CN104971764A - 一种低温高效脱硝催化剂及其制备方法 - Google Patents
一种低温高效脱硝催化剂及其制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 18
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 238000001354 calcination Methods 0.000 claims abstract description 10
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- 238000005406 washing Methods 0.000 claims abstract description 7
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- 239000000377 silicon dioxide Substances 0.000 claims abstract description 3
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
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- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 6
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Abstract
本发明属于氮氧化物污染控制领域,涉及一种低温高效脱硝催化剂及其制备方法。包含如下步骤:(1)配置硝酸铈水溶液;(2)将介孔氧化硅材料SBA-15浸渍于步骤(1)所得的溶液中,搅拌后,过滤、洗涤、干燥;(3)将步骤(2)制得的材料煅烧,得到均匀分散的CeO2-SBA-15材料;(4)配置硝酸锰乙醇溶液;(5)将步骤(3)所得的CeO2-SBA-15材料浸渍于步骤(4)所得的硝酸锰乙醇溶液中,然后挥发掉乙醇,并洗涤、干燥;(6)将步骤(5)制得的材料煅烧,得到均匀分散的MnxOy/CeO2-SBA-15脱硝催化剂。该制备方法的工艺简单,成本较低,制得的催化剂MnxOy/CeO2-SBA-15孔道均一有序、比表面积大,孔径分布窄,催化组分分散性好,催化活性高,低温段脱硝效果较好,可利用的脱硝温度范围较宽。
Description
技术领域
本发明属于氮氧化物污染控制领域,涉及一种低温高效脱硝催化剂MnxOy/CeO2-SBA-15及其制备方法。
背景技术
随着工业的发展和社会的进步,大气污染越来越受到人们的关注。十二五之前,我国在燃煤电厂的烟气治理方面,只着重控制SO2的排放,而忽视了对NOx排放的控制。有资料显示,NOx不仅具有生物毒性,危害人类健康,还会引起酸雨、光化学烟雾、臭氧层破坏等一系列环境问题。据报道,我国2008年NOx的排放量为2000万吨,如不加以控制,将在2020年达到3000万吨,并将成为第一大酸性气体污染物。正因为如此,十二五期间,全面推进燃煤电厂脱硝已成为国家的一项重大决策。就现阶段而言,国内外主要的脱硝技术包括选择性催化还原技术(SCR)和选择性非催化还原技术(SNCR)两大类,其中SCR脱硝技术是在催化剂存在的条件下,利用NH3选择性还原NOx,该技术相对于只用还原剂NH3的SNCR技术来说,不仅脱硝效率更高,而且NH3的消耗量和逃逸率较低,因此,SCR技术被认为是最经济有效的脱硝工艺。
SCR反应器有三种布置方式,分别称为高尘烟气SCR(High-Dust SCR,HD-SCR)、低尘烟气SCR(Low-Dust SCR,LD-SCR)和尾部SCR(Tail-End SCR,TE-SCR),所选用的催化剂多为商业催化剂V2O5-WO3/TiO2或V2O5-MoO3/TiO2。前两种布置方式需要将SCR反应器布置在脱硫塔之前,这样布置的弊端在于烟气中高浓度的SO2会造成催化剂的中毒,损失催化剂的活性。而采用TE-SCR工艺,将SCR反应器放在脱硫塔之后,可以大大降低SO2对催化剂性能的影响,但这种布置方式面临的最大问题在于目前商用钒基催化剂活性温度窗口在300-400℃之间,而脱硫塔出口烟气温度一般在80-150℃,这就需要在SCR反应器之前对烟气进行加热,大大增加了运营费用。因此,如何制备高效的低温SCR催化剂已成为SCR脱硝工艺的关键技术难题。SCR催化剂的组成包括活性组分和载体两大类,就脱硝催化剂而言,载体的选择倾向多样化,主要包括TiO2、沸石分子筛、Al2O3、活性炭等,这些催化剂有其优势,但也有无法避免的缺陷,如TiO2、Al2O3比表面积不够大,沸石分子筛、活性炭孔径较小等。因此,采用合适的催化剂载体,增加载体的可选择性显得尤其重要。而脱硝催化剂的活性组分也有从单组份向双组份甚至多组分发展的趋势,不仅包括常规的W、V等氧化物,还包括Fe、Mn、Cu、Ce等过渡金属氧化物。这些活性组分适用于不同的温度区间,通过它们之间的协同,能达到提高催化剂的低温脱硝活性,扩大脱硝温度窗口的目的。因此,通过活性组分与催化剂载体的设计组合,制备新型高效低温脱硝催化剂具有重大的意义。
发明内容
本发明的目的在于提供一种低温高效脱硝催化剂MnxOy/CeO2-SBA-15及其制备方法。
为实现上述目的,本发明采用以下技术方案:
一种低温高效脱硝催化剂MnxOy/CeO2-SBA-15的制备方法,包含如下步骤:
(1)配置硝酸铈水溶液;
(2)将介孔氧化硅材料SBA-15浸渍于步骤(1)所得的溶液中,搅拌、过滤、洗涤、干燥;
(3)将步骤(2)制得的材料置于马弗炉中煅烧,得到均匀分散的CeO2-SBA-15材料;
(4)配置硝酸锰乙醇溶液;
(5)将步骤(3)所得的材料浸渍于步骤(4)所得的溶液中,浸渍一段时间后,挥发掉乙醇,并洗涤、干燥;
(6)将步骤(5)制得的材料置于马弗炉中煅烧,得到均匀分散的MnxOy/CeO2-SBA-15材料。
所述的步骤(1)中硝酸铈溶液中硝酸铈的浓度均为0.1~1mol/L。
所述的步骤(2)中介孔氧化硅材料SBA-15的投加量为10~40g/L,浸渍时间为4~8h。
所述的步骤(3)中煅烧温度为300~500℃,煅烧时间为4-8h。
所述的步骤(4)中硝酸锰乙醇溶液中锰元素的质量为CeO2-SBA-15投加量的10~30%。
所述的步骤(5)中浸渍时间为1~3h。
所述的步骤(6)中煅烧温度为300~500℃,煅烧时间为4~8h。
一种上述方法制得的低温高效脱硝催化剂MnxOy/CeO2-SBA-15,其中,MnxOy/CeO2-SBA-15为MnO2/CeO2-SBA-15和Mn2O3/CeO2-SBA-15的混合物,该催化剂属于新结构高性能多孔脱硝催化剂,孔道为二维六方结构且均一有序,孔径较大,分布范围在6~7nm之间,比表面积为300~500m2/g,孔容范围为0.3~0.5cm3/g。
本发明具有如下有益效果:
本发明提供了一种低温高效脱硝催化剂MnxOy/CeO2-SBA-15的制备方法。该制备方法的工艺简单,成本较低,制得的催化剂MnxOy/CeO2-SBA-15孔道均一有序,低温段脱硝效果较好,可利用的脱硝温度范围较宽。
附图说明
图1为本发明实施例1所得催化剂的透射电镜图(简称TEM)。
具体实施方式
以下结合实施例和附图进一步说明本发明。
实施例1
(1)首先,配置0.5mol/L硝酸铈水溶液待用;
(2)其次,将2g SBA-15加入到100mL上述硝酸铈的水溶液中(20g/L)搅拌6h,然后过滤,洗涤,干燥;
(3)接着,将步骤(2)中所得样品置于马弗炉中,在300℃下煅烧6h即可得到均匀分散的CeO2-SBA-15材料;
(4)然后,配置硝酸锰乙醇溶液,其中锰元素的质量为CeO2-SBA-15投加量的20%;
(5)将步骤(3)中所得的材料浸渍于步骤(4)所得的溶液中,搅拌2h后挥发掉乙醇,并洗涤、干燥;
(6)最后,将步骤(5)中所得的材料置于马弗炉中,于300℃下煅烧6h得到均匀分散的MnxOy/CeO2-SBA-15脱硝催化剂,其中,MnxOy/CeO2-SBA-15为MnO2/CeO2-SBA-15和Mn2O3/CeO2-SBA-15的混合物,其结构参数如表1所示。
图1为实施例1中制得催化剂的TEM图,图中阴影部分即为成功负载于SBA-15上的活性金属颗粒。
实施例2
(1)首先,配置0.1mol/L硝酸铈的水溶液待用;
(2)其次,将1g SBA-15加入到100mL上述硝酸铈的水溶液中(10g/L)搅拌8h,然后过滤,洗涤,干燥;
(3)接着,将步骤(2)中所得样品置于马弗炉中,在500℃下煅烧4h即可得到均匀分散的CeO2-SBA-15材料;
(4)然后,配置硝酸锰乙醇溶液,其中锰元素的质量为CeO2-SBA-15投加量的30%;
(5)将步骤(3)中所得的材料浸渍于步骤(4)所得的溶液中,搅拌1h后挥发掉乙醇,并洗涤、干燥;
(6)最后,将步骤(5)中所得的材料置于马弗炉中,于400℃下煅烧4h得到均匀分散的MnxOy/CeO2-SBA-15脱硝催化剂,其中,MnxOy/CeO2-SBA-15为MnO2/CeO2-SBA-15和Mn2O3/CeO2-SBA-15的混合物,其结构参数如表1所示。
实施例3
(1)首先,配置1mol/L硝酸铈的水溶液待用;
(2)其次,将4g SBA-15加入到100mL上述硝酸铈的水溶液中(40g/L)搅拌4h,然后过滤,洗涤,干燥;
(3)接着,将步骤(2)中所得样品置于马弗炉中,在400℃下煅烧8h即可得到均匀分散的CeO2-SBA-15材料;
(4)然后,配置硝酸锰乙醇溶液,其中锰元素的质量为CeO2-SBA-15投加量的10%;
(5)再次,将步骤(3)中所得的材料浸渍于步骤(4)所得的溶液中,搅拌3h后挥发掉乙醇,并洗涤、干燥;
(6)最后,将步骤(5)中所得的材料置于马弗炉中,于500℃下煅烧8h得到均匀分散的MnxOy/CeO2-SBA-15脱硝催化剂,其中,MnxOy/CeO2-SBA-15为MnO2/CeO2-SBA-15和Mn2O3/CeO2-SBA-15的混合物,其结构参数如表1所示。
表1为实施例1至3中制得脱硝催化剂MnxOy/CeO2-SBA-15的结构参数。
表1
实施例 | 孔径(nm) | 孔容(cm3/g) | 比表面积(m2/g) |
实施例1 | 6.38 | 0.42 | 421 |
实施例2 | 6.27 | 0.35 | 397 |
实施例3 | 6.39 | 0.47 | 435 |
对实施例中制备的脱硝催化剂进行实验室小型烟气脱硝实验,模拟烟气空速为10000h-1,其中NO浓度为1000ppm,氧气为5%,载气为N2,按NH3/NO体积比1.2喷入NH3作为还原剂,采用EasyLine连续气体分析仪(EL3020)对反应前后NO浓度进行监测。脱硝反应器采用电加热管式炉,以维持稳定的反应温度。实施例中制备的催化剂在100~300℃下的脱硝效率如表2所示。
表2为实施例1至3中制得的脱硝催化剂MnxOy/CeO2-SBA-15在100~300℃下的脱硝效率。
表2
实施例1 | 实施例2 | 实施例3 | |
100℃ | 85% | 87% | 71% |
140℃ | 87% | 89% | 72% |
180℃ | 90% | 90% | 74% |
220℃ | 91% | 89% | 76% |
260℃ | 91% | 88% | 76% |
300℃ | 83% | 80% | 74% |
上述实验结果表明:
(1)在上述反应条件下,本发明所制备的脱硝催化剂MnxOy/CeO2-SBA-15具有较宽的温度适用范围,在100~300℃下均能取得70%以上的脱硝效率。
(2)在上述反应条件下,本发明所制备的脱硝催化剂MnxOy/CeO2-SBA-15在低温段具有较高的催化活性,其中锰含量为20%以上的催化剂在100~200℃条件下,脱硝效率均能达到近90%,明显优于普通催化剂。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和应用本发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于这里的实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (10)
1.一种脱硝催化剂的制备方法,其特征在于:包含如下步骤:
(1)配置硝酸铈水溶液;
(2)将介孔氧化硅材料SBA-15浸渍于步骤(1)所得的硝酸铈水溶液中,搅拌后,过滤、洗涤、干燥;
(3)将步骤(2)制得的材料煅烧,得到CeO2-SBA-15材料;
(4)配置硝酸锰乙醇溶液;
(5)将步骤(3)所得的CeO2-SBA-15材料浸渍于步骤(4)所得的硝酸锰乙醇溶液中,然后挥发掉乙醇,并洗涤、干燥;
(6)将步骤(5)制得的材料煅烧,得到MnxOy/CeO2-SBA-15脱硝催化剂。
2.根据权利要求1所述的制备方法,其特征在于:所述的步骤(1)中硝酸铈水溶液的浓度为0.1~1mol/L。
3.根据权利要求1所述的制备方法,其特征在于:所述的步骤(2)中介孔氧化硅材料SBA-15的投加量为10~40g/L。
4.根据权利要求1或3所述的制备方法,其特征在于:所述的步骤(2)中的浸渍时间为4~8h。
5.根据权利要求1所述的制备方法,其特征在于:所述的步骤(3)中煅烧温度为300~500℃,煅烧时间为4~8h。
6.根据权利要求1所述的制备方法,其特征在于:所述的步骤(4)中硝酸锰乙醇溶液中锰元素的质量为CeO2-SBA-15投加量的10~30%。
7.根据权利要求1所述的制备方法,其特征在于:所述的步骤(5)中浸渍时间为1~3h。
8.根据权利要求1所述的制备方法,其特征在于:所述的步骤(6)中煅烧温度为300~500℃,煅烧时间为4~8h。
9.一种由权利要求1至8中任一所述的制备方法制得的脱硝催化剂MnxOy/CeO2-SBA-15,其中,MnxOy为MnO2和Mn2O3。
10.根据权利要求9所述的脱硝催化剂MnxOy/CeO2-SBA-15,其特征在于:该催化剂的孔道为二维六方结构,孔径分布范围为6~7nm,比表面积为300~500m2/g,孔容范围为0.3~0.5cm3/g。
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