CN115196652A - 一种用于烯烃氧化的含钛沸石纳米片及其制备方法 - Google Patents
一种用于烯烃氧化的含钛沸石纳米片及其制备方法 Download PDFInfo
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- 239000010457 zeolite Substances 0.000 title claims abstract description 64
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 59
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 47
- 239000010936 titanium Substances 0.000 title claims abstract description 47
- 239000002135 nanosheet Substances 0.000 title claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 14
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 13
- 230000003647 oxidation Effects 0.000 title claims abstract description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000012847 fine chemical Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 238000001228 spectrum Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- -1 titanate compound Chemical class 0.000 claims description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 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
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims 1
- 239000002055 nanoplate Substances 0.000 claims 1
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 238000012216 screening Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 2
- 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 description 2
- 238000005406 washing Methods 0.000 description 2
- 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 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910011255 B2O3 Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical group [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 125000005624 silicic acid group Chemical group 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
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- 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
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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Abstract
本发明公开了一种用于烯烃氧化的含钛沸石纳米片及其制备方法，涉及无机材料技术领域。所述含钛MFS沸石纳米片的XRD谱图包含以下位置的衍射峰
11.2‑11.4、9.3‑9.5、6.9‑7.2、5.4‑5.7、4.5‑4.9、3.6‑4.0。本发明方法制备出的含钛MFS沸石纳米片具有极高的结晶度和充裕的接触面积，从而提高了此类沸石纳米片的烯烃氧化反应及筛分利用效率。
Description
技术领域
本发明涉及无机材料技术领域，特别是涉及一种用于烯烃氧化的含钛沸石纳米片及其制备方法。
背景技术
目前已经报道的用于烯烃氧化及绿色催化氧化的沸石分子筛如：TS-1 (沸石协会结构代码MFI，下同)、Ti-MCM-22(MWW)和Ti-MOR(MOR) 等含钛沸石材料，因其外在形貌规整，晶粒颗粒分布多在微米尺寸，从而导致相应沸石结构的孔道系统较长，往往存在较高的传质阻力，用于催化反应时，反应物或产物分子在沸石催化剂表面扩散阻力较大，容易造成催化剂表面深度反应产生积碳进而加速催化剂的孔口积碳失活。因此发展形貌规整且均一的沸石纳米片，缩短主要反应孔道是解决上述问题的有效途径之一。
MFS(国际沸石协会三字结构代码)沸石是一种结晶的高硅微孔沸石材料，它具有二维十元环及八元环的孔道结构。同时MFS沸石还具有较高的热稳定性，水热稳定性及可调变的酸性点分布特性。因此，MFS沸石在诸如烯烃氧化、小分子择形催化、芳烃烷基化、甲苯歧化及长链烷烃异构化等精细化工领域存在较高的实用价值。
与大晶粒尺寸(尺寸范围为微米级别)的MFS沸石晶体相比，具有较短孔道排列的MFS沸石纳米片(厚度为20-50nm)具有较优的传质取向，优异的热稳定性及高反应活性，机械强度高等优点，因此在精细化工行业有着极高的应用潜力。然而，MFS相较于MFI难合成；简单用于MFI合成的方案并不能简单直接移植到MFS沸石。另外钛位点是烯烃环氧化中的重要位点。体系中直接引入钛源，由于对体系的干扰极其难得到MFS薄片，目前基本没有含钛位点的MFS沸石的相关报道。
发明内容
基于上述内容，本发明提供一种用于烯烃氧化的含钛沸石纳米片及其制备方法，克服钛原子无法掺杂进MFS沸石纳米片的难题，使MFS沸石纳米片具有较短的孔道排列、较优的传质取向。同时本发明调控沸石维度并不需要额外引入无机或者有机化合物添加剂，极大简化了后续生产。
为实现上述目的，本发明提供了如下方案：
本发明技术方案之一，一种含钛MFS沸石纳米片，结构中含有钛原子，形貌为五角盘状的晶体盘片，粒径为0.2-2μm，厚度为20-50nm；
所述含钛MFS沸石纳米片的XRD谱图包含以下位置的衍射峰
11.2-11.4、9.3-9.5、6.9-7.2、5.4-5.7、4.5-4.9、3.6-4.0。
本发明技术方案之二，上述的含钛MFS沸石纳米片的制备方法，包括以下步骤：
步骤1，将四价无机氧化物TO2、含钛化合物、三价氧化物Y2O3、碱源OH-、有机模板剂R和水混合均匀，得到混合物；
步骤2，将所述混合物进行晶化反应，得到所述含钛MFS沸石纳米片。
进一步地，所述晶化反应具体为140-200℃下反应24-480小时。
进一步地，所述四价无机氧化物TO2、含钛化合物、三价氧化物Y2O3、碱源OH-、有机模板剂R和水的摩尔比为：
TO2/Y2O3为10-999，
TO2/含钛化合物为25-999，
OH-/TO2为0.01-1.0，
H2O/TO2为10-120，
R/TO2为0.05-1.0。
进一步地，所述TO2为硅源、锗源或锡源中的至少一种。
所述硅源选自正硅酸乙酯，硅胶，硅酸，白炭黑，硅溶胶，水玻璃和硅藻土中的至少一种；
所述锗源选自氧化锗；
所述锡源选自氧化锡，氯化锡中的至少一种；
进一步地，所述三价氧化物Y2O3为铝源、硼源或镓源中的至少一种；所述含钛化合物为有机钛酸酯类化合物、四氯化钛和二氧化钛中的至少一种。
所述铝源选自异丙醇铝，铝酸钠，铝箔，硫酸铝，氯化铝，硝酸铝，氢氧化铝，薄水铝石及拟薄水铝石中的至少一种；
所述硼源选自硼酸，硼酸钠，氧化硼中的至少一种；
所述镓源选自硝酸镓，三氯化镓中的至少一种；
选择三价氧化物Y2O3主要利用了过渡金属元素在氧化中的作用。
进一步地，所述碱源OH-为碱金属或碱土金属氢氧化物或有机季胺碱类化合物中的至少一种。
进一步地，有机模板剂R选自具有式I或式II所示化学结构式的化合物中的至少两种：
其中，n＝3-12。
进一步地，所述晶化处理后还包括分离、洗涤、干燥、焙烧的步骤。
所述干燥的条件为100℃，12小时；所述焙烧的条件为600℃，空气条件下焙烧6小时。
本发明技术方案之三，上述的含钛MFS沸石纳米片在精细化工行业中的应用。
进一步地，所述精细化工行业具体为烯烃氧化。
本发明公开了以下技术效果：
(1)本发明方法制备出的含钛MFS沸石纳米片不仅具有规则的形貌，还有着定向分布的沸石孔道系统；
(2)本发明方法制备出的含钛MFS沸石纳米片具有极高的结晶度和充裕的接触面积，从而提高了此类沸石纳米片的烯烃氧化反应及筛分利用效率；
(3)本发明方法制备出的含钛MFS沸石纳米片具有极高的长径比、较短的扩散程和较优的传质取向，从而提高了反应物扩散效率。同时本发明方法制备出的含钛MFS沸石纳米片具有优异的热稳定性及高反应活性，机械强度高，因此在精细化工行业尤其是在烯烃氧化方面有着极高的应用潜力。
(4)本发明制备方法简单，效率高，操作方便，污染小，适合工业化生产。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例中所需要使用的附图作简单的介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为实施例1制备的含钛MFS沸石纳米片的XRD谱图；
图2为实施例1制备的含钛MFS沸石纳米片的透射电镜图及元素分布谱图；其中，a为低倍形貌图，b为高倍形貌图，c为元素分布总图，d为钛元素分布图。
具体实施方式
现详细说明本发明的多种示例性实施方式，该详细说明不应认为是对本发明的限制，而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。
应理解本发明中所述的术语仅仅是为描述特别的实施方式，并非用于限制本发明。另外，对于本发明中的数值范围，应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明，否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料，但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入，用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时，以本说明书的内容为准。
在不背离本发明的范围或精神的情况下，可对本发明说明书的具体实施方式做多种改进和变化，这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见的。本发明说明书和实施例仅是示例性的。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等，均为开放性的用语，即意指包含但不限于。
本发明中所述的“份”如无特别说明，均按质量份计。
本发明实施例中所用原材料如无特殊说明，均自购买途径获得。
本发明实施例中分析方法如下：
利用日本理学(Rigaku)公司的Smartlab粉末X-射线射线衍射仪【Cu 靶，Kα12辐射源(λ＝0.15418nm)，电压40kV，电流100mA】进行粉末X 射线衍射物相分析(PXRD)。
利用Tecnai G2 F20 S-Twin型透射电子显微镜进行样品形貌及元素分析。
实施例1
按下面的摩尔比例配制初始凝胶：SiO2/Al2O3＝60，SiO2/TiO2＝100， OH-/SiO2＝0.5，(R1+R2)/SiO2＝0.2，H2O/SiO2＝40的配比将铝酸钠，氢氧化钠，四乙基溴化铵(R1)，溴代1,5-N,N’-六乙基戊烷(R2，R1、R2摩尔比为1:1)及钛酸四异丙酯，依次溶于去离子水中，然后在不断搅拌的条件下加入白炭黑得到混合物，之后将上述混合物装入晶化釜中于160℃反应120小时。将冷却后的反应液置于冷水浴中静置2小时，产生明显的分层后(下层淡黄色的粉末为MFS沸石纳米片)，分离，洗涤，干燥(100℃， 12小时)，后得到含钛MFS沸石纳米片(编号为Ti-MFS-1)，以投料的二氧化硅重量计，Ti-MFS-1的产率为92％。
图1为本实施例制备的含钛MFS沸石纳米片的XRD谱图；
经XRD分析(XRD结果见表1)，证实本实施例制备的含钛MFS沸石纳米片为纳米小晶粒堆积的五角盘状的MFS沸石纳米片，硅铝摩尔比例为19.8，硅钛摩尔比为89.4；经SEM表征，颗粒尺寸为2μm，厚度约为 50nm。
表1
图2为实施例1制备的含钛MFS沸石纳米片的透射电镜图及元素分布谱图；其中，a为低倍形貌图，b为高倍形貌图，c为元素分布总图，d为钛元素分布图。
由图2能够看出制备出的MFS为薄片状沸石；且钛元素被均匀引入至材料中。
将实施例1制备的含钛MFS沸石纳米片于600℃下通入空气焙烧6 小时脱除模板剂，然后测试样品的比表面积及孔容，样品具有高的BET 比表面积约为460m2/g，其中按照t-plot方法计算得到的微孔比表面积和微孔容积分别为320m2/g和0.15cm3/g。
将实施例1制备的含钛MFS沸石纳米片于600℃下通入空气焙烧6 小时脱除模板剂，然后采用透射电镜选区高分辨图像分辨样品晶面取向。可以发现含钛MFS的沸石薄片方向为[100]，即MFS沸石的十元环孔道方向。
实施例2、3、4
具体配料比例和晶化条件见表2，具体配料过程以及干燥、焙烧条件同实施例1。
对制备的含钛MFS沸石纳米片进行XRD分析，数据结果与表1(实施例1)接近，即衍射出峰位置和形状相近，依制备条件的变化峰相对峰度在±10％范围内波动，表明制备产物具有MFS沸石结构特征。
表2
表2中四价氧化物为硅酸，含钛化合物为钛酸四异丙酯，三价氧化物为铝酸钠，碱源为氢氧化钠，有机模板剂R1为四乙基溴化铵，R2为溴代 1,5-N,N’-六乙基戊烷，R1、R2质量比为1:2。
对比例1
与实施例1不同之处仅在于，将氢氧化钠替换为氢氧化钾，得到沸石样品。
经XRD测试，确认本对比例制备的沸石样品为MFS沸石晶相且形貌为五角状MFS沸石棱柱，晶粒尺寸为300-500nm，厚度为100-200nm，未形成MFS五角盘纳米片。以投料二氧化硅重量计，MFS沸石的产率为 86％。
对比实施例1-4以及对比例1能够发现，不同碱金属阳离子的调变会直接调变MFS沸石的形态。
以上所述的实施例仅是对本发明的优选方式进行描述，并非对本发明的范围进行限定，在不脱离本发明设计精神的前提下，本领域普通技术人员对本发明的技术方案做出的各种变形和改进，均应落入本发明权利要求书确定的保护范围内。
Claims (10)
1.一种含钛MFS沸石纳米片，其特征在于，所述含钛MFS沸石纳米片的XRD谱图包含以下位置的衍射峰
11.2-11.4、9.3-9.5、6.9-7.2、5.4-5.7、4.5-4.9、3.6-4.0。
2.一种权利要求1所述的含钛MFS沸石纳米片的制备方法，其特征在于，包括以下步骤：
步骤1，将四价无机氧化物TO2、含钛化合物、三价氧化物Y2O3、碱源OH-、有机模板剂R和水混合均匀，得到混合物；
步骤2，将所述混合物进行晶化反应，得到所述含钛MFS沸石纳米片。
3.根据权利要求2所述的制备方法，其特征在于，所述晶化反应具体为140-200℃下反应24-480小时。
4.根据权利要求2所述的制备方法，其特征在于，所述四价无机氧化物TO2、含钛化合物、三价氧化物Y2O3、碱源OH-、有机模板剂R和水的摩尔比为：
TO2/Y2O3为10-999，
TO2/含钛化合物为25-999，
OH-/TO2为0.01-1.0，
H2O/TO2为10-120，
R/TO2为0.05-1.0。
5.根据权利要求2所述的制备方法，其特征在于，所述四价无机氧化物TO2为硅源、锗源或锡源中的至少一种。
6.根据权利要求2所述的制备方法，其特征在于，所述三价氧化物Y2O3为铝源、硼源或镓源中的至少一种；所述含钛化合物为有机钛酸酯类化合物、四氯化钛和二氧化钛中的至少一种。
7.根据权利要求2所述的制备方法，其特征在于，所述碱源OH-为碱金属氢氧化物、碱土金属氢氧化物或有机季胺碱类化合物中的至少一种。
8.根据权利要求2所述的制备方法，其特征在于，有机模板剂R选自具有式I或式II所示化学结构式的化合物中的至少一种：
其中，n＝3-12。
9.如权利要求1所述的含钛MFS沸石纳米片在精细化工行业中的应用。
10.根据权利要求9所述的应用，其特征在于，所述精细化工行业具体为烯烃氧化。
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