereof |
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2004
- 2004-03-31 CN CN 200410029863 patent/CN1291787C/en not_active Expired - Lifetime
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