CN115400785B - 一种用于丙烷芳构化的核壳结构催化剂及其制备方法和应用 - Google Patents
一种用于丙烷芳构化的核壳结构催化剂及其制备方法和应用 Download PDFInfo
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 239000001294 propane Substances 0.000 title claims abstract description 43
- 239000011258 core-shell material Substances 0.000 title claims abstract description 36
- 238000005899 aromatization reaction Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002808 molecular sieve Substances 0.000 claims abstract description 56
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 16
- 239000010410 layer Substances 0.000 claims abstract description 13
- 239000012792 core layer Substances 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 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
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 claims description 4
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 3
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 claims description 2
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 36
- 239000007787 solid Substances 0.000 description 28
- 238000010438 heat treatment Methods 0.000 description 19
- 239000002253 acid Substances 0.000 description 17
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 16
- 238000001816 cooling Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000000227 grinding Methods 0.000 description 9
- 238000011049 filling Methods 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 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 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 229940044658 gallium nitrate Drugs 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000005216 hydrothermal crystallization Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
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- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
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- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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Abstract
一种用于丙烷芳构化的核壳结构催化剂及其制备方法和应用,所述催化剂核层为ZSM‑5分子筛,壳层为Silicate‑1分子筛,Pt和助剂M金属元素被封装于壳层Silicate‑1分子筛内。以质量百分比计,壳层Silicate‑1分子筛的质量百分含量为30%~70%,金属Pt的质量百分含量为0.01%~3%,M金属元素的质量百分含量为0.01%~10%,余量为核层ZSM‑5分子筛。催化剂制备采用水热合成法,制备方式简单,可直接用于丙烷芳构化反应中,芳烃产物选择性可达70%,其中轻质芳烃占比可达80%以上。催化剂制备过程简单,成本低廉,催化性能具有良好的应用前景。
Description
技术领域
本发明涉及催化材料制备及低碳烷烃转化和利用领域,尤其涉及一种用于丙烷芳构化的核壳结构催化剂及其制备方法和应用。
背景技术
芳烃是一种极为重要的基础化学品,在化学化工、生物医药、轻工电子等国民经济的各个方面有着广泛的应用。当前芳烃的主要来源为石脑油重整和煤焦油分馏,生产效率较低且能耗较大,又因全球环境问题的日益凸显和原油资源的减少,市场上的芳烃供给变得不可持续。而丙烷作为一种处理天然气或精炼原油得到的副产物,且在页岩气中占有较大比重,因此利用丙烷芳构化制得芳烃的技术开发具有重要意义。
ZSM-5分子筛因其优异的择形催化能力而被广泛应用于各类芳构化反应中,当前文献报道的用于丙烷芳构化的催化剂大多也是在ZSM-5分子筛上进行进一步的改性。尽管此类催化剂表现出了一定的催化活性,但仍无法满足工业需求。一方面,产物中低碳烃类产物占有较大比重,芳烃选择性不高;另一方面,生成的芳烃易于在ZSM-5分子筛表面的酸性位点上进一步发生芳构化,生成附加值较低的重质芳烃,且易发生积碳反应。
发明内容
本发明的目的在于解决现有技术中的上述问题,提供一种用于丙烷芳构化的核壳结构催化剂及其制备方法和应用,该核壳结构催化剂有着更高的丙烷芳构化性能,且能抑制催化剂表面的进一步芳构化。
为达到上述目的,本发明采用如下技术方案:
一种用于丙烷芳构化的核壳结构催化剂,所述催化剂的核层为ZSM-5分子筛,壳层为Silicate-1分子筛,金属Pt和助剂M金属元素被封装于壳层Silicate-1分子筛内;以质量百分比计,壳层Silicate-1分子筛为30%~70%,金属Pt为0.01%~3%,M金属元素为0.01%~10%,余量为核层ZSM-5分子筛。
所述M金属元素为Sn、Zn、Ga、Ir、Cu、Ag、Co中的至少一种。
一种用于丙烷芳构化的核壳结构催化剂的制备步骤如下:
1)将硅源、模板剂、铝源、去离子水混合后在一定温度下搅拌形成混合溶胶,将混合溶胶移至水热釜内晶化,对所得产物进行离心、洗涤、干燥、焙烧,得到ZSM-5分子筛;
2)将硅源、模板剂、去离子水混合后在一定温度下搅拌,加入计量的Pt盐溶液和M金属前驱体溶液,搅拌后加入步骤1)所制备的计量的ZSM-5分子筛得到混合物,将所得混合物移至水热釜内晶化,对所得产物进行离心、洗涤、干燥、焙烧,得到核壳结构催化剂。
在步骤1)中,所述硅源为正硅酸四乙酯、硅溶胶、白炭黑中的至少一种,模板剂为四丙基氢氧化铵、四丙基溴化铵、四丁基氢氧化膦中的至少一种,铝源为异丙醇铝、九水合硝酸铝、六水合氯化铝中的至少一种,模板剂摩尔量为硅源摩尔量的0.01~2倍,铝源摩尔量为硅源摩尔量的1/300~1/10,去离子水摩尔量为硅源摩尔量的10~300倍;搅拌温度20~80℃,搅拌时间为3~48h。
在步骤1)中,所述水热晶化过程的温度为120~220℃,晶化时间为24~120h;干燥包括真空干燥、鼓风干燥的至少一种,干燥温度为50~120℃,干燥时间为3~12h;焙烧温度为400~650℃,焙烧时间为3~10h。
在步骤2)中,所述硅源为正硅酸四乙酯、硅溶胶、发烟二氧化硅中的至少一种,模板剂为四丙基氢氧化铵、四丙基溴化铵、四丁基氢氧化膦中的至少一种,模板剂摩尔量为硅源摩尔量的0.01~2倍,去离子水摩尔量为硅源摩尔量的10~300倍;搅拌温度20~80℃,搅拌时间为3~48h。
在步骤2)中,所述Pt盐为硝酸盐、铵盐、卤化物中的一种或几种,溶液的质量浓度为0.01~50mg/mL;M金属元素前驱体为M金属元素的氧化物、无机盐、配合物中的至少一种,M金属元素前驱体溶液的摩尔浓度为0.1~50mmol/L。
在步骤2)中,所述水热晶化过程的温度为80~220℃,晶化时间为20~120h;干燥包括真空干燥、鼓风干燥的至少一种,干燥温度为50~120℃,干燥时间为3~12h;焙烧温度为400~650℃,焙烧时间为3~10h。
所述的一种用于丙烷芳构化的核壳结构催化剂的应用,用于丙烷芳构化反应制芳烃。
反应前需用5%~100%氢气的氢氩或氢氮混合气在300~600℃下处理1~4h,然后通入原料气,在一定的压力和温度下进行丙烷芳构化反应;反应在固定床、固定流化床、循环流化床或移动床反应器中进行,原料气为纯丙烷、丙烷/氮气或丙烷/氢气混合物,丙烷的体积含量不低于25%,反应温度为350~650℃,反应压力为0.1~1MPa,反应空速为1000~12000mL/h/g。
相对于现有技术,本发明技术方案取得的有益效果是:
(1)本发明所述的核壳结构催化剂将活性金属Pt和助剂元素封装在壳层Silicate-1分子筛中,可为丙烷提供脱氢位点生成丙烯。
(2)本发明所述的核壳结构催化剂核层为ZSM-5分子筛,可为丙烯提供芳构化酸性位点生成芳烃。
(3)本发明所述的核壳结构催化剂优势在于在ZSM-5分子筛表面继续生长一层Silicate-1分子筛,覆盖ZSM-5分子筛表面酸性位点,可阻止ZSM-5分子筛表面酸性位点上生成的高值轻质芳烃进一步芳构化生成重质芳烃。
(4)本发明所制备的核壳结构催化剂有着较好的丙烷芳构化性能,产物中总芳烃选择性可达70%,其中轻质芳烃占比可达80%以上。
(5)本发明制备的核壳结构催化剂原料易得,制作工艺简单,性能优异,适用于工业化生产。
附图说明
图1为实施例2的ZSM-5(30)分子筛以及实施例2的核壳结构催化剂PtZn-S1@ZSM-5(30)的X射线衍射谱图。
图2为实施例2的ZSM-5(30)分子筛以及实施例2的核壳结构催化剂PtZn-S1@ZSM-5(30)的NH3-TPD图。
图3为实施例2的ZSM-5(30)分子筛的SEM图。
图4为实施例2的核壳结构催化剂PtZn-S1@ZSM-5(30)的SEM图。
具体实施方式
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚、明白,以下结合附图和实施例,对本发明做进一步详细说明。
实施例1
将2.08g正硅酸四乙酯,5.29g四丙基氢氧化铵(25%水溶液),0.07g异丙醇铝和5.03g去离子水置于100mL烧杯中,在25℃下搅拌10h形成混合溶胶,将混合溶胶移至100mL水热釜中,在170℃烘箱中晶化72h,自然降温后,对水热釜中的固液混合物进行离心、洗涤,80℃下真空干燥6h;然后将固体研磨后放入马弗炉中,于空气气氛下550℃焙烧6h后得到ZSM-5(30)分子筛;将2.28g正硅酸四乙酯,0.35g四丙基氢氧化铵(25%水溶液)和41.0g去离子水置于100mL烧杯中,在25℃下搅拌6h后加入0.45mL氯铂酸水溶液(氯铂酸水溶液浓度为10mg/mL)和3.47mL硝酸镓水溶液(硝酸镓水溶液浓度为10mmol/L),搅拌4h后再加入0.5g制备的ZSM-5(30)分子筛,然后将混合物移至100mL水热釜中,在100℃烘箱中晶化24h,自然降温后,对水热釜中的固液混合物进行离心、洗涤,80℃下真空干燥6h;然后将固体研磨后放入马弗炉中,于空气气氛下550℃焙烧6h后得到核壳结构催化剂,记为PtGa-S1@ZSM-5(30)。
将0.5g 30~60目的上述催化剂装填入常压固定床石英反应管中,先在20mL/min的纯H2气流下以5℃/min的升温速率升温至500℃进行预处理,恒温4h,然后切换为N2(50mL/min)吹扫10min,同时以10℃/min的升温速率升温至600℃,接着通入原料气n(丙烷):n(氮气)=1:1,固定床反应器中的压力为0.1MPa,反应空速为6000mL/h/g。所述催化剂的催化性能如表1所示。
实施例2
如实施例1制备ZSM-5(30)分子筛;将2.28g正硅酸四乙酯,0.35g四丙基氢氧化铵(25%水溶液)和41.0g去离子水置于100mL烧杯中,在25℃下搅拌6h后加入0.45mL氯铂酸水溶液(氯铂酸水溶液浓度为10mg/mL)和3.47mL硝酸锌水溶液(硝酸锌水溶液浓度为10mmol/L),搅拌4h后再加入0.5g制备的ZSM-5(30)分子筛,然后将混合物移至100mL水热釜中,在100℃烘箱中晶化24h,自然降温后,对水热釜中的固液混合物进行离心、洗涤,80℃下真空干燥6h;然后将固体研磨后放入马弗炉中,于空气气氛下550℃焙烧6h后得到核壳结构催化剂,记为PtZn-S1@ZSM-5(30)。
将0.5g 30~60目的上述催化剂装填入常压固定床石英反应管中,先在20mL/min的纯H2气流下以5℃/min的升温速率升温至500℃进行预处理,恒温4h,然后切换为N2(50mL/min)吹扫10min,同时以10℃/min的升温速率升温至600℃,接着通入原料气n(丙烷):n(氮气)=1:1,固定床反应器中的压力为0.1MPa,反应空速为6000mL/h/g。所述催化剂的催化性能如表1所示。
实施例3
如实施例1制备ZSM-5(30)分子筛;将2.28g正硅酸四乙酯,0.35g四丙基氢氧化铵(25%水溶液)和41.0g去离子水置于100mL烧杯中,在25℃下搅拌6h后加入0.45mL氯铂酸水溶液(氯铂酸水溶液浓度为10mg/mL)和3.47mL氯化亚锡水溶液(氯化亚锡水溶液浓度为10mmol/L),搅拌4h后再加入0.5g制备的ZSM-5(30)分子筛,然后将混合物移至100mL水热釜中,在100℃烘箱中晶化24h,自然降温后,对水热釜中的固液混合物进行离心、洗涤,80℃下真空干燥6h;然后将固体研磨后放入马弗炉中,于空气气氛下550℃焙烧6h后得到核壳结构催化剂,记为PtSn-S1@ZSM-5(30)。
将0.5g 30~60目的上述催化剂装填入常压固定床石英反应管中,先在20mL/min的纯H2气流下以5℃/min的升温速率升温至500℃进行预处理,恒温4h,然后切换为N2(50mL/min)吹扫10min,同时以10℃/min的升温速率升温至600℃,接着通入原料气n(丙烷):n(氮气)=1:1,固定床反应器中的压力为0.1MPa,反应空速为6000mL/h/g。所述催化剂的催化性能如表1所示。
实施例4
将2.08g正硅酸四乙酯,5.29g四丙基氢氧化铵(25%水溶液),0.02g异丙醇铝和5.03g去离子水置于100mL烧杯中,在25℃下搅拌10h形成混合溶胶,将混合溶胶移至100mL水热釜中,在170℃烘箱中晶化72h,自然降温后,对水热釜中的固液混合物进行离心、洗涤,80℃下真空干燥6h;然后将固体研磨后放入马弗炉中,于空气气氛下550℃焙烧6h后得到ZSM-5(100)分子筛;将2.28g正硅酸四乙酯,0.35g四丙基氢氧化铵(25%水溶液)和41.0g去离子水置于100mL烧杯中,在25℃下搅拌6h后加入0.45mL氯铂酸水溶液(氯铂酸水溶液浓度为10mg/mL)和3.47mL硝酸锌水溶液(硝酸锌水溶液浓度为10mmol/L),搅拌4h后再加入0.5g制备的ZSM-5(100)分子筛,然后将混合物移至100mL水热釜中,在100℃烘箱中晶化24h,自然降温后,对水热釜中的固液混合物进行离心、洗涤,80℃下真空干燥6h;然后将固体研磨后放入马弗炉中,于空气气氛下550℃焙烧6h后得到核壳结构催化剂,记为PtZn-S1@ZSM-5(100)。
将0.5g 30~60目的上述催化剂装填入常压固定床石英反应管中,先在20mL/min的纯H2气流下以5℃/min的升温速率升温至500℃进行预处理,恒温4h,然后切换为N2(50mL/min)吹扫10min,同时以10℃/min的升温速率升温至600℃,接着通入原料气n(丙烷):n(氮气)=1:1,固定床反应器中的压力为0.1MPa,反应空速为6000mL/h/g。所述催化剂的催化性能如表1所示。
实施例5
将2.08g正硅酸四乙酯,5.29g四丙基氢氧化铵(25%水溶液),0.01g异丙醇铝和5.03g去离子水置于100mL烧杯中,在25℃下搅拌10h形成混合溶胶,将混合溶胶移至100mL水热釜中,在170℃烘箱中晶化72h,自然降温后,对水热釜中的固液混合物进行离心、洗涤,80℃下真空干燥6h;然后将固体研磨后放入马弗炉中,于空气气氛下550℃焙烧6h后得到ZSM-5(200)分子筛;将2.28g正硅酸四乙酯,0.35g四丙基氢氧化铵(25%水溶液)和41.0g去离子水置于100mL烧杯中,在25℃下搅拌6h后加入0.45mL氯铂酸水溶液(氯铂酸水溶液浓度为10mg/mL)和3.47mL硝酸锌水溶液(硝酸锌水溶液浓度为10mmol/L),搅拌4h后再加入0.5g制备的ZSM-5(200)分子筛,然后将混合物移至100mL水热釜中,在100℃烘箱中晶化24h,自然降温后,对水热釜中的固液混合物进行离心、洗涤,80℃下真空干燥6h;然后将固体研磨后放入马弗炉中,于空气气氛下550℃焙烧6h后得到核壳结构催化剂,记为PtZn-S1@ZSM-5(200)。
将0.5g 30~60目的上述催化剂装填入常压固定床石英反应管中,先在20mL/min的纯H2气流下以5℃/min的升温速率升温至500℃进行预处理,恒温4h,然后切换为N2(50mL/min)吹扫10min,同时以10℃/min的升温速率升温至600℃,接着通入原料气n(丙烷):n(氮气)=1:1,固定床反应器中的压力为0.1MPa,反应空速为6000mL/h/g。所述催化剂的催化性能如表1所示。
对比例1
如实施例1制备ZSM-5(30)分子筛;将2.28g正硅酸四乙酯,0.35g四丙基氢氧化铵(25%水溶液)和41.0g去离子水置于100mL烧杯中,在25℃下搅拌6h后加入0.45mL氯铂酸水溶液(氯铂酸水溶液浓度为10mg/mL),搅拌4h后再加入0.5g制备的ZSM-5(30)分子筛,然后将混合物移至100mL水热釜中,在100℃烘箱中晶化24h,自然降温后,对水热釜中的固液混合物进行离心、洗涤,80℃下真空干燥6h;然后将固体研磨后放入马弗炉中,于空气气氛下550℃焙烧6h后得到核壳结构催化剂,记为Pt-S1@ZSM-5(30)。
将0.5g 30~60目的上述催化剂装填入常压固定床石英反应管中,先在20mL/min的纯H2气流下以5℃/min的升温速率升温至500℃进行预处理,恒温4h,然后切换为N2(50mL/min)吹扫10min,同时以10℃/min的升温速率升温至600℃,接着通入原料气n(丙烷):n(氮气)=1:1,固定床反应器中的压力为0.1MPa,反应空速为6000mL/h/g。所述催化剂的催化性能如表1所示。
对比例2
将2.08g正硅酸四乙酯,5.29g四丙基氢氧化铵(25%水溶液)和5.03g去离子水置于100mL烧杯中,在25℃下搅拌10h后加入0.45mL氯铂酸水溶液(氯铂酸水溶液浓度为10mg/mL)和3.47mL硝酸锌水溶液(硝酸锌水溶液浓度为10mmol/L)形成混合溶胶,搅拌4h后将混合溶胶移至100mL水热釜中,在170℃烘箱中晶化72h,自然降温后,对水热釜中的固液混合物进行离心、洗涤,80℃下真空干燥6h;然后将固体研磨后放入马弗炉中,于空气气氛下550℃焙烧6h后得到分子筛催化剂,记为PtZn-S1。
将0.5g 30~60目的上述催化剂装填入常压固定床石英反应管中,先在20mL/min的纯H2气流下以5℃/min的升温速率升温至500℃进行预处理,恒温4h,然后切换为N2(50mL/min)吹扫10min,同时以10℃/min的升温速率升温至600℃,接着通入原料气n(丙烷):n(氮气)=1:1,固定床反应器中的压力为0.1MPa,反应空速为6000mL/h/g。所述催化剂的催化性能如表1所示。
表1 实施例1~5和对比例1~2催化剂的丙烷芳构化性能
图1为实施例2的ZSM-5(30)分子筛以及实施例2的核壳结构催化剂PtZn-S1@ZSM-5(30)的X射线衍射谱图。可以看出,催化剂均出现MFI分子筛的特征衍射峰,且未出现金属粒子的特征衍射峰,说明金属纳米粒子尺寸小且高度分散。
图2为实施例2的ZSM-5(30)分子筛以及实施例2的核壳结构催化剂PtZn-S1@ZSM-5(30)的NH3-TPD图。从中可以看出,ZSM-5(30)分子筛和PtZn-S1@ZSM-5(30)分子筛均有一个低温脱附峰和一个高温脱附峰,ZSM-5(30)分子筛的高温脱附峰酸量明显高于PtZn-S1@ZSM-5(30)分子筛,说明核壳结构催化剂外层的Silicate-1分子筛覆盖了内层ZSM-5分子筛的表面酸性位点。
图3为实施例2的ZSM-5(30)分子筛的SEM图。可以看出,ZSM-5(30)分子筛形状规整,呈六棱柱状。
图4为实施例2的核壳结构催化剂PtZn-S1@ZSM-5(30)的SEM图。可以看出,PtZn-S1@ZSM-5(30)催化剂与ZSM-5分子筛有着相似的结构。
Claims (8)
1.一种用于丙烷芳构化的核壳结构催化剂,其特征在于:所述核壳结构催化剂的核层为ZSM-5分子筛,壳层为Silicate-1分子筛,金属Pt和助剂M金属元素被封装于壳层Silicate-1分子筛内;以质量百分比计,壳层Silicate-1分子筛为30%~70%,金属Pt为0.01%~3%,M金属元素为0.01%~10%,余量为核层ZSM-5分子筛;所述M金属元素为Sn、Zn、Ga、Cu、Co中的至少一种;
其制备方法包括以下步骤:
1)将硅源、模板剂、铝源、去离子水混合搅拌形成混合溶胶,将混合溶胶移至水热釜内晶化,对所得产物进行离心、洗涤、干燥、焙烧,得到ZSM-5分子筛;
2)将硅源、模板剂、去离子水混合搅拌,加入Pt盐溶液和M金属前驱体溶液,搅拌后加入ZSM-5分子筛得到混合物,将所得混合物移至水热釜内晶化,对所得产物进行离心、洗涤、干燥、焙烧,得到核壳结构催化剂。
2.如权利要求1所述的一种用于丙烷芳构化的核壳结构催化剂,其特征在于:在步骤1)中,所述硅源为正硅酸四乙酯、硅溶胶、白炭黑中的至少一种,模板剂为四丙基氢氧化铵、四丙基溴化铵、四丁基氢氧化膦中的至少一种,铝源为异丙醇铝、九水合硝酸铝、六水合氯化铝中的至少一种,模板剂摩尔量为硅源摩尔量的0.01~2倍,铝源摩尔量为硅源摩尔量的1/300~1/10,去离子水摩尔量为硅源摩尔量的10~300倍;搅拌温度20~80℃,搅拌时间为3~48h。
3.如权利要求1所述的一种用于丙烷芳构化的核壳结构催化剂,其特征在于:在步骤1)中,所述晶化的温度为120~220℃,晶化时间为24~120h;干燥包括真空干燥、鼓风干燥的至少一种,干燥温度为50~120℃,干燥时间为3~12h;焙烧温度为400~650℃,焙烧时间为3~10h。
4.如权利要求1所述的一种用于丙烷芳构化的核壳结构催化剂,其特征在于:在步骤2)中,所述硅源为正硅酸四乙酯、硅溶胶、发烟二氧化硅中的至少一种,模板剂为四丙基氢氧化铵、四丙基溴化铵、四丁基氢氧化膦中的至少一种,模板剂摩尔量为硅源摩尔量的0.01~2倍,去离子水摩尔量为硅源摩尔量的10~300倍;搅拌温度20~80℃,搅拌时间为3~48h。
5.如权利要求1所述的一种用于丙烷芳构化的核壳结构催化剂,其特征在于:在步骤2)中,所述Pt盐为硝酸盐、铵盐、卤化物中的一种或几种,Pt盐溶液的质量浓度为0.01~50mg/mL;M金属元素前驱体为M金属元素的氧化物、无机盐、配合物中的至少一种,M金属元素前驱体溶液的摩尔浓度为0.1~50mmol/L。
6.如权利要求1所述的一种用于丙烷芳构化的核壳结构催化剂,其特征在于:在步骤2)中,所述晶化的温度为80~220℃,晶化时间为20~120h;干燥包括真空干燥、鼓风干燥的至少一种,干燥温度为50~120℃,干燥时间为3~12h;焙烧温度为400~650℃,焙烧时间为3~10h。
7.权利要求1~6任一项所述的一种用于丙烷芳构化的核壳结构催化剂的应用,其特征在于:用于丙烷芳构化反应制芳烃。
8.如权利要求7所述的应用,其特征在于:丙烷芳构化反应前需用纯氢气在300~600℃下处理1~4h,然后通入原料气,在一定的压力和温度下进行丙烷芳构化反应;反应在固定床、固定流化床、循环流化床或移动床反应器中进行,原料气为纯丙烷、丙烷/氮气或丙烷/氢气混合物,丙烷的体积含量不低于25%,反应温度为350~650℃,反应压力为0.1~1MPa,反应空速为1000~12000mL/h/g。
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