CN108862306B - Synthetic method of small-grain FER molecular sieve with layered stacking structure - Google Patents
Synthetic method of small-grain FER molecular sieve with layered stacking structure Download PDFInfo
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- CN108862306B CN108862306B CN201810820465.XA CN201810820465A CN108862306B CN 108862306 B CN108862306 B CN 108862306B CN 201810820465 A CN201810820465 A CN 201810820465A CN 108862306 B CN108862306 B CN 108862306B
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 104
- 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 104
- 238000010189 synthetic method Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 17
- 229910001868 water Inorganic materials 0.000 claims abstract description 16
- 230000004888 barrier function Effects 0.000 claims abstract description 9
- 238000009832 plasma treatment Methods 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 5
- 239000012265 solid product Substances 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 10
- 230000008878 coupling Effects 0.000 abstract description 7
- 238000010168 coupling process Methods 0.000 abstract description 7
- 238000005859 coupling reaction Methods 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- 210000002381 plasma Anatomy 0.000 abstract 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 239000011148 porous material Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002715 modification method Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005899 aromatization reaction Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003916 ethylene diamine group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 241001292396 Cirrhitidae Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008542 thermal sensitivity Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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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
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
- C07C5/2775—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
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Abstract
The invention discloses a method for synthesizing a small-grain FER molecular sieve with a layered stacking structure, which comprises the following steps: taking a silicon source, an aluminum source, alkali, an organic template and water as raw materials, carrying out rotary aging at a lower temperature to form initial gel, then carrying out dynamic crystallization to obtain a primary product, and removing the organic template by utilizing a large amount of low-temperature plasmas generated by a Dielectric Barrier Discharge (DBD) device under a mild condition to obtain the small-grain FER molecular sieve with a layered structure; and finally, performing steam coupling low-temperature plasma treatment on the prepared molecular sieve at different depths, so that not only can framework aluminum be removed and the acid ratio of the FER molecular sieve be modulated, but also the appearance and the structure of the molecular sieve can be further modified. The molecular sieve prepared by the invention has good stability and strong anti-carbon deposition capability, obtains excellent performance when being applied to the catalytic n-butene isomerization reaction, effectively enhances the catalyst stability and greatly improves the service life of the catalyst.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a synthetic method and application of a small-grain FER molecular sieve with a layered stacking structure.
Background
Isobutene is used as a basic organic chemical raw material with wide application, and can be used for producing various important organic chemical products such as butyl rubber, polyisobutylene, tert-butyl alcohol, tert-butyl amine, methyl tert-butyl ether (MTBE), Methyl Methacrylate (MMA) and the like, and the demand of isobutene is increasing day by day. At present, the main raw materials for industrially producing isobutene are ethylene prepared by naphtha steam cracking and a byproduct C in a fluidized cracking device of an oil refinery4And the byproduct tertiary butanol in the synthesis of the propylene oxide by using the Halcon method.
The methods for industrially producing isobutene at the present stage include an isobutane dehydrogenation method, a sulfuric acid extraction method, a resin dehydration method and an n-butene skeletal isomerization method. Among them, the first three production processes are gradually eliminated due to the complicated operation flow, corrosiveness to reaction devices, environmental pollution and other problems; in contrast, the n-butene skeletal isomerization process requires less equipment, is simple to operate, has good catalytic stability, and has remarkable advantages. The n-butene skeletal isomerization process can be divided into a gamma-alumina process and a molecular sieve process according to the used catalyst, wherein the gamma-alumina process has high reaction temperature (about 500 ℃), low isobutene selectivity (< 85%) and single-pass yield and short catalyst life, and compared with the molecular sieve process, the molecular sieve process has low reaction temperature (about 350 ℃), high isobutene selectivity (> 90%) and single-pass yield and better catalyst stability, and has obvious industrial application advantages. Of the molecular sieve processes, the most representative and commercially valuable is FER molecular sieves.
FER molecular sieve is a ferrierite with a mesoporous structure and has the main structural characteristics; eight-membered ring (0.48nm multiplied by 0.35nm) pore channels parallel to a [010] crystal plane and ten-membered ring (0.54nm multiplied by 0.45nm) pore channels parallel to a [001] crystal plane are mutually staggered to form a two-dimensional pore channel structure, and meanwhile, six-membered rings parallel to the ten-membered rings and the eight-membered rings are intersected to form an oval FER cage. Because of the unique structural system, the FER molecular sieve shows good catalytic effect in reaction systems of hydrocarbon isomerization, cracking, aromatization, dimethyl ether carbonylation and the like. Currently, FER molecular sieves are mainly hydrothermally synthesized by adding organic templates, wherein the common organic templates include ethylenediamine (US4016245), pyrrolidine (US4016245), pyridine (US4578259), cyclohexylamine, hexamethyleneimine (US4925548), butanediamine, etc. (US 4146584). However, the FER obtained by the related synthesis method is faced with large grains, so that the diffusion of reactant molecules and product molecules in the molecular sieve is inhibited to a certain extent, and as a result, the product cannot diffuse out in time, so that various side reactions occur, coking phenomenon is more serious, and the catalytic life of the FER is shortened. Therefore, FER obtained by general synthesis needs to be modified by different means to improve the catalytic performance, and then can be put into industrial application.
According to the reports of related documents, FER modification methods for catalyzing n-butene isomerization mainly fall into two categories, namely pre-synthesis modification and post-treatment modification. The modification method before synthesis comprises the methods of adding various surfactants, recrystallization, compounding templates and the like, and mainly aims to improve the size and the shape of FER crystal grains, increase mesopores and the like. The post-treatment modification comprises ion exchange, acid-base treatment, gas phase/liquid phase deposition, isomorphous replacement, water vapor treatment and the like, so that the effects of desiliconization and dealuminization are achieved, the regulation and control of the acid content and the acid density of the FER molecular sieve are finally realized, more abundant micropores and mesopores are created, and the catalytic activity and the stability of the FER molecular sieve are improved. For achieving an industrially useful FER, the post-treatment is often reasonable and easy to achieve in view of its economy and practical operability. Among them, the steam treatment is an economical, simple to operate and obvious in effect modification method, and has been applied to some molecular sieve catalytic systems. CN200610147672.0 discloses a method for preparing ethylene by modifying ZSM-5 with high-temperature water vapor and then combining acid treatment, wherein a large amount of mesopores are generated after treatment, and the diffusion of molecules in the reaction is improved. CN201310492001.8 discloses a catalyst for modifying HZSM-5 by water vapor and then loading an active metal component, which is used in the industrial field of Methanol To Gasoline (MTG). CN201610549306.1 discloses a modification treatment method of an HZSM-5 molecular sieve catalyst, which mainly comprises coupling acid-base treatment and steam treatment, and then is used for aromatization reaction of low-carbon hydrocarbon. In addition, CN201580017296.6 of England petrochemicals GmbH introduces a zeolite catalyst treated with steam with a molar weight of 1% or more, which is used for preparing methyl acetate by carbonylation of dimethyl ether with good effect. However, for the reaction system of FER catalysis n-butene isomerization, in addition to the fact that CN201310499341.3, a research institute of petrochemical engineering, reports a start-up method for producing isobutene through n-butene skeletal isomerization, wherein alkylbenzene and inert gas are introduced, and then water vapor is introduced (600-700 ℃), and a n-butene isomerization method disclosed in CN201410482724.4 adopts FER and water to carry out two types of contact and then acid to carry out three types of contact. They lack a comprehensive systematic exploration of the water vapor treatment conditions (e.g., temperature, flow, time, etc.) during the study.
When the molecular sieve synthesized by the traditional method is used for removing the organic template, a method of roasting at high temperature (more than or equal to 550 ℃) for a long time (more than or equal to 6 hours) is generally adopted. The method has the disadvantage that the nano-scale molecular sieve has higher thermal sensitivity to thermal change, and can induce the bridging of Si-O-Si bonds under the high-temperature roasting condition, so that the synthesized molecular sieve crystal grains generate the effect of agglomeration and growth. Therefore, it is necessary to develop a method for removing the template from the molecular sieve under milder conditions and improving the catalytic activity of the molecular sieve.
Disclosure of Invention
The invention aims to provide a method for synthesizing a small-grain FER molecular sieve with a layered stacking structure, and the solution of the invention is as follows:
a method for synthesizing a small-grain FER molecular sieve with a layered packing structure comprises the following steps:
(1) uniformly mixing a silicon source, an aluminum source, alkali and water, adding a template agent R, uniformly stirring the obtained mixture, and standing to obtain a mixture A; wherein the silicon source is alkaline silica sol, water glass or gas-phase SiO2The aluminum source is one or more of sodium metaaluminate, aluminum sulfate, aluminum nitrate or aluminum chloride, the alkali is one of sodium hydroxide or potassium hydroxide, the template agent R is one or more of pyrrolidine, pyridine, piperidine, ethylenediamine, triethylamine, isopropylamine or cyclohexylamine, and the molar ratio of the silicon source, the aluminum source, the alkali, the water and the template agent R is as follows: SiO 22:Al2O3:MOH:H2O:R＝1：0.21～0.32:0.06～0.09:1.30～1.60:30～32；
(2) Aging the mixture A to form gel;
(3) dynamically crystallizing the gel, cooling to room temperature, filtering, washing the obtained solid product with water, methanol or ethanol to remove part of sodium ions and part of template agent, drying, and placing the solid product in a dielectric barrier discharge device for low-temperature plasma treatment to remove the rest template agent to obtain the Na-FER molecular sieve;
(4) carrying out ammonia ion exchange reaction on the Na-FER molecular sieve to prepare NH4FER molecular sieves, then drying the NH4-placing FER molecular sieve in a dielectric barrier discharge device to continuously treat NH by using low-temperature plasma4-converting FER molecular sieve to H-FER molecular sieve;
(5) tabletting and screening the H-FER molecular sieve to 40-60 meshes, filling the H-FER molecular sieve into a reaction tube for water vapor treatment, and then carrying out N treatment on the obtained product2Drying and activating in atmosphere; and then the obtained product is moved to a dielectric barrier discharge device for low-temperature plasma treatment, and the small-grain FER molecular sieve with the layered stacking structure can be obtained.
Preferably, the conditions for aging to form a gel in step (2) are: the temperature is 40-80 ℃, and the aging time is 3-10 h.
Preferably, the dynamic crystallization conditions in step (3) are: the temperature is 170-220 ℃, and the crystallization time is 3-10 h.
Preferably, the conditions of the low-temperature plasma treatment in the step (3), the step (4) and the step (5) are as follows: the voltage is 110-420V, the discharge current is 0.5-6.0A, and the processing time is 20-150 min.
Preferably, the water vapor treatment time t in the step (5) is 5-60min, preferably 30 min; the water flow Q of the water vapor treatment is 0.5-4.0mL/min, preferably 1.0 mL/min; the temperature T of the steam treatment is 270-470 ℃, and the preferred temperature is 370 ℃.
Preferably, the low-temperature plasma treatment voltage in the step (5) is 380V, and the discharge current is 3.6A; the treatment time is preferably 60 min.
The small-grain FER molecular sieve prepared by the method for synthesizing the small-grain FER molecular sieve with the layered stacking structure is applied to catalyzing n-butene isomerization reaction.
The principle of the invention is as follows: the DBD low-temperature plasma template agent removing technology is introduced into FER molecular sieve synthesis, the organic template agent in the molecular sieve can be rapidly removed at a lower temperature (60-150 ℃) by utilizing ions, electrons, free radicals, metastable-state particles and the like in the plasma, the defect that molecular sieve grains are agglomerated and grown at a high temperature due to high-temperature roasting is completely avoided, and therefore the original pore channel structure of the synthesized molecular sieve can be retained to the maximum extent. In addition, the molecular sieve is treated by DBD plasma to different degrees, so that the influence on the surface appearance of the molecular sieve is very obvious, the number of micropores and mesopores of the molecular sieve can be increased, and the effect on the aspect of improving the specific surface area of the molecular sieve is also obvious. In addition, low-temperature plasma generated by air or oxygen has a remarkable effect on changing hydroxyl functional groups in the molecular sieve; for example, DBD low temperature plasma of oxygen or air can introduce a large number of oxygen-containing functional groups such as-OH and-COOH on the surface of the material.
Compared with the existing preparation method of the FER molecular sieve, the preparation method has the following advantages:
the invention creatively introduces the DBD low-temperature plasma method into the processes of template agent removal and coupling steam modification in the FER molecular sieve synthesis process, and obtains good effect. By introducing a DBD low-temperature plasma technology to replace the traditional high-temperature roasting process, the organic template agent can be removed efficiently, the synthesized FER molecular sieve crystal grains are rich in micro mesopores and have a layered structure, then the pore structure of the micro mesopores can be further enriched by a low-temperature plasma coupling water vapor modification method, the acid amount and the acid strength distribution are adjusted, and the surface morphology is improved. The synthesized FER molecular sieve crystal grains are used for catalyzing n-butene isomerization reaction, and the catalytic activity and the stability are obviously improved. In addition, the synthesis method provided by the invention has the advantages of simple process, mild treatment conditions and obvious effect, and is suitable for large-scale industrial application.
Drawings
FIG. 1 shows the morphology of FER molecular sieves synthesized by different templates: (a) H-FER-EDA; (b) H-FER-Py; (c) H-FER-CHA.
FIG. 2 is a graph of FER molecular sieve pore size distribution synthesized by different templates.
FIG. 3 high resolution transmission electron micrograph of FER molecular sieve HRTEM: a (1) to (4) respectively correspond to H-FER molecular sieve raw powder HRTEM images under different magnification factors (under the scales of 50mn, 20nm, 10mn and 5mn in sequence); b (1) - (4) respectively correspond to HRTEM images (on the scale of 50mn, 20nm, 10mn and 5 mn) of the FER molecular sieve after water vapor treatment at 3ml/min under different magnifications.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples. It is also to be understood that the following examples are intended to illustrate the present invention and are not to be construed as limiting the scope of the invention, and that the particular materials, reaction times and temperatures, process parameters, etc. listed in the examples are exemplary only and are intended to be exemplary of suitable ranges, and that insubstantial modifications and adaptations of the invention by those skilled in the art in light of the foregoing description are intended to be within the scope of the invention. The examples, where specific techniques or conditions are not indicated, are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by manufacturers, and are all conventional products which can be purchased in the market.
Example 1
The experimental procedure was as follows: under stirring, 11.6g of an alkaline silica sol, 0.175g of NaOH and 0.825g of NaAlO2Dissolving in 32.5mL of deionized water, uniformly mixing, slowly dripping 5.10mL of ethylenediamine, stirring for 1.0h, standing, transferring the obtained mixture into a polytetrafluoroethylene hydrothermal reaction kettle, packaging, and dynamically rotating and aging in a homogeneous reactor at 80 ℃ for 3h to form gel; then heating the obtained gel to 190 ℃ for dynamic crystallization for 4h, wherein the rotating speed of a motor is 150 rpm; after crystallization is finished, naturally cooling the reaction kettle to room temperature, filtering, washing the obtained solid product for 3-5 times by using deionized water and absolute ethyl alcohol for multiple times to remove partial Na+And a template agent, and then drying the mixture in a drying oven at 120 ℃ for 6 h. And transferring the dried molecular sieve product into a Dielectric Barrier Discharge (DBD) device, and treating for 30min under the conditions of 380V voltage and 2.5A current to obtain the Na-FER molecular sieve. Na-FER molecular sieve at 1.0M NH at 80 deg.C4NO3Carrying out ion exchange reaction in the solution for three times, wherein the exchange time is 3 hours each time, and the solid-to-liquid ratio is 1g:50mL to prepare NH4-FER molecular sieves. After the ion exchange is finished, NH is added4-FER molecular sieve is put into a drying ovenDrying at 120 deg.C for 6H, and transferring into Dielectric Barrier Discharge (DBD) device again for the same treatment to obtain H-FER-EDA molecular sieve. FIG. 1a is an SEM topography of the H-FER-EDA molecular sieve, the flake thickness of the molecular sieve is 60-80nm, and the pore size distribution curve is shown in FIG. 2.
Catalytic n-butene isomerization reaction
Filling 0.2g of 40-60-mesh FER catalyst in a quartz tube with the inner diameter of 12mm, and filling 20-40-mesh quartz sand on the upper layer of the catalyst; the reaction device is firstly heated to 350 ℃ by program, and N is introduced at the speed of 40ml/min2Activating for 1 h; at the temperature, reaction raw material gas n-butene is introduced, and the space velocity WHSV is kept to be 4h-1And the reaction product is analyzed and detected on line by GC-9160, the column temperature is 90 ℃, and the chromatographic column: 50m 0.35mm Na2SO4The capillary column, nitrogen as carrier gas, hydrogen flame detection, and the catalytic results are shown in table 1.
Example 2
Molecular Sieve preparation referring to example 1, 5.10mL of ethylenediamine was replaced with 6.30mL of pyrrolidine; and preparing the H-FER-Py molecular sieve under the same conditions. FIG. 1b is an SEM topography of the H-FER-Py molecular sieve, the flake thickness of the molecular sieve is 40-48nm, and the pore size distribution curve is shown in FIG. 2. The evaluation conditions were the same as in example 1, and the evaluation results are shown in Table 1.
Example 3
Molecular Sieve preparation referring to example 1, 5.10mL of ethylenediamine was replaced with 8.75mL of cyclohexylamine; the other conditions are the same, and the H-FER-CHA molecular sieve is prepared. FIG. 1c is an SEM topography of the H-FER-CHA molecular sieve, the flake thickness of the molecular sieve is 35-65nm, and the pore size distribution curve is shown in FIG. 2. The evaluation conditions were the same as in example 1, and the evaluation results are shown in Table 1.
TABLE 1 FER molecular sieve synthesis by different templates Performance a of n-butene isomerization catalysis
a test result of continuous reaction for 10h
Furthermore, as can be seen from the pore size distribution curve shown in fig. 2: the H-FER-Py molecular sieve synthesized by taking Py as a template has obvious mesoporous distribution in the ranges of 4-5nm and 20-40nm, while the FER molecular sieve synthesized by taking EDA and CHA as templates has the pore diameter mainly distributed in the range of 50-80nm and is in the macroporous distribution range.
Example 4
0.8g of the H-FER molecular sieve (40-60 mesh number) prepared in example 1 was charged in a quartz reaction tube, and 40mL/min of N was introduced into a heating furnace2Heating to 370 deg.C under atmosphere, introducing 3.0mL/min liquid water, gasifying into steam in quartz reaction tube for 5-60min, and introducing 40mL/minN2Drying and activating the atmosphere, and then treating the mixture in DBD low-temperature plasma, wherein the voltage is 380V, the current is 3.6A, and the treatment time is 60min, so that the modified FER molecular sieve can be prepared. The increase of mesopores is shown by micro/mesopore full static adsorption, as shown in fig. 3b (1) - (4), HRTEM images of FER molecular sieve treated by water vapor in the embodiment under different magnification (sequentially under the scale of 50mn, 20nm, 10mn and 5 mn) are shown, compared with HRTEM images a (1) - (4) of untreated H-FER molecular sieve raw powder, the FER molecular sieve treated by water vapor can clearly see mesopores. The evaluation conditions were the same as in example 1, and the evaluation results are shown in Table 2.
TABLE 2 FER molecular sieve Performance of N-butene isomerization catalysis after modification by low temperature plasma coupling with different steam treatment times t
Example 5
Preparation of molecular sieves referring to example 4, the flow rate of liquid water was changed to 0.5-4.0mL/min, and the treatment time was changed to 30 min; the modified FER molecular sieve B1-B5 is prepared under the same conditions. The XRD diffractogram analysis confirmed that the molecular sieve crystal structure was not destroyed under this treatment condition. The evaluation conditions were the same as in example 1, and the evaluation results are shown in Table 3.
TABLE 3FER molecular sieve Performance of n-butene isomerization catalysis after low-temperature plasma coupling and modification at different water flow rates Q
Example 6
Molecular sieve preparation referring to example 5, the heating temperature was changed to 270 ℃ and 470 ℃, and the flow rate of liquid water was changed to 1.0 mL/min; the other conditions are the same, and the modified FER molecular sieve C is prepared1-C5. The XRD diffractogram analysis confirmed that the molecular sieve crystal structure was not destroyed under this treatment condition. The evaluation conditions were the same as in example 1, and the evaluation results are shown in Table 4.
TABLE 4 FER molecular sieves Performance of n-butene isomerization catalysis after low temperature plasma coupling modification at different steam temperatures T
Claims (4)
1. A method for synthesizing a small-grain FER molecular sieve with a layered stacking structure is characterized by comprising the following steps:
(1) uniformly mixing a silicon source, an aluminum source, alkali and water, adding a template agent R, uniformly stirring the obtained mixture, and standing to obtain a mixture A; wherein the silicon source is alkaline silica sol, water glass or gas-phase SiO2The aluminum source is one or more of sodium metaaluminate, aluminum sulfate, aluminum nitrate or aluminum chloride, the alkali is sodium hydroxide, the template agent R is one or more of pyrrolidine, pyridine, piperidine, ethylenediamine, triethylamine, isopropylamine or cyclohexylamine, and the molar ratio of the silicon source, the aluminum source, the alkali, water and the template agent R is as follows: SiO 22: Al2O3: MOH: H2O : R =1：0.21~0.32:0.06~0.09:1.30~1.60:30~32；
(2) Aging the mixture A to form gel;
(3) dynamically crystallizing the gel, cooling to room temperature, filtering, washing the obtained solid product with water, methanol or ethanol to remove part of sodium ions and part of template agent, drying, and placing the solid product in a dielectric barrier discharge device for low-temperature plasma treatment to remove the rest template agent to obtain the Na-FER molecular sieve; the conditions of the low-temperature plasma treatment are as follows: the voltage is 110-420V, the discharge current is 0.5-6.0A, and the processing time is 20-150 min;
(4) carrying out ammonia ion exchange reaction on the Na-FER molecular sieve to prepare NH4FER molecular sieves, then drying the NH4-placing FER molecular sieve in a dielectric barrier discharge device to continuously treat NH by using low-temperature plasma4-converting FER molecular sieve to H-FER molecular sieve; the conditions of the low-temperature plasma treatment are as follows: the voltage is 110-420V, the discharge current is 0.5-6.0A, and the processing time is 20-150 min;
(5) tabletting and screening the H-FER molecular sieve to 40-60 meshes, filling the H-FER molecular sieve into a reaction tube for water vapor treatment, and then carrying out N treatment on the obtained product2Drying and activating in atmosphere; then the obtained product is moved into a dielectric barrier discharge device to be subjected to low-temperature plasma treatment, and the small-grain FER molecular sieve with the layered stacking structure can be obtained; wherein the processing voltage of the low-temperature plasma method is 380V, and the discharge current is 3.6A; the treatment time is 60 min; the water vapor treatment time t is 30 min; the water flow Q of the water vapor treatment is 1.0 mL/min; the steam treatment temperature T was 370 ℃.
2. The method for synthesizing a small grain FER molecular sieve having a layered packing structure as claimed in claim 1, wherein the aging gel-forming conditions in step (2) are as follows: the temperature is 40-80 ℃, and the aging time is 3-10 h.
3. The method for synthesizing a small-grained FER molecular sieve having a layered packing structure as claimed in claim 1, wherein the dynamic crystallization conditions in step (3) are as follows: the temperature is 170-220 ℃, and the crystallization time is 3-10 h.
4. Use of the small-grained FER molecular sieve with a layered packing structure prepared by the method according to any one of claims 1 to 3 in catalysis of n-butene isomerization reaction.
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