CN114538463A - 一种无粘结剂ets-4型分子筛颗粒及其制备方法和应用 - Google Patents
一种无粘结剂ets-4型分子筛颗粒及其制备方法和应用 Download PDFInfo
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- 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 66
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 65
- 239000002245 particle Substances 0.000 title claims abstract description 54
- 101100065719 Drosophila melanogaster Ets98B gene Proteins 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000243 solution Substances 0.000 claims abstract description 37
- 239000004094 surface-active agent Substances 0.000 claims abstract description 34
- 239000003921 oil Substances 0.000 claims abstract description 33
- 229910001868 water Inorganic materials 0.000 claims abstract description 32
- 238000001179 sorption measurement Methods 0.000 claims abstract description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000010936 titanium Substances 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 3
- 230000005595 deprotonation Effects 0.000 claims abstract description 3
- 238000010537 deprotonation reaction Methods 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 239000000741 silica gel Substances 0.000 claims description 16
- 229910002027 silica gel Inorganic materials 0.000 claims description 16
- 229920006395 saturated elastomer Polymers 0.000 claims description 12
- 238000005342 ion exchange Methods 0.000 claims description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000003349 gelling agent Substances 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical group 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 239000000499 gel Substances 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000003608 titanium Chemical class 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 13
- 239000003463 adsorbent Substances 0.000 abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 4
- 229920002994 synthetic fiber Polymers 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 58
- 239000007789 gas Substances 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical group [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- -1 alkylbenzene sulfonate Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 235000003270 potassium fluoride Nutrition 0.000 description 3
- 239000011698 potassium fluoride Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000001284 azanium sulfanide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 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
- 238000005516 engineering process Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical group 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical group [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- 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
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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
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- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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- B01J37/02—Impregnation, coating or precipitation
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Abstract
本发明提供了一种无粘结剂ETS‑4型分子筛颗粒及其制备方法和应用,属于无机合成材料技术领域,该方法包括以下步骤:(1)向溶有钛源的溶液中加入去质子化试剂,得到水相,在水相上部依次加入表面活性剂水溶液和油相,形成含油相、表面活性剂相和水相的三相溶液体系;(2)将硅凝胶混合物向步骤(1)中的溶液体系中滴加,使得硅凝胶混合物在油相中收缩成球形,穿过油相和表面活性剂相,到达水相,得到硅凝胶前驱体;(3)将油相与表面活性剂相抽出,将硅凝胶前驱体与水相陈化后晶化,即得无粘结剂ETS‑4型分子筛颗粒。本发明所制备的无粘结剂ETS‑4型分子筛颗粒可以直接作为吸附剂使用,在碳氢化合物中氮气的吸附脱除方面具有优势。
Description
技术领域
本发明属于无机合成材料技术领域,具体涉及一种无粘结剂ETS-4型分子筛颗粒及其制备方法和应用。
背景技术
中国是世界第一产煤大国,但大量的瓦斯未能得到利用,我国瓦斯的实际利用率还不到2%,主要是因为抽放的煤层气大多数情况下CH4浓度都很低,不能直接加以利用。加强对煤层气的抽放并科学合理地加以利用,就可以产生巨大的经济效益和社会效益。另一方面,油田气、气田气中较高含量的氮气导致天然气热值达不到质量标准。因此,从烃类混合物中选择性脱除氮气组分,实现烃类组分的富集利用十分重要。
煤层气在研究中可看成是CH4/空气体系,杂质气中的O2动力学半径小、分子扩散速率快,较容易除去。由于CH4的强吸附性,且CH4/N2具有相近的分子尺寸和超临界条件下相似的物理性质而成为难分离体系。国内对CH4/N2的分离主要针对甲烷含量较低的煤层气,主要采用基于平衡分离原理的活性炭,活性炭在PSA浓缩甲烷方面取得了一定成果,但仍限于理论研究阶段,效果不是很理想。国外PSA浓缩甲烷的研究主要是针对油田气,对煤层气和垃圾填埋气的研究相对较少。最早采用的吸附剂是斜发沸石分子筛,具有一定的分离效果。目前国内外关于PSA技术浓缩CH4的吸附剂主要是活性炭和碳分子筛,虽然在实验室取得了较好的效果,但距工程应用仍有一定距离。
沸石分子筛以其独特的有序微孔孔道、高比表面积和优异的热/水热稳定性,在石油加工、气体分离以及环境保护等领域均有广泛的应用。ETS(Engelhard TitanoSilicate)是一类含有硅四面体和钛八面体的混合氧化物。ETS-4分子筛是这类合成微孔物质中的重要代表,其最显著的特征是钛八面体仅通过四个氧桥与硅原子框架相连,结构上的独特性使得ETS-4分子筛在吸附及催化领域具有巨大的潜能。其微孔孔径为0.3~0.4nm,因此可用于分离分子尺寸在0.3~0.4nm氮气/甲烷混合体系的分离。
专利US4853202(Large-pored crystalline titanium molecular sievezeolites)、CN103043678A(一种由高硅工业原料制备钛硅分子筛ETS-4的方法)以及文献《ATitanosilicate Molecular Sieve with Adjustable Pores for Size-SelectiveAdsorption of Molecules》、《Synthesis and characterization of the microporoustitanosilicates ETS-4and ETS-10》和《Synthesis of microporous titanosilicatesETS-10and ETS-4using solid TiO2 as the source of titanium》均报道了ETS-4分子筛的不同合成方法。但这些方法均是通过水热合成制备ETS-4分子筛晶体粉末,在工业实际应用过程中,通常需要加入一定量(质量百分比约为20%)的粘结剂(粘土、高岭土、硅溶胶等)以使其具有特定的形状(条状、块状、球形等)及一定的机械强度。但是,所添加的粘结剂是吸附无效组分,因此粘结剂的加入不仅会稀释产品中有效组分的含量,导致吸附容量下降;而且还会堵塞分子筛的部分孔道,从而对吸附质在分子筛内部的扩散和传质造成不利影响,导致分子筛吸/脱附速率下降,极大地影响了分子筛的吸附性能。
目前,尚未见无粘结剂ETS-4型分子筛颗粒合成方法的报道。
发明内容
本发明针对现有技术存在的问题,提供了一种无粘结剂ETS-4型分子筛颗粒及其制备方法和应用,从而显著提高ETS-4型筛颗粒吸附性能。
为实现上述目的,本发明采用的技术方案如下:
本发明提供了一种无粘结剂ETS-4型分子筛颗粒的制备方法,包括以下步骤:
(1)向溶有钛源的溶液中加入去质子化试剂,得到水相,在水相上部依次加入表面活性剂水溶液和油相,形成含油相、表面活性剂相和水相的三相溶液体系;
(2)将胶凝剂与硅溶胶混合均匀得到硅凝胶混合物,将硅凝胶混合物向步骤(1)中的溶液体系中滴加,使得硅凝胶混合物在油相中收缩成球形,穿过油相和表面活性剂相,到达水相,得到硅凝胶前驱体;
(3)将油相与表面活性剂相抽出,将硅凝胶前驱体与水相陈化后晶化,即得无粘结剂ETS-4型分子筛颗粒。
进一步地,步骤(1)中所述三相溶液体系自上而下依次为油相、表面活性剂相和水相。
进一步地,步骤(1)中所述油相包括馏程在70-200℃范围内的烃类化合物的一种或多种,所述表面活性剂相为亲水亲油平衡值在8-18的饱和表面活性剂水溶液。
优选地,所述饱和表面活性剂水溶液为C12-C18烷基硫酸盐或烷基苯磺酸盐的饱和水溶液。
进一步优选地,所述的饱和表面活性剂水溶液为十二烷基硫酸钠饱和水溶液。
进一步地,所述溶有钛源的溶液是指溶解有可溶性钛盐、钛酸盐或有机钛的水溶液。
优选地,所述钛源为二氯化钛、三氯化钛、四氯化钛、硫酸钛或钛酸酯。
进一步地,所述溶有钛源的溶液,其质量浓度为1-50%,优选为5-30%。
进一步地,所述油相、水相和表面活性剂相的体积比为:8-10:20-25:4-5。
进一步地,所述去质子化试剂为卤素元素的碱金属或碱土金属化合物。
优选地,所述去质子化试剂为氟的碱金属或碱土金属化合物。
进一步优选地,所述去质子化试剂是氟化钾或氟化钠,更进一步优选为氟化钾。
进一步地,氟化钾与体系中TiO的摩尔比为1:5-100,优选为1:10-50。
进一步地,所述硅溶胶为均匀分散的二氧化硅纳米颗粒水溶液或碱金属/碱土金属的可溶性硅酸盐。
优选地,所述的硅溶胶为均匀分散的二氧化硅纳米颗粒水溶液,该溶液中二氧化硅含量为5-60%,优选为10-50%,进一步优选为20-40%,以所述硅溶胶的重量计;二氧化硅纳米颗粒的粒径为5-150nm,优选为10-100nm,进一步优选为10-60nm。
进一步地,步骤(3)所述陈化的温度为10-70℃,陈化的时间为1-80h,所述晶化的温度为80-300℃,晶化的时间为1-20h。
进一步地,所述凝胶剂包括氮化合物和/或有机胺化合物。
进一步地,所述含氮化合物包括氯化铵、硝酸铵、溴化铵、氟化铵、硫酸铵、硫酸氢铵、硫化铵、硫氢化铵、碳酸铵和碳酸氢铵中的一种或多种;所述有机胺化合物为以下物质的单一物质或其混合物:六亚甲基四胺及其衍生物。
优选地,所述凝胶剂为氯化铵水溶液;进一步地,所述氯化铵水溶液的质量分数为1-30%,优选为5-20%,进一步优选为5-15%。
进一步地,所述凝胶剂的用量为硅溶胶质量的1-50%,优选为10-30%。
在一些具体的实施方案中,所用的原料摩尔配比为:
n(TiO2):n(SiO2):n(Na2O):n(K2O):n(H2O)=1:2-20:2-30:0.5-10:10-1000,优选为
n(TiO2):n(SiO2):n(Na2O):n(K2O):n(H2O)-=1:4-10:3-10:1-5:30-500,原料以氧化物的形式表示。
进一步地,所述制备方法还包括以下步骤:(4)离子交换:将步骤(3)得到的无粘结剂ETS-4型分子筛颗粒进行离子交换,即得改性的无粘结剂ETS-4型分子筛颗粒。
在一些具体的实施方式中,在晶化结束后,还应对所得到的混合物进行如下处理:将混合物进行过滤,并用去离子水洗涤数次,收集固体,进行干燥。进一步地,所述干燥温度为20-200℃,优选为40-180℃,进一步优选为60-150℃;进一步地,所述干燥的时间为0.5-120h,优选为1-72h,进一步优选为2-48h。
进一步地,未改性的无粘结剂ETS-4型分子筛颗粒中所含金属离子为Na+和K+。
进一步地,步骤(4)所述离子交换具体为:将所制备的无粘结剂ETS-4型分子筛颗粒置于其他金属离子溶液中,在回流条件下处理一定时间后,用去离子水洗涤,焙烧,从而得到含有该金属离子的改性的无粘结剂ETS-4型分子筛颗粒。
进一步地,所述经离子改性的无粘结剂ETS-4型分子筛颗粒中的金属离子为Li+、Na+、Ag+、Ni2+、Ca2+、Mg2+、Zn2+、Sr2+、Cu2+和Co2+中的一种或几种离子,较佳地为Sr2+、Li+、Ni2+、Ca2+、Mg2+、Zn2+、Cu2+和Co2+中的一种或几种离子。
进一步地,所述金属离子溶液的浓度为0.01-10mol/L,优选为0.1-5mol/L,进一步优选为0.2-2mol/L。
进一步地,所述无粘结剂ETS-4型分子筛颗粒与金属离子溶液的质量比为1:5-1:50,优选为1:5-1:25,进一步优选为1:10-1:20。
进一步地,所述离子交换的交换温度为25-150℃,优选为40-120℃,进一步优选为50-100℃;所述交换的时间为1-72h,优选为3-48h,进一步优选为3-24h。
进一步地,所述焙烧的温度为150-600℃,优选为150-500℃,进一步优选为180-400℃;所述焙烧的时间为0.5-72h,优选为1-56h,进一步优选为2-48h。
本发明还提供了上述制备方法制备的无粘结剂ETS-4型分子筛颗粒。
进一步地,本发明所制备的无粘结剂ETS-4型分子筛颗粒具有以下一个或多个特征:
1)颗粒粒径约为0.5-5mm;
2)晶体颗粒尺寸1-10μm;
3)晶体颗粒呈均匀片状;
3)比表面积为200-600m2/g。
本发明还提供了上述制备方法制备的无粘结剂ETS-4型分子筛颗粒在吸附、分离、离子交换以及催化领域中的应用。
本发明所取得的技术效果是:
本发明通过广泛而深入的研究,首次意外地发现一种无粘结剂ETS-4型分子筛颗粒的制备方法。较传统无粘结剂分子筛颗粒的制备方法而言,本制备方法通过严格的合成工艺参数控制,可合成无粘结剂ETS-4型分子筛颗粒。在制备该无粘结剂ETS-4分子筛颗粒时,通过去质子化试剂以及特殊表面活性剂的使用以及对于各相之间的优化,最终得到的分子筛颗粒具有可期的更高的吸附性能。最后,通过本发明制备的无粘结剂ETS-4分子筛颗粒可以极大地提高ETS-4型分子筛在包括需要从含氮气和烃类等组分混合物中选择性脱除氮气进而富集烃类组分的场合,如天然气中氮气的脱除等。
附图说明
图1为本发明实施例1中所制备无粘结剂ETS-4型分子筛颗粒的XRD谱图;
图2为本发明实施例2中所制备无粘结剂ETS-4型分子筛颗粒的XRD谱图;
图3本发明实施例1所制备无粘结剂ETS-4型分子筛颗粒的SEM图;
图4本发明实施例2所制备无粘结剂ETS-4型分子筛颗粒的SEM图。
具体实施方式
值得说明的是,本发明中使用的原料均为普通市售产品,因此对其来源不做具体限定。
实施例1
(1)油相、表面活性剂相、水相三相体系的制备:
将4重量份三氯化钛溶解于400重量份去离子水中,加入0.15重量份KaF,得到水相,然后在所得到的400体积份水相上部依次加入80体积份的十二烷基硫酸钠饱和水溶液(表面活性剂相)和160体积份正庚烷(油相),从而形成含油相、表面活性剂相和水相的三相体系,作为硅凝胶前驱体成型的溶液体系。
(2)无粘结剂ETS-4型分子筛颗粒的制备:
称取20重量份硅溶胶(40wt.%,二氧化硅纳米粒子粒径约为20nm)与5重量份氯化铵溶液(10wt.%),快速搅拌均匀,得到二氧化硅凝胶混合物,将凝胶混合物逐滴滴加到上述制备的成型溶液体系中,即可得到二氧化硅凝胶前驱体。
(3)抽走并回收上层油相以及中间层的表面活性剂相后,将水相及二氧化硅凝胶前驱体转移到晶化釜中,先在25℃下陈化6h,再在120℃下晶化56h。晶化完成后,将混合物进行过滤,固体用去离子水洗涤数次,收集固体,并在100℃下干燥6h,得到无粘结剂ETS-4型分子筛颗粒。
本例中所制得ETS-4型分子筛的XRD谱图如图1所示,SEM图片如图3所示。采用物理吸附仪在77K温度条件下测定p/p0=1时的N2吸附量,吸附量测定结果如表1所示。
实施例2
(1)油相、表面活性剂相、水相三相体系的制备:
将5重量份三氯化钛溶解于500重量份去离子水中,加入0.19重量份NaF,得到水相,然后在所得到的500体积份水相上部依次加入100体积份的十二烷基硫酸钠饱和水溶液(表面活性剂相)和200体积份正庚烷(油相),从而形成含油相、表面活性剂相和水相的三相体系,作为硅凝胶前驱体成型的溶液体系。
(2)无粘结剂ETS-4型分子筛颗粒的制备:
称取20重量份硅溶胶(40wt.%,二氧化硅纳米粒子粒径约为20nm与5重量份氯化铵溶液(10wt.%),快速搅拌均匀,得到二氧化硅凝胶混合物,将凝胶混合物逐滴滴加到上述制备的成型溶液体系中,即可得到二氧化硅凝胶前驱体。
(3)抽走并回收上层油相以及中间层的表面活性剂相后,将水相及二氧化硅凝胶前驱体转移到晶化釜中,先在25℃下陈化12h,再在180℃下晶化48h。晶化完成后,将混合物进行过滤,固体用去离子水洗涤数次,收集固体,并在100℃下干燥6h,得到无粘结剂ETS-4型分子筛颗粒。
本例中所制得ETS-4型分子筛的XRD谱图如图2所示,SEM图片如图4所示。采用物理吸附仪在77K温度条件下测定p/p0=1时的N2吸附量,吸附量测定结果如表1所示。
实施例3
在实施例1的基础上进行步骤(4)离子交换:将所制备的无粘结剂ETS-4型分子筛颗粒置于Ni(NO3)2溶液中,在回流条件下处理一定时间后,用去离子水洗涤,焙烧,从而得到含有该金属离子的改性的无粘结剂ETS-4型分子筛颗粒。其中,金属离子溶液的浓度为1mol/L的,无粘结剂ETS-4型分子筛颗粒与金属离子溶液的质量比为1:15,离子交换的交换温度为80℃,交换的时间为8h,焙烧的温度为300℃,焙烧的时间为20h。
对比例1
与实施例1的区别仅在于,步骤(1)中不加入去质子化试剂,直接在溶有钛源的溶液上布一次加入表面活性剂等。
对比例2
与实施例1的区别仅在于,将十二烷基硫酸钠饱和水溶液替换为十六烷基三甲基溴化铵的饱和水溶液。
对比例3
与实施例1的区别仅在于,油相、水相和表面活性剂相的体积比为7:30:3(三者的总体积与实施例1一致)。
测试各实例中得到的ETS-4型分子筛在同条件下(25℃、100KPa)对于N2的吸附量,得到表1。
表1 N2吸附量
实例 | N<sub>2</sub>吸附量(cm<sup>3</sup>/g) |
实施例1 | 83.3 |
实施例2 | 91.5 |
实施例3 | 86.9 |
对比例1 | 61.5 |
对比例2 | 74.6 |
对比例3 | 47.9 |
由表1可知,实施例1-3成功合成了无粘结剂ETS-4型分子筛颗粒及对应改性的分子筛颗粒(如图1-4所示),三者具有较高的吸附性能,对于N2的吸附量高达83.3-91.5cm3/g,对比例1在不加入去质子化试剂、对比例2将十二烷基硫酸钠饱和水溶液替换为十六烷基三甲基溴化铵的饱和水溶液以及对比例3当油相、水相和表面活性剂相的体积比发生明显的改变时,分子筛颗粒对于N2的吸附量均有所下降。
最后应当说明的是,以上内容仅用以说明本发明的技术方案,而非对本发明保护范围的限制,本领域的普通技术人员对本发明的技术方案进行的简单修改或者等同替换,均不脱离本发明技术方案的实质和范围。
Claims (10)
1.一种无粘结剂ETS-4型分子筛颗粒的制备方法,其特征在于:包括以下步骤:
(1)向溶有钛源的溶液中加入去质子化试剂,得到水相,在水相上部依次加入表面活性剂水溶液和油相,形成含油相、表面活性剂相和水相的三相溶液体系;
(2)将胶凝剂与硅溶胶混合均匀得到硅凝胶混合物,将硅凝胶混合物向步骤(1)中的溶液体系中滴加,使得硅凝胶混合物在油相中收缩成球形,穿过油相和表面活性剂相,到达水相,得到硅凝胶前驱体;
(3)将油相与表面活性剂相抽出,将硅凝胶前驱体与水相陈化后晶化,即得无粘结剂ETS-4型分子筛颗粒。
2.根据权利要求1所述的制备方法,其特征在于:步骤(1)中所述三相溶液体系自上而下依次为油相、表面活性剂相和水相。
3.根据权利要求1所述的制备方法,其特征在于:步骤(1)中所述油相包括馏程在70-200℃范围内的烃类化合物的一种或多种,所述表面活性剂相为亲水亲油平衡值在8-18的饱和表面活性剂水溶液。
4.根据权利要求1所述的制备方法,其特征在于:所述溶有钛源的溶液是指溶解有可溶性钛盐、钛酸盐或有机钛的水溶液;所述去质子化试剂为卤素元素的碱金属或碱土金属化合物。
5.根据权利要求1所述的制备方法,其特征在于:所述油相、水相和表面活性剂相的体积比为:8-10:20-25:4-5。
6.根据权利要求1所述的制备方法,其特征在于:所述硅溶胶为均匀分散的二氧化硅纳米颗粒水溶液或碱金属/碱土金属的可溶性硅酸盐。
7.根据权利要求1所述的制备方法,其特征在于:步骤(3)所述陈化的温度为10-70℃,陈化的时间为1-80h,所述晶化的温度为80-300℃,晶化的时间为1-20h。
8.根据权利要求1所述的制备方法,其特征在于:还包括以下步骤:(4)离子交换:将步骤(3)得到的无粘结剂ETS-4型分子筛颗粒进行离子交换,即得改性的无粘结剂ETS-4型分子筛颗粒。
9.如权利要求1-8任一项所述的制备方法制备的无粘结剂ETS-4型分子筛颗粒。
10.如权利要求9所述的无粘结剂ETS-4型分子筛颗粒在吸附、分离、离子交换以及催化中的应用。
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