CN108472630B - 用于压缩天然气燃烧系统废气的氧化催化剂 - Google Patents
用于压缩天然气燃烧系统废气的氧化催化剂 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000007789 gas Substances 0.000 title claims abstract description 22
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 21
- 239000003345 natural gas Substances 0.000 title claims abstract description 20
- 230000003647 oxidation Effects 0.000 title abstract description 9
- 238000007254 oxidation reaction Methods 0.000 title abstract description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 55
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 53
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 27
- 229910052788 barium Inorganic materials 0.000 claims abstract description 26
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 22
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 229910052759 nickel Inorganic materials 0.000 description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 3
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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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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
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- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种用于防止用于压缩天然气燃烧系统的、载有含铂和钯的贵金属组分的废气净化催化剂失活的催化剂组合物。在其中将铂浸渍的第一氧化铝、钯浸渍的第二氧化铝和二氧化铈组分负载在陶瓷载体上的用于压缩天然气车辆或静态燃烧系统的废气氧化催化剂中,将所述第一氧化铝进一步用钡助催化剂浸渍,从而明显防止CNG稀燃发动机催化剂的失活。
Description
技术领域
本发明涉及用于压缩天然气燃烧系统的废气氧化催化剂,并且更具体地讲,涉及用于压缩天然气稀燃发动机的废气净化催化剂,其中将用于压缩天然气稀燃发动机的、载有含铂和钯的贵金属组分的常规废气净化催化剂进一步通过用作助催化剂的特定组分浸渍,从而防止催化剂失活。
背景技术
在包括车辆发动机在内的燃烧系统中使用CNG(压缩天然气)作为燃料是环境友好的,产生经济效益,并且特征在于有毒物质如HC、CO和PM(颗粒物)的排放低,因而几乎没有废气的气味和烟雾。在本发明中,燃烧系统包括车辆发动机,并且在一些情况下,除了用于车辆的燃烧系统之外的燃烧系统也被称为静态燃烧系统,它有别于用于车辆的称为动态燃烧系统的燃烧系统。
在用于压缩天然气车辆的废气净化催化剂及其净化方法的相关领域,本申请人的韩国专利第670221号公开了用于压缩天然气车辆的、载有含铂和钯的贵金属组分的废气氧化催化剂,这是一种用于提高对来自压缩天然气车辆的废气的氧化活性的催化剂,它被构造成使得将钯浸渍的第一氧化铝、铂浸渍的第二氧化铝、CeO2-ZrO2复合二氧化铈和氧化镍负载在陶瓷载体上。另外,如本申请人的韩国专利第1524054号中所公开的那样,用于压缩天然气燃烧系统的废气氧化催化剂,特别是用于提高对过量空气中的来自压缩天然气车辆或静态燃烧系统的废气的氧化活性的催化剂,被构造成使得将钯浸渍的第一氧化铝、铂浸渍的第二氧化铝和二氧化铈组分负载在陶瓷载体上,并将第一氧化铝用选自钡、镍、镧、钐和钇的助催化剂浸渍,以提高对过量空气中的来自压缩天然气车辆或静态燃烧系统的废气组分甲烷的氧化活性。
发明内容
技术问题
用于净化来自在燃料稀燃气氛中运转的CNG发动机的CNG废气的目前可用的催化剂在催化剂耐久性方面存在问题,即催化剂失活。尚未准确认识到用于净化来自CNG稀燃发动机的废气的铂/钯基催化剂失活的原因。本申请人已开发了一种用于解决CNG稀燃发动机催化剂失活问题的催化剂,其构造方式使得在用于压缩天然气燃烧系统的废气氧化催化剂中,将钯浸渍的第一氧化铝、铂浸渍的第二氧化铝和二氧化铈组分负载在陶瓷载体上,将钯浸渍的第一氧化铝进一步用选自钡、镍、镧、钐和钇的助催化剂浸渍,但仍然需要针对催化剂失活的解决方案。
技术方案
因此,本发明旨在提供一种用于防止用于压缩天然气燃烧系统的、载有含铂和钯的贵金属组分的废气净化催化剂失活的催化剂组合物。与常规技术不同,本发明人已确定将用作助催化剂的钡组分添加到其上负载有铂的载体可因而改善催化剂耐久性。具体而言,在被构造成使得将铂浸渍的第一氧化铝、钯浸渍的第二氧化铝和二氧化铈组分负载在陶瓷载体上的用于压缩天然气燃烧系统的废气氧化催化剂中,将铂浸渍的第一氧化铝进一步用钡助催化剂浸渍,由此,已经确认了可以防止CNG稀燃发动机催化剂的失活。不受此限制,在本发明中,分别浸渍在第一氧化铝和第二氧化铝上的铂和钯的重量比落在1:1至1:10的范围内。根据本发明,基于铂的量,钡助催化剂的添加量为1至20重量%,并且铂浸渍的氧化铝和钯浸渍的氧化铝的重量比落在15:15至15:150的范围内。
有利效果
根据本发明,借助于铂与钡助催化剂之间的相互作用,可以防止CNG稀燃发动机催化剂的失活。
附图说明
图1-4显示了在根据本发明实施例中的CNG稀燃发动机废气催化剂中的催化活性随时间而变化的结果;以及
图5示意性地显示了根据本发明的CNG稀燃发动机废气催化剂的耐久性测试。
具体实施方式
在下文中,将给出对本发明的详细描述,但不受限于其实施方案。
如上所述,用于净化CNG稀燃发动机废气的催化剂主要由铂(Pt)和钯(Pd)组成。最近开发的催化剂被构造成使得将助催化剂引入Pd附近,这基于以下事实:就甲烷转化效而言,Pd具有优于Pt的氧化性能。具体而言,向其上负载有Pd的载体添加助催化剂,诸如钡、镍、镧、钐或钇,其中助催化剂组分通过因络合作用而改变Pd的电子状态从而有助于催化剂耐久性。然而,出乎意料的是,本发明人已经确定,由于将助催化剂组分尤其是钡引入铂组分而不是钯附近,可以改善催化剂耐久性。
根据本发明,通过以下方式制备催化剂:用Pt和助催化剂前体(特别是乙酸钡)浸渍第一氧化铝,同时用Pd浸渍第二氧化铝,将第一氧化铝与第二氧化铝混合,然后向其中添加氧化铈,再均匀研磨和焙烧。优选地,分别浸渍在第一氧化铝和第二氧化铝上的铂和钯的重量比落在1:1至1:10的范围内,并且基于钯的量以1至20重量%的量向其上负载有铂的载体进一步添加钡助催化剂,且铂-钡浸渍的氧化铝和钯浸渍的氧化铝的重量比优选落在15:15至15:150的范围内。如果根据本发明的助催化剂的量基于铂的量小于1重量%,则助催化剂不起作用。另一方面,如果其量基于铂的量超过20重量%,则耐久性明显变差。根据本发明的催化剂被构造成使得将钡助催化剂仅浸渍在铂浸渍的载体上而不负载在用其他贵金属(例如钯)浸渍的载体上,这与最近开的基于钯-助催化剂的催化剂不同。铂-钡浸渍的氧化铝和钯浸渍的氧化铝的上述重量比是通过许多种测试获得的最佳范围。尽管没有在任何特定的理论中进行描述,但是助催化剂组分通过与铂组分的相互作用增强催化剂的耐久性。与传统的CNG稀燃发动机废气催化剂不同,本发明的催化剂不会失活并且即使在反应时间之后仍保持其活性。图1-4显示了在根据本发明实施例中的CNG稀燃发动机废气催化剂中的催化活性随时间的变化。基于图1至4所示的测试结果,采用10%的水通过补充5,000ppmCH4、15%O2、10%H2O而其余的为N2以60,000 1/h的空间速度(SV)使根据本发明的催化剂在850℃/10h下水热老化。这里,ΔT表示催化剂出口与催化剂入口之间的温差。图5示意性地示出耐久性测试。将本发明的助催化剂即钡另外掺入铂浸渍的载体中。与通常添加到钯组分中的Ba助催化剂相比,通过添加到铂组分中的Ba助催化剂来防止失活的效果显著增加了耐久性。
将通过以下实施例来更好地理解本发明,这些实施例不应被解释为限制本发明。特别地,贵金属和用于助催化剂的金属前体不受这些实施例限制,并且可以使用各种硝酸盐、乙酸盐、氯化物、硫酸盐等。出于简要描述的目的,举例说明了稀燃发动机车辆,但是本发明不限于此,并且可以应用于使用压缩天然气作为燃料的所有燃烧系统。
比较例1(CNG比较)
A.用氯铂酸浸渍15.0g/l的第一氧化铝粉末,并用硝酸钯和乙酸钡(基于Pd的量为10重量%的量)浸渍80.0g/l的第二氧化铝粉末,由此制备Pt浸渍的活性氧化铝和Pd-Ba浸渍的活性氧化铝,然后将二氧化铈粉末(氧化铝5重量%)分散在水中以得到浆料。这里,Pt和Pd的重量比为1:5。
b.研磨浆料,使得其中约90%具有6-8μm的粒度,并将处理过的浆料施加在堇青石蜂窝上,在150℃至160℃下干燥约10分钟,然后在530℃至550℃下焙烧约40至60分钟,从而完成比较催化剂。
比较例2
进行与比较例1中相同的程序,不同的是基于Pd的量将钡的量改为1重量%、5重量%和20重量%。结果显示在图1中。当钡的量为20重量%或更多时,耐久性显著变差。1重量%的钡和5重量%的钡对耐久性没有很大的影响。因此,本发明的催化剂基于1重量%的钡来设计。
比较例3
进行与比较例1中相同的程序,不同的是基于Pd的量将钡的量固定为1重量%并且将Pt和Pd的重量比从1:5变为1:6、1:7、1:8和1:9。结果显示在图2中。在1Pt/7Pd下耐久性得到优化。因此,本发明的催化剂基于1Pt/7Pd来设计。
比较例4
进行与比较例1中相同的程序,不同的是基于Pd的量将钡的量固定为1重量%并且将Pt和Pd的重量比固定为1:7,且将施加到Pd上的第二氧化铝粉末的量从80g/l变为100g/l、120g/l和140g/l。结果显示在图3中。在120g/l下耐久性得到优化。因此,本发明的催化剂基于这一点来设计。
实施例
在上述比较例的基础上,在以下条件下制备了铂-钡催化剂:基于Pt的量将钡的量设为1重量%,铂和钯的重量比为1:7,将作为钯载体的第二氧化铝粉末的量设为120g/L,并且改变钡助催化剂的浸渍位置,之后测试催化剂的耐久性。结果显示在图4中。令人惊讶的是,通过将钡助催化剂的浸渍位置从钯改变到铂改善了催化剂耐久性。尽管本领域的技术人员通过因与钯的络合作用而改变电子态来考虑助催化剂对催化剂耐久性的贡献,但出人意料的是,已证实通过将钡助催化剂与铂一起浸渍可防止催化剂失活。
Claims (3)
1.一种用于改善对过量空气中的来自压缩天然气车辆或静态燃烧系统的废气的氧化活性的催化剂,所述催化剂构造成使得将铂浸渍的第一氧化铝、钯浸渍的第二氧化铝和二氧化铈组分负载在陶瓷载体上,并且将所述第一氧化铝进一步用钡助催化剂浸渍,基于铂的量,钡助催化剂的添加量为1至20重量%,以改善对过量空气中的来自压缩天然气车辆或静态燃烧系统的废气组分甲烷的氧化活性。
2.根据权利要求1所述的催化剂,其中基于铂的量,所述钡助催化剂以1至10重量%的量添加。
3.根据权利要求1所述的催化剂,其中分别浸渍在所述第一氧化铝和所述第二氧化铝上的铂和钯的重量比为1:1至1:10。
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