CN102600855A - 一种三维有序大孔结构的La0.6Sr0.4Fe0.8Bi0.2O3、合成方法和用途 - Google Patents
一种三维有序大孔结构的La0.6Sr0.4Fe0.8Bi0.2O3、合成方法和用途 Download PDFInfo
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Abstract
一种三维有序大孔结构的La0.6Sr0.4Fe0.8Bi0.2O3、合成方法和用途，属于催化技术领域。单相正交晶相结构的三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3的合成方法：将含有表面活性剂的40％的乙醇水溶液用硝酸调节pH值至1，按照摩尔比0.6∶0.4∶0.8∶0.2溶入六水合硝酸镧、硝酸锶、九水合硝酸铁和五水合硝酸铋盐，搅拌均匀后加入柠檬酸，搅拌1h，加入PMMA微米球浸渍，经抽滤和干燥；在氮气气氛中，从室温升至500℃恒温灼烧3h，降至室温后，再通入空气升温至750℃并恒温灼烧3h即可。本发明的La0.6Sr0.4Fe0.8Bi0.2O3显示出优良的催化活性。
Description
技术领域
本发明涉及一种三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3、合成方法和应用于氧化消除甲苯的催化剂，具体涉及到合成出具有单相正交晶相结构的三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3，此结构有效提高了催化剂的比表面积和氧化还原能力，因此提高了La0.6Sr0.4Fe0.8Bi0.2O3氧化甲苯的催化性能，属于催化技术领域。
发明背景
挥发性有机化合物(VOC)是指熔点低于室温、沸点范围在50-260℃之间的挥发性有机物的总称，并且有浓度低、活性强、危害大等特点，甲苯便是其中一种，尤其威胁到人类健康，干扰人体内分泌系统，可导致各种急性和慢性病，甚至还能致癌。目前包括甲苯在内的VOC是继SO2、NOX及氟里昂之后，受到世界各国普遍重视的大气污染物，各国政府已经或正在制定严格的法律法规来控制其排放。因此，研究和开发高效消除VOC的方法和催化技术已成为全球研究热点。
VOC的治理方法主要有物理法和化学法。物理法包括吸附法、冷凝法、膜分离法等，这是一种非破坏性的方法，因此易引起二次污染；化学法包括焚烧法、等离子体法、生物法、光催化法和热催化法等，都属破坏性的方法，VOC去除率高。其中催化法为目前公认的最有效消除VOC的手段，催化剂的活性和稳定性是实现该过程的核心所在。负载型贵金属催化剂对VOC完全氧化反应的低温催化活性最好，但其价格昂贵。贱金属(复合)氧化物也具有催化活性，虽然其低温催化活性低于负载型贵金属催化剂的，但价格便宜。在贱金属复合氧化物中，钙钛矿型氧化物(ABO3)对VOC氧化反应显示出较好的高温催化活性。但迄今为止，有极少数文献报道采用钙钛矿型氧化物催化降解甲苯。一些研究显示，ABO3是一类具有结构缺陷(阴离子或阳离子空位)的复合氧化物，属于完全氧化型催化材料。在已研究过ABO3的催化剂中，将A位和B位阳离子用其他金属阳离子部分取代能有效提高催化活性。其中(La1-xA′x)(M1-yB′y) O3-δ(A′＝Sr，Ba，Ca，Ce；M＝Co，Mn，Fe；B′＝Cu，Bi，Ni)具有较好的催化活性(M.A.
et al.，Chem.Rev.2001，101：1981-2017)。Balasin-Aubé等将A位掺杂少量Sr2+后观察到La0.8Sr0.2MnO3+x对甲苯、苯、乙醇、丙醛、乙酸乙酯、甲乙酮等氧化反应的催化活性高于未掺杂的锰酸镧(V.Blasin-Aubé et al.，Appl.Catal.B.2003，43：175-186)；Huang等(H.Huang et al.，Catal.Commun.，2008，9：55-59)将La1-xSrxCo1-yFeyO3制成纳米粒子并用于丙醇、甲苯和环己烷的氧化反应，结果显示部分Sr2+取代的催化剂具有较高的催化活性。Rousseau等(S.Rousseau et al.，Appl.Catal.B.2009，88：438-447)用异价离子同时取代LaCoO3中的A、B位得到La1-xSrxCo1-yFeyO3，研究结果表明Sr和Fe离子同时取代可显著提高催化剂对甲苯氧化反应的催化活性。邓等(G.Deng et al.，Electrochimica Acta，2009，54：3910-3914)报道过采用草酸燃烧法合成出单相La1-xSrxFeO3化合物，与La0.8Sr0.2FeO3相比，La0.6Sr0.4FeO3具有较好的电化学储氢性能。若能在La1-xSrxFeO3中的B位掺杂一定量的Bi，使Fe和Bi离子的多种氧化态共存，可增强其氧化还原(Redox)能力，有利于促进催化剂的氧化还原过程，从而改善其催化活性。
体相ABO3催化剂的最大缺点是比表面积低。大量研究结果表明，对于完全氧化反应，在拥有类似缺陷密度情况下，ABO3的催化活性与其比表面积成正比(V.N.Stathopoulos et al.，React.Kinet.Catal.Lett.2001，72：49-55)。因此若将ABO3制成高比表面积的多孔结构，可以进一步提高其催化活性。但到目前为止，合成出的钙钛矿型氧化物催化剂绝大多数为低比表面积的微米颗粒。为制得具有多孔结构的ABO3，一些研究人员开始采取以聚苯乙烯(PS)微米球或聚甲基丙烯酸甲酯(PMMA)微米球作硬模板和以金属硝酸盐作金属源的方法，合成了具有三维有序大孔的钙钛矿型氧化物(F.Chem et al.，Chem.Lett.2001，30：1032；Y.N.Kim et al.，J.Mater.Chem.2004，14：1774)，但由于含Bi金属离子的盐试剂具有不溶性或水解性，在合成过程中很难控制Bi离子在溶剂中达到目标化学计量比。迄今为止，尚无文献报道过具有三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3的合成及其应用。
发明内容
本发明的目的在于提供具有三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3催化剂的制备方法和新用途，即作为甲苯氧化的催化剂，尤其是利用一种具有单相正交晶相结构的三维有序大孔结构的钙钛矿型氧化物La0.6Sr0.4Fe0.8Bi0.2O3催化剂来提高甲苯氧化的催化性能。
本发明提供的制备单相正交晶相结构的三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3的方法，将含有表面活性剂的40％的乙醇水溶液用硝酸调节pH值至1，按照摩尔计量比0.6∶0.4∶0.8∶0.2溶入六水合硝酸镧、硝酸锶、九水合硝酸铁和五水合硝酸铋盐，搅拌均匀后加入柠檬酸，再继续搅拌1h，加入排列规整的PMMA微米球浸渍30分钟，经抽滤和干燥；在氮气气氛中，以1℃/min的速率从室温升至500℃并恒温灼烧3h，在氮气气氛中降至室温后，再通入空气以相同速率1℃/min升温至750℃并恒温灼烧3h，即得单相正交晶相结构的三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3。
上述六水合硝酸镧、硝酸锶、九水合硝酸铁和五水合硝酸铋金属盐总物质的量每0.01mol，对应40％的乙醇水溶液10ml、1g表面活性剂和2.01g柠檬酸，其中表面活性剂选自三嵌段共聚物F127、聚乙二醇PEG10000、L-赖氨酸、或木糖醇。
本发明提供了制备的三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3的制备方法及将其作为催化剂用于催化氧化消除甲苯的反应。
将所制得的单相正交晶相结构的三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3进行压片，筛出40～60目的颗粒，将颗粒置入直径4mm的固定床石英微型反应器中，为保证气流温度均一，在催化剂的两端填充40～60目的石英砂。将装有甲苯溶液容器置入含冰水混合物的器皿中，可保证甲苯浓度为1000ppm，调整气体流量，控制在甲苯与氧气的摩尔比为1∶400，空速为20000mL/(g h)的条件下进行反应。
利用X射线衍射仪(XRD)测定催化剂的晶相结构，利用扫描电子显微镜(SEM)观察催化剂的形貌和孔结构。利用气相色谱和火焰离子检测器测定催化剂对甲苯氧化的催化活性。
附图说明
图1为三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3样品的XRD谱图，其中曲线(a)、(b)、(c)和(d)分别为实施例1、实施例2、实施例3和实施例4所制得的具有单相正交晶相结构的三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3样品的XRD谱图；
图2为三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3样品的SEM照片，其中图(a)、(b)、(c)和(d)分别为实施例1、实施例2、实施例3和实施例4样品的SEM照片；
图3为三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3下甲苯转化率与反应温度的关系图；其中曲线(a)、(b)、(c)和(d)分别为在实施例1、实施例2、实施例3和实施例4样品上甲苯转化率随反应温度的变化曲线(将附图中的e删除)；
图4为催化活性评价的工艺流程示意图。
具体实施方式
为进一步了解本发明，下面以实施例作催化剂合成方法和应用的详细说明，并给出附图描述本发明所采用三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3有效提高甲苯氧化的催化性能，其中催化氧化甲苯的工艺流程和装置为常规的，可参见图4，将催化剂颗粒置于直径为4mm的固定床石英微型反应器中，为保证气流温度均一，在催化剂的两端填充40～60目的石英砂，将装有甲苯溶液容器置入含冰水混合物的器皿中，调整气体流量，控制甲苯浓度。
实施例1：1g F127溶入10mL的40％乙醇水溶液中，搅拌均匀，用硝酸调节溶液pH值至1，将总计0.01mol金属源六水合硝酸镧、硝酸锶、九水合硝酸铁和五水合硝酸铋按化学计量摩尔比0.6∶0.4∶0.8∶0.2加入溶液中充分搅拌至溶解，再加入2.01g柠檬酸搅拌1h。将2.00g PMMA置入上述溶液中，静置30min后，经抽滤、干燥后，在管式炉中于氮气气氛(100mL/min)以1℃/min的速率分别从室温升至500℃并恒温灼烧3h后冷却至室温，再通入空气(100mL/min)以相同速率1℃/min升温至750℃并恒温灼烧3h，即得单相正交晶相结构的三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3催化剂。在甲苯浓度为1000ppm，甲苯与氧气的摩尔比为1∶400，空速为20000mL/(g h)的条件下，于330℃时甲苯转化率达到95％以上。
实施例2：1g PEG 10000溶入10mL的40％乙醇水溶液中，搅拌均匀，用硝酸调节溶液pH值至1，将总计0.01mol金属源六水合硝酸镧、硝酸锶、九水合硝酸铁和五水合硝酸铋按化学计量0.6∶0.4∶0.8∶0.2加入溶液中充分搅拌至溶解，再加入2.01g柠檬酸搅拌1h。将2.00g PMMA置入上述溶液中，静置30min后，经抽滤、干燥后，在管式炉中于氮气气氛(100mL/min)以1℃/min的速率分别从室温升至500℃并恒温灼烧3h后冷却至室温，再通入空气(100mL/min)都以相同速率1℃/min升温至750℃并恒温灼烧3h，即得正交晶相结构的三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3催化剂。在甲苯浓度为1000ppm，甲苯与氧气的摩尔比为1∶200，空速为20000mL/(g h)的条件下，于320℃时转化率达到95％以上。
实施例3：1g L-赖氨酸溶入10mL的40％乙醇水溶液中，搅拌均匀，用硝酸调节溶液pH值至1，将总计0.01mol金属源六水合硝酸镧、硝酸锶、九水合硝酸铁和五水合硝酸铋按化学计量0.6∶0.4∶0.8∶0.2加入溶液中充分搅拌至溶解，再加入2.01g柠檬酸搅拌1h。将2g PMMA置入上述溶液中，静置30min后，经抽滤、干燥后，在管式炉中于氮气气氛(100mL/min)以1℃/min的速率分别从室温升至500℃并恒温灼烧3h后冷却至室温，再通入空气(100mL/min)以相同速率升温至750℃并恒温灼烧3h，即得正交晶相结构的三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3催化剂。在甲苯浓度为1000ppm，甲苯与氧气的摩尔比为1∶200，空速为20000mL/(g h)的条件下，于310℃时转化率约达到95％。
实施例4：1g木糖醇溶入10mL的40％的乙醇水溶液中，用硝酸调节溶液pH值至1，将总计0.01mol金属源六水合硝酸镧、硝酸锶、九水合硝酸铁和五水合硝酸铋按化学计量0.6∶0.4∶0.8∶0.2加入溶液中充分搅拌至溶解，再加入2.01g柠檬酸搅拌1h。将2.00g PMMA置入上述溶液中，静置30min后，经抽滤、干燥后，在管式炉中于氮气气氛(100mL/min)以1℃/min的速率分别从室温升至500℃并恒温灼烧3h后冷却至室温，再通入空气(100mL/min)都以相同速率1℃/min升温至750℃并恒温灼烧3h，即得正交晶相结构的三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3催化剂。在甲苯浓度为1000ppm，甲苯与氧气的摩尔比为1∶400，空速为20000mL/(g h)的条件下，于295℃时转化率达到95％以上。
上述实施例1、实施例2、实施例3和实施例4所得具有单相正交晶相结构的三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3样品的XRD谱图分别见图1中的曲线(a)、(b)、(c)和(d)；实施例1样品、实施例2样品、实施例3和实施例4样品的SEM照片分别见图2的(a)、(b)、(c)和(d)；在甲苯浓度为1000ppm，甲苯与氧气的摩尔比为1∶400，空速为20000mL/(g h)的条件下，实施例1、实施例2、实施例3、实施例4三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3甲苯转化率与反应温度的关系图见图3中的曲线(a)、(b)、(c)和(d)。
Claims (3)
1.一种具有单相正交晶相结构的三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3。
2.权利要求1所述的一种具有单相正交晶相结构的三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3的合成方法，其特征在于，包括以下步骤：
将含有表面活性剂的40％的乙醇水溶液用硝酸调节pH值至1，按照摩尔计量比0.6∶0.4∶0.8∶0.2溶入六水合硝酸镧、硝酸锶、九水合硝酸铁和五水合硝酸铋盐，搅拌均匀后加入柠檬酸，再继续搅拌1h，加入排列规整的PMMA微米球浸渍30分钟，经抽滤和干燥；在氮气气氛中，以1℃/min的速率从室温升至500℃并恒温灼烧3h，在氮气气氛中降至室温后，再通入空气以相同速率1℃/min升温至750℃并恒温灼烧3h，即得单相正交晶相结构的三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3；
上述六水合硝酸镧、硝酸锶、九水合硝酸铁和五水合硝酸铋金属盐总物质的量每0.01mol，对应40％的乙醇水溶液10ml、1g表面活性剂和2.01g柠檬酸，其中表面活性剂选自三嵌段共聚物F127、聚乙二醇PEG10000、L-赖氨酸、或木糖醇。
3.权利要求1所述的具有单相正交晶相结构的三维有序大孔La0.6Sr0.4Fe0.8Bi0.2O3作为催化剂用于催化氧化消除甲苯的反应。
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| CN110292935A (zh) * | 2019-04-24 | 2019-10-01 | 武汉理工大学 | 一种Mn掺杂介孔LaCoO3钙钛矿型催化剂及其制备方法 |
| CN111229238A (zh) * | 2020-02-27 | 2020-06-05 | 湘潭大学 | 一种协同催化氧化no和甲苯的有序多孔钙钛矿催化剂及其制备方法和应用 |
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| CN103394345A (zh) * | 2013-07-18 | 2013-11-20 | 天津大学 | 稀燃缸内直喷内燃机微粒氧化催化器用催化剂 |
| CN110292935A (zh) * | 2019-04-24 | 2019-10-01 | 武汉理工大学 | 一种Mn掺杂介孔LaCoO3钙钛矿型催化剂及其制备方法 |
| CN111229238A (zh) * | 2020-02-27 | 2020-06-05 | 湘潭大学 | 一种协同催化氧化no和甲苯的有序多孔钙钛矿催化剂及其制备方法和应用 |
| CN111229238B (zh) * | 2020-02-27 | 2023-03-14 | 湘潭大学 | 一种协同催化氧化no和甲苯的有序多孔钙钛矿催化剂及其制备方法和应用 |
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