CN107138147B - 以介孔二氧化硅为硬模板制备高比表面二氧化锡催化剂的方法 - Google Patents
以介孔二氧化硅为硬模板制备高比表面二氧化锡催化剂的方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 18
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title abstract description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
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- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 6
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- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
一种以介孔二氧化硅为硬模板制备高比表面二氧化锡催化剂的方法。该催化剂采用微波法，辅以KCC‑1介孔二氧化硅为硬模板合成高比表面二氧化锡催化剂。在常压、反应气组成为500~1000 ppm甲苯，(20% ‑ 40% ) O2，N2平衡气，空速为20,000 mL/(g h)的条件下，以介孔二氧化硅为硬模板，由微波法合成的催化剂，甲苯转化的起始温度大幅度降低，其中SnO2‑KCC‑1‑Ultra‑OH催化剂在340℃时甲苯转化率可达98%。本发明利用微波法合成催化剂，步骤少，操作简单，大幅度缩短了合成时间，且所使用的各种原材料和溶剂均为环境友好型，因此具有实用价值。
Description
技术领域
本发明属于环境保护和大气污染治理领域，涉及一种消除易挥发有机物（VOCs）的催化剂。
技术背景
挥发性有机物污染主要包括室内与室外两类来源。室外来源主要是以石油产品为燃料的汽车、轮船和飞机等交通工具排放的尾气以及以煤、石油、天然气为燃料或原料的工业过程；室内来源主要是室内装修使用的油漆、添加剂或粘合剂等。室内挥发性有机物浓度过高或种类繁多会造成急性慢性中毒，严重影响身体健康；而室外挥发性有机物可导致温室效应，在光照下参与形成雾霾和光化学烟雾；大多数挥发性有机物易燃、易爆，且卤代挥发性有机物可加速大气臭氧层的消耗，造成臭氧层空洞。
目前，挥发性有机物的消除催化剂主要有负载型Pd、Pt等贵金属催化剂和非贵金属催化剂，如铜、锰、铬等金属氧化物。由于贵金属价格昂贵、资源短缺，因此发展廉价、高效、稳定的非贵金属氧化物催化剂，以减少贵金属用量或替代贵金属，得到更实用的环保催化剂成为此类催化剂的研究方向。
中国专利CN103978201公开了一种通过微波辅助对二氧化锡纳米棒进行纳米银修饰的方法，但是涉及的二氧化锡纳米棒不是微波法制备的。中国专利CN106058231公开了一种二氧化锡纳米晶嵌入三维中空碳球材料的制备方法，但是制备过程步骤繁琐，属于二次电池电极材料技术领域。中国专利CN106219597公开了一种介孔二氧化锡材料的制备方法，但是其制备过程复杂繁琐，而且会造成氧化铜资源的浪费并引起二次污染。中国专利CN10596722公开了一种二氧化锡纳米花的制备方法，但这种二氧化锡纳米花需要通过长达10-16小时的水热晶化时间。
发明内容
本发明的目的在于为制备高效催化挥发性有机物完全氧化的催化剂，提供一种简便、快速制备方法。该催化剂采用微波法，辅以KCC-1介孔二氧化硅为硬模板合成高比表面二氧化锡催化剂。普通沉淀法合成的二氧化锡多晶纳米颗粒活性很低，在450 ℃时甲苯转化率仅达70%。但是以介孔二氧化硅为硬模板，微波法合成的催化剂，甲苯转化的起始温度大幅度降低，其中SnO2-KCC-1-Ultra-OH催化剂在340 ℃时甲苯转化率可达98%。利用微波法合成催化剂，步骤少，操作简单，大幅度缩短了合成时间，且发明所使用的各种原材料和溶剂均为环境友好型，因此具有实用价值。
本发明特点在于使用KCC-1为硬模板，并辅以微波法快速合成高效的VOCs催化完全氧化催化剂。其比表面积达100~200 m2/g。
本发明所述的以介孔二氧化硅为硬模板制备高比表面二氧化锡催化剂的方法，其特征在于按如下步骤：
（1）按每1 g锡盐溶解于10~30 mL去离子水中的比例，将锡盐溶解或分散在去离子水中，混合均匀制得稳定的混合液；
（2）在连续磁力搅拌或超声处理作用下，按每10 g锡盐对应加入0.1-0.5g介孔二氧化硅的比例，向步骤（1）的混合液中加入介孔二氧化硅，持续搅拌或超声处理30~60 分钟，使之分散均匀；
（3）将步骤（2）的混合液转移至石英烧瓶中，在设定的500~1000 W微波功率，持续磁力搅拌或300~500 W超声功率下反应10~60分钟，使之反应完全后冷却至室温，利用去离子水离心洗涤沉淀物到洗出液TDS < 20，70~150℃干燥，400~600℃空气氛焙烧得到催化剂前体；
（4）在连续磁力搅拌的作用下，按每1 g催化剂前体对应20-60 mLNaOH溶液的比例，将步骤（3）中制得的催化剂前体分散于5-10 mol/L的NaOH溶液中，持续搅拌2 -8 小时。利用去离子水离心洗涤沉淀物到洗出液TDS < 20，70~150℃干燥得到成品催化剂粉末。
本发明所述的锡盐可以是四氯化锡、氯化亚锡或锡酸盐。
本发明所述的介孔二氧化硅硬模板是KCC-1。
本发明中的催化剂主要应用于常压，空速为20,000 mL/(g h)，反应气组成为500- 1000 ppm甲苯，(20%~40%) O2，N2平衡气，其中SnO2-KCC-1-Ultra-OH催化剂在340℃以下即可将甲苯转化完全，相较于普通沉淀法和普通微波法合成的二氧化锡纳米颗粒催化剂，完全转化温度降低了90 ℃以上。
本发明催化剂的特点是：
(1) 催化剂制备方法和步骤简单易行，合成时间短，材料来源广，成本低廉，适合规模化生产，且催化剂使用操作条件简单，具有工业化的前景。
(2) 催化剂氧化甲苯的起燃温度和完全燃烧温度较低，稳定性好，具有优良的实用价值。
附图说明
图1为以KCC-1为硬模板微波合成介孔高比表面二氧化锡用于甲苯催化氧化活性。
图2为本发明催化剂清除硅硬模板前的SEM照片。
图3为本发明催化剂清除硅硬模板后的SEM照片。
图4为本发明催化剂的N2吸附-脱附等温曲线。
具体实施方式
为了更清楚的说明本发明的内容，列举以下实施例，但其对本发明的范围无任何限制。
实施例1。
将20 g SnCl4·5H2O溶于400 mL去离子水中，搅拌30 分钟。随后加入0.5 g KCC-1介孔二氧化硅，继续搅拌30分钟。将上述混合液转移至石英烧瓶中，在微波功率800 W、搅拌速率600 r/min的条件下反应30 分钟。利用去离子水离心洗涤沉淀物到洗出液TDS < 20，110 ℃干燥，450 ℃空气氛焙烧4 小时，制得SnO2-KCC-1-Stir催化剂。测得催化剂比表面积为352 m2/g。
实施例2。
将20 g SnCl4·5H2O溶于400 mL去离子水中，搅拌30 分钟。随后加入0.5 g KCC-1介孔二氧化硅，超声波处理30分钟。将上述混合液转移至石英烧瓶中，在微波功率800 W、超声功率500 W的条件下反应30 分钟。利用去离子水离心洗涤沉淀物到洗出液TDS < 20，110℃干燥，450 ℃空气氛焙烧4 小时，制得SnO2-KCC-1-Ultra催化剂。测得催化剂比表面积为135 m2/g。
实施例3。
取1 g催化剂1加入适量10 mol/L NaOH溶液中，在连续磁力搅拌的条件下，70℃水浴5 h。利用去离子水离心洗涤沉淀物到洗出液TDS < 20，110 ℃干燥，制得SnO2-KCC-1-Stir-OH催化剂。测得催化剂比表面积为146 m2/g。
实施例4。
取1 g催化剂2加入10 mol/L NaOH溶液中，在连续磁力搅拌的条件下，70℃水浴5h。利用去离子水离心洗涤沉淀物到洗出液TDS<20，110℃干燥，制得SnO2-KCC-1-Ultra-OH催化剂。测得催化剂比表面积为108 m2/g。
实施例5。
将20 g SnCl4·5H2O溶于400 mL去离子水中，搅拌30 分钟。将上述混合液转移至石英烧瓶中，在微波功率800 W、超声功率500 W的条件下反应30 分钟。利用去离子水离心洗涤沉淀物到洗出液TDS < 20，110 ℃干燥，450 ℃空气氛焙烧4 小时，制得SnO2-microwave催化剂。测得催化剂比表面积为56 m2/g。
实施例6。
将1.05 g SnCl4·5H2O溶于10 g去离子水中，搅拌30 分钟。随后将SnCl4溶液逐滴加入到30 mL的1.08 mol/L NaOH溶液中，至pH约为9，继续搅拌30分钟，将混合溶液静置陈化2小时。利用去离子水离心洗涤沉淀物到洗出液TDS < 20，110 ℃干燥，450 ℃空气氛焙烧4 h，制得未改良的二氧化锡纳米颗粒SnO2-precipitation催化剂，测得其比表面积为56m2/g。
催化VOCs反应实施实例。
实例1-6(实施例1-6中的催化剂)。
取30 mg的催化剂1-5置于内径6 mm的石英管反应器中，通入1000 ppm甲苯, (20%~40%) O2, N2平衡气，空速为20,000 mL/(g h),结果列于图1。
活性测试如图可见，在常压、反应气组成为1000 ppm甲苯, 40% O2, N2平衡气，空速为20,000 mL/(g h) 的条件下，普通沉淀法的SnO2纳米颗粒活性较低，在450℃时甲苯转化率只有70%。但是以KCC-1为硬模板，微波合成的二氧化锡催化剂，甲苯转化的起始温度大幅度降低，其中SnO2-KCC-1-Ultra-OH催化剂在340℃时即可将甲苯转化完全。
Claims (2)
1.一种以介孔二氧化硅为硬模板制备的高比表面积二氧化锡催化剂在甲苯催化燃烧中的应用，其特征是所述的催化剂按如下步骤制备：
（1）按每1 g锡盐溶解于10~30 mL去离子水中的比例，将锡盐溶解或分散在去离子水中，混合均匀制得稳定的混合液；
（2）在连续磁力搅拌或超声处理作用下，按每10 g锡盐对应加入0.1-0.5g介孔二氧化硅的比例，向步骤（1）的混合液中加入介孔KCC-1二氧化硅硬模板，持续搅拌或超声处理30~60 分钟，使之分散均匀；
（3）将步骤（2）的混合液转移至石英烧瓶中，在设定的500~1000 W微波功率，持续磁力搅拌或300~500 W超声功率下反应10~60分钟，使之反应完全后冷却至室温，利用去离子水离心洗涤沉淀物到洗出液TDS < 20，70~150℃干燥，400~600℃空气氛焙烧得到催化剂前体；
（4）在连续磁力搅拌的作用下，按每1 g催化剂前体对应20-60 mLNaOH溶液的比例，将步骤（3）中制得的催化剂前体分散于5-10 mol/L的NaOH溶液中，持续搅拌2 -8 小时；利用去离子水离心洗涤沉淀物到洗出液TDS < 20，70~150℃干燥得到成品催化剂粉末。
2.根据权利要求1所述的应用，其特征是所述的锡盐是四氯化锡、氯化亚锡或锡酸盐。
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