CN115212919A - Catalyst containing ZSM-5/MOR eutectic zeolite and preparation method and application thereof - Google Patents
Catalyst containing ZSM-5/MOR eutectic zeolite and preparation method and application thereof Download PDFInfo
- Publication number
- CN115212919A CN115212919A CN202110417765.5A CN202110417765A CN115212919A CN 115212919 A CN115212919 A CN 115212919A CN 202110417765 A CN202110417765 A CN 202110417765A CN 115212919 A CN115212919 A CN 115212919A
- Authority
- CN
- China
- Prior art keywords
- zsm
- zeolite
- catalyst
- eutectic zeolite
- mor
- 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.)
- Pending
Links
- 239000010457 zeolite Substances 0.000 title claims abstract description 130
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 129
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- 230000005496 eutectics Effects 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 45
- 239000002808 molecular sieve Substances 0.000 claims abstract description 21
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 17
- 150000002739 metals Chemical class 0.000 claims abstract description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 57
- 238000001035 drying Methods 0.000 claims description 48
- 239000012298 atmosphere Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 38
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 claims description 36
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 34
- 239000000843 powder Substances 0.000 claims description 33
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 32
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- 239000001257 hydrogen Substances 0.000 claims description 29
- 238000005470 impregnation Methods 0.000 claims description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 238000006317 isomerization reaction Methods 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 15
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 15
- 239000011609 ammonium molybdate Substances 0.000 claims description 15
- 229940010552 ammonium molybdate Drugs 0.000 claims description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- 238000005342 ion exchange Methods 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052762 osmium Inorganic materials 0.000 claims description 5
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 101150003085 Pdcl gene Proteins 0.000 claims description 2
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- -1 VIB group metals Chemical class 0.000 abstract description 2
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 80
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 36
- 238000002791 soaking Methods 0.000 description 25
- 238000000465 moulding Methods 0.000 description 14
- 241000219782 Sesbania Species 0.000 description 12
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 11
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- WGSMMQXDEYYZTB-UHFFFAOYSA-N 1,2,4,5-tetramethylbenzene Chemical compound CC1=CC(C)=C(C)C=C1C.CC1=CC(C)=C(C)C=C1C WGSMMQXDEYYZTB-UHFFFAOYSA-N 0.000 description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052680 mordenite Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WZEYZMKZKQPXSX-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1.CC1=CC(C)=CC(C)=C1 WZEYZMKZKQPXSX-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 241000219793 Trifolium Species 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- MEGFZVZIOCKTCS-UHFFFAOYSA-N 1,2,3,4-tetramethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1C.CC1=CC=C(C)C(C)=C1C MEGFZVZIOCKTCS-UHFFFAOYSA-N 0.000 description 1
- YGARNADKFWBJEX-UHFFFAOYSA-N 1,2,3,4-tetramethylbenzene;1,2,3,5-tetramethylbenzene Chemical compound CC1=CC(C)=C(C)C(C)=C1.CC1=CC=C(C)C(C)=C1C YGARNADKFWBJEX-UHFFFAOYSA-N 0.000 description 1
- PWJVWPGENSWJGR-UHFFFAOYSA-N CC1=CC(C)=C(C)C(C)=C1.CC1=CC(C)=C(C)C=C1C Chemical compound CC1=CC(C)=C(C)C(C)=C1.CC1=CC(C)=C(C)C=C1C PWJVWPGENSWJGR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000005201 tetramethylbenzenes Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- UAIHPMFLFVHDIN-UHFFFAOYSA-K trichloroosmium Chemical compound Cl[Os](Cl)Cl UAIHPMFLFVHDIN-UHFFFAOYSA-K 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 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
- B01J29/80—Mixtures of different zeolites
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
- C07C5/2732—Catalytic processes
- C07C5/2737—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
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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
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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
- C07C2529/80—Mixtures of different zeolites
Abstract
The invention discloses a catalyst containing ZSM-5/MOR eutectic zeolite, a preparation method and application thereof. The catalyst takes a molecular sieve as a carrier, VIII group metals of Pt, pd, rh, ir, os and Ru as active components and VIB group metals as auxiliary metals, wherein the content of the VIII group metals is 0.01-5.00 wt% of the total mass of the carrier by weight, and the content of the auxiliary metals is 0.05-5.00 wt% of the total mass of the carrier by weight. The catalyst has double functions of metal function and acid function, and the catalyst has simple preparation process, high catalytic activity and low carbon deposit amount.
Description
Technical Field
The invention relates to a catalyst and a preparation method and application thereof, in particular to a catalyst containing ZSM-5/MOR eutectic zeolite and a preparation method and application thereof, and the catalyst containing ZSM-5/MOR eutectic zeolite can be applied to a tetramethylbenzene isomerization device.
Background
Pyromellitic dianhydride (PMDA) can be obtained by oxidation, and can be polymerized with diamine compounds to prepare engineering plastic polyimide with good high temperature resistance, insulating property and radiation resistance, wherein the polyimide is an important material for high-tech industries such as microelectronics, aerospace, military industry and the like. In addition, durene can also be used as an intermediate of medicines and dyes, and the oxidation product of the durene dianhydride (PMDA) is also an important raw material of a high-quality plasticizer, a curing agent and a powder coating flatting agent, and the demand of the durene dianhydride is increasing day by day.
At present, the production methods of durene include three methods, namely a C10 heavy aromatic hydrocarbon separation method, durene isomerization, pseudocumene and methanol alkylation and the like. The C10 heavy aromatic hydrocarbon separation method mainly separates heavy aromatic hydrocarbons which are difficult to utilize into products such as 1# solvent oil, 2# solvent oil, 3# solvent oil and high-added-value durene through the processes of rectification, freezing crystallization, centrifugal separation and the like. The durene product is not highly pure, and usually contains a certain amount of durene and durene, and it is necessary to convert the durene further into durene. The isomerization of tetramethylbenzene is mainly to isomerize the partial tetramethylbenzene (1, 2,3, 5-tetramethylbenzene) and the continuous tetramethylbenzene (1, 2,3, 4-tetramethylbenzene) into durene under certain temperature, pressure, space velocity and hydrogen circulation atmosphere. Therefore, in both the C10 heavy aromatic separation method and the direct isomerization of durene to durene, durene and durene in the raw materials need to be converted into durene as much as possible in order to obtain the desired durene to the maximum extent. Therefore, it is necessary and critical to develop a catalyst suitable for the catalytic conversion of durene and durene, and the catalyst of the prior art generally has the defects and deficiencies of low conversion rate of durene, low selectivity and the like, and cannot meet the actual requirements of industrial production.
CN107649171A discloses a catalyst for continuous isomerization production of durene, which comprises the following components by weight percentage: 4-7wt% of nickel oxide or palladium oxide, 2-5wt% of cerium oxide, 2-3wt% of vanadium oxide, 3-7 wt% of copper oxide and manganese oxide, wherein: oxide of copper: manganese oxide = 1. The carrier is mordenite; n (SiO) 2 ):n(Al 2 O 3 )＝20-28，ω(Na 2 O) =1% -5%, and the specific surface area is 400-600m 2 .g -1 Crystal grains (100-300 nm). The catalyst is used for producing durene by continuous isomerization, the weight percentage of durene in reaction products reaches 43-45%, the selectivity reaches more than 91.2, the yield reaches more than 54.7%, and the catalyst has good industrial application prospect.
CN1370620A discloses a catalyst for preparing durene by isomerizing durene and a preparation method thereof, wherein the preparation method comprises the following steps: (1) Crushing a hydrogen type beta molecular sieve (H beta) with the silicon-aluminum ratio of 20-100 to 50-200 meshes; (2) Subjecting gamma-Al 2 O 3 Pulverizing to 50-200 mesh; (3) Pulverizing to 50-200 mesh beta and gamma-Al 2 O 3 Mixing at a certain proportion of 30-80% of H beta and gamma-Al 2 O 3 20 to 70 percent; (4) With 0.5-2N HNO 3 Using water solution or water glass solution as adhesive, stirring and kneading, and extruding to form bar catalyst with phi 1.5-3.0 mm; (5) Drying the extruded bar-shaped catalyst with the diameter of 1.5-3.0mm under the following drying conditions: the drying temperature is 90-370 ℃ for 1-6 hours; (6) Will bakeRoasting the dried bar-shaped catalyst with the diameter of 1.5-3.0mm under the roasting conditions that: the roasting temperature is 400-700 ℃, and the roasting time is 2-7 hours; and (7) cooling to obtain a catalyst finished product.
U.S. Pat. No. 3,36177 describes the treatment of HF and BF 3 Durene is produced from tetramethylbenzene isomers such as durene and durene by isomerization in a liquid phase in the presence of a catalyst. This process suffers from the use of extremely corrosive and dangerous catalytic systems.
CN105457669A discloses a catalyst for preparing durene by methanol deoxidation and a preparation method thereof. The invention is characterized in that a catalyst matrix adopts a nano NaZSM-5 molecular sieve, an HZSM-5 molecular sieve is obtained after alkali treatment and ammonium exchange, then the molecular sieve, a binder and a pore-forming agent are extruded and formed according to a certain mass ratio, and finally the finished catalyst is obtained through hydrothermal treatment. The catalyst has rich mesoporous structure at the positions of 3-5 nm, 7-20 nm and 20-40 nm, the total pore volume is 0.38-0.45 mL/g, and the specific surface area is 310-340 m 2 /g。
CN104334693B discloses a process and a catalyst for upgrading gasoline comprising durene (1, 2,4, 5-tetramethylbenzene) and pseudocumene, the process comprising the hydroisomerization of durene and pseudocumene contained in gasoline in the presence of a catalyst comprising a sulfurized base metal supported on an acidic support, thereby converting durene (1, 2,4, 5-tetramethylbenzene) to durene (1, 2,3, 5-tetramethylbenzene) and netetratoluene (1, 2,3, 4-tetramethylbenzene) and pseudocumene (1, 2, 4-trimethylbenzene) to mesitylene (1, 3, 5-trimethylbenzene). The preparation of mesitylene (1, 3, 5-trimethylbenzene) with a simultaneous reduction of durene (1, 2,4, 5-tetramethylbenzene) makes it possible to compensate for any octane loss resulting from the hydrogenation and dealkylation/disproportionation reactions of other aromatic and olefinic compounds in the gasoline and even to improve the octane number in the final product. The catalyst consists of nickel 1-5wt%, ZSM-5 50-70wt% and alumina adhesive 50-30 wt%.
Liu Bai Jun, zeng xian Jun, he Lin, zhao Sha and the like found that the ZSM-5/MOR composite molecular sieve catalyst has good catalytic action on the conversion of mixed C4 hydrocarbon to prepare olefin and aromatic hydrocarbon (the journal of catalytic science, 2008, 29 (9): 940-944).
CN101428233A adopts at least one element or oxide thereof in IB group or IIB group of the periodic table of elements loaded on ZSM-5/mordenite coexisting molecular sieve, ZSM-5/beta zeolite coexisting molecular sieve or ZSM-5/Y zeolite coexisting molecular sieve to form the catalyst, thereby solving the problems of high use temperature and low ethylene and propylene yield of the existing catalyst for preparing ethylene and propylene by catalytic cracking.
For tetramethylbenzene isomerization reaction, because various reactions such as methyl transfer, disproportionation, demethylation and the like are involved in the reaction process, how to properly modulate the acid center and the metal active center of the catalyst is a very important technical problem in improving the selectivity and yield of durene, reducing carbon deposition in the using process of the catalyst and prolonging the service life of the catalyst. The ZSM-5 molecular sieve has unique catalytic performance due to the special pore channel structure and excellent hydrothermal stability, but has general isomerization performance; the mordenite has a larger one-dimensional straight-hole channel and excellent isomerization performance, but is easy to coke and deactivate, and has poor stability. The ZSM-5/MOR eutectic zeolite is prepared by a certain method, which is beneficial to combining the advantages of two molecular sieves and improving the overall performance of the zeolite catalytic material, so that the zeolite catalytic material is better applied to the isomerization reaction process of tetramethylbenzene.
Disclosure of Invention
The invention aims to provide a catalyst containing ZSM-5/MOR eutectic zeolite, and a preparation method and application thereof.
In order to achieve the aim, the invention provides a catalyst containing ZSM-5/MOR eutectic zeolite, which is prepared by taking a molecular sieve as a carrier, a VIII group metal as an active component and a VIB group element as an auxiliary metal by an impregnation method, and comprises the following components in parts by mass: 10-70 wt% of ZSM-5/MOR eutectic zeolite, 0.01-5.00 wt% of VIII group metal, 0.05-5.00 wt% of VIB group element and 25-85 wt% of binder.
Preferably, the catalyst containing ZSM-5/MOR eutectic zeolite comprises the following components in mass fraction: 30-50 wt% of ZSM-5/MOR eutectic zeolite, 0.2-1 wt% of VIII group metal, 1.00-3.00 wt% of VIB group element and 45-70 wt% of binder.
The binder of the present invention is alumina.
The ZSM-5/MOR eutectic zeolite contains silicon and aluminum, and the molar ratio of the silicon to the aluminum is SiO 2 /Al 2 O 3 Greater than 10. Preferably, the ZSM-5/MOR eutectic zeolite contains silicon and aluminum, and the molar ratio of the silicon to the aluminum is SiO 2 /Al 2 O 3 10 to 45, and the most preferable mole ratio of Si to Al is SiO 2 /Al 2 O 3 Is 15 to 30.
At least 90% of the ZSM-5/MOR eutectic zeolite is hydrogen-type ZSM-5/MOR eutectic zeolite, and preferably, all the ZSM-5/MOR eutectic zeolite is hydrogen-type ZSM-5/MOR eutectic zeolite.
The group VIII metal of the present invention is at least one of platinum, palladium, ruthenium, rhodium, osmium, and iridium.
The group VIB element of the invention is at least one of Mo, W and Cr. The invention also provides a preparation method of the ZSM-5/MOR eutectic zeolite catalyst, which comprises the following steps: after dissolving the precursors of the VIII group metal and the VIB group element, loading the VIII group metal and the VIB group element precursors on a carrier formed by mixing ZSM-5/MOR eutectic zeolite and a binder by adopting an immersion method in sequence or simultaneously, filtering to remove redundant solution, drying at 120 ℃ for 6 hours, and roasting at 500 ℃ for 2-4 hours in an air atmosphere.
The VIII group metal is at least one of platinum, palladium, ruthenium, rhodium, osmium and iridium; the precursor of the metal of group VIII being water-soluble H 2 PtCl 6 ·6H 2 O、PdCl 2 、RuCl 3 ·H 2 O、RhCl 3 ·H 2 O、OsCl 3 And H 2 IrCl 6 ·6H 2 At least one of O.
The VIB group element is at least one of Mo, W and Cr; the precursor of the VIB group element is at least one of ammonium molybdate, ammonium metatungstate, sodium molybdate, ammonium molybdate, sodium tungstate, ammonium tungstate, sodium phosphomolybdate, ammonium phosphomolybdate, sodium phosphotungstate, ammonium dichromate, ammonium chromate, chromium nitrate and chromic acid.
Preferably, the precursor of the group VIB element is ammonium molybdate and/or ammonium metatungstate.
The ZSM-5/MOR eutectic zeolite can be prepared by the following method:
step (1): slowly adding an aqueous solution containing aluminum sulfate into water glass under the condition of stirring, adjusting the pH of the system to 7-10 by using inorganic acid and alkali, then adding a NaZSM-5 molecular sieve, uniformly stirring, transferring into a reaction kettle, crystallizing for 24-48 hours at the temperature of 200-300 ℃, performing suction filtration and washing after crystallization is finished, and drying at the temperature of 110-120 ℃ to obtain zeolite raw powder;
step (2): performing ion exchange on 1g of zeolite raw powder for 1-3 times on a boiling water bath by using 15-20 mL of 1mol/L ammonium chloride solution, wherein each time is 30-60 min, converting the zeolite raw powder into an ammonia type, and then roasting in a muffle furnace at 500-600 ℃ for 4-12h to obtain ZSM-5/MOR eutectic zeolite;
the preparation method of the catalyst containing the ZSM-5/MOR eutectic zeolite specifically comprises the following steps:
step (1): mixing 10-70 parts by weight of ZSM-5/MOR eutectic zeolite, 25-85 parts by weight of pseudo-boehmite, 0.5-5 parts by weight of sesbania powder and 0.5-5 parts by weight of nitric acid, kneading for 0.5-2 h, and carrying out extrusion forming to obtain a formed carrier;
step (2): drying the formed carrier at 110-140 ℃ for 2-4 hours, and roasting at 500-580 ℃ for 2-4 hours to obtain the carrier;
and (3): adding the carrier in the step (2) into a solution containing VIII group metals and a solution containing VIB group elements for dipping at room temperature for 4-12h with the dipping liquid-solid ratio of 1.0-3.0, and then filtering and drying;
and (4): activating for 4-12h in the air atmosphere at 500-600 ℃, and then reducing for 4-12h in the hydrogen atmosphere to obtain the catalyst containing ZSM-5/MOR eutectic zeolite.
The invention also provides an application of the catalyst containing ZSM-5/MOR eutectic zeolite in tetramethylbenzene isomerization reaction.
The reaction conditions of the tetramethylbenzene isomerization reaction of the invention are as follows: the reaction temperature is 350-500 ℃; the reaction pressure is 0.1MPa to 2MPa; the weight hourly space velocity of the feeding is 0.5 to 10h -1 (ii) a The molar ratio of hydrogen to oil is 1-10.
Preferably, the reaction conditions are: the reaction temperature is 350-450 ℃; the reaction pressure is 0.1MPa to 2MPa; the weight hourly space velocity of the feeding material is 0.5 to 5h -1 (ii) a The molar ratio of hydrogen to oil is 1-5.
Compared with the prior art, the invention has the following advantages:
the eutectic zeolite containing ZSM-5/MOR is a bifunctional catalyst with a metal function and an acid function, and the preparation method of the eutectic zeolite containing ZSM-5/MOR is simple. The catalyst containing ZSM-5/MOR eutectic zeolite and the reaction conditions can effectively play the role of the rich multi-level pore canals and the acid centers of the ZSM-5/MOR eutectic zeolite in cooperative catalysis, are well matched with metal centers, can be applied to tetramethylbenzene isomerization reaction, can effectively improve the conversion rate of the tetramethylbenzene and the durene, obtain higher yield of the durene and higher product liquid yield, and can also reduce the carbon deposition amount of the catalyst.
Detailed Description
The following examples illustrate the invention without in any way limiting its scope.
Aiming at the current situation and the deficiency that the conversion rate of the single zeolite catalyst is low in the tetramethylbenzene isomerization reaction, the invention adopts ZSM-5/MOR eutectic zeolite to effectively combine the ten-membered ring framework and the specific acid system of the ZSM-5 zeolite with the twelve-membered ring framework and the specific acid system of the MOR zeolite, thereby having higher catalytic activity in the tetramethylbenzene catalytic conversion reaction process. Compared with the mechanical mixing of ZSM-5 zeolite and MOR zeolite, the ZSM-5/MOR eutectic zeolite can effectively combine the framework structures and the acid systems of the two zeolites, so that the acid centers of the two molecular sieves are more matched, and the synergistic catalytic effect can be better exerted.
In the preparation process of the catalyst containing the ZSM-5/MOR eutectic zeolite, an excessive impregnation method is adopted to introduce a certain amount of auxiliary agent, so that the metal function of the ZSM-5/MOR eutectic zeolite and the activity matching of the metal function and the acid function of the ZSM-5/MOR eutectic zeolite are further modulated, the activity of the catalyst is effectively improved, the selectivity of the catalyst is improved, and the side reaction activity is inhibited.
The catalyst containing ZSM-5/MOR eutectic zeolite comprises the following components in percentage by mass:
(1) The preparation method of the ZSM-5/MOR eutectic zeolite comprises the following steps: slowly adding an aluminum sulfate aqueous solution into water glass according to a certain proportion under the condition of stirring, adjusting the pH of a system to 7-10 by using inorganic acid and alkali, then adding a NaZSM-5 molecular sieve, continuously stirring for a period of time, transferring into a reaction kettle, crystallizing for a period of time at a certain temperature, performing suction filtration and washing after crystallization is finished, and drying at a certain temperature to obtain zeolite raw powder; performing ion exchange on 1g of zeolite raw powder for 3 times, each time for 30-60 min, by using 15-20 mL of 1mol/L ammonium chloride solution in a boiling water bath, converting the zeolite raw powder into an ammonia type, and finally roasting the ammonia type in a muffle furnace at 500-600 ℃ for 4h to obtain hydrogen type eutectic zeolite; uniformly mixing and molding the calcined ZSM-5/MOR eutectic zeolite and pseudo-boehmite, and then calcining;
(2) Alumina is used as a binder; (3) The metal component is at least one of noble metals of platinum, palladium, ruthenium, rhodium, osmium and iridium; and (4) the assistant metal is molybdenum, chromium or tungsten.
The catalyst comprises the following components in percentage by mass: 10-70 wt% of ZSM-5/MOR eutectic zeolite, 0.01-5.00 wt% of VIII group metal, 0.05-5.00 wt% of VIB group auxiliary agent metal and 25-85 wt% of binder.
The specific preparation method of the catalyst containing ZSM-5/MOR eutectic zeolite comprises the following steps:
(1) Slowly adding an aluminum sulfate aqueous solution into water glass according to a certain proportion under the condition of stirring, adjusting the pH of a system to 7-10 by using inorganic acid and alkali, then adding a NaZSM-5 molecular sieve, continuously stirring for a period of time, transferring into a reaction kettle, crystallizing for a period of time at a certain temperature, performing suction filtration and washing after crystallization is finished, and drying at a certain temperature to obtain zeolite raw powder;
(2) Performing ion exchange on 1g of zeolite raw powder by using 15-20 mL of 1mol/L ammonium chloride solution in a boiling water bath for 3 times, each time for 30-60 min, converting the zeolite raw powder into an ammonia type, and finally roasting the ammonia type in a muffle furnace at 500-600 ℃ for 4h to obtain hydrogen type eutectic zeolite;
(3) Uniformly mixing the roasted ZSM-5/MOR eutectic zeolite with pseudo-boehmite, and molding after uniform mixing, wherein the shape of the carrier used by the invention can be spherical, columnar, flaky, clover type and tetrafoil type, the columnar and clover type are preferred in the invention, and the columnar shape is more preferred, and roasting is carried out after molding;
(4) Adding the formed carrier into a solution containing VIII group metal elements and a solution containing VIB group elements for dipping at room temperature for 4-12h, wherein the solid-to-solid ratio of the dipping solution is 1.0-3.0, and then filtering and drying;
(5) Activating for 4-12h in air atmosphere at 500-600 deg.C, and reducing for 4-12h in hydrogen atmosphere.
The invention also relates to a method for applying the catalyst to isomerization reaction of C10 reformed heavy aromatics, which takes the C10 reformed heavy aromatics as raw materials and has the following operating conditions: the reaction temperature is 350-500 ℃; the reaction pressure is 0.1MPa to 2MPa; the weight hourly space velocity of the feeding is 0.5 to 10h -1 (ii) a The molar ratio of hydrogen to oil is 1-10. Preferably, the reaction conditions are: the reaction temperature is 350-450 ℃; the reaction pressure is 0.1MPa to 2MPa; the weight hourly space velocity of the feeding is 0.5 to 5h -1 (ii) a The molar ratio of hydrogen to oil is 1-5.
The catalyst containing the ZSM-5/MOR eutectic zeolite is prepared by adopting an impregnation method, and the liquid-solid ratio of impregnation liquid to a carrier is not less than 1.0, preferably 1.0-3.0, and most preferably 1.5-2 during impregnation; the impregnation solution is completely absorbed by the support. In order to obtain complete absorption and uniform distribution of the active ingredient by the support, the impregnation temperature is between 1 and 50 ℃ and preferably between 5 and 25 ℃. Because the adsorption speed of the active component metal on the surface of the carrier is greater than the penetration speed of the active component metal into the carrier, competitive adsorbents are selected in the preparation process of the catalyst to further uniformly distribute the active component metal, and the alternative competitive adsorbents are preferably acids, such as citric acid, hydrochloric acid, nitric acid and chloroacetic acid, and are preferably hydrochloric acid. After impregnation, the catalyst is taken out, dried under the conditions of normal pressure and the temperature of 100-200 ℃, preferably the temperature is 110-150 ℃, and then roasted, so that most of the metal components in the catalyst are converted into corresponding oxides, and the roasting time is preferably 0.5-10 hours. After roasting, the catalyst is reduced in a hydrogen atmosphere at 400-650 deg.C, preferably 450-550 deg.C.
Example 1
ZSM-5/MOR eutectic zeolite is prepared.
(1) Slowly adding an aluminum sulfate-containing aqueous solution into water glass under the condition of stirring, adjusting the pH of a system to 7-10 by using inorganic acid-base, adding a NaZSM-5 molecular sieve, continuously stirring for 1-4h, transferring into a reaction kettle, crystallizing for 24-48 h at 200-300 ℃, performing suction filtration and washing after crystallization is finished, and drying at 110-120 ℃ to obtain zeolite raw powder with different silica-alumina ratios (according to the feed ratio, the silica-alumina ratio is SiO) 2 /Al 2 O 3 Between 10 and 45, 13, 21, 35, 42, respectively);
(2) Performing ion exchange on 1g of zeolite raw powder for 3 times, each time for 30-60 min, by using 15-20 mL of 1mol/L ammonium chloride solution in a boiling water bath, converting the zeolite raw powder into an ammonia type, and finally roasting the ammonia type in a muffle furnace at 500-600 ℃ for 4h to obtain ZSM-5/MOR eutectic zeolite;
example 2
Preparation of eutectic zeolite (SiO) containing 30.0wt% of ZSM-5/MOR 2 /Al 2 O 3 = 21), 68.5wt% alumina, 0.2wt% platinum and 1.3wt% mo, the specific preparation method is as follows:
silicon to aluminum SiO prepared by the method of example 1 2 /Al 2 O 3 The 21 ZSM-5/MOR eutectic zeolite is fully mixed with pseudo-boehmite, then 1% nitric acid solution, 1% citric acid and 3% sesbania powder are added for extrusion molding, after molding, natural drying is carried out for 6h at room temperature, drying is carried out for 4h at 120 ℃, and then roasting is carried out for 4h in air at 500 ℃ to obtain the molded catalyst carrier. Vacuum soaking the obtained carrier in solution containing chloroplatinic acid and ammonium molybdate for 4h with a soaking liquid-solid ratio of 1.1, drying at 120 deg.C for 12h, calcining at 500 deg.C in air atmosphere for 4h, and hydrogen at 500 deg.CAnd reducing for 4 hours in a gas atmosphere to prepare the catalyst A.
Example 3
Preparation of eutectic zeolite (SiO) containing 34.5wt% of ZSM-5/MOR 2 /Al 2 O 3 = 13), 60.5wt% alumina, 0.5wt% platinum and 4.5wt% mo catalyst B was prepared specifically as follows:
silicon to aluminum SiO prepared by the method of example 1 2 /Al 2 O 3 The 13 ZSM-5/MOR eutectic zeolite is fully mixed with pseudo-boehmite, then 1 percent nitric acid solution, 1 percent citric acid and 3 percent sesbania powder are added for extrusion molding, after molding, the mixture is naturally dried for 6 hours at room temperature, dried for 3 hours at the temperature of 130 ℃, and then roasted for 3 hours in the air at the temperature of 550 ℃ to obtain the molded catalyst carrier. And (2) carrying out vacuum impregnation on the obtained carrier in a solution containing ammonium molybdate for 4h, wherein the impregnation liquid-solid ratio is 1.0, drying at the temperature of 120 ℃ for 12h after impregnation, roasting at the temperature of 500 ℃ in the air atmosphere for 4h, then carrying out vacuum impregnation in a solution containing chloroplatinic acid for 4h, wherein the impregnation liquid-solid ratio is 1.4, drying at the temperature of 120 ℃ for 12h after impregnation, roasting at the temperature of 500 ℃ in the air atmosphere for 4h, and finally reducing at the temperature of 500 ℃ in the hydrogen atmosphere for 4h to prepare the catalyst C.
Example 4
Preparation of eutectic zeolite (SiO) containing 51.0wt% of ZSM-5/MOR 2 /Al 2 O 3 = 42), 43.7wt% alumina, 0.3wt% platinum and 5.0wt% w catalyst D, the specific preparation method is as follows:
silicon to aluminum SiO prepared by the method of example 1 2 /Al 2 O 3 The 42 ZSM-5/MOR eutectic zeolite is fully mixed with pseudo-boehmite, then 1 percent nitric acid solution, 1 percent citric acid and 3 percent sesbania powder are added for extrusion molding, after molding, the mixture is naturally dried for 6 hours at room temperature, dried for 4 hours at the temperature of 110 ℃, and then roasted for 2 hours in air at the temperature of 560 ℃ to obtain the molded catalyst carrier. Vacuum-soaking the obtained carrier in a solution containing chloroplatinic acid for 4h with a soaking liquid-solid ratio of 1.0, drying at 120 deg.C for 12h, calcining at 500 deg.C in air atmosphere for 4h, vacuum-soaking in a solution containing ammonium metatungstate for 4h with a soaking liquid-solid ratio of 1.8, soaking at 120 deg.CDrying for 12h, roasting for 4h at 600 ℃ in an air atmosphere, and finally reducing for 6h at 500 ℃ in a hydrogen atmosphere to prepare the catalyst D.
Example 5
Preparation of eutectic zeolite (SiO) containing 69.0wt% of ZSM-5/MOR 2 /Al 2 O 3 = 35), 27.0wt% alumina, 0.1wt% platinum and 3.9wt% mo, the specific preparation method is as follows:
silicon to aluminum SiO prepared by the method of example 1 2 /Al 2 O 3 The method comprises the following steps of fully mixing 35 ZSM-5/MOR eutectic zeolite with pseudo-boehmite, adding a 1% nitric acid solution, 1% citric acid and 3% sesbania powder, extruding into strips, forming, naturally drying at room temperature for 6 hours after forming, drying at 140 ℃ for 2 hours, and roasting in air at 570 ℃ for 2 hours to obtain the formed catalyst carrier. And (2) vacuum-soaking the obtained carrier in a solution containing chloroplatinic acid for 4h, wherein the solid-to-solid ratio of the soaking solution is 1.5, drying at 120 ℃ for 12h after soaking, roasting at 500 ℃ in an air atmosphere for 4h, then vacuum-soaking in a solution containing ammonium molybdate for 4h, wherein the solid-to-solid ratio of the soaking solution is 1.0, drying at 120 ℃ for 12h after soaking, roasting at 530 ℃ in an air atmosphere for 8h, and finally reducing at 500 ℃ in a hydrogen atmosphere for 7h to prepare the catalyst E.
Example 6
Preparation of eutectic zeolite (SiO) containing 69.0wt% of ZSM-5/MOR 2 /Al 2 O 3 = 35), 26.0wt% alumina, 0.1wt% platinum and 3.9wt% Mo, 1.0wt% Cr catalyst F, the specific preparation method is as follows:
silicon to aluminum SiO prepared by the method of example 1 2 /Al 2 O 3 The method comprises the following steps of fully mixing 35 ZSM-5/MOR eutectic zeolite with pseudo-boehmite, adding 1% nitric acid solution, 1% citric acid and 3% sesbania powder, extruding into strips, forming, naturally drying at room temperature for 5 hours after forming, drying at 125 ℃ for 2 hours, and roasting at 555 ℃ in air for 2 hours to obtain the formed catalyst carrier. Vacuum-soaking the obtained carrier in a solution containing chloroplatinic acid for 4h with a soaking liquid-solid ratio of 1.72, drying at 125 deg.C for 4h, calcining at 580 deg.C in air atmosphere for 1h, and adding ammonium molybdate,And (2) carrying out vacuum impregnation in an ammonium dichromate solution for 4h with an impregnation liquid-solid ratio of 1.35, drying at 120 ℃ for 12h after impregnation, roasting at 540 ℃ in an air atmosphere for 4h, and finally reducing at 500 ℃ in a hydrogen atmosphere for 10h to prepare the catalyst F.
Example 7
Preparation of eutectic zeolite (SiO) containing 65.0wt% of ZSM-5/MOR 2 /Al 2 O 3 = 13), 30.0wt% alumina, 0.5wt% platinum and 2.4wt% cr, 2.1wt% catalyst G of w, the specific preparation method is as follows:
silicon to aluminum SiO prepared by the method of example 1 2 /Al 2 O 3 The 13 ZSM-5/MOR eutectic zeolite is fully mixed with pseudo-boehmite, then 1 percent nitric acid solution, 1 percent citric acid and 3 percent sesbania powder are added for strip extrusion molding, after molding, natural drying is carried out for 6 hours at room temperature, drying is carried out for 9 hours at the temperature of 133 ℃, and then roasting is carried out for 2 hours in air at the temperature of 545 ℃ to obtain the molded catalyst carrier. Vacuum dipping the obtained carrier in a solution containing chloroplatinic acid for 4h, wherein the dipping liquid-solid ratio is 1.5, drying at 120 ℃ for 6h after dipping, roasting at 575 ℃ in an air atmosphere for 7h, then vacuum dipping in a solution containing ammonium dichromate and ammonium metatungstate for 4h, wherein the dipping liquid-solid ratio is 1.2, drying at 120 ℃ for 12h after dipping, roasting at 545 ℃ in an air atmosphere for 8h, and finally reducing at 550 ℃ in a hydrogen atmosphere for 6h to prepare the catalyst G.
Example 8
Preparation of eutectic zeolite (SiO) containing 67.0wt% of ZSM-5/MOR 2 /Al 2 O 3 = 35), 29.0wt% alumina, 0.5wt% palladium and 1.9wt% Mo, 1.6wt% catalyst H of W, the specific preparation method is as follows:
silicon to aluminum SiO prepared by the method of example 1 2 /Al 2 O 3 The 35 ZSM-5/MOR eutectic zeolite is fully mixed with pseudo-boehmite, then 1% nitric acid solution, 1% citric acid and 3% sesbania powder are added for extrusion molding, after molding, natural drying is carried out for 6h at room temperature, drying is carried out for 2h at 140 ℃, and then roasting is carried out for 2h in air at 570 ℃ to obtain the molded catalyst carrier. Vacuum-impregnating the obtained carrier in a solution containing palladium chloride for 4h, and impregnatingThe liquid-solid ratio is 1.5, the catalyst H is dried for 12 hours at the temperature of 120 ℃ after impregnation, then is roasted for 4 hours at the temperature of 500 ℃ in the air atmosphere, then is vacuum-impregnated for 4 hours in the solution containing ammonium metatungstate and ammonium molybdate, the impregnation liquid-solid ratio is 1.0, the catalyst H is dried for 12 hours at the temperature of 120 ℃ after impregnation, then is roasted for 10 hours at the temperature of 520 ℃ in the air atmosphere, and finally is reduced for 8 hours at the temperature of 525 ℃ in the hydrogen atmosphere to prepare the catalyst H.
Example 9
Preparation of eutectic zeolite (SiO) containing 34.5wt% of ZSM-5/MOR 2 /Al 2 O 3 = 13), 60.5wt% alumina, 0.5wt% platinum and 4.5wt% mo catalyst B was prepared specifically as follows:
silicon to aluminum SiO prepared by the method of example 1 2 /Al 2 O 3 The 13 ZSM-5/MOR eutectic zeolite is fully mixed with pseudo-boehmite, then 1% nitric acid solution, 1% citric acid and 3% sesbania powder are added for strip extrusion molding, after molding, natural drying is carried out for 6 hours at room temperature, drying is carried out for 3 hours at the temperature of 130 ℃, and then roasting is carried out for 3 hours in air at the temperature of 550 ℃ to obtain the molded catalyst carrier. And (2) vacuum-soaking the obtained carrier in a solution containing ammonium molybdate for 4 hours, wherein the solid-to-solid ratio of the soaking solution is 1.0, drying at the temperature of 120 ℃ for 12 hours after soaking, roasting at the temperature of 500 ℃ in an air atmosphere for 4 hours, then vacuum-soaking in a solution containing ruthenium trichloride for 4 hours, wherein the solid-to-solid ratio of the soaking solution is 1.4, drying at the temperature of 120 ℃ for 12 hours after soaking, roasting at the temperature of 500 ℃ in an air atmosphere for 4 hours, and finally reducing at the temperature of 500 ℃ in a hydrogen atmosphere for 4 hours to prepare the catalyst I.
Example 10
Preparation of eutectic zeolite (SiO) containing 32.3wt% ZSM-5/MOR 2 /Al 2 O 3 = 35), 62.7wt% alumina, 0.5wt% platinum and 4.5wt% mo, the specific preparation method is as follows:
silicon to aluminum SiO prepared by the method of example 1 2 /Al 2 O 3 The 13 ZSM-5/MOR eutectic zeolite is fully mixed with pseudo-boehmite, 1.2 percent nitric acid solution, 1.5 percent citric acid and 3 percent sesbania powder are added for extrusion molding, after molding, natural drying is carried out for 6 hours at room temperature, drying is carried out for 3 hours at 130 ℃, then roasting is carried out for 3 hours in air at 550 ℃ to obtain molded productThe catalyst carrier of (1). The obtained carrier is soaked in a solution containing ammonium molybdate in vacuum for 4 hours, the solid-to-liquid ratio of the soaking solution is 1.1, the carrier is dried for 12 hours at the temperature of 120 ℃ after being soaked, then the carrier is roasted for 4 hours at the temperature of 510 ℃ in the air atmosphere, then the carrier is soaked in a methanol solution containing rhodium trichloride in vacuum for 4 hours, the solid-to-liquid ratio of the soaking solution is 1.3, the carrier is dried for 12 hours at the temperature of 120 ℃ after being soaked, then the carrier is roasted for 4 hours at the temperature of 500 ℃ in the air atmosphere, and finally the carrier is reduced for 4 hours at the temperature of 506 ℃ in the hydrogen atmosphere to prepare the catalyst J.
Example 11
Preparation of eutectic zeolite (SiO) containing 31.6wt% of ZSM-5/MOR 2 /Al 2 O 3 = 21), 63.3wt% alumina, 0.5wt% platinum and 4.6wt% mo, the specific preparation method is as follows:
silicon to aluminum SiO prepared by the method of example 1 2 /Al 2 O 3 The 13 ZSM-5/MOR eutectic zeolite is fully mixed with pseudo-boehmite, then 1% nitric acid solution, 1% citric acid and 3% sesbania powder are added for strip extrusion molding, after molding, natural drying is carried out for 6 hours at room temperature, drying is carried out for 3 hours at the temperature of 130 ℃, and then roasting is carried out for 3 hours in air at the temperature of 550 ℃ to obtain the molded catalyst carrier. And (2) vacuum-impregnating the obtained carrier in a solution containing ammonium molybdate for 4 hours, wherein the impregnation liquid-solid ratio is 1.3, drying at the temperature of 120 ℃ for 12 hours after impregnation, roasting at the temperature of 500 ℃ in an air atmosphere for 4 hours, then vacuum-impregnating in an aqueous solution containing osmium trichloride for 4 hours, wherein the impregnation liquid-solid ratio is 1.4, drying at the temperature of 120 ℃ for 12 hours after impregnation, roasting at the temperature of 500 ℃ in an air atmosphere for 4 hours, and finally reducing at the temperature of 500 ℃ in a hydrogen atmosphere for 4 hours to prepare the catalyst K.
Example 12
Preparation of eutectic zeolite (SiO) containing 32.6wt% of ZSM-5/MOR 2 /Al 2 O 3 = 42), 62.4wt% alumina, 0.5wt% platinum and 4.5wt% mo catalyst B was prepared specifically as follows:
silicon to aluminum SiO prepared by the method of example 1 2 /Al 2 O 3 13 of ZSM-5/MOR eutectic zeolite is fully mixed with pseudo-boehmite, 1 percent of nitric acid solution, 1 percent of citric acid and 3 percent of sesbania powder are added for strip extrusion forming, and the mixture is naturally dried for 6 hours at room temperature after being formedThereafter, the dried catalyst carrier was dried at a temperature of 130 ℃ for 3 hours, and then calcined in air at 550 ℃ for 3 hours to obtain a molded catalyst carrier. The obtained carrier is soaked in a solution containing ammonium molybdate in vacuum for 4 hours, the solid-to-liquid ratio of the soaking solution is 1.0, the carrier is dried at the temperature of 120 ℃ for 12 hours after being soaked, then the carrier is roasted at the temperature of 500 ℃ for 4 hours in the air atmosphere, then the carrier is soaked in an aqueous solution containing chloroiridic acid in vacuum for 4 hours, the solid-to-liquid ratio of the soaking solution is 1.5, the carrier is dried at the temperature of 120 ℃ for 12 hours after being soaked, then the carrier is roasted at the temperature of 500 ℃ for 4 hours in the air atmosphere, and finally the carrier is reduced for 4 hours in the hydrogen atmosphere at the temperature of 500 ℃ to prepare the catalyst L.
Comparative example 1
Using the ZSM-5/MOR eutectic zeolite prepared in example 1, extrusion, molding, drying, calcination and reduction were carried out in the same manner as in example 4, without adding the aid W during impregnation, to prepare a eutectic zeolite (SiO) containing 51.0wt% of ZSM-5/MOR eutectic zeolite 2 /Al 2 O 3 = 42), 48.7wt% alumina, 0.3wt% platinum catalyst M.
Comparative example 2
Adopting the NaZSM-5 molecular sieve in the embodiment 1, performing ion exchange on 1g of zeolite raw powder by using 15-20 mL of 1mol/L ammonium chloride solution on boiling water bath for 1-3 times, each time for 30-60 min, converting the zeolite raw powder into an ammonia type, and finally roasting the ammonia type in a muffle furnace at 500-600 ℃ for 4-12h to obtain hydrogen type ZSM-5 zeolite; the catalyst N was prepared by carrying out the processes of extrusion, molding, drying, calcination and reduction and the processes of noble metal and auxiliary metal in accordance with the preparation method of example 4.
Comparative example 3
Performing ion exchange on 1g of zeolite raw powder by using 15-20 mL of 1mol/L ammonium chloride solution for 1-3 times in boiling water bath for 30-60 min each time by using a NaMOR-5 molecular sieve, converting the zeolite raw powder into an ammonia type, and finally roasting the ammonia type in a muffle furnace at 500-600 ℃ for 4-12h to obtain hydrogen type ZSM-5 zeolite; the catalyst O was prepared by performing the processes of extruding, molding, drying, calcining and reducing, and the process of performing the noble metal and the auxiliary metal according to the preparation method of comparative example 2.
Test examples
This test example was conducted to test the catalysts prepared in examples 1 to 12 and comparative examples 1 to 3 for their catalytic activity and isomerization selectivity when used for catalyzing the reaction for the isomerization of tetramethylbenzene.
The performance of the catalysts A-L of the examples and the catalysts M-O of the comparative examples was evaluated using a fixed bed evaluation unit, and the feedstock was reformed into heavy aromatics using an aromatics complex having the composition shown in Table 1, under the preferred operating conditions of the present invention: the reaction temperature is 350-450 ℃; the reaction pressure is 0.1MPa to 2MPa; the weight hourly space velocity of the feeding is 0.5 to 5h -1 (ii) a The results of the evaluation were shown in Table 2, with the hydrogen/oil molar ratio being 1 to 5.
TABLE 1 reformed heavy aromatics composition for evaluation
Partial and continuous tetramethylbenzene conversion rate = (partial and continuous tetramethylbenzene content in raw material-partial and continuous tetramethylbenzene content in product)
The content of tetradurene in the raw material is multiplied by the liquid yield of the reaction product is multiplied by 100 percent
Durene yield = durene content in product × liquid yield of reaction product × 100%
TABLE 2
The evaluation results shown in Table 2 show that under the same reaction conditions, the catalysts A-L containing the ZSM-5/MOR eutectic zeolite have higher durene selectivity while keeping higher durene and durene conversion activities, the percentage content of durene in the reaction product is obviously improved compared with that of the comparative catalyst M-O, and the carbon deposition amount after 500h of reaction is also obviously lower than that of the comparative catalyst.
Under the same reaction condition, compared with the catalyst without the addition of the auxiliary metal, the catalyst with the addition of the auxiliary metal W or Mo has the advantages that the tetramethylbenzene conversion rate and the selectivity are obviously improved, and the carbon deposition amount of the catalyst with the addition of the auxiliary metal W or Mo after reaction for 500 hours is also obviously lower than that of the catalyst without the addition of the auxiliary metal W or Mo.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (19)
1. The catalyst containing the ZSM-5/MOR eutectic zeolite is characterized by being prepared by taking a molecular sieve as a carrier, a VIII group metal as an active component and a VIB group element as an auxiliary metal by adopting an impregnation method, and comprising the following components in parts by mass: 10-70 wt% of ZSM-5/MOR eutectic zeolite, 0.01-5.00 wt% of VIII group metal, 0.05-5.00 wt% of VIB group element and 25-85 wt% of binder.
2. The ZSM-5/MOR eutectic zeolite-containing catalyst of claim 1, wherein the ZSM-5/MOR eutectic zeolite-containing catalyst comprises the following mass fraction of components: 30-50 wt% of ZSM-5/MOR eutectic zeolite, 0.2-1 wt% of VIII group metal, 1.00-3.00 wt% of VIB group element and 45-70 wt% of binder.
3. The catalyst containing ZSM-5/MOR eutectic zeolite of claim 1, wherein the binder is alumina.
4. The catalyst containing ZSM-5/MOR eutectic zeolite of claim 1, wherein the ZSM-5/MOR eutectic zeolite is characterized in thatThe zeolite is hydrogen type ZSM-5/MOR eutectic zeolite; the ZSM-5/MOR eutectic zeolite contains silicon and aluminum, wherein the ratio of silicon to aluminum is SiO 2 /Al 2 O 3 Greater than 10.
5. The ZSM-5/MOR eutectic zeolite-containing catalyst of claim 4, wherein the silica alumina is SiO to SiO 2 /Al 2 O 3 Is 10 to 45.
6. The ZSM-5/MOR eutectic zeolite-containing catalyst of claim 5, wherein the silica-alumina is SiO to SiO 2 /Al 2 O 3 Is 15 to 30.
7. The ZSM-5/MOR eutectic zeolite-containing catalyst of claim 1, wherein the group VIII metal is at least one of platinum, palladium, ruthenium, rhodium, osmium, and iridium.
8. The catalyst containing ZSM-5/MOR eutectic zeolite of claim 1, wherein the group VIB element is at least one of Mo, W and Cr.
9. A process for the preparation of a catalyst containing ZSM-5/MOR eutectic zeolite according to any of claims 1-8, comprising: dissolving precursors of VIII group metals and VIB group elements, loading the VIII group metals and the VIB group elements on a carrier formed by mixing ZSM-5/MOR eutectic zeolite and a binder by adopting an impregnation method sequentially or simultaneously, filtering to remove redundant solution, drying at 120 ℃ for 6 hours, and roasting at 500 ℃ for 2-4 hours in an air atmosphere.
10. The method of preparing a catalyst containing ZSM-5/MOR eutectic zeolite as claimed in claim 9, wherein the group VIII metal is at least one of platinum, palladium, ruthenium, rhodium, osmium and iridium; the precursor of the VIII group metal is water-soluble H 2 PtCl 6 ·6H 2 O、PdCl 2 、RuCl 3 ·H 2 O、RhCl 3 ·H 2 O、OsCl 3 And H 2 IrCl 6 ·6H 2 At least one of O.
11. The method of preparing a catalyst containing ZSM-5/MOR eutectic zeolite according to claim 9, wherein the group VIB element is at least one of Mo, W and Cr; the precursor of the VIB group element is at least one of ammonium molybdate, ammonium metatungstate, sodium molybdate, ammonium molybdate, sodium tungstate, ammonium tungstate, sodium phosphomolybdate, ammonium phosphomolybdate, sodium phosphotungstate, ammonium dichromate, ammonium chromate, chromium nitrate and dichromate.
12. The method of claim 11, wherein the precursor of the group VIB element is ammonium molybdate and/or ammonium metatungstate.
13. The method of preparing a catalyst containing ZSM-5/MOR eutectic zeolite as claimed in claim 9, wherein the ZSM-5/MOR eutectic zeolite is prepared by:
step (1): slowly adding an aqueous solution containing aluminum sulfate into water glass under the condition of stirring, adjusting the pH of the system to 7-10 by using inorganic acid and alkali, then adding a NaZSM-5 molecular sieve, uniformly stirring, transferring into a reaction kettle, crystallizing for 24-48 hours at the temperature of 200-300 ℃, performing suction filtration and washing after crystallization is finished, and drying at the temperature of 110-120 ℃ to obtain zeolite raw powder;
step (2): performing ion exchange on 1g of zeolite raw powder for 1-3 times by using 15-20 mL of 1mol/L ammonium chloride solution in boiling water bath, wherein each time is 30-60 min, converting the zeolite raw powder into ammonia type, and then roasting in a muffle furnace at 500-600 ℃ for 4-12h to obtain the ZSM-5/MOR eutectic zeolite.
14. The method of preparing a catalyst containing ZSM-5/MOR eutectic zeolite according to claim 9, wherein the method of preparing the catalyst containing ZSM-5/MOR eutectic zeolite specifically comprises the steps of:
step (1): mixing 10-70 parts by weight of ZSM-5/MOR eutectic zeolite, 25-85 parts by weight of pseudo-boehmite, 0.5-5 parts by weight of sesbania powder and 0.5-5 parts by weight of nitric acid, kneading for 0.5-2 h, and carrying out extrusion forming to obtain a formed carrier;
step (2): drying the formed carrier at 110-140 ℃ for 2-4 hours, and roasting at 500-580 ℃ for 2-4 hours to obtain the carrier;
and (3): adding the carrier obtained in the step (2) into a solution containing VIII group metals and a solution containing VIB group elements for dipping at room temperature for 4-12h, wherein the dipping liquid-solid ratio is 1.0-3.0, and then filtering and drying;
and (4): activating for 4-12h in air atmosphere at 500-600 ℃, and then reducing for 4-12h in hydrogen atmosphere to obtain the catalyst containing ZSM-5/MOR eutectic zeolite.
15. The method of preparing a catalyst containing ZSM-5/MOR eutectic zeolite according to claim 14, wherein the impregnation in step (3) is performed under vacuum condition, the impregnation liquid-solid ratio is 1.5-2; the vacuum degree is-0.02-0 MPa.
16. The method of claim 15, wherein the vacuum is between-0.01 MPa and 0MPa.
17. Use of a catalyst containing ZSM-5/MOR eutectic zeolite according to any one of claims 1 to 8 in a tetramethylbenzene isomerization reaction.
18. The use according to claim 17, wherein the reaction temperature of the tetramethylbenzene isomerization reaction is 350 to 500 ℃; the reaction pressure is 0.1 MPa-2 MPa; the weight hourly space velocity of the feeding material is 0.5 to 10h -1 (ii) a The molar ratio of hydrogen to oil is 1-10.
19. Use according to claim 18, characterised in thatThe reaction temperature is 350-450 ℃; the feeding weight hourly space velocity is 0.5 to 5h -1 (ii) a The molar ratio of hydrogen to oil is 1-5.
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| US4585748A (en) * | 1983-05-25 | 1986-04-29 | Research Association For Residual Oil Processing | Crystalline catalyst compositions for the conversion of hydrocarbons |
| CN1102360A (en) * | 1993-11-05 | 1995-05-10 | 中国石油化工总公司 | Alleyl aromatics isomerizating catalyzer |
| US5759950A (en) * | 1995-06-10 | 1998-06-02 | China Petrochemical Corporation | Catalyst supported with noble metal(s) for the isomerization of alkylaromatics |
| CN107952471A (en) * | 2016-10-18 | 2018-04-24 | 中国石油化工股份有限公司 | Alkyl aromatic hydrocarbon isomerization catalyst and preparation and application |
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| US4585748A (en) * | 1983-05-25 | 1986-04-29 | Research Association For Residual Oil Processing | Crystalline catalyst compositions for the conversion of hydrocarbons |
| CN1102360A (en) * | 1993-11-05 | 1995-05-10 | 中国石油化工总公司 | Alleyl aromatics isomerizating catalyzer |
| US5759950A (en) * | 1995-06-10 | 1998-06-02 | China Petrochemical Corporation | Catalyst supported with noble metal(s) for the isomerization of alkylaromatics |
| CN107952471A (en) * | 2016-10-18 | 2018-04-24 | 中国石油化工股份有限公司 | Alkyl aromatic hydrocarbon isomerization catalyst and preparation and application |
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