CN114950423B - 室内低浓度甲醛净化催化剂产品及其制备方法 - Google Patents
室内低浓度甲醛净化催化剂产品及其制备方法 Download PDFInfo
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Abstract
室内低浓度甲醛净化催化剂产品及其制备方法。该催化剂产品由基体和涂覆在基体上的催化剂涂层构成。本发明的催化剂涂层包含两种混合或分层涂覆的催化剂，第一种催化剂比表面积大，对室内低浓度甲醛具有优良的吸附作用，第二种催化剂则可以为活性组分提供更多的氧离子，从而提高催化剂的催化氧化反应，达到高效催化净化室内低浓度甲醛的目的。
Description
技术领域
本发明总体涉及一种甲醛净化催化剂。
背景技术
室内装修的胶合板、人造板、胶水等排放的甲醛、甲苯、苯等VOCs物种可引起慢性呼吸道疾病，新生儿染色体异常、白血病、智力下降等，甲醛、甲苯和苯已经被世界卫生组织确定为高度致癌物质。通常情况下，装潢和家具材料中的甲醛在室温条件下会缓慢释放出来，持续时间长达两年以上，导致室内环境中长期存在低浓度但处于超标状态的甲醛物质。因此，室内颗粒物和甲醛及其他VOCs污染物严重危害居民的身体健康，亟需得到治理。
活性炭吸附是用于室内甲醛净化最常用的技术手段，但由于活性炭对低浓度甲醛吸附强度和吸附容量都较低，在实际使用过程中去除甲醛的效率低，且达到饱和就失去净化效率，不能高效去除室内甲醛和长期使用，甚至存在二次释放的问题。另外，工业VOCs净化技术主要针对高浓度甲醛(甲醛浓度10-100ppm)，无法适用于净化低浓度的室内甲醛(实际浓度约为0.01-0.6ppm)。
发明内容
本发明的目的是提供一种适于净化室内低浓度甲醛的产品。
根据本发明的第一方面，提供了一种甲醛净化催化剂产品，其包括基体和涂覆在基体上的催化剂涂层，催化剂涂层包含第一催化剂和第二催化剂，其中
第一催化剂由第一活性组分和第一载体构成，第一活性组分选自Pt、Pd和Co中的至少一种，第一载体为由CeO2，ZrO2和MnO2组成的CexZryMnzO(2z+2x+2y)复合材料，其中x,y,z＝0.1～0.9，第一活性组分为第一催化剂总质量的0.1wt％～1.5wt％；
第二催化剂由第二活性组分和第二载体构成，第二活性组分选自Pt、Pd、Co和Mn中的至少一种，第二载体选自由Ce、La和/或SiO2所改性的Al2O3复合材料中的至少一种，第二活性组分为第二催化剂总质量的0.1wt％～1.5wt％。
在根据本发明的催化剂涂层中，第一催化剂与第二催化剂的重量比例优选为9:1～1:9，更优选为5:1～1:5。
根据本发明的甲醛净化催化剂产品，其中基体由多孔材料制成，优选为堇青石蜂窝陶瓷。
在根据本发明的第一催化剂中，第一载体优选为例如通过共沉淀法+沉积沉淀法制成。第一活性组分则可以由例如可溶性金属盐溶液通过原位还原或沉积沉淀的方法负载在第一载体表面；这可以提高活性组分的分散性和稳定性。第一活性组分优选为Pt。
在根据本发明的第二催化剂中，第二载体优选为由La所改性的Al2O3复合材料，可以例如通过共沉淀法制成。第二活性组分则可以由例如可溶性金属盐溶液通过原位还原或沉积沉淀的方法负载在第二载体表面；这可以提高活性组分的分散性和稳定性。第二活性组分优选为Mn。
根据本发明的第二方面，提供了一种上述甲醛净化催化剂产品的制备方法，包括：将第一催化剂和第二催化剂与粘结剂混合后涂敷在基体上，干燥后经焙烧即制得。
第一催化剂和第二催化剂可以与粘结剂分别单独混合后分层涂敷，也可以一起混合后进行涂敷。干燥温度优选为80℃～100℃。焙烧温度优选为450℃～600℃，时间优选为1～3h。
本发明的第一催化剂比表面积大，对室内低浓度甲醛具有优异的吸附作用，第二催化剂则可以为活性组分提供更多的氧离子，提高催化剂的催化氧化反应。二者协同作用，从而可以达到高效催化净化室内低浓度甲醛的目的。
附图说明
图1为根据本发明制备的Ce0.25Zr0.75O2固溶体的XRD图；
图2为本发明实施例1制备的催化剂产品的甲醛降解率时间曲线图。
图3为本发明实施例1制备的低浓度甲醛净化催化剂产品的照片。
具体实施方式
下面结合实施例和附图对本发明做进一步说明，本领域技术人员应该理解，实施例和附图只是为了更好地理解本发明，并不用于任何限制目的。
实施例1
制备第一催化剂
按照Ce:Zr:Mn摩尔比＝0.25:0.75:0.5称取14.33g六水硝酸铈、17.49g碳酸氧锆、11.99g硝酸锰备用以下步骤1)和2)。
1)共沉淀法准备CeO2-ZrO2载体材料
用浓硝酸溶解上述备用的碳酸氧锆形成碳酸氧锆硝解溶液，其中浓硝酸质量：碳酸氧锆质量＝1:10。将碳酸氧锆硝解溶液和上述备用的硝酸铈混合后采用去离子水稀释至1000倍溶液，形成CeO2-ZrO2前驱体稀释溶液。将氨水和碳铵混合(摩尔量均为3mol)后形成1000ml的缓冲溶液作为沉淀剂，将前驱体稀释溶液和缓冲溶液共同滴入沉淀罐中，所得沉淀物经过滤、洗涤，在100℃干燥12h，再在600℃焙烧3h后得到具有Ce0.25Zr0.75O2固溶体晶相CeO2-ZrO2复合载体材料，其XRD图如图1所示。
2)沉积沉淀法准备Ce0.25Zr0.75Mn0.5O3复合载体材料
将尿素和上述备用的硝酸锰混合在去离子水中准备硝酸锰前驱体溶液，其中尿素与Mn的摩尔比为5:1(尿素质量为20.12g)，并将步骤1)所制得的CeO2-ZrO2载体材料搅拌分散其中。之后在100℃水浴中连续沉积沉淀12h，所得悬浮溶液在100℃下干燥，600℃焙烧3h后得到20g Ce0.25Zr0.75Mn0.5O3复合载体材料。
3)原位还原法准备单金属Pt纳米催化剂(第一催化剂：其中Pt含量为0.5wt％)
按照上述Ce0.25Zr0.75Mn0.5O3复合载体材料与单金属Pt的质量比为99.5:0.5称取0.56gPt(NO3)2溶液(Pt含量为18wt％)，并采用2ml去离子水进行稀释，超声混合均匀后得到Pt金属稀释溶液。再按照PVP质量:单金属Pt质量＝20:1称取聚乙烯吡咯烷酮(PVP-K30)2g，并将PVP粉末超声震荡溶解在去离子水中形成PVP溶液，其中PVP质量:去离子水质量＝15:1。将Pt金属稀释溶液滴加到PVP溶液中，超声震荡1h使其混合均匀，并添加去离子水对Pt2 +—PVP混合溶液进行稀释，其中去离子水体积：Pt2+—PVP溶液＝20:1，之后超声震荡+搅拌1h后获得混合均匀的Pt2+—PVP稀释溶液。再将步骤2)制得的Ce0.25Zr0.75Mn0 . 5O3复合载体材 料加入Pt2+—PVP稀释溶液，并搅拌均匀。之后按照Pt金属摩尔量:还原剂摩尔量＝1:10的量添加0.90g还原剂抗坏血酸，并在100℃反应3h，冷却至室温(25℃)，100℃干燥12h，500℃焙烧3h，即获得第一催化剂。
制备第二催化剂
1)共沉淀法准备La-Al2O3复合载体材料
按照待制备的复合载体材料中La的质量百分含量为5wt％称取99.04g九水硝酸铝和0.32g的六水硝酸镧，并将二者采用去离子水稀释至1000倍溶液形成前驱体稀释溶液。再采用上述制备的氨水和碳铵混合的缓冲溶液作为沉淀剂，将前驱体稀释溶液和缓冲溶液共同滴入沉淀罐中，所得沉淀物经过滤、洗涤，在100℃干燥12h，再在600℃焙烧3h，得到5wt％La-Al2O3载体材料10g。
2)原位还原法准备单金属Mn纳米催化剂(第二催化剂：其中Mn含量为0.5wt％)
按照上述La-Al2O3载体材料与单金属Mn的质量比为99.5:0.5称取0.16g的Mn(NO3)4溶液，采用20ml去离子水进行稀释，超声混合均匀后形成Mn金属前驱体稀释溶液。按照PVP质量:单金属Mn质量＝20:1称取1g聚乙烯吡咯烷酮(PVP-K30)。将PVP粉末超声震荡溶解在去离子水中形成PVP溶液，其中PVP质量:去离子水质量＝15:1。再将Mn金属稀释溶液滴加到PVP溶液中，超声1h使其混合均匀后形成Mn4+—PVP混合溶液。然后添加去离子水对Mn4 +—PVP混合溶液进行稀释，其中去离子水体积:Mn4+—PVP溶液＝20:1，之后超声震荡+搅拌1h后获得混合均匀的Mn4+—PVP稀释溶液。接下来将上述La-Al2O3载体材料加入Mn4+—PVP稀释溶液(活性组分前驱体溶液)，并搅拌均匀。之后按照Mn金属摩尔量:还原剂摩尔量＝10:1添加0.0034g还原剂硼氢化钠，并在100℃反应3h；再冷却至室温(25℃)，过滤、洗涤，100℃干燥12h，500℃焙烧3h后即制得第二催化剂。
制备甲醛净化催化剂产品
将第一催化剂、第二催化剂(二者质量比3:2)与铝溶胶(Al2O3·nH2O，含量为催化剂总质量的3wt％)混合，然后将所得混合浆料涂覆在孔目数为400cell/in2，体积为80ml的蜂窝陶瓷基体上，涂覆量为150g/L，完成12g催化材料涂覆后，100℃干燥12h，550℃焙烧3h，即得到本发明的甲醛催化剂产品，见图3。
对实施例1的催化剂产品进行活性评价实验，实验条件如下：
模拟密闭室为3立方米，内空气组成：甲醛：3500ppm，氧气：21％，氮气：平衡气，舱内湿度65±5RH、温度23±1℃。采用轴流风机实现室内空气循环并确保循环风通过催化剂。
如图2所示：在60min内，甲醛降解率达到90％以上。
实施例2
第一催化剂和第二催化剂的制备同实施例1。
将第一催化剂和第二催化剂分别与铝溶胶(含量为催化剂总质量的3wt％)混合，分别球磨30min后得到第一和第二催化剂浆料。先将第二催化剂浆料涂覆在孔目数为400cell/in2，体积为80ml的蜂窝陶瓷基体上，涂覆量为60g/L；完成4.8g第二催化剂涂覆后，100℃干燥12h，550℃焙烧3h，得到第二催化剂涂覆的蜂窝陶瓷基体材料。再将第一催化剂浆料涂覆在涂覆有第二催化剂的蜂窝陶瓷基体材料上，涂覆量为90g/L；完成7.2g第一催化剂涂覆后，100℃干燥12h，550℃焙烧3h，即得到分层涂覆的催化剂产品。
Claims (5)
1.一种甲醛净化催化剂产品，包括基体和涂覆在基体上的催化剂涂层，催化剂涂层包含第一催化剂和第二催化剂，其中
第一催化剂由第一活性组分和第一载体构成，第一活性组分选自Pt、Pd和Co中的至少一种，第一载体为由CeO2，ZrO2和MnO2组成的CexZryMnzO(2z+2x+2y)复合材料，其中x,y,z＝0.1～0.9，第一活性组分为第一催化剂总质量的0.1wt％～1.5wt％；
第二催化剂由第二活性组分和第二载体构成，第二活性组分选自Pt、Pd、Co和Mn中的至少一种，第二载体选自由Ce、La和/或SiO2所改性的Al2O3复合材料中的至少一种，第二活性组分为第二催化剂总质量的0.1wt％～1.5wt％。
2.根据权利要求1所述的甲醛净化催化剂产品，其中催化剂涂层中的第一催化剂与第二催化剂的重量比例为9:1～1:9。
3.根据权利要求1所述的甲醛净化催化剂产品，其中基体材料为堇青石蜂窝陶瓷。
4.根据权利要求1所述的甲醛净化催化剂产品，其中第二载体为由La所改性的Al2O3复合材料。
5.一种根据权利要求1所述的甲醛净化催化剂产品的制备方法，包括：将第一催化剂和第二催化剂与粘结剂混合后涂敷在基体上，干燥后经焙烧即制得。
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