WO2016078292A1 - 抗二氧化硫型低温锰-铁氧化物脱硝催化剂及其制备方法 - Google Patents

抗二氧化硫型低温锰-铁氧化物脱硝催化剂及其制备方法 Download PDF

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WO2016078292A1
WO2016078292A1 PCT/CN2015/076060 CN2015076060W WO2016078292A1 WO 2016078292 A1 WO2016078292 A1 WO 2016078292A1 CN 2015076060 W CN2015076060 W CN 2015076060W WO 2016078292 A1 WO2016078292 A1 WO 2016078292A1
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manganese
iron oxide
catalyst
carbon nanotubes
temperature
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郑玉婴
张延兵
陈桓
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福州大学
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts 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
    • B01J23/84—Catalysts 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
    • B01J23/889—Manganese, technetium or rhenium

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  • the invention belongs to the field of flue gas denitration, and particularly relates to a sulfur dioxide-resistant low-temperature manganese-iron oxide denitration catalyst and a preparation method thereof.
  • NO x as a common air pollutant, has given rise to a series of environmental problems such as acid rain, photochemical ozone pollution and destruction, States have enacted stringent NO x emissions law.
  • researchers from various countries have also invested a lot of energy in researching flue gas denitration technology.
  • ammonia-selective catalytic reduction of NO (NH 3 -SCR) is recognized as the most mature and effective denitration technology.
  • the NH 3 -SCR technology is characterized in that ammonia or other reducing gas selectively reduces NO to N 2 and H 2 O under the action of a catalyst, thereby achieving the purpose of removing NO.
  • Vanadium-titanium catalyst system is a commercially NH 3 -SCR catalyst.
  • its operating temperature window is high (300-400 ° C) and is susceptible to deactivation by the influence of SO 2 in the flue gas. Therefore, such catalysts need to be installed after flue gas desulfurization and electrostatic precipitator equipment.
  • the temperature after flue gas desulfurization and dedusting is usually lower than 200 ° C, which makes the vanadium-titanium catalyst with a higher operating temperature window difficult to function. Therefore, the development of anti-SO 2 type NH 3 -SCR catalyst with excellent catalytic effect at low temperature ( ⁇ 200 ° C) has become the focus of research at this stage.
  • the object of the present invention is to provide a sulfur dioxide-resistant low-temperature manganese-iron oxide denitration catalyst and a preparation method thereof, in view of the deficiencies of the prior art.
  • the invention adopts carbon nanotubes with special physical and chemical properties as a carrier, and obtains a sulfur dioxide-resistant low-temperature denitration catalyst by supporting a manganese-iron oxide active component, and the catalyst has excellent activity at low temperature (80-180° C.) and is resistant to SO. 2 significant advantages of performance.
  • the present invention adopts the following solutions:
  • An anti-sulphur dioxide type low-temperature manganese-iron oxide denitration catalyst comprising a carbon nanotube carrier and a manganese-iron oxide active component; the carbon nanotube has a diameter of 40 to 60 nm, and the active component has a precursor
  • the body is manganese acetate and iron nitrate.
  • a sulfur dioxide-resistant low-temperature manganese-iron oxide denitration catalyst having a composition of yMn z -FeO x /CNTs, wherein y and z represent molar ratios of (Mn+Fe)/CNTs and Mn/(Mn+Fe), respectively .
  • the molar ratio of (Mn + Fe) / CNTs in the catalyst was 0.3% to 1.8%; and the molar ratio of Mn / (Mn + Fe) was 0.75%.
  • step 2) using an equal volume impregnation method, the solution prepared in step 2) is added dropwise to the oxidized modified carbon nanotubes, immersed at room temperature, dried at 100 ° C, and then calcined at 300 ° C to obtain anti-sulphur dioxide-type low-temperature manganese-iron oxide denitration. catalyst.
  • the low-temperature supported denitration catalyst prepared by the invention has excellent denitration activity at low temperature (80 ° C ⁇ 180 ° C), and the denitration rate (NO) is more than 40%;
  • the catalyst prepared by the invention has a lower conversion rate of NO in the presence of sulfur dioxide, but is still much higher than the conversion rate of other denitration catalysts, indicating that the catalyst prepared by the invention has good anti-sulfur dioxide effect.
  • Figure 1 is a NO conversion map of the catalyst prepared by the present invention
  • Figure 2 is a TEM (a), (b) and EDX map (c), (d) of the catalyst prepared by the present invention
  • Figure 3 is an XRD pattern of the catalyst prepared by the present invention.
  • Figure 4 is an anti-SO 2 performance of a catalyst prepared in accordance with the present invention.
  • step 2) The solvent prepared in step 2) is added dropwise to 0.3 g of carbon nanotubes, immersed at room temperature for 24 h, dried at 100 ° C for 12 h, and finally calcined at 280 ° C for 30 min in a tube furnace to obtain 0.3% Mn 0.75 -FeO x /CNTs.
  • step 2) The solvent prepared in step 2) is added dropwise to 0.3 g of carbon nanotubes, immersed at room temperature for 24 h, dried at 100 ° C for 12 h, and finally calcined at 300 ° C for 30 min in a tube furnace to obtain 0.8% Mn 0.75 -FeO x /CNTs.
  • 3g ethanol solution should be prepared, and finally the solution is: 3g ethanol, 0.2757g manganese acetate and 0.1525g iron nitrate;
  • step 2) The solvent prepared in step 2) is added dropwise to 0.3 g of carbon nanotubes, immersed at room temperature for 24 h, dried at 100 ° C for 12 h, and finally calcined at 290 ° C for 30 min in a tube furnace to obtain 1.2% Mn 0.75 -FeO x /CNTs.
  • step 2) The solvent prepared in step 2) is added dropwise to 0.3 g of carbon nanotubes, immersed at room temperature for 24 h, dried at 100 ° C for 12 h, and finally calcined at 280 ° C for 30 min in a tube furnace to obtain a low temperature of 1.8% Mn 0.75 -FeO. x /CNTs.
  • the NO conversion test of the denitration catalyst prepared in the examples was carried out, and the test results are shown in Fig. 1. It can be seen from Fig. 1 that in the range of 80 °C - 120 °C, the NO conversion rate of the catalyst increases remarkably with the increase of temperature to a temperature range of 120 ° C - 140 ° C, and slowly increases to 140 ° C - In the interval of 180 °C, the NO conversion tends to be stable; indicating the denitration of the present invention
  • the catalyst has a very high catalytic activity in the range of 80 ° C to 180 ° C;
  • Figure 2 is a TEM (a), (b) and EDX map (c), (d) of the catalyst prepared by the present invention
  • Figure 3 is an XRD pattern of the catalyst prepared by the present invention.

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Abstract

本发明属于烟气脱硝领域，具体涉及一种抗二氧化硫型低温锰-铁氧化物脱硝催化剂及其制备方法。该脱硝催化剂由碳纳米管(CNTs)载体，锰-铁氧化物(Mn-FeOx)活性组分组成。通过掺杂铁氧化物，得到抗SO2型低温Mn-FeOx/CNTs催化剂，所制备的催化剂具有低温(80～180℃)活性优异、抗SO2性能显著和制备工艺简单等优点。

Description

抗二氧化硫型低温锰-铁氧化物脱硝催化剂及其制备方法 技术领域
本发明属于烟气脱硝领域，具体涉及一种抗二氧化硫型低温锰-铁氧化物脱硝催化剂及其制备方法。
背景技术
NOx作为一种常见的大气污染物，已经引起一系列的环境问题，如酸雨、光化学污染和臭氧破坏等，因此各国都制定了严格的NOx排放法。同时，各国科研人员也投入大量的精力研究烟气脱硝技术。其中,氨气选择性催化还原NO(NH3-SCR)被公认为是最成熟和有效的脱硝技术。NH3-SCR技术的特点是,氨气或其它还原性气体在催化剂的作用下选择性地还原NO为N2和H2O，以此达到脱除NO的目的。
钒钛催化剂体系是一种商业化的NH3-SCR催化剂。但是，其操作温度窗口较高(300-400℃)，且易受烟气中SO2的影响而减活。因此，该类催化剂需安装在烟气脱硫和静电除尘设备之后。而烟气经过脱硫和除尘后的温度通常低于200℃，这使操作温度窗口较高的钒钛催化剂难以发挥作用。因此，开发低温(<200℃)催化效果优良的抗SO2型NH3-SCR催化剂成为现阶段研究的重点。
发明内容
本发明的目的在于针对现有技术的不足，提供一种抗二氧化硫型低温锰-铁氧化物脱硝催化剂及其制备方法。本发明采用具有特殊物理和化学性质的碳纳米管为载体，通过负载锰-铁氧化物活性组分，得到抗二氧化硫型低温脱硝催化剂，该催化剂具有低温(80～180℃)活性优异、抗SO2性能显著的优点。
为了实现上述发明目的，本发明采用如下解决方案：
一种抗二氧化硫型低温锰-铁氧化物脱硝催化剂，包括碳纳米管载体和锰-铁氧化物活性组分；所述碳纳米管的管径为40～60nm，所述的活性组分其前驱体为乙酸锰和硝酸铁。
一种抗二氧化硫型低温锰-铁氧化物脱硝催化剂，其组成为：yMnz-FeOx/CNTs，其中y，z分别代表(Mn+Fe)/CNTs和Mn/(Mn+Fe)的摩尔比。
所述的催化剂中(Mn+Fe)/CNTs摩尔比为0.3％～1.8％；Mn/(Mn+Fe)的摩尔比为0.75％。
一种制备上所述的抗二氧化硫型低温锰-铁氧化物脱硝催化剂的制备方法，包括以下步骤：
1)将碳纳米管置于65～68wt％的硝酸中回流12h后，经处理得到氧化改性的碳纳米管；
2)按摩尔比Mn/(Mn+Fe)＝0.75％，(Mn+Fe)/CNTs＝0.3％～1.8％，将乙酸锰和硝酸配制成乙醇溶液；
3)采用等体积浸渍法，将步骤2)配制的溶液滴加到氧化改性的碳纳米管上，常温浸渍，100℃烘干，然后300℃煅烧得到抗二氧化硫型低温锰-铁氧化物脱硝催化剂。
本发明的有益效果在于：
1)本发明制得的低温负载型脱硝催化剂，在低温(80℃～180℃)具有优异的脱硝活性，脱硝率(NO)大于40％；
2)本发明制得的催化剂在二氧化硫存在的情况下，NO的转化率虽有所下降，但是比其他脱硝催化剂的转化率仍然高出很多，说明本发明制得的催化剂抗二氧化硫效果好。
附图说明
图1是本发明制备的催化剂的NO转化率图谱；
图2是本发明制备的催化剂的TEM(a)、(b)和EDX图谱(c)、(d)；
图3是本发明制备的催化剂的XRD图谱；
图4是本发明制备的催化剂的抗SO2性能。
具体实施方式
以下结合具体的实施方式对本发明做进一步阐述，旨在使阅读人容易理解本专利的实施过程。
实施例1
1)硝酸(65～68％)处理碳纳米管12h，抽滤，水洗，105℃烘干12h，研磨得到氧化改性的碳纳米管；
2)将0.3g步骤1)得到的碳纳米管置于坩埚(0.3g碳纳米管能够等体积吸附0.6g乙醇)，按(Mn+Fe)/C摩尔比为0.3％，Mn/(Mn+Fe)＝0.75％计算得出，0.6g乙醇中溶剂需0.01379g乙酸锰、0.007575g硝酸铁，为保证浸渍液量充足，需配制3g乙醇溶液，最后配制溶液量为：3g乙醇、0.06895g乙酸锰和0.03788g硝酸铁；
3)将步骤2)配制的溶剂等体积滴加到0.3g碳纳米管中，室温浸渍24h，100℃烘干12h，最后在管式炉中280℃煅烧30min，得到0.3％Mn0.75-FeOx/CNTs。
实施例2
1)硝酸(65～68％)处理碳纳米管12h，抽滤，水洗，105℃烘干12h，研磨得到氧化改性的碳纳米管；
2)将0.3g步骤1)得到的碳纳米管置于坩埚(0.3g碳纳米管能够等体积吸附0.6g乙醇)，按(Mn+Fe)/C摩尔比为0.8％，Mn/(Mn+Fe)＝0.75％计算得出，0.6g乙醇中溶剂需溶剂0.03677g乙酸锰、0.0202g硝酸铁。为保证浸渍液量充足，需配制3g乙醇溶液，最后配制溶液为：3g乙醇、0.1838g乙酸锰和0.101g硝酸铁；
3)将步骤2)配制的溶剂等体积滴加到0.3g碳纳米管中，室温浸渍24h，100℃烘干12h，最后在管式炉中300℃煅烧30min，得到0.8％Mn0.75-FeOx/CNTs。
实施例3
1)硝酸(65～68％)处理碳纳米管12h，抽滤，水洗，105℃烘干12h，研磨得到氧化改性的碳纳米管；
2)将0.3g步骤1)得到的碳纳米管置于坩埚(0.3g碳纳米管能够等体积吸附0.6g乙醇)，按(Mn+Fe)/C摩尔比为1.2％，Mn/(Mn+Fe)＝0.75％计算得出，0.6g乙醇中溶剂需溶剂0.05515g乙酸锰、0.0303g硝酸铁。为保证浸渍液量充足，需配制3g乙醇溶液，最后配制溶液为：3g乙醇、0.2757g乙酸锰和0.1525g硝酸铁；
3)将步骤2)配制的溶剂等体积滴加到0.3g碳纳米管中，室温浸渍24h，100℃烘干12h，最后在管式炉中290℃煅烧30min，得到1.2％Mn0.75-FeOx/CNTs。
其他步骤相同，只是Mn含量不同，制备得到1.2％Mn1-FeOx/CNTs作为对比。
实施例4
1)硝酸(65～68％)处理碳纳米管12h，抽滤，水洗，105℃烘干12h，研磨得到氧化改性的碳纳米管；
2)将0.3g步骤1)得到的碳纳米管置于坩埚(0.3g碳纳米管能够等体积吸附0.6g乙醇)，按(Mn+Fe)/C摩尔比为1.8％，Mn/(Mn+Fe)＝0.75％计算得出，0.6g乙醇中溶剂需溶剂0.08272g乙酸锰、0.04545g硝酸铁；为保证浸渍液量充足，需配制3g乙醇溶液，最后配制溶液为：3g乙醇、0.4136g乙酸锰和0.2273g硝酸铁；
3)将步骤2)配制的溶剂等体积滴加到0.3g碳纳米管中，室温浸渍24h，100℃烘干12h，最后在管式炉中280℃煅烧30min，得到低温1.8％Mn0.75-FeOx/CNTs。
性能测试：
1)NO转化率测试：
对实施例所制得的脱硝催化剂进行NO转化率测试，测试结果如图1所示。从图1中可得出，在80℃-120℃的范围内，催化剂的NO转化率随着温度的升高显著增大，至120℃-140℃温度区间，缓慢增长，而至140℃-180℃区间，NO转化率趋于稳定；说明本发明的脱硝 催化剂在80℃-180℃区间，催化活性非常高；
图2是本发明制备的催化剂的TEM(a)、(b)和EDX图谱(c)、(d)；
图3是本发明制备的催化剂的XRD图谱；
2)抗二氧化硫测试：
从图4中可以看出，当在催化体系中加入SO2的时候，1.2％Mn0.75-FeOx/CNTs脱硝催化剂的NO转化率下降至60％以后稳定，而1.2％Mn1-FeOx/CNTs的脱硝催化剂的NO转化率急剧下降至28％左右，说明按本发明方法制备的脱硝催化剂抗二氧化硫效果显著。
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 (3)

  1. 一种抗二氧化硫型低温锰-铁氧化物脱硝催化剂，其特征在于：包括碳纳米管载体和锰-铁氧化物活性组分；所述碳纳米管的管径为40～60nm，所述的活性组分其前驱体为乙酸锰和硝酸铁。
  2. 根据权利要求1所述的一种抗二氧化硫型低温锰-铁氧化物脱硝催化剂，其特征在于：所述的催化剂中(Mn+Fe)/CNTs摩尔比为0.3％～1.8％；Mn/(Mn+Fe)的摩尔比为0.75％。
  3. 一种制备如权利要求1所述的抗二氧化硫型低温锰-铁氧化物脱硝催化剂的制备方法，其特征在于：包括以下步骤：
    1)将碳纳米管置于硝酸中回流12h后，经处理得到氧化改性的碳纳米管；
    2)按摩尔比Mn/(Mn+Fe)＝0.75％，(Mn+Fe)/CNTs＝0.3％～1.8％，将乙酸锰和硝酸配制成乙醇溶液；
    3)采用等体积浸渍法，将步骤2)配制的溶液滴加到氧化改性的碳纳米管上，常温浸渍，100℃烘干，然后280℃～300℃煅烧得到抗二氧化硫型低温锰-铁氧化物脱硝催化剂。
PCT/CN2015/076060 2014-11-18 2015-04-08 抗二氧化硫型低温锰-铁氧化物脱硝催化剂及其制备方法 WO2016078292A1 (zh)

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