CN112808298A - Catalyst containing hierarchical pore Y-type molecular sieve and preparation method thereof - Google Patents
Catalyst containing hierarchical pore Y-type molecular sieve and preparation method thereof Download PDFInfo
- Publication number
- CN112808298A CN112808298A CN201911126333.8A CN201911126333A CN112808298A CN 112808298 A CN112808298 A CN 112808298A CN 201911126333 A CN201911126333 A CN 201911126333A CN 112808298 A CN112808298 A CN 112808298A
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- CN
- China
- Prior art keywords
- molecular sieve
- ions
- acid
- type molecular
- hierarchical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 193
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- -1 hydrogen ions Chemical class 0.000 claims abstract description 43
- 239000003929 acidic solution Substances 0.000 claims abstract description 35
- 238000001035 drying Methods 0.000 claims abstract description 32
- 238000005406 washing Methods 0.000 claims abstract description 32
- 238000001914 filtration Methods 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 70
- 239000002253 acid Substances 0.000 claims description 49
- 230000008569 process Effects 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 16
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 8
- 239000004927 clay Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 6
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 claims description 6
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 4
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 claims description 4
- 229910001679 gibbsite Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 229940102127 rubidium chloride Drugs 0.000 claims description 3
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 3
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000344 rubidium sulfate Inorganic materials 0.000 claims description 2
- GANPIEKBSASAOC-UHFFFAOYSA-L rubidium(1+);sulfate Chemical compound [Rb+].[Rb+].[O-]S([O-])(=O)=O GANPIEKBSASAOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 50
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 32
- 239000011148 porous material Substances 0.000 description 28
- 239000000047 product Substances 0.000 description 28
- 239000010457 zeolite Substances 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 26
- 239000000243 solution Substances 0.000 description 26
- 229910021536 Zeolite Inorganic materials 0.000 description 25
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 25
- 239000004310 lactic acid Substances 0.000 description 25
- 235000014655 lactic acid Nutrition 0.000 description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 23
- 238000005342 ion exchange Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 238000012512 characterization method Methods 0.000 description 13
- 238000009826 distribution Methods 0.000 description 13
- 238000004537 pulping Methods 0.000 description 12
- 238000007429 general method Methods 0.000 description 11
- 238000010306 acid treatment Methods 0.000 description 10
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 10
- MSMNVXKYCPHLLN-UHFFFAOYSA-N azane;oxalic acid;hydrate Chemical compound N.N.O.OC(=O)C(O)=O MSMNVXKYCPHLLN-UHFFFAOYSA-N 0.000 description 10
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical group [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 235000006408 oxalic acid Nutrition 0.000 description 8
- 238000003795 desorption Methods 0.000 description 7
- 229910001419 rubidium ion Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910001422 barium ion Inorganic materials 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 150000001282 organosilanes Chemical class 0.000 description 6
- 229910001427 strontium ion Inorganic materials 0.000 description 6
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical group [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- NCCSSGKUIKYAJD-UHFFFAOYSA-N rubidium(1+) Chemical compound [Rb+] NCCSSGKUIKYAJD-UHFFFAOYSA-N 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 239000013589 supplement Substances 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- XDFCIPNJCBUZJN-UHFFFAOYSA-N barium(2+) Chemical compound [Ba+2] XDFCIPNJCBUZJN-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229960004106 citric acid Drugs 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000001066 destructive effect Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 150000005837 radical ions Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- 241000275449 Diplectrum formosum Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- IHTRHZMXELXCEJ-UHFFFAOYSA-N azane;helium Chemical compound [He].N IHTRHZMXELXCEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000002119 pyrolysis Fourier transform infrared spectroscopy Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
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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
- B01J29/08—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J2029/081—Increasing the silica/alumina ratio; Desalumination
-
- 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
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Abstract
The invention provides a preparation method of a catalyst containing a hierarchical pore Y-shaped molecular sieve, which is characterized by comprising the steps of contacting the Y-shaped molecular sieve with an acidic solution simultaneously containing hydrogen ions and at least two different carboxylate ions, adjusting the pH value to 4.5-5.5, filtering, washing and drying to obtain the hierarchical pore Y-shaped molecular sieve, and mixing with a matrix material.
Description
Technical Field
The invention relates to a catalyst containing a Y-type molecular sieve and a preparation method thereof, and further relates to a catalyst containing a hierarchical pore Y-type molecular sieve and a preparation method thereof.
Background
At the end of the fifty years, Milton and Breck successfully synthesized Y-type molecular sieves due to the SiO in the structure of NaY molecular sieves2/Al2O3The ratio is larger than that of the X-type molecular sieve, so that the thermal stability and the water stability are improved. In the early seventies, Grace company developed a guide agent method for synthesizing NaY molecular sieve, and water glass was used as a raw materialThe glass replaces expensive silica sol, the process is simplified, and the growth cycle is shortened, so that the NaY molecular sieve can be rapidly and widely applied to the field of petrochemical industry, particularly petroleum cracking catalysis. Of the hundreds of molecular sieves that have been developed so far, the largest amount used industrially is the Y-type molecular sieve. At present, the synthesis of NaY molecular sieve mainly adopts a crystal gel method in industry. Due to the use and improvement of the crystal seed gel, the synthesis crystallization time of the Y-type molecular sieve is greatly shortened, and a foundation is laid for the industrialization of the Y-type molecular sieve. The industrial application and development put higher demands on the synthesis of the molecular sieve and the product performance thereof, which in turn promotes the deep research of the synthesis of the molecular sieve, and the synthesis of the Y-type molecular sieve with hierarchical pores and regular mesopores becomes a new hot spot.
The preparation of molecular sieves with hierarchical pore structures is yet another solution. In designing catalysts, it is desirable to both maximize the accessibility of the active sites to fully exploit their catalytic potential and to minimize the pore space for higher catalytic activity. There is therefore a need to find an optimum balance between active site accessibility and active site bulk density, i.e. to create an optimum hierarchical pore distribution in the catalytic material. The hierarchical pore molecular sieve really realizes the functions of hierarchical pore structure, namely hierarchical pore distribution and hierarchical acid strength distribution.
The methods for preparing the hierarchical pore molecular sieves reported at present can be mainly divided into a "constructive" method and a "destructive" method. The "constructive" method is also called a template method, and is classified into a hard template method and a soft template method according to the type of template. The hierarchical pore structure zeolite synthesized by using the hard template has large mesopore volume and wide pore distribution, and the pore volume and the pore size are completely dependent on the particle size and the dispersity of the hard template because the hard template and a molecular sieve synthesis raw material do not have direct action. The medium pore volume of the hierarchical pore structure zeolite synthesized by using the soft template is smaller than that of a sample synthesized by using a hard template, and is generally concentrated at 0.2-0.5 cm3The mesoporous pore distribution is narrow between the/g. The common soft template mainly comprises a high molecular polymer, organosilane, a surfactant and the like, and the cost for synthesizing a sample by using the soft template is high. The destructive method is mainly divided into dealuminationModification and desiliconization modification. Typical dealumination methods include hydrothermal dealumination and acid treatment dealumination. Dealumination modification can generate a large amount of secondary mesoporous defects in the molecular sieve framework. For the silicon-aluminum molecular sieve with low silicon-aluminum ratio, dealumination treatment is a simple and easy method for forming intracrystalline mesopores. For Y-type molecular sieve, the method for preparing hierarchical pores which is most widely applied in industry at present is to prepare mesopores by using a hydrothermal treatment method, and the method has easy operability and low industrial amplification cost, but like other dealumination modification, closed mesopore cavities can be inevitably introduced. Therefore, the modification method has no obvious advantages for improving the mass transfer performance of the molecular sieve.
In the synthesis of the hierarchical pore zeolite molecular sieve, another research focus is to utilize organosilane to regulate the crystallization of the zeolite molecular sieve, and the long-chain alkyl silane coupling agent can limit the growth of the zeolite molecular sieve and synthesize the nano zeolite. The zeolite molecular sieve with disordered mesoporous channels in the crystal can be successfully synthesized by adopting a partially silanized polymer as a template. In 2006, Serrano et al found that organosilanes, which are stable with conventional silica-alumina species under hydrothermal conditions in Hierarchical pore zeolite molecular sieves, were stable in the synthesis of Zeolites (Serrano D.P., Aguado J., Escorea J.M., Rodriguez J.M., Peral A: structural Zeolites with Enhanced therapeutic and Catalytic Properties Synthesized from organic functionalized feeds [ J ] chem.Mater.,2006,18: 2462-. The organosilane can limit the growth of the zeolite molecular sieve, and the organosilane can form a multi-stage pore channel with conventional silicon-aluminum species under hydrothermal conditions in the synthesis process of the zeolite. According to the method, organosilane is added into pre-crystallized zeolite molecular sieve synthesis gel to synthesize Si-C bonds of the zeolite molecular sieve with disordered mesoporous channels in crystals, and the growth of the zeolite molecular sieve is limited, so that the aggregate of the nano zeolite molecular sieve is obtained. The nano zeolite agglomerates have a very small particle size and a large number of mesopores are present. CN102774854A discloses a method for synthesizing a meso-microporous NaY molecular sieve, which uses a reaction product substituted by NH group polymer and aliphatic epoxy silane amine as a template agent, and adds the template agent in the process of synthesizing a Y-type molecular sieve to generate a meso-microporous structure in situ.
CN102936017B discloses a mesoporous nano zeolite aggregate and a preparation method thereof. The method comprises the steps of firstly silanizing the surface of nano silicon dioxide, then adding a template agent and an aluminum source into the silicon source, and carrying out hydrothermal crystallization under a certain condition to obtain the Beta nano zeolite aggregate formed by self-polymerization of nano zeolite grains with intragranular mesopores. Overcomes the defect that the nano Beta zeolite is not easy to separate in the synthesis and use processes.
CN102874836A discloses a method for synthesizing a mesoporous A-type molecular sieve. The method comprises the steps of taking a mixture of a multiwalled carbon nanotube and a silane coupling agent after bridging as a template agent, adding another silane coupling agent after adding the mixture into a silicon source, treating the mixture under a heating condition to react, transferring the mixture into an aluminum source after the reaction is finished, stirring, crystallizing, filtering, washing, drying, and removing the template agent through high-temperature calcination to obtain the mesoporous A-type molecular sieve.
US20070258884 reports that 3- (2, 3-epoxypropoxy) propyltrimethoxysilane is adopted to modify polyethyleneimine to prepare a mixed template agent, mesopores are generated in situ in the synthesis process of a ZSM-5 molecular sieve, and the aperture of the mesopores is concentrated at about 3 nm.
In the above patents, the template agent is added during the synthesis of the molecular sieve, and the micropores and mesopores are prepared in situ. When the method is used for hydrothermal synthesis of the Y-type molecular sieve, P-type mixed crystals are easily generated, synthesis of the Y-type molecular sieve is influenced, and generation of micropores and mesopores is further influenced.
Disclosure of Invention
The invention aims to provide a preparation method of a catalyst containing a hierarchical pore Y-type molecular sieve and the catalyst obtained by the method, aiming at the problems of reduced crystallinity and reduced B acid strength of an active component Y-type molecular sieve in the existing catalyst after two steps of dealumination and desiliconization.
Therefore, the preparation method of the catalyst containing the hierarchical pore Y-type molecular sieve is characterized by comprising the steps of contacting the Y-type molecular sieve with an acidic solution simultaneously containing hydrogen ions and at least two different carboxylate ions, adjusting the pH value to 4.5-5.5, filtering, washing and drying to obtain the hierarchical pore Y-type molecular sieve, and mixing with a matrix material.
The invention also provides a catalyst containing the hierarchical pore Y-shaped molecular sieve obtained by the preparation method.
The preparation method of the invention adopts special treatment steps, has obvious protection effect on the crystallinity of the molecular sieve, only relates to dealumination in the process, and avoids the damage of the removal of framework silicon to strong B acid.
Drawings
FIG. 1 is a TEM photograph of a sample A containing a hierarchical pore type Y molecular sieve obtained in example 1.
FIG. 2 is a TEM photograph of sample B containing hierarchical pore type Y molecular sieve obtained in example 2.
FIG. 3 is a TEM photograph of sample C containing hierarchical pore type Y molecular sieve obtained in example 3.
Fig. 4 is a mesoporous pore size distribution curve of the samples a and C containing the hierarchical pore Y-type molecular sieve obtained in examples 1 and 3, respectively.
Detailed Description
The invention provides a preparation method of a catalyst containing a hierarchical pore Y-shaped molecular sieve, which is characterized by comprising the steps of contacting the Y-shaped molecular sieve with an acidic solution simultaneously containing hydrogen ions and at least two different carboxylate ions, adjusting the pH value to 4.5-5.5, filtering, washing and drying to obtain the hierarchical pore Y-shaped molecular sieve, and mixing with a matrix material.
In the preparation method, the Y-shaped molecular sieve containing the hierarchical pores is obtained by contacting the Y-shaped molecular sieve with an acidic solution, adjusting the pH value to 4.5-5.5, and performing filtering, washing and drying, wherein the acidic solution simultaneously contains hydrogen ions and at least two different carboxylate ions. The pH value, the dealumination rate and the aluminum supplement rate of the molecular sieve in the acidic solution are adjusted by controlling the type and the concentration of carboxylate ions in the acidic solution. When the dealumination rate is higher than the aluminum supplement rate to a certain extent, mesopores can be introduced into the molecular sieve. When the dealumination rate is approximately equal to the aluminum supplement rate or is far greater than the aluminum supplement rate, mesopores cannot be formed. Different carboxylate ions have different abilities to promote dealumination or aluminum replenishment.
The ratio of the acidic solution to the Y-type molecular sieve is 8-25: 1, wherein the acidic solution is in volume (mL) and the Y-type molecular sieve is in mass (g).
The carboxylate ions are selected from at least two of oxalate ions, lactate ions and citrate ions. The concentration of the carboxylate ions is 0.1-0.5 mol/L. The carboxylate ions are preferably oxalate ions and lactate ions. The ratio of oxalate ions to lactate ions is 0.4-2.5 in terms of the molar amount of carboxylate ions: 1
In the process of contacting the Y-type molecular sieve with the acidic solution, the acidic solution can be prepared by mixing ammonium salts of one carboxylic acid and another carboxylic acid, or can be prepared by preparing a mixed acid solution from the two carboxylic acids and then dropwise adding ammonia water to adjust the pH value to 4.5-5.5. In the process of contacting the Y-type molecular sieve with the acidic solution, the temperature is 20-100 ℃, preferably 80-100 ℃, and the time is 1-12 hours, preferably 2-4 hours.
In the preparation method of the invention, the Y-type molecular sieve can be NaY or NH4Y molecular sieve, among which NH is preferred4And (4) Y molecular sieve.
More preferred Y-type molecular sieves should feature a uniform aluminum distribution. The chemical dealumination method of acid treatment is an outside-in dealumination method, which often causes uneven dealumination, namely the dealumination degree of the outer surface of the molecular sieve is the largest, while the dealumination degree in the molecular sieve is smaller, so that the inside and the outside of the acid site distribution of the molecular sieve are uneven, the inside acid sites with lower accessibility are more, the outside surface layer with higher accessibility is less, and the acid distribution inevitably affects the catalytic effect of the Y molecular sieve. In order to solve the problem of non-uniform dealumination in the chemical dealumination method under the conventional acid treatment, the more preferable Y-type molecular sieve is prepared by the following steps: NH (NH)4And (3) contacting the Y molecular sieve with a salt solution containing alkali metal ions and/or a salt solution containing alkaline earth metal ions, and filtering, washing and drying to obtain the product, wherein the alkali metal is selected from rubidium and cesium, and the alkaline earth metal is selected from strontium and barium. Wherein the salt solution containing alkali metal ions is selected from rubidium chloride, cesium chloride, and mixtures thereof,Rubidium nitrate, cesium nitrate, rubidium sulfate and cesium sulfate, wherein the salt solution of alkaline earth metal ions is selected from strontium chloride, barium chloride and strontium nitrate. The concentration of the alkali metal ion-containing salt solution or the alkaline earth metal ion-containing salt solution is 0.1-2 mol/L. Preferably, the alkali metal is cesium or rubidium, and the concentration of the alkali metal ion solution is 0.5-1 mol/L of NH4The Y molecular sieve is contacted with a salt solution containing alkali metal ions and/or a salt solution containing alkaline-earth metal ions at the temperature of 20-80 ℃ for 0.2-2 hours.
In the preparation method of the invention, the matrix material is selected from one or more of alumina, silica and clay. The alumina precursor is, for example, hydrated alumina or alumina sol. The hydrated alumina is selected from one or more of hydrated aluminas commonly used in cracking catalysts, such as one or more of hydrated aluminas having pseudo-Boehmite structure (Pseudoboemite), diaspore (Boehmite), Gibbsite (Gibbsite) and Bayer stone (Bayerite), preferably pseudo-Boehmite and/or Gibbsite. The precursor of the silica is silica sol. The Y-type molecular sieve containing the hierarchical holes is mixed with a base material to form slurry with the solid content of 35-40%. The acid is selected from hydrochloric acid, nitric acid or phosphoric acid. In a preferred embodiment, the Y-type molecular sieve containing hierarchical pores is mixed with the matrix material, and the components are added in the order of adding acid into pseudo-boehmite, adding clay, adding the Y-type molecular sieve containing hierarchical pores after uniformly mixing, and finally adding aluminum sol, silica sol and water. In the preferred embodiment, the clay is partially peptized under the action of the pseudo-boehmite and the acid, the carrier and the molecular sieve are bonded after the molecular sieve is added, the strength of the catalyst can be improved, and finally the aluminum sol and the silica sol are added to ensure that the molecular sieve and the carrier are uniformly mixed to the maximum extent.
The invention also provides a catalyst containing the hierarchical-pore Y-type molecular sieve, which is prepared by the preparation method and has the micropore specific surface area of 400-650 m2The volume of the micropores is 0.25-0.35 cm3The mesoporous specific surface area is 30-200 m2The mesoporous volume is 0.07-0.85 cm3The mesoporous aperture is 2.0-6.0 nm, and the strength is 8.5-13.5N/mm.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
In the examples and comparative examples, the relative crystallinity of the molecular sieve was determined by X-ray diffraction (XRD). The experimental apparatus is an XPert Powder X-ray diffractometer of the Parnat corporation in the Netherlands. The test process is as follows: tube voltage 40kV, tube current 40mA, Cu target ka radiation, scanning speed 2(°)/min, scanning range 2 θ is 5 ° to 35 °. And (3) calculating the relative crystallinity of the molecular sieve by adopting the peak area of the (5,3,3) crystal face.
In the examples and comparative examples, the pore structure parameters of the molecular sieves were determined by the low temperature nitrogen adsorption capacity method (BET). The experimental apparatus is an ASAP24000 adsorption apparatus of Micromrteritics company in the United states. The test process is as follows: degassing the sample at 300 ℃ for 6h, performing nitrogen adsorption and desorption tests at 77.4K to obtain a nitrogen adsorption-desorption curve, calculating the specific surface area of the sample by using a BET formula, and calculating the mesoporous pore size distribution by using a BJH method.
In the examples and comparative examples, the mesoporous morphology of the molecular sieve was observed by a Transmission Electron Microscope (TEM). The experimental apparatus was a transmission electron microscope F20G 2 from FEI.
In the examples and comparative examples, the acid content of the molecular sieves was determined from NH3Temperature programmed desorption (NH 3-TPD). The experimental instrument is an Autochem II 2920 temperature programmed desorption instrument of Michman, USA. The test process is as follows: weighing 0.15g of molecular sieve powder, placing the molecular sieve powder into a sample tube, placing the sample tube into a thermal conductivity cell heating furnace, taking helium as carrier gas (25mL/min), heating to 550 ℃ at the speed of 20 ℃/min, and purging for 60min to remove impurities adsorbed on the surface of the molecular sieve. Then cooling to 100 ℃, keeping the temperature for 10min, switching ammonia-helium mixed gas (10.02% NH3+ 89.98% He) to adsorb for 30min, and continuing to purge for 90min with helium until the baseline is stable so as to desorb the physically adsorbed NH 3. Programmed heating to 250 deg.C at a rate of 10 deg.C/min, maintaining for 30min for desorption, programmed heating to 350 deg.C at a rate of 10 deg.C/min, maintaining for 30min for desorption, programmed heating to 450 deg.C at a rate of 10 deg.C/min, maintaining for 30min for desorption, programmed heating to 550 deg.C at a rate of 10 deg.C/min, and maintaining for 30miAnd n, carrying out desorption. The TCD detector is used for detecting the change of gas components, and the instrument automatically integrates to obtain the acid amount at each temperature.
In the examples and comparative examples, the B acid acidity of the molecular sieves was measured by pyridine absorption Infrared Spectroscopy (Py-FTIR). The experimental instrument was a Bruker company tencor ii infrared spectrometer. The test process is as follows: taking about 20mg of molecular sieve tablet, placing the molecular sieve tablet in an in-situ pool of an infrared spectrometer, sealing, heating to 500 ℃ at the speed of 10 ℃/min, and vacuumizing for 2h to desorb impurities such as water molecules physically adsorbed by the molecular sieve. After cooling to room temperature, the background spectrum was collected and pyridine was adsorbed for 10 min. Heating to 200 ℃ at the speed of 10 ℃/min, vacuumizing for 30min, cooling to room temperature, measuring the pyridine adsorption infrared spectrum, and integrating to calculate the total acid amount; and then heating to 350 ℃, vacuumizing for 30min, measuring the pyridine adsorption infrared spectrum after cooling to room temperature, and integrating to calculate the strong acid amount.
In the examples and comparative examples, the catalyst strength was measured by tabletting and pulverizing the catalyst into 20-40 mesh granules, and measuring the granules on a DL3 type granule strength measuring instrument produced by Daliangchui technology.
The starting materials used in the examples were, unless otherwise specified, analytical reagents.
Example 1
This example illustrates the process of dealuminizing a Y-type molecular sieve with lactic acid/ammonium oxalate to obtain a Y-type molecular sieve containing hierarchical pores.
3.60g of lactic acid (national chemical Co., Ltd., the same below) and 5.68g of ammonium oxalate monohydrate (national chemical Co., Ltd., the same below) were mixed, and water was added thereto to give 200mL of an acidic solution containing lactate and oxalate. Wherein the concentration of lactate ions and the concentration of oxalate ions are both 0.2 mol/L.
10g of NaY molecular sieve (from Long-range catalyst works, n (Si)/n (Al) 2.5, Na)2Mixing NaY molecular sieve and 120g/L ammonium chloride solution, pulping at a solid-to-liquid ratio of 1:3.75, heating to 85 deg.C, treating for 1 hr, and vacuum filtering; repeating the above steps for 1 time, performing suction filtration and washing, adding distilled water into a filter cake, pulping, adjusting the pH to 8.0-8.5 by using dilute ammonia water, performing suction filtration, and drying; the obtained sample is roasted for 2h at the temperature of 550 ℃,repeating the ammonium exchange step for 4 times, filtering, washing and drying. ) Ammonium exchange is carried out to obtain NH4And (4) Y molecular sieve. Reacting the obtained NH4And adding the Y molecular sieve into the 200mL of acidic solution, heating to 100 ℃, adjusting the pH of the solution to 4.5-5.5, treating for 2h, filtering, washing and drying to obtain the product A.
The relative crystallinity and pore structure parameters of the sample A are shown in Table 1, the acid data are shown in Table 2, the bulk phase and surface composition characterization of the molecular sieve is shown in Table 3, the morphology of the sample A is shown in a TEM photograph shown in FIG. 1, and the mesoporous pore size distribution is shown in FIG. 4.
Comparative example 1
This comparative example illustrates the reaction of NH4The Y molecular sieve is subjected to a 0.2mol/L lactic acid treatment process and the obtained comparative sample.
Ammonium exchange is carried out on 10g NaY molecular sieve according to a general method to prepare NH4And (4) Y molecular sieve. Reacting the obtained NH4Adding a Y molecular sieve into 200mL of 0.2mol/L lactic acid solution, heating to 100 ℃, treating for 2h, filtering, washing and drying to obtain a product, namely DB 1.
The relative crystallinity and pore structure parameters of comparative sample DB1 are shown in table 1, the acid data are shown in table 2, and the bulk and surface composition characterization of the molecular sieve is shown in table 3.
Comparative example 2
This comparative example illustrates the reaction of NH4The Y molecular sieve is subjected to the process of 0.2mol/L oxalic acid treatment and the obtained comparative sample.
Ammonium exchange is carried out on 10g NaY molecular sieve according to a general method to prepare NH4And (4) Y molecular sieve. Reacting the obtained NH4Adding a Y molecular sieve into 200mL of 0.2mol/L oxalic acid solution, heating to 100 ℃, treating for 2h, filtering, washing and drying to obtain a product, namely DB 2.
The relative crystallinity and pore structure parameters of comparative sample DB2 are shown in table 1, the acid data are shown in table 2, and the bulk and surface composition characterization of the molecular sieve is shown in table 3.
Comparative example 3
This comparative example illustrates the reaction of NH4The Y molecular sieve was subjected to only the lactic acid/oxalic acid mixed acid treatment process and the resulting comparative sample.
3.60g of lactic acid (molecular weight: 90.08) and 5.04g of oxalic acid dihydrate (national chemical group, the same shall apply hereinafter) were mixed and added with water to 200mL to prepare a mixed acid solution of lactic acid and oxalic acid. Wherein the concentration of the lactic acid and the concentration of the oxalic acid are both 0.2 mol/L.
Ammonium exchange is carried out on 10g NaY molecular sieve according to a general method to prepare NH4And (4) Y molecular sieve. Reacting the obtained NH4Adding a Y molecular sieve into the mixed acid solution, heating to 100 ℃, treating for 2h, filtering, washing and drying to obtain a product, namely DB 3.
The relative crystallinity and pore structure parameters of comparative sample DB3 are shown in table 1, the acid data are shown in table 2, and the bulk and surface composition characterization of the molecular sieve is shown in table 3.
Example 2
This example illustrates the process of dealuminizing a Y zeolite with lactic acid/ammonium oxalate to obtain a Y-type zeolite with hierarchical pores.
3.60g of lactic acid and 5.68g of ammonium oxalate monohydrate were mixed, and water was added to 200mL to prepare an acidic solution containing lactate and oxalate. Wherein the concentration of lactate ions and the concentration of oxalate ions are both 0.2 mol/L.
And adding 10g of NaY molecular sieve into the 200mL of acidic solution, heating to 100 ℃, adjusting the pH of the solution to 4.5-5.5, treating for 2h, filtering, washing and drying to obtain a product B.
The relative crystallinity and pore structure parameters of sample B are shown in table 1, the acid data are shown in table 2, and the bulk and surface composition characterization of the molecular sieve is shown in table 3. The morphology of sample B is shown in the TEM photograph of FIG. 2.
Example 3
This example illustrates the process of dealuminizing a Y zeolite with lactic acid/ammonium oxalate to obtain a Y-type zeolite with hierarchical pores.
3.60g of lactic acid and 11.37g of ammonium oxalate monohydrate are mixed and added with water to 200mL to prepare acidic solution containing lactate and oxalate, wherein the concentration of lactate ions is 0.2mol/L and the concentration of oxalate ions is 0.4 mol/L.
Ammonium exchange is carried out on 10g NaY molecular sieve according to a general method to prepare NH4And (4) Y molecular sieve. Reacting the obtained NH4Adding the Y molecular sieve into the 200mL of acid solution, heating to 100 ℃, adjusting the pH of the solution to 4.5-5.5, and treating 2h, filtering, washing and drying to obtain the product C.
The relative crystallinity and pore structure parameters for sample C are shown in table 1, the acid data are shown in table 2, and the bulk and surface compositional characterizations are shown in table 3. The morphology of the sample C is shown in a TEM photograph as shown in FIG. 3, and the mesoporous size distribution is shown in FIG. 4.
Comparative example 4
The comparative example provides NH obtained by ammonium exchange of NaY molecular sieve directly4The Y molecular sieve sample, designated DB4, was used to compare the B acid strength of the samples obtained by the process of the present invention with the comparative sample DB 4.
The relative crystallinity and pore structure parameters of comparative sample DB4 are shown in table 1 and the acid data are shown in table 2. The bulk and surface composition of the molecular sieves are characterized in Table 3
Example 4
This example illustrates the process of oxalic acid/citric acid dealumination of a Y zeolite to produce a Y zeolite with hierarchical pores.
Ammonium exchange is carried out on 10g of NaY molecular sieve according to a general method to prepare NH4And (3) mixing 10.08g of oxalic acid dihydrate and 16.81g of citric acid monohydrate by using a Y molecular sieve, and adding water to 200mL to prepare an oxalic acid/citric acid mixed acid solution, wherein the concentrations of oxalate and citrate ions are both 0.2 mol/L. Heating the mixed acid solution to 80 ℃, dropwise adding ammonia water at the temperature till the pH of the solution is 4.5-5.5, and reacting the NH4Adding a Y molecular sieve into the solution, treating for 4h at 80 ℃, filtering, washing and drying to obtain a product D.
The relative crystallinity and pore structure parameters for sample D are shown in table 1 and the acid data are shown in table 2. The bulk and surface composition of the molecular sieve are characterized in table 3.
Sample D showed similar characteristics to sample A, i.e., mesopores appeared, the relative crystallinity was high, and the acid amount and B acid strength were slightly increased, but the mesopore diameter was not uniform.
Example 5
This example illustrates the procedure for cesium ion exchange and dealumination of lactic acid/ammonium oxalate treatment of a Y-type molecular sieve to produce a Y-type molecular sieve containing hierarchical pores.
10g NaY molecular sieves (from Long-green catalyst Mill, n (Si))/n(Al)＝2.5，Na2Mixing NaY molecular sieve and 120g/L ammonium chloride solution, pulping at a solid-to-liquid ratio of 1:3.75, heating to 85 deg.C, treating for 1 hr, and vacuum filtering; repeating the above steps for 1 time, performing suction filtration and washing, adding distilled water into a filter cake, pulping, adjusting the pH to 8.0-8.5 by using dilute ammonia water, performing suction filtration, and drying; roasting the obtained sample at 550 ℃ for 2h, repeating the ammonium exchange step for 4 times, performing suction filtration, washing and drying. ) Ammonium exchange is carried out to obtain NH4And (4) Y molecular sieve. Reacting the obtained NH4Adding Y molecular sieve into 40mL distilled water, stirring and pulping at 30 ℃, adding 3.37g cesium chloride (Allandine reagent (Shanghai) Co., Ltd.), exchanging for 0.5h, filtering, washing and drying to obtain cesium ion exchange product.
3.60g of lactic acid (national chemical Co., Ltd., the same below) and 5.68g of ammonium oxalate monohydrate (national chemical Co., Ltd., the same below) were mixed, and water was added thereto to give 200mL of an acidic solution containing lactate and oxalate.
And adding the product of the cesium ion exchange into the 200mL of acidic solution, heating to 100 ℃, adjusting the pH of the solution to 4.5-5.5, treating for 2 hours, filtering, washing and drying, and performing ammonium exchange on the obtained sample for 4-6 times to obtain the product E.
The relative crystallinity and pore structure parameters for sample E are shown in table 1, the acid data are shown in table 2, and the bulk and surface compositional characterizations are shown in table 3.
The molecular sieve morphology of sample E was similar to sample A, with a large number of relatively uniform mesopores.
Comparative example 5
This comparative example illustrates sodium ion exchange and lactic acid/ammonium oxalate dealumination of a Y molecular sieve.
3.60g of lactic acid and 5.68g of ammonium oxalate monohydrate were mixed, and water was added to 200mL to prepare an acidic solution containing lactate and oxalate.
Ammonium exchange is carried out on 10g NaY molecular sieve according to a general method to prepare NH4And (4) Y molecular sieve. Reacting the obtained NH4Adding Y molecular sieve into 40mL distilled water, stirring and pulping at 30 deg.C, adding 2.34g sodium chloride (Allantin reagent (Shanghai) Co., Ltd.), exchanging for 0.5h, and filteringAnd washing and drying to obtain a sodium ion exchanged sample. And adding the obtained sample into the acidic solution, heating to 100 ℃, adjusting the pH value of the solution to 4.5-5.5, treating for 2 hours, filtering, washing and drying, and performing ammonium exchange on the obtained sample for 4-6 times to obtain the product DB 5. This comparative example sample DB5 was used to compare to the E sample above, indicating Cs+With Na+Different roles in the process.
The relative crystallinity and pore structure parameters of comparative sample DB5 are shown in table 1, the acid data are shown in table 2, and the bulk and surface composition characterizations are shown in table 3.
Example 6
This example illustrates the process of obtaining a hierarchical pore containing Y-type molecular sieve by rubidium ion exchange and lactic acid/ammonium oxalate dealumination on a Y-type molecular sieve.
Ammonium exchange is carried out on 10g NaY molecular sieve according to a general method to prepare NH4And (4) Y molecular sieve. Reacting the obtained NH4Adding a Y molecular sieve into 40mL of distilled water, stirring and pulping at 80 ℃, adding 9.68g of rubidium chloride (Aladdin reagent (Shanghai) Co., Ltd.), exchanging for 2 hours, filtering, washing and drying to obtain a rubidium ion exchange product.
3.60g of lactic acid and 5.68g of ammonium oxalate monohydrate were mixed, and water was added to 200mL to prepare an acidic solution containing lactate and oxalate.
And adding the obtained rubidium ion exchange product into the acidic solution, heating to 100 ℃, adjusting the pH of the solution to 4.5-5.5, treating for 2 hours, filtering, washing, drying, and performing ammonium exchange on the obtained sample for 4-6 times, wherein the obtained product is marked as F.
The relative crystallinity and pore structure parameters for sample F are shown in table 1, the acid data are shown in table 2, and the bulk and surface compositional characterizations are shown in table 3.
Example 7
This example illustrates the process of performing strontium ion exchange and lactic acid/ammonium oxalate dealumination on a Y-type molecular sieve to obtain a Y-type molecular sieve containing hierarchical pores.
Ammonium exchange is carried out on 10g NaY molecular sieve according to a general method to prepare NH4And (4) Y molecular sieve. Reacting the obtained NH4Adding Y molecular sieve into 40mL of distilled water, stirring and pulping at 20 ℃, and then addingTo this was added 6.34g of strontium chloride (alatin reagent (shanghai) ltd.), exchanged for 1h, filtered, washed, and dried strontium ion exchanged product.
3.60g of lactic acid and 11.37g of ammonium oxalate monohydrate were mixed, and water was added to 200mL to prepare an acidic solution containing lactate and oxalate.
And adding a product of strontium ion exchange into the 200mL of acidic solution, heating to 100 ℃, adjusting the pH of the solution to 4.5-5.5, treating for 2h, filtering, washing, drying, performing ammonium exchange on the obtained sample for 4-6 times, and marking the obtained product as G.
The relative crystallinity and pore structure parameters for sample G are shown in table 1, the acid data are shown in table 2, and the bulk and surface compositional characterizations are shown in table 3.
Example 8
This example illustrates the process of barium ion exchange and lactic acid/ammonium oxalate dealumination of a Y molecular sieve to produce a Y-type molecular sieve containing hierarchical pores.
Ammonium exchange is carried out on 10g NaY molecular sieve according to a general method to prepare NH4And (4) Y molecular sieve. Reacting the obtained NH4Adding Y molecular sieve into 40mL distilled water, stirring and pulping at 20 ℃, adding 2.50g barium chloride (Aladdin reagent (Shanghai) Co., Ltd.), exchanging for 1h, filtering, washing and drying to obtain a barium ion exchange product.
3.60g of lactic acid and 11.37g of ammonium oxalate monohydrate were mixed, and water was added to 200mL to prepare an acidic solution containing lactate and oxalate.
And adding a product of barium ion exchange into 200mL of acidic solution containing lactate and oxalate, heating to 100 ℃, adjusting the pH of the solution to 4.5-5.5, treating for 2 hours, filtering, washing, drying, and performing ammonium exchange on the obtained sample for 4-6 times, wherein the obtained product is marked as H.
The relative crystallinity and pore structure parameters for sample H are shown in table 1, the acid data are shown in table 2, and the bulk and surface compositional characterizations are shown in table 3.
Example 9
This example illustrates the procedure for cesium ion exchange and dealumination of lactic acid/ammonium oxalate treatment of a Y-type molecular sieve to produce a Y-type molecular sieve containing hierarchical pores.
Ammonium exchange is carried out on 10g NaY molecular sieve according to a general method to prepare NH4And (4) Y molecular sieve. Reacting the obtained NH4Adding Y molecular sieve into 40mL distilled water, stirring and pulping at 80 ℃, adding 6.74g cesium chloride (Allandine reagent (Shanghai) Co., Ltd.), exchanging for 0.5h, filtering, washing and drying to obtain cesium ion exchange product.
3.60g of lactic acid and 5.68g of ammonium oxalate monohydrate were mixed, and water was added to 200mL to prepare an acidic solution containing lactate and oxalate.
Adding the product of cesium ion exchange into 200mL of acidic solution containing lactate and oxalate, heating to 100 ℃, adjusting the pH of the solution to 4.5-5.5, treating for 2 hours, filtering, washing, drying, and performing ammonium exchange on the obtained sample for 4-6 times, wherein the obtained product is marked as I.
The relative crystallinity and pore structure parameters for sample I are shown in table 1, the acid data are shown in table 2, and the bulk and surface compositional characterizations are shown in table 3.
Example 10
This example illustrates the procedure for cesium ion exchange and dealumination of lactic acid/ammonium oxalate treatment of a Y-type molecular sieve to produce a Y-type molecular sieve containing hierarchical pores.
Ammonium exchange is carried out on 10g NaY molecular sieve according to a general method to prepare NH4And (4) Y molecular sieve. Reacting the obtained NH4Adding Y molecular sieve into 40mL of distilled water, stirring and pulping at 30 ℃, adding 1.69g of cesium chloride (Allandine reagent (Shanghai) Co., Ltd.), exchanging for 2h, filtering, washing and drying to obtain a cesium ion exchange product.
3.60g of lactic acid and 11.37g of ammonium oxalate monohydrate were mixed, and water was added to 200mL to prepare an acidic solution containing lactate and oxalate.
Heating 200mL of acidic solution containing lactate and oxalate of a cesium ion exchange product to 100 ℃, adjusting the pH of the solution to 4.5-5.5, treating for 2 hours, filtering, washing, drying, and performing ammonium exchange on the obtained sample for 4-6 times, wherein the obtained product is marked as J.
The relative crystallinity and pore structure parameters for sample J are shown in table 1, the acid data are shown in table 2, and the bulk and surface compositional characterizations are shown in table 3.
TABLE 1
TABLE 2
As can be seen from table 1 and fig. 1, a large number of mesopores were present in the sample a, while no mesopores were generated in the samples DB1, DB2, and DB 3. This indicates that neither single treatment with lactic acid, oxalic acid, nor a simple mixture of both can be applied to NH4Mesoporous is introduced into the Y molecular sieve, and NH can be treated by using the acid solution which contains two acid radical ions and has the pH value of 4.5-5.5 only as shown in example 14Mesopores are introduced into the Y molecular sieve, and higher crystallinity is kept.
As shown in Table 1 and FIG. 2, a larger amount of mesopores appeared in the sample B, but the area and volume of the mesopores were slightly smaller than those of the sample A, indicating that the treatment was also effective on NaY molecular sieves, except that the introduction effect of the mesopores was slightly worse than that of NH4And (4) Y molecular sieve.
In example 3, the amount of oxalate ions was increased as compared to example 1, and as shown in table 1, fig. 3 and fig. 4, the mesoporous size of the sample C obtained by increasing the amount of oxalate ions was also significantly larger than that of the sample a, and the degree of mesoporous nonuniformity was also increased. This shows that the method can adjust the mesoporous aperture by changing the dosage of acid radical ions.
In addition, as can be seen from table 2, the Y-type molecular sieve containing hierarchical pores obtained by the method has increased acid content and B-acid strength to different extents compared to those before treatment.
TABLE 3
As seen from Table 3, passing Cs+、Rb+、Sr2+、Ba2+After the exchange, the acid treatment is carried outThe sample of (1) has a significantly reduced amount of surface dealumination, wherein Cs is+、Rb+The surface protection effect is obvious, so the surface silicon-aluminum ratio of the sample E, F is obviously smaller than the bulk silicon-aluminum ratio; and Sr2+、Ba2+The surface protection is weaker and the surface silica to alumina ratio of sample G, H of examples 7 and 8 is still greater than or similar to the bulk silica to alumina ratio, but significantly lower than the comparative examples. Through Na+The post-exchange acid treated sample DB5 of comparative example 5, which was not significantly different from samples A-C of sample examples 1-3, all showed severe surface dealumination; sample I is treated with high concentration of Cs+Exchange and low-concentration acid treatment, the dealumination degree is light, and the dealumination degree is Cs+The lower surface is protected from almost dealumination; sample J is a low concentration of Cs+Exchange and high acid treatment, the degree of dealumination was severe, but Cs was still visible+Protection of surface aluminum. The optimum metal ion for uniform aluminum distribution that can be selected is Cs+Or Rb+The optimum metal ion solution concentration is 0.5-1 mol/L.
The preferred technical scheme for obtaining the Y-shaped molecular sieve containing the hierarchical pores is NH4Y passes through Cs+、Rb+、Sr2+、Ba2+After the exchange, acid treatment is easily carried out by using acid which simultaneously contains hydrogen ions and at least two different carboxylate ions and has a pH value of 4.5-5.5.
The following examples illustrate the preparation of the process of the invention and the catalysts obtained.
Examples 11 to 20
Adding acid into a certain amount of hydrated alumina under stirring, adding clay, pulping for 10 minutes under high shear, uniformly mixing, adding the hierarchical pore Y-shaped molecular sieve samples A-J, and finally adding aluminum sol, silica sol and water. Kneading the obtained slurry, extruding, rolling ball, sieving and the like. The catalysts corresponding to the catalysts containing the hierarchical pore Y-type molecular sieve samples A to J are numbered as a to J.
Table 4 gives the slurry dry basis composition, slurry solids content, alumina content provided by the hydrated alumina and the alumina sol, and silica content provided by the silica sol.
Table 5 gives the various parameters of catalyst surface area, pores and strength.
Comparative examples 6 to 10
The same as example 11, except for comparative Y molecular sieve samples DB 1-DB 5 of comparative examples 1-5. The corresponding comparative catalyst numbers are Z1-Z5.
Table 4 gives the slurry dry basis composition, slurry solids content, alumina content provided by the hydrated alumina and the alumina sol, and silica content provided by the silica sol.
Table 5 gives the various parameters of catalyst surface area, pores and strength.
TABLE 4
TABLE 5
Claims (19)
1. A preparation method of a catalyst containing a hierarchical pore Y-shaped molecular sieve is characterized by comprising the steps of contacting the Y-shaped molecular sieve with an acidic solution containing hydrogen ions and at least two different carboxylate ions at the same time, adjusting the pH value to 4.5-5.5, filtering, washing and drying to obtain the hierarchical pore Y-shaped molecular sieve, and mixing with a matrix material.
2. The method of claim 1, wherein the matrix material is selected from one or more of alumina, silica and clay.
3. The process according to claim 1, wherein the hierarchical pore-containing Y-type molecular sieve is contained in an amount of 38 to 90% by weight on a dry basis of the catalyst.
4. The process of claim 1 wherein the ratio of acidic solution to Y-type molecular sieve is from 8 to 25: 1, wherein the acidic solution is measured in mL, and the Y-type molecular sieve is measured in g.
5. The production method according to claim 1, wherein the carboxylate ion is at least two selected from the group consisting of oxalate ion, lactate ion and citrate ion.
6. The method according to claim 1, wherein the concentration of said carboxylate ions is 0.1 to 0.5 mol/L.
7. The method of claim 1, wherein the contacting of the Y-type molecular sieve with an acidic solution is carried out at a temperature of 20 to 100 ℃ for 1 to 12 hours.
8. The process according to claim 1, wherein the Y-type molecular sieve is NH4And (4) Y molecular sieve.
9. The preparation method according to claim 1, wherein the carboxylate ions are oxalate ions and lactate ions, and the ratio of the oxalate ions to the lactate ions is 0.4 to 2.5: 1.
10. the process according to claim 1, wherein the Y-type molecular sieve is NH4And (3) contacting the Y molecular sieve with a salt solution containing alkali metal ions and/or a salt solution containing alkaline earth metal ions, and filtering, washing and drying to obtain the product, wherein the alkali metal is selected from rubidium and cesium, and the alkaline earth metal is selected from strontium and barium.
11. The method according to claim 10, wherein said alkali metal ion-containing salt solution is selected from the group consisting of rubidium chloride, cesium chloride, rubidium nitrate, cesium nitrate, rubidium sulfate and cesium sulfate, and said alkaline earth metal ion-containing salt solution is selected from the group consisting of strontium chloride, barium chloride and strontium nitrate.
12. The method according to claim 11, wherein the concentration of the alkali metal ion-containing salt solution or the alkaline earth metal ion-containing salt solution is 0.1 to 2 mol/L.
13. The process according to claim 11, wherein said NH is4The Y molecular sieve is contacted with a salt solution containing alkali metal ions and/or a salt solution containing alkaline-earth metal ions at the temperature of 20-80 ℃ for 0.2-2 hours.
14. The preparation method according to claim 1, wherein the step of mixing the Y-type molecular sieve containing hierarchical pores with the matrix material is to mix the Y-type molecular sieve containing hierarchical pores with hydrated alumina, alumina sol, silica sol, acid, water and optionally clay to form slurry with a solid content of 35-40%.
15. The method according to claim 14, wherein the hydrated alumina is pseudoboehmite and/or gibbsite.
16. The method of claim 15, wherein the acid is selected from the group consisting of hydrochloric acid, nitric acid and phosphoric acid.
17. The method of claim 1, wherein the base material is mixed with the acid and clay in the order of adding the components to the pseudo-boehmite, the Y-type molecular sieve having the hierarchical pores is added after mixing, and finally the alumina sol, silica sol and water are added.
18. A catalyst comprising a hierarchical pore Y-type molecular sieve obtainable according to claims 1 to 17.
19. The catalyst according to claim 18, having a specific micropore surface area of 400 to 650m2The volume of the micropores is 0.25-0.35 cm3The mesoporous specific surface area is 30-200 m2The mesoporous volume is 0.07-0.85 cm3The mesoporous aperture is 2.0-6.0 nm, and the strength is 8.5～13.5N/mm。
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