CN112279267A - 含钛量高的ts-1分子筛的制备方法 - Google Patents
含钛量高的ts-1分子筛的制备方法 Download PDFInfo
- Publication number
- CN112279267A CN112279267A CN201910666302.5A CN201910666302A CN112279267A CN 112279267 A CN112279267 A CN 112279267A CN 201910666302 A CN201910666302 A CN 201910666302A CN 112279267 A CN112279267 A CN 112279267A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- preparation
- titanium content
- mixed solution
- silicon source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 35
- 239000010936 titanium Substances 0.000 title claims abstract description 35
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 31
- 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 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 19
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 14
- 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
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000006735 epoxidation reaction Methods 0.000 abstract description 8
- 238000011068 loading method Methods 0.000 abstract description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000011056 performance test Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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
- 239000004094 surface-active agent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 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
- C01B39/06—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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种含钛量高的TS‑1分子筛的制备方法。所述方法先将硅源和钛源的混合溶液缓慢加入到四丙基氢氧化铵和聚乙烯吡咯烷酮(K88‑96)的混合溶液中，在50±5℃下搅拌至混合溶液变为澄清透明后，升温至80±5℃进行赶醇操作，得到前驱液，再将前驱液升温至145±20℃下进行水热处理，最后在550～600℃下煅烧，去除四丙基氢氧化铵，制得含钛量高的TS‑1分子筛。本发明方法简便，制备的TS‑1分子筛不仅含钛量高而且粒径较小，负载Au后在催化丙烯直接气相环氧化的反应中，表现出优良的催化性能。
Description
技术领域
本发明属于催化剂制备技术领域，涉及一种含钛量高的TS-1分子筛的制备方法。
背景技术
丙烯环氧化是钛硅分子筛(TS-1)在工业上的一个重要应用，反应产物环氧丙烷作为重要的有机化工原料，在丙烯衍生物中产量仅次于聚丙烯和丙烯腈，主要用来生产聚醚多元醇，以进一步加工制造聚氨酯。工业上生产环氧丙烷主要采用氯醇法和共氧化法。前者工艺成熟、选择性好、收率高、投资费用小，但生产过程中产生大量的含氯污水和废渣，设备腐蚀严重，严重污染环境。后者污染较轻，设备腐蚀小，但工艺较复杂、流程长、对设备要求高，投资费用高，且受到联产物销路的制约。
由于现有工艺存在上述缺点,因此需积极开发新的环氧丙烷生产工艺。丙烯的氧气直接氧化生产环氧丙烷引起了研究人员的高度重视,成为目前研究的热点。丙烯用氧气直接氧化制环氧丙烷的工艺具有过程简单、生产成本低、环境友好等优点。TS-1在丙烯气相环氧化中表现出氧化性能。而影响TS-1性能的主要因素是粒径的大小和骨架钛的含量。Thangaraj等人用钛酸四丁酯代替钛酸四乙酯作钛源，改变原料的加入顺序，成功合成了较高骨架钛含量的TS-1，其合成的TS-1平均粒径为<1μm(A.Thangaraj,S.Sivasanker,ANIMPROVED METHOD FOR TS-1 SYNTHESIS-SI-29 NMR-STUDIES,Journal of the ChemicalSociety-Chemical Communications,(1992)123-124.)。Khomane R B等人将非离子型表面活性剂吐温20加入到合成体系中，合成的结晶度更高，粒径较小，为150～200nm，非骨架钛含量低，具有很高的辛烯环氧化活性(R.B.Khomane,B.D.Kulkarni,A.Paraskar,S.R.Sainkar,Synthesis,characterization and catalytic performance of titaniumsilicalite-1prepared in micellar media,Materials Chemistry and Physics,76(2002)99-103)。
发明内容
针对如何提高TS-1分子筛中骨架钛含量以及抑制骨架外钛产生的问题，本发明提供一种含钛量高的TS-1分子筛的制备方法，该方法制备得到的TS-1分子筛骨架钛含量高，且颗粒粒径较小。
本发明的技术解决方案是：
含钛量高的TS-1分子筛的制备方法，包括如下步骤：
步骤1，将硅源和钛源的混合溶液缓慢加入到四丙基氢氧化铵和聚乙烯吡咯烷酮(K88-96)的混合溶液中，在50±5℃下搅拌至混合溶液变为澄清透明后，升温至80±5℃进行赶醇操作，得到前驱液；
步骤2，将前驱液升温至145±20℃下进行水热处理，反应结束后，离心干燥，最后在550～600℃下煅烧，去除四丙基氢氧化铵，制得含钛量高的TS-1分子筛。
优选地，所述的硅源的原料选自正硅酸乙酯，正硅酸丁酯或硅溶胶，所述的钛源选自钛酸四丁酯或钛酸四乙酯。
优选地，所述的聚乙烯吡咯烷酮(K88-96)与硅源的摩尔比为2×10-6～7×10-6:1。
优选地，所述的赶醇操作时间为30分钟以上。
优选地，所述的四丙基氢氧化铵、硅源和钛源的摩尔比为0.01～0.03:1:0.007～0.02。
优选地，所述的水热处理时间为24～36h。
优选地，所述的煅烧时间为8～10h。
本发明与现有技术相比，具有以下优点：
本发明通过在合成体系中加入表面活性剂聚乙烯吡咯烷酮(K88～96)控制TS-1的分子筛的粒径大小，以四丙基氢氧化铵为模板剂，采用水热合成成功制备了骨架钛含量高且粒径小的TS-1分子筛，在催化丙烯直接气相环氧化合成环氧丙烷应用中具有较好的催化性能，显著提高了环氧丙烷的产率。
附图说明
图1为实施例1-4和对比例1的钛硅分子筛的XRD图。
图2为实施例1和对比例1的钛硅分子筛的紫外可见光谱图。
图3为对比例1的TS-1分子筛的透射电子显微镜图。
图4为实施例1的PTS-1-0.10分子筛的透射电子显微镜图。
图5为实施例3的PTS-1-0.25分子筛的透射电子显微镜图。
图6为实施例1、3、4和对比例1的钛硅分子筛性能测试环氧丙烷的生成速率随时间的变化图。
具体实施方式
通过下列实施例和附图对本发明做进一步详述。
实施例1
将3.9ml的四丙基氢氧化铵(TPAOH，2.0mol/L)，0.10g聚乙烯吡咯烷酮(PVP，K88～96)和8.8ml的去离子水加入烧杯中，在室温下进行搅拌。再逐滴缓慢得滴加7.5ml的正硅酸乙酯(TEOS，AR)和0.115ml的钛酸四丁酯(TBOT，AR)的混合液，在50℃下水浴加热搅拌30min。接着将温度升高到80℃进行赶醇操作，这个过程大约维持30min，并且在此过程中不断补水以保证溶液总质量基本不变。然后将溶液转移至聚四氟乙烯反应釜中，再放入145℃的烘箱中水热合成24h。反应液经过多次离心、水洗后，在25℃下干燥过夜。最后在马弗炉内550℃煅烧8h，除去有机模板剂，得到含钛量高的TS-1分子筛，标记为PTS-1-0.10，聚乙烯吡咯烷酮(K88-96)与硅源的摩尔比为2.31×10-6:1。负载Au后，经性能测试发现环氧丙烷的产率为190gPOh-1kgCat -1，选择性为94％，见表1。
实施例2
参照实施例1，将聚乙烯吡咯烷酮(K88～96)添加量改为0.20g，标记为PTS-1-0.20，聚乙烯吡咯烷酮(K88-96)与硅源的摩尔比为4.62×10-6:1。负载Au后，经性能测试发现环氧丙烷的产率为180gPOh-1kgCat -1，选择性为92％，见表1。
实施例3
参照实施例1，将聚乙烯吡咯烷酮(K88～96)添加量改为0.25g，标记为PTS-1-0.25，聚乙烯吡咯烷酮(K88-96)与硅源的摩尔比为5.78×10-6:1。负载Au后，经性能测试发现环氧丙烷的产率为180gPOh-1kgCat -1，选择性为91％，见表1。
实施例4
参照实施例1，将聚乙烯吡咯烷酮(K88～96)添加量改为0.30g，标记为PTS-1-0.30，聚乙烯吡咯烷酮(K88-96)与硅源的摩尔比为6.93×10-6:1。负载Au后，经性能测试发现环氧丙烷的产率为150gPOh-1kgCat -1，选择性为89％，见表1。
对比例1
本对比例与实施例2基本相同，唯一不同的是在合成过程中不加入表面活性剂PVP(K88～96)，标记为TS-1。负载Au后，经性能测试发现环氧丙烷的产率为95gPOh-1kgCat-1，选择性为96％，见表1。
对比例2
本对比例与实施例2基本相同，唯一不同的是采用PVP(K29～32)为表面活性剂。负载Au后，经性能测试发现环氧丙烷的产率为100gPOh-1kgCat -1，选择性为95％。
应用实施例
TS-1分子筛负载Au后的丙烯直接气相环氧化催化性能测定实验
在催化固定床微反应器中对TS-1或PTS-1分子筛样品进行丙烯直接气相环氧化的催化性能测试，将0.15g负载Au以后的催化剂(60-80目)加入到固定床中。反应物混合物由常压下丙烯(C3H6,99.5％)/氮气(N2,99.999％)/氧气(O2,99.999％)/氢气(H2,99。999％)＝3.5:17.5:3.5:10.5ml min-1(空间速度14000mL h-1gcat -1)。将丙烯的环氧化反应温度设置为200℃，从室温升到200℃，升温速率为1℃min-1。催化剂在反应前不经过任何预处理，直接在反应物混合物中被激活。采用北京北芬瑞丽分析仪器有限公司生产的FID(KB-wax毛细管柱)和TCD(Chromsorb 102填充柱)在线气相色谱(GC；SP-3420A)对反应产物进行分析。
表1总结了各种催化剂的物质信息和催化性能对比
如图1所示，在2θ＝7.8°，8.8°，23.2°和24.3°时，实施例和对比例均有明显的衍射峰，说明所有样品都具有典型的MFI拓扑结构(双十环交叉通道)。在图2的紫外-可见光谱图中，发现在添加了PVP和没有添加PVP合成的钛硅分子筛中钛元素均以四配位的形态存在于骨架中。另外通过对实施例1、实施例3和对比例1的透射电子显微镜图对比可以发现，实施例1的分子筛平均粒径为170nm(见图3)，实施例3的分子筛平均粒径为200nm(见图4)，而对比例1的分子筛平均粒径为220nm(见图5)，因此PVP的添加起到了控制分子筛粒径的作用。研究发现粒径越小其传质速率越高，故其催化性能越好。最后通过对实施例1、3、4和对比例1的钛硅分子筛性能测试环氧丙烷的生成速率随时间的变化(见图6)，研究发现，在反应8～9h后所有样品均仍然具有良好的催化活性。
Claims (8)
1.含钛量高的TS-1分子筛的制备方法，其特征在于，包括如下步骤：
步骤1，将硅源和钛源的混合溶液缓慢加入到四丙基氢氧化铵和聚乙烯吡咯烷酮(K88-96)的混合溶液中，在50±5℃下搅拌至混合溶液变为澄清透明后，升温至80±5℃进行赶醇操作，得到前驱液；
步骤2，将前驱液升温至145±20℃下进行水热处理，反应结束后，离心干燥，最后在550～600℃下煅烧，去除四丙基氢氧化铵，制得含钛量高的TS-1分子筛。
2.根据权利要求1所述的制备方法，其特征在于，所述的硅源的原料选自正硅酸乙酯，正硅酸丁酯或硅溶胶。
3.根据权利要求1所述的制备方法，其特征在于，所述的钛源选自钛酸四丁酯或钛酸四乙酯。
4.根据权利要求1所述的制备方法，其特征在于，所述的聚乙烯吡咯烷酮(K88-96)与硅源的摩尔比为2×10-6～7×10-6:1。
5.根据权利要求1所述的制备方法，其特征在于，所述的赶醇操作时间为30分钟以上。
6.根据权利要求1所述的制备方法，其特征在于，所述的四丙基氢氧化铵、硅源和钛源的摩尔比为0.01～0.03:1:0.007～0.02。
7.根据权利要求1所述的制备方法，其特征在于，所述的水热处理时间为24～36h。
8.根据权利要求1所述的制备方法，其特征在于，所述的煅烧时间为8～10h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910666302.5A CN112279267B (zh) | 2019-07-23 | 2019-07-23 | 含钛量高的ts-1分子筛的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910666302.5A CN112279267B (zh) | 2019-07-23 | 2019-07-23 | 含钛量高的ts-1分子筛的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112279267A true CN112279267A (zh) | 2021-01-29 |
| CN112279267B CN112279267B (zh) | 2023-11-03 |
Family
ID=74418778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910666302.5A Active CN112279267B (zh) | 2019-07-23 | 2019-07-23 | 含钛量高的ts-1分子筛的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112279267B (zh) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070112208A1 (en) * | 2005-11-17 | 2007-05-17 | Bi Le-Khac | Epoxidation catalyst |
| CN101456562A (zh) * | 2009-01-06 | 2009-06-17 | 北京科技大学 | 一种介孔钛硅分子筛的制备方法 |
| CN101618339A (zh) * | 2008-06-30 | 2010-01-06 | 中国石油化工股份有限公司 | 一种钛硅分子筛的改性方法 |
| CN103395799A (zh) * | 2013-08-07 | 2013-11-20 | 华东理工大学 | 一种钛硅分子筛制备方法和用途 |
| CN105084382A (zh) * | 2014-05-08 | 2015-11-25 | 中国石油化工股份有限公司 | 一种介孔钛硅材料及其合成方法 |
-
2019
- 2019-07-23 CN CN201910666302.5A patent/CN112279267B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070112208A1 (en) * | 2005-11-17 | 2007-05-17 | Bi Le-Khac | Epoxidation catalyst |
| CN101618339A (zh) * | 2008-06-30 | 2010-01-06 | 中国石油化工股份有限公司 | 一种钛硅分子筛的改性方法 |
| CN101456562A (zh) * | 2009-01-06 | 2009-06-17 | 北京科技大学 | 一种介孔钛硅分子筛的制备方法 |
| CN103395799A (zh) * | 2013-08-07 | 2013-11-20 | 华东理工大学 | 一种钛硅分子筛制备方法和用途 |
| CN105084382A (zh) * | 2014-05-08 | 2015-11-25 | 中国石油化工股份有限公司 | 一种介孔钛硅材料及其合成方法 |
Non-Patent Citations (2)
| Title |
|---|
| 阳辉;靳鹏;郑晓广;王向宇;: "钛硅分子筛的制备、表征及其催化丙烯环氧化工艺的研究" * |
| 陈晓晖,蔡丽蓉,魏可镁: "表面活性剂Tween对TS-1合成及催化性能影响的研究" * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112279267B (zh) | 2023-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6970298B2 (ja) | オレフィンエポキシ化触媒、その調製方法およびその適用 | |
| US6380119B1 (en) | Method for regenerating a zeolitic catalyst | |
| JP5203208B2 (ja) | チタノケイ酸塩ゼオライトｔｓ−１の調製 | |
| CA2327765A1 (en) | Production of a shaped body | |
| MXPA99011269A (en) | Method for oxidizing an organic compound containing at least on c-c double bond | |
| JP2007522066A (ja) | メソ細孔性またはメソ細孔性およびミクロ細孔性の組み合わせの無機酸化物を製造する方法 | |
| JP2017521227A5 (zh) | ||
| CN103896302B (zh) | 一种硅分子筛及其制备方法 | |
| CN106964400A (zh) | 钛硅分子筛的成型方法和成型催化剂及其应用和环己酮氧化的方法 | |
| CN108821304B (zh) | 高活性多级孔钛硅分子筛及其制备方法和应用 | |
| CN111841623B (zh) | 分子筛催化剂及其制备方法及用途 | |
| Wróblewska et al. | Regeneration of the Ti-SBA-15 catalyst used in the process of allyl alcohol epoxidation with hydrogen peroxide | |
| CN113457727B (zh) | 碱金属调控多级孔Au/ZSM-5催化剂及合成方法和应用 | |
| CN106391106A (zh) | 一种含有金属的核壳结构分子筛的制备方法 | |
| CN112279267B (zh) | 含钛量高的ts-1分子筛的制备方法 | |
| US5777163A (en) | Preparation of hydroxylamines from ammonia or the corresponding amines, hydrogen and oxygen | |
| AU768171B2 (en) | Catalyst support material and use thereof | |
| US20220105496A1 (en) | Cobalt-Based Single-Atom Dehydrogenation Catalysts Having High Selectivity and Regenerability and Method for Producing Corresponding Olefins from Paraffins Using the Same | |
| CN115518683A (zh) | 负载型催化剂及其制备方法和应用以及均四甲苯气相氧化合成均酐的方法 | |
| CN111977663A (zh) | 一种多级孔道结构沸石分子筛及其制备方法和应用 | |
| CN114425438A (zh) | 一种含钛催化剂的制备方法、含钛催化剂以及制备环氧化合物的方法 | |
| CN114713212B (zh) | 用于丙烯氢氧环氧化制备环氧丙烷的钛硅材料及制备方法 | |
| JPH10316417A (ja) | チタン含有ベータゼオライトの製造方法 | |
| CN114904572B (zh) | 一种钛硅分子筛催化剂及其制备方法、应用 | |
| Liu et al. | Simple synthesis of hierarchical Co-Meso-UTL zeolite for efficient epoxidation of styrene |
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 |