CN103889572B - 用于制备介孔化催化剂的方法、由此获得的催化剂及其在催化工艺中的用途 - Google Patents
用于制备介孔化催化剂的方法、由此获得的催化剂及其在催化工艺中的用途 Download PDFInfo
- Publication number
- CN103889572B CN103889572B CN201280051897.XA CN201280051897A CN103889572B CN 103889572 B CN103889572 B CN 103889572B CN 201280051897 A CN201280051897 A CN 201280051897A CN 103889572 B CN103889572 B CN 103889572B
- Authority
- CN
- China
- Prior art keywords
- zeolite
- mesoporousization
- catalyst
- hya
- metal
- 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.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 96
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 230000008569 process Effects 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 230000003197 catalytic effect Effects 0.000 title description 8
- 239000010457 zeolite Substances 0.000 claims abstract description 162
- 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 161
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 157
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 95
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 42
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- 239000004411 aluminium Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 239000013335 mesoporous material Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000007791 liquid phase Substances 0.000 abstract description 7
- -1 ammonium ions Chemical class 0.000 abstract description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 48
- 239000000463 material Substances 0.000 description 27
- 239000011148 porous material Substances 0.000 description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000004517 catalytic hydrocracking Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000007848 Bronsted acid Substances 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000004400 29Si cross polarisation magic angle spinning Methods 0.000 description 4
- 238000001116 aluminium-27 magic angle spinning nuclear magnetic resonance spectrum Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 150000004767 nitrides Chemical group 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- BNWPUUZJGBXAFM-UHFFFAOYSA-N azane oxalonitrile Chemical compound N.N#CC#N BNWPUUZJGBXAFM-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 229910001657 ferrierite group Inorganic materials 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 229910019975 (NH4)2SiF6 Inorganic materials 0.000 description 1
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 1
- 206010027336 Menstruation delayed Diseases 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241000251778 Squalus acanthias Species 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000002152 aqueous-organic solution Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
-
- 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
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/043—Noble metals
-
- 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
-
- 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
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/068—Noble metals
-
- 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
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
-
- 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
- B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- 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
- B01J29/90—Regeneration or reactivation
-
- B01J35/30—
-
- B01J35/60—
-
- B01J35/66—
-
- B01J35/69—
-
- B01J35/695—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/08—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using ammonia or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/026—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or compounds thereof
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/14—After treatment, characterised by the effect to be obtained to alter the inside of the molecular sieve channels
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/22—After treatment, characterised by the effect to be obtained to destroy the molecular sieve structure or part thereof
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/36—Steaming
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/38—Base treatment
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- C07C2529/068—Noble metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
本发明涉及用于制备包含介孔化沸石的催化剂的方法,包括以下步骤:‑制备质子型介孔化沸石,其包含至少一种微孔网络和至少一种介孔网络,以及‑在含有氨或铵离子的气相或液相中处理。本发明还涉及所获得的催化剂和该催化剂在加氢转化工艺中的用途。
Description
本发明涉及用于制备含有介孔的催化剂的方法、由此获得的催化剂和由此获得的催化剂在工业过程中的用途。
本文所述催化剂含有介孔化沸石,并且可用在许多加氢转化工艺中,特别是加氢裂解过程中。
现有技术
不同的沸石通过不同的结构和性质区分,并且是本领域中熟知的。在WO2010/072976中公开了催化剂领域中常用的一些结构,以下给出了其中一些。
沸石Y(FAU)是具有大孔的三维沸石,其结构具有大的腔,所述腔通过由12元环形成的通道互相连接,每一个环具有12个(Si4+和Al3+)阳离子和12个O2-阴离子。
β沸石(BEA)是具有大孔的三维沸石,其在全部方向都包含由12元环形成的孔。
沸石ZMS-5(MFI)是具有中型孔的几乎三维的沸石,其在一个方向上包含由10元环形成的孔,所述孔通过由10元环形成的曲折通道互相连接(这就是为何这种结构被认为是几乎三维)。
丝光沸石(MOR)是具有由12元环形成的大孔的沸石,其通道仅在一个方向上延伸,并且其在这些通道之间具有由8元环形成的小袋。
镁碱沸石(FER)是具有中型孔的二维沸石,其包含由10元环形成的主通道,这些主通道通过由8元环形成的旁通道相互连接。
沸石是重要的催化材料,并且被广泛应用在酸催化反应如裂解(例如,加氢裂解、FCC、烯烃裂解)、异构化反应(例如,烷烃和烯烃的异构化反应)和最近的甲醇转化技术(例如,MTO、MTP、MTG)中。对于所有这些反应,沸石是催化剂的核心,呈现了由微孔沸石结构诱导的高催化活性、高稳定性以及最后但同样重要的高产品选择性。尽管微孔的存在对于形状选择性具有正面影响,但是微孔也可能具有负面影响,其通常通过催化作用中分子进入沸石晶体的低速率或对反应物和/或产品的不希望的吸附作用来说明。这些空间限制降低了在催化作用中沸石微孔体积的可及性,可认为沸石催化剂并非总能有效地使用。
在开发新的沸石催化剂中的重要问题之一是保证活性位点对于反应物和/或产品分子足够的可及性从而使催化剂的效力最大化。使扩散限制最小化的简单的解决方案是缩短晶体内的扩散路径长度。一种可能性是降低沸石晶粒大小。另一种获得具有足够可及性的材料的策略是在微孔沸石晶体内部产生由介孔(2-50nm)组成的次级孔系统。传统上,通过脱铝作用向沸石和沸石样晶体中引入介孔,其使用水热处理如汽提(steaming)(US3293192、US3506400和US5069890)和酸浸技术(US3506400、US4093560和US5601798)。或者,还提议了化学处理,利用例如EDTA(US3506400和US4093560)或(NH4)2SiF6(EP0082211)。对于通过多种方法在沸石中产生介孔的更详细的文献综述,由van Donk等给出(S.vanDonk等,Catalysis Reviews45(2003)297)。
尽管过去几年在这些结构化介孔材料的合成、表征和形成机制的理解方面取得了相当大的进展,但是其在工业中的有效应用因为其高成本仍然高度受限,所述高成本部分地与有机模板的高成本有关。因此,从成本角度来说,传统的水热处理和酸浸技术依然具有很大吸引力,这就解释了为何这些技术今天在工业中大量使用。但是,通过这些方法引入介孔不容易控制,并且获得的材料通常具有无规和非优化的介孔。在Janssen等的论文(A.H.Janssen等,Angew.Chem.Int.Ed.40(2001)1102)中,使用三维电子显微镜证明,市售汽提和酸浸沸石Y(CBV780,Zeolyst Int.)中很大一部分介孔是未最佳地连接到沸石结晶的外表面的腔。显然,对于催化剂,预期结晶内的互相连接的圆筒形介孔系统比介孔腔更能增强反应物的可及性和反应产品的扩散。
近年来,作为对合成沸石材料的传统的水热处理和酸浸的替代选择,提议了另外的形成介孔的方法(M.Ogura等,Chem.Lett.(2000)82;M.Ogura,Appl.Catal.A Gen.219(2001)33;J.C.Groen等,Microporous Mesoporous Mater.69(2004)29;J.C.Groen,等,J.Phys.Chem.B,108(2004)13062)。这种替代方法基于通过在碱性介质中的处理对合成沸石仔细脱硅作用。该技术在二十世纪八十年代晚期首次被开发用于研究沸石Y和ZSM-5的溶解现象和结构变化。此外,对于Shell在具有2至12.5at/at的Si/Al比的超稳定和极度超稳定Y沸石的改进(EP0528494)以及它们在加氢过程中的应用(EP0519573),授予了两个专利。
最近,本申请人在专利申请WO2010/072976中公开了通过对脱铝八面沸石仔细脱硅作用制备的改进的沸石Y,得到了具有晶体内和互相连接孔的独特的三峰系统的材料。这种沸石在多种加氢裂解反应中表现出改进的性能,对中间馏分有更高选择性并抑制过度裂解。中间馏分包括一系列来自原油桶的中沸点级分的产品。
随着在欧洲对处理较重质和污染更严重的原料的需要以及对中间馏分需求的增加,加氢裂解变得很重要。因此,中间馏分选择性加氢裂解催化剂是所寻求的。
然而,与基于纯微孔沸石的催化剂相比,通过破坏性技术合成的介孔催化剂的活性通常显著较低。对介孔沸石扩散性的改进通常通过损失长程结晶度、微孔孔隙率、骨架铝的量和密切相关的布朗斯特酸( )位点的量来实现。这些性质通常负责催化剂的活性,特别是在酸催化反应中。铝配位作用的变化改变了催化剂中布朗斯特酸位点的数目,其与催化剂活性直接相关(N.Katada等,Micropor.Mesopor.Mater.75(2004)61)。
在沸石β中,形成了八面体配位的铝,并且可以通过吸附碱分子(例如,氨)以及通过用钠和钾阳离子取代质子来转变成四面体铝(E.Bourgeat-Lami等,Appl.Catal.72(1991)139)。还在沸石ZSM-5(G.L.Woolery等,Zeolites19(1997)288)、MOR(A.Omegna等,J.Phys.Chem.B.107(2003)8854)和Y(B.H.Wouters等,J.Am.Chem.Soc.120(1998)11419;B.Xu等,J.Catal.241(2006)66)中发现了在氨吸附上可逆地转变配位的铝物质的存在。在非晶氧化硅铝中发现了类似行为(A.Omegna等,J.Phys.Chem.B.107(2003)8854)。在酸性沸石中,在室温与水接触后发生铝配位由四面体向八面体的转变,在超过400K的温度下,八面体配位不稳定(J.A.van Bokhoven等,J.Am.Chem.Soc.125(2003)7435)并返回四面体配位,但是布朗斯特酸位点未恢复(A.Omegna等,J.Phys.Chem.B.107(2003)8854)。
因此,为了结合介孔结构的扩散优点和保持的沸石性能,应考虑在引入介孔后的合成后处理。这样的合成后处理可通过将骨架外铝重新插入到骨架位置中来帮助恢复被部分破坏的沸石结构。
发明内容
现在,本申请人发现了制备含有介孔化沸石的催化剂的方法,由于通过对介孔材料的合成后处理所致的所谓的“恢复”沸石结构,所述催化剂表现出良好的催化活性,尤其是在加氢转化反应中。
根据第一个方面,本发明的一个主题是用于制备含有介孔化沸石的催化剂的方法,其包括以下步骤:
A-制备质子型介孔化沸石,其包含至少一种微孔网络和至少一种介孔网络,以及
B-在含有氨或铵离子的气相或液相中处理。
根据该方法,在步骤B中,通过将骨架外的铝(即,通常认为是八面体配位中的Al原子)重新插入到骨架位置(即,通常也认为是四面体配位中的Al原子)中,恢复了在步骤A)后被部分破坏的沸石结构。另外,八面体铝与四面体铝的比率可以为0至0.5,特别是0至0.4,更特别地,为0至0.3。这些作用导致了改进的催化活性,特别是当这些材料用在加氢转化反应中时。
因此,根据本发明的方法(特别是在步骤B)之后)有利地由将骨架外铝重新插入到所述催化剂的骨架位置中组成。
所述方法使得能够制备包含具有恢复的沸石结构的介孔化沸石的催化剂,其在本说明书中也被称作“最终介孔化沸石催化剂”。在一些实施方案中,像这样的催化剂由具有恢复的沸石结构的介孔化沸石组成。
在步骤B)之后获得的最终介孔化沸石催化剂具有以下特征:
-结晶度为0至100%,优选0至98%,例如0至95%,高于在步骤A)中制备的材料;
-比表面积(BET)为100至850m2/g,例如150至800m2/g;
-外比表面积为20至500m2/g,例如30至400m2/g;
-总孔体积为0.2至0.9ml/g,例如0.25至0.6ml/g;
-微孔体积为0.01至0.5mL/g,特别是0.002至0.4mL/g;
-介孔体积(2至50nm的孔)为0.1至0.9mL/g,特别是0.12至0.8mL/g;
-与步骤A)制备的材料中的相比,八面体配位的Al的量较低;
-沸石骨架中原子Si/Al比为7至40,例如8至40;
-布朗斯特酸位点的量:0.1至0.6mmol NH3/g,例如0.15至0.5mmolNH3/g,高于在步骤A)中制备的材料。
在一些方面,在步骤A)中用作原料的沸石或包含沸石的复合材料优选地表现出10至50的骨架原子Si/Al比。
有利地,原料是FAU骨架类型的沸石,在一些方面,是沸石Y。
总的来说,某些或预定骨架原子Si/Al比的沸石通过碱处理被介孔化,使其沸石结构被部分破坏(步骤A))。在上述NH3或铵离子处理(步骤B))后,由于骨架外Al重新插入到了骨架位置中,恢复了材料的沸石部分,而依然保留了介孔孔隙率。制备了具有恢复的沸石结构的介孔化沸石。介孔孔隙率和恢复的沸石结构的结合可导致对中间馏分的选择性和在多种反应中高活性的最优组合。
因此,根据本发明的方法特别地包括:在碱性pH介质中处理作为原料的具有预定骨架原子Si/Al比的沸石(步骤A)),以及在包含氨或铵离子的气相或液相中处理在步骤A)中获得的质子型介孔化沸石。
步骤A)
质子型介孔化沸石是具有质子作为抗衡离子的沸石。
制备质子型介孔化沸石的步骤A)可包括以下步骤:
a)在磁性或机械搅拌下于室温将作为原料的母体沸石或包含其的复合材料悬浮在碱性水溶液中,所述溶液包含浓度为例如0.001至2M的至少一种强碱(特别是NaOH或KOH)和/或无机或有机弱碱(例如,碳酸钠、柠檬酸钠或四烷基氢氧化铵);
b)通过在搅拌下于室温下添加浓度为例如0.005至2M的至少一种酸来中和所述介质;
c)从液体中分离获得的沸石,并任选地用溶剂特别是极性溶剂(例如,水)洗涤;
d)任选地干燥经洗涤的沸石;
e)任选地对步骤c)的沸石或步骤d)的任选地干燥的沸石进行至少一次离子交换处理;
f)任选地洗涤所述沸石;
g)煅烧获得的沸石;以及
h)回收沸石,即,质子型介孔化沸石。
非限制性的步骤a)包括通过将母体沸石悬浮在碱性溶液中来处理母体沸石。母体沸石还可以是包含其的复合材料,特别是以相对于复合材料的总重含量为至少5重量%的含量。
复合材料是包含母体沸石的某些级分但是任选地还包含在母体沸石的改性过程中产生的无定形相和/或粘合剂的材料,所述粘合剂为金属氧化物或金属氧化物的混合物。在所述方法的步骤a)期间使用的沸石优选地表现出大于或等于12的本体原子Si/Al比。
还可以例如在例如用至少一种酸和/或水蒸气进行至少一次脱铝处理特别是部分脱铝处理之后获得这样的原子骨架Si/Al比的沸石。这些处理可导致(i)降低材料的酸度,(ii)增加(虽然轻微)在理论上是纯微孔的初始材料的介孔孔隙率。最特别地,这些处理相当于在专利US5601798中描述的那些。
在步骤a)中,碱性pH溶液/沸石的重量比可以为4至100,或甚至20至100,优选5至80,特别是30至80,特别地是40至60,或甚至可以是约50。
在步骤a)中,溶液的碱浓度可以为0.001至2M,特别是0.005至1M,特别是0.01至0.5M,或甚至可以是约0.05M。
在步骤a)中,与碱溶液的接触放置可持续5至120分钟,特别是10至60分钟,特别是15至30分钟。在该接触放置过程中,可以搅拌悬液,特别是通过磁性或机械搅拌。
根据步骤b)的中和可以通过使大量材料在工业条件下与含有酸的溶液(例如,硫酸)接触来进行。中和步骤同样可在水的存在下进行。该中和有利地在磁性或机械搅拌下于室温进行。
含有酸的溶液包含至少一种酸,所述至少一种酸在搅拌下于室温浓度为例如0.005至2M。
中和的目的是终止脱硅过程并防止对材料的不希望破坏,这些破坏可导致沸石的晶体结构大量损失、微孔孔隙率损失以及诱导材料固有活性降低。
所述方法在步骤b)之后还包括通过任何已知方法从经中和溶液中分离介孔化沸石以获得固体介孔化沸石,接着洗涤步骤的步骤c)。
然后可以干燥介孔化沸石(步骤d))。干燥步骤可以在大于或等于70℃,特别是大于或等于75℃,或者甚至大于或等于80℃的温度下进行。其可以为1至36小时,特别地,1至24小时,以及特别是1至15小时。干燥可以在空气中或在惰性气氛下进行。
干燥步骤可以持续直到产品的重量不再改变,特别地,当在时间t时产品的重量与加热2小时后该产品的重量之间的差异改变相对于产品的总重小于0.1重量%时。
步骤e)可包括使经洗涤(步骤c))或任选地经干燥(步骤d))的沸石与含有铵离子的溶液接触放置以进行至少一次离子交换处理。
离子交换溶液(有利地包括含有铵离子(特别是NH4NO3)的溶液)与介孔化沸石的重量比可以为3至75,特别是3至50,特别是3至30。步骤e)的溶液的NH4NO3浓度可以为0.01至0.5M,特别是0.05至0.4M,特别是0.1至0.3M,或甚至可以是约0.2M。
与含有铵离子的溶液接触放置(步骤e))可以持续1至24小时,特别是1至12小时,特别是1至8小时。该步骤可以进行1至3次。
有利地,步骤e)可以在室温下进行,因此不需要加热。
对于本发明的目的,术语“室温”意指10至55℃,特别是15至35℃的温度。
洗涤步骤f)在一些方面可以是任选的,并且如果这样的话可以用水进行。
煅烧步骤(步骤g))可以在大于或等于400℃,特别是大于或等于450℃,或者甚至大于或等于500℃的温度下进行。加热可以持续1至8小时,特别是1至6小时,或者甚至1至5小时。加热可以包括以0.5至2℃/分钟,特别是1℃/分钟升高温度。加热可以在空气中或在惰性气氛下进行。
然后,回收基本上由质子型介孔化沸石组成的催化剂(步骤h))。
通过实施所述方法的步骤A),可以获得表现出三峰孔隙率的质子型介孔化沸石催化剂,所述三峰孔隙率通过至少一种微孔网络和至少一种介孔网络表示,后者有利地包括至少一种平均直径为2至5nm的小介孔网络和至少一种平均直径为10至50nm的大介孔网络,这些不同网络是互相连接的。
因此,本发明的质子型介孔化沸石可具有三峰晶体内孔隙率,即在每一个晶体内含有三种不同平均直径的孔网络。
更具体地说,质子型介孔化沸石表现出比开始的沸石的微孔体积小10%,特别地是小20%,特别是小30%或甚至小50%的微孔体积。
质子型介孔化沸石可具有比开始的沸石的介孔体积大10%,特别是大20%,特别是大30%或甚至大55%的介孔体积。特别地,介孔体积的增加基本上是由于产生了小介孔。
质子型介孔化沸石的原子本体Si/Al比可以为小于或等于50,特别是小于或等于40,或甚至小于或等于30,更特别是小于或等于25,甚至更特别是小于或等于23,任选地小于或等于20。
本体Si/Al原子比可以大于或等于5,特别是大于或等于6,或甚至大于或等于7。
原子骨架Si/Al比可以为7至40。
质子型介孔化沸石小介孔的体积(Vs)与大介孔的体积(Vl)的比率Vs/Vl有利地为大于或等于1,特别是大于或等于1.20,或甚至大于或等于1.60,更特别是大于或等于1.80,甚至更特别是大于或等于2。
质子型介孔化沸石的总介孔体积为大于或等于0.20ml/g,特别是大于或等于0.25ml/g,特别地是大于或等于0.35ml/g,或甚至大于或等于0.40ml/g。
质子型介孔化沸石的微孔体积为小于或等于0.20ml/g,特别是小于或等于0.18ml/g,特别是小于或等于0.16ml/g,或甚至小于或等于0.125ml/g,以及更特别是小于或等于0.10ml/g。
根据步骤A)制备的沸石的总介孔体积/微孔体积的比率为大于或等于1,特别是大于或等于1.5,特别是大于或等于3,或甚至大于或等于3.5,更特别是大于或等于4,甚至更特别是大于或等于4.5或甚至大于或等于5。
质子型介孔化沸石的外表面积Sext可以为大于或等于100m2/g,特别是大于或等于150m2/g,特别是大于或等于200m2/g,或甚至大于或等于250m2/g,以及更特别是大于或等于300m2/g。
通过氨的TPD(TPD NH3)测量的酸位点密度可以为小于或等于0.5mmol/g,特别是小于或等于0.48mmol/g,特别是小于或等于0.45mmol/g或甚至小于或等于0.4mmol/g。
任选地,在进行步骤A)之后且在进行步骤B)之前,进行利用水蒸气特别是温度为250℃至450℃的水蒸气处理1至6小时的步骤。该所谓的“汽提步骤”可有助于修复/水解在碱处理中可能被破坏的与铝的键。
任选地,代替汽提步骤或/和在汽提步骤之后,在机械或磁搅拌下于室温使材料与浓度为0.01M至1M的酸的水溶液接触5至60分钟。
步骤B)
在步骤B)中,使在步骤A)中获得的质子介孔材料在含有氨或铵离子的气相或液相中进行处理。
在气相中的处理可以通过利用能够释放气态氨(原位)或铵离子的化合物处理在步骤A)中获得的任选地经汽提的质子型介孔化沸石来进行。因此,可以在含有氨和/或铵离子的源的气相或液相中进行处理。
该化合物或化合物的混合物可以是纯的或用惰性气体如氮、氦或氩稀释的。氨/铵离子释放化合物或氨/铵离子源的体积百分比可以为1至50体积%,特别是3至40体积%,以及特别是5至30体积%。步骤B)的处理可以在15至600℃,优选20至350℃的温度下进行。
任选地,可以将质子介孔化和任选地经汽提的沸石在处理之前在温度高达650℃的氧化气氛如氧气、空气、亚硝气或/和惰性气氛如氮、氦或氩中进行干燥,然后原位煅烧。
处理可以在15至600℃的温度下进行,特别是20至350℃,特别是20至300℃。处理的持续时间可以为30分钟至24小时,特别是1至5小时。
任选地,煅烧步骤可以在之前进行,于氧化气氛如氧气、空气、亚硝气或/和惰性气氛如氮、氦或氩中(惰性气体是优选的)以0.1至5℃/分钟的升温速率将温度升高至650℃,优选高至550℃。煅烧可持续30分钟至12小时,特别是1至5小时。
可以使用分解成氨或形成氨的每一含N分子作为氨源。其中,有铵盐、氢氧化铵、胺、硝酸盐、亚硝酸盐、氮化物配体、脲、氮化物、氰氨、氨基甲酸盐/酯、酰胺、碳二亚胺、(聚)氨基酸、(聚)亚氨基酸、(聚)氨基酸盐、(聚)亚氨基酸盐、(聚)氨基羧酸盐/酯、(聚)亚氨基羧酸盐/酯或其混合物。
在液相中的处理可以通过在含有能够离解成铵离子或形成铵离子的化合物的水溶液中处理在步骤A)中获得的任选地经汽提的质子型介孔化沸石来进行。这种化合物或化合物的混合物可以是例如:铵盐、氢氧化铵、胺、硝酸盐、亚硝酸盐、氮化物配体、脲、氮化物、氰氨、氨基甲酸盐/酯、酰胺、碳二亚胺、(聚)氨基酸、(聚)亚氨基酸、(聚)氨基酸盐、(聚)亚氨基酸盐、(聚)氨基羧酸盐/酯、(聚)亚氨基羧酸盐/酯或其混合物等。铵释放化合物的重量百分比可以为1至80重量%,特别是3至70重量%,以及特别是5至60重量%。处理可以在10至150℃的温度下进行,优选15至120℃,最可能在20至100℃的温度下进行。处理的持续时间可以为10分钟至24小时,特别是30分钟至7小时。处理可以在机械或磁搅拌下,任选地在回流下进行多次、1至3次。
优选地,在液相中处理时,可任选地使用溶剂,在气相中处理期间,可以使用纯化合物或用惰性气体稀释的化合物。
任选地,可以将经改性沸石在处理之前在氧化气氛如氧气、空气、亚硝气或/和惰性气氛如氮、氦或氩中以0.1至5℃/分钟的升温速率升高至650℃的温度下干燥然后原位煅烧。
步骤B的最终介孔化沸石催化剂具有以下特征:
-结晶度为0至100%,优选0至98%,例如0至95%,高于在步骤A)中制备的材料;
-比表面积(BET)为100至850m2/g,例如150至800m2/g;
-外比表面积为20至500m2/g,例如30至400m2/g;
-总孔体积为0.2至0.9ml/g,例如0.25至0.6ml/g;
-微孔体积为0.01至0.5mL/g,特别是0.02至0.4mL/g;
-介孔体积(2至50nm的孔)为0.1至0.9mL/g,特别是0.12至0.8mL/g;
-与步骤A)制备的材料中的相比,八面体配位的Al的量较低;
-沸石骨架中原子Si/Al比为7至40,例如8至40;
-布朗斯特酸位点的量:0.1至0.6mmol NH3/g,例如0.15至0.5mmolNH3/g,高于在步骤A)中制备的材料。
因此,含有至少一种微孔网络和至少一种介孔网络的最终介孔化沸石催化剂表现出的原子骨架Si/Al比大于或等于2.3,特别是大于或等于3,更特别是大于或等于6,有利地为7至40,例如8至40。所述最终介孔化沸石非常有利地为加氢转化催化剂。
最终介孔化沸石催化剂含有比在步骤A)中制备的沸石即质子型介孔化沸石或具有未恢复的沸石结构的介孔化沸石少的骨架外铝。通常,含量降低至少5%,有利地至少10%,更优选至少20%,特别是骨架外铝的含量为5%以下,而骨架外铝用八面体配位的物质表示,并且特征为在27AlMAS NMR谱中具有约0ppm的峰。对于在步骤B)中制备的样品,八面体铝与四面体铝的比率可以为0至0.5,特别是0至0.4,更特别是0至0.3。
在步骤B)中制备的最终介孔化沸石有利地具有0.01至0.5mL/g,特别是0.02至0.4mL/g的微孔体积。
介孔体积(2至50nm的孔)处于0.1至0.9mL/g,特别是0.12至0.8mL/g。
所述方法可有利地包括最终介孔化沸石催化剂(步骤B))或质子型介孔化沸石(步骤A))利用金属的改性步骤和/或挤出步骤。
可以将所获得经改性沸石在步骤B)之前或之后挤出并根据已知方法(优选浸渍)利用金属改性。金属有利地为催化金属,优选选自第VIII族、第VIB族的化合物及其混合物。之前的步骤可以后接煅烧步骤。第VIB族对应于IUPAC元素周期表(2007年6月22日版)的第6族,包括Cr、Mo和W。第VIII(VIIIB)族对应于IUPAC元素周期表(2007年6月22日版)的第8、9和10族,包括Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt。
在挤出的过程中,所使用的粘合剂可选自氧化铝、二氧化硅、二氧化钛、二氧化硅-氧化铝、氧化镁及一种或更多种这些化合物的混合物。
浸渍可通过初湿浸渍(incipient wetness impregnation)或离子交换进行。通常,将活性金属前体溶解在水溶液或有机溶液中。然后将如此获得的溶液添加到经改性沸石中,添加的溶液体积等于或大于经改性沸石的孔体积。
初湿浸渍可以在10至100℃的温度下使用多种溶剂(优选水)进行。
作为选择,可以通过离子交换进行催化金属的引入,其通常通过本领域中已知的方法进行。但是,优选实施这种特定的浸渍法,因为其容易实施并且在某些情况下得到好的所追求结果。
在催化金属中,可以使用铂、钯、镍、钴、钨或钼,但是也可以使用其他过渡金属,只要它们在上述介质中可溶即可。
有利地,催化剂含有0.1重量%至10重量%的来自第VIII族的金属(例如,镍和/或钴和/或铂)和1重量%至25重量%的来自第VIB族的金属(例如,钼)。
利用催化金属的挤出步骤和改性步骤主要在步骤B)之后应用,但是,如之前提到的,其也可以在步骤A)之后且在步骤B)之前应用。
根据一些实施方案,使用质子型介孔化沸石在步骤A)之后且在步骤B)之前应用挤出步骤,接着进行步骤B),接着进行随后利用金属的改性步骤,所述金属选自第VIII族、第VIB族的化合物及其混合物,并且通常接着煅烧步骤。如之前提到的,改性步骤优选浸渍步骤。
本发明的另一个方面涉及烃原料加氢转化的方法,例如加氢裂解或加氢异构化,其中将待处理的原料与根据本发明的催化剂接触放置,所述催化剂为例如根据本发明方法制备的。
烃原料有利地选自轻质循环油、常压馏出物、真空馏出物如真空汽油、来自芳族提取单元的进料、来自基础润滑油的溶剂脱蜡的进料、来源于脱硫过程的馏出物、脱沥青油、植物油或动物油、由藻类或细菌产生的油,其单独地或在混合物中。原料还可以包括角鲨烷。
特别地,本发明的另一个方面涉及根据本发明获得的催化剂在加氢裂解过程中的用途。
表征方法
用于进行多种特征的测量的方法通常是标准技术。更具体地,在本发明上下文中使用以下技术:
i)通过X射线荧光光谱确定化学组成,特别是本体Si/Al原子比和Pt含量;
ii)通过X射线衍射(XRD)确定沸石的结构。使用0.02°的步长和1秒的时间/步,利用Cu Kα1射线在5至70°的Bruker D8Discover衍射仪上进行XRD。通过背景扣除法确定样品的相对结晶度;
iii)在液氮温度下在Micromeritics Tristar3000机器上进行氮吸附和脱附测量。在每次测量之前,将样品在300℃的氮下脱气840分钟。使用通过应用现有技术方法在77K记录的吸附等温线,通过氮的容积法确定质构特性,质构特性由外表面积(Sext)、微孔体积(Vmicro)和介孔体积(Vmeso)限定(Barett,E.P.;Joyner,L.G.;Halenda,P.P.J.Am.Chem.Soc.1951,73,373-380.Rouquerol,F.;Rouquerol,J.;Sing,K.Adsorptionbypowders and porous solids;Academic Press:San Diego,1999)。使用BET法(S.Brunauer,P.H.Emmett and E.Teller,J.Am.Chem.Soc.,1938,60,309)计算比表面积。通过t-plot法确定外比表面积和比孔体积,所述t-plot法为以相同化学组成和表面性质的多孔样品和无孔样品的等温吸附数据的比较为基础的经验半定量方法(K.S.W.Sing,Chem.and Ind.,(1968)1520);借助Harkins-Jura公式计算统计学厚度。t-plot法以相同化学组成和表面性质的多孔样品和无孔样品的等温吸附数据的比较为基础;
iv)在配备有4mm MAS探头的500MHz Bruker Avance光谱仪A500上获得27Al和29SiMAS NMR光谱。旋转速度为15000Hz。由光谱确定Al和Si物质的配位。将29Si MAS NMR光谱解卷积以计算沸石骨架中原子Si/Al比;
v)通过导电率监测脱附的氨,在100至650℃通过氨的程序升温脱附(TPD NH3)确定催化剂的酸度(Niwa,M.;Iwamoto,M.;Segawa,K.B.Chem.Soc.Jpn.1986,59);
vi)通过透射电子显微镜法和扫描电子显微镜法表征晶体的形状和大小以及特定晶体内的孔隙率。
附图简述
现在参照所附的非限制性附图描述本发明,其中:
-图1分别表示Pt交换的沸石Y(HY30,CBV760,Zeolyst Int.)、汽提前的介孔化沸石Y(HYA)、汽提后的介孔化沸石Y(HYA-st)、氨处理未汽提(HYA-NH3)和氨处理汽提(HYA-st-NH3)样品的X射线衍射图。
-图2分别示出了Pt交换的沸石Y(HY30,CBV760,Zeolyst Int.)、汽提前的介孔化沸石Y(HYA)、汽提后的介孔化沸石Y(HYA-st)、氨处理未汽提(HYA-NH3)和氨处理汽提(HYA-st-NH3)样品的孔径分布。
-图3分别示出了Pt交换的沸石Y(HY30,CBV760,Zeolyst Int.)、汽提前的介孔化沸石Y(HYA)、汽提后的介孔化沸石Y(HYA-st)、氨处理未汽提(HYA-NH3)和氨处理汽提(HYA-st-NH3)样品的27Al MAS NMR光谱。
-图4分别示出了Pt交换的沸石Y(HY30,CBV760,Zeolyst Int.)、汽提前的介孔化沸石Y(HYA)、汽提后的介孔化沸石Y(HYA-st)、氨处理未汽提(HYA-NH3)和氨处理汽提(HYA-st-NH3)样品的29Si MAS NMR光谱。
实施例
沸石Y(CBV760,Zeolyst Int.)被称为HY30。
HY30的特征在表2中给出,并且用图表示在图1至5中。
实施例1:介孔化沸石Y(HYA)及其汽提(HYA-st)的制备
对化合物HY30进行以下碱处理:
-在搅拌下于室温将HY30(200g)与0.05M NaOH水溶液(2500ml)接触放置15分钟,
-滤出所得产品并用水洗涤,
-将滤出的产品在80℃干燥12小时,
-将0.20M NH4NO3水溶液(2500ml)添加到干燥的产品中,并将其整体在搅拌下于室温静置5小时。该操作进行三次(trice)。
-将获得的产品利用水洗涤,
-然后将产品在空气流中于500℃煅烧4小时(温度梯度为1℃/分钟),以及然后
-回收HYA。
通过将HYA在300℃下汽提4小时(温度梯度为5℃/分钟)来制备HYA-st。
样品的特征在表2中给出,用图表示在图1至5中,并且在实施例3和4中讨论。
实施例2:将汽提前和后的介孔化沸石(HYA/HYA-st)利用气态NH
3
进行处理(HYA-
NH3/HYA-st-NH3)
将HYA和HYA-st分别进行以下处理:
-将样品(2g)放置在U形玻璃管中并在He流下于550℃煅烧(1℃/分钟)6小时
-然后,将样品在He流下冷却至150℃并稳定30分钟;
-将气体由纯He改变为He中的10体积%NH3;
-将样品在He中的10体积%NH3的流中冷却至室温并稳定30分钟;
-分别回收HYA-NH3和HYA-st-NH3。
样品的特征在表1和2中给出,用图表示在图1至5中,并且在实施例3和4中讨论。
实施例3:Pt浸渍前化合物HYA-st和HYA-st-NH3的表征
表1总结了HYA-st和HYA-st-NH3的多个特性。在NH3处理后,骨架原子Si/Al降低,表明一些骨架外Al重新插入到了骨架位置中。不同Al物质的分布表明在NH3处理后大部分五面体Al转变成了四面体骨架Al。Al重新插入到骨架位置中可能与沸石Y的结构的恢复有关。
总的来说,脱铝沸石Y通过碱处理进一步介孔化,部分地破坏了其沸石结构。在上述NH3处理后,由于骨架外Al重新插入到骨架位置中,材料的沸石部分得到恢复,而依然保留了介孔孔隙率。制备了具有恢复的沸石结构的介孔化沸石Y。介孔孔隙率和恢复的沸石结构的结合可导致对中间馏份的选择性和在多种反应中高活性的最优组合。
[表1]
HYA-st和HYA-st-NH3的特征结果的总结
a沸石骨架中的Si/Al原子
b来自27Al MAS NMR光谱的解卷积
实施例4:用于进一步催化测试的与Pt离子交换的化合物HY30、HYA、HYA-st、HYA-
NH3和HYA-st-NH3的表征
X射线衍射
图1分别示出了Pt交换的沸石Y(HY30,CBV760,Zeolyst Int.)、汽提前的介孔化沸石Y(HYA)、汽提后的介孔化沸石Y(HYA-st)、氨处理未汽提(HYA-NH3)和氨处理汽提(HYA-st-NH3)样品的X射线衍射图。
HYA在6.1、9.97、11.69和15.39度2θ附近显示出非常弱的反射,其相当于FAU结构的反射。反射弱且宽,可能是由于样品小的晶粒大小。在HYA-st的衍射图中没有可见的反射。在用气态氨处理后,在HYA-NH3和HYA-st-NH3衍射图中出现了FAU-典型的反射,表明长程沸石结构恢复。
NH3处理的样品的结晶度增加(表2)。
[表2]Pt修饰的HY30、HYA、HYA-st、HYA-NH3和HYA-st-NH3的特征结果的总结
a沸石骨架中的Si/AlbBET表面积;c外表面积
d总孔体积;e微孔体积;f介孔体积;g未确定.
氮吸附
样品HY30、HYA和HYA-st的BET表面积为285至300m2/g。在NH3处理后,相应样品的BET表面积增加,结果HYA-NH3为467m2/g,HYA-st-NH3为385m2/g。对于氨处理前的样品,BET表面积与外表面积一致,表明样品中不存在微孔。在氨处理后,微孔体积从0增加到HYA-NH3的0.07mL/g和HYA-st-NH3的0.04mL/g。
在氨处理后,介孔体积和总孔体积增加,HYA-NH3的达到0.32mL/g。图2示出了HYA、HYA-st、HYA-NH3和HYA-st-NH3的孔径分布。所有催化剂在介孔区表现出两个最大值。HYA和HYA-st具有约3nm和19nm的最大值,而氨处理的样品具有约3.1nm和16nm的最大值。因此,考虑到这些样品中存在微孔,其具有至少三峰孔隙率。
元素分析
27
Al MAS NMR光谱
图3分别示出了Pt交换HY30、汽提前的介孔化沸石Y(HYA)、汽提后的介孔化沸石Y(HYA-st)、氨处理未汽提(HYA-NH3)和氨处理汽提(HYA-st-NH3)样品的27Al MAS NMR光谱。
所有样品在约55ppm显示强峰,对应于四面体配位的Al物质。HY30、HYA和HYA-st包含少量八面体配位的Al,其由在约0ppm的峰表示。在利用氨处理后,八面体配位的Al消失,而55ppm的峰变得更显著。因为在氨处理的过程中未进行洗涤步骤,我们假设在利用氨处理后,八面体和五面体配位的Al重新插到了沸石的骨架位置中。
29
Si MAS NMR光谱
图4分别示出了Pt交换的HY30、汽提前的介孔化沸石Y(HYA)、汽提后的介孔化沸石Y(HYA-st)、氨处理未汽提(HYA-NH3)和氨处理汽提(HYA-st-NH3)样品的29Si MAS NM R光谱。所有光谱在-ll5至-90ppm之间显示出重叠峰,对应于与一个或两个Al原子配位的Si。HY30、HYA和HYA-st的光谱类似,而在利用氨处理后,较高ppm值处的峰增加。这表明Si(1Al)和可能还有Si(2Al)物质的相对量增加,表明重建了沸石结构。
氨的程序升温脱附(TPD-NH
3
)
HY30显示了0.36mmol NH3/g。在脱硅后(HYA),酸位点的量减少到0.33mmol NH3/g。汽提导致总酸度小幅增加到0.38mmol NH3/g。通过在气态氨存在下处理HYA和HYA-st,HYA的总酸度增加到0.46mmolNH3/g,HYA-st的停留在0.38mmol NH3/g。
透射和扫描电子显微镜法
实施例5:角鲨烷的催化加氢裂解
在角鲨烷(Alfa Aesar,98.8%)的加氢裂解中催化地测试含有0.5重量%Pt的样品HY30、HYA、HYA-st、HYA-NH3和HYA-st-NH3。使用塞流反应器在以下操作条件下进行测试:
H2压:20巴(表压)
温度:180至300℃
WHSV:3小时-1
H2/角鲨烷比:4mol/mol。
使用1mL催化剂(过筛到120至160um),在氢气流中于450℃(1℃/分钟)活化4小时来进行测试。
图5示出了所有样品的转化对温度的曲线
图6示出了在75%转化率下产品分布曲线(重量百分比对C-cuts),其基于通过在不同温度下所获得产品的模拟蒸馏获得的数据。
Claims (19)
1.一种用于制备包含介孔化沸石的催化剂的方法,包括以下步骤:
A)制备质子型介孔化沸石,其包含至少一种微孔网络和至少一种介孔网络,以及
B)在含有氨的气相中处理在步骤A)中获得的质子型介孔材料以将骨架外的八面体配位的Al原子重新插入到其中Al原子为四面体配位的骨架位置,并得到含有比在步骤A)中制备的沸石少的骨架外Al原子的催化剂,
其中根据步骤B)的所述处理在15℃至600℃的温度下进行。
2.根据权利要求1所述的方法,其中所述步骤A)包括以下步骤:
a)在磁性或机械搅拌下于室温使作为原料的母体沸石或包含其的复合材料悬浮在碱性pH的水溶液中,所述水溶液包含浓度为0.001M至2M的至少一种强碱,和/或无机或有机弱碱;
b)通过在搅拌下于室温添加浓度为0.005M至2M的至少一种酸来中和所述介质;
c)从所述液体中分离所获得的沸石,并任选地用溶剂洗涤;
d)任选地干燥经洗涤的沸石;
e)任选地对来自步骤c)的所述沸石或来自步骤d)的任选干燥的所述沸石进行至少一次离子交换处理;
f)任选地洗涤所述沸石;
g)煅烧所获得的沸石;以及
h)回收所述质子型介孔化沸石。
3.根据权利要求2所述的方法,其中所述强碱是NaOH或KOH,所述无机或有机弱碱是碳酸钠、柠檬酸钠或四烷基氢氧化铵,所述溶剂是极性溶剂。
4.根据权利要求2所述的方法,其中所述原料沸石或包含其的复合材料具有10至50的骨架原子Si/Al比。
5.根据权利要求2至4中任一项所述的方法,其中在步骤a)中所述碱性pH溶液/沸石的重量比为4至100。
6.根据权利要求2至4中任一项所述的方法,其中在步骤e)中离子交换溶液/介孔化沸石的重量比为3至75。
7.根据权利要求1至4中任一项所述的方法,其中根据步骤B)的处理在含有氨的源的气相中进行。
8.根据权利要求7所述的方法,其中所述氨的源的体积百分比为1体积%至50体积%。
9.根据权利要求7所述的方法,其中所述氨的源的体积百分比为3体积%至40体积%。
10.根据权利要求7所述的方法,其中所述氨的源的体积百分比为5体积%至30体积%。
11.根据权利要求7所述的方法,其中根据步骤B)的所述处理在20℃至350℃的温度下进行。
12.根据权利要求1至4中任一项所述的方法,包括利用金属对最终介孔化沸石催化剂或质子型介孔化沸石的改性步骤和/或挤出步骤,接着进行煅烧步骤,所述金属选自第VIII族、第VIB族的化合物及其混合物。
13.根据权利要求1至4中任一项所述的方法,包括使用所述质子型介孔化沸石在步骤A)之后且在步骤B)之前施用的挤出步骤,接着进行步骤B),然后进行利用金属的随后改性步骤,接着进行煅烧步骤,所述金属选自第VIII族、第VIB族的化合物及其混合物。
14.根据权利要求12所述的方法,其中第VIB族的金属选自Cr、Mo和W,第VIII族的金属选自Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt。
15.根据权利要求13所述的方法,其中第VIB族的金属选自Cr、Mo和W,第VIII族的金属选自Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt。
16.根据权利要求1至4中任一项所述的方法,其中在所述步骤A)之后且在所述步骤B)之前,所述方法包括利用水蒸气处理所述质子型介孔化沸石的步骤。
17.一种根据权利要求1至16中任一项的方法可获得的加氢转化催化剂,包含具有恢复的沸石结构的介孔化沸石,所述介孔化沸石含有至少一种微孔网络和至少一种介孔网络,具有大于或等于2.3的所述骨架中的原子Si/Al比,相对于不具有恢复的沸石结构的介孔化沸石表现出减少量的骨架外的铝。
18.一种用于烃原料的加氢转化的方法,其中将待处理的所述原料与根据权利要求1至16中任一项所述的方法获得的或由权利要求17所限定的催化剂接触。
19.一种通过实施根据权利要求1至16中任一项所述的方法获得的或由权利要求17所限定的催化剂在加氢转化工艺中的用途。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1159618A FR2981584B1 (fr) | 2011-10-24 | 2011-10-24 | Procede de preparation d'un catalyseur d'hydroconversion, catalyseur ainsi obtenu et son utilisation dans un procede d'hydroconversion |
FR1159618 | 2011-10-24 | ||
FR1162520 | 2011-12-29 | ||
FR1162520 | 2011-12-29 | ||
PCT/EP2012/071017 WO2013060705A2 (en) | 2011-10-24 | 2012-10-24 | Process for preparing a mesoporized catalyst, catalyst thus obtained and use thereof in a catalytic process |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103889572A CN103889572A (zh) | 2014-06-25 |
CN103889572B true CN103889572B (zh) | 2017-02-15 |
Family
ID=47143871
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201280051897.XA Expired - Fee Related CN103889572B (zh) | 2011-10-24 | 2012-10-24 | 用于制备介孔化催化剂的方法、由此获得的催化剂及其在催化工艺中的用途 |
Country Status (6)
Country | Link |
---|---|
US (2) | US10343150B2 (zh) |
EP (1) | EP2771116A2 (zh) |
KR (1) | KR101996326B1 (zh) |
CN (1) | CN103889572B (zh) |
CA (1) | CA2848343A1 (zh) |
WO (1) | WO2013060705A2 (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014181293A1 (en) * | 2013-05-10 | 2014-11-13 | Saudi Basic Industries Corporation | Modified zeolite catalyst and methods for producing and using same |
US10227539B2 (en) | 2014-06-09 | 2019-03-12 | Exxonmobil Research And Engineering Company | Noble metal hydrogenation catalysts and aromatic saturation methods |
KR101767658B1 (ko) | 2014-10-20 | 2017-08-14 | 주식회사 엘지화학 | 다공성 알루미노실리케이트를 포함하는 진공 단열재용 심재와 이를 구비한 진공 단열재 |
CA3029555C (en) * | 2016-06-30 | 2023-12-12 | Exxonmobil Research And Engineering Company | Noble metal hydrogenation catalysts and aromatic saturation methods |
CN108404916B (zh) * | 2018-05-04 | 2020-09-11 | 河南科技学院 | 一种金属钴催化剂的制备方法及其在催化丁二烯加氢反应中的应用 |
GB201815581D0 (en) * | 2018-09-25 | 2018-11-07 | Croda Int Plc | A zeolite and its use in fatty avid isomerisation |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3293192A (en) | 1965-08-23 | 1966-12-20 | Grace W R & Co | Zeolite z-14us and method of preparation thereof |
US3506400A (en) | 1966-05-25 | 1970-04-14 | Exxon Research Engineering Co | High silica crystalline zeolites and process for their preparation |
US3929672A (en) | 1971-10-20 | 1975-12-30 | Union Oil Co | Ammonia-stable Y zeolite compositions |
US4093560A (en) | 1976-05-20 | 1978-06-06 | Mobil Oil Corporation | Ultra high silicon-content zeolites and preparation thereof |
EP0082211B2 (en) | 1981-12-20 | 1993-07-28 | Union Carbide Corporation | Silicon substituted zeolite compositions and process for preparing same |
US5207892A (en) * | 1988-04-07 | 1993-05-04 | Uop | Hydrocarbon conversion process employing a modified form of zeolite Y |
US5069890A (en) | 1989-06-19 | 1991-12-03 | Texaco Inc. | Zeolite treating process |
ES2071419T3 (es) | 1991-06-21 | 1995-06-16 | Shell Int Research | Catalizador y procedimiento de hidrogenacion. |
TW223029B (zh) | 1991-08-16 | 1994-05-01 | Shell Internat Res Schappej B V | |
US5601798A (en) * | 1993-09-07 | 1997-02-11 | Pq Corporation | Process for preparing zeolite Y with increased mesopore volume |
US5952535A (en) * | 1996-09-18 | 1999-09-14 | Catalytica, Inc. | Selective catalytic conversion of a C9 aromatic feedstock containing substantial amounts of ethyl substituted aromatic components to a product rich in toluene and/or xylenes |
FR2940265B1 (fr) | 2008-12-22 | 2011-06-10 | Total Raffinage Marketing | Zeolithes y modifiees, leur procede de fabrication et leur utilisation |
-
2012
- 2012-10-24 EP EP12783173.3A patent/EP2771116A2/en not_active Withdrawn
- 2012-10-24 WO PCT/EP2012/071017 patent/WO2013060705A2/en active Application Filing
- 2012-10-24 CN CN201280051897.XA patent/CN103889572B/zh not_active Expired - Fee Related
- 2012-10-24 CA CA2848343A patent/CA2848343A1/en not_active Abandoned
- 2012-10-24 US US14/347,159 patent/US10343150B2/en not_active Expired - Fee Related
- 2012-10-24 KR KR1020147013939A patent/KR101996326B1/ko active IP Right Grant
-
2019
- 2019-05-13 US US16/410,084 patent/US20190262810A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
KR20140095510A (ko) | 2014-08-01 |
EP2771116A2 (en) | 2014-09-03 |
WO2013060705A3 (en) | 2013-08-22 |
US20140249344A1 (en) | 2014-09-04 |
CN103889572A (zh) | 2014-06-25 |
WO2013060705A2 (en) | 2013-05-02 |
US10343150B2 (en) | 2019-07-09 |
CA2848343A1 (en) | 2013-05-02 |
KR101996326B1 (ko) | 2019-07-04 |
US20190262810A1 (en) | 2019-08-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103889572B (zh) | 用于制备介孔化催化剂的方法、由此获得的催化剂及其在催化工艺中的用途 | |
KR101792229B1 (ko) | Na-Y 분자체, H-Y 분자체 및 이의 제조 방법과 수소첨가분해 촉매 및 수소첨가분해 방법 | |
CN108698842B (zh) | 对分子筛的受控碱处理 | |
CN105032478B (zh) | 一种用于f-t合成中间馏分油异构降凝的催化剂与其专用的核壳结构复合分子筛 | |
CN105712379B (zh) | 一种多级孔zsm-5分子筛的合成方法 | |
CN105621445B (zh) | 一种NaY型分子筛及其制备方法 | |
CN106430238B (zh) | 以植物纤维素为模板剂制备多级孔道sapo-11分子筛的方法及应用 | |
CN107670700A (zh) | 用于制备包含介孔的催化剂的方法、由此获得的催化剂及其在加氢转化方法中的用途 | |
CN101343559B (zh) | 加氢裂化催化剂及其制备方法 | |
CN101343561A (zh) | 一种加氢裂化催化剂及其制备方法 | |
CN107345153B (zh) | 一种生产低凝柴油的加氢裂化方法 | |
CN102050466A (zh) | 以硅铝为基质原位合成y型分子筛的方法 | |
CN107344105B (zh) | 加氢裂化催化剂及其制备方法 | |
CN107344102B (zh) | 一种加氢裂化催化剂及其制法 | |
JPH10236819A (ja) | 脱アルミニウムゼオライトim−5 | |
CN105713657A (zh) | 一种加氢裂化的方法 | |
CN107344120B (zh) | 加氢裂化催化剂载体及其制法 | |
CN116060106A (zh) | 一种Al-SBA-15/β核壳型复合分子筛及其制备方法和应用 | |
CN100384731C (zh) | 制备小晶粒β沸石的方法 | |
CN107344117B (zh) | 加氢裂化催化剂及其制法 | |
CN107345159B (zh) | 一种生产低凝柴油的加氢裂化方法 | |
CN105709845A (zh) | 加氢裂化催化剂载体及其制备方法 | |
CN107867699B (zh) | 含规整超大微孔的y沸石、制备方法及其用途 | |
CN105709844B (zh) | 加氢裂化催化剂载体及其制法 | |
CN107344116A (zh) | 加氢裂化催化剂及其制法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170215 Termination date: 20201024 |
|
CF01 | Termination of patent right due to non-payment of annual fee |