CN108889299A - 一种丙烯环氧化催化剂Au-V2O5-SrTiO3的制备方法及应用 - Google Patents
一种丙烯环氧化催化剂Au-V2O5-SrTiO3的制备方法及应用 Download PDFInfo
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Abstract
本发明涉及一种丙烯环氧化催化剂Au‑V2O5‑SrTiO3的制备方法及应用。该催化剂的制备方法为:以偏钒酸铵为前驱体,一水合柠檬酸为络合剂,通过溶胶凝胶法制备出V2O5;然后将V2O5加入TiCl4和Sr(OH)2·8H2O溶液中,调节pH,搅拌后置于水热釜内加热,产物经洗涤干燥得到V2O5‑SrTiO3;最后以聚乙烯醇为保护剂,通过硼氢化钠还原法制备出高分散性的Au‑V2O5‑SrTiO3催化剂。将上述制备的催化剂填充在固定床反应器中,按一定比例通入丙烯、氧气和稀释气,紫外光照下丙烯能够高效地转化为环氧丙烷,其最佳生成速率为62.94gPO·h‑1·kg‑1 cat。本发明反应过程简单,催化剂使用寿命长,对环境友好,能够将丙烯转化成附加值更高的有机化工产品。
Description
技术领域
本发明涉及紫外光照条件下丙烯环氧化生产环氧丙烷过程,具体涉及到一种新型三元复合催化剂Au-V2O5-SrTiO3的制备方法及应用。
背景技术
环氧丙烷(PO)是一种重要的有机化工原料,可用于生产聚醚多元醇、丙二醇、异丙醇胺、碳酸丙烯酯等产品。每年丙烯产量的10%左右用于生产PO。当前,PO的主要生产工艺有氯醇法、共氧化法和过氧化氢直接氧化法(HPPO法)。但是,氯醇法资源消耗大、设备腐蚀严重,同时还产生大量废水和废渣;共氧化法工艺流程长、副产物多、对生产设备要求高;HPPO法则存在催化剂寿命短、能耗高、溶剂量大、H2O2利用率低等问题。
光催化技术是一种绿色技术,在能源与环境领域得到广泛关注并有着很好的发展前景,已经有文献报道在分子氧存在条件下光催化丙烯环氧化生成环氧丙烷。但是,该反应的反应深度较难控制,光催化过程中容易发生部分氧化和完全氧化,故中间产物较多,PO的选择性较低。目前,光催化丙烯环氧化领域的研究热点主要集中在SiO2负载的金属氧化物体系,一般分为钛基催化剂和钒基催化剂两类。Nguyen等研究了V2O5/SiO2、Au/TiO2、TS-1以及V-Ti/MCM-41催化剂的光催化丙烯气相环氧化性能(Chem.Eng.J.,2012,179,285-294)。此外,SrTiO3作为一种传统的钙钛矿类光催化材料,具有良好的电子-空穴分离与输运特性,在近些年被广泛研究。
针对上述问题,本发明构建了一种由Au、V2O5和SrTiO3组成的三元复合光催化剂。该新型催化剂高效稳定、成本低,且使用寿命长,在光催化丙烯环氧化领域具有良好的应用前景。
发明内容
技术问题:本发明的目的是提供一种丙烯环氧化催化剂Au-V2O5-SrTiO3的制备方法及应用,为光催化丙烯高效、高选择性地转化为环氧丙烷提供一种新的途径,尤其是一种三元复合催化剂Au-V2O5-SrTiO3的制备方法及应用。
技术方案:本发明公开了一种丙烯环氧化催化剂Au-V2O5-SrTiO3的制备方法,所述的催化剂为V2O5和SrTiO3形成的复合材料上负载Au纳米颗粒;该制备方法包括以下具体步骤:
1)将偏钒酸铵与一水合柠檬酸按照摩尔比1:1~5溶于去离子水中,50~100℃下恒温搅拌,蒸发水分形成凝胶后于100~150℃保温发泡12~24h,产物研磨后放入马弗炉,400~700℃焙烧2~5h,即可得到V2O5粉末;
2)将制备的V2O5粉末、TiCl4和Sr(OH)2·8H2O加入盐酸溶液中,超声搅拌混合均匀后,加入NaOH溶液调节pH为8~11,形成的白色均相胶状浆体装于水热釜中,在150~220℃下反应24~72h,产物经多次洗涤、真空干燥、研磨后,即可得到V2O5-SrTiO3粉末;
3)将氯金酸溶液与去离子水混合,然后加入0.1wt%~3wt%聚乙烯醇溶液,接着快速加入新鲜制备的0.01~0.5mol/L NaBH4溶液,生成Au溶胶;常温下磁力搅拌0.1~2h后,加入预先制备的V2O5-SrTiO3粉末,继续搅拌1~5h,所得悬浮液经离心、洗涤、真空干燥后即得到所述Au-V2O5-SrTiO3催化剂。
所述的V2O5的质量为催化剂质量的0.01~20倍,TiCl4和Sr(OH)2·8H2O的摩尔比为1:1~10。
所述Au-V2O5-SrTiO3催化剂,以载体的质量计,Au的负载量为0.25wt%~4.0wt%。
采用所述方法制备的丙烯环氧化催化剂Au-V2O5-SrTiO3的应用方法为:将所述催化剂与石英砂均匀混合后填充在固定床反应器中,在50~150W高压汞灯照射下,通入丙烯、氧气和稀释气进行反应制备环氧丙烷;反应产物由气相色谱检测分析。
所述丙烯、氧气和稀释气的体积比为1:1:(5~10);空速为7000~12000mL·gcat -1·h-1;反应温度为50~200℃。
有益效果:与现有技术相比,本发明的优点在于:
(1)本发明方法的原料廉价、反应条件简单易控制,有利于环氧丙烷绿色合成工艺的进一步开发及工业化应用。
(2)本发明制备的催化剂高效稳定、成本低,且使用寿命长,用于光催化丙烯环氧化效果显著。
(3)本发明制备的催化剂中V2O5与SrTiO3复合形成异质结,有利于抑制光生电子和空穴的结合,从而提高光催化效率,加快环氧丙烷的产生。
具体实施方式
下面通过实施例对本发明技术方案作进一步详细说明。
实施例1:将5.85g偏钒酸铵与9.60g一水合柠檬酸溶于50mL去离子水中,90℃下恒温搅拌,蒸发水分形成凝胶后于120℃保温发泡12h,产物研磨后放入马弗炉,550℃焙烧3.5h,得到V2O5粉末;将0.5g的V2O5粉末、1.1mL的TiCl4和2.66g的Sr(OH)2·8H2O溶于盐酸溶液中,超声搅拌混合均匀后,加入6mol/L的NaOH溶液,将pH调节到10,形成的白色均相胶状浆体装于水热釜中,在180℃下反应48h,产物经多次洗涤、真空干燥、研磨后,即可得到V2O5-SrTiO3粉末;取1.6mL氯金酸溶液(0.6231g/100mL),与30mL去离子水混合后,加入0.75g质量浓度为1wt%的聚乙烯醇溶液,接着快速加入1.3mL新鲜制备的浓度为0.1mol/L的硼氢化钠溶液。常温下磁力搅拌0.5h后,加入0.5g预先制备的V2O5-SrTiO3粉末,继续搅拌2h,所得悬浮液经离心、去离子水洗涤、真空干燥后即得到Au-V2O5-SrTiO3催化剂。取0.1g该催化剂与2g石英砂均匀混合填充在固定床反应器中,光源选用100W高压汞灯,反应温度为75℃,丙烯、氧气和稀释气的体积比为1:1:8,空速为9000mL·gcat -1·h-1。通过气相色谱测得PO生成速率为29.36gPO·h-1·kg-1 cat。
实施例2:将5.85g偏钒酸铵与9.60g一水合柠檬酸溶于50mL去离子水中,90℃下恒温搅拌,蒸发水分形成凝胶后于120℃保温发泡12h,产物研磨后放入马弗炉,550℃焙烧3.5h,得到V2O5粉末;将0.5g的V2O5粉末、1.1mL的TiCl4和2.66g的Sr(OH)2·8H2O溶于盐酸溶液中,超声搅拌混合均匀后,加入6mol/L的NaOH溶液,将pH调节到10,形成的白色均相胶状浆体装于水热釜中,在180℃下反应48h,产物经多次洗涤、真空干燥、研磨后,即可得到V2O5-SrTiO3粉末;取3.2mL氯金酸溶液(0.6231g/100mL),与30mL去离子水混合后,加入1.5g质量浓度为1wt%的聚乙烯醇溶液,接着快速加入2.6mL新鲜制备的浓度为0.1mol/L的硼氢化钠溶液。常温下磁力搅拌0.5h后,加入0.5g预先制备的V2O5-SrTiO3粉末,继续搅拌2h,所得悬浮液经离心、去离子水洗涤、真空干燥后即得到Au-V2O5-SrTiO3催化剂。取0.1g该催化剂与2g石英砂均匀混合填充在固定床反应器中,光源选用100W高压汞灯,反应温度为75℃,丙烯、氧气和稀释气的体积比为1:1:8,空速为9000mL·gcat -1·h-1。通过气相色谱测得PO生成速率为62.94gPO·h-1·kg-1 cat。
实施例3:将5.85g偏钒酸铵与9.60g一水合柠檬酸溶于50mL去离子水中,90℃下恒温搅拌,蒸发水分形成凝胶后于120℃保温发泡12h,产物研磨后放入马弗炉,550℃焙烧3.5h,得到V2O5粉末;将0.5g的V2O5粉末、1.1mL的TiCl4和2.66g的Sr(OH)2·8H2O溶于盐酸溶液中,超声搅拌混合均匀后,加入6mol/L的NaOH溶液,将pH调节到10,形成的白色均相胶状浆体装于水热釜中,在180℃下反应48h,产物经多次洗涤、真空干燥、研磨后,即可得到V2O5-SrTiO3粉末;取4.8mL氯金酸溶液(0.6231g/100mL),与30mL去离子水混合后,加入2.3g质量浓度为1wt%的聚乙烯醇溶液,接着快速加入3.9mL新鲜制备的浓度为0.1mol/L的硼氢化钠溶液。常温下磁力搅拌0.5h后,加入0.5g预先制备的V2O5-SrTiO3粉末,继续搅拌2h,所得悬浮液经离心、去离子水洗涤、真空干燥后即得到Au-V2O5-SrTiO3催化剂。取0.1g该催化剂与2g石英砂均匀混合填充在固定床反应器中,光源选用100W高压汞灯,反应温度为75℃,丙烯、氧气和稀释气的体积比为1:1:8,空速为9000mL·gcat -1·h-1。通过气相色谱测得PO生成速率为50.33gPO·h-1·kg-1 cat。
实施例4:将5.85g偏钒酸铵与9.60g一水合柠檬酸溶于50mL去离子水中,90℃下恒温搅拌,蒸发水分形成凝胶后于120℃保温发泡12h,产物研磨后放入马弗炉,550℃焙烧3.5h,得到V2O5粉末;将0.3g的V2O5粉末、1.1mL的TiCl4和2.66g的Sr(OH)2·8H2O溶于盐酸溶液中,超声搅拌混合均匀后,加入6mol/L的NaOH溶液,将pH调节到10,形成的白色均相胶状浆体装于水热釜中,在180℃下反应48h,产物经多次洗涤、真空干燥、研磨后,即可得到V2O5-SrTiO3粉末;取3.2mL氯金酸溶液(0.6231g/100mL),与30mL去离子水混合后,加入1.5g质量浓度为1wt%的聚乙烯醇溶液,接着快速加入2.6mL新鲜制备的浓度为0.1mol/L的硼氢化钠溶液。常温下磁力搅拌0.5h后,加入0.5g预先制备的V2O5-SrTiO3粉末,继续搅拌2h,所得悬浮液经离心、去离子水洗涤、真空干燥后即得到Au-V2O5-SrTiO3催化剂。取0.1g该催化剂与2g石英砂均匀混合填充在固定床反应器中,光源选用100W高压汞灯,反应温度为75℃,丙烯、氧气和稀释气的体积比为1:1:8,空速为9000mL·gcat -1·h-1。通过气相色谱测得PO生成速率为42.89gPO·h-1·kg-1 cat。
实施例5:将5.85g偏钒酸铵与9.60g一水合柠檬酸溶于50mL去离子水中,90℃下恒温搅拌,蒸发水分形成凝胶后于120℃保温发泡12h,产物研磨后放入马弗炉,550℃焙烧3.5h,得到V2O5粉末;将0.8g的V2O5粉末、1.1mL的TiCl4和2.66g的Sr(OH)2·8H2O溶于盐酸溶液中,超声搅拌混合均匀后,加入6mol/L的NaOH溶液,将pH调节到10,形成的白色均相胶状浆体装于水热釜中,在180℃下反应48h,产物经多次洗涤、真空干燥、研磨后,即可得到V2O5-SrTiO3粉末;取3.2mL氯金酸溶液(0.6231g/100mL),与30mL去离子水混合后,加入1.5g质量浓度为1wt%的聚乙烯醇溶液,接着快速加入2.6mL新鲜制备的浓度为0.1mol/L的硼氢化钠溶液。常温下磁力搅拌0.5h后,加入0.5g预先制备的V2O5-SrTiO3粉末,继续搅拌2h,所得悬浮液经离心、去离子水洗涤、真空干燥后即得到Au-V2O5-SrTiO3催化剂。取0.1g该催化剂与2g石英砂均匀混合填充在固定床反应器中,光源选用100W高压汞灯,反应温度为75℃,丙烯、氧气和稀释气的体积比为1:1:8,空速为9000mL·gcat -1·h-1。通过气相色谱测得PO生成速率为39.65gPO·h-1·kg-1 cat。
实施例6:将5.85g偏钒酸铵与9.60g一水合柠檬酸溶于50mL去离子水中,90℃下恒温搅拌,蒸发水分形成凝胶后于120℃保温发泡12h,产物研磨后放入马弗炉,550℃焙烧3.5h,得到V2O5粉末;将0.5g的V2O5粉末、1.1mL的TiCl4和2.66g的Sr(OH)2·8H2O溶于盐酸溶液中,超声搅拌混合均匀后,加入6mol/L的NaOH溶液,将pH调节到10,形成的白色均相胶状浆体装于水热釜中,在180℃下反应48h,产物经多次洗涤、真空干燥、研磨后,即可得到V2O5-SrTiO3粉末;取3.2mL氯金酸溶液(0.6231g/100mL),与30mL去离子水混合后,加入1.5g质量浓度为1wt%的聚乙烯醇溶液,接着快速加入2.6mL新鲜制备的浓度为0.1mol/L的硼氢化钠溶液。常温下磁力搅拌0.5h后,加入0.5g预先制备的V2O5-SrTiO3粉末,继续搅拌2h,所得悬浮液经离心、去离子水洗涤、真空干燥后即得到Au-V2O5-SrTiO3催化剂。取0.1g该催化剂与2g石英砂均匀混合填充在固定床反应器中,光源选用100W高压汞灯,反应温度为50℃,丙烯、氧气和稀释气的体积比为1:1:8,空速为9000mL·gcat -1·h-1。通过气相色谱测得PO生成速率为52.38gPO·h-1·kg-1 cat。
Claims (5)
1.一种丙烯环氧化催化剂Au-V2O5-SrTiO3的制备方法,其特征在于:所述的催化剂为V2O5和SrTiO3形成的复合材料上负载Au纳米颗粒;该制备方法包括以下具体步骤:
1)将偏钒酸铵与一水合柠檬酸按照摩尔比1:1~5溶于去离子水中,50~100℃下恒温搅拌,蒸发水分形成凝胶后于100~150℃保温发泡12~24h,产物研磨后放入马弗炉,400~700℃焙烧2~5h,即可得到V2O5粉末;
2)将制备的V2O5粉末、TiCl4和Sr(OH)2·8H2O加入盐酸溶液中,超声搅拌混合均匀后,加入NaOH溶液调节pH为8~11,形成的白色均相胶状浆体装于水热釜中,在150~220℃下反应24~72h,产物经多次洗涤、真空干燥、研磨后,即可得到V2O5-SrTiO3粉末;
3)将氯金酸溶液与去离子水混合,然后加入0.1wt%~3wt%聚乙烯醇溶液,接着快速加入新鲜制备的0.01~0.5mol/L NaBH4溶液,生成Au溶胶;常温下磁力搅拌0.1~2h后,加入预先制备的V2O5-SrTiO3粉末,继续搅拌1~5h,所得悬浮液经离心、洗涤、真空干燥后即得到所述Au-V2O5-SrTiO3催化剂。
2.根据权利要求1所述的一种丙烯环氧化催化剂Au-V2O5-SrTiO3的制备方法,其特征在于:所述的V2O5的质量为催化剂质量的0.01~20倍,TiCl4和Sr(OH)2·8H2O的摩尔比为1:1~10。
3.根据权利要求1所述的一种丙烯环氧化催化剂Au-V2O5-SrTiO3的制备方法,其特征在于:所述Au-V2O5-SrTiO3催化剂,以载体的质量计,Au的负载量为0.25wt%~4.0wt%。
4.一种采用权利要求1所述方法制备的丙烯环氧化催化剂Au-V2O5-SrTiO3的应用方法,其特征在于:将所述催化剂与石英砂均匀混合后填充在固定床反应器中,在50~150W高压汞灯照射下,通入丙烯、氧气和稀释气进行反应制备环氧丙烷;反应产物由气相色谱检测分析。
5.根据权利要求4所述的一种丙烯环氧化催化剂Au-V2O5-SrTiO3的应用方法,其特征在于:所述丙烯、氧气和稀释气的体积比为1:1:(5~10);空速为7000~12000mL·gcat -1·h-1;反应温度为50~200℃。
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