CN112023871A - 一种CO2扩散法制备纳米方解石VOCs吸附剂的方法 - Google Patents
一种CO2扩散法制备纳米方解石VOCs吸附剂的方法 Download PDFInfo
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Abstract
一种CO2扩散法制备纳米方解石VOCs吸附剂的方法，涉及VOCs吸附剂制备技术领域。首先利用碳酸氢钠和盐酸制备二氧化碳，然后将二氧化碳持续通入石灰水中，并在超声波反应器中反应制备得到纳米方解石VOCs吸附剂。本发明通过CO2扩散法制备了纳米方解石吸附剂，观察其对挥发性有机污染物(VOCs)的吸附现象，以吸附剂在微观结构与表界面物理化学性能影响的因素，利用恒温吸附实验装置，进行吸附VOCs实验测试，深入探讨VOCs在CO2扩散法制备纳米方解石吸附剂方形表界面复杂的表面物理化学状态和相互作用机制。本发明对CO2扩散法制备纳米方解石吸附剂进行表征。
Description
技术领域
本发明涉及VOCs吸附剂制备技术领域，具体是涉及一种CO2扩散法制备纳米方解石VOCs吸附剂的方法。
背景技术
挥发性有机化合物(volatile organic compounds，VOCs)是一类有机化合物的统称，也是室内影响人体健康的主要有害物质，主要包括酮类、烃类、芳烃类、酸类、醇类、脂类、胺类和有机酸等等，在常温下它们的蒸发速率大，易挥发。1989年，世界卫生组织(WHO)对VOCs的定义是溶点低于室温，沸点范围在50-260℃之间的挥发性有机化合物的总称。VOCs是强挥发、有特殊气味、有刺激性以及有毒的有机气体，部分己被列为致癌物。VOCs人为排放量主要来自使用有机溶剂的工业活动、燃料燃烧和交通运输过程，据估算，因工业活动而导致的VOCs排放量占整个人为源的40％，并且呈逐年增加趋势，特别是家具制造、汽车制造、石油化工、包装印刷及涂料加工等行业VOCs污染尤为突出。
在我国，VOCs是指常温下饱和蒸汽压大于133.32Pa、常压下沸点在50-260℃以下的有机化合物，或在常温常压下任何能挥发的有机固体或液体。按照化学结构来讲，VOCs可分为八类：烷类、芳烃类、烯类、卤烃类、酯类、醛类、酮类和其他。它的主要成分有烃类、卤代烃、氧烃和氮烃，包括苯系物、有机氯化物、氟里昂系列、有机酮、胺、醇、醚、酯、酸和石油烃化合物等。VOCs的危害：大多数VOCs具有刺激性气味或臭味，可引起人们感官上的不愉快，严重降低人们的生活质量。VOCs成分复杂，有特殊气味且具有渗透、挥发及脂溶等特性，具有毒性、刺激性及致畸致癌作用，苯、甲苯、二甲苯、甲醛等对人体健康的危害最大，长期接触会使人患上贫血症与白血病。某些VOCs如苯、甲苯、丙酮、二甲基胺及硫代烃等易燃，这些物质的排放浓度较高时如果遇到静电火花或其他火源，容易引起火灾。部分VOCs如氟氯烃物质可破坏臭氧层，臭氧层的破坏使到达地面的紫外线辐射量增加，对人类皮肤、眼睛及免疫系统有较大的危害。
工业源VOCs种类多，具有排放强度大、持续时间长、波动大及毒害大等特点，其严重危害人类健康和影响环境质量，所以，对其控制方法的研究一直是暖通和环保领域的热点问题之一。VOCs控制技术可以简单分为两大类：一类称为破坏性方法，包括氧化法和生物法，氧化法又可分为直接燃烧法、催化氧化法和热力燃烧法；另一类称为回收性方法，常用的有吸收法、吸附法、浓缩法和膜分离法。其中，吸附法由于具有操作工艺简单、易实现自动化控制、无二次污染以及吸附剂可再生重复利用等优点而被广泛用于VOCs控制。
吸附是通过多孔性固体物质跟流体混合物接触，使流体中某一组分或多个组分在固体表面处产生富集进而以分离的一种方法。固体称为吸附剂，被吸附的物质称为吸附质。因为吸附净化法处理效率高，设备简单，操作方便，且能实现自动控制，因此吸附操作已广泛应用于有机化工、石油化工、环境工程等生产领域，成为一种必不可少的操作单元。
发明内容
本发明要解决的技术问题是提出一种CO2扩散法制备纳米方解石VOCs吸附剂的方法，以制备性能优越的吸附剂材料。对制备高比表面积、多尺度方形表界面和高表面氧含量的功能纳米方解石吸附剂及其应用在环保领域具有重要的指导意义。
为了实现上述目的，本发明所采用的技术方案为：一种CO2扩散法制备纳米方解石VOCs吸附剂的方法，首先利用碳酸氢钠和盐酸制备二氧化碳，然后将二氧化碳持续通入石灰水中，并在超声波反应器中反应制备得到纳米方解石VOCs吸附剂。
作为本发明的CO2扩散法制备纳米方解石VOCs吸附剂的方法的优选技术方案，具体步骤如下：
1)、向A反应容器中加入碳酸氢钠溶液，并安装搅拌装置、滴液漏斗以及气体扩散装置，滴液漏斗中装入盐酸溶液，气体扩散装置另一端通入B反应容器中；
2)、B反应容器中装有石灰水，且B反应容器置于超声波反应器中，并安装有搅拌装置；
3)、搅拌条件下，将滴液漏斗中的盐酸溶液滴入A反应容器中；开启超声波反应器，并开启B反应容器中的搅拌装置；
4)、反应结束后，再经过过滤、洗涤和干燥工序，制备获得纳米方解石VOCs吸附剂。
作为本发明的CO2扩散法制备纳米方解石VOCs吸附剂的方法的进一步优选技术方案，所述碳酸氢钠和盐酸的摩尔比为1：1，滴液漏斗滴液速度为1-2d/s，产生的二氧化碳与B反应容器中氢氧化钙的摩尔比为1～1.5：1。超声波反应器的超声功率为800W，反应时间为0.1～1h。制备获得纳米方解石VOCs吸附剂时干燥温度为100～200℃，干燥时间为1～2h。
与现有技术相比，本发明的有益效果表现在：
1)、本发明通过CO2扩散法制备了纳米方解石吸附剂，观察其对挥发性有机污染物(VOCs)的吸附现象，以吸附剂在微观结构与表界面物理化学性能影响的因素，利用恒温吸附实验装置，进行吸附VOCs实验测试，深入探讨VOCs在CO2扩散法制备纳米方解石吸附剂方形表界面复杂的表面物理化学状态和相互作用机制。
2)、本发明研究了CO2扩散法制备纳米方解石吸附剂的孔结构对吸附性能的影响，实验研究发现，吸附剂内部结构越复杂，传质速率越慢，良好的孔结构梯度分布有助于加强方解石内部吸附质的扩散。吸附质分子直径越小，越容易扩散；利用不同孔径区间下的孔容与吸附量之间的相关系数关系可以较好地解释吸附质在方解石内部的扩散过程。对于VOCs分子在方解石孔结构中的扩散过程与扩散机理给出了科学解释，研究发现随着进气浓度的变化，方解石内部能够产生有效吸附作用的孔结构也会发生转移。
3)、本发明借助XRD衍射分析、显微观测分析、穿透实验等手段，对CO2扩散法制备纳米方解石吸附剂进行表征。利用理论方法分析吸附性能等参数，结合CO2扩散法制备纳米方解石吸附剂表征结果，探讨了纳米方解石吸附性能与吸附质和吸附剂物性的宏观微观构效关系，为新型纳米方解石吸附剂制备以及吸附净化VOCs工业过程优化设计提供技术支撑。
附图说明
以下结合实施例和附图对本发明的CO2扩散法制备纳米方解石VOCs吸附剂的方法作出进一步的详述。
图1是实施例1制备吸附剂产物与纯的碳酸钙的XRD对比图。
图2a、b依次是实施例1制备吸附剂产物与纯的碳酸钙的SEM图。
图3是实施例1制备吸附剂产物的TG-TGA曲线图。
图4a、b是不同吸附质在实施例1制备吸附剂产物与纯的碳酸钙上的穿透数据图。
具体实施方式
实施例1
CO2扩散法制备纳米方解石VOCs吸附剂的方法，具体步骤如下：
1)、向A反应容器中加入碳酸氢钠溶液，并安装搅拌装置、滴液漏斗以及气体扩散装置，滴液漏斗中装入盐酸溶液，气体扩散装置另一端通入B反应容器中。碳酸氢钠和盐酸的摩尔比为1：1，滴液漏斗滴液速度为1.5d/s，产生的二氧化碳与B反应容器中氢氧化钙的摩尔比为1：1。
2)、B反应容器中装有石灰水，且B反应容器置于超声波反应器中，并安装有搅拌装置。
3)、搅拌条件下，将滴液漏斗中的盐酸溶液滴入A反应容器中。开启超声波反应器，并开启B反应容器中的搅拌装置。超声波反应器的超声功率为800W，反应时间为0.5h。
4)、反应结束后，再经过过滤、洗涤和干燥工序，制备获得纳米方解石VOCs吸附剂。干燥温度为200℃，干燥时间为1h。
图1是实施例1制备吸附剂产物与纯的碳酸钙的XRD对比图。
由图1易知，2种样品的主要特征衍射峰位置相似。对照PDF标准卡(PDF No：41-1475，05-0586)的有关数据，可以确定纳米碳酸钙样品的晶型为方解石型，且无杂质峰存在。对照PDF标准卡在2θ＝23.04°，29.40°，36.00°，39.40°，43.16°，47.48°和48.50°，57.20°，64.89°位置附近的各衍射峰处均出现较强的的特征衍射峰和所对应的衍射面分别为(012)，(104)，(110)，(11-3)，(202)，(018)和(11-6)，(122)，(300)。
同时，由图1可知，纯的纳米碳酸钙的特征衍射峰强度要弱很多，这是碳酸钙微晶纳米化的结果。在纳米化过程中，碳酸钙微晶从微米级降至纳米级，会造成碳酸钙微晶的结晶度下降，引起XRD特征衍射峰强度的大幅度下降。而实施例1通过CO2扩散法制备的纳米方解石吸附剂有明显的衍射峰，而且都比较尖锐，结晶度相对较好，说明合成的吸附剂在物相上与实验设计目标物相吻合。
图2a、b依次是实施例1制备吸附剂产物与纯的碳酸钙的SEM图。由图2易知，两种样品的粒径分布主要在500nm以内，方形都有分布，大小方形比例较小。通过对比可以发现，纯的碳酸钙样品中微方形分布相对偏少，而实施例1制备的纳米方解石吸附剂的小方形结构表现分布多，更能呈现多尺度分布，且这种多级表面结构有利于多元VOCs污染物的去除，这是因为良好的表面结构梯度分布将有助于加强表面吸附质的扩散，吸附质分子直径越小，其在吸附剂表面越容揚扩散。同时，不同粒径下的方形结构对于吸附质的吸附效果会因吸附质的不同而不同；并且，随着进气浓度的增加，能够产生有效吸附作用的方形结构也会发生转移；当进口浓度很低时，进入表面的吸附质吸附势能比较低，增加了其停留在表面方形结构位置的不确定性。这表明实施例1制备的吸附剂表面的纳米方形结构对于其吸附VOCs起到了决定性作用。
图3是实施例1制备吸附剂产物的TG-TGA曲线图。由图3易看出，在程序控温下，吸附剂的质量随温度的变化关系为：热解过程主要出现在温度为30-100℃的阶段，质量损失率分别为4％。当温度低于为30℃时，一些可能存在的有机物、水分和无机等吸附在方解石表面，也导致其质量明显增加。在温度高于140℃时，质量变化不明显。温度为30-100℃时，吸附在纳米方解石内分子质量较小的有机物、水分和无机杂质受热分解，造成纳米方解石质量下降。
图4为甲醛、苯、二甲苯、苯乙烯在实施例1制备吸附剂产物与纯的碳酸钙样品上的穿透数据图。假定出口浓度为C，进口浓度为C0，当C/C0＝0.1时，吸附VOCs达到了穿透点；当C/C0＝0.95时，吸附剂吸附VOCs达到了吸附饱和。在此假设条件下，由图4易知，对于不同VOCs(甲醛、苯、二甲苯、苯乙烯)在同一方解石上吸附，均是甲醛穿透时间最短，最快达到平衡吸附量；苯穿透时间最长，最慢达到平衡吸附量；二甲苯、苯乙烯穿透时间和达到饱和吸附量的时间都居中。由此可见，甲醛、苯、二甲苯、苯乙烯4种吸附质物性不同，其吸附行为表现也存在差异。同理，由于方解石结构和表面化学性质的差异，对于同一吸附质在不同吸附剂上的吸附，其穿透时间和吸附饱和时间也不同。吸附质主要有：甲醛，乙醛，甲苯，二甲苯，丙酮，正丁醇，环己醇，环己酮，二甲基胺，苯乙烯，三氯甲烷等。对甲醛、苯、二甲苯、苯乙烯4种吸附质而言，实施例1制备的纳米方解石吸附剂的吸附量明显大于纯的碳酸钙样品。
本发明研究了制备纳米方解石吸附剂吸附VOCs在不同形成条件下物性的变化，探讨了组分物性对于VOCs吸附性能的作用和影响。较短的改性时间的条件下，可以改性制得具有较大比表面积、多尺度方形表面和较高表面氧含量的纳米方解石矿物。本本申请研究对制备高比表面积、多尺度方形表界面和高表面氧含量的功能纳米方解石吸附剂及其应用在环保领域具有重要的指导意义。
实施例2
CO2扩散法制备纳米方解石VOCs吸附剂的方法，具体步骤如下：
1)、向A反应容器中加入碳酸氢钠溶液，并安装搅拌装置、滴液漏斗以及气体扩散装置，滴液漏斗中装入盐酸溶液，气体扩散装置另一端通入B反应容器中。碳酸氢钠和盐酸的摩尔比为1：1，滴液漏斗滴液速度为1d/s，产生的二氧化碳与B反应容器中氢氧化钙的摩尔比为1.5：1。
2)、B反应容器中装有石灰水，且B反应容器置于超声波反应器中，并安装有搅拌装置。
3)、搅拌条件下，将滴液漏斗中的盐酸溶液滴入A反应容器中。开启超声波反应器，并开启B反应容器中的搅拌装置。超声波反应器的超声功率为800W，反应时间为1h。
4)、反应结束后，再经过过滤、洗涤和干燥工序，制备获得纳米方解石VOCs吸附剂。干燥温度为100℃，干燥时间为2h。
实施例3
CO2扩散法制备纳米方解石VOCs吸附剂的方法，具体步骤如下：
1)、向A反应容器中加入碳酸氢钠溶液，并安装搅拌装置、滴液漏斗以及气体扩散装置，滴液漏斗中装入盐酸溶液，气体扩散装置另一端通入B反应容器中。碳酸氢钠和盐酸的摩尔比为1：1，滴液漏斗滴液速度为2d/s，产生的二氧化碳与B反应容器中氢氧化钙的摩尔比为1：1。
2)、B反应容器中装有石灰水，且B反应容器置于超声波反应器中，并安装有搅拌装置。
3)、搅拌条件下，将滴液漏斗中的盐酸溶液滴入A反应容器中。开启超声波反应器，并开启B反应容器中的搅拌装置。超声波反应器的超声功率为800W，反应时间为0.2h。
4)、反应结束后，再经过过滤、洗涤和干燥工序，制备获得纳米方解石VOCs吸附剂。干燥温度为150℃，干燥时间为1.5h。
以上内容仅仅是对本发明的构思所作的举例和说明，所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代，只要不偏离发明的构思或者超越本权利要求书所定义的范围，均应属于本发明的保护范围。
Claims (5)
1.一种CO2扩散法制备纳米方解石VOCs吸附剂的方法，其特征在于，首先利用碳酸氢钠和盐酸制备二氧化碳，然后将二氧化碳持续通入石灰水中，并在超声波反应器中反应制备得到纳米方解石VOCs吸附剂。
2.如权利要求1所述的方法，其特征在于，具体步骤如下：
1)、向A反应容器中加入碳酸氢钠溶液，并安装搅拌装置、滴液漏斗以及气体扩散装置，滴液漏斗中装入盐酸溶液，气体扩散装置另一端通入B反应容器中；
2)、B反应容器中装有石灰水，且B反应容器置于超声波反应器中，并安装有搅拌装置；
3)、搅拌条件下，将滴液漏斗中的盐酸溶液滴入A反应容器中；开启超声波反应器，并开启B反应容器中的搅拌装置；
4)、反应结束后，再经过过滤、洗涤和干燥工序，制备获得纳米方解石VOCs吸附剂。
3.如权利要求2所述的方法，其特征在于，所述碳酸氢钠和盐酸的摩尔比为1：1，滴液漏斗滴液速度为1-2d/s，产生的二氧化碳与B反应容器中氢氧化钙的摩尔比为1～1.5：1。
4.如权利要求2所述的方法，其特征在于，超声波反应器的超声功率为800W，反应时间为0.1～1h。
5.如权利要求2所述的方法，其特征在于，制备获得纳米方解石VOCs吸附剂时干燥温度为100～200℃，干燥时间为1～2h。
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