CN112645345B - 一种基于金属有机骨架晶体调控钛硅分子筛形貌的方法 - Google Patents
一种基于金属有机骨架晶体调控钛硅分子筛形貌的方法 Download PDFInfo
- Publication number
- CN112645345B CN112645345B CN202011446570.5A CN202011446570A CN112645345B CN 112645345 B CN112645345 B CN 112645345B CN 202011446570 A CN202011446570 A CN 202011446570A CN 112645345 B CN112645345 B CN 112645345B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- titanium
- morphology
- regulating
- metal organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 50
- 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 50
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000013078 crystal Substances 0.000 title claims abstract description 16
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 16
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims description 5
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000010936 titanium Substances 0.000 claims abstract description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 230000001276 controlling effect Effects 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 11
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000499 gel Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- LSVGWBIORRJVIM-UHFFFAOYSA-M C(C)NCC.[Br-].C(CC)[N+](CCC)(CCC)CCC Chemical compound C(C)NCC.[Br-].C(CC)[N+](CCC)(CCC)CCC LSVGWBIORRJVIM-UHFFFAOYSA-M 0.000 claims description 2
- PMHZXBOGQYOVEW-UHFFFAOYSA-M C(C)O.[OH-].C(CC)[N+](CCC)(CCC)CCC Chemical compound C(C)O.[OH-].C(CC)[N+](CCC)(CCC)CCC PMHZXBOGQYOVEW-UHFFFAOYSA-M 0.000 claims description 2
- 239000013148 Cu-BTC MOF Substances 0.000 claims description 2
- ZNIKHHQQQZPXEO-UHFFFAOYSA-M NCCCCCCN.[Br-].C(CC)[N+](CCC)(CCC)CCC Chemical compound NCCCCCCN.[Br-].C(CC)[N+](CCC)(CCC)CCC ZNIKHHQQQZPXEO-UHFFFAOYSA-M 0.000 claims description 2
- 239000013207 UiO-66 Substances 0.000 claims description 2
- FLLFDAJITUNVLF-UHFFFAOYSA-M [Br-].NCCN.CCC[N+](CCC)(CCC)CCC Chemical compound [Br-].NCCN.CCC[N+](CCC)(CCC)CCC FLLFDAJITUNVLF-UHFFFAOYSA-M 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 2
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 claims description 2
- -1 MIL-125 Chemical compound 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 41
- 239000003054 catalyst Substances 0.000 abstract description 17
- 239000011259 mixed solution Substances 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 239000002585 base Substances 0.000 description 9
- 238000005119 centrifugation Methods 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006146 oximation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
- C01B39/085—Group IVB- metallosilicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- 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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/45—Aggregated particles or particles with an intergrown morphology
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
本发明公开了一种基于金属有机骨架晶体调控钛硅分子筛形貌的方法,属于分子筛催化剂制备技术领域。其制备方法是让硅源在导向剂和水的混合的溶液中水解,钛源与金属有机骨架基材溶于异丙醇,然后,在剧烈搅拌下两种溶液混合反应,最后转移到反应釜中进行水热反应,冷却后进行离心、洗涤、干燥、煅烧得到MOFs为模板或晶种的不同形貌的TS‑1分子筛催化剂。本发明的优点在于:1)基于MOFs,通过水热反应法制备具有不同相貌的TS‑1分子筛催化剂;2)用本发明提供的方法制备的不同形貌的TS‑1分子筛催化剂可以通过调节所加入MOFs量实现分子筛粒径的调控以及分子筛形貌的转变;3)本发明有利于扩大TS‑1催化剂的应用范围。
Description
技术领域
本发明属于分子筛催化剂制备技术领域,主要涉及一种基于金属有机骨架材料调控钛硅分子筛形貌的制备方法。
背景技术
沸石分子筛作为一种高效的催化材料在石油化工领域受到了广泛的关注,并且在化工生产中产生了巨大经济价值。在20世纪80年代,具有高效择形氧化能力的钛硅分子筛的制备及发展,进一步丰富了沸石分子筛应用范围。
TS-1分子筛作为钛硅分子筛家族的重要成员,由Ti原子取代部分分子筛骨架中Si原子而形成一种杂原子分子筛,具有MFI拓扑结构。TS-1分子筛由钛氧四面体与硅氧四面体组成初级结构单元,然后通过氧桥进一步构成五元环结构,最终构成具有微孔结构的三维骨架。TS-1分子筛中平行于a轴呈S型的十元环与平行于b轴呈直线型的十元环相互交叉构成孔道结构。由于钛氧四面体具有较高的能量极易接受电子,因此TS-1分子筛能够与H2O2/有机过氧化物产生强烈吸附作用。目前,TS-1分子筛已经在环已酮肟化、苯酚羟基化、烯烃环氧化领域取得优异的成效。虽然TS-1分子筛的形貌对性能有着重大影响,但是对于TS-1分子筛形貌的调控却不被重视。传统改变TS-1分子筛形貌主要是改变四丙基氢氧化铵用量或添加碱源,两者均会造成设备的腐蚀以及水源的污染,从而造成不必要的损耗。
金属有机骨架材料(MOFs)是一种新型纳米多孔材料,通过过渡金属离子或金属簇与有机配体的自组装,形成具有周期性无限网络结构的多孔材料。由于金属粒子与有机配体都可以进行可控调节,因此MOFs被广泛用作模板剂或晶种从而调控材料形貌。但由于TS-1分子筛催化剂合成过程使用强导向作用的四丙基氢氧化铵等,导致TS-1分子筛的形貌调控困难,多数调控方法仅停留在TS-1分子筛尺寸控制上,而对于显著改变TS-1分子筛形貌的研究仍存在巨大挑战。所以以MOFs为模板或晶种显著调控TS-1分子筛催化剂的形貌具有重要的研究价值。
发明内容
本发明的目的在于以金属有机骨架为模板剂或晶种制备具有不同形貌的TS-1分子筛催化剂,从而扩大TS-1催化剂的应用范围。
本发明的技术方案是:首先在导向剂和水的混合溶液中加入硅源,通过搅拌使硅源完全水解,记为溶液A;钛源与金属有机骨架基材溶于异丙醇,记为溶液B;然后,在剧烈搅拌下溶液B逐滴加入溶液A,并在水浴/油浴中搅拌除醇。最后转移到反应釜中进行水热反应。冷却后进行离心、洗涤、干燥、煅烧得到基于MOFs的不同形貌的TS-1分子筛催化剂。
具体制备步骤为:
常温下将导向剂溶液与水混合均匀后再加入硅源,剧烈搅拌,使硅源完全水解,标记为溶液A,钛源溶于有机溶剂,再加入MOFs基材,标记为溶液B,其中各用料摩尔比值为:硅源:钛酸:导向剂:水:MOFs:有机溶剂=1:(0.03~0.04):(0.15~0.3):22:(0.01~0.05):(0.013~0.052),然后在剧烈搅拌下将溶液B逐滴滴加到溶液A中,继续搅拌1~8h,形成凝胶,接着将凝胶转移到反应釜内,在120~170℃保温24~72h,自然冷却后,离心、洗涤、干燥,最后在400~600℃高温煅烧4~10h。
所述的MOFs基材包括ZIF-8(Zn)、MIL-125(Ti)、Cu-BTC(Cu)、UiO-66(Zr)、ZIF-67(Co)等的其中几种或一种,其中优先选用ZIF-8(Zn)。
所述导向剂包括四丙基氢氧化铵、四丙基溴化铵、四乙基氢氧化铵、四丁基氢氧化铵,也包括四丙基氢氧化铵-乙醇混合液、四丙基溴化铵-乙二胺混合液、四丙基溴化铵-己二胺混合液、四丙基溴化铵-二乙胺混合液中的几种或一种,其中优选四丙基氢氧化铵。
所述有机溶剂包括异丙醇、甲醇、乙醇、丙醇、丁醇、乙二醇、丙三醇、异丁醇中的几种或一种,其中优选异丙醇。
所述硅源为正硅酸乙酯、硅酸四甲酯、硅胶、硅酸丙脂中的一种,其中优选正硅酸乙酯;
所述钛源为钛酸四丁酯、钛酸异丙酯、四氯化钛、三氯化钛中的一种或两种,其中优选钛酸四丁酯。
加入MOFs基材时,可以加在钛源中,也可以加在硅源中。
本发明的优点在于:1)基于MOFs,通过水热反应法制备具有不同相貌的TS-1分子筛催化剂;2)用本发明提供的方法制备的不同形貌的TS-1分子筛催化剂可以通过调节加入MOFs用量实现分子筛粒径的调控以及分子筛形貌的变化;3)本发明提供了基于MOFs构建不同形貌TS-1分子筛的新方法,有利于扩大TS-1催化剂的应用范围。
附图说明
图1为本发明实施案例1得到的基于MOFs的TS-1分子筛催化剂的扫描电镜图。
图2为本发明实施案例2得到的基于MOFs的TS-1分子筛催化剂的扫描电镜图。
图3为本发明实施案例3得到的基于MOFs的TS-1分子筛催化剂的扫描电镜图。
图4为本发明实施案例3得到的基于MOFs的TS-1分子筛催化剂的傅里叶红外图。
具体实施方式
下面结合具体的实施方式对本发明的技术方案做进一步说明。
实施案例1
常温下将2.4403mL四丙基氢氧化铵溶液(25wt%)与3.96mL水混合均匀,在加入2.2353mL正硅酸乙酯,剧烈搅拌2h,使正硅酸乙酯完全水解,标记为溶液A;0.1025mL钛酸四丁酯溶于1mL异丙醇,再加入0.0208g ZIF-8基材,标记为溶液B。然后在剧烈搅拌下将溶液B逐滴滴加到溶液A中,继续搅拌2h。接着把混合溶液转移到反应釜内,在130℃保温48h。自然冷却后,离心洗涤,在80℃干燥6h。最后在550℃煅烧6h。从图1中可知,通过MOFs基材调控了钛硅分子筛TS-1的形貌,所获得产物的形貌为类棺材的椭圆形颗粒,表面有凸起,粒径为800nm。
实施案例2
常温下将8.9412mL四丙基氢氧化铵溶液(25wt%)与15.84mL水混合均匀,在加入9.7612mL正硅酸乙酯,剧烈搅拌2h,使正硅酸乙酯完全水解,标记为溶液A;0.4084mL钛酸四丁酯溶于4mL异丙醇,再加入0.0833g ZIF-8基材,标记为溶液B。然后在剧烈搅拌下将溶液B逐滴滴加到溶液A中,继续搅拌2h,然后升温80℃继续搅拌,直至成黄色凝胶。接着把凝胶转移到反应釜内,在170℃保温48h。自然冷却后,离心洗涤,在80℃干燥6h。最后在550℃煅烧6h。从图2中可知,通过MOFs基材调控了钛硅分子筛TS-1的形貌,所获得产物为形貌规整的平板状,直径约为140nm。
实施案例3
常温下将2.4403mL四丙基氢氧化铵溶液(25wt%)与3.96mL水混合均匀,在加入2.2353mL正硅酸乙酯,剧烈搅拌2h,使正硅酸乙酯完全水解,标记为溶液A;0.1025mL钛酸四丁酯溶于1mL异丙醇,再加入0.0624g ZIF-8基材,标记为溶液B。然后在剧烈搅拌下将溶液B逐滴滴加到溶液A中,继续搅拌2h。接着把混合溶液转移到反应釜内,在130℃保温48h。自然冷却后,离心洗涤,在80℃干燥6h。最后在550℃煅烧6h。从图3中可知,所获得产物为小平板堆积而成的大颗粒,表面粗糙,具有明显台阶,粒径为200nm。从图4中可知,在800和960cm-1处吸收带表明成功合成了具有MFI拓扑结构的钛硅分子筛TS-1。
实施案例4
常温下将2.4403mL四丙基氢氧化铵(25wt%)和乙醇的混合液与3.96mL水混合均匀,在加入2.2353mL正硅酸乙酯,剧烈搅拌使正硅酸乙酯完全水解,标记为溶液A;0.1025mL钛酸四丁酯溶于1mL乙醇,再加入0.0208g MIL-125基材,标记为溶液B。然后在剧烈搅拌下将溶液B逐滴滴加到溶液A中,继续搅拌2h。接着把混合溶液转移到反应釜内,在160℃保温60h。自然冷却后,离心洗涤,在80℃干燥6h。最后在500℃煅烧10h。
实施案例5
常温下将2.4403mL四丙基氢氧化铵溶液(25wt%)与3.96mL水混合均匀,在加入2.2353mL正硅酸乙酯,剧烈搅拌2h,使正硅酸乙酯完全水解,标记为溶液A;0.1025mL钛酸异丙酯溶于1mL异丙醇,再加入0.0208g ZIF-67基材,标记为溶液B。然后在剧烈搅拌下将溶液B逐滴滴加到溶液A中,继续搅拌至成黄色透明凝胶。接着把混合溶液转移到反应釜内,在150℃保温48h。自然冷却后,离心洗涤,在80℃干燥6h。最后在600℃煅烧4h。
Claims (12)
1.一种基于金属有机骨架晶体调控钛硅分子筛形貌的方法,其特征在于,常温下将导向剂溶液与水混合均匀后再加入硅源,剧烈搅拌,使硅源完全水解,标记为溶液A,将钛源溶于有机溶剂,再加入MOFs基材,标记为溶液B,然后在剧烈搅拌下将溶液B逐滴滴加到溶液A中,继续搅拌1~8 h,其中各用料摩尔比值为:硅源:钛酸:导向剂:水:MOFs:有机溶剂=1:(0.03~0.04): (0.15~0.3): 22: (0.01~0.05): (0.013~0.052),形成凝胶,接着将凝胶转移到反应釜内,在120~170℃保温24~72 h,自然冷却后,离心、洗涤、干燥,最后在400~600℃高温煅烧4~10 h。
2.根据权利要求1所述的基于金属有机骨架晶体调控钛硅分子筛形貌的方法,其特征在于,所述的MOFs基材包括ZIF-8、MIL-125、Cu-BTC、UiO-66、ZIF-67中的几种或一种。
3.根据权利要求1或2所述的基于金属有机骨架晶体调控钛硅分子筛形貌的方法,其特征在于,所述的MOFs基材选用ZIF-8。
4.根据权利要求1所述的基于金属有机骨架晶体调控钛硅分子筛形貌的方法,其特征在于,所述导向剂包括四丙基氢氧化铵、四丙基溴化铵、四乙基氢氧化铵、四丁基氢氧化铵、四丙基氢氧化铵-乙醇混合液、四丙基溴化铵-乙二胺混合液、四丙基溴化铵-己二胺混合液、四丙基溴化铵-二乙胺混合液中的几种或一种。
5.根据权利要求1或4所述的基于金属有机骨架晶体调控钛硅分子筛形貌的方法,其特征在于,所述的导向剂选用四丙基氢氧化铵。
6.根据权利要求1所述的基于金属有机骨架晶体调控钛硅分子筛形貌的方法,其特征在于,所述有机溶剂包括异丙醇、甲醇、乙醇、丙醇、丁醇、乙二醇、丙三醇中的几种或一种。
7.根据权利要求1或6所述的基于金属有机骨架晶体调控钛硅分子筛形貌的方法,其特征在于,所述有机溶剂选用异丙醇。
8.根据权利要求1所述的基于金属有机骨架晶体调控钛硅分子筛形貌的方法,其特征在于,所述硅源包括正硅酸乙酯、硅酸四甲酯、硅胶、硅酸丙脂中的一种。
9.根据权利要求1或8所述的基于金属有机骨架晶体调控钛硅分子筛形貌的方法,其特征在于,所述硅源为正硅酸乙酯。
10.根据权利要求1所述的基于金属有机骨架晶体调控钛硅分子筛形貌的方法,其特征在于,所述钛源包括钛酸四丁酯、钛酸异丙酯、四氯化钛、三氯化钛中的一种或两种。
11.根据权利要求1或10所述的基于金属有机骨架晶体调控钛硅分子筛形貌的方法,其特征在于,所述钛源选用钛酸四丁酯。
12.根据权利要求1所述的基于金属有机骨架晶体调控钛硅分子筛形貌的方法,其特征在于,MOFs基材加在钛源或硅源中。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011446570.5A CN112645345B (zh) | 2020-12-11 | 2020-12-11 | 一种基于金属有机骨架晶体调控钛硅分子筛形貌的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011446570.5A CN112645345B (zh) | 2020-12-11 | 2020-12-11 | 一种基于金属有机骨架晶体调控钛硅分子筛形貌的方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112645345A CN112645345A (zh) | 2021-04-13 |
CN112645345B true CN112645345B (zh) | 2022-04-19 |
Family
ID=75353585
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011446570.5A Active CN112645345B (zh) | 2020-12-11 | 2020-12-11 | 一种基于金属有机骨架晶体调控钛硅分子筛形貌的方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112645345B (zh) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105197956A (zh) * | 2015-10-09 | 2015-12-30 | 北京旭阳化工技术研究院有限公司 | Ts-1钛硅分子筛的制备方法 |
CN106006665A (zh) * | 2016-05-13 | 2016-10-12 | 浙江师范大学 | 一种钛硅分子筛ts-1的制备方法 |
CN106348311A (zh) * | 2016-08-19 | 2017-01-25 | 青岛文创科技有限公司 | 一种钛硅分子筛催化剂的制备方法 |
CN111470517A (zh) * | 2020-04-28 | 2020-07-31 | 大连理工大学 | 具有优异扩散性能的大颗粒钛硅分子筛及其制备方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI480100B (zh) * | 2011-04-27 | 2015-04-11 | China Petrochemical Dev Corp Taipei Taiwan | Titanium-silicon molecular sieve and its preparation method and method for producing cyclohexanone oxime using the molecular sieve |
TWI508935B (zh) * | 2011-08-11 | 2015-11-21 | China Petrochemical Dev Corp Taipei Taiwan | Titanium-silicon molecular sieve and its preparation method and method for producing cyclohexanone oxime using the molecular sieve |
-
2020
- 2020-12-11 CN CN202011446570.5A patent/CN112645345B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105197956A (zh) * | 2015-10-09 | 2015-12-30 | 北京旭阳化工技术研究院有限公司 | Ts-1钛硅分子筛的制备方法 |
CN106006665A (zh) * | 2016-05-13 | 2016-10-12 | 浙江师范大学 | 一种钛硅分子筛ts-1的制备方法 |
CN106348311A (zh) * | 2016-08-19 | 2017-01-25 | 青岛文创科技有限公司 | 一种钛硅分子筛催化剂的制备方法 |
CN111470517A (zh) * | 2020-04-28 | 2020-07-31 | 大连理工大学 | 具有优异扩散性能的大颗粒钛硅分子筛及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN112645345A (zh) | 2021-04-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107915234B (zh) | 一种多级孔ts-1纳米沸石聚集体分子筛的制备方法 | |
KR102580277B1 (ko) | 계층적 다공성 ts-1 분자체의 제조 방법 | |
CN110813373A (zh) | 钛硅分子筛催化剂、制备方法及其在烯烃环氧化反应中的应用 | |
CN114014334A (zh) | 一种中硅铝比zsm-5杂合纳米片分子筛及其制备方法 | |
CN111017946B (zh) | 一种用于烯烃环氧化工艺含钛分子筛的制备方法 | |
CN111924852B (zh) | 一种钛硅分子筛的制备方法 | |
CN112645345B (zh) | 一种基于金属有机骨架晶体调控钛硅分子筛形貌的方法 | |
CN111153414A (zh) | 一种钛硅分子筛ts-1的快速水热合成方法 | |
CN109748291A (zh) | 一种具有超大介孔的多级孔结构沸石分子筛的制备方法 | |
WO2020097878A1 (zh) | 一种制备多级孔ts-1分子筛的方法 | |
CN112850740B (zh) | 一种片状mfi拓扑结构分子筛的合成方法 | |
CN112624146B (zh) | 分子筛及其制备方法和应用 | |
CN112978754B (zh) | 一种碱性钛硅分子筛ts-1的制备方法及其应用 | |
CN109399659A (zh) | 一种小尺寸金纳米颗粒负载的钛硅沸石及其制备方法 | |
CN113526512A (zh) | 一种二氧化硅溶胶及其制备方法 | |
CN103121983B (zh) | 氯丙烯环氧化反应的方法 | |
CN112707409A (zh) | 一种纳米全硅Beta分子筛的绿色制备方法 | |
CN111468182A (zh) | 一种中空钛硅分子筛ts-1的合成方法 | |
CN110436479B (zh) | 一种钛硅分子筛及其制备方法和应用 | |
CN112850742A (zh) | 一种多级孔y型分子筛及其合成方法 | |
CN114920262B (zh) | 一种以芳香羧酸为调节剂制备无锐钛矿型ts-1分子筛的方法 | |
CN112624143B (zh) | 一种以MOFs为钛源制备TS-1分子筛催化剂的方法 | |
CN103121980B (zh) | 丙烯环氧化的方法 | |
CN112978748B (zh) | 具有大孔-微孔复合孔道结构的ts-1分子筛、其制备方法和应用 | |
CN113683097B (zh) | 一种富含骨架四配位钛的ts-1分子筛的制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |