CN116251590B - 用于丙烷脱氢制丙烯的氧化铝基催化剂的制备方法 - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
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- 239000007864 aqueous solution Substances 0.000 claims description 7
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- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 7
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- 238000004108 freeze drying Methods 0.000 claims description 6
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- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 7
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- 239000002243 precursor Substances 0.000 abstract description 2
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- 229910052797 bismuth Inorganic materials 0.000 description 2
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- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
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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 description 1
- 238000003980 solgel method Methods 0.000 description 1
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Abstract
本发明涉及催化剂技术领域,且公开了用于丙烷脱氢制丙烯的氧化铝基催化剂的制备方法,以羟基聚乙烯亚胺模板剂,经过络合和硼氢化钠还原,得到聚乙烯亚胺模板剂负载Pt纳米簇,最后煅烧除去模板,得到Pt纳米簇,制备方法简单高效;以拟薄水铝石粉作为前驱体,通过喷雾干燥法制备了多孔γ‑氧化铝微球作为载体,负载的Pt/Sn作为催化活性物质,具有丙烷转化率高,丙烯选择性好的优点。
Description
技术领域
本发明涉及催化剂技术领域,具体为一种用于丙烷脱氢制丙烯的氧化铝基催化剂的制备方法。
背景技术
烯烃类化合物如丙烯、丁二烯等,是一类重要的石油化工原料,近年来随着对烯烃类化合物需求量的快速增长,以传统技术生产的丙烯已经不能满足工业生产和需求;以低碳烷烃作为原料,通过催化脱氢制取烯烃化合物的工艺是研究热点;目前通过丙烷脱氢制取丙烯的催化剂体系主要是铂基催化剂,催化剂载体通常由二氧化钛、氧化铝、分子筛等组成,如公开号为CN106588546B的专利《一种丙烷脱氢制备丙烯的方法》,公开了脱氢催化剂含有氧化铝载体以及负载在载体上的活性组分铂族金属和助剂铋,通过在脱氢催化剂中引入助剂铋,得到丙烷脱氢制取丙烯的催化剂;但是现有的氧化铝脱氢催化剂存在对丙烷转化率较低,丙烯选择性较差等问题。
Pt纳米簇具有比表面大、独特的宏观量子隧道效应、量子尺寸效应等,催化活性高,催化位点多,在催化剂方面有着广阔的应用前景。如采用新型高效的方法制备Pt纳米簇应用于丙烷脱氢制备丙烯具有重要的意义,文献《Pt纳米簇催化剂上丙烷脱氢反应的研究》报道了以溶胶凝胶法制备的SiO2作为载体,异丙醇为还原剂,制备了Pt纳米簇和负载型Pt/SiO2催化剂,用于丙烷脱氢反应中;目前以二氧化硅作为载体的丙烷脱氢催化剂的活性比氧化铝基催化剂低。本发明供制备一种高转化效率的负载Pt/Sn的氧化铝基催化剂,应用于丙烷脱氢制丙烯中。
发明内容
针对现有技术的不足,本发明提供了一种高转化效率的负载Pt/Sn的氧化铝基催化剂,应用于丙烷脱氢制丙烯中。
一种用于丙烷脱氢制丙烯的氧化铝基催化剂的制备方法,包括以下步骤:
(1)将聚乙烯亚胺溶解到乙醇溶剂中,然后加入环氧丙醇,在25-40℃中搅拌反应10-20h,反应后减压蒸馏除去乙醇,产物在透析袋中透析纯化,然后进行冷冻干燥,得到端羟基聚乙烯亚胺模板剂;
(2)将端羟基聚乙烯亚胺模板剂溶解到乙醇中,然后加入氯铂酸的水溶液,在室温下搅拌12-24h,再加入硼氢化钠的乙醇溶液,在室温下还原反应12-24h,减压蒸馏除去溶剂,产物在透析袋中透析纯化,得到聚乙烯亚胺模板剂负载Pt纳米簇;
(3)将聚乙烯亚胺模板剂负载Pt纳米簇置于气氛炉空气氛围中进行煅烧,去离子水洗涤煅烧产物,得到Pt纳米簇;
(4)将多孔γ-氧化铝微球分散到蒸馏水中,再加入二氯化锡的乙醇溶液,混合均匀后加入Pt纳米簇,浸渍6-18h,将溶液真空干燥,产物在气氛炉空气氛围下进行煅烧,去离子水洗涤煅烧产物,得到负载Pt/Sn的氧化铝基催化剂。
优选的,所述(1)中环氧丙醇的用量为聚乙烯亚胺质量的60-120%。
优选的,所述(2)中氯铂酸的用量为端羟基聚乙烯亚胺模板剂质量的45-80%。
优选的,所述(3)中煅烧温度为550-650℃,时间为2-4h。
优选的,所述(4)中煅烧温度为450-600℃,时间为2-3h。
优选的,所述(4)中氧化铝基催化剂中Pt的负载量为0.3-0.8 wt%。
优选的,所述(4)中氧化铝基催化剂中Sn的负载量为0.2-0.5 wt%。
优选的,所述(4)中多孔γ-氧化铝微球的制备方法为:将拟薄水铝石粉研磨均匀,分散到去离子水中,然后滴加浓硝酸调节溶液pH至2-3,在45-60℃中搅拌反应2-5h,将溶液采用喷雾干燥机制成粉末,控制进料速度150-250 mL/h,喷雾干燥机进口温度170-200℃,出风口温度为90-100℃,将粉末产物在气氛炉空气氛围下进行煅烧,温度为800-950℃,时间为2-4h,得到多孔γ-氧化铝微球。
本发明的有益效果:本发明以羟基聚乙烯亚胺模板剂,经过络合和硼氢化钠还原,得到聚乙烯亚胺模板剂负载Pt纳米簇,最后煅烧除去模板,得到Pt纳米簇,制备方法简单高效;以拟薄水铝石粉作为前驱体,通过喷雾干燥法制备了多孔γ-氧化铝微球作为载体,负载的Pt/Sn作为催化活性物质,具有丙烷转化率高,丙烯选择性好的优点。
附图说明
图1是Pt纳米簇的扫描电镜。
图2是丙烷制取丙烯的转换效率测试。
具体实施方式
实施例1:(1)将3g的聚乙烯亚胺溶解到80mL的乙醇溶剂中,然后加入1.5g的环氧丙醇,在30℃中搅拌反应12h,反应后减压蒸馏除去乙醇,产物在透析袋中透析纯化,然后进行冷冻干燥,得到端羟基聚乙烯亚胺模板剂;
(2)将4g的端羟基聚乙烯亚胺模板剂溶解到50mL的乙醇中,然后加入30mL的含有1.8g的氯铂酸的水溶液,在室温下搅拌18h,再加入20mL的含有2.5g的硼氢化钠的乙醇溶液,在室温下还原反应24h,减压蒸馏除去溶剂,产物在透析袋中透析纯化,得到聚乙烯亚胺模板剂负载Pt纳米簇;
(3)将聚乙烯亚胺模板剂负载Pt纳米簇置于气氛炉空气氛围中进行煅烧,煅烧温度为600℃,时间为3h,去离子水洗涤煅烧产物,得到Pt纳米簇;
(4)将拟薄水铝石粉研磨均匀,分散到去离子水中,然后滴加浓硝酸调节溶液pH至2,在60℃中搅拌反应5h,将溶液采用喷雾干燥机制成粉末,控制进料速度150mL/h,喷雾干燥机进口温度180℃,出风口温度为100℃,将粉末产物在气氛炉空气氛围下进行煅烧,温度为850℃,时间为3h,得到多孔γ-氧化铝微球;
(5)将多孔γ-氧化铝微球分散到蒸馏水中,再加入二氯化锡的乙醇溶液,混合均匀后加入Pt纳米簇,浸渍12h,将溶液真空干燥,产物在气氛炉空气氛围下进行煅烧,煅烧温度为600℃,时间为3h,去离子水洗涤煅烧产物,得到负载Pt/Sn的氧化铝基催化剂,控制氧化铝基催化剂中Pt的负载量为0.3 wt%,Sn的负载量为0.2 wt%。
实施例2:(1)将3g的聚乙烯亚胺溶解到80mL的乙醇溶剂中,然后加入2.5g的环氧丙醇,在40℃中搅拌反应10h,反应后减压蒸馏除去乙醇,产物在透析袋中透析纯化,然后进行冷冻干燥,得到端羟基聚乙烯亚胺模板剂;
(2)将4g的端羟基聚乙烯亚胺模板剂溶解到50mL的乙醇中,然后加入30 mL的含有2.5g的氯铂酸的水溶液,在室温下搅拌18h,再加入20mL的含有3.2 g的硼氢化钠的乙醇溶液,在室温下还原反应12h,减压蒸馏除去溶剂,产物在透析袋中透析纯化,得到聚乙烯亚胺模板剂负载Pt纳米簇;
(3)将聚乙烯亚胺模板剂负载Pt纳米簇置于气氛炉空气氛围中进行煅烧,煅烧温度为550℃,时间为4h,去离子水洗涤煅烧产物,得到Pt纳米簇;
(4)将拟薄水铝石粉研磨均匀,分散到去离子水中,然后滴加浓硝酸调节溶液pH至3,在45℃中搅拌反应2h,将溶液采用喷雾干燥机制成粉末,控制进料速度200mL/h,喷雾干燥机进口温度170℃,出风口温度为90℃,将粉末产物在气氛炉空气氛围下进行煅烧,温度为950℃,时间为3h,得到多孔γ-氧化铝微球;
(5)将多孔γ-氧化铝微球分散到蒸馏水中,再加入二氯化锡的乙醇溶液,混合均匀后加入Pt纳米簇,浸渍6h,将溶液真空干燥,产物在气氛炉空气氛围下进行煅烧,煅烧温度为500℃,时间为2h,去离子水洗涤煅烧产物,得到负载Pt/Sn的氧化铝基催化剂,控制氧化铝基催化剂中Pt的负载量为0.4 wt%,Sn的负载量为0.3 wt%。
实施例3:(1)将3g的聚乙烯亚胺溶解到80mL的乙醇溶剂中,然后加入4g的环氧丙醇,在25℃中搅拌反应20h,反应后减压蒸馏除去乙醇,产物在透析袋中透析纯化,然后进行冷冻干燥,得到端羟基聚乙烯亚胺模板剂;
(2)将4g的端羟基聚乙烯亚胺模板剂溶解到50mL的乙醇中,然后加入30mL的含有3.2g的氯铂酸的水溶液,在室温下搅拌12h,再加入20mL的含有6g的硼氢化钠的乙醇溶液,在室温下还原反应18h,减压蒸馏除去溶剂,产物在透析袋中透析纯化,得到聚乙烯亚胺模板剂负载Pt纳米簇;
(3)将聚乙烯亚胺模板剂负载Pt纳米簇置于气氛炉空气氛围中进行煅烧,煅烧温度为650℃,时间为2h,去离子水洗涤煅烧产物,得到Pt纳米簇;
(4)将拟薄水铝石粉研磨均匀,分散到去离子水中,然后滴加浓硝酸调节溶液pH至3,在50℃中搅拌反应3h,将溶液采用喷雾干燥机制成粉末,控制进料速度250mL/h,喷雾干燥机进口温度200℃,出风口温度为95℃,将粉末产物在气氛炉空气氛围下进行煅烧,温度为950℃,时间为4h,得到多孔γ-氧化铝微球;
(5)将多孔γ-氧化铝微球分散到蒸馏水中,再加入二氯化锡的乙醇溶液,混合均匀后加入Pt纳米簇,浸渍18h,将溶液真空干燥,产物在气氛炉空气氛围下进行煅烧,煅烧温度为500℃,时间为2h,去离子水洗涤煅烧产物,得到负载Pt/Sn的氧化铝基催化剂,控制氧化铝基催化剂中Pt的负载量为0.6 wt%,Sn的负载量为0.4 wt%。
实施例4:(1)将3g的聚乙烯亚胺溶解到80mL的乙醇溶剂中,然后加入6g的环氧丙醇,在25℃中搅拌反应12h,反应后减压蒸馏除去乙醇,产物在透析袋中透析纯化,然后进行冷冻干燥,得到端羟基聚乙烯亚胺模板剂;
(2)将4g的端羟基聚乙烯亚胺模板剂溶解到50mL的乙醇中,然后加入30mL的含有2.5g的氯铂酸的水溶液,在室温下搅拌24h,再加入20mL的含有4.2g的硼氢化钠的乙醇溶液,在室温下还原反应24h,减压蒸馏除去溶剂,产物在透析袋中透析纯化,得到聚乙烯亚胺模板剂负载Pt纳米簇;
(3)将聚乙烯亚胺模板剂负载Pt纳米簇置于气氛炉空气氛围中进行煅烧,煅烧温度为550℃,时间为3h,去离子水洗涤煅烧产物,得到Pt纳米簇;
(4)将拟薄水铝石粉研磨均匀,分散到去离子水中,然后滴加浓硝酸调节溶液pH至3,在60℃中搅拌反应3h,将溶液采用喷雾干燥机制成粉末,控制进料速度250mL/h,喷雾干燥机进口温度200℃,出风口温度为100℃,将粉末产物在气氛炉空气氛围下进行煅烧,温度为900℃,时间为2h,得到多孔γ-氧化铝微球;
(5)将多孔γ-氧化铝微球分散到蒸馏水中,再加入二氯化锡的乙醇溶液,混合均匀后加入Pt纳米簇,浸渍18h,将溶液真空干燥,产物在气氛炉空气氛围下进行煅烧,煅烧温度为450℃,时间为3h,去离子水洗涤煅烧产物,得到负载Pt/Sn的氧化铝基催化剂,控制氧化铝基催化剂中Pt的负载量为0.8 wt%,Sn的负载量为0.5 wt%。
对比例1:(1)将拟薄水铝石粉研磨均匀,分散到去离子水中,然后滴加浓硝酸调节溶液pH至2,在60℃中搅拌反应2h,将溶液采用喷雾干燥机制成粉末,控制进料速度250mL/h,喷雾干燥机进口温度180℃,出风口温度为100℃,将粉末产物在气氛炉空气氛围下进行煅烧,温度为850℃,时间为3h,得到多孔γ-氧化铝微球;
(2)将多孔γ-氧化铝微球加入到含有氯铂酸和二氯化锡的水溶液中,浸渍1h,然后将溶液在气氛炉中,先在空气气氛中进行煅烧,煅烧温度为550℃,时间为3h,再在氢气气氛中,进行热还原,温度为500℃,时间为6h,得到负载Pt/Sn的氧化铝基催化剂,控制氧化铝基催化剂中Pt的负载量为0.5 wt%,Sn的负载量为0.3 wt%。
通过连续管式固定床反应器测试负载Pt/Sn的氧化铝基催化剂的丙烷脱氢制取丙烯的催化活性,催化剂装填量5mL。向固定床反应器中通入体积比为1:1的丙烷和氢气的混合气体,总空速为3600 h-1,反应温度为550℃,压力为0.05 MPa。反应器出口产生的气体通过气相色谱仪进行分析。
实施例1-4以Pt纳米簇为催化活性组分,制备的负载Pt/Sn的氧化铝基催化剂催化丙烷制取丙烯,其丙烷转化率达到28.1-34.4%,丙烯选择性达到93.8-96.0%。
Claims (4)
1.一种用于丙烷脱氢制丙烯的氧化铝基催化剂的制备方法,其特征在于:包括以下步骤:
(1)将聚乙烯亚胺溶解到乙醇溶剂中,然后加入环氧丙醇,在25-40℃中搅拌反应10-20h,反应后减压蒸馏除去乙醇,产物在透析袋中透析纯化,然后进行冷冻干燥,得到端羟基聚乙烯亚胺模板剂;
(2)将端羟基聚乙烯亚胺模板剂溶解到乙醇中,然后加入氯铂酸的水溶液,在室温下搅拌12-24h,再加入硼氢化钠的乙醇溶液,在室温下还原反应12-24h,减压蒸馏除去溶剂,产物在透析袋中透析纯化,得到聚乙烯亚胺模板剂负载Pt纳米簇;
(3)将聚乙烯亚胺模板剂负载Pt纳米簇置于气氛炉空气氛围中进行煅烧,煅烧温度为550-650℃,时间为2-4h,去离子水洗涤煅烧产物,得到Pt纳米簇;
(4)将多孔γ-氧化铝微球分散到蒸馏水中,再加入二氯化锡的乙醇溶液,混合均匀后加入Pt纳米簇,浸渍6-18h,将溶液真空干燥,产物在气氛炉空气氛围下进行煅烧,去离子水洗涤煅烧产物,得到负载Pt/Sn的氧化铝基催化剂;其中氧化铝基催化剂中Pt的负载量为0.3-0.8 wt%,Sn的负载量为0.2-0.5 wt%。
2.根据权利要求1所述的用于丙烷脱氢制丙烯的氧化铝基催化剂的制备方法,其特征在于:所述(1)中环氧丙醇的用量为聚乙烯亚胺质量的60-120%。
3.根据权利要求1所述的用于丙烷脱氢制丙烯的氧化铝基催化剂的制备方法,其特征在于:所述(2)中氯铂酸的用量为端羟基聚乙烯亚胺模板剂质量的45-80%。
4.根据权利要求1所述的用于丙烷脱氢制丙烯的氧化铝基催化剂的制备方法,其特征在于:所述(4)中煅烧温度为450-600℃,时间为2-3h。
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