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WO2015161627A1 - 一种用于400℃～600℃烟气蜂窝脱硝催化剂及其制备方法 - Google Patents

一种用于400℃～600℃烟气蜂窝脱硝催化剂及其制备方法 Download PDF

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WO2015161627A1
WO2015161627A1 PCT/CN2014/088193 CN2014088193W WO2015161627A1 WO 2015161627 A1 WO2015161627 A1 WO 2015161627A1 CN 2014088193 W CN2014088193 W CN 2014088193W WO 2015161627 A1 WO2015161627 A1 WO 2015161627A1
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catalyst
honeycomb
denitration catalyst
coating
ceramic
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PCT/CN2014/088193
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English (en)
French (fr)
Inventor
范建伟
闵弘扬
冉献强
孙宇
潘荣幸
邹立寅
姜序
李丹丹
陈旺源
陈敏骏
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同济大学
上海同济科蓝环保设备工程有限公司
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Application filed by 同济大学, 上海同济科蓝环保设备工程有限公司 filed Critical 同济大学
Publication of WO2015161627A1 publication Critical patent/WO2015161627A1/zh
Priority to US15/275,617 priority Critical patent/US20170007990A1/en

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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
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    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Definitions

  • the invention belongs to the technical field of environmental materials, environmental catalysis and environmental protection, and relates to a honeycomb denitration catalyst suitable for exhaust gas of 400 ° C to 600 ° C discharged from a coal bed gas power plant and a preparation method thereof.
  • Nitrogen oxide emissions have become one of the main causes of environmental pollution and have caused a series of environmental problems such as photochemical smog, acid rain, ozone layer damage and greenhouse effect. Selective catalytic reduction is one of the most effective methods for removing nitrogen oxides, and the choice of catalyst is crucial.
  • the present invention provides a honeycomb denitration catalyst for high temperature denitration and a preparation method thereof.
  • the present invention adopts the following technical solutions:
  • the present invention has developed a denitration catalyst having excellent high-temperature denitration activity, high sulfur and water resistance, high stability, and excellent NOx removal performance by adding a catalytic aid.
  • a honeycomb denitration catalyst for flue gas of 400 ° C to 600 ° C comprising a catalyst coating and a honeycomb ceramic; wherein the catalyst coating is coated on the surface of the honeycomb ceramic, and the ceramic ceramic acts as a carrier, wherein the catalyst coating comprises the following The mass percentage of the slurry component is made:
  • the catalyst coating accounts for 8-15% of the total mass of the honeycomb denitration catalyst.
  • the zeolite is selected from one or more of a ZSM-5 type molecular sieve, a type A zeolite molecular sieve, an X type zeolite molecular sieve or a Y type zeolite molecular sieve.
  • the catalytic auxiliary agent is selected from one or more of the group consisting of ammonium molybdate, cerium nitrate, ferrous chloride, ammonium tungstate, chloroplatinic acid or palladium nitrate.
  • the binder is selected from an inorganic binder or an organic binder
  • the inorganic binder is a nitrate, preferably one or more of cerium nitrate or iron nitrate.
  • the organic binder is polyvinyl alcohol.
  • the denitration catalyst is a honeycomb catalyst; the denitration effect can be maintained above 90% at a high temperature (400 ° C to 600 ° C).
  • a preparation method of the above honeycomb denitration catalyst for flue gas of 400 ° C to 600 ° C comprising the following steps:
  • the mass percentage is 15-25% zeolite, 5-10% ⁇ -alumina, 5-10% catalytic aid, 5% binder and 50-70% deionized water are mixed. Stir well to homogeneity in the blender;
  • the coated honeycomb ceramic is dried and calcined for use in a flue gas honeycomb denitration catalyst at 400 ° C to 600 ° C.
  • the ball milling time of the step (2) is 24 to 72 hours.
  • the immersion time of the step (3) is 5-20 min.
  • the step (4) of the drying and roasting treatment conditions is: drying at 120 ° C for 12 hours, and then baking at 500 to 550 ° C for 5 hours.
  • W is the loading amount (%) of the honeycomb ceramic
  • m 0 is the mass (g) of the blank honeycomb ceramic before the coating is applied
  • m 1 is the mass (g) of the honeycomb ceramic after the coating is applied and calcined.
  • the catalyst active coating prepared by the method has the characteristics of high loading, uniform coating coating and strong bonding force between the coating and the honeycomb ceramic carrier.
  • the catalyst has a high out-of-stock activity (NO conversion of 90% or more) in the temperature range of 400 to 600 ° C, and is well tolerated by SO 2 and water vapor.
  • the coated honeycomb ceramic was dried at 120 ° C for 12 hours and then calcined at 500 ° C for 5 hours to obtain a honeycomb catalyst.
  • the catalyst coating accounts for 8% of the total mass of the catalyst.
  • the coated honeycomb ceramic was dried at 120 ° C for 12 hours and then calcined at 550 ° C for 5 hours to obtain a honeycomb catalyst.
  • the catalyst coating accounts for 12% of the total mass of the catalyst.
  • the coated honeycomb ceramic was dried at 120 ° C for 12 hours and then calcined at 600 ° C for 5 hours to obtain a honeycomb catalyst.
  • the catalyst coating accounts for 14% of the total mass of the catalyst.
  • the coated honeycomb ceramic was dried at 120 ° C for 12 hours and then calcined at 500 ° C for 5 hours to obtain a honeycomb catalyst.
  • the catalyst coating accounts for 15% of the total mass of the catalyst.

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Abstract

一种400℃-600℃烟气的蜂窝脱硝催化剂及其制备方法。该蜂窝脱硝催化剂包括催化剂涂层和蜂窝陶瓷，其中催化剂涂层浆料由包括以下质量百分比的组分制成：沸石15-25%，γ型氧化铝5-10%，催化剂助剂5-10%，粘结剂5%，去离子水50-70%。将蜂窝陶瓷反复浸渍在上述催化剂涂层浆料，涂覆完毕进行烘干和焙烧得到催化剂。该蜂窝脱硝催化剂中包含催化助剂，具有优异的高温脱硝活性、抗硫耐水、稳定性和NO X去除性。

Description

一种用于400℃～600℃烟气蜂窝脱硝催化剂及其制备方法 技术领域
本发明属于环境材料、环境催化和环境保护技术领域，涉及一种适用于煤层气发电厂等排放的400℃～600℃烟气的蜂窝脱硝催化剂及其制备方法。
背景技术
氮氧化物的排放已经成为环境污染的主要原因之一，并引发一系列环境问题，如光化学烟雾、酸雨、臭氧层破坏和温室效应等。选择性催化还原是目前去除氮氧化物最有效的方法之一，其中催化剂的选择至关重要。
国内外许多学者对催化剂体系进行了深入而系统的研究，如钒钛系、铜锰系等等。目前，工业化应用的氨选择性SCR催化剂中，大多是在450℃以下进行脱硝处理的，在450℃以上的脱硝效果急剧降低，甚至无任何效果。而煤层气发电厂等排出的废气温度在500℃左右，以往的催化剂的脱硝能力在高温下被抑制。因此，如何针对高温NOx废气开发新型催化剂，无需换热降温、并能实现催化剂的高活性、高稳定性，决定着煤层气发电厂等排放高温废气的企业的节能减排的效果。目前，研究开发高温脱硝催化剂是煤层气发电厂等企业的一项急须解决的难点。
发明内容
为了克服现有脱硝催化剂在高温条件下的失活现象，本发明提供了一种用于高温脱硝的蜂窝脱硝催化剂及其制备方法。
为实现上述目的，本发明采用以下技术方案：
本发明在以往研究的基础上，通过加入催化助剂、开发了具有优异的高温脱硝活性、抗硫耐水、稳定性高、NOx去除性能优异的脱硝催化剂。
一种用于400℃～600℃烟气的蜂窝脱硝催化剂，包括催化剂涂层和蜂窝陶瓷；其中，催化剂涂层涂覆在蜂窝陶瓷表面，蜂窝陶瓷充当一个载体，其中催化剂涂层的由包括以下质量百分比的浆料组分制成：
Figure PCTCN2014088193-appb-000001
所述的催化剂涂层占蜂窝脱硝催化剂总质量的8～15％。
所述的沸石选自ZSM-5型分子筛、A型沸石分子筛、X型沸石分子筛或Y型沸石分子筛等中的一种或一种以上。
所述的催化助剂选自包括钼酸铵、硝酸铈、氯化亚铁、钨酸铵、氯铂酸或硝酸钯等中的一种或一种以上。
所述的粘结剂选自无机粘结剂或有机粘结剂；
所述的无机粘结剂为硝酸盐，优选硝酸铈或硝酸铁等中的一种或一种以上。
所述的有机粘结剂为聚乙烯醇。
所述的脱硝催化剂为蜂窝催化剂；可在高温(400℃～600℃)下，脱硝效果保持在90％以上。
一种上述用于400℃～600℃烟气的蜂窝脱硝催化剂的制备方法，包括以下步骤：
(1)按上述配比，将质量百分比为15-25％沸石、5-10％γ-氧化铝、5-10％催化助剂、5％粘结剂和50-70％去离子水混合后在搅拌器中充分搅拌至均匀；
(2)将步骤(1)得到的混合液移入球磨机中，充分球磨后得到涂层浆料；
(3)将蜂窝陶瓷反复浸渍在上述涂层浆料中，然后通过高压空气吹扫蜂窝陶瓷表面多余的涂层浆料；
(4)将涂覆完毕的蜂窝陶瓷进行烘干和焙烧处理，用于400℃～600℃烟气蜂窝脱硝催化剂。
所述的步骤(2)的球磨时间为24～72h。
所述的步骤(3)的浸渍时间为5-20min。
所述的步骤(4)烘干焙烧处理条件为：120℃下干燥12小时，然后在500～550℃下焙烧5小时。
本发明中蜂窝陶瓷的负载量计算方法为:W＝(m1-m0)/m0×100％。
其中，W为蜂窝陶瓷的负载量(％)，m0为负载涂层之前的空白蜂窝陶瓷的质量(g)，m1为负载涂层并焙烧之后的蜂窝陶瓷质量(g)。
本发明具有以下有益效果：
本方法制备出的催化剂活性涂层具有负载量高、涂层涂覆均匀和涂层与蜂窝陶瓷载体之间的结合力较强的特点。催化剂在400～600℃的温度区间中，有很高的脱销活性(NO转化率90％以上)，并且对SO2和水蒸气有很好的耐受性。
具体实施方式
以下结合实施例对本发明作进一步的说明。
实施例1
(1)按质量百分比15％沸石、5％γ-氧化铝、5％催化助剂、5％粘结剂和70％去离子水,称取15g ZSM-5型沸石分子筛、5gγ-氧化铝、5g催化助剂(包括钼酸铵、硝酸铈、氯化亚铁、钨酸铵和氯铂酸，其中按摩尔比Mo:Ce:Fe:W:Pt＝60:200:80:120:1)、5g粘结剂(硝酸铁)和70g去离子水，在搅拌器中充分搅拌至均匀；
(2)将上述混合液移入球磨机中，进行充分球磨后得到涂层浆料，球磨时间24小时；
(3)将蜂窝陶瓷反复浸渍在上述涂层浆料中，浸渍时间为5分钟，然后通过高压空气吹扫蜂窝陶瓷表面多余的涂层浆料；
(4)将涂覆完毕的蜂窝陶瓷在120℃下烘干12小时，再在500℃下焙烧5小时即得蜂窝催化剂。其中催化剂涂层占催化剂总质量的8％。
模拟脱硝测试表明，当NO体积浓度为1000ppm、NH3/NO＝1、氧气浓度5％、空速10000h-1时，催化剂脱硝活性在400℃时达到90％。
实施例2
(1)按质量百分比25％沸石、10％γ-氧化铝、10％催化助剂、5％粘结剂和50％去离子水，称取25g A型沸石分子筛、10gγ-氧化铝、10g催化助剂(包括钼酸铵、硝酸铈、氯化亚铁、钨酸铵、氯铂酸和硝酸钯，其中按摩尔比Mo：Ce：Fe：W：Pt：Pd＝20：160：120：140：1：1)、5g粘结剂(硝酸铈)和50g去离子水，在搅拌器中充分搅拌至均匀；
(2)将上述混合液移入球磨机中，进行充分球磨后得到涂层浆料，球磨时间36小时；
(3)将蜂窝陶瓷反复浸渍在上述涂层浆料中，浸渍时间为10分钟，然后通过高压空气吹扫蜂窝陶瓷表面多余的涂层浆料；
(4)将涂覆完毕的蜂窝陶瓷在120℃下烘干12小时，再在550℃下焙烧5小时即得蜂窝催化剂。其中催化剂涂层占催化剂总质量的12％。
模拟脱硝测试表明，当NO体积浓度为1000ppm、NH3/NO＝1:1.1、氧气浓度5％、空速10000h-1时，催化剂脱硝活性在450℃时达到90％。
实施例3
(1)按质量百分比20％沸石、7.5％γ-氧化铝、7.5％催化助剂、5％粘结剂和60％去离子水，称取20g X型沸石分子筛、7.5gγ-氧化铝、7.5g催化助剂(包括钼酸铵、硝酸铈、氯化亚铁、钨酸铵、氯铂酸和硝酸钯，其中按摩尔比Mo：Ce：Fe：W：Pt：Pd＝60：200：160：160：1：1)、5g粘结剂(包括硝酸铈和硝酸铁，其中按摩尔比Ce：Fe＝5:1)和60g去离子水，在搅拌器中充分搅拌至均匀；
(2)将上述混合液移入球磨机中，进行充分球磨后得到涂层浆料，球磨时间48小时；
(3)将蜂窝陶瓷反复浸渍在上述涂层浆料中，浸渍时间为15分钟，然后通过高压空气吹扫蜂窝陶瓷表面多余的涂层浆料；
(4)将涂覆完毕的蜂窝陶瓷在120℃下烘干12小时，再在600℃下焙烧5小时即得蜂窝催化剂。其中催化剂涂层占催化剂总质量的14％。
模拟脱硝测试表明，当NO体积浓度为1000ppm、NH3/NO＝1:1.2、氧气浓度5％、空速10000h-1时，催化剂脱硝活性在500℃时达到98％。
实施例4
(1)按质量百分比25％沸石、10％γ-氧化铝、5％催化助剂、5％粘结剂和55％去离子水，称取25g Y型沸石分子筛、10gγ-氧化铝、5g催化助剂(钼酸铵、硝酸铈、氯化亚铁、钨酸铵和硝酸钯，其中按摩尔比Mo：Ce：Fe：W：Pd＝60：160：120：160：1)、5g粘结剂(包括硝酸铈和硝酸铁，其中按摩尔比Ce：Fe＝1:1)和55g去离子水，在搅拌器中充分搅拌至均匀；
(2)将上述混合液移入球磨机中，进行充分球磨后得到涂层浆料，球磨时间72小时；
(3)将蜂窝陶瓷反复浸渍在上述涂层浆料中，浸渍时间为20分钟，然后通过高压空气吹扫蜂窝陶瓷表面多余的涂层浆料；
(4)将涂覆完毕的蜂窝陶瓷在120℃下烘干12小时，再在500℃下焙烧5小时即得蜂窝催化剂。其中催化剂涂层占催化剂总质量的15％。
模拟脱硝测试表明，当NO体积浓度为1000ppm、NH3/NO＝1、氧气浓度5％、空速10000h-1时，催化剂脱硝活性在600℃时达到90％。
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. 一种用于400℃～600℃烟气的蜂窝脱硝催化剂，其特征在于：包括催化剂涂层和蜂窝陶瓷，其中催化剂涂层涂覆在蜂窝陶瓷表面，所述的催化剂涂层由包括以下质量百分比的浆料组分制成：
    Figure PCTCN2014088193-appb-100001
  2. 根据权利要求1所述的蜂窝脱硝催化剂，其特征在于：所述的催化剂涂层占催化剂总质量的2～15％。
  3. 根据权利要求1所述的蜂窝脱硝催化剂，其特征在于：所述的沸石选自ZSM-5型分子筛、A型沸石分子筛、X型沸石分子筛或Y型沸石分子筛中的一种或一种以上。
  4. 根据权利要求1所述的蜂窝脱硝催化剂，其特征在于：所述的催化助剂选自钼酸铵、硝酸铈、氯化亚铁、钨酸铵、氯铂酸或硝酸钯中的一种或一种以上。
  5. 根据权利要求1所述的蜂窝脱硝催化剂，其特征在于：所述的粘结剂选自无机粘结剂或有机粘结剂。
  6. 根据权利要求5所述的蜂窝脱硝催化剂，其特征在于：所述的无机粘结剂为硝酸盐，优选硝酸铈或硝酸铁中的一种或一种以上；
    所述的有机粘结剂为聚乙烯醇。
  7. 一种权利要求1-6中任一所述的用于400℃～600℃烟气的蜂窝脱硝催化剂的制备方法，其特征在于：包括以下步骤：
    (1)按权利要求1所述的配比，将质量百分比为15-25％沸石、5-10％γ-氧化铝、5-10％催化助剂、5％粘结剂和50-70％去离子水混合后在搅拌器中充分搅拌至均匀；
    (2)将步骤(1)得到的混合液移入球磨机中，充分球磨后得到涂层浆料；
    (3)将蜂窝陶瓷反复浸渍在上述涂层浆料中，然后通过高压空气吹扫蜂窝陶瓷表面多余的涂层浆料；
    (4)将涂覆完毕的蜂窝陶瓷进行烘干和焙烧处理，得到用于400℃～600℃烟气的蜂窝脱硝催化剂。
  8. 根据权利要求7所述的制备方法，其特征在于：所述的步骤(2)的球磨时间为24～72h。
  9. 根据权利要求7所述的制备方法，其特征在于：所述的步骤(3)的浸渍时间为5-20min。
  10. 根据权利要求7所述的制备方法，其特征在于：所述的步骤(4)烘干焙烧处理条件为：120℃下干燥12小时，然后在500～550℃下焙烧5小时。
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