CN106311260B - 一种合成气制低碳醇催化剂的低温热等离子体制法和应用 - Google Patents
一种合成气制低碳醇催化剂的低温热等离子体制法和应用 Download PDFInfo
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- B01J23/85—Chromium, molybdenum or tungsten
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Abstract
本发明提供了一种采用低温热等离子体法制备合成气制低碳醇催化剂的方法，属于化工催化剂制备领域。本发明的具体原理是首先产生低温热等离子体，进而将钼源与钴源化合物的混合物通过高温等离子体弧处理制得催化剂活性组分，然后以浸渍法引入碱金属盐后制得目标催化剂。该目标催化剂在合成气制低碳醇反应中具有催化活性高、醇类选择性高、反应寿命长等优点。该方法制备过程简单快捷，易于大规模生产。
Description
技术领域
本发明涉及化工催化剂技术领域，具体涉及一种用于合成气制低碳醇的催化剂制备方法和反应条件，尤其是涉及一种以射频感应低温热等离子体方法制备催化剂。
背景技术
低碳混合醇燃料就是以甲醇或乙醇为主，混合有甲醇或乙醇以及丙醇、丁醇、戊醇等高级醇的多醇混合物。低碳混合醇是一种良好的车用燃料，其辛烷值较高，与汽油的掺混性较好，可替代甲基叔丁基醚（MTBE）作为汽油添加剂，具有燃烧清洁、低污染的优点。因此，低碳醇与汽油混合代用燃料受到各国的普遍重视。另外，对低碳混合醇进行分离后，可得到甲醇、乙醇、丙醇、丁醇和戊醇等单一醇类，可作为制备精细化学品的原料。
与传统生产低碳醇工艺（生物发酵法和间接化学转化法）相比，合成气（CO+H2）催化合成低碳醇路线最直接、工艺步骤最少。因而，合成气制低碳醇产品的应用和产业链延伸范围更广，工艺更简单。从合成气直接合成低碳醇是煤化工科学界和产业界几十年来梦寐以求的目标。合成气催化合成低碳醇的非均相催化剂从广义上可分为两大类：（1）贵金属基催化剂（US Patent 4014913，4096164），包括Rh、Ru和Re，常以SiO2、γ-Al2O3、CeO2、ZrO2、MgO等做载体，这类催化剂可以直接催化CO加氢合成高级醇；其中Rh基催化剂由于具有较高的乙醇选择性而得到广泛研究，但由于贵金属基催化剂原料成本高而限制了其商业应用。（2）非贵金属基催化剂，可以分为三类：a.改性的甲醇合成催化剂（EP-0034338-A2,US Patent4513100），主要由甲醇合成催化剂添加碱金属或碱土金属化合物改性而成；b.改性的费托合成催化剂，以Cu-Co系高级醇合成催化剂为代表，它是由IFP（法国石油研究院）首先合成（US Patent 4122110，4291126）；c.钼基催化剂，如MoO2，具有优异的抗硫性和良好的水煤气变换性能及较高的C2+OH选择性，因而能在较高含硫量和较低H2/CO摩尔比(0.7～1)的条件下使用，被认为是一类颇有前景的催化剂（US Patent 4882360）。非贵金属基催化剂由于其低廉的成本日益受到研究者的青睐，然而这类催化剂通常得到碳原子数为C1～C6分布的混合醇，其中甲醇的选择性较高，C2+OH选择性较低。
除了催化剂组成上的影响，传统的合成气制低碳醇催化剂制备方法（浸渍法、溶胶凝胶法、共沉淀法等）仍存在一些不足，如催化活性低、易中毒、机械稳定性差等。为了提高催化剂的反应活性，近几十年出现了多种新型催化剂制备技术，例如等离子体、超声波和微波等技术，取得了积极的效果。中国专利CN103495427A 采用气体放电将硫化氢气体电离，形成低温冷等离子体，与金属盐前驱体相互作用形成硫化物。其制备的催化剂颗粒尺寸更小，分散度更高。但是目前对于等离子体改性催化剂，所用的等离子体多属冷等离子体，与冷等离子体相比，热等离子体具有如下优点：第一，拥有高达15000K的高温，所以很容易产生各种活跃的组分；第二，发生在等离子体火焰区的快速淬灭过程(105-106K/s)可以有效形成高度分散的纳米粒子，同时在纳米粒子表面形成多种缺陷结构，从而有利于提高催化剂活性；第三，高温下纳米粒子表面发生钝化，可阻止催化反应过程中纳米粒子团聚而导致的催化活性下降，从而提高催化剂的运行稳定性。
发明内容
本发明目的在于提供一种合成气制低碳醇高效钼基催化剂的新型制备方法，即采用射频感应低温热等离子体法制备。该催化剂具有优异的合成气制低碳醇活性、选择性和运行稳定性，成本低廉制作方便，具有很好的实际应用价值。
本发明主要包括催化剂原料的制备、等离子体仪器调控和催化剂反应评价等步骤。以下为本发明的操作步骤及原理性说明：
（1）将钼源与钴源化合物以不同比例机械混合，Co与Mo的原子摩尔比为0∶1～3∶1。烘干后，冷却至室温，过筛，作为原料加入等离子体设备的进料器内。
（2）所采用等离子体为射频低温热等离子体，等离子体设备的调控参数为：所用气体均为高纯惰性气体和（或）氮气，进料速度为0～30 g/min，中气流速为0.1～2.0 m3/h，边气流速为1.0～10.0 m3/h，载气流速为0～2m3/h，仪器功率为5～25kW。
（3）从等离子体仪器中收集得到的产品，以碱金属盐类的溶液按一定比例浸渍，然后在一定温度下烘干，得到非负载型催化剂。
本发明的合成气催化合成低碳醇反应条件为：温度200～400℃，压力1～20MPa，原料气H2/CO为0.5/1～3/1，空速500～100000h-1。
本发明提供的催化剂制备方法有如下特点：
（1）原料制备简单，等离子体设备参数可根据要求进行调节，制备过程简单快捷，易于大规模生产。
（2）制备出的催化剂粒径较常规方法小、比表面积大、分散性好。
（3）本发明的催化剂具有活性高、总醇和C2+醇选择性高、抗积碳和寿命长等特点。
附图说明
图1为实施例1中催化剂的X射线衍射（XRD）图谱；
图2为实施例1中催化剂的透射电镜（TEM）照片。
具体实施方式
下面结合具体实施例对本发明做进一步说明，本发明包括但不限于下面的实施例。
实施例1
称取钼酸铵61.79g，三氧化二钴14.51g（Co/Mo为1∶2），机械混合均匀后，烘箱中120℃下烘干24h，待冷却至室温后，研钵研碎过80目网筛后加入到等离子体仪器进料仓内。
等离子体设备参数调控如下：所用气体均为高纯氩气，中气0.5 m3/h，边气4.5 m3/h，载气0.2 m3/h，进料速度为7.27 g/min，仪器功率为10kW。
将产品以碳酸钾溶液浸渍（nK/（nMo+ nCo）=5%），浸渍后120℃下烘干24h，冷却后压片过筛，收集40-60目的催化剂。
将上述方法制备的K-Co-MoO2催化剂在不锈钢固定床反应器中进行催化性能评价。反应器内径8mm，催化剂装填量2mL，混合40-60目石英砂填装于恒温段，上部预热段和下部保温段均填装石英砂。反应条件：温度300℃，压力9.0MPa，空速3000h-1，合成气H2/CO=1∶1。反应产生的醇类产物使用装有RESTEK的Stabilwax毛细管柱的GC-2014C气相色谱（Shimadzu制造）分析，使用FID检测器；烃类产物分析由装有Propack-Q固定相色谱柱的Shimadzu公司的GC-2014C气相色谱分析，使用FID检测器；反应产物尾气中H2、CO、CO2由装有TDX-01碳分子筛柱的Shimadzu公司的GC-2014C气相色谱分析，使用TCD检测器。
对以上催化剂进行合成低碳醇催化性能评价结果显示，CO转化率40.5%，总醇选择性67.9%，C2+醇选择性65.2%，时空产率为287.3mg/mL/h，运行500h催化剂活性无明显下降。该催化剂显示出良好的催化活性和稳定性，是优良的合成气制低碳醇催化剂 。
实施例2
将三氧化二钴的质量变为29.03g，钼酸铵的质量仍为61.79g（Co/Mo为1∶1），其他条件同实施例1。催化评价结果为，CO转化率46.8%，总醇选择性51.6%，C2+醇选择性71.7%，时空产率为178.7mg/mL/h。
实施例3
将三氧化二钴的质量变为58.06g，钼酸铵的质量仍为61.79g（Co/Mo为2∶1），其他条件同实施例1。催化评价结果为，CO转化率51.5%，总醇选择性50.4%，C2+醇选择性70.5%，时空产率为222.1mg/mL/h。
Claims (3)
1.一种合成气制低碳醇催化剂的低温热等离子体制法，其特征在于制法包括制备步骤和反应条件，制备步骤为：将钼源与钴源化合物以不同比例机械混合均匀，烘干过筛后作为原料加入低温热等离子体设备的进料器内进行等离子体反应；从等离子体设备中收集得到的产品与碱金属盐溶液按一定比例浸渍，烘干后得到非负载型催化剂；反应条件为：所采用的等离子体为射频感应低温热等离子体，仪器功率为5～25kW，进料速度为0～30g/min，所用的中气、边气、载气均为高纯惰性气体，中气流速为0.1～2.0m3/h，边气流速为1.0～10.0m3/h，载气流速为0～2m3/h。
2.根据权利要求1所述的一种合成气制低碳醇催化剂的低温热等离子体制法，其特征在于制备步骤中的钼源为钼的含氧酸盐、卤化物、氧化物，钴源为钴的含氧酸盐、卤化物、氧化物，Co与Mo的原子摩尔比为0/1～3/1；碱金属盐（M）为碳酸钾、碳酸钠、醋酸钾、碳酸铯，加入量为nM/（nMo+nCo）=1%～100%。
3.根据权利要求1所述的制法制备得到的合成气制低碳醇催化剂的应用，其特征在于催化剂的使用条件为：反应温度200～400℃，反应压力1～20MPa，原料气H2/CO为0.5/1～3/1，空速500～100000h-1。
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