CN113351008A - 钙钛矿复合氧化物材料在低温羰基硫水解反应中的应用 - Google Patents

钙钛矿复合氧化物材料在低温羰基硫水解反应中的应用 Download PDF

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CN113351008A
CN113351008A CN202010141663.0A CN202010141663A CN113351008A CN 113351008 A CN113351008 A CN 113351008A CN 202010141663 A CN202010141663 A CN 202010141663A CN 113351008 A CN113351008 A CN 113351008A
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carbonyl sulfide
composite oxide
gas
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张雨萌
张鑫
魏征
郝郑平
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Research Center for Eco Environmental Sciences of CAS
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Abstract

本发明属于硫资源回收技术领域，具体涉及一种ABO3钙钛矿复合氧化物催化剂在低温羰基硫水解反应中的应用，属于硫资源回收技术领域。其中，A可为:Mg，La，Ce，Sm中的至少一种。B可为Fe、Cu、Co、Ni、Ti中的至少一种。所述羰基硫气体来源于石油开采、天然气开采、石油化工、煤化工、天然气化工中至少一种领域。ABO3钙钛矿复合氧化物催化剂表现出了优异的催化活性，具有较好的应用前景。

Description

钙钛矿复合氧化物材料在低温羰基硫水解反应中的应用
技术领域
本发明涉及一种钙钛矿复合氧化物材料在低温羰基硫水解反应中的应用，属于硫资源回收技术领域。
背景技术
羰基硫是广泛存在于天然气、水煤气和工业尾气中的一种有毒有害的含硫有机气体。传统脱硫技术对无机H2S的脱除能达到国家一类气标准，但对有机硫脱除存在脱硫深度不足、催化剂易失活等问题，严重污染环境，还产生大量固体废催化剂，造成二次环境污染，迫使生产、利用这些化石资源的企业停采或停产。低温催化水解法因其能耗低、操作简便、副反应少而被认为是一种具有较好应用前景的方法，其原理为羰基硫气体在催化剂的作用下催化分解为H2S气体，进而进一步处理H2S气体。因此，开发高效的低温催化水解催化剂对低温水解技术的应用起到重要的推动作用。
钙钛矿属于简单立方结构，其中A位多为离子半径较大的镧系稀土元素或碱土元素，B位通常为过渡金属元素。在钙钛矿结构中B位离子和六个氧离子构成六配位的BO6八面体，八个八面体由共享的氧离子分布在立方体的八个顶点上，A位离子位于立方体中心，被十二个氧离子包围。该材料具有表面酸碱性质和良好的热稳定性，其A位和B位易于被不同价态或半径的阳离子取代，使得B位离子的价态发生改变，产生氧空位等晶格缺陷，可根据需要选择取代离子以调控催化材料的氧化还原能力或氧移动性等，形成具有高活性的催化活性位。
发明内容
本发明的目的是将钙钛矿复合氧化物催化剂应用于低温羰基硫水解反应中，具有催化活性高和稳定性好等优点。
本发明所述的钙钛矿复合氧化物通式为ABO3。
其中，A可为:Mg，La，Ce，Sm中的至少一种。B可为Fe、Cu、Co、Ni、Ti中的至少一种。
所述羰基硫气体来源于石油开采、天然气开采、石油化工、煤化工、天然气化工中至少一种领域。
上述方法中，所述羰基硫气体中的体积百分浓度为0-2000ppm，空速为1000～30000h-1。
上述方法中，所述反应的反应条件如下：
温度为70℃，反应压力为常压。
附图说明
图1CaTiO3催化剂的XRD图谱。
图2MgTiO3催化剂的XRD图谱。
图3为实施CaTiO3催化剂的羰基硫去除活性图。
具体实施方式
实施案例一
CaTiO3材料的合成
室温下称取7.085gCa(NO3)2·4H2O、9.16ml钛酸四异丙酯先后溶解于50ml乙醇溶液中，配成溶液A；称取18.913g一水柠檬酸溶于150mL乙醇，配成溶液B；将溶液A、B转入分液漏斗，在室温和机械搅拌条件下，滴入盛有50mL蒸馏水的烧杯中。滴加完毕后，120℃至于真空干燥箱中干燥10h，得到干凝胶后研磨。最后将研磨粉体置于马弗炉中，650℃焙烧6h。即得到CaTiO3催化剂。
催化剂活性评价
在石英反应管中填充上述制备的催化剂，利用质量流量计控制一定量的COS气体和经过水蒸气发生器的N2气体通入催化剂床层进行反应，并将反应后的气体连接气相色谱进行检测，考察反应后气体的成分及浓度。催化剂的体积为0.5mL；粒径为40-60目；催化剂床层温度为70℃；COS浓度为1000ppm，反应气体总流量为50mL/min，相对湿度为3.6％，反应压力为常压。由实验可知，材料表现出了较好的催化活性。
羰基硫转化率＝(进口气中COS气体的浓度-出口气中剩余COS气体的浓度)/进口气中COS气体的浓度*100％。
硫化氢收率＝出口气中剩余H2S气体的浓度/进口气中COS气体的浓度*100％。

Claims (4)

1.一种钙钛矿复合氧化物材料在低温羰基硫水解反应中的应用，其通式为ABO3。
2.如权利要求1所述，其特征是：A可为:Mg，La，Ce，Sm中的至少一种，B可为Fe、Cu、Co、Ni、Ti中的至少一种。
3.如权利要求1所述酸性气体来源于石油开采、天然气开采、石油化工、煤化工、天然气化工中至少一种领域。
4.根据权利要求1所述，所述酸性气体中硫化氢的体积百分浓度为0-2000ppm，温度为70℃，反应压力为常压。
CN202010141663.0A 2020-03-04 2020-03-04 钙钛矿复合氧化物材料在低温羰基硫水解反应中的应用 Pending CN113351008A (zh)

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WO2023016145A1 (zh) * 2021-08-09 2023-02-16 中国科学院大学 适用于克劳斯工艺的有机硫水解催化剂及其制备方法和应用

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023016145A1 (zh) * 2021-08-09 2023-02-16 中国科学院大学 适用于克劳斯工艺的有机硫水解催化剂及其制备方法和应用

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Application publication date: 20210907