CN106238057B - 一种低温scr催化剂及其制备方法和应用 - Google Patents

一种低温scr催化剂及其制备方法和应用 Download PDF

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CN106238057B
CN106238057B CN201610545209.5A CN201610545209A CN106238057B CN 106238057 B CN106238057 B CN 106238057B CN 201610545209 A CN201610545209 A CN 201610545209A CN 106238057 B CN106238057 B CN 106238057B
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nitrate
low
temperature scr
scr catalyst
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CN106238057A (zh
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何丹农
高振源
杨玲
赵昆峰
袁静
蔡婷
张涛
金彩虹
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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    • B01D53/8621Removing nitrogen compounds
    • B01D53/8625Nitrogen oxides
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889Manganese, technetium or rhenium
    • B01J23/8892Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts

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Abstract

本发明公开了一种低温SCR催化剂及其制备方法,将硝酸锰和其他硝酸盐溶于100 mL去离子水中,加入活性氧化铝粉末,然后缓慢滴加浓氨水,调节pH至到10‑11,继续搅拌2~6h后抽滤,50~100℃烘箱烘干,然后在200~500℃马弗炉中焙烧2~8h;该催化剂是以活性氧化铝或堇青石粉末为载体,活性组分是氧化锰或者其复合氧化物。活性组分在催化剂中的质量百分比为5%‑15%,其余为载体。该催化剂属于环境友好型催化剂,催化剂活性窗口为125~200℃范围内脱硝率达到80%以上,且具有较长的使用寿命。

Description

一种低温SCR催化剂及其制备方法和应用
技术领域
本发明涉及一种低温SCR催化剂及其制备方法,属于工业脱硝技术领域。
背景技术
氮氧化物是人类活动排放到大气环境中的常见污染物,其中所占比例最大的是NO和NO2。大气中高浓度的NOx对人的呼吸系统有强烈的刺激作用,容易引起支气管炎、肺气肿甚至癌症。同时,氮氧化物能够产生环境污染,排入到大气后与氧、水反应后形成酸雨、酸雾,与碳氢化合物形成光化学烟雾。
以氨等作为还原气体的SCR催化技术能够有效的解决工业排放的氮氧化物气体。按照催化剂适用的烟气温度条件分类,可将SCR催化剂分为高温、中温,低温三种不同的SCR催化剂。高温SCR一般指的是催化剂的适用温度在450~600℃及以上,中温SCR是指催化剂的适用温度在300~450℃,而低温SCR催化剂是指催化剂的适用温度在120~300℃或更低温度。各催化剂都具有自己的优点及缺点,需根据实际工况来选择。
低温SCR催化剂在国内外的研究和应用中,技术相对不成熟一些,脱硝效率较低,应用较少。低温SCR装置一般放置在脱硫和除尘装置后,SO2浓度和粉尘浓度较低,有利于提高催化剂的使用寿命,但是对于现有的催化剂在相对较低温下的脱硝性能不够理想,因此限制了低温SCR催化剂的推广和应用。本发明通过将氧化锰和其他氧化物,复合负载到载体上,提高了催化剂的低温脱硝性能,为实际应用打下基础。
发明内容
本发明的目的是为了克服现有技术的不足,提供一种操作简单、脱硝效率高、反应温度低的SCR催化剂及其制备方法。
一种低温SCR催化剂的制备方法,其特征在于, 所述的低温SCR催化剂采用沉淀法制备,包括以下步骤:
将硝酸锰和其他硝酸盐溶于100 mL去离子水中,加入活性氧化铝粉末,然后缓慢滴加浓氨水,调节pH至到10-11,继续搅拌2~6h后抽滤,50~100℃烘箱烘干,然后在200~500℃马弗炉中焙烧2~8h;
所述的其他硝酸盐为硝酸钴、硝酸铁的一种或两种,硝酸锰与其他硝酸盐摩尔比为5:1~1:1。
一种低温SCR催化剂,其特征在于,根据上述方法制备得到;该催化剂的活性组分为氧化锰或其复合氧化物,载体为活性氧化铝粉末或堇青石粉末;所述活性组分在催化剂中的质量百分比为5%-15%,其余为载体。
一种低温SCR催化剂在低温SCR脱硝反应的应用。
上述技术方法将硝酸钴、硝酸铁和硝酸锰一起负载到载体表面,提高了催化剂的脱硝效率,有益效果显著,并且该催化剂成本低廉,环保无危害,生产工艺简单快捷,实用性好。
具体实施方式
以下实例用于更详细的说明本发明,但本发明并不限于此。
对比例:
将0.90g Mn(NO3)2溶于100 mL去离子水中,加入5g 活性氧化铝粉末,然后缓慢滴加浓氨水,调节pH至到10-11,继续搅拌2h后抽滤,100℃烘箱烘干,然后在400℃马弗炉中焙烧4h。
对上述制备的催化剂进行NH3-SCR脱硝性能测试:空速300000 mL/(g·h),模拟烟气成分:200ppm NO、200ppm NH3、5% O2、平衡气为N2。使用二氧化碳分析仪(Thermo,Model42i)进行产物分析,测试结果见表1。
对比例2:
将0.90g Mn(NO3)2溶于100 mL去离子水中,加入5g 堇青石粉末,然后缓慢滴加浓氨水,调节pH至到10-11,继续搅拌2h后抽滤,100℃烘箱烘干,然后在400℃马弗炉中焙烧4h。
催化剂评价方法同对比例1,。测试结果见表1。
实施例1:
将0.90g Mn(NO3)2和0.73g Co(NO3)2溶于100 mL去离子水中,加入5g 活性氧化铝粉末,然后缓慢滴加浓氨水,调节pH至到10-11,继续搅拌2h后抽滤,100℃烘箱烘干,然后在400℃马弗炉中焙烧4h。
催化剂评价方法同对比例。测试结果见表1。
实施例2:
将实施例1中0.73g Co(NO3)2改成1.01g Fe (NO3)3,其余制备方法同实施例1。催化剂评价方法同对比例。测试结果见表1。
实施例3:
将实施例1中5g活性氧化铝粉末改成5g堇青石粉末,其余制备方法同对比例。催化剂评价方法同对比例。测试结果见表1。
实施例4:
将实施例2中5g活性氧化铝粉末改成5g堇青石粉末,其余制备方法同对比例。催化剂评价方法同对比例。测试结果见表1。
表1 催化剂脱硝率数据
.

Claims (2)

1.一种低温SCR催化剂的制备方法,该催化剂的活性组分为氧化锰或其复合氧化物,载体为活性氧化铝粉末或堇青石粉末;所述活性组分在催化剂中的质量百分比为5%-15%,其余为载体,其特征在于, 所述的低温SCR催化剂采用沉淀法制备,包括以下步骤:
将硝酸锰和其他硝酸盐溶于100 mL去离子水中,加入活性氧化铝粉末,然后缓慢滴加浓氨水,调节pH至到10-11,继续搅拌2~6h后抽滤,50~100℃烘箱烘干,然后在200~500℃马弗炉中焙烧2~8h;
所述的其他硝酸盐为硝酸钴、硝酸铁的一种或两种,硝酸锰与其他硝酸盐摩尔比为5:1~1:1。
2.根据权利要求1所述方法制备得到的低温SCR催化剂在低温SCR脱硝反应的应用。
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CN110721673A (zh) * 2019-09-12 2020-01-24 华中科技大学 一种Mn-Ce/Al2O3/堇青石低温脱硝催化剂及其制备方法

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