WO2018045672A1 - 在滤料上原位生成纳米花状二氧化锰催化剂的方法 - Google Patents

在滤料上原位生成纳米花状二氧化锰催化剂的方法 Download PDF

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WO2018045672A1
WO2018045672A1 PCT/CN2016/111417 CN2016111417W WO2018045672A1 WO 2018045672 A1 WO2018045672 A1 WO 2018045672A1 CN 2016111417 W CN2016111417 W CN 2016111417W WO 2018045672 A1 WO2018045672 A1 WO 2018045672A1
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filter material
manganese dioxide
potassium permanganate
situ
sodium lauryl
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PCT/CN2016/111417
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English (en)
French (fr)
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郑玉婴
陈健
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福州大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
    • B01D39/1623—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/02—Particle separators, e.g. dust precipitators, having hollow filters made of flexible material
    • 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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    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
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    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
    • B01J20/3225—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating involving a post-treatment of the coated or impregnated product
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    • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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    • B01D2239/04—Additives and treatments of the filtering material
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D2255/915—Catalyst supported on particulate filters

Definitions

  • the invention belongs to the technical field of functional filter materials, and in particular relates to a method for generating a nano flower-like manganese dioxide catalyst in situ on a filter material.
  • China is in the stage of rapid economic development, and the demand for energy is very large, especially the demand for electricity is increasing.
  • China's coal-themed energy structure determines that China's electricity is mainly based on thermal power generation, and most of the power plants are coal-fired power plants.
  • Coal-fired power plants in addition to the guarantee rapid economic development, the president of the students a lot of pollutants such as dust, sulfur dioxide and NO x toxic gases.
  • the industry mainly uses filter bag dust collector to control a large amount of dust and trace particles generated by coal-fired power station boilers, the core of which is filter material.
  • PPS filter material polyphenylene sulfide filter material
  • the layer is chelated with divalent manganese ions, and potassium permanganate is used as an oxidant to form a denitration catalyst in situ on the surface of the polydopamine-coated filter fiber to prepare a composite filter material having denitration function.
  • the disadvantage is that the surface of the filter material is modified by dopamine, and the uniformly coated polydopamine layer affects the gas permeability of the filter material, thereby affecting the dust removal function; and the preparation process is complicated.
  • the denitration catalyst is directly attached to the filter fiber, there is a disadvantage that the catalyst load is uneven, the gas permeability is poor, the low temperature activity is poor, and the binding force between the catalyst and the filter fiber is weak. Therefore, it is very important to study a composite filter material capable of uniformly and firmly supporting a denitration catalyst and having excellent low-temperature activity.
  • the filter material obtained by the invention has excellent low-temperature activity, and can achieve a conversion rate of more than 97% at 160 ° C, and the composite filter material has excellent bonding strength, gas permeability and catalytic stability.
  • a method for in situ formation of a nano flower-like manganese dioxide catalyst on a filter material immersing the filter material in a solution containing sodium lauryl sulfate and nitric acid, firstly using sodium lauryl sulfate to the surface of the filter material Modification, the surface is wound with a layer of charge, fully adsorbing H + in the solution; then potassium permanganate is added to the solution to make the potassium permanganate react with the H + on the surface of the filter material.
  • the nanoflower-like manganese dioxide is formed to produce a composite filter material having a denitration function.
  • the solution containing sodium lauryl sulfate and nitric acid has a concentration of sodium dodecyl sulfate of 0.1 - 2 g / L and a concentration of nitric acid of 0.01 - 0.2 M.
  • the filter material is a polyphenylene sulfide needle felt filter material.
  • step 2) After the reaction system of step 1) is heated to 60-80 ° C, potassium permanganate is added, and the reaction is further stirred for 0.5-2 h to react the potassium permanganate with the H + surface of the filter material to form nano-flowers in situ.
  • the filter material obtained in the step 2) is rinsed with deionized water and ethanol, and dried in a vacuum oven at 110 ° C for 6 hours to obtain a composite filter material having a denitration function.
  • the concentration of potassium permanganate in the reaction system in step 2) is 0.01 to 0.2M.
  • the nano-flower-shaped manganese dioxide catalyst formed on the filter material in situ is prepared by the following chemical equation:
  • a prepared as described above denitration functional composite can be used for the simultaneous removal of PM2.5 filter and NO x, and excellent in denitration rate, 160 °C conversion can reach 97% or more.
  • the invention utilizes sodium lauryl sulfate to modify the surface of the filter material, does not affect the surface of the filter material, and does not affect the gas permeability (see Figure 1); the surface of the filter fiber is uniformly coated.
  • a layer of nano-flower-shaped manganese dioxide, and the morphology of manganese dioxide has a larger specific surface area and higher pore volume than ordinary manganese dioxide, and is more conducive to the diffusion of reactive gases, which
  • the catalytic filter material has excellent low-temperature activity, and can achieve a conversion rate of more than 97% at 160 ° C, and the composite filter material has excellent bonding strength, gas permeability and catalytic stability;
  • the preparation method of the invention is simple and environmentally friendly; the reagents used in the experiment are cheap and easy to obtain, and the experiment process is easy to operate, and the reaction process only takes 2 to 3 hours, so it is suitable for large-scale experimental production.
  • Figure 1 is an SEM image of the original polyphenylene sulfide needle felt filter material (A, B) and the denitration function polyphenylene sulfide composite filter material (C, D);
  • FIG. 2 TEM image of original polyphenylene sulfide needle felt filter material (A) and denitrification function polyphenylene sulfide composite filter material (B, C), and EDX diagram of denitration function polyphenylene sulfide composite filter material (D) ;
  • Fig. 4 is a diagram showing the NO conversion rate of the denitration function polyphenylene sulfide composite filter at 160 ° C;
  • Figure 5 shows the bonding strength of the denitration function polyphenylene sulfide composite filter
  • Fig. 6 The gas permeability of the original polyphenylene sulfide needle felt filter material and the denitration function polyphenylene sulfide composite filter material.
  • a method for in situ formation of a nanoflower-like manganese dioxide catalyst on a filter material comprising the steps of:
  • step b) immersing a circular polyphenylene sulfide filter material having a diameter of 3.8 cm into the suspension solution of step a), ultrasonically dispersing in an ultrasonic cleaner for 1 h, so that sodium lauryl sulfate is sufficiently adsorbed on the surface of the filter material;
  • the filter material obtained in the step c) is rinsed with deionized water and ethanol, and dried in a vacuum oven at 110 ° C for 6 hours to obtain a composite filter material having a denitration function.
  • a method for in situ formation of a nanoflower-like manganese dioxide catalyst on a filter material comprising the steps of:
  • step b) immersing a circular polyphenylene sulfide filter material having a diameter of 3.8 cm into the suspension solution of step a), ultrasonically dispersing in an ultrasonic cleaner for 1 h, so that sodium lauryl sulfate is sufficiently adsorbed on the surface of the filter material;
  • step d) The filter material obtained in step c) is rinsed with deionized water and ethanol, and dried in a vacuum oven at 110 ° C for 6 h. A composite filter material having a denitration function is obtained.
  • a method for in situ formation of a nanoflower-like manganese dioxide catalyst on a filter material comprising the steps of:
  • step b) immersing a circular polyphenylene sulfide filter material having a diameter of 3.8 cm into the suspension solution of step a), ultrasonically dispersing in an ultrasonic cleaner for 1 h, so that sodium lauryl sulfate is sufficiently adsorbed on the surface of the filter material;
  • the filter material obtained in the step c) is rinsed with deionized water and ethanol, and dried in a vacuum oven at 110 ° C for 6 hours to obtain a composite filter material having a denitration function.
  • a method for in situ formation of a nanoflower-like manganese dioxide catalyst on a filter material comprising the steps of:
  • step b) immersing a circular polyphenylene sulfide filter material having a diameter of 3.8 cm into the suspension solution of step a), ultrasonically dispersing in an ultrasonic cleaner for 1 h, so that sodium lauryl sulfate is sufficiently adsorbed on the surface of the filter material;
  • the filter material obtained in the step c) is rinsed with deionized water and ethanol, and dried in a vacuum oven at 110 ° C for 6 hours to obtain a composite filter material having a denitration function.

Abstract

一种在滤料上原位生成纳米花状二氧化锰催化剂的方法及由其制备的滤料。方法包括将滤料浸入含有十二烷基硫酸钠和硝酸的溶液中，利用十二烷基硫酸钠对滤料的表面进行改性，使其表面缠绕一层荷电层，然后加入高锰酸钾作为氧化剂，使高锰酸钾与滤料表面的H +反应，在滤料的表面原位生成纳米花状二氧化锰，从而制得具有脱硝功能的复合滤料。

Description

在滤料上原位生成纳米花状二氧化锰催化剂的方法 技术领域
本发明属于功能滤料技术领域，尤其涉及一种在滤料上原位生成纳米花状二氧化锰催化剂的方法。
背景技术
我国正处于经济高速发展阶段，能源需求量很大，尤其是对电力的需求更是有增无减。而我国以煤炭为主题的能源结构，决定了我国电力以火力发电为主，电厂大部分为燃煤电厂。燃煤电厂除了保障经济快速发展以外，会长生大量的污染物，如粉尘、二氧化硫及NOx有毒气体等。目前，工业上主要采用滤袋除尘器控制燃煤电站锅炉产生的大量粉尘和微量颗粒物，其核心是滤料。其中，聚苯硫醚滤料(PPS滤料)因其具有稳定的化学结构、耐酸碱腐蚀性、耐水解性及尺寸稳定性等优点，成为燃煤电厂滤袋上的首选材料。
但是，滤袋除尘器对工业尾气中的氮氧化物的排放，还没有有效的控制方法。因此，研究一种能够同时具备除尘和脱硝功能的复合功能滤料，已经成为众多研究人员关注的热点。公开号为CN 103949115 A的中国专利申请公开了一种在滤料上原位生成脱硝催化剂的方法，首先利用多巴胺的氧化自聚合反应在滤料表面均匀包覆一层聚多巴胺，然后利用聚多巴胺层与二价锰离子的螯合作用，以高锰酸钾作为氧化剂，在聚多巴胺包覆的滤料纤维表面原位生成脱硝催化剂，从而制得具有脱硝功能的复合滤料。然而其缺点在于利用多巴胺对滤料表面进行改性，均匀包覆的聚多巴胺层会影响滤料的透气性，从而影响其除尘功能；并且制备过程复杂。
而如果将脱硝催化剂直接附着在滤料纤维上，则存在催化剂负载不均匀，透气性差，低温活性较差，且催化剂与滤料纤维间的结合力很弱等缺点。因此，研究一种能够均匀且牢固地负载脱硝催化剂，并具有优异低温活性的复合滤料具有非常重要的意义。
发明内容
本发明的目的在于针对现有技术的不足，提供了一种在滤料上原位生成纳米花状二氧化锰催化剂的方法。本发明所得的滤料低温活性十分优异，160℃可达到97％以上的转化率，且该复合滤料的结合强度、透气性能及催化稳定性能均十分优异。
为实现上述发明目的，本发明采用如下技术方案：
一种在滤料上原位生成纳米花状二氧化锰催化剂的方法：将滤料浸入含有十二烷基硫酸钠和硝酸的溶液中，首先利用十二烷基硫酸钠对滤料的表面进行改性，使其表面缠绕一层荷电 层，充分吸附溶液中的H+；然后往溶液中加入高锰酸钾，使高锰酸钾与滤料表面的H+反应，在滤料表面原位生成纳米花状二氧化锰，从而制得具有脱硝功能的复合滤料。
所述的含有十二烷基硫酸钠和硝酸的溶液，十二烷基硫酸钠的浓度为0.1–2g/L，硝酸的浓度为0.01～0.2M。
所述的滤料为聚苯硫醚针刺毡滤料。
所述的在滤料上原位生成纳米花状二氧化锰催化剂的方法，具体制备步骤为：
1)将滤料浸入含有十二烷基硫酸钠和硝酸的溶液中，超声分散1h，使十二烷基硫酸钠充分吸附在滤料表面；
2)将步骤1)的反应体系升温至60～80℃后，加入高锰酸钾，继续搅拌反应0.5–2h，使高锰酸钾与滤料表面的H+反应原位生成纳米花状二氧化锰；
3)将步骤2)获得的滤料用去离子水和乙醇冲洗干净，放入110℃真空干燥箱中干燥6h，得到具有脱硝功能的复合滤料。
步骤2)中反应体系中高锰酸钾的浓度为0.01～0.2M。
滤料上原位生成纳米花状二氧化锰催化剂，是由以下化学方程式制得：
4MnO4 –+4H+→4MnO2+3O2+2H2O。
一种如上述方法制得的脱硝功能复合滤料可用于同时脱除PM2.5和NOx，并且具有优异的脱硝率，160℃可达到97％以上的转化率。
与现有技术相比，本发明的有益效果在于：
1、本发明利用十二烷基硫酸钠对滤料表面进行改性，并未对滤料表面造成影响，也不会影响其透气性(见图1)；由于滤料纤维表面均匀地包覆了一层纳米花状二氧化锰，而该形貌的二氧化锰与普通的二氧化锰相比，具有更大的比表面积和更高的孔容，且更有利于反应气体的扩散，这就使得催化过滤滤料低温活性十分优异，160℃可达到97％以上的转化率，且该复合滤料的结合强度、透气性能及催化稳定性能均十分优异；
2、本发明的制备方法简单，对环境友好；实验所用试剂廉价易得，且实验过程容易操作，反应过程只需2～3h，因此适合大规模实验生产。
附图说明
图1原始聚苯硫醚针刺毡滤料(A，B)与脱硝功能聚苯硫醚复合滤料(C，D)的SEM图；
图2原始聚苯硫醚针刺毡滤料(A)与脱硝功能聚苯硫醚复合滤料(B，C)的TEM图，及脱硝功能聚苯硫醚复合滤料的EDX图(D)；
图3脱硝功能聚苯硫醚复合滤料纤维表面元素成分分析；
图4脱硝功能聚苯硫醚复合滤料在160℃时的NO转化率图；
图5脱硝功能聚苯硫醚复合滤料的结合强度；
图6原始聚苯硫醚针刺毡滤料和脱硝功能聚苯硫醚复合滤料的透气性能。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。下面结合附图及具体实施例对本发明的应用原理作进一步描述。
实施例1
一种在滤料上原位生成纳米花状二氧化锰催化剂的方法，包括以下步骤：
a)将0.042g十二烷基硫酸钠固体颗粒和微量浓硝酸加入到去离子水中搅拌溶解，配置成浓度为0.84g/L的十二烷基硫酸钠溶液，控制硝酸浓度为0.05M；
b)将直径为3.8cm的圆形聚苯硫醚滤料浸入步骤a)的悬浮溶液中，在超声波清洗器进行超声分散1h，使十二烷基硫酸钠充分吸附在滤料表面；
c)将反应体系升温至70℃，滴加高锰酸钾溶液，高锰酸钾浓度为0.05M，继续搅拌反应1.5h，使高锰酸钾与滤料表面的H+反应原位生成纳米花状二氧化锰；
d)将步骤c)获得的滤料用去离子水和乙醇冲洗干净，放入110℃真空干燥箱中干燥6h，得到具有脱硝功能的复合滤料。
该复合滤料的脱硝性能在自制管式SCR反应器中进行评价。测试条件：[NO]＝[NH3]＝400ppm，[O2]＝5％，N2为平衡气，气体流速为700mL·min-1，温度设置为160℃，用英国KM940烟气分析仪测得脱硝效率为97％。
实施例2
一种在滤料上原位生成纳米花状二氧化锰催化剂的方法，包括以下步骤：
a)将0.024g十二烷基硫酸钠固体颗粒和微量浓硝酸加入到去离子水中搅拌溶解，配置成浓度为0.48g/L的十二烷基硫酸钠溶液，控制硝酸浓度为0.1M；
b)将直径为3.8cm的圆形聚苯硫醚滤料浸入步骤a)的悬浮溶液中，在超声波清洗器进行超声分散1h，使十二烷基硫酸钠充分吸附在滤料表面；
c)将反应体系升温至80℃，滴加高锰酸钾溶液，高锰酸钾浓度为0.1M，继续搅拌反应2h，使高锰酸钾与滤料表面的H+反应原位生成纳米花状二氧化锰；
d)将步骤c)获得的滤料用去离子水和乙醇冲洗干净，放入110℃真空干燥箱中干燥6h， 得到具有脱硝功能的复合滤料。
该复合滤料的脱硝性能在自制管式SCR反应器中进行评价。测试条件：[NO]＝[NH3]＝400ppm,[O2]＝5％，N2为平衡气，气体流速为700mL·min-1，温度设置为160℃，用英国KM940烟气分析仪测得脱硝效率为100％。
实施例3
一种在滤料上原位生成纳米花状二氧化锰催化剂的方法，包括以下步骤：
a)将0.042g十二烷基硫酸钠固体颗粒和微量浓硝酸加入到去离子水中搅拌溶解，配置成浓度为0.84g/L的十二烷基硫酸钠溶液，控制硝酸浓度为0.02M；
b)将直径为3.8cm的圆形聚苯硫醚滤料浸入步骤a)的悬浮溶液中，在超声波清洗器进行超声分散1h，使十二烷基硫酸钠充分吸附在滤料表面；
c)将反应体系升温至65℃，滴加高锰酸钾溶液，高锰酸钾浓度为0.02M，继续搅拌反应1.5h，使高锰酸钾与滤料表面的H+反应原位生成纳米花状二氧化锰；
d)将步骤c)获得的滤料用去离子水和乙醇冲洗干净，放入110℃真空干燥箱中干燥6h，得到具有脱硝功能的复合滤料。
该复合滤料的脱硝性能在自制管式SCR反应器中进行评价。测试条件：[NO]＝[NH3]＝400ppm，[O2]＝5％，N2为平衡气，气体流速为700mL·min-1，温度设置为160℃，用英国KM940烟气分析仪测得脱硝效率为95％。
实施例4
一种在滤料上原位生成纳米花状二氧化锰催化剂的方法，包括以下步骤：
a)将0.042g十二烷基硫酸钠固体颗粒和微量浓硝酸加入到去离子水中搅拌溶解，配置成浓度为0.84g/L的十二烷基硫酸钠溶液，控制硝酸浓度为0.05M；
b)将直径为3.8cm的圆形聚苯硫醚滤料浸入步骤a)的悬浮溶液中，在超声波清洗器进行超声分散1h，使十二烷基硫酸钠充分吸附在滤料表面；
c)将反应体系升温至65℃，滴加高锰酸钾溶液，高锰酸钾浓度为0.05M，继续搅拌反应2.5h，使高锰酸钾与滤料表面的H+反应原位生成纳米花状二氧化锰；
d)将步骤c)获得的滤料用去离子水和乙醇冲洗干净，放入110℃真空干燥箱中干燥6h，得到具有脱硝功能的复合滤料。
该复合滤料的脱硝性能在自制管式SCR反应器中进行评价。测试条件：[NO]＝[NH3]＝400ppm，[O2]＝5％，N2为平衡气，气体流速为700mL·min-1，温度设置为160℃，用英国KM940烟气分析仪测得脱硝效率为96％。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (6)

  1. 一种在滤料上原位生成纳米花状二氧化锰催化剂的方法，其特征在于：将滤料浸入含有十二烷基硫酸钠和硝酸的溶液中，首先利用十二烷基硫酸钠对滤料的表面进行改性，使其表面缠绕一层荷电层，充分吸附溶液中的H+；然后往溶液中加入高锰酸钾，使高锰酸钾与滤料表面的H+反应，在滤料表面原位生成纳米花状二氧化锰，从而制得具有脱硝功能的复合滤料。
  2. 根据权利要求1所述的在滤料上原位生成纳米花状二氧化锰催化剂的方法，其特征在于：所述的含有十二烷基硫酸钠和硝酸的溶液，十二烷基硫酸钠的浓度为0.1–2g/L，硝酸的浓度为0.01～0.2M。
  3. 根据权利要求1所述的在滤料上原位生成纳米花状二氧化锰催化剂的方法，其特征在于：所述的滤料为聚苯硫醚针刺毡滤料。
  4. 根据权利要求1所述的在滤料上原位生成纳米花状二氧化锰催化剂的方法，其特征在于：具体制备步骤为：
    1)将滤料浸入含有十二烷基硫酸钠和硝酸的溶液中，超声分散1h，使十二烷基硫酸钠充分吸附在滤料表面；
    2)将步骤1)的反应体系升温至60～80℃后，加入高锰酸钾，继续搅拌反应0.5–2h，使高锰酸钾与滤料表面的H+反应原位生成纳米花状二氧化锰；
    3)将步骤2)获得的滤料用去离子水和乙醇冲洗干净，放入110℃真空干燥箱中干燥6h，得到具有脱硝功能的复合滤料。
  5. 根据权利要求4所述的在滤料上原位生成纳米花状二氧化锰催化剂的方法，其特征在于：步骤2)中反应体系中高锰酸钾的浓度为0.01～0.2M。
  6. 根据权利要求1-5任一项所述的方法制得的滤料，其特征在于：可用于同时脱除PM2.5和NOx。
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CN114229903B (zh) * 2021-11-23 2023-10-31 湖北大学 一种MnO2电极材料及其制备方法和应用
CN114570445A (zh) * 2022-03-03 2022-06-03 广州大学 一种用于合成二氧化锰纳米花的微流控芯片及其应用方法
CN114573033A (zh) * 2022-03-25 2022-06-03 南京信息工程大学 一种团簇MnO2的制法、二次锌锰电池正极材料及二次锌锰电池
CN114573033B (zh) * 2022-03-25 2023-04-28 南京信息工程大学 一种团簇MnO2的制法、二次锌锰电池正极材料及二次锌锰电池

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