CN111545243A - 一种复合光热催化剂及其制备方法和应用 - Google Patents
一种复合光热催化剂及其制备方法和应用 Download PDFInfo
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- CN111545243A CN111545243A CN202010488979.7A CN202010488979A CN111545243A CN 111545243 A CN111545243 A CN 111545243A CN 202010488979 A CN202010488979 A CN 202010488979A CN 111545243 A CN111545243 A CN 111545243A
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- 241000282414 Homo sapiens Species 0.000 description 1
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- 239000004570 mortar (masonry) Substances 0.000 description 1
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- B01J29/42—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 iron group metals, noble metals or copper
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Abstract
本发明提供一种复合光热催化剂及其制备方法和应用，该复合光热催化剂主要包括两部分，用X/Y的通式来表示，其中，Y是主体催化剂，主要成分是SAPO‑34分子筛、ZSM‑5分子筛、氧化铝、氧化硅中的一种或多种混合；X是光热转换材料，光热转换材料负载在主体催化剂上，主要成分是缺陷半导体X1或贵金属X2。该催化剂可利用太阳光驱动甲醇脱水制乙烯和有机物的反应，同时所用催化剂在可见和红外光区有强烈的吸收，可有效利用太阳能，得到较高的光热转化效率，同时该反应相比工业上甲醇脱水反应具有成本低、制备方法简单、绿色环保等优点，属于乙烯制备技术领域。
Description
技术领域
本发明涉及一种复合光热催化剂及其制备方法和应用，属于光热催化反应技术领域。
背景技术
随着社会的发展和工业化进程加速，化石燃料大量消耗不仅导致这些不可再生资源的枯竭，同时造成地球环境污染日益严重。工业生产尤其是传统热催化消耗了大量的能源，因此有必要开发清洁、低能耗的工业生产新工艺。太阳能是取之不尽用之不竭的可再生能源，而且分布广泛，如果可实现对太阳能的高效、清洁利用，将显著降低人类对化石燃料的依赖，具有显著的现实意义和战略意义。如果传统热催化可以利用太阳能来驱动，将显著改善该行业的碳足迹和能源结构。然而太阳能的能量密度较低，同时大部分催化剂对太阳能的吸收非常有限，不能利用占太阳光大多数且具有强烈光热转换的可见光和红外光，使的工业上利用传统催化剂实现催化反应的光热转换较为困难。因此开发具有全光谱响应的催化剂非常有必要。
局域等离子体共振(LSPR)是通过材料吸收光能与材料表面的自由电子发生集体振荡，电磁场被局限在金属表面很小的范围内并发生增强的现象。LSPR现象已被应用于拉曼增强、光热治疗、光催化、光热催化等诸多领域，大量工作已经表面其增强机制主要体现在四个方面：光散射效应、热电子效应、局域电场增强效应和光热效应。常见的具有LSPR效应材料主要集中在Au、Ag、Cu等贵金属，高昂的价格阻碍了其进一步应用。
发明内容
本发明提供一种复合光热催化剂及其制备方法和应用，该方法可利用太阳光驱动甲醇脱水制乙烯和有机物的反应，同时所用催化剂在可见和红外光区有强烈的吸收，可有效利用太阳能，得到较高的光热转化效率，同时该反应相比工业上甲醇脱水反应具有成本低、制备方法简单、绿色环保等优点。
为实现上述目的，拟采用这样一种复合光热催化剂，主要包括两部分，用X/Y的通式来表示，其中，Y是主体催化剂，主要成分是SAPO-34分子筛、ZSM-5分子筛、氧化铝、氧化硅中的一种或多种混合；X是光热转换材料，光热转换材料负载在主体催化剂上，主要成分是缺陷半导体X1或贵金属X2，缺陷半导体X1包括氧化钨(WO3-x)、氧化钼(MoO3-x)、氧化锰(MnO2-x)、氧化钛(TiO2-x)中的一种或多种混合，一般含缺陷/非化学计量比/的氧化物都这么表示，x表示氧空位，贵金属X2包括金、银、铜中的一种或多种混合。
X1/Y的制备方法：将金属前驱体WCl6、MoCl5、MnCl4或TiCl4溶解到无水乙醇中，同时将主体催化剂分散到该溶液中，超声后搅拌直至溶液变成黄色透明溶液，然后将前驱体溶液倒入聚四氟乙烯内衬中，放入不锈钢水热反应釜中，在150-200℃下反应6-15小时，反应结束后，自然冷却至室温，用无水乙醇洗涤4-6次，然后在40-80真空干燥箱烘干得到复合光热催化剂。
X2/Y的制备方法：贵金属/主体催化剂的制备采用光沉积、沉积-沉淀法、浸渍法或气相化学沉积法，然后在氢气气氛中还原，以浸渍法为例说明：将贵金属前驱体氯金酸、硝酸银或硝酸铜和主体催化剂硅铝分子筛、氧化铝或氧化硅分散在水醇溶液中，研磨搅拌直至溶液挥发，然后放入炉子中退火，最后在氢气气氛中还原，形成Au/Y、Ag/Y或Cu/Y的复合结构。
所述复合光热催化剂应用于光热催化醇类脱水制乙烯和其他有机产物，可直接将醇类脱水生产乙烯和醚类有机产物，不需要额外加热，具体包括如下步骤：
(1)将光热催化剂置于密闭反应器中，先将反应器抽真空，然后通入氮气，使反应器中充满惰性气体；
(2)在反应器中通入一定量的反应气体(甲醇或乙醇)，光照反应60分钟，每10分钟取一个样，反应物和产物浓度用气相色谱分析。
与现有技术相比，本发明公开了一种复合光热催化剂及其制备方法，并将其应用于醇类脱水反应，所制备的复合催化剂可实现较高的光热转换效率，为催化反应提供足够热量，主体催化剂的引入可提供醇类脱水反应的催化活性位点，显著提高光热催化效率，传统醇类脱水反应往往需要在高温下反应，能耗较高，本发明能够只在光照下使反应发生，显著降低醇类脱水反应对能源的消耗，同时由于主体催化剂的引入，提高了醇类反应的反应活性和对乙烯的选择性，本发明为该类反应提供了新的思路，实现规模化生产后可获得巨大经济效益。
本发明还具有以下特点：
(1)采用催化剂的制备方法简单，工艺过程简单、设备简单、成本低。
(2)复合催化剂可有效利用太阳光，无需加热即可驱动催化反应发生，相比传统热催化，可节省大量能源。
(3)与传统醇类脱水反应相比，该催化剂的烯烃类产物只有乙烯，因此可以节省乙烯和丙烯气体分离的步骤和能量消耗。
附图说明
图1为W18O49/SAPO-34光热催化剂的扫描照片；
图2为Au/SAPO-34光热催化剂的透射照片；
图3为W18O49/SAPO-34光热催化剂的紫外-可见吸收光谱；
图4为Au/SAPO-34光热催化剂的紫外-可见吸收光谱；
图5为甲醇脱水反应示意图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将结合附图对本发明作进一步的详细说明，应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。
实施例1
参照附图1-5，本实施例提供一种光热催化醇类脱水制乙烯和有机产物的方法，具体如下：
1)X1/Y型催化剂的制备过程如下：称取0.1g的氯化钨溶于60mL的乙醇溶液中，将0.1g SAPO-34分子筛分散在上述溶液中，超声并搅拌20分钟，得到透明澄清溶液。将上述溶液倒入100mL水热反应釜中于180℃中反应12小时，反应结束后，自然冷却至室温。用无水乙醇洗涤5次，然后在60℃真空干燥箱烘干，并收集样品，得到复合光热催化剂X1/Y。
2)甲醇脱水反应在密闭容器中进行，称取0.2g催化剂平铺放入样品槽内，将石英盖盖到反应器上，把四个紧固夹子夹紧，使反应器密闭隔绝空气。通过两个进样口将反应器用氮气吹扫10分钟，排除反应器中的空气，然后用进样垫封住进样口。用进样针在反应器内充入50μL的液体甲醇(1.24mmol)，用锡纸包住反应器暗反应10小时，达到吸脱附平衡。光热反应时，以300W的氙灯作为光源，并配以不同滤光片，光强调到最大值，光从反应器的顶部照射到催化剂表面，光源可以完全覆盖催化剂，氙灯到反应器顶盖的距离固定在10cm，以保证每次反应光强一致。
实施例2
将实施例1中步骤1)的氯化钨的量变为0.2g，其他条件保持不变。
实施例3
将实施例1中步骤1)的氯化钨的量变为0.3g，其他条件保持不变。
实施例4
将实施例1中步骤1)的氯化钨的量变为0.6g，其他条件保持不变。
实施例5
将实施例1中步骤1)的氯化钨的量变为0.9g，其他条件保持不变。
实施例6
将实施例1中步骤1)的氯化钨换为氯化钼，其他条件保持不变。
实施例7
将实施例1中步骤1)的氯化钨换为氯化钛，其他条件保持不变。
实施例8
将实施例1中步骤1)的氯化钨换为氯化锰，其他条件保持不变。
实施例9
将实施例1中步骤1)的水热反应温度变为150℃，其他条件保持不变。
实施例10
将实施例1中步骤1)的水热反应温度变为200℃，其他条件保持不变。
实施例11
将实施例1中步骤1)的SAPO-34分子筛变为ZSM-5分子筛，其他条件保持不变。
实施例12
将实施例1中步骤1)的SAPO-34分子筛变为氧化铝，其他条件保持不变。
实施例13
将实施例1中步骤1)的SAPO-34分子筛变为二氧化硅，其他条件保持不变。
实施例14
将实施例1中步骤2)的甲醇改为乙醇、丙醇或其他醇类，其他条件保持不变。
实施例15
1)X2/Y型催化剂的制备过程如下：将1g的SAPO-34分子筛加入2mL的乙醇和0.5mL的去离子水中，然后加入4mL的HAuCl4溶液(1g/100mL)，放入研钵中研磨、搅拌直至溶液蒸干，然后将其放入马弗炉中于250℃退火，最后在氢气气氛中于250℃还原，得到X2/Y型复合光热催化剂。
2)光热醇类脱水催化反应过程同实施例1中步骤2)相同。
实施例16
将实施例14中步骤1)中的SAPO-34分子筛变为ZSM-5分子筛，其他条件保持不变。
实施例17
将实施例14中步骤1)中的SAPO-34分子筛变为氧化铝，其他条件保持不变。
实施例18
将实施例14中步骤1)中的硅铝分子筛变为二氧化硅，其他条件保持不变。
实施例19
将实施例14中步骤1)中的HAuCl4溶液的含量改为1mL，其他条件保持不变。
实施例20
将实施例14中步骤(1)中的HAuCl4溶液的含量改为2mL，其他条件保持不变。
实施例21
将实施例14中步骤1)中的HAuCl4溶液改为AgNO3溶液，其他条件保持不变。
实施例22
将实施例14中步骤1)中的HAuCl4溶液改为Cu(NO3)2溶液，其他条件保持不变。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。
Claims (4)
1.一种复合光热催化剂，主要包括两部分，用X/Y的通式来表示，其中，Y是主体催化剂，主要成分是SAPO-34分子筛、ZSM-5分子筛、氧化铝、氧化硅中的一种或多种混合；X是光热转换材料，光热转换材料负载在主体催化剂上，主要成分是缺陷半导体X1或贵金属X2，缺陷半导体X1包括WO3-x、MoO3-x、MnO2-x、TiO2-x中的一种或多种混合，贵金属X2包括金、银、铜中的一种或多种混合。
2.权利要求1所述复合光热催化剂的制备方法，其特征在于，X1/Y的制备方法如下：将金属前驱体WCl6、MoCl5、MnCl4或TiCl4溶解到无水乙醇中，同时将主体催化剂分散到该溶液中，超声后搅拌直至溶液变成黄色透明溶液，然后将前驱体溶液倒入聚四氟乙烯内衬中，放入不锈钢水热反应釜中，在150-200℃下反应6-15小时，反应结束后，自然冷却至室温，用无水乙醇洗涤4-6次，然后在40-80℃真空干燥箱烘干得到复合光热催化剂。
3.权利要求1所述复合光热催化剂的制备方法，其特征在于，X2/Y的制备方法：贵金属/主体催化剂的制备采用光沉积、沉积-沉淀法、浸渍法或气相化学沉积法，然后在氢气气氛中还原，以浸渍法为例说明：将贵金属前驱体氯金酸、硝酸银或硝酸铜和主体催化剂硅铝分子筛、氧化铝或氧化硅分散在水醇溶液中，研磨搅拌直至溶液挥发，然后放入马弗炉中退火，最后在氢气气氛中还原，形成Au/Y、Ag/Y或Cu/Y的复合结构。
4.权利要求1所述复合光热催化剂的应用，其特征在于：所述复合光热催化剂应用于光热催化醇类脱水制乙烯和其他有机产物。
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