CN105854890B - VOCs热催化剂及其制备方法 - Google Patents
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Abstract
本发明属于工业催化领域,具体涉及VOCs催化剂及其制备方法。首先,以FeSO4·7H2O和Na2SnO3·4H2O为原料,利用离子交换法合成(FeSnO(OH)5)微纳材料,将微纳材料在空气气氛下煅烧制备出(Fe‑Sn‑O)非晶态热催化剂;或者将(FeSnO(OH)5)微纳材料利用浸渍法在其表面负载Pt纳米颗粒,最后将样品在空气气氛下煅烧制备出Pt/(Fe‑Sn‑O)复合热催化剂。在离子交换反应时,通过控制不同溶液的滴加顺序与速度,使得原料同时沉淀,制得的载体组分分布均匀,尺寸均一,形貌良好,为后期载铂提供良好载体,从而制得催化效率高的热催化剂。
Description
技术领域
本发明属于工业催化领域,具体涉及VOCs热催化剂及其制备方法。
背景技术
随着城乡一体化进程的不断推进,人民生活质量不断提高,更多的人开始密切关注身边居住环境中的空气质量问题。众所周知,空气是人类赖以生存的重要外界环境之一,据不完全统计人的一生大约需要吸入约 700 万升空气,那么对于人们吸入的空气质量就必须要有所保障,否则吸入过多恶质空气必将对人的身体产生重大伤害。据有关调查报告指出,现代人的生活工作超过 87%的时间待在室内空间,人体与室内空气的热量与质量交换时刻都在进行。早在20世纪初,人类就发明了房间空调器用于控制室内空气的温度和湿度以改善舒适性,然而对室内空气中有害成分的研究和控制直到最近几十年才逐渐开展起来。一项对国外近六十年来室内空气污染物成分的研究表明,挥发性有机化合物(VOCs)是室内空气中的主要污染物之一,且室内VOCs的种类随着各种新化学物质的使用日益增多。目前常见的室内VOCs主要有苯、甲苯、二甲苯、氯苯、甲醛等一些有毒物质。并且相关研究人员通过研究发现室内空气中的VOC 过量可引起病态建筑综合症(Sick BuildingSyndrome,简称 SBS),即当人暴露在这样的环境中时,可能会产生眼鼻喉刺激、头痛、头晕、昏睡、精神不集中、恶心、胸闷等不适症状,而离开该环境以后,这些症状会缓解或消失;还有一些医学专业研究人员从病理学角度解释了VOCs与病态建筑综合症之间的相关性;世界卫生组织(WHO)的研究报告表明,长期暴露在含甲醛、苯等高危害性VOCs成分的空气中,可能会导致癌症、白血病等恶性疾病的产生;另有研究显示,保持良好的室内空气品质可以提高人们的工作效率:美国研究人员对通过改善空气品质提高生产率的潜力进行了评估,结果显示仅通过减少病态建筑综合症一项,就可给美国节约 150-380 亿美元/年。因此,如何处理好这些对人体有害的VOCs物质就显得十分重要。当前,国内外都在对利用热催化技术处理VOC物质的相关领域进行广泛深入的研究。热催化作为两种催化氧化技术常用于处理高温的工业废气和汽车尾气。而近几年的研究发现,通过对材料的掺杂改性,可使热催化材料具有在低温下有效降解甲醛而无需输入额外能量的特点,且未发现有害副产物。目前绝大多数的热催化材料一般以金属氧化物(如TiO2, γ-Al2O3, SnO2等)和氮化物(如BN)为载体,并在载体表面载上约 1.0%的贵金属(如Pt、Pd等)作为主要活性成分来提高热催化活性。Lin Chih-An等人利用浸渍法在六方BN表面上负载0.37%Pt研究发现Pt/BN在热催化氧化降解苯方面表现出了比γ-Al2O3更为优异的热催化活性,高活性温度大致在140-170℃之间,且在185℃高活性稳定性优异能达到80h,同时作者还指出γ-Al2O3高活性稳定性会随着时间的延长而逐渐下降即γ-Al2O3高活性稳定性不好。Li Zenghe等人研究表明Pt/ TiO2同样在热催化氧化降解苯方面表现出了优异的热催化活性,并且最优的苯降解转化率接近100%时对应的温度为160℃。Hashimoto Yoshihito等人实验结果表明γ-Al2O3在热催化降解氯苯等物质时表现出了优良的高活性,但却存在催化剂失活-复活转变现象,即γ-Al2O3存在催化活性不稳定的缺点。目前大部分热催化载体研究之所以较为局限的选用金属氧化物和氮化物作为载体,主要是由于这两大类物资本身热稳定性好,在高温下不会受热分解且能起到较好的热催化活性,从而得到广泛研究关注。虽然这些热催化剂已在较高端的甲醛净化产品中得到应用,但目前尚难以在低温下降解除甲醛以外的VOCs,如苯,甲苯等。拓宽热催化剂载体的范围,制备出新型载铂催化剂可以有助于降低VOCs的降解温度,具有重要的研究意义和实用价值。非晶态材料具有短程有序、各向同性的特点,对热催化降解如苯、甲苯等难降解的VOC物质能起到意想不到的优良效果。
发明内容
本发明的目的在于针对现有技术的不足,提供一类新型VOCs催化剂及其制备方法。本发明通过控制不同溶液的滴加顺序与速度,使得原料同时沉淀,制得的载体组分分布均匀,尺寸均一,形貌良好,为后期载铂提供良好载体,从而制得催化效率高的载铂热催化剂。
为实现上述目的,本发明采用如下技术方案:
一种(Fe-Sn-O)非晶态热催化剂:以FeSO4·7H2O和Na2SnO3·4H2O为原料,利用离子交换法合成(FeSnO(OH)5)微纳材料,将微纳材料在空气气氛下煅烧制备出 (Fe-Sn-O)非晶态热催化剂。
所述的(Fe-Sn-O)非晶态热催化剂的方法,包括以下步骤: (1)离子交换反应:将FeSO4·7H2O固体粉末溶于去离子水中配成溶液A;再将Na2SnO3·4H2O固体粉末溶于去离子水中配成溶液B;然后将溶液B逐滴加入溶液A中,并将混合液置于温度为0℃的水浴环境中搅拌5h,搅拌速度为400~600 rpm,制得沉淀物;
(2)沉淀产物的清洗和干燥:将步骤(1)制得的沉淀物用去离子水和乙醇离心清洗各3次,放入干燥箱中干燥;
(3)样品研磨:将步骤(2)干燥后的样品研磨成粉末,制得前躯体(FeSnO(OH)5)微纳材料粉末;
(4)将(FeSnO(OH)5)粉末在空气气氛下400℃煅烧2h制备出(Fe-Sn-O) 非晶态热催化剂。
具体的,步骤(1)中FeSO4·7H2O和Na2SnO3·4H2O的摩尔比为1:1;溶液A的浓度为0.1 mmol/mL,溶液B的浓度为0.5 mmol/mL。
具体的,步骤(2)所述的离心清洗速度为6000~8000 rpm,离心后干燥温度为70℃,干燥时间为12h。
一种Pt/ (Fe-Sn-O)复合热催化剂:以FeSO4·7H2O和Na2SnO3·4H2O为原料,利用离子交换法合成(FeSnO(OH)5)微纳材料,再利用浸渍法在其表面负载Pt纳米颗粒,最后将样品在空气气氛下煅烧制备出Pt/ (Fe-Sn-O)复合热催化剂。
一种制备如上所述的Pt/ (Fe-Sn-O)复合热催化剂的方法,包括以下步骤:
(1)前躯体(FeSnO(OH)5)微纳材料粉末的制备;
(2)用移液枪移取氯铂酸加到冰水里,制得氯铂酸水溶液;再将抗坏血酸水溶液缓慢加入到氯铂酸水溶液中,制得混合溶液;然后取步骤(1)的FeSnO(OH)5粉末加入到混合溶液中,搅拌10min,超声1h,浸渍24h,制得的沉淀物用去离子水和乙醇离心清洗各3次,放入干燥箱中干燥;
(3)将步骤(2)的样品在空气气氛下400℃煅烧2h制备出Pt/ (Fe-Sn-O)热催化剂。
具体的,步骤(2)中氯铂酸水溶液的浓度为0.019 mol/L,用量为0.665ml;抗坏血酸溶液的浓度为0.1mol/L,用量为10ml。
具体的,步骤(2)所述的离心清洗速度为6000~8000 rpm,离心后干燥温度为70℃,干燥时间为12h。
具体的,步骤(3)中所制得的复合热催化剂中,Pt的负载量为0.25~1 wt%。
本发明的有益效果在于:
(1)本发明所用的原料丰富,绿色环保,价格低廉,降低了热催化剂的生产成本;所采用的工艺和设备简单,易于实施,操作简便,制备过程没有有害气体产生;而且在热催化剂的制备过程中通过控制溶液A、B滴加顺序与速度,使得原料同时沉淀,制得的载体组分分布均匀,尺寸均一,形貌良好,为后期载铂提供良好载体,从而制得催化效率高的热催化剂;
(2)所制得的(Fe-Sn-O)非晶态热催化剂颗粒粒径为20nm左右,在催化剂 (Fe-Sn-O)用量为0.1g、苯气流速为180mL/min的条件下测试得到催化燃烧降解苯的起燃温度(转化率为50%时所对应的温度)为295℃,高活性温度(转化率为90%时所对应的温度)为345℃;
(3)所制得的Pt/ (Fe-Sn-O)复合热催化剂颗粒粒径为20nm左右,在催化剂Pt/(Fe-Sn-O)用量为0.1g、苯气流速为180mL/min的条件下测试得到催化燃烧降解苯的起燃温度(转化率为50%时所对应的温度)为125℃,高活性温度(转化率为90%时所对应的温度)为149℃。上述结果表明通过本方法制备出了催化性能比工业催化领域常用的Pt/γ-Al2O3更为优异、高效的催化剂。
附图说明
图1是实施例1-2制备的热催化剂的XRD测试照片;
图2是实施例1制备的热催化剂的扫描电镜照片;
图3是实施例2制备的热催化剂的扫描电镜照片;
图4是实施例1、对比例1制备的热催化剂的催化燃烧降解苯的性能测试照片;
图5是实施例2、对比例2制备的热催化剂的催化燃烧降解苯的性能测试照片;
图6是实施例2制备热催化剂的催化燃烧降解苯的稳定性测试照片。
具体实施方式
本发明用下列实施例来进一步说明本发明,但本发明的保护范围并不限于下列实施例。
实施例1
热催化剂化学式:(Fe-Sn-O),其制备过程包括以下步骤:
(一)前躯体(FeSnO(OH)5)的合成
(1)备料:称取10 mmol FeSO4·7H2O和10 mmol Na2SnO3·4H2O固体粉末;
(2)离子交换反应:将称取好的FeSO4·7H2O固体粉末溶于100 mL去离子水中配成溶液A;再将称取好的Na2SnO3·4H2O固体粉末溶于20 mL去离子水中配成溶液B;然后将溶液B逐滴加入溶液A中,并将混合液置于温度为0℃的水浴环境中搅拌5h,搅拌速度为500 rpm,制得沉淀物;
(3)沉淀产物的清洗和干燥:将步骤(2)制得的沉淀物用去离子水和乙醇(分析纯)离心清洗各3次,放入干燥箱中干燥;
(4)样品研磨:将步骤(3)干燥后的样品研磨成粉末,制得前躯体(FeSnO(OH)5)粉末;
(二)(Fe-Sn-O)非晶态热催化剂的合成
将前躯体(FeSnO(OH)5)样品在空气气氛下400℃煅烧2h制备出(Fe-Sn-O) 非晶态热催化剂。
所制得的(Fe-Sn-O)非晶态热催化剂颗粒粒径为20nm左右,在催化剂 (Fe-Sn-O)用量为0.1g、苯气流速为180mL/min的条件下测试得到催化燃烧降解苯的起燃温度(转化率为50%时所对应的温度)为295℃,高活性温度(转化率为90%时所对应的温度)为345℃。
实施例2
热催化剂化学式:Pt/ (Fe-Sn-O),其制备过程包括以下步骤:
(一)前躯体(FeSnO(OH)5)的合成
(1)备料:称取10 mmol FeSO4·7H2O和10 mmol Na2SnO3·4H2O固体粉末;
(2)离子交换反应:将称取好的FeSO4·7H2O固体粉末溶于100 mL去离子水中配成溶液A;再将称取好的Na2SnO3·4H2O固体粉末溶于20 mL去离子水中配成溶液B;然后将溶液B逐滴加入溶液A中,并将混合液置于温度为0℃的水浴环境中搅拌5h,搅拌速度为400 rpm,制得沉淀物;
(3)沉淀产物的清洗和干燥:将步骤(2)制得的沉淀物用去离子水和乙醇(分析纯)离心清洗各3次,放入干燥箱中干燥;
(4)样品研磨:将步骤(3)干燥后的样品研磨成粉末,制得前躯体(FeSnO(OH)5)粉末。
(二)Pt/ (Fe-Sn-O)复合热催化剂的合成
利用浸渍法制得载铂(Pt)0.5wt% 的复合热催化剂(Pt/ (Fe-Sn-O)),即用移液枪将0.665 ml的0.019 mol/L的氯铂酸(H2PtCl6·6H2O)加到10 ml冰水里搅拌;再取10 ml,0.1 mol/L的抗坏血酸(C6H8O6)冰水,缓慢加入到上述溶液;然后再取0.5g FeSnO(OH)5粉末加入上述混合溶液,搅拌10 min,超声1 h,浸渍24 h,制得的沉淀物用去离子水和分析乙醇离心清洗各3次,放入干燥箱中干燥。最后将样品在空气气氛下400℃煅烧2h制备出Pt/(Fe-Sn-O)热催化剂。
温度为0℃的水浴环境中所得到的催化剂载体颗粒平均粒径为20nm,在催化剂Pt/(Fe-Sn-O)用量为0.1g、苯气流速为180mL/min的条件下测试得到催化燃烧降解苯的起燃温度(转化率为50%时所对应的温度)为125℃;高活性温度(转化率为90%时所对应的温度)为149℃;完全转化温度(转化率为100%时所对应的温度)为178℃;稳定性可达80h。
对比例1
热催化剂化学式:γ-Al2O3,其制备过程包括以下步骤:
备料:直接从山东铝业公司购买商业γ-Al2O3;
商业γ-Al2O3所得到的催化剂载体颗粒平均粒径为400 nm,在催化剂γ-Al2O3用量为0.1 g、苯气流速为180 mL/min的条件下测试得到催化燃烧降解苯的起燃温度(转化率为50%时所对应的温度)为345 ℃;高活性温度(转化率为90%时所对应的温度)为420 ℃。
对比例2
热催化剂化学式:Pt/γ-Al2O3,其制备过程包括以下步骤:
(一)载体(γ-Al2O3)的合成
(1)备料:直接从山东铝业公司购买商业γ-Al2O3;
(二)复合热催化剂(Pt/γ-Al2O3)的合成
利用浸渍法制得载铂(Pt)0.5 wt% 的复合热催化剂(Pt/γ-Al2O3),即用移液枪将0.665 ml的0.019 mol/L的氯铂酸(H2PtCl6·6H2O)加到10 mL冰水里搅拌;再取10 ml,0.1mol/L的抗坏血酸(C6H8O6)冰水,缓慢加入到上述溶液;然后再取0.5 g γ-Al2O3粉末加入上述混合溶液,搅拌10 min,超声1 h,浸渍24 h,制得的沉淀物用去离子水和分析乙醇离心清洗各3次,放入干燥箱中干燥。
所得到的Pt/γ-Al2O3催化剂载体颗粒平均粒径为400 nm,在催化剂Pt/γ-Al2O3用量为0.1 g、苯气流速为180 mL/min的条件下测试得到催化燃烧降解苯的起燃温度(转化率为50%时所对应的温度)为155 ℃;高活性温度(转化率为90%时所对应的温度)为167 ℃;完全转化温度(转化率为100%时所对应的温度)为180 ℃。
由实施例1的结果与对比例1的结果对比可知,当载体合成温度为0℃时,所制得的(Fe-Sn-O)非晶态热催化剂的催化活性与对比例1的γ-Al2O3样品相比催化活性有明显的提高。同样,由实施例2的结果与对比例2的结果对比可知,当载体合成温度为0℃时,所制得的Pt/ (Fe-Sn-O)复合热催化剂的催化活性与对比例1的Pt/γ-Al2O3样品相比催化活性也有明显的提高。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (8)
1.一种制备Fe-Sn-O非晶态热催化剂的方法,其特征在于:包括以下步骤:
(1)离子交换反应:将FeSO4·7H2O固体粉末溶于去离子水中配成溶液A;再将Na2SnO3·4H2O固体粉末溶于去离子水中配成溶液B;然后将溶液B逐滴加入溶液A中,并将混合液置于温度为0℃的水浴环境中搅拌5h,搅拌速度为400~600 rpm,制得沉淀物;
(2)沉淀产物的清洗和干燥:将步骤(1)制得的沉淀物用去离子水和乙醇离心清洗各3次,放入干燥箱中干燥;
(3)样品研磨:将步骤(2)干燥后的样品研磨成粉末,制得前躯体FeSnO(OH)5微纳材料粉末;
(4)将FeSnO(OH)5粉末在空气气氛下400℃煅烧2h制备出(Fe-Sn-O) 非晶态热催化剂。
2.根据权利要求1所述的制备方法,其特征在于:步骤(1)中FeSO4·7H2O和Na2SnO3·4H2O的摩尔比为1:1;溶液A的浓度为0.1 mmol/mL,溶液B的浓度为0.5 mmol/mL。
3.根据权利要求1所述的制备方法,其特征在于:步骤(2)所述的离心清洗速度为6000~8000 rpm,离心后干燥温度为70℃,干燥时间为12h。
4.一种Pt/ Fe-Sn-O复合热催化剂,其特征在于:以FeSO4·7H2O和Na2SnO3·4H2O为原料,利用离子交换法合成FeSnO(OH)5微纳材料,再利用浸渍法在其表面负载Pt纳米颗粒,最后将样品在空气气氛下煅烧制备出Pt/ Fe-Sn-O复合热催化剂。
5.一种制备如权利要求4所述的Pt/ Fe-Sn-O复合热催化剂的方法,其特征在于:包括以下步骤:
(1)前躯体FeSnO(OH)5微纳材料粉末的制备;
(2)用移液枪移取氯铂酸加到冰水里,制得氯铂酸水溶液;再将抗坏血酸水溶液缓慢加入到氯铂酸水溶液中,制得混合溶液;然后取步骤(1)的FeSnO(OH)5粉末加入到混合溶液中,搅拌10min,超声1h,浸渍24h,制得的沉淀物用去离子水和乙醇离心清洗各3次,放入干燥箱中干燥;
(3)将步骤(2)的样品在空气气氛下400℃煅烧2h制备出Pt/ Fe-Sn-O热催化剂。
6.根据权利要求5所述的制备方法,其特征在于:步骤(2)中氯铂酸水溶液的浓度为0.019 mol/L,用量为0.665ml;抗坏血酸溶液的浓度为0.1mol/L,用量为10ml。
7.根据权利要求5所述的制备方法,其特征在于:步骤(2)所述的离心清洗速度为6000~8000 rpm,离心后干燥温度为70℃,干燥时间为12h。
8.根据权利要求5所述的制备方法,其特征在于:步骤(3)中所制得的复合热催化剂中,Pt的负载量为0.25~1 wt%。
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