CN107362800A - 一种VOCs消除催化剂及其制备方法 - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000012855 volatile organic compound Substances 0.000 title abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 229910052723 transition metal Inorganic materials 0.000 claims description 14
- 150000003624 transition metals Chemical class 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002070 nanowire Substances 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000002057 nanoflower Substances 0.000 claims description 6
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- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000003546 flue gas Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 57
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
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- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 description 25
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910020632 Co Mn Inorganic materials 0.000 description 2
- 229910020678 Co—Mn Inorganic materials 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 229910052763 palladium Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
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Abstract
本发明公开了一种VOCs消除催化剂及其制备方法，通过水热方法，通过加入还原剂，促进剂，并调节Co与Mn的摩尔比，调控催化剂的形貌和纳米粒子尺寸。该催化剂在较宽的温度范围内均表现较高的苯催化氧化活性。催化剂在207oC的苯催化转化率达到了90%。本发明提供催化剂的净化效果优于传统苯催化氧化催化剂。且制备工艺简单，操作方便，成本低，苯转化率高，具有明显的工业应用价值。
Description
技术领域
本发明属于纳米技术领域，具体涉及Co-Mn复合氧化物催化剂的形貌可控合成及应用于固定源中及移动源排放的有机污染物的净化。
背景技术
人类生存与发展离不开适宜的环境，随着工业的发展，环境污染日益严重，甚至威胁到人类的生存与发展，因此对环境的保护刻不容缓。挥发性有机物(VOCs)是重要的环境污染物之一，既可能直接对人体的健康造成损害，也可能转化为光化学烟雾或者 PM 2.5 ，造成二次污染。因此去除 VOCs 对环境保护具有重大的意义。催化氧化法是去除 VOCs 的有效方法之一，贵金属Pt, Pd, Au和Ag等贵金属基催化剂呈现出低温VOCs消除性能，然而，由于贵金属的昂贵价格，高温易烧结及贵金属储量有限等原因，限制了贵金属基催化剂在工业上的广泛应用。近年来，过渡金属氧化物因价格低廉及优异的VOCs净化性能而被众多学者研究，在本专利中，我们通过调节Co:Mn的摩尔比，从而调控Mn7O13晶种的形成，实现过渡金属Co-Mn氧化物的形貌和尺寸的可控，并研究发现形貌和尺寸对催化剂的结构，织构和催化性能均产生了极大的影响。
发明内容
本发明的目的是提供一种用于挥发性有机物消除的过渡金属基氧化物催化剂及其制备方法，该催化剂是一种低温、高活性、抗水的廉价催化剂，主要应用固定源排放的苯消除，且在较宽的温度范围内均表现高的苯催化氧化活性，且可操作窗口为200-400 oC。
本发明提供了用于固定源排放的苯消除的催化剂，包含Co及Mn。所述催化剂的形貌可控，可以包括纳米线，纳米花，空心球，实心球及纳米块等。
所述催化剂的制备采用如下方式：（1）将一定量的Co及Mn的硝酸盐，及尿素，溶解在一定量的水，乙醇和HCl混合溶液中；（2）140 °C 进行水热反应 10 h；（3）将上述（2）反应后的溶液，离心，并采用水和乙醇交替洗涤数次；（4）在-46 oC 真空冷冻干燥 10 h，最后烘干和焙烧。
具体技术方案如下：
一种用于挥发性有机物消除的过渡金属基氧化物催化剂，该催化剂包含一种或两种过渡金属元素，所述过渡金属元素为Co和Mn，并通过Co与Mn摩尔比的调节，调控催化剂的微观结构，实现催化剂活性的调控。
所述催化剂的形貌结构通过Co:Mn的摩尔比调节，Co:Mn摩尔比在一定范围内，形成Mn7O13晶种，晶种的形成调控了催化剂的形貌。
当Co:Mn的摩尔比在1:0-5:1范围内，制备的催化剂均为纳米线形貌结构；当Co:Mn的摩尔比在2:1-1:1范围内，制备的催化剂均为空心或实心纳米花形貌结构；当Co:Mn的摩尔比在1:5-0:1范围内，制备的催化剂均为纳米块形貌结构。
所述的过渡金属基氧化物催化剂的方法，采用前驱体，还原剂，促进剂及溶剂进行水热反应，并将水热反应产物进行焙烧得到催化剂。
水热温度为140-180 oC, 水热时间为2-12 h。
所述催化剂的焙烧温度为400 oC，焙烧时间为2-6 h，升温速率为1 oC/min。
所述前驱体为硝酸镁和硝酸钴中的一种或两种，还原剂为尿素，促进剂为盐酸或硝酸，溶剂为水或乙醇；促进剂的浓度为3 mol/L。
催化剂应用于发动机尾气排放及燃煤烟气排放的有机挥发物的净化。
本发明的显著优点在于：
本发明通过调节Co与Mn的摩尔比，调控催化剂的形貌和纳米粒子尺寸。当Co:Mn的摩尔比在1:0-5:1范围内，制备的催化剂均为纳米线形貌结构；当Co:Mn的摩尔比在2:1-1:1范围内，制备的催化剂均为空心或实心纳米花形貌结构；当Co:Mn的摩尔比在1:5-0:1范围内，制备的催化剂均为纳米块形貌结构。
该催化剂在较宽的温度范围内均表现较高的苯催化氧化活性。催化剂在207 oC的苯催化转化率达到了90%。本发明提供催化剂的净化效果优于传统苯催化氧化催化剂。且制备工艺简单，操作方便，成本低，苯转化率高，具有明显的工业应用价值。
附图说明
图1为实施例1-4制得的催化剂的扫描电镜图：(A) Co3O4 纳米线；(B) Co5Mn1O纳米针；(C) Co1Mn1O 纳米花；(D) MnO2纳米立方块。
图2为实施例1-4制得的催化剂在不同温度点的苯转化率。
具体实施方式
本发明用于火电厂和硝酸厂等固定源中排放的VOCs中的苯的净化，可以以颗粒形式使用，也可以作为涂层负载于堇青石等蜂窝状的载体上制备成整体式多孔式催化剂。
下面结合实施例更具体的对本发明的催化剂加以说明，但这些实施例对本发明的范围无任何限制。
实施例1
以Co3O4 纳米线为例，原料为硝酸钴，尿素，乙醇和HCl。具体为： 称取: 100 mg Co(NO3)2·6H2O (分子量291.0)，100 mg尿素（分子量60），然后加入35 mL水和 15 mL乙醇的混合溶剂中，并向上述溶液中添加1 mL的HCl (3M)，在室温下搅拌1 h，转入到水热釜中，140oC反应10 h，离心，乙醇和水洗5-6次。放入-46 oC下进行真空冷冻处理10 h，120 oC烘干24h，接着入马弗炉焙烧，以1 oC/min的升温速率升到400 oC，在400 oC下处理4 h。经过以上步骤合成的样品标记为Co3O4 纳米线，合成的纳米线直径为20-30 纳米，长度为3-12 μm (如图1中的A)。
实施例2
以Co5Mn1O纳米针为例，原料为硝酸钴和硝酸锰，尿素，乙醇和HCl。具体为： 称取:85.28 mg Co(NO3)2·6H2O (分子量291.0)，14.71 mg Mn(NO3)2·4H2O(分子量251.01)，100mg尿素（分子量60），然后加入35mL水和 15 mL乙醇的混合溶剂中，向上述溶液中添加1 mL的的HCl (3M)，在室温下搅拌1 h，转入到水热釜中，140 oC反应10 h，离心，乙醇和水洗5-6次。放入-46 oC下进行真空冷冻处理10 h，120 oC烘干24 h接着入马弗炉焙烧，以1 oC/min的升温速率升到400 oC，在400 oC下处理4 h。经过以上步骤合成的样品标记为Co5Mn1O 纳米针，合成的纳米针直径为210纳米，长度为3-12 μm之间(如图1中的B)。
实施例3
以Co1Mn1O 纳米花为例，原料为硝酸钴和硝酸锰，尿素，乙醇和HCl。具体为： 称取:53.69 mg Co(NO3)2·6H2O(分子量291.0)，46.30 mg Mn(NO3)2·4H2O(分子量251.01)，100 mg尿素（分子量60），然后加入35mL水和 15 mL乙醇的混合溶剂中，向上述溶液中添加1 mL的的HCl (3M)，在室温下搅拌1 h，转入到水热釜中，140 oC反应10 h，离心，乙醇和水洗5-6次。放入-46 oC下进行真空冷冻处理10 h，120 oC烘干24 h接着入马弗炉焙烧，以1 oC/min的升温速率升到400 oC，在400 oC下处理4 h。经过以上步骤合成的样品标记为Co1Mn1O 空心球，空心球是由均匀的纳米带组成，其直径为400 nm左右(如图1中的C)。
实施例4
以MnO2纳米立方块为例，原料为硝酸锰，尿素，乙醇和HCl。具体为： 称取: 100 mg Mn(NO3)2·4H2O (分子量251.01)，100 mg尿素（分子量60），然后加入35 mL水和 15mL乙醇的混合溶剂中，并向上述溶液中添加1 mL的的HCl (3M)，在室温下搅拌1 h，转入到水热釜中，140 oC反应10 h，离心，乙醇和水洗5-6次。放入-46 oC下进行真空冷冻处理10 h，120 oC烘干24 h接着入马弗炉焙烧，以1 oC/min的升温速率升到400 oC，在400 oC下处理4h。经过以上步骤合成的样品标记为MnO2纳米立方块，合成的纳米线立方块直径为750 nm，表面光滑(如图1中的D)。
下面对实施例催化剂的性能进行评价
测试1 （不同温度下催化剂的苯氧化率）
分别采用实施例1-4的催化剂各0.1g，质量空速90,000 mL/(g. h)，在连续流动微型固定床上进行苯转化率测定，尾气中苯浓度变化通过气相色谱， CO2的选择性通过O2-TPSR实验测定, 反应气体组成为：1000 ppm 苯, 20vol%O2及N2为平衡气。在120 -400 °C 下测定催化剂对苯的转化效果，测试结果见图2。
从图2可以看出，所述的MnO2催化剂在207 oC的苯转化率就达到了90%，可以与贵金属基催化剂相媲美。
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 (9)
1.一种用于挥发性有机物消除的过渡金属基氧化物催化剂，其特征在于：该催化剂包含一种或两种过渡金属元素，所述过渡金属元素为Co和Mn，并通过Co与Mn摩尔比的调节，调控催化剂的微观结构，实现催化剂活性的调控。
2.根据权利要求1所述的过渡金属基氧化物催化剂，其特征在于：催化剂的形貌结构通过Co:Mn的摩尔比调节，Co:Mn摩尔比在一定范围内，形成Mn7O13晶种，晶种的形成调控了催化剂的形貌。
3.根据权利要求2所述的过渡金属基氧化物催化剂，其特征在于：当Co:Mn的摩尔比在1:0-5:1范围内，制备的催化剂均为纳米线形貌结构；当Co:Mn的摩尔比在2:1-1:1范围内，制备的催化剂均为空心或实心纳米花形貌结构；当Co:Mn的摩尔比在1:5-0:1范围内，制备的催化剂均为纳米块形貌结构。
4.一种制备如权利要求1-3任一所述的过渡金属基氧化物催化剂的方法，其特征在于：采用前驱体，还原剂，促进剂及溶剂进行水热反应，并将水热反应产物进行焙烧得到催化剂。
5.根据权利4所述的过渡金属基氧化物催化剂的制备方法，其特征在于：水热温度为140-180 oC, 水热时间为2-12 h。
6.根据权利4所述的过渡金属基催化剂，其特征在于：所述催化剂的焙烧温度为400 oC，焙烧时间为2-6 h，升温速率为1 oC/min。
7.根据权利4所述的过渡金属基氧化物催化剂的制备方法，其特征在于：所述前驱体为硝酸镁和硝酸钴中的一种或两种，还原剂为尿素，促进剂为盐酸或硝酸，溶剂为水或乙醇。
8.根据权利要求7所述的过渡金属基氧化物催化剂的制备方法，其特征在于：促进剂的浓度为3 mol/L。
9.如权利要求1所述的催化剂的应用，其特征在于，用于发动机尾气排放及燃煤烟气排放的有机挥发物的净化。
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