CN106140175A - 一种催化燃烧含氟、氯VOCs催化剂的制备方法 - Google Patents
一种催化燃烧含氟、氯VOCs催化剂的制备方法 Download PDFInfo
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Abstract
本发明涉及催化剂的制备技术,旨在提供一种催化燃烧含氟、氯VOCs催化剂的制备方法。该方法包括:以CeO2与含镧化合物通过浸渍法制备La‑CeO2粉末,然后通过浸渍法与含钴化合物制备Co/La‑CeO2粉末催化剂;再与聚乙烯醇和胶体氧化铝混合搅匀成浆料,将单体形式的蜂窝陶瓷载体浸入其中,然后重复浸渍和干燥的操作,直至达到负载总重量的目标值;最后焙烧得到Co/La‑CeO2整体式催化剂。本发明具有耐高温,在900℃左右焙烧时,无烧结;涂层粘附牢固,超声脱落率为1.6%‑2.1%。该催化剂有良好的抗毒能力,对含氟、氯VOCs有很高的催化活性,且原料易得,工艺简便,成本较低,易实现工业化生产。重复使用活性稳定、合成工艺环保,不产生污染副产物,适用范围广。
Description
技术领域
本发明涉及一种催化燃烧含氟、氯VOCs催化剂的制备方法,属于环境保护催化材料和大气污染治理技术领域。
背景技术
VOCs大多数化学成分具有毒性,可对人类健康和生态环境构成极大的威胁,如急、慢性中毒,甚至致癌和突变。作为PM2.5的前驱体,VOCs在光照条件下与空气中的氮氧化物反应形成光化学烟雾,对人体健康造成直接或间接的危害。卤代烃类的VOCs扩散至臭氧层时,会与臭氧发生化学反应,导致臭氧浓度的降低,形成臭氧漏洞,能引发温室效应等一系列生态灾害。
催化燃烧法在处理大分量、低浓度、成分复杂的VOCs时,在较低温度(200-500℃)下,可实现VOCs的完全氧化,具有设备简单、能耗低、净化效率高以及不产生二次污染等优点。由于催化燃烧是无火焰燃烧,安全性比较高,已成为VOCs治理最有前景的方法之一,该技术的核心是催化剂,以块状载体作为骨架基体的催化剂称为整体式催化剂。整体式催化剂具有大量宏观的中空孔道,与粉末催化剂相比,在传热、传质和压降性能上有很大优势。常用的载体为堇青石蜂窝陶瓷,其本身的比表面小于1g/m2,必须使负载的活性组分散在基质材料表面。常用的活性组分多为贵金属如Pt、Pd、Ru等,处理效果较理想。但含卤VOCs催化氧化时,如含氯有机物,C-Cl键的断裂取代了C-H键的断裂,生成的Cl物种会强吸附在贵金属催化剂表面或与活性组分化合形成挥发性的金属氯化物,导致活性组分流失,催化剂中毒失活,同时生成的Cl2以及与其它有机物反应生成多氯有机物,造成二次污染。活性组分为过渡金属氧化物时,抗卤代物性能好,但是催化效果不理想。
针对以上技术瓶颈,研究和开发低成本、高活性、抗毒性能强的VOCs氧化降解催化剂是目前环境催化材料研究领域中极重要的课题之一,受到广泛的关注。
发明内容
本发明要解决的技术问题是,克服现有技术的不足,提供一种催化燃烧含氟、氯VOCs催化剂的制备方法。
为解决技术问题,本发明的解决方案是:
提供一种催化燃烧含氟、氯VOCs催化剂的制备方法,包括以下步骤:
(1)将CeO2粉末与含镧化合物的水溶液混合,常温搅拌1~4h,浸渍8-16h;50℃-90℃下蒸发,100℃-150℃干燥2-8h;350℃-700℃焙烧4-8h,研磨得到La-CeO2粉末;控制CeO2粉末与含镧化合物水溶液的用量,使La-CeO2粉末中La的质量分数为5%-15%;
(2)将La-CeO2粉末与含钴化合物的水溶液混合,常温搅拌1-4h,浸渍8-16h;50℃-90℃蒸发,100℃-150℃下干燥2-8h;350℃-700℃下焙烧3-6h,研磨得到Co/La-CeO2粉末催化剂;控制La-CeO2粉末与含钴化合物水溶液的用量,使Co/La-CeO2粉末催化剂中Co的质量分数为10%-20%;
(3)将Co/La-CeO2粉末催化剂与40-100ml蒸馏水混合后,添加聚乙烯醇和胶体氧化铝,搅匀成浆料,并调节pH值至2-6;使浆料中的Co/La-CeO2粉末催化剂、聚乙烯醇和胶体氧化铝的用量分别为2-5g/L、7.2-18g/L和20-50g/L;所述聚乙烯醇是平均分子量为110000-130000的中黏度聚乙烯醇;
(4)将单体形式的蜂窝陶瓷载体浸入步骤(3)制得的浆料中,然后在100℃-150℃下干燥1-3h;称重,再重复浸渍和干燥的操作,直至达到负载总重量的目标值;最后在350℃-900℃下焙烧3-6h,得到Co/La-CeO2整体式催化剂。
本发明中,所述的含镧化合物为La(NO3)3·6H2O或La(CH3COO)2·4H2O;所述的含钴化合物为Co(NO3)2·6H2O或Co(CH3COO)2·4H2O。
本发明中,所制得的Co/La-CeO2整体式催化剂为Co3O4尖晶石结构,比表面积为40.7-180.4m2/g。
相对于现有技术,本发明的优点在于:
1、本发明中的催化剂为整体式催化剂,将过渡金属与稀土元素结合,以蜂窝陶瓷为载体,具有耐高温,在900℃左右焙烧时,无烧结;涂层粘附牢固,超声脱落率为1.6%-2.1%。
2、本发明制得的催化剂有良好的抗毒能力,对含氟、氯VOCs有很高的催化活性,且原料易得,工艺简便,成本较低,易实现工业化生产。
3、本发明的催化剂重复使用活性稳定,克服了传统贵金属催化剂易烧结、易中毒等特点;催化剂合成工艺环保,不产生污染副产物,符合可持续发展战略。该催化剂适用范围广,还可用于工业废气中其它挥发性有机物如醛、烃、醚等的催化燃烧。
附图说明
图1为本发明VOCs催化燃烧高性能催化剂的制备流程图。
图2为实施例3所制备Co/La-CeO2粉末催化剂的XRD图。
具体实施方式
下面结合实施例来对本发明进一步详细说明,但本发明不限于这些实例。
实施例1
(1)将0.1981g La(NO3)3·6H2O溶于100mL的蒸馏水中,搅拌至完全溶解,形成含镧化合物的水溶液。
(2)取1g CeO2粉末与(1)所得溶液混合,经磁力搅拌器常温搅拌1h,浸渍8h,50℃蒸发,100℃干燥8h,于350℃下焙烧8h,研磨后得到La(5.00wt.%)-CeO2粉末,其中La的质量分数为5.00%。
(3)将1.2206g Co(CH3COO)2·4H2O溶于100mL的蒸馏水中,搅拌至完全溶解,形成含钴化合物的水溶液。
(4)取1g(2)所得粉末与(3)所得溶液混合,经磁力搅拌器常温搅拌4h,浸渍16h,50℃蒸发,100℃干燥8h,于350℃下焙烧6h,研磨后得到Co(20.00wt.%)/La(5.00wt.%)-CeO2粉末催化剂,其中Co的质量分数为20.00%。
(5)取200mg(4)所得粉末与100mL的蒸馏水混合,并添加0.72g的中黏度聚乙烯醇和2.0g的胶体氧化铝,用乙酸调pH至2,制成浸渍浆料。
(6)将蜂窝陶瓷载体浸入(5)所得浆料中,之后100℃干燥3h,称重,再重复涂覆多次,于350℃下焙烧6h,得到负载量为180mg/载体的Co/La-CeO2整体式催化剂,测得其比表面积为40.7m2/g。
实施例2
(1)将0.3000g La(CH3COO)3·4H2O溶于100mL的蒸馏水中,搅拌至完全溶解,形成含镧化合物的水溶液。
(2)取1g CeO2粉末与(1)所得溶液混合,经磁力搅拌器常温搅拌2h,浸渍10h,60℃蒸发,110℃干燥7h,于450℃下焙烧7h,研磨后得到La(8.08wt.%)-CeO2粉末,其中La的质量分数为8.08%。
(3)将1.0000g Co(CH3COO)2·4H2O溶于100mL的蒸馏水中,搅拌至完全溶解,形成含钴化合物的水溶液。
(4)取1g(2)所得粉末与(3)所得溶液混合,经磁力搅拌器常温搅拌3h,浸渍14h,60℃蒸发,110℃干燥7h,于450℃下焙烧6h,研磨后得到Co(17.35wt.%)/La(8.08wt.%)-CeO2粉末催化剂,其中Co的质量分数为17.35%。
(5)取200mg(4)所得粉末与80mL的蒸馏水混合,并添加0.72g的中黏度聚乙烯醇和2.0g的胶体氧化铝,用乙酸调pH至3,制成浸渍浆料。
(6)将蜂窝陶瓷载体浸入(5)所得浆料中,之后110℃干燥3h,称重,再重复涂覆多次,于500℃下焙烧5h,得到负载量为180mg/载体的Co/La-CeO2整体式催化剂,测得其比表面积为50.2m2/g。
实施例3
(1)将0.4000g La(NO3)3·6H2O溶于100mL的蒸馏水中,搅拌至完全溶解,形成含镧化合物的水溶液。
(2)取1g CeO2粉末与(1)所得溶液混合,经磁力搅拌器常温搅拌2h,浸渍12h,70℃蒸发,120℃干燥6h,于500℃下焙烧6h,研磨后得到La(9.45wt.%)-CeO2粉末,其中La的质量分数为9.45%。
(3)将1.0000g Co(NO3)2·6H2O溶于100mL的蒸馏水中,搅拌至完全溶解,形成含钴化合物的水溶液。
(4)取1g(2)所得粉末与(3)所得溶液混合,经磁力搅拌器常温搅拌2h,浸渍12h,70℃蒸发,120℃干燥6h,于500℃下焙烧5h,研磨后得到Co(15.45wt.%)/La(9.45wt.%)-CeO2粉末催化剂,其中Co的质量分数为15.45%。
(5)取200mg(4)所得粉末与60mL的蒸馏水混合,并添加0.72g的中黏度聚乙烯醇和2.0g的胶体氧化铝,用乙酸调pH至4.5,制成浸渍浆料。
(6)将蜂窝陶瓷载体浸入(5)所得浆料中,之后120℃干燥2h,称重,再重复涂覆多次,于650℃下焙烧4h,得到负载量为180mg/载体的Co/La-CeO2整体式催化剂,测得其比表面积为74.5m2/g。
经XRD表征,Co/La-CeO2粉末催化剂为Co3O4尖晶石结构。尖晶石结构有利于增加催化剂的饱和吸附量,从而提高催化剂活性。
实施例4
(1)将0.5000g La(CH3COO)3·4H2O溶于100mL的蒸馏水中,搅拌至完全溶解,形成含镧化合物的水溶液。
(2)取1g CeO2粉末与(1)所得溶液混合,经磁力搅拌器常温搅拌3h,浸渍14h,80℃蒸发,140℃干燥4h,于650℃下焙烧5h,研磨后得到La(12.55wt.%)-CeO2粉末,其中La的质量分数为12.55%。
(3)将0.7000g Co(CH3COO)2·4H2O溶于100mL的蒸馏水中,搅拌至完全溶解,形成含钴化合物的水溶液。
(4)取1g(2)所得粉末与(3)所得溶液混合,经磁力搅拌器常温搅拌2h,浸渍10h,80℃蒸发,140℃干燥3h,于650℃下焙烧4h,研磨后得到Co(13.21wt.%)/La(12.55wt.%)-CeO2粉末催化剂,其中Co的质量分数为13.21%。
(5)取200mg(4)所得粉末与40mL的蒸馏水混合,并添加0.72g的中黏度聚乙烯醇和2.0g的胶体氧化铝,用乙酸调pH至5,制成浸渍浆料。
(6)将蜂窝陶瓷载体浸入(5)所得浆料中,之后140℃干燥2h,称重,再重复涂覆多次,于750℃下焙烧3h,得到负载量为180mg/载体的Co/La-CeO2整体式催化剂,测得其比表面积为126.8m2/g。
实施例5
(1)将0.6944g La(NO3)3·6H2O溶于100mL的蒸馏水中,搅拌至完全溶解,形成含镧化合物的水溶液。
(2)取1g CeO2粉末与(1)所得溶液混合,经磁力搅拌器常温搅拌4h,浸渍16h,90℃蒸发,150℃干燥2h,于700℃下焙烧4h,研磨后得到La(15.00wt.%)-CeO2粉末,其中La的质量分数为15.00%。
(3)将0.4991g Co(CH3COO)2·4H2O溶于100mL的蒸馏水中,搅拌至完全溶解,形成含钴化合物的水溶液。
(4)取1g(2)所得粉末与(3)所得溶液混合,经磁力搅拌器常温搅拌1h,浸渍8h,90℃蒸发,150℃干燥2h,于700℃下焙烧3h,研磨后得到Co(10.00wt.%)/La(15.00wt.%)-CeO2粉末催化剂,其中Co的质量分数为10.00%。
(5)取200mg(4)所得粉末与50mL的蒸馏水混合,并添加0.72g的中黏度聚乙烯醇和2.0g的胶体氧化铝,用乙酸调pH至6,制成浸渍浆料。
(6)将蜂窝陶瓷载体浸入(5)所得浆料中,之后150℃干燥1h,称重,再重复涂覆多次,于900℃下焙烧3h,得到负载量为180mg/载体的Co/La-CeO2整体式催化剂,测得其比表面积为180.4m2/g。
负载效果试验
对实施例1-5涂层的负载效果通过振荡实验进行评定,将样品放入到介质为水的超声波清洗器中,经超声振荡30min后,计算脱落率。所得结果见表1。
表1涂层超声脱落率
对含卤VOCs催化燃烧的活性测试。
将本实施例1-5制备的催化剂填于固定床反应装置内,进行含卤有机废气的催化燃烧性能评价,反应气体成分为二氟一氯甲烷、二氯甲烷和氯苯,浓度为1500ppm,空速为18000h-1,用气相色谱仪在线分析,催化活性以T10和T90行表示。反应结果见表2。
表2催化剂对甲苯、乙酸乙酯及氯苯的催化燃烧效果
注:T10为转化率达10%时的反应温度;T90为转化率达90%时的反应温度。
Claims (3)
1.一种催化燃烧含氟、氯VOCs催化剂的制备方法,其特征在于,包括以下步骤:
(1)将CeO2粉末与含镧化合物的水溶液混合,常温搅拌1~4h,浸渍8-16h;50℃-90℃下蒸发,100℃-150℃干燥2-8h;350℃-700℃焙烧4-8h,研磨得到La-CeO2粉末;控制CeO2粉末与含镧化合物水溶液的用量,使La-CeO2粉末中La的质量分数为5%-15%;
(2)将La-CeO2粉末与含钴化合物的水溶液混合,常温搅拌1-4h,浸渍8-16h;50℃-90℃蒸发,100℃-150℃下干燥2-8h;350℃-700℃下焙烧3-6h,研磨得到Co/La-CeO2粉末催化剂;控制La-CeO2粉末与含钴化合物水溶液的用量,使Co/La-CeO2粉末催化剂中Co的质量分数为10%-20%;
(3)将Co/La-CeO2粉末催化剂与40-100ml蒸馏水混合后,添加聚乙烯醇和胶体氧化铝,搅匀成浆料,并调节pH值至2-6;在浆料中,Co/La-CeO2粉末催化剂、聚乙烯醇和胶体氧化铝的浓度分别为2-5g/L、7.2-18g/L和20-50g/L;所述聚乙烯醇是平均分子量为110000-130000的中黏度聚乙烯醇;
(4)将单体形式的蜂窝陶瓷载体浸入步骤(3)制得的浆料中,然后在100℃-150℃下干燥1-3h;称重,再重复浸渍和干燥的操作,直至达到负载总重量的目标值;最后在350℃-900℃下焙烧3-6h,得到Co/La-CeO2整体式催化剂。
2.根据权利要求1所述的方法,其特征在于,所述的含镧化合物为La(NO3)3·6H2O或La(CH3COO)2·4H2O;所述的含钴化合物为Co(NO3)2·6H2O或Co(CH3COO)2·4H2O。
3.根据权利要求1所述的方法,其特征在于,所制得的Co/La-CeO2整体式催化剂为Co3O4尖晶石结构,比表面积为40.7-180.4m2/g。
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