CN105582806B - 一种二维晶体化合物Ti2C作为吸附剂在吸附分解低浓度瓦斯中甲烷的应用 - Google Patents
一种二维晶体化合物Ti2C作为吸附剂在吸附分解低浓度瓦斯中甲烷的应用 Download PDFInfo
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Abstract
本发明公开了一种二维晶体化合物Ti2C作为吸附剂在吸附低浓度瓦斯中甲烷的应用。二维晶体化合物Ti2C具有类石墨烯的二维层状结构，由上下表面的钛原子与中间的碳原子层组成。这种材料具有高比表面积和光催化性能。可以吸附低浓度瓦斯中的甲烷分子，并且在甲烷压强下降时，吸附的甲烷分子不会重新进入到环境中。材料的光催化性能可以把具有危害性的甲烷分解为无害的二氧化碳和水。这种新型吸附分解材料为低浓度瓦斯的无害化处理提供了一种新的有效途径。
Description
技术领域
本发明属于环保新材料领域，具体涉及一种二维晶体化合物Ti2C作为吸附剂在吸附分解低浓度瓦斯中甲烷的应用。
背景技术
瓦斯是有机质在煤化作用过程中生成的、主要以吸附状态储存于煤层及其围岩中的可燃气体，其主要成分是甲烷，化学式为CH4，瓦斯是威胁煤矿安全的一种有害气体。虽然纯净的甲烷气体是一种清洁能源，但是由于大量煤井瓦斯中的甲烷浓度很低，无法得到有效利用。这些大量存在的低浓度瓦斯留在矿井之中，如果富集到一定程度，会对煤矿的安全生产造成极大的危害。如果排到大气中，甲烷是一种非常有害的温室气体，温室效应比二氧化碳高25倍。
常见的甲烷处理方法是用活性炭进行吸附，由于活性炭具有非常高的比表面积、孔隙率高、化学稳定性好、成本低廉，因此是非常常见的甲烷吸附材料。但由于活性炭对瓦斯气体（甲烷）的吸附为纯吸附，吸附的甲烷在一定的条件下又回到大气中。所以甲烷的危害性并没有解决。因此，有必要寻找新的吸附材料，在吸附甲烷的同时可以留存甲烷，甚至完成对甲烷的无害化处理。
发明内容
本发明的目的是提供一种二维晶体化合物Ti2C作为吸附剂在吸附分解低浓度瓦斯（甲烷体积浓度：6% ~ 25%）中甲烷的应用。
基于上述目的，本发明采取了如下技术方案：
一种二维晶体化合物Ti2C作为吸附剂在吸附分解低浓度瓦斯中甲烷的应用。
二维晶体化合物Ti2C通过选择性刻蚀层状陶瓷材料Ti2AlC粉体而制备，Ti2C用作吸附剂吸附甲烷气体分子，在吸附甲烷分子的同时，在甲烷压强下降时可以留存甲烷，在5MPa的甲烷压强、室温条件下，甲烷的吸附量为：6~20 cm3/g；甲烷压强下降至0.1~0.8MPa、室温条件下，甲烷的吸附量为：4~10 cm3/g，甲烷分子不会重新释放到环境中。
二维碳化钛（Ti2C）是二维晶体MXene的一种，具有与石墨烯类似的结构。其晶体结构是2层钛原子层夹着1层碳原子层。因为二维结构，该材料具有较高的比表面积以及良好的吸附性能。因为表面的钛原子层以及表面上少量因为氧化产生的二氧化钛颗粒的作用，该材料具有良好的光催化性能，可以把有机物转变成无害的水与二氧化碳。
本发明二维晶体化合物Ti2C纳米粉体作为吸附剂在吸附分解低浓度瓦斯中甲烷的应用时，具有下述优点：甲烷压强高时，吸附大量甲烷分子到材料的微孔结构中；甲烷压强下降，吸附的甲烷分子不会重新释放进入环境中。因为Ti2C对有机物的光催化特性，吸附的甲烷分子会通过光催化作用分解为二氧化碳和水。
附图说明
图1为本发明实施例1用氟化铵和盐酸的混合溶液刻蚀Ti2AlC 制备的二维晶体化合物Ti2C的XRD图；
图2为实施例1制得的二维晶体化合物Ti2C的场发射扫描电镜照片；
图3为实施例1制得的二维晶体化合物Ti2C的甲烷吸附性能测试结果；
图4为实施例1制得的二维晶体化合物Ti2C的光催化性能测试结果。
具体实施方式
以下结合具体实施例对本发明的技术方案作进一步详细说明，但本发明的保护范围并不局限于此。
实施例1
二维晶体化合物Ti2C纳米粉体的制备，包括如下步骤：
(1) 配制氟化铵和盐酸的混合溶液
量取20 ml浓度为36 wt%的盐酸，加入20 ml去离子水，稀释成浓度约为6 mol/L的盐酸。称取2 g氟化铵（也可以是氟化钠、氟化钾或氟化锂）粉末溶解于上述稀释后的盐酸中，超声10分钟，使氟盐粉末充分溶解在盐酸中，即得到6 mol/L 的氟盐溶液；
(2) 二维晶体化合物Ti2C的制备
将粒径为500目的2 g Ti2AlC粉末浸没于40 ml 步骤 (1) 的氟盐溶液中，在40℃下搅拌48 h，倒入离心管中，以6000转每分钟的速度将混合溶液离心，离心后，吸出上层溶液，加入去离子水洗涤后离心，如此反复数次至离心管中的溶液呈中性，吸出上层溶液，将离心管底部留下的样品放于真空干燥箱中80℃下干燥12 h，得到二维晶体化合物Ti2C, 为黑色粉末，其X射线衍射图谱见图1，场发射扫描电镜照片见图2，由图2可以看出，Ti2C层间距为20-150 nm，层的厚度在20-80 nm。
甲烷吸附脱附性能：
利用北京金埃谱公司生产的高温高压气体吸附仪测试甲烷吸附性能。在5 MPa的纯甲烷压强下，室温条件下甲烷的吸附量为：6~20 cm3/g，压强下降到常压，甲烷的吸附量仍然保持在 4~10 cm3/g。
称取质量不少于0.1 g实施例1所制备的二维晶体化合物Ti2C，放入样品管中，采用北京金埃谱公司生产的高温高压气体吸附仪，以氦气为标定气体类型，在纯甲烷氛围、5MPa、 80℃下进行样品预处理120分钟。然后将处理后的样品在压强为 0到5 MPa之间、室温条件下进行甲烷吸附性能的测试：测试结果见图3，根据吸附曲线，甲烷压强上升时，甲烷吸附量持续上升，在5MPa的甲烷压强、室温条件下，对应的吸附量为8.5 cm3/g STP；当甲烷压强下降时，可以从脱附曲线看出，甲烷的吸附量下降的非常缓慢；当甲烷压强下降至0.5MPa、室温条件下，甲烷的吸附量仍然达到6.2 cm3/g STP；相对于最高吸附量，73%的甲烷在实验结束时仍然留存于Ti2C吸附材料中。
样品对罗丹明B的光催化性能测试：
利用TU-1901紫外可见分光光度计测试Ti2C的光催化性能。因为甲烷以及甲烷的分解产物二氧化碳与水都是无色无味，本专利使用常见的有机物染色剂罗丹明B的分解来表征Ti2C对有机物光催化分解的性能。配置罗丹明B的水溶液，加入Ti2C粉体，测试在紫外光下照射不同时间后，溶液样品的吸光度来表征Ti2C样品光催化分解性能。
将质量为0.1 g 的Ti2C粉体与体积为100 ml、浓度为20 mg/L 的罗丹明B溶液避光混合搅拌30 min，同时开启温度为10℃的循环冷凝水，30 min后，开启紫外灯，然后每隔5min，10 min，15 min，20 min，30 min，40 min，50 min，60 min分别取样标号。采用紫外可见分光光度计依次测试所取样品的紫外光波长，研究Ti2C的光催化降解性能，测试结果见图4，由图4可知: 随着紫外光照射时间的增加，在550nm处紫外吸光度的波峰逐渐减弱，罗丹明B逐渐降解完全，表明Ti2C对于有机物具有显著的光催化分解性能。
最后要说明的是，以上实例的说明只是用于帮助理解本发明的方法及其核心思想。并非用以限定本发明的实质技术内容范围，本领域的技术人员可以在此基础上对本发明做出各种改进来优化本方案。在不脱离本发明原理得前提下，进行的任何修改和修饰等均应包含在本发明权利要求的范围内。
Claims (3)
1.一种二维晶体化合物Ti2C作为吸附剂在吸附分解低浓度瓦斯中甲烷的应用，其特征在于：Ti2C具有光催化性，可催化降解吸附的甲烷为无害的水与二氧化碳。
2.根据权利要求1所述的二维晶体化合物Ti2C作为吸附剂在吸附分解低浓度瓦斯中甲烷的应用，其特征在于：甲烷压强上升，甲烷吸附量增加，在5MPa 的纯甲烷压强、室温条件下，甲烷的吸附量为：6~20 cm3/g。
3.根据权利要求1所述的二维晶体化合物Ti2C作为吸附剂在吸附分解低浓度瓦斯中甲烷的应用，其特征在于：甲烷压强下降至0.1~0.8 MPa、室温条件下，甲烷的吸附量为：4~10cm3/g，被吸附的甲烷分子不会重新释放到环境中。
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