CN108114712B - 一种Pt/TiO2整体式氧化催化剂制备方法 - Google Patents
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Abstract
本发明公开了一种Pt/TiO2整体式氧化催化剂的制备方法,通过将无水乙醇和去离子水混合并加入酸调解pH值,置于恒温水浴中搅拌成混合溶液,再滴入钛酸四丁酯,搅拌得到TiO2分散液,再加入氯铂酸,边搅拌边滴加硼氢化钠或水合肼溶液,再加去离子水定容后即得Pt/TiO2分散液;再将Pt/TiO2分散液在任意整体材质的基体上通过简单的喷洒制得整体式催化剂。本方法制备简单、活性组分不易团聚且与载体结合能力强,并且在保持性能的情况下贵金属Pt用量少,可削减催化剂工业化生产的成本,应用潜力巨大。
Description
技术领域
本发明涉及催化剂技术领域,特别涉及用于挥发性有机废气 (VOCs)治理的Pt/TiO2整体式催化剂的制备方法。
背景技术
随着经济的快速发展及工业化进程加快,排放到空气中的挥发性有机化合物(volatile organic compounds,简称VOCs)迅速增加,成为当今主要的大气污染物之一。VOCs来源十分广泛,主要有石油化工、皮革合成、涂料、烤漆、印刷、制药、电子、汽车尾气等行业生产过程。除了各种工业废气、汽车尾气的排放使得空气质量恶化外,室内空气的安全问题也备受关注,尤其是新装修的房屋中存在大量的挥发性有机物(如甲醛、苯、二甲苯等),必须通过较长时间的通风换气后方可入住,而因室内装修导致的室内空气污染致使人们健康受到危害的报道已屡见不鲜。因此VOCs的治理已成为我国大气污染防治工作的重点。
目前,VOCs主要治理方法有吸附、冷凝、直接燃烧、催化燃烧、生物处理等。如中国专利(CN106540754 A,CN106064087 A等)所述催化燃烧法具有净化效率高、无二次污染、能耗低、工艺简单、使用范围广等特点,为VOCs的治理提供了独特经济的解决办法,成为当前有机废气治理研究及应用的主流。
研究表明,Pt纳米粒子是优良的VOCs催化氧化与燃烧催化剂。贺泓等(科学通报,2009,54(3):279)首次报道了1%Pt/TiO2催化剂能在室温下完全氧化甲醛。Zhang(Chem.Eng.J.,2017,334:12) 报道了使用HPMOR分子筛负载1%Pt的催化剂时,甲苯催化燃烧T90为190℃。但Pt价格昂贵,属于稀缺资源,因此寻找一种能减少催化剂中Pt用量且保持催化剂高活性的制备方法一直是研究的重点 (Chen et al.,Chem.Rev.,2010,110:3784)。
另外,在工业废气治理中多采用整体式催化剂,目前常用堇青石蜂窝陶瓷作为整体式基体,整体式催化剂具体制备流程为:先在整体式基体上涂覆氧化物涂层,再通过涂覆或浸渍负载贵金属Pt活性组分,活化后制得整体式催化剂,或将制得的粉末催化剂配成浆料直接涂覆在基体上,再经活化处理后得到整体式催化剂。整个技术路线较为复杂,且制得的催化剂其表面活性组分易团聚,且在载体表面的牢固度不高,并且受工艺限制,载体需具备一定规则的形状。现有的整体式催化剂制备方法局限性较大,不够灵活。因此如何在不同材质和结构的基体上迅速并牢固的负载上催化剂也一直是一个难点。
发明内容
针对现有技术存在的不足,本发明的目的在于提供一种Pt/TiO2整体式氧化催化剂的制备方法。利用所述方法可以在任意整体材质的基体上通过简单的喷洒制得整体式催化剂。本方法制备简单、活性组分不易团聚且与载体结合能力强,并且在保持性能的情况下贵金属 Pt用量少,可削减催化剂工业化生产的成本,应用潜力巨大。
为达此目的,本发明采用以下技术方案:
本发明的目的是提供一种Pt/TiO2整体式催化剂的制备方法,所述制备方法包括如下步骤:
(1)将无水乙醇和去离子水以体积比1~5:1混合并加入酸调节 pH为1~5,置于恒温水浴中搅拌成混合溶液;
(2)将钛酸四丁酯滴加至步骤(1)的混合溶液中,在室温~90℃ (优选室温~60℃)下搅拌1~7h,得到TiO2分散液;所述的钛酸四丁酯与步骤(1)所述的去离子水体积比为1:1~5;
(3)在步骤(2)所得的TiO2分散液中加入氯铂酸,边搅拌边滴加硼氢化钠或水合肼溶液,随后在室温~90℃(优选室温~60℃)下搅拌3~12h;再加去离子水定容后得到TiO2质量含量为0.5~3%的 Pt/TiO2分散液;所得Pt/TiO2分散液中铂质量含量为TiO2质量含量的 0.1~1%;所述Pt/TiO2分散液中理论TiO2物质的量与步骤(2)所加入的钛酸四丁酯的物质的量相等,所述氯铂酸加入的物质的量与所述 Pt/TiO2分散液中理论铂的物质的量相等;所述的硼氢化钠或水合肼与氯铂酸物质的量比为0.5~5:1;
(4)取步骤(3)所得Pt/TiO2分散液在整体式基体上进行均匀喷洒,干燥后即得Pt/TiO2整体式催化剂。
在本发明中所得Pt/TiO2分散液中,步骤(2)加入的钛酸四丁酯中的钛元素均以TiO2形式存在,即所述Pt/TiO2分散液中理论TiO2物质的量与步骤(2)所加入的钛酸四丁酯的物质的量相等,这是本领域技术人员公知的现有技术,现有文献[李建业,杨建伟,姜绍龙, 等.低温水热纳米二氧化钛分散液制备工艺探索研究[J].山东化工, 2017,46(14):24-27.]、[张烨,许宝奎.锐钛矿型二氧化钛溶胶的低温制备及其在棉织物上的应用[J].科技风,2015(4):96-96.]等均有报道,本发明实施例中也有数据证明。
优选地,步骤(1)所述酸可为有机酸或无机酸,如甲酸,乙酸,盐酸,硝酸,硫酸等中的一种或多种。
步骤(3)中加去离子水定容量根据所要制备的Pt/TiO2分散液的 TiO2质量含量确定。Pt/TiO2分散液中的TiO2质量含量根据实际情况按需求确定,通常TiO2质量含量为0.5~3%。以上含量皆为质量分数。
步骤(3)中氯铂酸的加入量根据Pt/TiO2分散液中的铂含量确定 (元素守恒,加入的氯铂酸的铂元素物质的量等于Pt/TiO2分散液所含铂元素的物质的量,即所述氯铂酸加入的物质的量与所得Pt/TiO2分散液中理论铂的物质的量相等),Pt/TiO2分散液中的铂含量根据实际情况按需求确定,通常Pt/TiO2分散液中铂含量为TiO2含量的 0.1~1%。以上含量皆为质量分数。
步骤(4)中Pt/TiO2分散液喷洒量根据所要制备的Pt/TiO2整体式催化剂的负载量确定。通常,Pt/TiO2整体式催化剂中Pt与TiO2的总负载量为1~10%。
步骤(4)中所述的整体式基体可以为任意材质和结构,本发明推荐为堇青石蜂窝陶瓷、泡沫碳化硅、泡沫氧化铝。
进一步,为获得Pt/TiO2整体式催化剂更优活性,可将干燥后的催化剂于300~800℃下焙烧1~5h。
进一步,所得Pt/TiO2分散液中TiO2质量含量优选为0.8~2.4%。
进一步,所得Pt/TiO2分散液中铂质量含量优选为TiO2质量含量的0.12~0.6%。
进一步,步骤(1)中所述无水乙醇和去离子水的体积比优选为 1~3:1。
进一步,所述的钛酸四丁酯与步骤(1)所述的去离子水体积比优选为1:1~3。
进一步,所述的硼氢化钠或水合肼物质的量用量优选为氯铂酸物质的量的1~3倍。
本发明提供的方法与以往整体式制备方法相比操作简单灵活。首先制备高活性的Pt/TiO2分散液,然后通过喷洒把活性纳米粒子直接负载到基体表面,烘干后即可得到Pt/TiO2整体式催化剂。本发明有益效果主要体现在:(1)对基体的形状大小以及材质理论上没有任何要求,适用范围广;(2)活性组分以纳米分散液的形式存在便于保存,通过喷洒可在基体表面高度分散,因此催化剂在低Pt含量的情况下也能表现出高活性;(3)催化剂失活后可通过再次喷洒恢复活性,非常容易实现再生,具有相当大的应用潜力;(4)整个制备过程无废水产生,且无需进一步焙烧活化也可得到性能良好的催化剂,整个过程可在低温下进行,能耗低,符合节能减排的要求。
附图说明
图1是实施例1制得的Pt/TiO2分散液XRD图。
具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此。
实施例1
按1:1的体积比例混合无水乙醇(10ml)和去离子水(10ml) 于室温下搅拌,加入甲酸,使pH=2,随后滴加与去离子水等体积的钛酸四丁酯(10ml),室温下搅拌7h,加入0.006g无水氯铂酸,边搅拌边滴加与氯铂酸等摩尔量的水合肼,随后在室温下搅拌12h,反应结束,将获得的溶液定容100ml,最终得到TiO2质量浓度为2.4%的Pt/TiO2分散液,其中Pt含量为TiO2含量的0.12%。
上述制得的Pt/TiO2分散液的XRD见图1,均为锐钛矿TiO2晶相,无其他杂相;将分散液烘干,得到3.281g固体,焙烧掉表面有机物后固体量为2.378g。以上数据可证明分散液中钛元素以TiO2的形式存在。
实施例2
与实施例1分散液制备过程相同,不同之处为调节pH=3,最终得到TiO2质量浓度为2.4%的Pt/TiO2分散液,其中Pt含量为TiO2含量的0.12%。
实施例3
与实施例1分散液制备过程相同,不同之处为加入钛酸四丁酯后于60℃搅拌1h,最终得到TiO2质量浓度为2.4%的Pt/TiO2分散液,其中Pt含量为TiO2含量的0.12%。
实施例4
与实施例1分散液制备过程相同,不同之处为水合肼改为硼氢化钠,最终得到TiO2质量浓度为2.4%的Pt/TiO2分散液,其中Pt含量为TiO2含量的0.12%。
实施例5
与实施例1分散液制备过程相同,不同之处为加入水合肼后于 60℃下搅拌3h,最终得到TiO2质量浓度为2.4%的Pt/TiO2分散液,其中Pt含量为TiO2含量的0.12%。
实施例6
与实施例1分散液制备过程相同,不同之处为加入1/3去离子水体积的钛酸四丁酯(3.3ml),最终得到TiO2质量浓度为0.8%的 Pt/TiO2分散液,其中Pt含量为TiO2含量的0.36%。
实施例7
与实施例1分散液制备过程相同,不同之处为加入乙酸,最终得到TiO2质量浓度为2.4%的Pt/TiO2分散液,其中Pt含量为TiO2含量的0.12%。
实施例8
与实施例1分散液制备过程相同,不同之处为加入盐酸,最终得到质量浓度为2.4%的Pt/TiO2分散液,其中Pt含量为TiO2含量的 0.12%。
实施例9
与实施例1分散液制备过程相同,不同之处为加入硝酸,最终得到TiO2质量浓度为2.4%的Pt/TiO2分散液,其中Pt含量为TiO2含量的0.12%。
实施例10
与实施例1分散液制备过程相同,不同之处为加入硫酸,最终得到TiO2质量浓度为2.4%的Pt/TiO2分散液,其中Pt含量为TiO2含量的0.12%。
实施例11
按3:1的体积比例混合无水乙醇(30ml)和去离子水(10ml) 于室温下搅拌,加入乙酸,使pH=2,随后滴加1/3去离子水等体积的钛酸四丁酯(3.3ml),室温下搅拌7h,加入0.01g氯铂酸,边搅拌边滴加与3倍氯铂酸摩尔量的水合肼,随后在室温下搅拌12h,反应结束,将获得的溶液定容50ml,最终得到TiO2质量浓度为1.6%的Pt/TiO2分散液,其中Pt含量为TiO2含量的的0.6%。
实施例12
Pt/TiO2分散液制备如实施例11,各取10ml Pt/TiO2分散液分别喷洒在堇青石蜂窝陶瓷、泡沫碳化硅、泡沫氧化铝基体(约8g)上,干燥后,得到不同基体的总负载量为2%的Pt/TiO2整体式催化剂。
实施例13
将实施例12制备的各整体式催化剂用于甲苯催化燃烧性能测试:进料浓度为2000ppm,反应空速为2000h-1。各催化剂在260℃时甲苯可完全燃烧。
实施例14
将实施例12制备的各整体式催化剂焙烧后(300℃5h,500℃1 h)用于甲苯催化燃烧性能测试:进料浓度为2000ppm,反应空速为2000h-1。各焙烧条件下的各催化剂甲苯均能在230℃时完全燃烧。
实施例15
将实施例12制备的各整体式催化剂400℃焙烧3h后用于甲醛催化氧化性能测试:进料浓度为1.5ppm,反应空速为2000h-1。各催化剂室温条件下甲醛转化率可达95%以上。
Claims (10)
1.一种Pt/TiO2整体式催化剂的制备方法,其特征在于所述制备方法包括如下步骤:
(1)将无水乙醇和去离子水以体积比1~5:1混合并加入酸调解pH为1~5,置于恒温水浴中搅拌成混合溶液;
(2)将钛酸四丁酯滴加至步骤(1)所得的混合溶液中,在室温~90℃下搅拌1~7h,得到TiO2分散液;所述的钛酸四丁酯与步骤(1)所述的去离子水体积比为1:1~5;
(3)在步骤(2)所得的TiO2分散液中加入氯铂酸,边搅拌边滴加硼氢化钠或水合肼溶液,随后在室温~90℃下搅拌3~12h;再加去离子水定容后得到TiO2质量含量为0.5~3%的Pt/TiO2分散液;所得Pt/TiO2分散液中铂质量含量为TiO2质量含量的0.1~1%;所述Pt/TiO2分散液中理论TiO2物质的量与步骤(2)所加入的钛酸四丁酯的物质的量相等,所述氯铂酸加入的物质的量与所述Pt/TiO2分散液中理论铂的物质的量相等;所述的硼氢化钠或水合肼与氯铂酸物质的量比为0.5~5:1;
(4)取步骤(3)所得Pt/TiO2分散液在整体式基体上进行均匀喷洒,干燥后即得Pt/TiO2整体式催化剂。
2.如权利要求1所述的制备方法,其特征在于:步骤(1)中所述酸为有机酸或无机酸。
3.如权利要求1所述的制备方法,其特征在于:步骤(1)中所述酸为为甲酸、乙酸、盐酸、硝酸、硫酸中的一种或多种。
4.如权利要求1所述的制备方法,其特征在于:所述的整体式基体为堇青石蜂窝陶瓷、泡沫碳化硅或泡沫氧化铝。
5.如权利要求1所述的制备方法,其特征在于:所的Pt/TiO2分散液中TiO2质量含量为0.8~2.4%。
6.如权利要求1所述的制备方法,其特征在于:所得Pt/TiO2分散液中铂质量含量为TiO2质量含量的0.12~0.6%。
7.如权利要求1所述的制备方法,其特征在于:步骤(1)中所述无水乙醇和去离子水的体积比为1~3:1。
8.如权利要求1所述的制备方法,其特征在于:所述的钛酸四丁酯与步骤(1)所述的去离子水体积比为1:1~3。
9.如权利要求1所述的制备方法,其特征在于:所述的硼氢化钠或水合肼物质的量用量为氯铂酸物质的量的1~3倍。
10.如权利要求1所述的制备方法,其特征在于:步骤(4)中干燥后再于300~800℃下焙烧1~5h,得到Pt/TiO2整体式催化剂。
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