CN1531582A - FCC process incorporating crystalline microporous oxide catalysts having increased lewis acidity - Google Patents
FCC process incorporating crystalline microporous oxide catalysts having increased lewis acidity Download PDFInfo
- Publication number
- CN1531582A CN1531582A CNA018148557A CN01814855A CN1531582A CN 1531582 A CN1531582 A CN 1531582A CN A018148557 A CNA018148557 A CN A018148557A CN 01814855 A CN01814855 A CN 01814855A CN 1531582 A CN1531582 A CN 1531582A
- Authority
- CN
- China
- Prior art keywords
- crystalline microporous
- oxide
- zeolite
- microporous oxide
- metal compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000003054 catalyst Substances 0.000 title abstract description 58
- 230000008569 process Effects 0.000 title abstract description 12
- 239000010457 zeolite Substances 0.000 claims description 69
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 67
- 229910021536 Zeolite Inorganic materials 0.000 claims description 65
- 150000002736 metal compounds Chemical class 0.000 claims description 50
- 239000000463 material Substances 0.000 claims description 37
- 229910052782 aluminium Inorganic materials 0.000 claims description 28
- 238000005336 cracking Methods 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 25
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 239000004411 aluminium Substances 0.000 claims description 16
- -1 aluminum compound Chemical class 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052733 gallium Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052645 tectosilicate Inorganic materials 0.000 claims description 3
- 229910001723 mesolite Inorganic materials 0.000 claims 2
- 229910052809 inorganic oxide Inorganic materials 0.000 abstract description 16
- 150000001875 compounds Chemical class 0.000 abstract description 14
- 238000009835 boiling Methods 0.000 abstract description 10
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 9
- 239000011159 matrix material Substances 0.000 abstract description 8
- 239000003208 petroleum Substances 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract 2
- 238000004231 fluid catalytic cracking Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 description 27
- 235000010210 aluminium Nutrition 0.000 description 26
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 24
- 239000003921 oil Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 21
- 229930195733 hydrocarbon Natural products 0.000 description 20
- 150000002430 hydrocarbons Chemical class 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- KILURZWTCGSYRE-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]alumanyloxypent-3-en-2-one Chemical group CC(=O)\C=C(\C)O[Al](O\C(C)=C/C(C)=O)O\C(C)=C/C(C)=O KILURZWTCGSYRE-LNTINUHCSA-K 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 12
- 230000002378 acidificating effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000000571 coke Substances 0.000 description 7
- 229910000765 intermetallic Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 150000002910 rare earth metals Chemical group 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000004523 catalytic cracking Methods 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 description 3
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 3
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 3
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 3
- 229940009827 aluminum acetate Drugs 0.000 description 3
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 3
- 125000003963 dichloro group Chemical group Cl* 0.000 description 3
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000007517 lewis acids Chemical group 0.000 description 3
- AKTIAGQCYPCKFX-FDGPNNRMSA-L magnesium;(z)-4-oxopent-2-en-2-olate Chemical compound [Mg+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AKTIAGQCYPCKFX-FDGPNNRMSA-L 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 description 2
- 240000005373 Panax quinquefolius Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical class O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 150000001457 metallic cations Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical class [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 229910052663 cancrinite Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052677 heulandite Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052679 scolecite Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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Abstract
A catalyst component, a catalyst, and a process for making the component and catalyst are disclosed herein. Also disclosed herein is a fluid catalytic cracking process for converting petroleum feedstocks to lower boiling products wherein the feedstock is contacted with the catalyst. The catalyst component is a crystalline microporous oxide catalyst to which a compound for promoting dehydrogenation and increasing Lewis acidity is effectively added. This catalyst component can be included in an inorganic oxide matrix material and used as a catalyst. Preferably, the compound for promoting dehydrogenation and increasing Lewis acidity is effectively added to a non-framework portion of the crystalline microporous oxide.
Description
Background
The present invention relates to catalyst component, composition and preparation and use method for compositions, said composition comprises crystalline microporous oxide, and described crystalline microporous oxide contains and can promote dehydrogenation and increase lewis acidity and do not increase the promoter metal compounds of the unit cell dimension of crystalline microporous oxide.
For many years, crystalline microporous oxide such as zeolite material have commercial use always in various industry.These materials have value because of it especially as the fluid separation ability of molecular sieve and because of its ability as catalyzer.
Crystalline microporous oxide is particularly useful as the catalyzer that the big paraffin molecules of hydrocarbon mixture can be changed into littler, more undersaturated molecule such as alkene and aromatics.Method for transformation commonly used comprises fluid catalystic cracking and hydrocracking.For this conversion process being maximized many structure propertiess such as aperture, pore volume, lewis acidity and the Bronsted acidity of necessary equilibrium catalyst.If the structure properties of conversion catalyst is balance suitably not, then to change into the transformation efficiency of product low for hydrocarbon mixture, and product quality is poor, or the rapid inactivation of conversion catalyst.
Useful especially is to obtain the high crystalline microporous oxide catalysts of catalytic activity by the skeleton of equilibrium catalyst and the Bronsted acidity and the lewis acidity of non-skeleton part.By the skeleton of balance crystalline structure and the composition of non-skeleton part, can optimize catalytic activity effectively.Under the situation of cracking catalyst, the alkene of bigger paraffin molecules can be formed reaction and more effectively connect with the micromolecular scission reaction that forms in the end product.
General introduction
A kind of embodiment of the present invention comprises catalyzer, this catalyzer comprise (i) substrate material and (ii) introduce substrate material or with substrate material bonded crystalline microporous oxide.Crystalline microporous oxide comprises non-skeleton part and has certain unit cell dimension.Non-skeleton portion branch comprises the promoter metal compounds of the non-skeleton part of only introducing crystalline microporous oxide.Promoter metal compounds does not increase the unit cell dimension of crystalline microporous oxide in fact.
In the another embodiment of catalyzer, crystalline microporous oxide comprises the Y zeolite of introducing substrate material.Y zeolite comprises non-skeleton part, and its unit cell dimension is greater than about 24.30 , and comprises the aluminum oxide of the non-skeleton part of only introducing crystalline microporous oxide, so that aluminum oxide can increase lewis acidity, but does not increase the unit cell dimension of zeolite in fact.
In the another embodiment of catalyzer, crystalline microporous oxide comprises non-skeleton part, described non-skeleton portion branch comprises the promoter metal compounds that can increase lewis acidity and only introduce the non-skeleton part of crystalline microporous oxide, so that promoter metal compounds does not increase the unit cell dimension of crystalline microporous oxide in fact.
The embodiment of described catalyzer can be used for FCC apparatus, isomerization unit or hydroeracking unit by catalyzer is contacted with suitable raw material.
Another embodiment of the present invention comprises the method for preparing catalyzer.This method comprises that (a) contacts crystalline microporous oxide with the promotor precursor that comprises the promoter metal that can form promoter metal compounds, and described crystalline microporous oxide comprises non-skeleton part and has certain unit cell dimension; (b) with the mixture heating up to 150 of step (a) ℃ to 550 ℃; The promoter metal compounds that wherein will comprise described promoter metal is only introduced the non-skeleton part of crystalline microporous oxide, and wherein promoter metal compounds does not increase the unit cell dimension of crystalline microporous oxide in fact.
Another embodiment of the present invention is a kind of method that comprises following steps: (a) crystalline microporous oxide is contacted with the promotor precursor, crystalline microporous oxide comprises non-skeleton part and has certain unit cell dimension, and the promotor precursor comprises the promoter metal that can form promoter metal compounds; (b), form the promoter metal compounds that comprises described promoter metal oxide form thus with described promotor precursors decompose; (c) described promoter metal compounds only is distributed in the non-skeleton part of described crystalline microporous oxide; Wherein promoter metal compounds does not increase the unit cell dimension of crystalline microporous oxide in fact.
Another embodiment of the present invention is a kind of method that comprises following steps: the zeolite that (a) will comprise non-skeleton part and have certain unit cell dimension is calcined; (b) zeolite is contacted with the promotor precursor that comprises the promoter metal that can form promoter metal compounds, wherein said promoter metal is selected from magnesium, chromium, iron, lanthanum, gallium, manganese and aluminium, and wherein said promotor precursor is selected from aluminium acetylacetonate, aluminum isopropylate, hexafluoroacetylacetone aluminium, dichloro two hydrated aluminums (aluminum dichlorohydrol), aluminum ethylate, three [2,2,6,6-tetramethyl--3,5-heptadione root closes] aluminium-III[Al (TMHD)
3], aluminum acetate, aluminum nitrate, Tripropoxyaluminum, magnesium acetylacetonate, chromium acetylacetonate, ferric acetyl acetonade, methyl ethyl diketone gallium, manganese acetylacetonate and lanthanon acetylacetonate; (c) with the mixture heating up to 150 of step (b) ℃ to 550 ℃; (d) product of step (b) is introduced substrate material, the promoter metal compounds that wherein will comprise described promoter metal is only introduced the non-skeleton part of zeolite, and wherein promoter metal compounds can not increase the unit cell dimension of zeolite basically.
Another embodiment of the present invention is a kind of method that comprises the steps: the crystalline microporous oxide after (a) will calcining contacts with the promotor precursor that comprises the promoter metal that can form promoter metal compounds, and described crystalline microporous oxide comprises non-skeleton part and has certain unit cell dimension; (b) described promoter metal compounds is activated, wherein said promoter metal compounds is only introduced the non-skeleton part of crystalline microporous oxide, and wherein promoter metal compounds can not increase the unit cell dimension of crystalline microporous oxide basically.
Another embodiment of the present invention is a kind of method that comprises the steps: (a) calcining crystalline microporous oxide, crystalline microporous oxide comprise non-skeleton part and have certain unit cell dimension; (b) contact is selected from the aluminum alkyls of trimethyl aluminium, triethyl aluminum, tri-tert aluminium and triisobutyl aluminium; (c) product of step (b) is handled to form promoter metal compounds with oxygen carrier, wherein promoter metal compounds can not increase the unit cell dimension of crystalline microporous oxide basically.
Other embodiment of the present invention comprises the product by method preparation of the present invention.Substrate material can be introduced or do not introduced to these products, but the preferred substrate material of introducing uses in process unit then.
Describe in detail
Can promote dehydrogenation and increase the lewis acidity of crystalline microporous oxide and do not increase the promoter metal compounds of its unit cell dimension by introducing effectively, can improve for example catalytic activity of zeolite of crystalline microporous oxide.Although crystalline microporous oxide can be used alone as catalyzer, preferably crystalline microporous oxide is introduced substrate material, preferred inorganic oxide.The catalyst component or the on-catalytic component that in substrate material, also can have other.
Crystalline microporous oxide of the present invention can be used for the elementary product catalytic pyrolysis of catalytic cracking reaction is become refined products, as petroleum naphtha that is used as fuel and the alkene that is used as chemical feedstocks.Crystalline microporous oxide is preferably selected from crystalloid aluminosilicate zeolite (below be called zeolite), tectosilicate, the aluminophosphates (ALPOs) of positive tetrahedron and the silicoaluminophosphates (SAPOs) of positive tetrahedron.More preferably crystalline microporous oxide is a zeolite.
Suitable zeolite comprises natural and synthetic zeolite.Suitable natural zeolite comprises sarcolite, chabazite, dachiardite, clinoptilolite, faujusite, heulandite, levyne, erionite, cancrinite, scolecite, offretite, mordenite and ferrierite.Suitable synthetic zeolite is X zeolite, Y zeolite, L zeolite, ZK-4 zeolite, ZK-5 zeolite, E zeolite, H zeolite, J zeolite, M zeolite, Q zeolite, T zeolite, Z zeolite, α and β zeolite, ZSM type zeolite and omega zeolite.Preferred faujusite, preferred especially unit cell dimension more than or equal to 24.30 , more preferably greater than or equal Y zeolite and the X zeolite of about 24.40 .Aluminium in the zeolite and silicon components can replace with other skeleton component.For example, aluminum portions can replace with boron, gallium, titanium or the trivalent metal composition heavier than aluminium.Germanium can be used for replacing the silicon part.
In the catalyst product of making, crystalline microporous oxide is preferably included in the inorganic oxide matrix material that catalyst component is bonded together, and is enough to bear between particle and the collision of wall of reactor so that final catalyst is very hard.The inorganic oxide matrix material can be made by inorganic oxide sol or gel, thereby this inorganic oxide sol or gel are dried with catalyst component " bonding " together.Preferred inorganic oxide matrix material comprises the oxide compound of silicon and aluminium.The inorganic oxide matrix material also can comprise active porous inorganic oxide catalyst component and inert catalyst component.The all components of preferred catalyst keeps together by being attached on the inorganic oxide matrix material.
Active porous inorganic oxide catalyst component is generally too big and can not enter the formation that the hydrocarbon molecule of crystalline microporous oxide comes the elementary product of catalysis by the cracking volume.The active porous inorganic oxide catalyst component that can introduce cracking catalyst is the porous inorganic oxide preferably, compares with the blank thing of acceptable heat, and the hydrocarbon cracking that described porous inorganic oxide will be a large amount of relatively becomes more low-molecular-weight hydrocarbon.The silicon-dioxide of low surface area (for example quartzy) is one type the blank thing of acceptable heat.(little activity test ASTM#D3907-8) can be measured the cracking degree with any for example MAT in the various ASTM tests.Preferably be disclosed in Greensfelder, B.S. waits the people, Industrial and Engineering Chemistry, pp.2573-83, those compounds of Nov.1949.Preferred compound is aluminum oxide, silica-alumina and silica-alumina-zirconium white.
The inert catalyst component can increase density, intensity usually and serve as the holder of protectiveness.Can introduce the cracking activity of the inert catalyst component of cracking catalyst of the present invention does not preferably want obviously greater than the blank thing of acceptable heat.The clay of kaolin and other and Alpha-alumina, titanium dioxide, zirconium white, quartz and silicon-dioxide are the examples of suitable inert component.
Preferably discontinuous aluminum oxide is introduced the inorganic oxide matrix material mutually.Can use aluminum oxyhydroxide class-gama-alumina, boehmite, diaspore and transitional alumina for example Alpha-alumina, beta-alumina, gama-alumina, δ-aluminum oxide, ε-aluminum oxide, к-aluminum oxide, ρ-aluminum oxide.Preferred alumina type is for example gibbsite, bayerite, promise gibbsite or doyelite of three aluminium hydroxides.
In one embodiment of the present invention, the crystalline microporous oxide catalysts component comprises the compound that can promote dehydrogenation and increase lewis acidity, and this compound is called promoter metal compounds in this article.The distribution of promoter metal compounds in crystalline microporous oxide can not cause any substantive the increasing of crystalline microporous oxide unit cell dimension, and the unit cell dimension of crystalline microporous oxide material is substantially the same.
Promoter metal compounds preferably be in can promote paraffinic hydrocarbons and cyclanes compound in the hydrocarbon incoming flow effectively dehydrogenation to form the chemical state of alkenes compounds.For example, aluminum oxide (Al
2O
3) comprise suitable promoter metal (aluminium).The oxide compound of aluminium is to be in a kind of like this effective chemical attitude.
Crystalline microporous oxide comprises skeleton part and non-skeleton part.The number of the effective metal cation-bit of the non-skeleton part by increasing crystalline microporous oxide increases the lewis acidity of crystalline microporous oxide and does not increase unit cell dimension.Normally, when the skeleton portion timesharing of material being introduced material, unit cell dimension will increase.When promoter metal compounds of the present invention being introduced in the crystalline microporous oxide material of the present invention, it is identical that unit cell dimension keeps basically.Therefore, preferably promoter species is only introduced the non-skeleton part of crystalline microporous oxide material.Referring to W.O.Haag, " utilize the katalysis-Science and Technology of zeolite ", Zeolites andRelated Microporous Materials, J.Weitkamp, H.G.Karge, H.Pfeifer and W.Holderich edit, Vol.84, Elsevier Science B.V., 1994, wherein pp.1375-1394 has discussed the mutual relationship of lewis acidity position, at this document is incorporated herein by reference.In this article, metallic cation is meant metal ion or metal ion oxygenates ionic species.
A kind of embodiment of the present invention is the method for preparing active catalytic components.Other embodiment is the active catalytic components and the final catalyst product that comprises substrate material by this method preparation.
A kind of embodiment of the inventive method comprises by mixing or other appropriate means, crystalline microporous oxide is contacted with the promotor precursor that can form promoter metal compounds.In this article, mix being meant, might not need any mechanical stirring each component merging.The promotor precursor is contacted the non-skeleton part that makes the promotor precursor be dispensed into crystalline microporous oxide with crystalline microporous oxide.Preferably the decomposition by the promotor precursor activates promoter metal compounds then, produces remaining organic moiety and absorption or is distributed to promoter metal compounds in the non-skeleton part of crystalline microporous oxide.In order to increase effective number of the non-skeleton acidic site of metallic cation, promoter metal compounds by liquid phase or gas-phase reaction for example the gas phase transmission be adsorbed onto on the crystalline microporous oxide.
The time that the promotor precursor contacts with crystalline microporous oxide, should be enough to make crystalline microporous oxide to keep the promoter metal oxide compound by the generation of promotor precursors decompose of 40 to 60% weight, preferred about 50% weight.Measure reserving degree by the weight of measuring crystalline microporous oxide/promotor precursor mixture in the activation/heating steps process.With crystalline microporous oxide and promotor precursor with crystalline microporous oxide: the promotor precursor is that mix 100: 15 to 100: 200, preferred 100: 15 to 100: 100 weight ratio.For example, with in zeolite and the embodiment that aluminium acetylacetonate contacts, aluminium acetylacetonate is about 15.7% Al because of decomposition/reaction produces a kind of
2O
3Suppose after decomposition/reaction, from the Al of aluminium acetylacetonate
2O
3In about 55% weight be distributed to the non-skeleton part of zeolite and kept here by zeolite, in order to make 15 gram Al
2O
3Be distributed on the 100 gram zeolites and (increase 15%Al
2O
3), 100 gram zeolites should be mixed with about 175 gram aluminium acetylacetonates:
15g Al
2O
3/ (0.157 Al
2O
3/ aluminium acetylacetonate * 0.55 (percentage ratio of decomposition)))=173.4 restrains aluminium acetylacetonate.
By being contacted with suitable oxygen-containing gas with the burning organic moiety, organic moiety removes remaining organic moiety.Also can use other proper method well known in the art.
Promoter metal compounds is polyvalent metal compounds preferably.Preferred polyvalent metal compounds is the compound that contains divalence or trivalent metal, is preferably selected from magnesium, chromium, iron, lanthanum, gallium, manganese and aluminium.
The preferred promoter precursor is stable in gas phase, and preferably its boiling point less than about 550 ℃, be more preferably less than about 500 ℃.The example of preferred promotor precursor includes but not limited to aluminium acetylacetonate, aluminum isopropylate, hexafluoroacetylacetone aluminium, dichloro two hydrated aluminums, aluminum ethylate, three [2,2,6,6-tetramethyl--3,5-heptadione root closes] aluminium-III[Al (TMHD)
3], aluminum alkyls for example trimethyl aluminium, triethyl aluminum and triisobutyl aluminium, aluminum acetate, aluminum nitrate, Tripropoxyaluminum, methyl ethyl diketone gallium, manganese acetylacetonate, magnesium acetylacetonate, chromium acetylacetonate, ferric acetyl acetonade and lanthanon Acetyl Acetone thing.
In a kind of specific embodiment, preferably by means commonly known in the art crystalline microporous oxide is calcined, then it is contacted with the promotor precursor, described promotor precursor includes but not limited to aluminium acetylacetonate, aluminum isopropylate, hexafluoroacetylacetone aluminium, dichloro two hydrated aluminums, aluminum ethylate, three [2,2,6,6-tetramethyl--3,5-heptadione root closes] aluminium-III[Al (TMHD)
3], aluminum acetate, aluminum nitrate, Tripropoxyaluminum, magnesium acetylacetonate, chromium acetylacetonate, ferric acetyl acetonade, manganese acetylacetonate, methyl ethyl diketone gallium and lanthanon Acetyl Acetone thing, its activation back forms promoter metal compounds.
By the mixture heating up of crystalline microporous oxide/promotor precursor is come the active cocatalyst metallic compound to about 150 ℃ to about 550 ℃.Heating steps becomes remaining organic moiety with the promotor precursors decompose and can be dispensed into the promoter metal compounds of the non-skeleton part of crystalline microporous oxide.The activatory crystalline microporous oxide catalysts component of Sheng Chenging can be mixed with suitable substrate material and as catalyzer then.In this embodiment, preferred promotor precursor comprises that in one embodiment crystalline microporous oxide is a zeolite, preferred Y zeolite, and the promotor precursor is an aluminium acetylacetonate, generates the aluminum oxide promoter metal compounds of aluminum oxide.
In another kind of specific embodiment, preferably, then it is contacted with the promotor precursor that comprises aluminum alkyls by means commonly known in the art with the crystalline microporous oxide calcining.Suitable aluminum alkyls includes but not limited to trimethyl aluminium, triethyl aluminum, tri-tert aluminium, triisobutyl aluminium.In this embodiment, contact the active cocatalyst metallic compound by mixture and oxygen carrier with crystalline microporous oxide/promotor precursor.Suitable oxygen carrier includes but not limited to air, oxygen, water and alcohols for example methyl alcohol, ethanol, Virahol and butanols.Oxygen carrier and aluminum alkyls reaction come the active cocatalyst metallic compound by the organic moiety that forms aluminum oxide and remnants thus.Reactions steps becomes the promotor precursors decompose can be distributed in the non-skeleton part of crystalline microporous oxide and enters the promoter metal compounds of remaining organic moiety, if desired, can the organic moiety of remnants be removed according to top description.The activatory crystalline microporous oxide catalysts component of Sheng Chenging can be mixed with suitable substrate material and as catalyzer then.The preferred promoter metal comprises aluminium, and crystalline microporous oxide comprises zeolite.
The method of earlier paragraphs is obtained, comprise the crystalline microporous oxide material and be incorporated into the product of promoter metal compounds of the non-skeleton part of crystalline microporous oxide material, join in the aforesaid inorganic oxide matrix material to form catalyzer, be preferably formed fresh free of contamination catalyzer.Then this catalyzer is sent in the process unit with as described below and carries out suitable application.
Although other catalyst component and material can be introduced catalyzer, substrate material can constitute the surplus of finished catalyst composition.About 40% weight that the preferred substrate material accounts for catalyzer is to about 90% weight, more preferably from about 50% weight is to about 80% weight, according to total restatement of catalyzer.Microporous oxide, clay and the carbon monoxide oxidation promotor of other type are introduced catalyzer also within the scope of the invention.Catalyzer of the present invention is preferably freshly prepd in being sent to cracking technology the time, and just, catalyzer is substantially free of the metal that can pollute catalyzer in catalytic cracking process.Described metal includes but not limited to nickel, vanadium, sodium and iron.
Catalyzer of the present invention can be used for various oil and chemical process, particularly wherein needs those processes of paraffin dehydrogenation.For example, they can be used for the reaction in catalysis fluid catalystic cracking, hydrocracking and the isomerization.Promoter metal compounds is adsorbed onto on the crystalline microporous oxide part of catalyzer in the mode that can promote paraffinic hydrocarbons and naphthenic hydrocarbon dehydrogenation.Result as paraffinic hydrocarbons contacts with crystalline microporous oxide preferably becomes alkene with bigger paraffin conversion.Preferably alkene is changed into littler paraffin molecules, olefin hydrocarbon molecules and aromatics molecule with the ratio that fuel Products needs then.
Fluid catalystic cracking is used to high boiling oil oils is changed into more valuable low-boiling products, comprises gasoline and intermediate oil for example kerosene, aviation kerosene and heated oil.The charging commonly used of catalytic cracking unit has higher boiling point and comprises residual oil itself, perhaps the mixture of residual oil and other high boiling fraction.The most frequently used charging is a gas oil, its initial boiling point usually above about 230 ℃, more generally be higher than about 350 ℃, terminal point is the highest to be about 620 ℃.Gas oil commonly used comprises straight run (normal pressure) gas oil, vacuum gas oil and coker gas oil.As those of ordinary skill in the art understands, owing in the petroleum hydrocarbon cut, have so much dissimilar compound, so be difficult to accurately define described hydrocarbon-fraction by initial boiling point.Hydrocarbon-fraction in this boiling range comprises gas oil, thermal oil, residual oil, turning oil, topped oil and whole crude, tar sand oils, shale oil, synthol, the heavy hydrocarbon fractions that derives from coking, tar, wood pitch, petroleum pitch and derives from any hydrotreated feed in the aforementioned substances.
Fluidized bed catalytic cracker comprises reactor usually, and raw material contacts therein with the hot fine catalyst that heats in revivifier.Conveyer line connects two containers to remove catalyst particle to and fro.Cracking reaction is preferably carried out under the following conditions: temperature be about 450 ℃ to about 680 ℃, more preferably from about 480 ℃ to about 560 ℃, pressure be about 5 to 60psig, more preferably from about 5 to 40psig, duration of contact (catalyzer contacts with charging) for the ratio of about 0.5 to 15 second, more preferably from about 1 to 6 second, catalyzer and oils be about 0.5 to 10, more preferably from about 2 to 8.
In the cracking reaction process, form low-boiling products, and some hydrocarbons and nonvolatile sedimentation of coke are to catalyst particle.By stripping catalyst, preferably remove hydrocarbons with the steam stripped catalyzer.Nonvolatile coke is made up of height condensed aromatic hydrocarbon usually.Along with hydrocarbons and coke build-up on catalyzer, cracking catalyst active and the catalyst selectivity that generates the gasoline adulterant reduce.Remove most hydrocarbons by stripping, and remove coke, can recover most of initial activity of catalyst particle by suitable oxidation regeneration.Therefore, catalyst particle is sent to stripper, is sent to revivifier then.
By with oxygen-containing gas for example the deposits of coke on the air combustion catalyst surface realize the regeneration of catalyzer.Catalyst temperature in the regenerative process is about 560 ℃ to about 760 ℃.Granules of catalyst after the regeneration is returned to reactor by conveyer line then, and because its heat can maintain reactor the required temperature of cracking reaction.Combustion of coke is thermopositive reaction; Therefore, in utilizing the conventional fluidized bed catalytic cracker of conventional charging, do not need to add other fuel.In implementation process of the present invention used raw material mainly because of the content of its lower aromatics and because of the duration of contact in reactor or conveyer line shorter relatively, may not with enough sedimentation of coke to the catalyst particle in revivifier, to reach required temperature.Therefore, may need to use other fuel so that the higher temperature in the revivifier to be provided, the heat of getting back to the catalyst particle of reactor like this is enough to keep cracking reaction.The suitable non-limitative example of adding fuel comprises the C that derives from catalytic cracking process itself
2Gas, Sweet natural gas and torch oil.Preferred C
2Gas.
Isomerization is the another kind of method that wherein can use catalyzer of the present invention.Can carry out isomerized hydro carbons by method of the present invention and comprise and contain 4-20, preferred 4-12, the more preferably from about paraffinic hydrocarbons and the olefinic hydro carbons of 4-6 carbon atom usually, and aromatics dimethylbenzene for example.Preferred charging is made up of the paraffinic hydrocarbons that with butane, pentane, hexane, heptane etc. is representative.Isomerisation conditions comprises: temperature is about 80 ℃ to about 350 ℃, preferred about 100 ℃ to 260 ℃; Pressure be about 0 to 1000psig, preferred about 0 to 300psig; Liquid hourly space velocity is about 0.1 to 20, preferred about 0.1 to 2; Hydrogen gas rate in standard cubic feet per barrel is about 1000 to 5000, preferred about 1500 to 2500.Service temperature and catalyst activity and air speed is interrelated, handle thereby under the catalyst deactivation rate of maximum stream time of the catalyzer that can guarantee regeneration period, provide the reasonable raw material rapid processing.
Catalyzer of the present invention also can be used for hydrocracked, treated.Hydrocracking has improved the total refining yield of premium blending compound.In fixed-bed reactor, hydrocracking can utilize low-quality relatively gas-oil feed (otherwise this gas oil will be impregnated in distillate fuel) and with its conversion in the presence of hydrogen and suitable catalyzer.Usually raw material mixed, is heated to about 140 ℃ to 400 ℃ with hydrogen, be forced into about 1200 to 3500psi, be fed to first step reactor then, the raw material reaction of about 40 to 50% weight disinthibites cracking reaction and makes the nitrogen of product quality reduction and the compound of sulphur to remove in this reactor.The logistics cooling that to flow out from first step reactor, liquefy and pass separator, in this separator, take out butane and light gas.Bottom fraction is sent to second stage reactor and carries out cracking with higher temperature and pressure, wherein generate other gasoline blending compound and isocrackate.
With reference to the following embodiment that is used to illustrate embodiment of the present invention, can further understand the present invention.
Embodiment 1
The three kinds of enterprising column criterion MAT test of independent commercially available crystalline microporous oxide (for example little activity tests, ASTM#D3907-8): USY is (available from W.R.Grace, the Z14USY of Davison Division, or derive from LZY 82 or the LZY 84 of UOP), LZ-210 is (available from Katalystiks, Inc.) and the Y (CREY of incinerating rare earth exchanged, available from W.R.Grace, Davison Division).Before carrying out MAT test, with crystalline microporous oxide and substrate material (Ludox is available from DuPont) mix be incorporated in 1400 °F with steam treatment 16 hours with the generation cracking catalyst.
Each catalyzer of testing comprises 20% weight zeolite and 80% weight substrate material.The result is illustrated in as in the following table 1.
Table 1
MAT is USY LZ-210 CREY as a result
Transformation efficiency (% weight, 400 °F-) 42.5 47.7 64.1
H
2(% weight) 0.0113 0.0186 0.0064
C (% weight) 1.480 1.891 1.760
Surface-area (m
2/ g) 200 189 130
Pore volume (cm
3/ g) 0.439 0.023 0.254
Unit cell dimension () 24.21 24.24 24.51
Embodiment 2
According to A.Dyer, An Introduction to Zeolite Molecular Sieves, the 6th chapter, " as the zeolite of ion-exchanger ", John Wiley ﹠amp; Sons, the method for carrying out cationic exchange in zeolite described in 1998 is carried out metal ion exchanged with the crystalline microporous oxide of embodiment 1, at this these chapters and sections is incorporated herein by reference.After crystalline microporous oxide carries out ion-exchange, it is mixed with substrate material and use steam treatment, carry out the MAT test of standard then according to the description among the embodiment 1.The results are shown in the table 2.
Table 2
MAT is USY LZ-210 CREY as a result
+Al
2O
3 +Al
2O
3 +Al
2O
3
Transformation efficiency (% weight, 400 °F-) 29.8 38.5 51.1
H
2(% weight) 0.0047 0.0055 0.0056
C (% weight) 1.119 1.737 1.516
Surface-area (m
2/ g) 194 172 161
Pore volume (cm
3/ g) 0.346 0.314 0.318
Unit cell dimension () 24.25 24.22 24.36
The result shows: compare with the non-commutative crystalline microporous oxide of embodiment 1, the crystalline microporous oxide of metal ion exchanged significantly reduces the transformation efficiency of product.This shows that the metal ion exchanged step causes the loss of the non-skeleton effective metal cation-bit partly of crystalline microporous oxide, because the balance between Bronsted position and the Louis position is unfavorable for required activity.
Embodiment 3
MAT three kinds of independent enterprising column criterions of commercially available crystalline microporous oxide tests: utilize the CREY (RECREY) of the method for Dyer with the prepared rare earth exchanged of a part of the CREY of rare-earth ion solution switching implementation example 1; Method NH according to Dyer
4 +About 4% weight Na of exchange CREY
+The Y (HCREY) of prepared hydrogen incinerating rare earth exchanged; With according to R.Szostak, " modified zeolite " (the 5th chapter), Introduction to ZeoliteScience and Practice, Vol.58, H.Van Bekkum, E.M.Flanigan and J.C.Jansen edit, Elsevier, the method of describing among 1991 the reference 6-13 is by calcining NH
4The Y (USCREY) of the prepared overstable incinerating rare earth exchanged of CREY.Before carrying out the MAT test, with zeolite and substrate material (10% weight zeolite; 30% weight SiO
2, for available from Unimin Specialty Minerals, the IMSIL-A-8 of Inc.; 60% weight SiO
2-Al
2O
3, from deriving from W.R.Grace, the gel of Davison Division makes, and this gel drying also provides 25% weight Al when washing
2O
3, SiO
2-Al
2O
3) mix to generate cracking catalyst.The results are shown in the table 3.
Table 3
MAT is RECREY HCREY USCREY as a result
Transformation efficiency (% weight, 430 °F-) 45.3 50.1 44.0
C (% weight) 1.34 1.39 1.33
650+product (% weight) 32.4 27.4 32.7
Surface-area (m
2/ g) 101 129 113
Unit cell dimension () 24.49 24.45-
Embodiment 4
In independent container, each crystalline microporous oxide of embodiment 3 is mixed (ratio of zeolite and aluminium acetylacetonate was near 1: 1.4, and the decomposition temperature of aluminium acetylacetonate is higher than 320 ℃ a little) with aluminium acetylacetonate.Each container is all placed baking oven and is heated to 150 ℃, kept 1 hour, purge baking oven with the nitrogen amount that is enough to wash out the degradation production that decomposes of methyl ethyl diketone that may be inflammable then.Behind the purging, with baking oven for heating to 500 ℃ and kept cooling then 1 hour.Then baking oven was heated 2 hours at 500 ℃ in air.Weight meter according to product can calculate the result as adition process, about 45% weight estimate that from the aluminium acetylacetonate amount available aluminum oxide is retained in the zeolite.The zeolite that will contain the aluminum oxide of adding according to the description among the embodiment 3 is made catalyzer then, and tests under the MAT of standard condition then.The results are shown in the table 4.
Table 4
MAT is RECREY HCREY USCREY as a result
+Al
2O
3 +Al
2O
3 +Al
2O
3
Transformation efficiency (% weight, 430 °F-) 55.2 58.2 60.8
C (% weight) 1.63 1.57 1.65
650+product (% weight) 22.6 19.3 17.4
Surface-area (m
2/ g) 118 81 143
Unit cell dimension ()-24.43 24.46
The result shows: compare with the crystalline microporous oxide that does not add metal of embodiment 3, the crystalline microporous oxide that contains the metallic compound that can promote dehydrogenation and lewis acidity of interpolation obviously raises to the transformation efficiency of gasoline product.This shows that the adding metallic compound has increased the number of the non-skeleton effective metal cation-bit partly of crystalline microporous oxide.In other words, the adding of metallic compound causes the lewis acidity position obviously to increase.This point be also illustrated in by the acidic site number of the every gram catalyzer of direct mensuration as in the following table 5.
If after carrying out steam treatment according to the description among the embodiment 3, with pyridine adsorption to catalyzer, heating under vacuum to 250 ℃ is to inhale any pyridine in nonacid position from more weak acidolysis then, infrared spectra can be used for measuring the relative quantity that is adsorbed onto the pyridine on the Bronsted acidity position with pyridinium ion, and with the amount of coordination pyridine adsorption to the strong lewis acid position.When the catalyzer after the desorb is carried out described Infrared spectroscopy, can on three kinds of catalyzer, observe the following band intensity of the pyridine of absorption.
Three kinds of different materials are arranged: 1) RECREY, the zeolite of the rare earth exchanged of FAU structure-type in table 5.This is the raw material of two samples in back in this table.2) aluminum oxide-I of RECREY+ adding, it is the sample that has added aluminum oxide with method teaching herein in RECREY, described aluminum oxide is the aluminum oxide that effectively adds.3) aluminum oxide-II of RECREY+ adding, it is the sample that has added aluminum oxide in RECREY, the adding mode of described aluminum oxide can not effectively increase Lewis acid.
People such as R.J.Gorte [Journal of Catalysis 148,213-223, (1994), and reference wherein] and people [Journal of Catalysis 148 such as G.L.Price, 228-236, (1994)] Jiao Dao method is used for quantitatively determining total acidity, be characterized by the amount of the amount of strong acidic site (intensity is enough to make Tri N-Propyl Amine resolve into propylene and ammonia when thermal desorption) and slightly acidic position (this acidity keeps amine because of itself and Tri N-Propyl Amine 50 ℃ of interactions, but when temperature raises with the desorb Tri N-Propyl Amine).This mensuration can be measured Bronsted and lewis acidity position simultaneously.Tart is measured with the milligramequivalent of every gram material and is represented (1 mmole amine is counted and the reaction of 1 mmole acidic site).
Table 5
RECREY RECREY+ RECREY+
The Al that adds
2O
3The Al that adds
2O
3
Total Al
2O
3(% weight) 19.7 30.5 27.0
Strongly-acid, MEQV/G 0.46 0.38 0.40
Slightly acidic, MEQV/G 2.64 2.99 2.59
Total acidic, MEQV/G 3.10 3.37 2.99
Table 5 explanation: only under the situation that adds aluminum oxide effectively (I), slightly acidic just increases together together with total acidic.The amount of simple increase aluminum oxide that shows another embodiment (II) differs increases acidity surely.
According to the description among the embodiment 3, aforesaid each zeolite sample is used to prepare catalyzer, then with embodiment 3 described identical conditions under with these composite catalysts with steam treatment so that its inactivation.
Part with every kind of catalyst sample is pressed into thin disk then.Each disk is weighed and measure its diameter and thickness.Then each disk is placed vacuum chamber and heating to remove all water or the gas of other absorption.Then it is cooled to 50 ℃ and contact in short time with the pyridine steam.Then sample is kept in a vacuum a few hours and measured its infrared spectra, particularly at 1400cm
-1To 1600cm
-1Between infrared spectra.Then sample is heated to 250 ℃ and keep a few hours, measures its infrared spectra once more.The temperature of this rising and high vacuum are removed the pyridine of all physical adsorptions.
On the material before the pyridine adsorption, measure 1400cm
-1To 1600cm
-1Between infrared spectra, from the spectrum of the sample that contains pyridine, deduct this spectrum.The spectrum that obtains is because the acidic site results of interaction of pyridine and catalyzer.
In this SPECTRAL REGION, 1540cm
-1To 1550cm
-1The peak at place is owing to carrying out the coordinate pyridine with proton from the Bronsted acidity position.1440cm
-1To 1460cm
-1Between the peak receive position (Lewis acid) interactional pyridine owing to the electron pair on the nitrogen and solid electronics.At this SPECTRAL REGION 1440cm
-1To 1660cm
-1In, 1480cm
-1To 1500cm
-1Between other bands of a spectrum are the results that are adsorbed onto the bands of a spectrum combination of the pyridine on Bronsted and the Louis position.
For the composite catalyst that the zeolite of crossing with steam treatment, usefulness is shown in Table 5 is made, table 6 has been listed because of there being the observed band intensity of Bronsted and Louis position on the catalyzer.
Table 6
RECREY RECREY+ADA RECREY+ADA
I II
The reason of band intensity:
(absolute units/gram)
Bronsted position 22 33 33
Lewis acidity position 55 104 60
These results show that effective adding of this metallic compound has increased the lewis acidity of active catalyst really.
Now describe the present invention fully, it should be appreciated by those skilled in the art, in claims wide parameter area required for protection, can carry out the present invention.
Claims (17)
1, a kind of fluid catalystic cracking method, this method comprises:
Under the fluid catalystic cracking condition raw material is contacted with freshly prepd catalyzer, this freshly prepd catalyzer comprises:
(i) substrate material
The crystalline microporous oxide of (ii) introducing substrate material or combining with described substrate material, described crystalline microporous oxide comprises non-skeleton part and has certain unit cell dimension, described non-skeleton portion branch comprises the promoter metal compounds of the non-skeleton part of only introducing crystalline microporous oxide, and wherein promoter metal compounds can not increase the unit cell dimension of crystalline microporous oxide in fact.
2, the described method of claim 1, wherein promoter metal compounds is a polyvalent metal compounds.
3, the described method of claim 1, wherein promoter metal compounds is an aluminum compound.
4, the described method of claim 1, wherein crystalline microporous oxide is a zeolite.
5, the described method of claim 4, wherein crystalline microporous oxide is X or Y zeolite.
6, the described method of claim 5, wherein crystalline microporous oxide is the Y zeolite that unit cell dimension is equal to or greater than 24.30 .
7, the described method of claim 5, wherein crystalline microporous oxide is the Y zeolite that unit cell dimension is equal to or greater than 24.40 .
8, the described method of claim 1, wherein said crystalline microporous oxide is selected from zeolite, tectosilicate, tetrahedral aluminophosphates and tetrahedral silicoaluminophosphates.
9, the described method of claim 1, wherein said crystalline microporous oxide is a zeolite, and wherein said promoter metal compounds is an aluminum oxide.
10, the described method of claim 1, wherein said promoter metal compounds is a metal oxide, the metal of wherein said metal oxide is selected from magnesium, chromium, iron, lanthanum, gallium, manganese and aluminium.
11, a kind of fluid catalystic cracking method, this method comprises:
Under the fluid catalystic cracking condition raw material is contacted with freshly prepd catalyzer, this freshly prepd catalyzer comprises:
(i) substrate material
(ii) introduce the Y zeolite of described substrate material, described Y zeolite comprises non-skeleton part and has unit cell dimension greater than about 24.30 , described non-skeleton portion branch comprises the aluminum oxide of the non-skeleton part of only introducing crystalline microporous oxide, and wherein aluminum oxide has increased lewis acidity and do not increased the unit cell dimension of zeolite in fact.
12, a kind of fluid catalystic cracking method, this method comprises:
Under the fluid catalystic cracking condition raw material is contacted with freshly prepd catalyzer, this freshly prepd catalyzer comprises:
(i) substrate material
(ii) introduce the crystalline microporous oxide of described substrate material, described crystalline microporous oxide comprises non-skeleton part and has certain unit cell dimension, described non-skeleton portion branch comprises can increase lewis acidity, only introduce the promoter metal compounds of the non-skeleton part of crystalline microporous oxide, and wherein promoter metal compounds does not increase the unit cell dimension of crystalline microporous oxide in fact.
13, the described method of claim 12, wherein said crystalline microporous oxide is selected from zeolite, tectosilicate, tetrahedral aluminophosphates and tetrahedral silicoaluminophosphates.
14, the described method of claim 12, wherein said crystalline microporous oxide is a zeolite, and wherein said promoter metal compounds is an aluminum oxide.
15, the described method of claim 12, wherein said promoter metal compounds is a metal oxide, the metal of wherein said metal oxide is selected from magnesium, chromium, iron, lanthanum, gallium, manganese and aluminium.
16, the described method of claim 14, its mesolite is the Y zeolite that unit cell dimension is equal to or greater than 24.30 .
17, the described method of claim 14, its mesolite is the Y zeolite that unit cell dimension is equal to or greater than 24.40 .
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| US09/653,136 | 2000-08-31 | ||
| US09/653,135 | 2000-08-31 | ||
| US09/653,135 US6482313B1 (en) | 1994-10-03 | 2000-08-31 | FCC process incorporating crystalline microporous oxide catalysts having increased Lewis acidity |
| US09/653,136 US6673734B1 (en) | 1994-10-03 | 2000-08-31 | Crystalline microporous oxide catalysts having increased Lewis acidity and methods for the preparation thereof |
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| AU8509001A (en) * | 2000-08-31 | 2002-03-13 | Exxonmobil Res & Eng Co | Crystalline microporous oxide catalysts having increased lewis acidity and methods for the preparation thereof |
| WO2008026681A1 (en) * | 2006-08-31 | 2008-03-06 | Nippon Oil Corporation | Fluid catalytic cracking method |
| JP5390857B2 (en) * | 2006-08-31 | 2014-01-15 | Ｊｘ日鉱日石エネルギー株式会社 | Fluid catalytic cracking method |
| BRPI0803718A2 (en) * | 2008-08-29 | 2010-06-15 | Petroleo Brasileiro Sa | method for the production of light olefins in catalytic cracking units with energy deficiency |
| RU2548362C2 (en) | 2009-06-25 | 2015-04-20 | Чайна Петролеум & Кемикал Корпорейшн | Catalyst for catalytic cracking and method of increasing catalyst selectivity (versions) |
| EP2463028A1 (en) * | 2010-12-11 | 2012-06-13 | Umicore Ag & Co. Kg | Process for the production of metal doped zeolites and zeotypes and application of same to the catalytic removal of nitrogen oxides |
| US8945373B2 (en) | 2011-12-22 | 2015-02-03 | Iogen Corporation | Method for producing renewable fuels |
| CN106179386B (en) * | 2015-04-30 | 2018-10-12 | 中国石油化工股份有限公司 | The preparation method of Hydrobon catalyst |
| CN106179461B (en) * | 2015-04-30 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocracking catalyst |
| CN106179391B (en) * | 2015-04-30 | 2019-01-25 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN106179378B (en) * | 2015-04-30 | 2018-12-21 | 中国石油化工股份有限公司 | The preparation method of hydrotreating catalyst |
| CN106179381B (en) * | 2015-04-30 | 2019-03-19 | 中国石油化工股份有限公司 | The preparation method of Hydrobon catalyst |
| CN106179384B (en) * | 2015-04-30 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of preparation method of Hydrobon catalyst |
| CN106179377B (en) * | 2015-04-30 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of preparation method of Hydrobon catalyst composition |
| CN106179382B (en) * | 2015-04-30 | 2019-02-22 | 中国石油化工股份有限公司 | A kind of preparation method of body phase hydrotreating catalyst |
| CN106179388B (en) * | 2015-04-30 | 2019-01-25 | 中国石油化工股份有限公司 | A kind of preparation method of hydrotreating catalyst |
| CN106179390B (en) * | 2015-04-30 | 2019-01-25 | 中国石油化工股份有限公司 | A kind of hydrotreating catalyst and preparation method thereof |
| CN106179379B (en) * | 2015-04-30 | 2018-11-06 | 中国石油化工股份有限公司 | A kind of preparation method of hydrotreating catalyst |
| CN106179466B (en) * | 2015-04-30 | 2019-01-25 | 中国石油化工股份有限公司 | The preparation method of hydrocracking catalyst |
| CN106179385B (en) * | 2015-04-30 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of preparation method of Hydrobon catalyst |
| CN106179464B (en) * | 2015-04-30 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocracking catalyst |
| CN106179383B (en) * | 2015-04-30 | 2018-11-06 | 中国石油化工股份有限公司 | The preparation method of hydrotreating catalyst |
| CN106179389B (en) * | 2015-04-30 | 2019-01-25 | 中国石油化工股份有限公司 | Hydrobon catalyst and preparation method thereof |
| CN106179387B (en) * | 2015-04-30 | 2019-01-25 | 中国石油化工股份有限公司 | The preparation method of Hydrobon catalyst composition |
| CN106179465B (en) * | 2015-04-30 | 2018-12-21 | 中国石油化工股份有限公司 | The preparation method of hydrocracking catalyst |
| JP6203910B2 (en) * | 2016-06-28 | 2017-09-27 | 住友化学株式会社 | Insulating porous layer for non-aqueous electrolyte secondary battery and laminated separator for non-aqueous electrolyte secondary battery |
| CN107837819B (en) * | 2017-11-20 | 2020-07-24 | 运城学院 | MnY catalyst for indoor formaldehyde catalytic removal and preparation method thereof |
| CN109061778B (en) * | 2018-09-12 | 2020-04-24 | 江西泰华光电科技股份有限公司 | Mobile phone lens processing method |
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| NL8103069A (en) * | 1980-10-28 | 1982-05-17 | Grace W R & Co | METHOD FOR PREPARING CATALYTIC CRACKING CATALYSTS |
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| EP0130251B1 (en) * | 1983-07-04 | 1987-09-16 | Mobil Oil Corporation | Process for converting propane to aromatics over zinc-gallium zeolite |
| JPS6042228A (en) * | 1983-08-15 | 1985-03-06 | モビル オイル コ−ポレ−シヨン | Processing method for zeolites |
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| US6482313B1 (en) * | 1994-10-03 | 2002-11-19 | Exxonmobil Research And Engineering Company | FCC process incorporating crystalline microporous oxide catalysts having increased Lewis acidity |
| CA2177293C (en) * | 1995-06-23 | 2003-12-09 | William Lee Schuette | Crystalline microporous oxide having increased lewis acidity and fluid catalytic cracking process using same |
| AU8509001A (en) * | 2000-08-31 | 2002-03-13 | Exxonmobil Res & Eng Co | Crystalline microporous oxide catalysts having increased lewis acidity and methods for the preparation thereof |
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| AU2001285091B2 (en) | 2005-11-10 |
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| CA2419668A1 (en) | 2002-03-07 |
| CN1449306A (en) | 2003-10-15 |
| CN1319647C (en) | 2007-06-06 |
| CN1288225C (en) | 2006-12-06 |
| CA2419253A1 (en) | 2002-03-07 |
| WO2002018516A1 (en) | 2002-03-07 |
| AU8509101A (en) | 2002-03-13 |
| TW583021B (en) | 2004-04-11 |
| AU2001285090B2 (en) | 2005-11-10 |
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| TW592816B (en) | 2004-06-21 |
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