CN112076770B - 层状多金属氢氧化物在甲烷光化学转化中的应用 - Google Patents
层状多金属氢氧化物在甲烷光化学转化中的应用 Download PDFInfo
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Abstract
本发明公开了层状多金属氢氧化物在甲烷光化学转化中的应用，利用层状多金属氢氧化物材料实现了甲烷的光化学偶联，可以将甲烷转化为乙烯、乙烷、丙烷和丁烷中的一种或几种。与传统的甲烷热转化反应相比，本发明在室温条件下实现了甲烷的光化学转化，避免产生积碳，增加了材料的稳定性，能够循环利用；与现有的甲烷光化学转化反应相比，本发明可以得到乙烷、乙烯、丙烷或丁烷等高级烃中的一种或几种，且转化效率高，产物种类可调控。本发明的甲烷光化学转化方法反应过程绿色，环境友好，具有实际工业化的前景。
Description
技术领域
本发明属于甲烷光化学转化技术领域，具体涉及一种层状多金属氢氧化物在甲烷光化学转化方面的应用。
背景技术
甲烷作为天然气的主要组成部分，是一种重要的气体矿藏，世界上已探明的储量高达150.19×1012m3。但是甲烷分子的碳氢键极其稳定，难以打破，很难发生可控的化学反应，不适合用做化工行业的原料。目前，甲烷主要作为燃料使用。在工业生产方面，将甲烷和水蒸气在高温下重整为合成气(CO和H2)，并作为合成氨等的原料。尽管热催化转化甲烷氧化偶联制备乙烯已经得到了比较广泛的研究，并取得了一定成果，但是热催化甲烷转化反应普遍需要在700-1000℃的温度下进行，因此，其能耗和生产成本较高，在温和条件下将甲烷转化为高级的烯烃和烷烃仍然是个难题。而光化学反应是由具有一定能量的光子所引发的，可以在室温乃至低温条件下完成。利用光驱动的方法，将甲烷转化为高附加值的乙烷、乙烯和丙烷等高级烃，相应的能耗比较低，选择性较高，有潜在的工业应用前景。
经检索专利和文献，目前主要有两类光化学甲烷转化材料，一类材料为分子筛和金属-分子筛复合材料，比如Zn-ZSM-5(公开号CN 102069006 A,Angew.Chem.Int.Ed.2011,50,8299-8303)，Ga-ETS-10(Angew.Chem.Int.Ed.2012,51,4702-4706)，β分子筛(J.Am.Chem.Soc.2011,133,17257-17261)，这些材料中Zn-ZSM-5需要在500℃下真空气氛中制备，催化材料合成过程不能接触空气；β分子筛光催化反应在波长为180nm的高能量深紫外光激发中进行反应，和实际应用的要求还有一定距离。另一类材料是半导体氧化物，例如Ga2O3(J.Catal.,2008,257,396-402),SiO2-Al2O3-TiO2(J.Phys.Chem.B,2003,107(33),8355-8362),MoO3/SiO2(J.Chem.Soc.Faraday Trans.,1995,91(11),1647-1654)。这几种半导体材料的甲烷转化效率都比较低。
发明内容
本发明的目的在于提供一种新的光化学甲烷转化材料，以克服现有光化学转化材料转化效率低、制备复杂的缺陷。
层状双金属氢氧化物(LDH)是一种十分容易合成的材料，广泛应用于烯烃氧化聚合、醇醛缩合、烯烃异构化、亲核卤代、烷基化、烯烃环氧化、Claisen-Schmidt反应等。本发明首次发现层状双金属氢氧化物可用于甲烷的光化学转化。这种材料的甲烷转化效率明显高于上述两类材料，并且制备方法简单，反应操作过程简便。更为重要的是，在产物中有大比例的乙烯产生，这是化学工业上十分重要的反应单体。本发明利用层状多金属氢氧化物材料实现了甲烷的光化学偶联，可以将甲烷转化为乙烯、乙烷、丙烷和丁烷中的一种或几种，该方法还未见报道。
本发明以层状多金属氢氧化物为光催化剂，经过室温真空处理除去体系中的空气后向体系内充入甲烷气体，在室温条件下通过活化碳氢化学键使甲烷转化为乙烯和丙烷等烃类。
本发明应用于光化学甲烷转化的材料为层状多金属氢氧化物，所述层状多金属氢氧化物的化学组成为[AmBnCq(OH)x](CO3)y，其中A、B、C代表不同的金属阳离子，m、n、q、x、y代表原子数目，m、n、x和y均大于0，q≥0；A、B、C阳离子的电荷值分别为a、b、c，有a×m+b×n+c×q＝x+2y；其中金属阳离子组成阳离子层板，层板间通过OH-、CO3 2-起到平衡电荷作用。
优选的，所述阳离子A、B、C选自Zn2+、Mg2+、Al3+、Ga3+、Ti4+、Ni2+中的两种或三种。
更优选的，所述层状多金属氢氧化物在层间和/或表面上担载金属纳米粒子，所述金属纳米粒子包括Pt、Au、Ag、Rh、Ru、Ni、Fe等的一种或多种金属纳米粒子。
所述层状多金属氢氧化物可以根据文献(例如J.Am.Chem.Soc.2009,131,13833-13839；Solid State Sci.2006,8(10)1181-1186及ACS Appl.Mater.Interfaces,2013,5(20)10233-10239)报道的方法合成。典型的层状多金属氢氧化物为层状双金属氢氧化物，例如Zn20Ti7(OH)54(CO3)7、Zn18Ti9(OH)54(CO3)9、Zn6Ga2(OH)16(CO3)等。
在无空气存在和紫外光照射的条件下，使甲烷和所述层状多金属氢氧化物接触，即可使甲烷转化为乙烯、乙烷、丙烯、丙烷的一种或多种。通过调节催化剂的组成和结构，能够对产物种类和含量调控。比如，在固定烷烃反应物量的条件中，Zn-Ti-LDH材料使用高压紫外光光照得到乙烯、乙烷、丙烯、丙烷混合产物；当用～400nm的光进行光催化，产物主要为乙烷；当Zn-Ti-LDH在400℃中煅烧处理后，光催化反应中的产物主要为乙烯。在Zn-Ti-LDH中负载Pt、Pd等贵金属，能显著提高高级烯烃的选择性。
利用层状多金属氢氧化物进行甲烷光化学转化的方法，具体步骤如下：
1、取层状多金属氢氧化物铺展在石英反应器的内表面上，将反应器中的空气气氛置换为甲烷气氛；
2、向步骤1中表面铺有层状多金属氢氧化物的石英反应器内充入纯度为99～99.99％的甲烷；
3、将石英反应器铺有层状多金属氢氧化物的一面用紫外光(波长200～400nm)照射一定时间，将甲烷转化为高级的烃。
上述步骤3中，光照时间一般为10min～3h，可以采用高压汞灯产生的紫外光照射，用配有FID检测器的气相色谱检测产物的组成。
本发明首次发现层状多金属氢氧化物可用于甲烷的室温光化学转化，此方法的反应过程绿色环保，层状多金属氧化物及甲烷可以循环使用，无有害废物产生，甲烷的转化效率达0.11mmol·g-1·h-1。该方法对于降低人们对石油产品的依赖有十分积极的意义。本发明具有以下优点：
1、与传统的热转化甲烷转化反应相比，在室温条件下实现甲烷的光化学转化，避免产生积碳，增加了材料的稳定性，能够循环利用，有实际工业化的前景；
2、与已报道的甲烷光化学转化反应相比，本发明的方法可以得到乙烷、乙烯、丙烷或丁烷等高级烃中的一种或几种，且转化效率高于已有的材料，并且产物种类可调控；
3、反应过程绿色，对环境友好。
附图说明
图1为实施例1中获得的锌-钛层状双金属氢氧化物(Zn-Ti-LDH)固体粉末的SEM图；
图2为实施例1中获得的锌-钛层状双金属氢氧化物(Zn-Ti-LDH)固体粉末的XRD图；
图3为实施例1中获得的锌-钛层状双金属氢氧化物(Zn-Ti-LDH)固体粉末的FT-IR图；
图4为实施例1中获得的锌-钛层状双金属氢氧化物(Zn-Ti-LDH)固体粉末进行甲烷光化学转化的反应数据饼图。
具体实施方式
下面通过实施例并结合附图对本发明作进一步说明，但本发明的保护范围不限于下述的实施例。
实施例1
将6g碳酰胺、3g六水合硝酸锌、0.5g钛酸异丙醇酯混合到水中，在90℃中加热搅拌反应2天，得到的白色固体粉末材料Zn-Ti-LDH，用蒸馏水清洗干净。通过扫描电子显微镜表征，结果显示材料为纳米尺寸(图1)，X射线晶体学衍射表征结果显示为晶化的层状材料(图2)，红外吸收光谱测试结果显示材料有大量羟基峰，对应于材料中的Ti-OH、Zn-OH，并且有对应于CO3 2-的吸收峰(图3)。根据相关文献，该合成材料Zn-Ti-LDH的化学组成为Zn20Ti7(OH)54(CO3)7。
取0.2g Zn-Ti-LDH均匀铺展到石英反应器的表面上。向反应器中充入5mL(约200μmol)甲烷气体，在室温条件下用125W高压汞灯照射反应器3h，产物组成通过配备有FID检测器的气相色谱分析，分析数据如表1和图4所示。产物组成为：乙烯76.4％，乙烷1.37％，丙烯1.63％，丙烷20.6％，丁烷<0.1％。
表1
实施例2
在室温条件下用150W高压汞灯照射反应器10min，其余与实施例1相同。转化率为4.5％，产物组成为：乙烯83.22％，乙烷1.75％，丙烯2.63％，丙烷12.4％，丁烷<0.1％，其余为未反应的甲烷。
实施例3
在室温条件下用150W高压汞灯照射反应器3h，其余与实施例1相同。转化率为13.6％，产物组成为：乙烯72.05％，乙烷2.41％，丙烷1.71％，丁烷23.8％，其余为未反应的甲烷。
实施例4
将2.3g水合硝酸锌、1.02g水合硝酸镓溶解于60mL水中，将0.96g氢氧化钠、2.12g碳酸钠溶解于80mL水中，随后将两种溶液混合，在80℃中老化24h，得到Zn-Ga-LDH。参考相关文献，该材料Zn-Ga-LDH的化学组成为Zn7Ga3(OH)20(CO3)1.5。取0.2g Zn-Ga-LDH，其余与实施例1相同。转化率为0.79％，产物组成为：乙烯59.55％，乙烷29.21％，其余为少量丙烷、丙烯和未反应的甲烷。
实施例5
将6g碳酰胺、3g六水合硝酸镍、0.5g钛酸异丙醇酯混合到水中，在90℃中加热搅拌反应2天，得到的白色固体粉末材料Ni-Ti-LDH，用蒸馏水清洗干净。参照文献，该材料Ni-Ti-LDH的化学组成为Ni3Ti(OH)8CO3。由于合成过程中碳酰胺水解反应不完全，材料中可能含有CNO(部分水解阴离子)。取0.2g Ni-Ti-LDH，其余与实施例1相同。转化率为3.46％，产物组成为：乙烯58.77％，乙烷16.56％，丙烯10.39％，丙烷14.29％，其余为未反应的甲烷。
实施例6
在室温条件下用150W高压汞灯照射反应器1h(使用截止滤光片控制光源范围在395～405nm)，其余与实施例1相同。转化率为6.47％，产物组成主要为乙烷，痕量乙烯、丙烷、丙烯，其余为未反应的甲烷。
实施例7
将实施例1中合成的Zn-Ti-LDH材料在400℃中煅烧2h后作为光催化剂，其余与实施例1相同。转化率为4.64％，产物组成为：乙烯94.54％，乙烷2.1％，丙烯1.09％，丙烷2.18％，还有少量丁烷，剩余为未反应的甲烷。
Claims (8)
1.层状多金属氢氧化物作为光催化剂在甲烷光化学转化为乙烯、乙烷、丙烯、丙烷的一种或多种中的应用，所述层状多金属氢氧化物的化学组成为[AmBnCq(OH)x](CO3)y，其中A、B、C代表不同的金属阳离子，选自Zn2+、Mg2+、Al3+、Ga3+、Ti4+、Ni2+中的两种或三种，m、n、q、x、y代表原子数目，m、n、x和y均大于0，q≥0；A、B、C阳离子的电荷值分别为a、b、c，有a×m+b×n+c×q = x+2y；其中金属阳离子组成阳离子层板，层板间通过OH-、CO3 2-起到平衡电荷作用。
2.如权利要求1所述的应用，其特征在于，所述层状多金属氢氧化物在层间和/或表面上担载金属纳米粒子。
3.如权利要求2所述的应用，其特征在于，所述金属纳米粒子选自Pt、Au、Ag、Rh、Ru、Ni、Fe中一种或多种金属纳米粒子。
4.一种甲烷光化学转化的方法，在无空气存在和紫外光照射的条件下，使甲烷和层状多金属氢氧化物接触，使甲烷转化为乙烯、乙烷、丙烯、丙烷的一种或多种；所述层状多金属氢氧化物的化学组成为[AmBnCq(OH)x](CO3)y，其中A、B、C代表不同的金属阳离子，选自Zn2+、Mg2+、Al3+、Ga3+、Ti4+、Ni2+中的两种或三种，m、n、q、x、y代表原子数目，m、n、x和y均大于0，q≥0；A、B、C阳离子的电荷值分别为a、b、c，有a×m+b×n+c×q = x+2y；其中金属阳离子组成阳离子层板，层板间通过OH-、CO3 2-起到平衡电荷作用。
5.如权利要求4所述的方法，其特征在于，所述层状多金属氢氧化物在层间和/或表面上担载金属纳米粒子。
6.如权利要求5所述的方法，其特征在于，所述金属纳米粒子选自Pt、Au、Ag、Rh、Ru、Ni、Fe中一种或多种金属纳米粒子。
7.如权利要求4~6任一所述的方法，其特征在于，所述方法包括以下步骤：
1）取层状多金属氢氧化物铺展在石英反应器的内表面上，将石英反应器中的空气气氛置换为甲烷气氛；
2）向步骤1）表面铺有层状多金属氢氧化物的石英反应器内充入纯度为99~99.99%的甲烷；
3）将石英反应器铺有层状多金属氢氧化物的一面用紫外光照射一定时间，将甲烷转化为高级的烃。
8.如权利要求7所述的方法，其特征在于，步骤3）中光照时间为10 min ~ 3 h。
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