CN115445651A - 用于甲烷催化燃烧的纯硅分子筛负载钯催化剂及制备方法 - Google Patents
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 112
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 92
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 66
- 239000010703 silicon Substances 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 60
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 49
- 238000007084 catalytic combustion reaction Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 21
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- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
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- 229910017052 cobalt Inorganic materials 0.000 description 2
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000684 Cobalt-chrome Inorganic materials 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 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
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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Abstract
本发明涉及催化剂制备技术,旨在提供一种用于甲烷催化燃烧的纯硅分子筛负载钯催化剂及制备方法。该催化剂包含作为活性组分的金属钯纳米颗粒和作为载体的纯硅分子筛材料;其中,金属钯纳米颗粒的粒径为2~5nm,金属钯纳米颗粒与纯硅分子筛的质量比0.001~0.02︰1;纯硅分子筛材料中只含有硅和氧两种元素。该产品所用纯硅分子筛在甲烷催化燃烧反应中有利于产物水的快速脱附,从而促进反应平衡移动提高催化燃烧效率;可在较温和条件下实现甲烷完全催氧化为二氧化碳和水,且具有良好的稳定性;贵金属含量低,催化剂成本低;同时还具有好的稳定性,低温活性;能够用于甲烷燃烧,可用于天然气汽车和工业源尾气净化领域。
Description
技术领域
本发明涉及催化剂制备技术,特别涉及一种用于甲烷催化燃烧的纯硅分子筛负载钯催化剂及制备方法。
背景技术
甲烷是天然气汽车和工业源尾气排放的重要污染物之一,是温室效应系数很高的温室气体,如何控制和消除甲烷排放也成为环境领域研究的热点之一。
采用催化燃烧技术是有效控制甲烷排放的最有效方法之一,催化燃烧方法具有净化效率高,处理废气浓度宽,无二次污染等优点,其核心是设计和制备高性能的催化剂。
在甲烷的催化燃烧技术中,最常用的是负载型贵金属钯基催化剂。专利CN105457653A公开了一种用于低浓度甲烷催化燃烧的表面强化型钯基催化剂及其制备方法,该催化剂由活性组分钯和尖晶石界面强化层组成,所述尖晶石界面强化层由金属M盐和氧化铝载体原位高温反应生成,以催化剂的重量为100%计,贵金属活性组分钯的质量百分比为0.05%~5%,M的质量百分比为0.05%~20%;所述M为镍、钴或锰。该催化剂在300℃时甲烷最高转化率43%,在400℃条件下连续转化50h甲烷转化率均有所下降。专利CN102626640A公开了一种用于甲烷低温氧化反应的整体式催化剂及其制备,由堇青石蜂窝陶瓷载体及涂覆在载体上的涂层组成,述涂层的表达式为Pd/CoxCry-M/Al2O3,式中Pd为贵金属钯;CoxCry为钴铬复合氧化物,其中钴铬摩尔比介于0.001~100;M为掺杂的金属,M为铈、锆、镧、铁、镍、锰中的一种或一种以上,当为两种或两种以上时,其间比例任意,且掺杂量(摩尔比)M∶(Co+Cr+M)<0.10;Al2O3为具有高热稳定性的γ-Al2O3。该催化剂具有较好的甲烷起燃温度,但未对甲烷的全转化最低温度以及连续反应条件下稳定性问题做出进一步研究。
发明内容
本发明要解决的技术问题是,克服现有技术的缺陷,提供一种用于甲烷催化燃烧的纯硅分子筛负载钯催化剂及制备方法。
为了解决技术问题,本发明的解决方案是:
提供一种用于甲烷催化燃烧的纯硅分子筛负载钯催化剂,该催化剂包含作为活性组分的金属钯纳米颗粒和作为载体的纯硅分子筛材料;其中,金属钯纳米颗粒的粒径为2~5nm,金属钯纳米颗粒与纯硅分子筛的质量比0.001~0.02︰1;纯硅分子筛材料中只含有硅和氧两种元素。
作为本发明的优选方案,所述纯硅分子筛的骨架类型为MFI、*BEA、CHA、AEI、MEL中的一种,或者是两种以上的混合物。
本发明进一步提供了前述纯硅分子筛负载钯催化剂的制备方法,包括以下步骤:
(1)按照聚乙烯醇︰硝酸钯︰水的质量比为3︰1︰20,将聚乙烯醇和硝酸钯溶解在去离子水中;然后在剧烈搅拌条件下迅速加入NaBH4水溶液,NaBH4与Pd2+的质量比为2︰1;
(2)向上述溶液中加入纯硅分子筛,纯硅分子筛与Pd2+的质量比为100︰1;搅拌5h后,经离心洗涤、室温干燥和焙烧处理,得到纯硅分子筛负载钯催化剂。
作为本发明的优选方案,所述步骤(1)中,所述剧烈搅拌是指搅拌速度为120转/分钟;NaBH4水溶液的质量浓度为5%。
作为本发明的优选方案,所述步骤(2)中,所述焙烧温度为500℃,焙烧时间为4小时。
本发明还提供了前述纯硅分子筛负载钯催化剂的应用方法,是将所述催化剂置于天然气汽车或煤矿乏风瓦斯的后处理系统中,通过催化燃烧反应将甲烷完全转变成水和二氧化碳。
与现有技术相比,本发明的有益效果在于:
1、纯硅分子筛具有较好的疏水性能,在甲烷催化燃烧反应中有利于产物水的快速脱附,从而促进反应平衡移动提高催化燃烧效率。
2、本发明制备的催化剂可在较温和条件下实现甲烷完全催氧化为二氧化碳和水,且具有良好的稳定性。
3、本发明制备的催化剂贵金属含量低,催化剂成本低;同时还具有好的稳定性,低温活性。
4、本发明的催化剂能够用于甲烷燃烧,可用于天然气汽车和工业源尾气净化领域,例如天然气汽车或煤矿乏风瓦斯中的甲烷消除。
4、本发明制备方法简单,且易于工业大规模生产。
具体实施方式
为更好地说明本发明,便于理解本发明的技术方案,本发明的典型单非限制性的实例如下:
实施例1
本实施例的催化剂包括活性组分金属钯纳米颗粒和纯硅MFI分子筛载体,金属钯纳米颗粒与纯硅分子筛的质量比为0.001︰1;金属钯纳米颗粒的平均粒径为2nm;纯硅分子筛材料中只含有硅和氧两种元素。
该催化剂通过下述方式制备获得:(1)将聚乙烯醇和硝酸钯溶解在去离子水中(聚乙烯醇、硝酸钯和水的质量比为3:1:20);在剧烈搅拌(120转/分)的条件下迅速加入NaBH4水溶液(质量浓度为5%),NaBH4用量与Pd2+的质量比为2︰1;(2)向上述溶液中加入纯硅分子筛,纯硅分子筛与Pd2+的质量比为100︰1;搅拌5h,经离心洗涤和室温干燥、在500℃焙烧4小时处理后,得到纯硅分子筛负载钯催化剂。
该催化剂的使用方法:将纯硅分子筛负载钯催化剂置于天然气汽车或煤矿乏风瓦斯的后处理系统中,通过催化燃烧反应将甲烷完全转变成水和二氧化碳。
实施例2
本实施例的催化剂包括活性组分金属钯纳米颗粒和纯硅*BEA分子筛载体,金属钯纳米颗粒与纯硅分子筛的质量比为0.002︰1;金属钯纳米颗粒的平均粒径为2.5nm;纯硅分子筛材料中只含有硅和氧两种元素。
该催化剂的制备方法参照实施例1,对金属钯纳米颗粒与纯硅分子筛的用量进行相应调整;制备所得催化剂的使用方法也参照实施例1。
实施例3
本实施例的催化剂包括活性组分金属钯纳米颗粒和纯硅CHA分子筛载体,金属钯纳米颗粒与纯硅分子筛的质量比为0.005︰1;金属钯纳米颗粒的平均粒径为3nm;纯硅分子筛材料中只含有硅和氧两种元素。
该催化剂的制备方法参照实施例1,对金属钯纳米颗粒与纯硅分子筛的用量进行相应调整;制备所得催化剂的使用方法也参照实施例1。
实施例4
本实施例的催化剂包括活性组分金属钯纳米颗粒和纯硅AEI分子筛载体,金属钯纳米颗粒与纯硅分子筛的质量比为0.01︰1;金属钯纳米颗粒的平均粒径为5nm;纯硅分子筛材料中只含有硅和氧两种元素。
该催化剂的制备方法参照实施例1,对金属钯纳米颗粒与纯硅分子筛的用量进行相应调整;制备所得催化剂的使用方法也参照实施例1。
实施例5
本实施例的催化剂包括活性组分金属钯纳米颗粒和纯硅MEL分子筛载体,金属钯纳米颗粒与纯硅分子筛的质量比为0.02︰1;金属钯纳米颗粒的平均粒径为3.5nm;纯硅分子筛材料中只含有硅和氧两种元素。
该催化剂的制备方法参照实施例1,对金属钯纳米颗粒与纯硅分子筛的用量进行相应调整;制备所得催化剂的使用方法也参照实施例1。
实施例6
本实施例的催化剂包括活性组分金属钯纳米颗粒和纯硅MFI掺混*BEA分子筛载体,金属钯纳米颗粒与纯硅分子筛的质量比为0.01︰1;金属钯纳米颗粒的平均粒径为3nm;纯硅分子筛材料中只含有硅和氧两种元素。
该催化剂的制备方法参照实施例1,对金属钯纳米颗粒与纯硅分子筛的用量进行相应调整;制备所得催化剂的使用方法也参照实施例1。
性能测定
取0.1g甲烷催化燃烧催化剂置于内径为6mm的固定床反应器中,以N2为平衡气,空速为60000ml/g.h-1,反应气体连续通入固定床反应器,反应气体甲烷的浓度为1500ppm,其中氧气含量占5vol.%。
各实施例催化剂产品在催化燃烧反应中的相应温度如下表所示。
表1
序号 | 甲烷转化率达到90%所需的温度(℃) |
实施例1 | >450 |
实施例2 | 450 |
实施例3 | 430 |
实施例4 | 390 |
实施例5 | 350 |
实施例6 | 380 |
从表1可以看出:本发明提供的甲烷催化燃烧催化剂,其甲烷转化率达到90%时的燃烧温度通常在400℃左右,最低燃烧温度可下探至350℃。相对于CN113648995A文献记载的催化燃烧温度>425℃而言,在相对更低的燃烧温度条件下,本发明的甲烷催化燃烧催化剂具有更高甲烷转化率,故具有更好的催化活性。
另外,相对于CN114904569A文献记载的催化剂中质量占比在1-5%的范围而言,本发明的甲烷催化燃烧催化剂中金属钯纳米颗粒与纯硅分子筛的质量比0.001~0.02︰1,所使用贵金属含量相对更低,能够大大节约催化剂的成本。
申请人声明,本发明通过上述实例来说明所述吸附剂的详细组成,但本发明并不局限于上述详细组成,即不意味着本发明必须依赖上述详细组成才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料的等效替换以及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (6)
1.一种用于甲烷催化燃烧的纯硅分子筛负载钯催化剂,其特征在于,该催化剂包含作为活性组分的金属钯纳米颗粒和作为载体的纯硅分子筛材料;其中,金属钯纳米颗粒的粒径为2~5nm,金属钯纳米颗粒与纯硅分子筛的质量比0.001~0.02︰1;纯硅分子筛材料中只含有硅和氧两种元素。
2.根据权利要求1所述的纯硅分子筛负载钯催化剂,其特征在于,所述纯硅分子筛的骨架类型为MFI、*BEA、CHA、AEI、MEL中的一种,或者是两种以上的混合物。
3.权利要求1所述纯硅分子筛负载钯催化剂的制备方法,其特征在于,包括以下步骤:
(1)按照聚乙烯醇︰硝酸钯︰水的质量比为3︰1︰20,将聚乙烯醇和硝酸钯溶解在去离子水中;然后在剧烈搅拌条件下迅速加入NaBH4水溶液,NaBH4与Pd2+的质量比为2︰1;
(2)向上述溶液中加入纯硅分子筛,纯硅分子筛与Pd2+的质量比为100︰1;搅拌5h后,经离心洗涤、室温干燥和焙烧处理,得到纯硅分子筛负载钯催化剂。
4.根据权利要求3所述的方法,其特征在于,所述步骤(1)中,所述剧烈搅拌是指搅拌速度为120转/分钟;NaBH4水溶液的质量浓度为5%。
5.根据权利要求3所述的方法,其特征在于,所述步骤(2)中,所述焙烧温度为500℃,焙烧时间为4小时。
6.权利要求1所述纯硅分子筛负载钯催化剂的应用方法,其特征在于,是将所述催化剂置于天然气汽车或煤矿乏风瓦斯的后处理系统中,通过催化燃烧反应将甲烷完全转变成水和二氧化碳。
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