CN111841619A - Modified ZSM-5 molecular sieve catalyst, preparation method and application thereof - Google Patents
Modified ZSM-5 molecular sieve catalyst, preparation method and application thereof Download PDFInfo
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- CN111841619A CN111841619A CN202010788496.9A CN202010788496A CN111841619A CN 111841619 A CN111841619 A CN 111841619A CN 202010788496 A CN202010788496 A CN 202010788496A CN 111841619 A CN111841619 A CN 111841619A
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- molecular sieve
- acid
- zsm
- catalyst
- preparation
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 96
- 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 96
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 54
- 238000005406 washing Methods 0.000 claims abstract description 38
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 24
- 239000010452 phosphate Substances 0.000 claims abstract description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 230000004048 modification Effects 0.000 claims abstract description 13
- 238000012986 modification Methods 0.000 claims abstract description 13
- 238000005554 pickling Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 claims description 58
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 57
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 45
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 11
- 238000005470 impregnation Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 229910001038 basic metal oxide Inorganic materials 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 39
- 238000007654 immersion Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 28
- 238000002791 soaking Methods 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 11
- 229910000397 disodium phosphate Inorganic materials 0.000 description 11
- 235000019800 disodium phosphate Nutrition 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 229930040373 Paraformaldehyde Natural products 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 229920002866 paraformaldehyde Polymers 0.000 description 10
- 238000007598 dipping method Methods 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229960005069 calcium Drugs 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910001463 metal phosphate Inorganic materials 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- NSPPRYXGGYQMPY-UHFFFAOYSA-N 3-Methylbuten-2-ol-1 Natural products CC(C)C(O)=C NSPPRYXGGYQMPY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910008066 SnC12 Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229960001714 calcium phosphate Drugs 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229940043350 citral Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 description 1
- 229910000395 dimagnesium phosphate Inorganic materials 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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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
-
- 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
- B01J35/63—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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
-
- 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
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of a modified ZSM-5 molecular sieve catalyst, which comprises the steps of sequentially carrying out steam treatment, acid washing treatment and roasting on a ZSM-5 molecular sieve, and then carrying out immersion modification in an alkaline phosphate aqueous solution to obtain the modified ZSM-5 molecular sieve catalyst; the temperature of the steam treatment is 200-800 ℃, the time of the steam treatment is 0.5-6 hours, and the airspeed of the steam is 0.1-3 h < -1 >; the concentration of the acid liquor used in the acid washing treatment is 0.1-2 mol/L, and the solid-to-liquid ratio in the acid washing treatment is 1 g: (6-12) mL, wherein the pickling temperature is 30-120 ℃, and the pickling time is 1-12 hours. The modified ZSM-5 catalyst of the invention can reduce the reaction temperature and the reaction pressure, and simultaneously keep high product yield. The invention also provides a modified ZSM-5 molecular sieve catalyst and application thereof.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a modified ZSM-5 molecular sieve catalyst, and a preparation method and application thereof.
Background
3-methyl-3-buten-1-ol is an important intermediate in the organic synthesis industry, and can be widely used in production and life. 3-methyl-3-buten-1-ol is useful for producing isoprene, which is used as a raw material for synthetic rubber. Can also be isomerized into 3-methyl-2-buten-1-ol, and can be used as synthetic pyrethroid pesticide, citral, etc. Can also be used as a raw material for producing a new generation of polycarboxylic acid series high-efficiency water reducing agent, and can be used as food, medicine additives and the like.
The catalyst for preparing 3-methyl-3-butylene-1-alcohol by condensation reaction of isobutene and formaldehyde mainly comprises an acidic catalyst and a basic catalyst. The earliest British patent 1205397 reported as SnCl4And ZnC12The catalyst is prepared by reacting isobutene with formaldehyde at 15-100 ℃, the conversion rate of the formaldehyde is low, and chloride is used to cause severe corrosion. CN102659518 SnC12The immobilized silicon-aluminum molecular sieve is used as a catalyst, isobutene and formaldehyde are adopted to prepare 3-methyl-3-buten-1-ol, the yield of the product 3-methyl-3-buten-1-ol is improved, but highly toxic SnC1 is used2So that its application is limited. In the patent US4028424, phosphate is used as a catalyst, paraformaldehyde and isobutene are used at 150-200 ℃, and 3-methyl-3-butene-1-ol with yield of 65-92% and 1-6% of 3-methyl-2-butene-1-ol can be obtained, but the boiling points of the 3-methyl-3-butene-1-ol and the 3-methyl-2-butene-1-ol are very close, and high separation cost is needed in the later stage. Gunn Yanxia of China eastern institute of technology university etc. (Industrial catalysis, 2005, 13, 346) 348), take isobutene and paraformaldehyde as raw materials, adopt sodium dihydrogen phosphate, hydrogen phosphate modified ZSM-5 molecular sieve as catalyst, 3-methyl-3-butene-1-ol yield reaches 85%. However, a great deal of literature and patent experiments prove that phosphate is directly used as a catalyst, and the phosphate is directly loaded on ZSM-When 5 molecular sieves are used as the catalyst, the yield of the 3-methyl-3-buten-1-ol is difficult to reach 85 percent. Japanese patents JP55-113732 and JP58-164534 adopt ZSM series catalysts to react for 7 hours at 102 ℃ and 0.98MPa, the conversion rate of formaldehyde is only 58.2 percent, the total selectivity of enol is 79.8 percent, and the conversion rate of formaldehyde is lower.
The existing preparation method for preparing 3-methyl-3-butene-1-ol by isobutene and formaldehyde, particularly the Prins condensation reaction preparation method adopting a catalyst, has the problems of low catalyst efficiency, high corrosivity to reaction equipment and serious environmental pollution. Therefore, providing a more suitable catalyst is one of the problems that one skilled in the art needs to solve.
Disclosure of Invention
The invention aims to provide a modified ZSM-5 molecular sieve catalyst, a preparation method and application thereof, wherein the modified ZSM-5 molecular sieve catalyst has a good catalytic effect, the method avoids the problems of equipment corrosion and environment pollution of the traditional acid catalyst, and simultaneously effectively reduces the reaction temperature and the reaction pressure for preparing 3-methyl-3-buten-1-ol.
The invention provides a preparation method of a modified ZSM-5 molecular sieve catalyst, which comprises the following steps:
sequentially carrying out steam treatment, acid washing treatment and roasting on the ZSM-5 molecular sieve, and then carrying out impregnation modification on the alkaline phosphate aqueous solution to obtain a modified ZSM-5 molecular sieve catalyst;
the temperature of the steam treatment is 200-800 ℃, the time of the steam treatment is 0.5-6 hours, and the airspeed of the steam is 0.1-3 h < -1 >;
the concentration of the acid liquor used in the acid washing treatment is 0.1-2 mol/L, and the solid-to-liquid ratio in the acid washing treatment is 1 g: (6-12) mL, wherein the pickling temperature is 30-120 ℃, and the pickling time is 1-12 hours.
Preferably, the ZSM-5 molecular sieve has a specific surface area>300m2G, pore volume>0.2cm3The silicon-aluminum ratio is 3-800, and the grain size is 30-3000 nm.
Preferably, the roasting temperature is 300-600 ℃; the roasting time is 2-5 hours.
Preferably, the acid used in the acid washing treatment is one or more of hydrochloric acid, nitric acid, phosphoric acid, acetic acid, citric acid and oxalic acid.
Preferably, the alkaline phosphate is one or more of alkaline metal phosphate, alkaline metal dihydrogen phosphate and alkaline metal hydrogen phosphate;
the alkaline metal is one or more of sodium, potassium, cesium, barium, magnesium and calcium;
the concentration of the alkaline phosphate is 0.1-15 wt%.
Preferably, the dipping temperature is 20-60 ℃, and the dipping time is 2-24 hours.
Preferably, the ZSM-5 molecular sieve after the acid washing treatment is sequentially dried and roasted, and then impregnated.
Preferably, the impregnated ZSM-5 molecular sieve is dried and roasted in sequence to obtain the modified ZSM-5 molecular sieve.
The invention provides a modified ZSM-5 molecular sieve catalyst, which is prepared according to the preparation method;
the active component in the modified ZSM-5 molecular sieve is P2O5And a basic metal oxide, said P2O5The mass fraction of the alkali metal oxide is 5-30%, and the mass fraction of the alkali metal oxide is 1-25%;
the alkaline metal oxide is one or more of oxides of sodium, potassium, cesium, barium, magnesium and calcium.
Use of a modified ZSM-5 molecular sieve catalyst as described above as a catalyst in the condensation of isobutene with formaldehyde to produce 3-methyl-3-buten-1-ol.
The invention provides a preparation method of a modified ZSM-5 molecular sieve catalyst, which comprises the following steps: sequentially carrying out steam treatment, acid washing treatment and roasting on the ZSM-5 molecular sieve, and then carrying out impregnation modification in an alkaline phosphate aqueous solution to obtain a modified ZSM-5 molecular sieve catalyst; the temperature of the steam treatment is 200-800 ℃, the time of the steam treatment is 0.5-6 hours, and the airspeed of the steam is 0.1-3 h < -1 >; the concentration of the acid liquor used in the acid washing treatment is 0.1-2 mol/L, and the solid-to-liquid ratio in the acid washing treatment is 1 g: (6-12) mL, wherein the pickling temperature is 30-120 ℃, and the pickling time is 1-12 hours. The water vapor, acid washing treatment and alkaline phosphate modification treatment in the invention can adjust the pore structure distribution and acid properties (strength and acid amount) of the ZSM-5 molecular sieve, so as to obtain the catalyst with proper acidity and alkalinity and proper pore channel size. Compared with the prior art, the modified ZSM-5 catalyst has higher catalytic activity and better product diffusivity, can reduce reaction temperature and reaction pressure, and simultaneously keeps high product yield. Experimental results show that the modified ZSM-5 molecular sieve catalyst is applied to the reaction of preparing 3-methyl-3-butene-1-ol through condensation reaction of isobutene and paraformaldehyde, the highest yield of the product 3-methyl-3-butene-1-ol is 95% and the conversion rate of formaldehyde is up to 100% relative to formaldehyde under the conditions that the reaction temperature is 180-230 ℃, the reaction pressure is 8-15 MPa and the molar ratio of isobutene to formaldehyde is 5-15: 1, and the preparation efficiency is effectively improved. And the catalyst is easy to separate after the reaction, so that the operation and energy consumption in the separation aspect are reduced, and the problems of equipment corrosion and environmental pollution caused by the liquid acid catalyst in the traditional production process are solved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows the yield of 3-methyl-3-buten-1-ol as a function of the number of catalyst applications, n, in the examples of the present invention.
Detailed Description
The invention provides a preparation method of a modified ZSM-5 molecular sieve catalyst, which comprises the following steps:
sequentially carrying out steam treatment, acid washing treatment and roasting on the ZSM-5 molecular sieve, and then carrying out impregnation modification in an alkaline phosphate aqueous solution to obtain a modified ZSM-5 molecular sieve catalyst;
the temperature of the steam treatment is 200-800 ℃, the time of the steam treatment is 0.5-6 hours, and the airspeed of the steam is 0.1-3 h < -1 >;
the concentration of the acid liquor used in the acid washing treatment is 0.1-2 mol/L, and the solid-to-liquid ratio in the acid washing treatment is 1 g: (6-12) mL, wherein the pickling temperature is 30-120 ℃, and the pickling time is 1-12 hours.
The ZSM-5 molecular sieve catalyst is subjected to steam treatment, acid washing treatment, roasting and alkaline phosphate modification in sequence to obtain the catalyst with proper acidity and alkalinity and proper pore channel size, and the catalyst has high catalytic activity.
Specifically, the ZSM-5 molecular sieve catalyst is preferably subjected to steam treatment and acid washing treatment in sequence, filtering, drying and roasting are performed in sequence after acid washing, and finally, the ZSM-5 molecular sieve catalyst is immersed in an alkaline phosphate aqueous solution, and is dried and roasted again to obtain the modified ZSM-5 molecular sieve catalyst.
In the present invention, the specific surface area of the ZSM-5 molecular sieve>300m2G, pore volume>0.2cm3The silicon-aluminum ratio is 3-800, and the grain size is 30-3000 nm. In one embodiment of the invention, the silicon to aluminum ratio is 60. The physical and chemical properties of the ZSM-5 molecular sieves of different crystallite sizes used in the specific examples of the present invention are shown in Table 1.
TABLE 1 physical and chemical Properties of ZSM-5 molecular sieves of different crystallite sizes
| Grain size | SBET a(m2·g-1) | VT b(cm3·g-1) |
| 80nm | 383 | 0.41 |
| 200nm | 378 | 0.24 |
| 800nm | 354 | 0.22 |
| 3μm | 294 | 0.18 |
a:BET surface area；b:Totalpore volume at P/Po＝0.99。
The ZSM-5 molecular sieve is preferably placed in a fixed bed tubular reactor for steam treatment; the temperature of the steam treatment is 200-800 ℃, preferably 300-700 ℃, and more preferably 300-500 ℃; specifically, in the embodiment of the present invention, it may be 300 ℃, 500 ℃ or 700 ℃; the time of the steam treatment is 0.5 to 6 hours, preferably 1 to 3 hours. The airspeed of the water vapor treatment is 0.1-3 h-1Preferably 1 to 1.5 hours-1. In one embodiment of the invention, the space velocity of the steam treatment is 1h-1The time is 1 h. And discharging the molecular sieve from the tubular reactor after the water vapor treatment is finished.
Soaking the ZSM-5 molecular sieve subjected to water vapor treatment in an acid solution, and carrying out acid washing treatment, wherein the acid solution is preferably an inorganic acid aqueous solution or an organic acid aqueous solution, and the inorganic acid is preferably one or more of hydrochloric acid, nitric acid and phosphoric acid; the organic acid is preferably one or more of acetic acid, citric acid and oxalic acid; the concentration of the acid solution is preferably 0.1 to 2mol/L, more preferably 0.2 to 0.8mol/L, and specifically, in the embodiment of the present invention, the concentration may be 0.2mol/L, 0.5mol/L, or 0.8 mol/L. The solid-to-liquid ratio of the ZSM-5 molecular sieve subjected to the steam treatment to the inorganic acid aqueous solution is preferably 1 g: (6-12) mL, more preferably 1 g: (8-10) mL; specifically, in the embodiment of the present invention, the ratio of 1 g: 10 mL; the solid-to-liquid ratio of the ZSM-5 molecular sieve subjected to the steam treatment to the organic acid aqueous solution is preferably 1 g: (6-12) mL, more preferably 1 g: (8-10) mL; specifically, in the embodiment of the present invention, the ratio of 1 g: 10 mL. Soaking in acid solution preferably for multiple times; the soaking frequency is preferably 1-3 times; the time of each soaking is preferably 2-4 h.
Filtering the ZSM-5 molecular sieve soaked by the acid solution, and then drying and roasting the molecular sieve in sequence. The drying temperature is preferably 80-120 ℃, more preferably 90-110 ℃, and most preferably 100 ℃; specifically, in one embodiment of the present invention, the drying temperature may be 120 ℃; the drying time is preferably 4-24 hours, more preferably 6-20 hours, and most preferably 8-15 hours; specifically, in one embodiment of the present invention, the drying time may be 12 hours.
The roasting temperature is preferably 400-600 ℃, more preferably 500 ℃, and specifically, in one embodiment of the invention, the roasting temperature is 500 ℃; the calcination time is preferably 2 to 6 hours, more preferably 3 to 5 hours, and specifically, in one embodiment of the present invention, may be 5 hours.
The method comprises the steps of dipping the roasted ZSM-5 molecular sieve in an alkaline phosphate aqueous solution, taking out the ZSM-5 molecular sieve, and drying and roasting the ZSM-5 molecular sieve again to obtain the modified ZSM-5 molecular sieve catalyst.
In the invention, the alkaline phosphate is preferably one or more of alkaline metal phosphate, alkaline metal dihydrogen phosphate and alkaline metal hydrogen phosphate, the alkaline metal in the invention is alkali metal and/or alkaline earth metal, and the alkali metal preferably comprises one or more of sodium, potassium and cesium; the alkaline earth metal preferably comprises one or more of barium, magnesium and calcium. Specifically, the alkaline phosphate may be one or more of sodium phosphate, potassium phosphate, calcium phosphate, barium phosphate, magnesium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, sodium hydrogen phosphate, and magnesium hydrogen phosphate, and specifically, in one embodiment of the present invention, may be sodium hydrogen phosphate. The concentration of the alkaline phosphate is preferably 0.1-6 wt%.
In the invention, the dipping temperature is preferably 20-60 ℃, more preferably 30-50 ℃, and most preferably 20-30 ℃, specifically, in the embodiment of the invention, the dipping can be carried out at normal temperature, namely, the dipping is carried out at 20-25 ℃; the dipping time is preferably 2 to 24 hours, more preferably 5 to 24 hours, and most preferably 8 to 20 hours. The impregnation is preferably carried out in a multiple impregnation mode; the time for each dipping is preferably 2-6 h; the number of dipping times is preferably 3 to 5.
The secondary drying temperature is preferably 80-120 ℃, more preferably 90-110 ℃, and most preferably 100 ℃; specifically, in one embodiment of the present invention, the drying temperature may be 120 ℃; the drying time is preferably 4-24 hours, more preferably 6-20 hours, and most preferably 8-15 hours; specifically, in one embodiment of the present invention, the drying time may be 12 hours.
The secondary roasting temperature is preferably 400-600 ℃, more preferably 500 ℃, and specifically, in one embodiment of the invention, the roasting temperature is 500 ℃; the calcination time is preferably 2 to 6 hours, more preferably 3 to 5 hours, and specifically, in one embodiment of the present invention, may be 5 hours.
The modification method comprises the steps of firstly carrying out steam treatment on the ZSM-5 molecular sieve, and adjusting the silica-alumina ratio of the molecular sieve to a certain degree, wherein the steam treatment can generate a certain proportion of secondary holes due to the removal of framework aluminum of the molecular sieve, but the removed framework aluminum can block the pore channels and generate a certain proportion of L acid, so that an acidic aqueous solution with a certain concentration is required to be adopted for treatment, and non-framework aluminum generated due to the steam treatment or non-framework aluminum contained in the molecular sieve before the treatment is removed, so that the blocked pore channels of the molecular sieve can be exposed, and the diffusion performance of reactants and products and the capacity of containing carbon deposition are improved; and simultaneously, the acid amount of the molecular sieve and the ratio of the B acid to the L acid are adjusted. Finally, the active component alkaline phosphate is loaded, so that the molecular sieve has proper acid amount, acid strength and a proper pore channel structure, and has better reaction performance and stability. The modification method has the advantages that the steam treatment temperature, time and airspeed are reduced in the steam treatment process; selecting acid types, the concentration of an acidic aqueous solution, the acid treatment temperature, the acid treatment time and the solid-to-liquid ratio in the acid washing process; both the active component loading and the type can have a large impact on the final catalyst performance.
The invention also provides a modified ZSM-5 molecular sieve catalyst prepared according to the preparation method.
Active component P of modifier in modified ZSM-5 molecular sieve catalyst in the invention2O5And alkali/alkaline earth metal oxides; calculated as the weight of the entire solid catalyst after modification, P2O5The content of the alkali metal/alkaline earth metal oxide is 5-30% by mass, and the content of the alkali metal/alkaline earth metal oxide is 1-25% by mass. Specifically, in the embodiment of the invention, the active component of the modifier in the modified ZSM-5 molecular sieve catalyst comprises 25% of P2O5And 20% of Na2O。
The invention also provides application of the modified ZSM-5 molecular sieve catalyst as a catalyst in preparing 3-methyl-3-butene-1-alcohol by condensing isobutene and formaldehyde, namely, the invention also provides a preparation method of the 3-methyl-3-butene-1-alcohol, which comprises the following steps:
in the presence of a catalyst, reacting isobutene with paraformaldehyde to obtain 3-methyl-3-butene-1-ol; preferably, paraformaldehyde, toluene and isobutene are mixed and reacted in the presence of a catalyst to obtain 3-methyl-3-buten-1-ol;
the catalyst is a modified ZSM-5 molecular sieve catalyst as described above.
In the invention, the molar ratio of isobutene to formaldehyde is preferably (5-15): 1, more preferably (8-12): specifically, in the embodiment of the present invention, the ratio of 15: 1; the reaction temperature is preferably 180-230 ℃, more preferably 190-220 ℃, and most preferably 200-210 ℃, specifically, in the embodiment of the invention, 180 ℃, 200 ℃ or 230 ℃; the reaction pressure is preferably 5-15 MPa, more preferably 8-12 MPa, and specifically, in the embodiment of the invention, the reaction pressure can be 5MPa, 8MPa or 15 MPa; the reaction time is preferably 1 to 5 hours, more preferably 2 to 4 hours, and most preferably 2 to 3 hours, and specifically, in an embodiment of the present invention, may be 2 hours.
The invention provides a preparation method of a modified ZSM-5 molecular sieve catalyst, which comprises the following steps: sequentially carrying out steam treatment, acid washing treatment and roasting on the ZSM-5 molecular sieve, and then carrying out impregnation modification in an alkaline phosphate aqueous solution to obtain a modified ZSM-5 molecular sieve catalyst; the temperature of the steam treatment is 200-800 ℃, the time of the steam treatment is 0.5-6 hours, and the airspeed of the steam is 0.1-3 h < -1 >; the concentration of the acid liquor used in the acid washing treatment is 0.1-2 mol/L, and the solid-to-liquid ratio in the acid washing treatment is 1 g: (6-12) mL, wherein the pickling temperature is 30-120 ℃, and the pickling time is 1-12 hours. The water vapor, acid washing treatment and alkaline phosphate modification treatment in the invention can adjust the pore structure distribution and acid properties (strength and acid amount) of the ZSM-5 molecular sieve, so as to obtain the catalyst with proper acidity and alkalinity and proper pore channel size. Compared with the prior art, the modified ZSM-5 catalyst has higher catalytic activity and better product diffusivity, can reduce reaction temperature and reaction pressure, and simultaneously keeps high product yield. Experimental results show that the modified ZSM-5 molecular sieve catalyst is applied to the reaction of preparing 3-methyl-3-butene-1-ol through condensation reaction of isobutene and paraformaldehyde, the highest yield of the product 3-methyl-3-butene-1-ol is 95% and the conversion rate of formaldehyde is up to 100% relative to formaldehyde under the conditions that the reaction temperature is 180-230 ℃, the reaction pressure is 8-15 MPa and the molar ratio of isobutene to formaldehyde is 5-15: 1, and the preparation efficiency is effectively improved. And the catalyst is easy to separate after the reaction, so that the operation and energy consumption in the separation aspect are reduced, and the problems of equipment corrosion and environmental pollution caused by the liquid acid catalyst in the traditional production process are solved.
In order to further illustrate the present invention, the following examples are provided to describe the modified ZSM-5 molecular sieve catalyst, its preparation method and application in detail, but should not be construed as limiting the scope of the present invention.
Example 1
Molecular sieve ZSM-5 (silica-alumina ratio 60, grain size 80nm) is firstly processed at 300 ℃ for 1h-1Treating with water vapor for 1h, then washing with 0.2mol/L dilute nitric acid for 1h, filtering, drying at 120 ℃, roasting at 500 ℃ for 5h, finally soaking in sodium hydrogen phosphate aqueous solution at normal temperature for 3-5 times, wherein the soaking time is 2-6 h each time, drying at 120 ℃ for 12h, and roasting at 500 ℃ for 5h to obtain the modified ZSM-5 molecular sieve catalyst, which is marked as Z-1.
Example 2
Molecular sieve ZSM-5 (silica-alumina ratio 60, grain size 80nm) is firstly heated at 500 ℃ for 1h-1Treating with water vapor for 1h, then washing with 0.2mol/L dilute nitric acid for 1h, filtering, drying at 120 ℃, roasting at 500 ℃ for 5h, finally soaking in sodium hydrogen phosphate aqueous solution at normal temperature for 3-5 times, wherein the soaking time is 2-6 h each time, drying at 120 ℃ for 12h, and roasting at 500 ℃ for 5h to obtain the modified ZSM-5 molecular sieve catalyst, which is recorded as Z-2.
Example 3
Molecular sieve ZSM-5 (silica-alumina ratio 60, grain size 80nm) is firstly processed at 700 ℃ for 1h-1Treating with water vapor for 1h, then washing with 0.2mol/L dilute nitric acid for 1h, filtering, drying at 120 ℃, roasting at 500 ℃ for 5h, finally soaking in sodium hydrogen phosphate aqueous solution at normal temperature for 3-5 times, wherein the soaking time is 2-6 h each time, drying at 120 ℃ for 12h, and roasting at 500 ℃ for 5h to obtain the modified ZSM-5 molecular sieve catalyst, which is marked as Z-3.
Example 4
Molecular sieve ZSM-5 (silica-alumina ratio 60, grain size 80nm) is firstly heated at 500 ℃ for 1h-1Treating with water vapor for 1h, then washing with 0.2mol/L dilute nitric acid for 3h, filtering, drying at 120 ℃, roasting at 500 ℃ for 5h, finally soaking in sodium hydrogen phosphate aqueous solution at normal temperature for 3-5 times, wherein the soaking time is 2-6 h each time, drying at 120 ℃ for 12h, and roasting at 500 ℃ for 5h to obtain the modified ZSM-5 molecular sieve catalyst, which is recorded as Z-4.
Example 5
Molecular sieve ZSM-5 (silica-alumina ratio 60, grain size 80nm) is firstly heated at 500 ℃ for 1h-1Treating with water vapor for 1h, then washing with 0.5mol/L dilute nitric acid for 1h, filtering, drying at 120 ℃, roasting at 500 ℃ for 5h, finally soaking in sodium hydrogen phosphate aqueous solution at normal temperature for 3-5 times, wherein the soaking time is 2-6 h each time, drying at 120 ℃ for 12h, and roasting at 500 ℃ for 5h to obtain the modified ZSM-5 molecular sieve catalyst, which is marked as Z-5.
Example 6
Molecular sieve ZSM-5 (silica-alumina ratio 60, grain size 80nm) is firstly heated at 500 ℃ for 1h-1Treating with water vapor for 1h, then washing with 0.8mol/L dilute nitric acid for 1h, filtering, drying at 120 ℃, roasting at 500 ℃ for 5h, finally soaking in sodium hydrogen phosphate aqueous solution at normal temperature for 3-5 times, wherein the soaking time is 2-6 h each time, drying at 120 ℃ for 12h, and roasting at 500 ℃ for 5h to obtain the modified ZSM-5 molecular sieve catalyst, which is marked as Z-6.
Example 7
Molecular sieve ZSM-5 (silica-alumina ratio 60, grain size 200nm) is firstly heated at 500 ℃ for 1h-1Treating with water vapor for 1h, then washing with 0.2mol/L dilute nitric acid for 1h, filtering, drying at 120 ℃, roasting at 500 ℃ for 5h, finally soaking in sodium hydrogen phosphate aqueous solution at normal temperature for 3-5 times, wherein the soaking time is 2-6 h each time, drying at 120 ℃ for 12h, and roasting at 500 ℃ for 5h to obtain the modified ZSM-5 molecular sieve catalyst, which is recorded as Z-7.
Example 8
Molecular sieve ZSM-5 (silica-alumina ratio 60, grain size 800nm) is firstly processed at 500 ℃ for 1h-1Treating with water vapor for 1h, then washing with 0.2mol/L dilute nitric acid for 1h, filtering, drying at 120 ℃, roasting at 500 ℃ for 5h, finally soaking in sodium hydrogen phosphate aqueous solution at normal temperature for 3-5 times, wherein the soaking time is 2-6 h each time, drying at 120 ℃ for 12h, and roasting at 500 ℃ for 5h to obtain the modified ZSM-5 molecular sieve catalyst, which is recorded as Z-8.
Example 9
Molecular sieve ZSM-5 (silica-alumina ratio 60, grain size 3 μm) is firstly processed at 500 ℃ for 1h-1Treating with water vapor for 1h, washing with 0.2mol/L dilute nitric acid for 1h, filtering, drying at 120 ℃, roasting at 500 ℃ for 5h, and finally soaking in sodium hydrogen phosphate aqueous solution at normal temperature for 3-5 times, wherein each timeAnd the secondary impregnation time is 2-6 hours, the product is dried for 12 hours at 120 ℃ and roasted for 5 hours at 500 ℃ to obtain the modified ZSM-5 molecular sieve catalyst, which is marked as Z-9.
The activity of the catalysts prepared in examples 1 to 9 was evaluated. The evaluation conditions were: a500 mL high-pressure reaction kettle is adopted, 1.0g of catalyst, 6g of paraformaldehyde and 60g of toluene are filled in the high-pressure reaction kettle, the high-pressure reaction kettle is sealed, and nitrogen is introduced to remove air in the kettle. And starting an isobutene metering pump, and controlling the isobutene feeding amount to be 160 g. The molar ratio of isobutene to formaldehyde was 15. Controlling the reaction temperature at 230 ℃ and the reaction pressure at 15MPa, reacting for 2h, and removing the residual isobutene and the catalyst. After the reaction, the formaldehyde conversion rate of the sample is obtained by liquid chromatography and potentiometric titration quantitative analysis, and the 3-methyl-3-butene-1-ol yield is obtained by gas chromatography quantitative analysis. The results data are the average results under these conditions. The specific reaction results are shown in Table 2.
TABLE 2 reactivity of different catalysts
The catalysts of ZSM-5 molecular sieves with different crystal grain sizes (80nm, 200nm, 800nm and 3 mu m) after water vapor treatment, acid washing treatment, roasting and alkaline phosphate modification respectively correspond to Z2, Z7, Z8 and Z9, and are used for preparing 3-methyl-3-buten-1-ol from isobutene and paraformaldehyde, and the yield of the 3-methyl-3-buten-1-ol is shown in figure 1 along with the change of the using times n of the catalyst under optimized reaction conditions. As can be seen from the figure, the yield of the 3-methyl-3-buten-1-ol is not obviously reduced after the catalyst Z2 is repeatedly used for 10 times, the yield of the 3-methyl-3-buten-1-ol is obviously reduced after the catalyst Z7 is repeatedly used for 10 times, the yield of the 3-methyl-3-buten-1-ol is obviously reduced after the catalyst Z8 is repeatedly used for 5 times, and the yield of the 3-methyl-3-buten-1-ol is obviously reduced after the catalyst Z9 is repeatedly used for 3 times.
According to the data obtained in the experimental examples 1-9, the modified ZSM-5 molecular sieve catalyst provided by the invention is used for synthesizing 3-methyl-3-butene-1-ol from isobutene and paraformaldehyde, the yield of the 3-methyl-3-butene-1-ol relative to formaldehyde can reach 95% at most under the optimized reaction condition, the conversion rate of the formaldehyde reaches 100%, and the preparation efficiency is effectively improved. Compared with the existing catalyst which is used for synthesizing the 3-methyl-3-butene-1-ol by taking isobutene and paraformaldehyde as raw materials, the catalyst can effectively reduce the reaction temperature and the reaction pressure, effectively reduce the cost and has better commercial value.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a modified ZSM-5 molecular sieve catalyst comprises the following steps:
sequentially carrying out steam treatment, acid washing treatment and roasting on the ZSM-5 molecular sieve, and then carrying out impregnation modification on the alkaline phosphate aqueous solution to obtain a modified ZSM-5 molecular sieve catalyst;
the temperature of the steam treatment is 200-800 ℃, the time of the steam treatment is 0.5-6 hours, and the airspeed of the steam is 0.1-3 h < -1 >;
the concentration of the acid liquor used in the acid washing treatment is 0.1-2 mol/L, and the solid-to-liquid ratio in the acid washing treatment is 1 g: (6-12) mL, wherein the pickling temperature is 30-120 ℃, and the pickling time is 1-12 hours.
2. The method of claim 1, wherein the ZSM-5 molecular sieve has a specific surface area>300m2G, pore volume>0.2cm3The silicon-aluminum ratio is 3-800, and the grain size is 30-3000 nm.
3. The preparation method of claim 1, wherein the roasting temperature is 300-600 ℃; the roasting time is 2-5 hours.
4. The preparation method according to claim 1, wherein the acid used in the acid washing treatment is one or more of hydrochloric acid, nitric acid, phosphoric acid, acetic acid, citric acid and oxalic acid.
5. The preparation method according to claim 1, wherein the alkali phosphate is one or more of a phosphate of an alkali metal, a dihydrogen phosphate of an alkali metal and a hydrogen phosphate of an alkali metal;
the alkaline metal is one or more of sodium, potassium, cesium, barium, magnesium and calcium;
the concentration of the alkaline phosphate is 0.1-15 wt%.
6. The method according to claim 1, wherein the temperature of the impregnation is 20 to 60 ℃ and the time of the impregnation is 2 to 24 hours.
7. The preparation method of claim 1, wherein the acid-washed ZSM-5 molecular sieve is sequentially dried and calcined, and then impregnated.
8. The preparation method of claim 1, wherein the impregnated ZSM-5 molecular sieve is sequentially dried and calcined to obtain the modified ZSM-5 molecular sieve.
9. A modified ZSM-5 molecular sieve catalyst prepared by the preparation method of any one of claims 1 to 8;
the active component in the modified ZSM-5 molecular sieve is P2O5And a basic metal oxide, said P2O5The mass fraction of the alkali metal oxide is 5-30%, and the mass fraction of the alkali metal oxide is 1-25%;
the alkaline metal oxide is one or more of oxides of sodium, potassium, cesium, barium, magnesium and calcium.
10. Use of the modified ZSM-5 molecular sieve catalyst of claim 9 as a catalyst in the condensation of isobutylene and formaldehyde to produce 3-methyl-3-buten-1-ol.
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