CN110980750B - 一种介孔硅酸镁的制备方法及其应用 - Google Patents
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- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
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- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种介孔硅酸镁的制备方法及其应用，其以镁盐和硅酸盐为原料，经过溶解、过滤、混合搅拌等处理步骤，调节pH值至8‑14，并将所得混合碱液在60‑110℃加热搅拌1‑8 h，经过洗涤、干燥后得到大比表面积的介孔硅酸镁。该方法采用无模板剂合成方法，大大降低了制备成本，同时所制备的硅酸镁具有较大的比表面积，良好的孔道结构和丰富的表面羟基，在羰基硫催化水解过程中展示出优异的催化活性。
Description
技术领域
本发明属于无机功能材料制备技术领域，具体涉及一种介孔硅酸镁的制备方法及其应用。
背景技术
全球经济迅猛增长，对能源的需求与日俱增。然而，能源的低效率使用造成严重的污染，环境问题愈加严重。大气中的污染物严重影响空气质量和威胁人类健康。有毒害的含硫化物是造成大气污染的重要原因。羰基硫（COS）是硫化物的典型代表，但其化学性质不活泼，在脱除上比较困难。
目前，工业上脱除COS的方法主要有加氢转化法、吸收法、氧化转化法、光解法、水解法。水解反应（COS+H2O→CO2+H2S）是工业上应用最为广泛的反应之一。γ-Al2O3是最常见的中低温COS水解催化剂载体，其本身具有一定的活性。进一步负载碱性组分后可明显增强碱性中心，进一步提高水解活性。但以γ-Al2O3为载体的催化剂稳定性一般，并且当原料气的含量高时，其转化率较低。活性炭因具有丰富的微孔结构和良好的电子传导性等特点，也被作为载体应用到COS水解反应中。但硫化物及硫酸盐的沉积易导致催化剂中毒，影响其寿命。专利CN106861665A公布了一种在γ-Al2O3上负载草酸钾的水解催化剂，所公布的催化剂具有优良的催化水解性能，但催化剂载体γ-Al2O3的制备需要多种模板剂，制备成本高，过程繁琐。专利CN101703928A公布了一种活性炭载体的水解催化剂，其制备过程简单，水解催化活性良好，但其抗硫酸盐性能较差，催化寿命较短。
基于上述问题，我们提出一种无模板制备大比表面介孔硅酸镁的制备方法。将镁盐和硅酸盐经过简单的溶解、过滤、混合搅拌处理后调节pH值至8-14，再进行简单热处理和洗涤后得到大比表面积的介孔硅酸镁。所制备的硅酸镁不仅比表面积大，且具有良好的孔道结构和丰富的表面羟基，可展示出优异的催化活性。
发明内容
本发明提供了一种介孔硅酸镁的制备方法及其应用，通过在无模板剂的合成条件下制备大比表面积的介孔硅酸镁，且具有丰富的表面羟基。所制备的介孔硅酸镁可应用于催化COS水解领域，在无需负载其他活性组分的条件下便可达到较高的催化转化率。
为实现上述目的，本发明采用如下技术方案：
以镁盐和硅酸盐为原料，经过溶解、过滤、混合搅拌，再通过碱液调节至一定的pH值，然后进行热处理、洗涤、干燥后得到介孔硅酸镁，可用于有机硫催化水解反应。
进一步地，所述的镁盐为氯化镁、硝酸镁、硫酸镁中的一种，所述的硅酸盐为硅酸钠，所用的碱液为氢氧化钠溶液或氢氧化钾溶液中的一种，镁盐和硅酸盐的摩尔比为0.5-2。
进一步地，所述的溶解过程是将可溶性镁盐和硅酸钠溶于水搅拌溶解，搅拌速率为500-800 rpm。
进一步地，所述的pH调节过程是通过逐滴滴加碱溶液的方式，将pH值调节至8-14。
进一步地，所述热处理的温度为60-110 ℃，热处理的时间为1-8 h。
进一步地，所述洗涤过程为用大量热去离子水洗涤至pH值为7。
所述的硅酸镁在COS催化水解反应中的应用，具体以COS和N2为原料气体，并通入水蒸气进行COS催化水解反应。原料气体流速为20 mL/min，反应温度为30~170 ℃，升温速率为3℃/min，反应中水蒸气温度为40℃。
本发明的优势在于：
1. 本发明制备的大比表面积硅酸镁，采用无模板法合成，与传统水热法和模板法相比，该方法制备工艺简单，制备过程无需模板即可得到大比表面积和介孔结构，成本更低，有利于大规模生产。
2. 本发明制备的介孔硅酸镁，可应用于COS水解，无需负载其他活性组分，而达到较高的催化转化率。
附图说明
图1为介孔硅酸镁的物理吸附的吸脱附曲线；
图2为介孔硅酸镁的孔径分布图。
具体实施方式
以下结合实施例进一步阐述本发明，但本发明的保护范围不限于下述实施例。为进一步说明本发明的实验操作及其实验结果，本部分结合发明的实施例进行更为详细的描述。
实施例1
称取6 g硫酸镁溶于17 ml去离子水中搅拌溶解，过滤并取其澄清液，得到硫酸镁溶液。称取5 g硅酸钠溶于13 ml去离子水中搅拌溶解，过滤并取其澄清液，得到硅酸钠溶液。将配制好的硅酸钠溶液逐滴加入配制好的硫酸镁溶液中。逐滴加入30 wt% 的氢氧化钠溶液，至体系pH为8。将得到的混合体系移入烧瓶中并于90 ℃油浴锅中保持3小时，混合体系冷却后用大量热水洗涤并过滤。得到的产物于烘箱120℃干燥24小时。产物记为硅酸镁-1，该催化剂的比表面积为361 m2/g。
实施例2
称取7 g硫酸镁溶于17 ml去离子水中搅拌溶解，过滤并取其澄清液，得到硫酸镁溶液。称取5 g硅酸钠溶于13 ml去离子水中搅拌溶解，过滤并取其澄清液，得到硅酸钠溶液。将配制好的硅酸钠溶液逐滴加入配制好的硫酸镁溶液中。逐滴加入30 wt% 的氢氧化钠溶液，至体系pH为13。将得到的混合体系移入烧瓶中并于120℃油浴锅中保持5小时，混合体系冷却后用大量热水洗涤并过滤。得到的产物于烘箱120 ℃干燥24小时。产物记为硅酸镁-2，该催化剂的比表面积为535 m2/g。
实施例3
称取10 g硫酸镁溶于17 ml去离子水中搅拌溶解，过滤并取其澄清液，得到硫酸镁溶液。称取5 g硅酸钠溶于13 ml去离子水中搅拌溶解，过滤并取其澄清液，得到硅酸钠溶液。将配制好的硅酸钠溶液逐滴加入配制好的硫酸镁溶液中。逐滴加入30 wt% 的氢氧化钾溶液，至体系pH为14。将得到的混合体系移入烧瓶中并于100 ℃油浴锅中保持5小时，混合体系冷却后用大量热水洗涤并过滤。得到的产物于烘箱120℃干燥24小时。产物记为硅酸镁-3，该催化剂的比表面积为599 m2/g。
实施例4
称取12 g硫酸镁溶于17 ml去离子水中搅拌溶解，过滤并取其澄清液，得到硫酸镁溶液。称取5 g硅酸钠溶于13 ml去离子水中搅拌溶解，过滤并取其澄清液，得到硅酸钠溶液。将配制好的硅酸钠溶液逐滴加入配制好的硫酸镁溶液中。逐滴加入30 wt% 的氢氧化钾溶液，至体系pH为9。将得到的混合体系移入烧瓶中并于90℃油浴锅中保持3小时，混合体系冷却后用大量热水洗涤并过滤。得到的产物于烘箱120 ℃干燥24小时。产物记为硅酸镁-4，该催化剂的比表面积为356 m2/g。
参比例1
采用商业γ-Al2O3脱硫催化剂（国药集团化学试剂有限公司），动态平衡水吸附量≥25%（100% RH，20 ℃），堆积密度≤0.96 g/ml，抗压强度≥50 N，记为催化剂A。
参比例2
采用商业分子筛SBA-15（南京吉仓纳米科技有限公司），记为催化剂B。
表征分析：
N2物理吸附：采用美国Micrometric公司的TriStarⅡ 3020分析仪在液氮温度（-196 ℃）下进行测定样品比表面积和孔尺寸，样品先在180℃下脱气6 h，用BET(Brunauer-Emmett-Teller )法计算样品的比表面积，孔径分布曲线根据BJH（Barrett-Joyner-Halenda）法求出。
如图1所示，为本发明实例1~4的硅酸镁样品的N2物理吸脱附曲线。从N2物理吸脱附曲线中可以看出，硅酸镁-1的曲线均呈现I型吸脱附曲线，说明样品中微孔和大孔所占的比例较大，介孔含量相对较小。硅酸镁2~4样品的曲线均呈现IV型吸脱附曲线以及H2型滞后环，说明样品中均存在介孔结构。
如图2所示，为本发明实施例1~4的硅酸镁样品的孔径分布图。孔径分布图主要显示了样品介孔的分布情况。从孔径分布图中可以看出样品均含有丰富的介孔，孔径分布主要集中在3-4 nm。
COS水解催化性能测试：
催化性能测试条件：催化剂质量为0.2 g，原料气浓度为110 mg/cm3 COS/N2，原料气浓度为20 ml/min-1，反应管内径为5 mm，反应物中的水蒸气温度为40℃，活性以COS的转化率（%）表示。测试结果由表1所示。
表1为本发明实施例 1~4，对比例A和B的催化水解COS反应的COS转化率表。
由表中数据可以看出，无模板法制备的大比表面积硅酸镁具有优异的COS催化效率。其中硅酸镁-2的COS转化率要明显高于其它硅酸镁材料和对比催化剂，硅酸镁-2在70℃时COS的转化率便可达到45.8%，在130℃时COS的转化率便可达到100%。且随着温度的进一步升高其活性保持不变。与对比样γ-Al2O3和SBA-15催化剂相比，硅酸镁-2在COS水解反应中的具有明显的催化性能优势，尤其在低温反应区域。
以上所述的具体实施方式，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施方式而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (4)
1.一种介孔硅酸镁在COS催化水解反应中的应用，其特征在于：以COS和N2为原料气体，并通入水蒸气进行COS催化水解反应；
所述介孔硅酸镁的制备方法包括以下步骤：以镁盐和硅酸盐为原料，经过溶解、过滤、混合搅拌后得到混合溶液，再使用碱液调节pH值，然后进行热处理、洗涤、干燥后得到介孔硅酸镁；所述镁盐为氯化镁、硝酸镁、硫酸镁中的一种，所述硅酸盐为硅酸钠，所述镁盐与硅酸盐的摩尔比为0.5-2，所用碱液为氢氧化钠溶液或氢氧化钾溶液；所述热处理的温度为60-110℃，热处理的时间为1-8 h。
2.根据权利要求1所述的介孔硅酸镁在COS催化水解反应中的应用，其特征在于：所述的溶解过程是以水为溶剂，并将镁盐和硅酸盐溶于水后剧烈搅拌溶解，溶解搅拌速度为500~800 rpm。
3.根据权利要求1所述的介孔硅酸镁在COS催化水解反应中的应用，其特征在于：所述调节pH值是通过逐滴滴加碱液的方式进行调整，pH值为8-14。
4.根据权利要求1所述的介孔硅酸镁在COS催化水解反应中的应用，其特征在于：所述洗涤过程是用热去离子水进行多次洗涤，洗至pH值为7。
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