CN102897717B - 一种自平衡高压高剪切反应釜及其在层状复合金属氢氧化物制备中的应用 - Google Patents

一种自平衡高压高剪切反应釜及其在层状复合金属氢氧化物制备中的应用 Download PDF

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CN102897717B
CN102897717B CN201210445903.1A CN201210445903A CN102897717B CN 102897717 B CN102897717 B CN 102897717B CN 201210445903 A CN201210445903 A CN 201210445903A CN 102897717 B CN102897717 B CN 102897717B
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林彦军
李凯涛
宁波
李殿卿
段雪
闻陈法
谭徐昌
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Beijing University of Chemical Technology
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Abstract

本发明公开了属于无机功能材料制备技术领域的一种自平衡高压高剪切反应釜并将其用于层状复合金属氢氧化物的制备。本发明创造性地将高剪切乳化机的机头置于反应釜内，将驱动系统置于反应釜外，利用自平衡机械密封装置维护体系压力稳定，解决了乳化机不能用于高压体系的难题，既保证了晶化反应在高压条件下进行，又实现了高剪切效果，使得高压高剪切晶化技术得以实施。该装置充分利用了大型装置可以加装大型外加设备的优势，消除了放大过程中的体积效应，使反应效果反而优于小试产品。采用该自平衡高压高剪切反应釜反应时间从过去24h缩短到2-6h，反应温度从180℃降低到140℃，得到了粒径较小、粒径分布较窄的层状复合金属氢氧化物产品。

Description

一种自平衡高压高剪切反应釜及其在层状复合金属氢氧化物制备中的应用
技术领域：
本发明属于无机功能材料制备技术领域，特别涉及一种自平衡高压高剪切反应釜并将其用于层状复合金属氢氧化物的制备。
背景技术：
层状复合金属氢氧化物（Layered Double Hydroxides，简称LDHs），又叫水滑石，是一种典型的阴离子型层状材料，其化学组成式为[M2+ 1-xM3+ x(OH)2]An- x/n·mH2O，其中M2+、M3+分别代表二价和三价金属阳离子，An-是层间阴离子，x为M3+离子的摩尔分数，m为结晶水的数量。LDHs主体层板的元素种类及组成比例、层间客体的种类及数量可以根据需要在较宽范围内调变，从而获得一系列具有特殊结构和性能的材料。
专利（CN1994888A）提出了一种采用清洁工艺制备层状复合金属氢氧化物的方法，该方法是以我国富产的水镁石矿作为原料，使其和氢氧化铝在高温水热条件下发生反应生成LDHs产品。根据反应原理，水镁石在高温下在水中溶解成镁离子，然后在氢氧化铝表面沉淀成核。由于目前所采用的反应釜为常规的桨式搅拌反应器，不能及时将形成的晶粒剥离氢氧化铝表面，成核后的晶粒会阻碍后续反应的进一步进行，不但影响了反应速率，而且反应不易完全，合成的水滑石粒子尺寸较大，粒度分散较宽，使其性能受到很大影响，限制了层状复合金属氢氧化物的应用。
发明内容：
为加快反应速率，获得纯度高、粒径小、粒径分布较窄的层状复合金属氢氧化物产品，本发明提供了一种自平衡高压高剪切反应釜并将其用于层状复合金属氢氧化物的制备。
本发明的技术方案是：将氢氧化物混合浆液在砂磨机中细化，然后投入自平衡高压高剪切反应釜中加热，通入CO2或加入酸HnAn，反应完成后，直接过滤干燥得到层状复合金属氢氧化物。
本发明所述的自平衡高压高剪切反应釜，将高剪切乳化机机头装入反应釜内；反应釜顶端为自平衡机械密封装置，自平衡机械密封装置由隔离式活塞自动推进式平衡罐和机械密封层组成；高剪切乳化机的连接轴通过机械密封层伸入反应釜内，连接轴下端连接机头，机头距反应釜底距离为釜体高度的1/5-1/2，连接轴上端连接电机驱动装置，电机驱动装置置于反应釜外；连接轴为套轴设计，外轴为定轴连接机头定子，内轴为转轴连接机头转子。
所述的隔离式活塞自动推进式平衡罐，罐底有连接管通入反应釜内，平衡罐上端有连接管与机械密封层连接，在反应釜内压力上升时，压力推动平衡罐活塞底部，压迫活塞上升，推压平衡罐内密封液由平衡罐进入机械密封层，密封液进入机械密封层后产生压力，达到与釜内压力平衡，起到密封作用。
将上述自平衡高压高剪切反应釜用于层状复合金属氢氧化物的制备，其具体步骤为：
A．将M2+和M3+的氢氧化物，按照M2+／M3+摩尔比为1-4的比例进行混合，加入固体总质量0.25~999倍的去离子水，经过砂磨机预处理，转入自平衡高压高剪切反应釜中；
B．100-300℃下，开启高剪切乳化机，设置剪切速度为500-3000rpm，同时以0.1-1000ml/min的速度通入CO2气体，或者按照M3+／An-摩尔比为n的比例加入酸HnAn，反应0.1-3天后取出固体产物，直接过滤后干燥，得到层间为CO3 2-或相应酸根阴离子An-的层状复合金属氢氧化物。
其中M2+代表二价金属阳离子Mg2+、Zn2+、Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cd2+、Be2+中的一种或两种，优选Mg2+、Zn2+、Ca2+、Ni2+中的一种或两种；M3+代表三价金属阳离子Al3+、Ni3+、Co3+、Fe3+、Mn3+、Cr3+、V3+、Ti3+、In3+、Ga3+中的一种或两种，优选Al3+、Ni3+、Fe3+中的一种或两种。
酸根阴离子An-选自下述酸根阴离子中的一种或几种：（1）无机酸阴离子：F-、Cl-、Br-、I-、NO3 -、ClO3 -、ClO4 -、IO3 -、H2PO4 -、CO3 2-、SO3 2-、S2O3 2-、HPO4 -、WO4 2-、CrO4 2-、PO4 3-；（2）有机酸阴离子：对苯二甲酸根、己二酸根、丁二酸根、十二烷基磺酸根、对羟基苯甲酸根、苯甲酸根；（3）同多、杂多酸阴离子：Mo7O24 6-、V10O28 6-、PW11CuO39 6-、SiW9W3O40 7-；An-优选Cl-、NO3 -、CO3 2-、SO3 2-、PO4 3-、苯二甲酸根、丁二酸根、苯甲酸根、Mo7O24 6-中的一种；n为酸根阴离子的价数，n=1-7。
步骤B通入CO2气体替换为加入干冰，干冰与M3+的摩尔比为0.5-20。
有益效果：本发明根据清洁生产工艺制备层状复合金属氢氧化物时水镁石溶解后在氢氧化铝表面成核，成核后晶粒会阻碍后续反应的现象，设计了一种自平衡高压高剪切反应釜，创造性地将高剪切乳化机的机头置于反应釜内，将驱动系统置于反应釜外，利用自平衡机械密封装置维护体系压力稳定，解决了乳化机不能用于高压体系的难题，既保证了晶化反应在高压条件下进行，又实现了高剪切效果，使得高压高剪切晶化技术得以实施。该装置充分利用了大型装置可以加装大型外加设备的优势，消除了放大过程中的体积效应，使反应效果反而优于小试产品。采用该自平衡高压高剪切反应釜反应时间从过去24h缩短到2-6h，反应温度从180℃降低到140℃，产品一次粒径从5-10μm减少到0.5-2μm，二次粒径d90<3um，得到了粒径较小、粒径分布较窄的层状复合金属氢氧化物产品。
附图说明
图1本发明设计的自平衡高压高剪切反应釜的结构示意图；1-电机驱动装置，2-机械密封层，3-转轴，4-定轴，5-机头定子，6-机头转子，7-反应釜，8-隔离式活塞自动推进式平衡罐。
图2是实施例1所得层状复合金属氢氧化物的XRD谱图；
图3是实施例1所得层状复合金属氢氧化物的SEM谱图；
图4是实施例1所得层状复合金属氢氧化物的激光粒度分布图。
具体实施方式
实施例1：
步骤A：将Mg(OH)2和Al(OH)3按照Mg2+／Al3+摩尔比为2:1的比例混合，取1kg混合物至于9kg去离子水中，经过砂磨机预处理，再加到自平衡高压高剪切反应釜中；
步骤B：开启高剪切乳化机，于剪切转速1000rpm下升温至120℃，以1L/min的速度通入CO2气体，反应6h，停止通气结束反应，得到的产物于70℃干燥8小时，得到分子式为Mg4Al2(OH)12CO3·4H2O的层状复合金属氢氧化物。
所述的自平衡高压高剪切反应釜，如图1所示，是将高剪切乳化机机头装入反应釜内；在反应釜顶端为自平衡机械密封装置，自平衡机械密封装置由隔离式活塞自动推进式平衡罐和机械密封层组成；高剪切乳化机的连接轴通过机械密封层伸入反应釜内，连接轴下端连接机头，机头距反应釜底距离为釜体高度的1/3，连接轴上端连接电机驱动装置，电机驱动装置置于反应釜外；连接轴为套轴设计，外轴为定轴连接机头定子，内轴为转轴连接机头转子。
所述的隔离式活塞自动推进式平衡罐，罐底有连接管通入反应釜内，平衡罐上端有连接管与机械密封层连接，在反应釜内压力上升时，压力推动平衡罐活塞底部，压迫活塞上升，推压平衡罐内密封液由平衡罐进入机械密封层，密封液进入机械密封层后产生压力，达到与釜内压力平衡，起到密封作用；密封液为液压油。
采用日本岛津公司的XRD-6000型X-射线粉末衍射仪对产品进行晶体结构表征。图2为XRD谱图，从图中可以看出，在2θ＝11.7°、23.4°、34.5°和60.8°左右处出现了Mg2Al-CO3-LDHs的特征衍射峰，且峰形尖耸，基线低平，说明产品晶体结构完整。
采用德国ZEISS公司的supra55型扫描电镜观察晶粒尺寸和形貌。图3是SEM相片，由图可见，制得的产品粒径处于1um左右。
采用英国马尔文公司的Mastersizer2000型激光粒度仪测量样品的粒径大小。图4是激光粒度分布图，从图中可以看出，产物的平均团聚粒径为0.14um，d90=2.3um。
实施例2：
步骤A：将Zn(OH)2、Mg(OH)2和Al(OH)3按照Zn2+:Mg2+:Al3+摩尔比为1:3:2的比例混合，取2kg混合物置于8kg去离子水中，经过砂磨机预处理，再加到实施例1所述的自平衡高压高剪切反应釜中；
步骤B：在自平衡高压高剪切反应釜中加入4kg干冰，于剪切转速1500rpm条件下升温至140℃，反应4h，将得到的产物于70℃干燥8小时，得到分子式为ZnMg3Al2(OH)12CO3·4H2O的层状复合金属氢氧化物。
实施例3:
步骤A：将Mg(OH)2和Al(OH)3按照Mg2+／Al3+摩尔比为3:1的比例混合，取1kg混合物至于9kg去离子水中，经过砂磨机预处理，再加到实施例1所述的自平衡高压高剪切反应釜中；
步骤B：开启高剪切乳化机，于剪切转速1500rpm下升温至140℃，以1L/min的速度通入CO2气体，反应6h，停止通气结束反应，得到的产物于70℃干燥8小时，得到分子式为Mg6Al2(OH)16CO3·4H2O的层状复合金属氢氧化物。
实施例4：
步骤A：将Ni(OH)2和Fe(OH)3按照Ni2+／Fe3+摩尔比为4:1的比例混合，取500g混合物置于9kg去离子水中，经过砂磨机预处理，再加到实施例1所述的自平衡高压高剪切反应釜中；
步骤B：向自平衡高压高剪切反应釜中加入58g对苯二甲酸，开启高剪切乳化机，于剪切速度2000rpm下升温至100℃，反应5h，将得到的产物于70℃干燥8小时，得到分子式为Ni8Fe2(OH)20(C8H4O4)·4H2O的层状复合金属氢氧化物。
实施例5:
步骤A：将Zn(OH)2、Mg(OH)2和Al(OH)3按照Zn2+:Mg2+:Al3+摩尔比为1:1:1的比例混合，取1.5kg混合物置于8.5kg去离子水中，经过砂磨机预处理，再加到实施例1所述的自平衡高压高剪切反应釜中；
步骤B：向自平衡高压高剪切反应釜中加入4kg干冰，于剪切转速2000rpm下升温至140℃，反应6h，将得到的产物于70℃干燥8小时，得到分子式为ZnMg3Al2(OH)12CO3·4H2O的层状复合金属氢氧化物。

Claims (2)

1.一种采用自平衡高压高剪切反应釜制备层状复合金属氢氧化物的方法，其特征在于，其具体步骤为：
A.将M2+和M3+的氢氧化物，按照M2+/M3+摩尔比为1-4的比例进行混合，加入固体总质量0.25～999倍的去离子水，经过砂磨机预处理，转入自平衡高压高剪切反应釜中；
B.100-300℃下，开启高剪切乳化机，设置剪切速度为500-5000rpm，同时以0.1-1000ml/min的速度通入CO2气体，或者按照M3+/An-摩尔比为n的比例加入酸HnAn，反应0.1-3天后取出固体产物，直接过滤后干燥，得到层间为CO3 2-或相应酸根阴离子An-的层状复合金属氢氧化物；产品的一次粒径为0.5-2μm，二次粒径d90<3μm；
所述的自平衡高压高剪切反应釜是将高剪切乳化机机头装入反应釜内；反应釜顶端为自平衡机械密封装置，自平衡机械密封装置由隔离式活塞自动推进式平衡罐和机械密封层组成；高剪切乳化机的连接轴通过机械密封层伸入反应釜内，连接轴下端连接机头，机头距反应釜底距离为釜体高度的1/5-1/2，连接轴上端连接电机驱动装置，电机驱动装置置于反应釜外；连接轴为套轴设计，外轴为定轴连接机头定子，内轴为转轴连接机头转子；
所述的隔离式活塞自动推进式平衡罐，罐底有连接管通入反应釜内，平衡罐上端有连接管与机械密封层连接，在反应釜内压力上升时，压力推动平衡罐活塞底部，压迫活塞上升，推压平衡罐内密封液由平衡罐进入机械密封层，密封液进入机械密封层后产生压力，达到与釜内压力平衡，起到密封作用；
所述的M2+代表二价金属阳离子Mg2+、Zn2+、Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cd2+、Be2+中的一种或两种；M3+代表三价金属阳离子Al3+、Ni3+、Co3+、Fe3+、Mn3+、Cr3+、V3+、Ti3+、In3+、Ga3+中的一种或两种；
所述的酸根阴离子An-选自下述酸根阴离子中的一种或几种：(1)无机酸阴离子：F-、Cl-、Br-、I-、NO3 -、ClO3 -、ClO4 -、IO3 -、H2PO4 -、CO3 2-、SO3 2-、S2O3 2-、HPO4 2-、WO4 2-、CrO4 2-、PO4 3-；(2)有机酸阴离子：对苯二甲酸根、己二酸根、丁二酸根、十二烷基磺酸根、对羟基苯甲酸根、苯甲酸根；(3)同多、杂多酸阴离子：Mo7O24 6-、V10O28 6-、PW11CuO39 6-、SiW9W3O40 7-；n为酸根阴离子的价数，n＝1-7。
2.根据权利要求1所述的方法，其特征在于，步骤B通入CO2气体替换为加入干冰，干冰与M3+的摩尔比为0.5-20。
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