CN111495410B - Honeycomb ceramic-porous carbon monolithic catalyst, honeycomb ceramic-porous carbon monolithic adsorbent, preparation method and application thereof - Google Patents
Honeycomb ceramic-porous carbon monolithic catalyst, honeycomb ceramic-porous carbon monolithic adsorbent, preparation method and application thereof Download PDFInfo
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- CN111495410B CN111495410B CN202010354196.XA CN202010354196A CN111495410B CN 111495410 B CN111495410 B CN 111495410B CN 202010354196 A CN202010354196 A CN 202010354196A CN 111495410 B CN111495410 B CN 111495410B
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Abstract
本发明公开了一种蜂窝陶瓷‑多孔炭整体式催化剂、蜂窝陶瓷‑多孔炭整体式吸附剂及其制备方法和应用，所示蜂窝陶瓷‑多孔炭整体式催化剂由蜂窝陶瓷和多孔炭组成，蜂窝陶瓷为载体，多孔炭为活性组分，通过化学气相聚合法在蜂窝陶瓷表面生成聚吡咯类化合物，然后通过高温碳化活化方法在蜂窝陶瓷表面生成一层氮、磷掺杂的多孔炭，及生成蜂窝陶瓷‑多孔炭整体式复合材料，该催化剂在室温下有较高的臭氧催化分解活性。蜂窝陶瓷‑多孔炭整体式吸附剂由蜂窝陶瓷‑多孔炭复合材料载体和有机胺组成，通过浸渍法在蜂窝陶瓷‑多孔炭复合材料载体负载有机胺，即得到蜂窝陶瓷‑多孔炭‑有机胺整体式吸附剂，该吸附剂可表现出良好的二氧化碳吸附性能。
The invention discloses a honeycomb ceramic-porous carbon integral catalyst, a honeycomb ceramic-porous carbon integral adsorbent and a preparation method and application thereof. The honeycomb ceramic-porous carbon integral catalyst is composed of honeycomb ceramics and porous carbon, and the honeycomb ceramic-porous carbon integral The ceramic is the carrier, and the porous carbon is the active component. Polypyrrole compounds are generated on the surface of the honeycomb ceramics by chemical vapor polymerization, and then a layer of porous carbon doped with nitrogen and phosphorus is formed on the surface of the honeycomb ceramics by high-temperature carbonization activation method, and the formation of Honeycomb ceramic-porous carbon monolithic composite material, the catalyst has high ozone catalytic decomposition activity at room temperature. The honeycomb ceramic-porous carbon monolithic adsorbent is composed of a honeycomb ceramic-porous carbon composite material carrier and an organic amine, and the honeycomb ceramic-porous carbon composite material carrier is loaded with an organic amine by an impregnation method to obtain a honeycomb ceramic-porous carbon-organic amine monolith The adsorbent exhibits good carbon dioxide adsorption performance.
Description
技术领域technical field
本发明涉及蜂窝陶瓷-多孔炭整体式复合材料特别是涉及一种蜂窝陶瓷-多孔炭整体式催化剂、蜂窝陶瓷-多孔炭整体式吸附剂及其制备方法和应用。The invention relates to a honeycomb ceramic-porous carbon integral composite material, in particular to a honeycomb ceramic-porous carbon integral catalyst, a honeycomb ceramic-porous carbon integral adsorbent and a preparation method and application thereof.
背景技术Background technique
自工业化革命以来，由于化石燃料的大量使用，大气中的二氧化碳浓度持续增加，2019年已超过415ppm，这使得全球由温室效应引起的气候变暖现象在不断加剧。目前，人们主要利用有机胺溶液捕捉石油燃烧产生的CO2气体，所使用的有机胺包括乙醇胺(MEA)，二乙醇胺(DEA)，四乙烯五胺(TEPA)等。虽然采用有机胺溶液捕捉CO2的方法十分有效，但有机胺化学稳定性较差，气体传输效率低，再生耗能大，对仪器腐蚀性强。因此，开发一种新型的二氧化碳分离和捕捉技术，来减少二氧化碳排放，于缓解气候变暖是非常必要且迫切的。Since the industrial revolution, due to the extensive use of fossil fuels, the concentration of carbon dioxide in the atmosphere has continued to increase, exceeding 415ppm in 2019, which has intensified global warming caused by the greenhouse effect. At present, people mainly use organic amine solution to capture CO 2 gas produced by petroleum combustion. The organic amine used includes ethanolamine (MEA), diethanolamine (DEA), tetraethylenepentamine (TEPA) and so on. Although the method of using organic amine solution to capture CO2 is very effective, the organic amine has poor chemical stability, low gas transmission efficiency, high regeneration energy consumption, and strong corrosion to the instrument. Therefore, it is very necessary and urgent to develop a new carbon dioxide separation and capture technology to reduce carbon dioxide emissions and alleviate climate warming.
此外，大气中有一定量的臭氧。普通人在一小时内可接受的臭氧极限浓度是260ug/m3，在320ug/m3臭氧环境中活动1小时就会咳嗽、呼吸困难及肺功能下降。臭氧还能参与生物体中的不饱和脂肪酸、氨基及其他蛋白质反应，使长时间直接接触高浓度臭氧的人出现疲乏、咳嗽、胸闷胸痛、皮肤起皱、恶心头痛、脉搏加速、记忆力衰退、视力下降等症状。因此，开发一种新型的臭氧催化分解技术，减少环境中的臭氧是研究者一直努力的目标。In addition, there is a certain amount of ozone in the atmosphere. The acceptable limit concentration of ozone for ordinary people within one hour is 260ug/m 3 , and one hour of activities in an ozone environment of 320ug/m 3 will lead to coughing, dyspnea and decreased lung function. Ozone can also participate in the reaction of unsaturated fatty acids, amino groups and other proteins in organisms, causing fatigue, coughing, chest tightness and chest pain, wrinkled skin, nausea and headache, rapid pulse, memory loss, vision loss, etc. symptoms such as decline. Therefore, developing a new type of ozone catalytic decomposition technology to reduce the ozone in the environment is the goal that researchers have been working hard for.
Xiaochun Xu等(Energy&Fuels，2002，16，1463-1469)报道了一种“分子篮”二氧化碳吸附剂，他们将有机胺负载介孔氧化硅MCM-41的孔道内，形成氧化硅-有机胺整体式复合物吸附剂，这种吸附剂外观为固态粉末状，吸附量大且再生能耗小。然而吸附剂呈现为粉末状，因此难以在工业上实现大批量应用，主要原因是由于大量使用粉末材料会堵塞管路设备，在吸附剂前后形成压力降。Xiaochun Xu et al. (Energy & Fuels, 2002, 16, 1463-1469) reported a "molecular basket" carbon dioxide adsorbent. They loaded organic amines into the pores of mesoporous silica MCM-41 to form a monolithic silica-organic amine Composite adsorbent, this kind of adsorbent has a solid powder appearance, large adsorption capacity and low regeneration energy consumption. However, the adsorbent is in the form of powder, so it is difficult to realize large-scale application in industry. The main reason is that the large-scale use of powder materials will block the pipeline equipment and form a pressure drop before and after the adsorbent.
中国专利CN103495409B公开了一种将预先经过酸化处理的堇青石蜂窝陶瓷浸没于树脂中，取出后吹去多余的树脂，加热50～200℃进行固化处理，最后在氩气气氛下，400～600℃温度下进行炭化处理，制得所述炭-蜂窝陶瓷整体式催化剂。然而，该方法制备的炭-蜂窝陶瓷整体式催化剂由于需要浸渍在树脂中，蜂窝陶瓷的孔道很容易被堵塞。中国专利CN202700366U公开了一种将陶瓷浆料和活性炭经过高温烧结制备出带有机械控的机械孔的陶瓷蜂窝活性炭体。该方法由于将陶瓷浆料和活性炭一起高温烧结，因此整体式复合材料的结构比较脆，非常容易破碎，因此其稳定性大大降低。Chinese patent CN103495409B discloses a method of immersing cordierite honeycomb ceramics that have been acidified in advance in resin, blowing off excess resin after taking it out, heating at 50-200°C for curing treatment, and finally curing at 400-600°C under an argon atmosphere. Carry out carbonization treatment at low temperature to prepare the carbon-honeycomb ceramic monolithic catalyst. However, the carbon-honeycomb ceramic monolithic catalyst prepared by this method needs to be impregnated in resin, and the pores of the honeycomb ceramic are easily blocked. Chinese patent CN202700366U discloses a ceramic honeycomb activated carbon body with mechanically controlled mechanical pores prepared by sintering ceramic slurry and activated carbon at high temperature. In this method, since the ceramic slurry and activated carbon are sintered at high temperature together, the structure of the monolithic composite material is relatively brittle and easily broken, so its stability is greatly reduced.
综上，现有技术中对臭氧的分解以及二氧化碳的吸附问题尚需要进一步去研究探讨，以研发出能有效分解臭氧以及吸附二氧化碳的材料，优化材料的制备工艺，提高材料性能，使其具有更好的应用效果。To sum up, the problems of ozone decomposition and carbon dioxide adsorption in the prior art still need to be further researched and discussed in order to develop materials that can effectively decompose ozone and absorb carbon dioxide, optimize the preparation process of materials, improve the performance of materials, and make them more efficient. Good application effect.
发明内容Contents of the invention
为了解决现有技术中存在的问题，本发明提供了一种蜂窝陶瓷-多孔炭整体式催化剂、蜂窝陶瓷-多孔炭整体式吸附剂及其制备方法，该催化剂和吸附剂制备工艺简单易控，重现性好，活性高，稳定性好，能有效分解臭氧以及吸附二氧化碳。In order to solve the problems existing in the prior art, the present invention provides a honeycomb ceramic-porous carbon monolithic catalyst, a honeycomb ceramic-porous carbon monolithic adsorbent and a preparation method thereof. The preparation process of the catalyst and the adsorbent is simple and easy to control, Good reproducibility, high activity, good stability, can effectively decompose ozone and absorb carbon dioxide.
为实现上述目的，本发明采取的技术方案是一种蜂窝陶瓷-多孔炭整体式催化剂，所述整体式催化剂为蜂窝陶瓷-多孔炭整体式复合材料，所述整体式催化剂由载体和活性组分组成，所述活性组分的含量为整体式催化剂总质量的1～15wt％，所载体为整体式蜂窝陶瓷，所述活性组分为氮、磷掺杂的多孔炭。In order to achieve the above object, the technical solution adopted by the present invention is a honeycomb ceramic-porous carbon monolithic catalyst, the monolithic catalyst is a honeycomb ceramic-porous carbon monolithic composite material, and the monolithic catalyst consists of a carrier and an active component Composition, the content of the active component is 1-15% by weight of the total mass of the monolithic catalyst, the carrier is monolithic honeycomb ceramics, and the active component is porous carbon doped with nitrogen and phosphorus.
于本发明一实施例中，所述活性组分通过化学气相聚合和高温碳化活化的方法进行负载，所载体为整体式堇青石蜂窝陶瓷。In an embodiment of the present invention, the active component is loaded by chemical vapor phase polymerization and high-temperature carbonization activation, and the carrier is a monolithic cordierite honeycomb ceramic.
一种蜂窝陶瓷-多孔炭整体式催化剂的制备方法，包括以下步骤:A preparation method of honeycomb ceramics-porous carbon monolithic catalyst, comprising the following steps:
步骤1，通过浸渍法将磷酸和/或焦磷酸负载在整体式蜂窝陶瓷表面，烘干后，在反应釜中140～220℃通过化学气相聚合法在整体式蜂窝陶瓷表面生成一层聚吡咯类化合物；Step 1. Load phosphoric acid and/or pyrophosphoric acid on the surface of monolithic honeycomb ceramics by impregnation method. After drying, a layer of polypyrrole is formed on the surface of monolithic honeycomb ceramics by chemical vapor polymerization in a reaction kettle at 140-220°C. compound;
步骤2，再次通过浸渍法负载磷酸和/或焦磷酸；Step 2, loading phosphoric acid and/or pyrophosphoric acid by impregnation method again;
步骤3，通过高温碳化活化的方法将所述聚吡咯类化合物转化为多孔炭材料，所述高温碳化活化的温度为500～1000℃，时间为1～3h，从而得到蜂窝陶瓷-多孔炭整体式催化剂。Step 3, converting the polypyrrole compound into a porous carbon material by high-temperature carbonization activation, the temperature of the high-temperature carbonization activation is 500-1000° C., and the time is 1-3 hours, thereby obtaining a honeycomb ceramic-porous carbon monolith catalyst.
其中，步骤1中，当磷酸和焦磷酸同时作为聚合剂加入时，所添加的所述磷酸和焦磷酸混合物的摩尔比为(1～5):(0.5～5)；步骤2中，如果磷酸和焦磷酸同时作为活化剂加入时，则所述磷酸和焦磷酸的摩尔比为(1～5):(0.5～5)。Wherein, in step 1, when phosphoric acid and pyrophosphoric acid are added as a polymerization agent at the same time, the molar ratio of the added phosphoric acid and pyrophosphoric acid mixture is (1～5):(0.5～5); in step 2, if phosphoric acid When it is added as an activator simultaneously with pyrophosphoric acid, the molar ratio of phosphoric acid to pyrophosphoric acid is (1-5):(0.5-5).
于本发明一实施例中，所述聚吡咯类化合物的前驱体为吡咯、2-甲基吡咯、3-甲基吡咯中任意一种或任意两种及两种以上的混合物。所述吡咯、2-甲基吡咯和3-甲基吡咯三者混合时，所述吡咯、2-甲基吡咯和3-甲基吡咯之间的质量比为(0.5～5):(0.5～5):(0.5～5)。In an embodiment of the present invention, the precursor of the polypyrrole compound is any one of pyrrole, 2-methylpyrrole, and 3-methylpyrrole, or a mixture of any two or more of them. When the pyrrole, 2-methylpyrrole and 3-methylpyrrole are mixed, the mass ratio between the pyrrole, 2-methylpyrrole and 3-methylpyrrole is (0.5～5):(0.5～ 5): (0.5～5).
于本发明一实施例中，所述整体式蜂窝陶瓷为整体式堇青石蜂窝陶瓷。In one embodiment of the present invention, the monolithic honeycomb ceramic is a monolithic cordierite honeycomb ceramic.
将堇青石蜂窝陶瓷浸入一定浓度的磷酸和焦硫酸的混合溶液中浸渍，取出后烘干除去水分，得到了表面负载磷酸和焦磷酸的蜂窝陶瓷材料。将表面负载磷酸和焦磷酸的蜂窝陶瓷材放在反应釜中，并在反应釜内放置一小瓶，小瓶内加入吡咯、2-甲基吡咯、3-甲基吡咯的混合物，密封好反应釜。将反应釜放入140～220℃烘箱中8小时，吡咯、2-甲基吡咯、3-甲基吡咯在高温下挥发成为吡咯类气体，吡咯类气体遇到蜂窝陶瓷材料孔道表面负载的磷酸和焦磷酸后发生聚合反应，在蜂窝陶瓷孔道表面生成聚吡咯类化合物。将表面负载聚吡咯类化合物的蜂窝陶瓷从反应釜中取出，再次放入磷酸和焦硫酸的混合溶液中浸渍5分钟，然后取出放入管式炉中，在惰性气体气氛500-1000℃碳化1～3小时，得到蜂窝陶瓷-多孔炭整体式复合材料。Immerse the cordierite honeycomb ceramics in a mixed solution of phosphoric acid and pyrosulfuric acid at a certain concentration, take it out and dry it to remove water, and obtain a honeycomb ceramic material with phosphoric acid and pyrophosphoric acid on the surface. Place the honeycomb ceramic material loaded with phosphoric acid and pyrophosphoric acid on the surface in a reaction kettle, and place a small bottle in the reaction kettle, add a mixture of pyrrole, 2-methylpyrrole, and 3-methylpyrrole into the small bottle, and seal the reaction kettle. Put the reaction kettle in an oven at 140-220°C for 8 hours. Pyrrole, 2-methylpyrrole, and 3-methylpyrrole volatilize at high temperature to become pyrrole-like gases. Pyrrole-like gases encounter phosphoric acid and Polymerization occurs after pyrophosphoric acid, and polypyrrole compounds are formed on the surface of honeycomb ceramic pores. Take out the honeycomb ceramics loaded with polypyrrole compounds on the surface from the reaction kettle, put it into the mixed solution of phosphoric acid and pyrosulfuric acid for 5 minutes, then take it out and put it into a tube furnace, and carbonize it in an inert gas atmosphere at 500-1000°C for 1 ~3 hours, the honeycomb ceramics-porous carbon monolithic composite material is obtained.
再次浸渍磷酸和焦硫酸混合溶液的目的是通过磷酸和焦磷酸在碳化的过程中起到活化作用，从而可以在蜂窝陶瓷表面获得高比表面积碳材料，且碳材料与蜂窝陶瓷结合紧密，不容易脱落。蜂窝陶瓷-多孔炭整体式复合材料即为臭氧分解催化剂，可直接应用于臭氧催化分解反应。The purpose of impregnating the mixed solution of phosphoric acid and pyrosulfuric acid again is to activate phosphoric acid and pyrophosphoric acid in the process of carbonization, so that carbon materials with high specific surface area can be obtained on the surface of honeycomb ceramics, and the carbon materials are tightly combined with honeycomb ceramics, which is not easy fall off. The honeycomb ceramic-porous carbon integral composite material is the ozone decomposition catalyst, which can be directly applied to the ozone catalytic decomposition reaction.
所述的蜂窝陶瓷-多孔炭整体式催化剂在臭氧分解中的应用。Application of the honeycomb ceramic-porous carbon monolithic catalyst in ozone decomposition.
一种蜂窝陶瓷-多孔炭整体式吸附剂，所述吸附剂由吸附剂载体和吸附剂活性组分组成，所述吸附剂载体为蜂窝陶瓷-多孔炭整体式复合材料，所述吸附剂活性组分为有机胺A honeycomb ceramic-porous carbon monolithic adsorbent, the adsorbent is composed of an adsorbent carrier and an adsorbent active component, the adsorbent carrier is a honeycomb ceramic-porous carbon monolithic composite material, and the adsorbent active component organic amines
于本发明一实施例中，所述有机胺采用共浸渍法进行负载，所述有机胺为四乙烯五胺、五乙烯六胺、聚乙烯亚胺中的任意一种或任意两种及两种以上的混合物。当三者混合使用时，所述四乙烯五胺、五乙烯六胺和聚乙烯亚胺之间的质量比为(0.1～5):(0.1～5):(0.1～5)。In an embodiment of the present invention, the organic amine is loaded by a co-impregnation method, and the organic amine is any one or any two or two of tetraethylenepentamine, pentaethylenehexamine, and polyethyleneimine. a mixture of the above. When the three are mixed and used, the mass ratio among the tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine is (0.1-5):(0.1-5):(0.1-5).
一种蜂窝陶瓷-多孔炭整体式吸附剂的制备方法，将蜂窝陶瓷-多孔炭整体式复合材料浸入一定质量比的四乙烯五胺、五乙烯六胺和聚乙烯亚胺的甲醇混合溶液中，所述四乙烯五胺、五乙烯六胺和聚乙烯亚胺的质量比为(0.1～5):(0.1～5):(0.1～5)，超声处理，然后取出在真空干燥箱中除去溶剂，得到蜂窝陶瓷-多孔炭-有机胺整体式复合材料。A method for preparing a honeycomb ceramic-porous carbon monolithic adsorbent, immersing the honeycomb ceramic-porous carbon monolithic composite material in a methanol mixed solution of tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine in a certain mass ratio, The mass ratio of described tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine is (0.1～5):(0.1～5):(0.1～5), ultrasonic treatment, then take out and remove solvent in vacuum oven , to obtain honeycomb ceramics-porous carbon-organic amine monolithic composite material.
本发明吸附剂通过采用蜂窝陶瓷-多孔炭整体式复合材料为载体，四乙烯五胺、五乙烯六胺和聚乙烯亚胺为吸附剂活性成分，实现了低传质阻力二氧化碳吸附，而且吸附剂工艺十分简单，效率高，稳定性好，不易失活，能实现吸附剂的重复利用和放大化，应用范围也比较广泛。The adsorbent of the present invention adopts honeycomb ceramic-porous carbon monolithic composite material as the carrier, tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine as the active components of the adsorbent, and realizes carbon dioxide adsorption with low mass transfer resistance, and the adsorbent The process is very simple, the efficiency is high, the stability is good, and it is not easy to deactivate. It can realize the reuse and amplification of the adsorbent, and the application range is relatively wide.
所述的蜂窝陶瓷-多孔炭整体式吸附剂在二氧化碳吸附中的应用。The application of the honeycomb ceramic-porous carbon monolithic adsorbent in carbon dioxide adsorption.
本技术方案具有以下有益效果：The technical solution has the following beneficial effects:
本发明通过采用蜂窝陶瓷为载体，将磷酸和焦磷酸负载在蜂窝陶瓷表面，作为吡咯类化合物的聚合试剂，在反应釜将吡咯类化合物挥发，吡咯类蒸汽接触到蜂窝陶瓷表面在蜂窝陶瓷表面发生化学气相聚合反应，生成聚吡咯类化合物，再次浸渍磷酸和焦磷酸作为化学活化剂，然后在氮气下高温碳化和活化，成功地实现了蜂窝陶瓷表面生成一层氮、磷掺杂的多孔炭材料，即为蜂窝陶瓷-多孔炭整体式复合材料。蜂窝陶瓷-多孔炭整体式复合材料可以直接作为臭氧催化分解催化剂，实现了常温下的臭氧的催化分解，解决了粉末催化剂的压力降问题。In the present invention, by using honeycomb ceramics as the carrier, phosphoric acid and pyrophosphoric acid are loaded on the surface of the honeycomb ceramics as polymerization reagents for pyrrole compounds, and the pyrrole compounds are volatilized in the reactor, and pyrrole vapors contact the surface of the honeycomb ceramics to generate Chemical vapor phase polymerization reaction to generate polypyrrole compounds, impregnated with phosphoric acid and pyrophosphoric acid as chemical activators, and then carbonized and activated at high temperature under nitrogen, successfully achieved a layer of nitrogen and phosphorus doped porous carbon materials on the surface of honeycomb ceramics , which is a honeycomb ceramic-porous carbon monolithic composite material. The honeycomb ceramic-porous carbon integral composite material can be directly used as an ozone catalytic decomposition catalyst, which realizes the catalytic decomposition of ozone at room temperature and solves the pressure drop problem of the powder catalyst.
通过在蜂窝陶瓷-多孔炭整体式复合材料上负载有机胺，制备出蜂窝陶瓷-多孔炭-有机胺整体式吸附剂，实现了混合气体中二氧化碳气体的完全脱除，减少了碳排放，同样也解决了粉末吸附剂的压力降问题。By loading organic amine on the honeycomb ceramic-porous carbon monolithic composite material, the honeycomb ceramic-porous carbon-organic amine monolithic adsorbent is prepared, which realizes the complete removal of carbon dioxide gas in the mixed gas, reduces carbon emissions, and also Solved the pressure drop problem of powder adsorbent.
本发明所开发的蜂窝陶瓷-多孔炭整体式复合材料具有制作工艺简单、活性高、稳定性良好等特点，解决了实际应用中的压力降问题，能实现催化剂或吸附剂的放大使用。The honeycomb ceramic-porous carbon integral composite material developed by the present invention has the characteristics of simple manufacturing process, high activity, good stability, etc., solves the problem of pressure drop in practical applications, and can realize the enlarged use of catalysts or adsorbents.
附图说明Description of drawings
图1中a为蜂窝陶瓷原材料，b为实施例5所制备的蜂窝陶瓷-多孔炭整体式复合材料；Among Fig. 1, a is the honeycomb ceramic raw material, and b is the prepared honeycomb ceramic-porous carbon monolithic composite material in Example 5;
图2中a为蜂窝陶瓷原材料的扫描电子显微镜照片，b为实施例5所制备的蜂窝陶瓷-多孔炭整体式复合材料的扫描电子显微镜照片；Among Fig. 2, a is a scanning electron micrograph of the honeycomb ceramic raw material, and b is a scanning electron micrograph of the honeycomb ceramic-porous carbon monolithic composite material prepared in Example 5;
图3为实施例5制备的蜂窝陶瓷-多孔炭整体式复合材料的透射电子显微镜照片；Fig. 3 is the transmission electron micrograph of the honeycomb ceramics-porous carbon monolithic composite material prepared in
图4中a和b分别为蜂窝陶瓷原材料和实施例5所制备的蜂窝陶瓷-多孔炭整体式复合材料的XPS谱图；Among Fig. 4, a and b are respectively the XPS spectra of the honeycomb ceramic raw material and the honeycomb ceramic-porous carbon monolithic composite material prepared in Example 5;
图5为实施例5所制备的1块、2块和3块蜂窝陶瓷-多孔炭整体式复合材料催化剂对臭氧催化去除的转化率对比图；Fig. 5 is the comparison chart of the conversion ratio of 1 block, 2 blocks and 3 blocks of honeycomb ceramics-porous carbon monolithic composite material catalyst prepared in
图6为实施例5所制备的1块、2块和3块蜂窝陶瓷-多孔炭-有机胺整体式复合吸附剂在75℃的二氧化碳穿透曲线图。Fig. 6 is a carbon dioxide breakthrough curve at 75° C. of 1, 2 and 3 honeycomb ceramic-porous carbon-organic amine monolithic composite adsorbents prepared in Example 5.
具体实施方式detailed description
下面结合实施例及附图1至6对本发明作进一步描述。The present invention will be further described below in conjunction with the embodiments and accompanying drawings 1 to 6 .
实施例1Example 1
(1)蜂窝陶瓷-多孔炭整体式复合材料的制备：(1) Preparation of honeycomb ceramic-porous carbon monolithic composite material:
称取一根直径20mm，高度为50mm的200目堇青石蜂窝陶瓷(约10.00g)放入20ml磷酸和焦磷酸混合水溶液(浓度分别为2.00M/L和0.50M/L)中浸泡30分钟，取出后烘干。将负载磷酸和焦磷酸的蜂窝陶瓷放入反应釜中。移取1.00g吡咯、1.00g 2-甲基吡咯、1.00g 3-甲基吡咯(即吡咯、2-甲基吡咯、3-甲基吡咯按质量比1:1:1进行混合)至玻璃瓶中，将玻璃瓶一并放入反应釜中。把反应釜放入160℃烘箱中反应8小时，取出后再次放入20ml磷酸和焦磷酸混合水溶液(浓度分别为2.00M/L和0.50M/L)中浸泡30分钟，取出后烘干。然后在氮气氛围下500℃焙烧90分钟，得到蜂窝陶瓷-多孔炭整体式复合材料，重约11.00g。Weigh a 200-mesh cordierite honeycomb ceramic (about 10.00g) with a diameter of 20mm and a height of 50mm and put it into 20ml of phosphoric acid and pyrophosphoric acid mixed aqueous solution (concentrations are 2.00M/L and 0.50M/L respectively) and soak for 30 minutes, Take out and tumble dry. Put the honeycomb ceramics loaded with phosphoric acid and pyrophosphoric acid into the reaction kettle. Pipette 1.00g pyrrole, 1.00g 2-methylpyrrole, 1.00g 3-methylpyrrole (that is, pyrrole, 2-methylpyrrole, 3-methylpyrrole are mixed according to the mass ratio of 1:1:1) to the glass bottle Put the glass bottle into the reaction kettle together. Put the reaction kettle into an oven at 160°C for 8 hours, take it out and put it into 20ml of phosphoric acid and pyrophosphoric acid mixed aqueous solution (concentrations are 2.00M/L and 0.50M/L respectively) to soak for 30 minutes, take it out and dry it. Then it was calcined at 500° C. for 90 minutes under a nitrogen atmosphere to obtain a honeycomb ceramic-porous carbon monolithic composite material, weighing about 11.00 g.
(2)蜂窝陶瓷-多孔炭-有机胺整体式复合材料的制备：(2) Preparation of honeycomb ceramic-porous carbon-organic amine monolithic composite material:
将蜂窝陶瓷-多孔炭整体式复合材料放入到含有0.33g四乙烯五胺、0.33g五乙烯六胺和0.33g聚乙烯亚胺(即四乙烯五胺、五乙烯六胺和聚乙烯亚胺按质量比1:1:1进行混合)的25mL甲醇混合溶液中，超声5分钟，然后放入真空干燥箱中除去溶剂，得到重约12.00g蜂窝陶瓷-多孔炭-有机胺整体式复合材料，即为二氧化碳吸附剂。Put the honeycomb ceramics-porous carbon monolithic composite into a mixture containing 0.33g tetraethylenepentamine, 0.33g pentaethylenehexamine and 0.33g polyethyleneimine (i.e. tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine Mix in 25mL methanol mixed solution at a mass ratio of 1:1:1), ultrasonic for 5 minutes, then put into a vacuum oven to remove the solvent, and obtain a honeycomb ceramic-porous carbon-organic amine monolithic composite material weighing about 12.00g, It is carbon dioxide adsorbent.
(3)臭氧催化分解性能测试：(3) Ozone catalytic decomposition performance test:
吸附剂的性能评价是在内径为22mm，长200mm的不锈钢反应器中进行，将制得的蜂窝陶瓷-多孔炭整体式复合材料直接装入管中。催化剂用量1块蜂窝陶瓷-多孔炭整体式复合材料，重量约为11.00g，其中约10.00g为蜂窝陶瓷，1.00g为多孔炭，多孔炭为臭氧分解催化剂。也可同时使用2块、3块或者多块蜂窝陶瓷-多孔炭整体式复合材料作为催化剂。原料气组成为(原料气体积组成)：22ppm O3+空气，气体流速为为1.2L/min。催化反应温度为25℃。催化剂的活性以催化剂连续工作10.5h后臭氧的转化率来表示，催化反应性能见表1。The performance evaluation of the adsorbent is carried out in a stainless steel reactor with an inner diameter of 22 mm and a length of 200 mm, and the prepared honeycomb ceramic-porous carbon monolithic composite material is directly loaded into the tube. Catalyst dosage 1 piece of honeycomb ceramic-porous carbon integral composite material, weighing about 11.00g, of which about 10.00g is honeycomb ceramic, 1.00g is porous carbon, and the porous carbon is an ozone decomposition catalyst. It is also possible to use 2, 3 or more honeycomb ceramic-porous carbon monolithic composite materials as catalysts at the same time. The composition of raw material gas is (volume composition of raw material gas): 22ppm O 3 +air, and the gas flow rate is 1.2L/min. The catalytic reaction temperature is 25°C. The activity of the catalyst is represented by the conversion rate of ozone after the catalyst has worked continuously for 10.5 hours. The catalytic performance is shown in Table 1.
(4)吸附剂性能测试：(4) Adsorbent performance test:
吸附剂的性能评价是在内径为22mm，长200mm的固定床反应器中进行，将蜂窝陶瓷-多孔炭-有机胺整体式复合材料装入固定床反应器中，通过穿透曲线法测试二氧化碳吸附量。吸附剂用量1块蜂窝陶瓷-多孔炭-有机胺整体式复合材料，重量约为12.00g，其中约10.00g为蜂窝陶瓷，1.00g为多孔炭，1.00g为有机胺。也可同时使用2块、3块或者多块蜂窝陶瓷-多孔炭-有机胺整体式复合材料作为吸附剂。原料气组成为(原料气体积组合)：10％CO2+90％N2，混合气体流速为10ml·min-1。吸附温度为75℃。吸附剂的性能以单位质量吸附剂的二氧化碳吸附量来表示，具体算法为二氧化碳吸附量除以(多孔炭和有机胺的质量之和，在本实施例中为2.00g)，蜂窝陶瓷作为载体，其质量不计算在吸附剂总质量内。吸附剂的吸附性能见表1。The performance evaluation of the adsorbent is carried out in a fixed-bed reactor with an inner diameter of 22 mm and a length of 200 mm. The honeycomb ceramic-porous carbon-organic amine monolithic composite material is loaded into the fixed-bed reactor, and the carbon dioxide adsorption is tested by the breakthrough curve method. quantity. Amount of Adsorbent One piece of honeycomb ceramic-porous carbon-organic amine integral composite material weighs about 12.00g, of which about 10.00g is honeycomb ceramic, 1.00g is porous carbon, and 1.00g is organic amine. It is also possible to use 2, 3 or more honeycomb ceramic-porous carbon-organic amine monolithic composite materials as the adsorbent at the same time. The raw material gas composition is (combination of raw material gas volume): 10% CO 2 +90% N 2 , and the flow rate of the mixed gas is 10 ml·min -1 . The adsorption temperature is 75°C. The performance of the adsorbent is represented by the carbon dioxide adsorption capacity of the unit mass adsorbent, and the specific algorithm is to divide the carbon dioxide adsorption capacity by (the sum of the mass of porous carbon and organic amine, which is 2.00g in this embodiment), and the honeycomb ceramics are used as the carrier. Its mass is not included in the total mass of the adsorbent. The adsorption properties of the adsorbents are listed in Table 1.
实施例2Example 2
(1)蜂窝陶瓷-多孔炭整体式复合材料的制备：(1) Preparation of honeycomb ceramic-porous carbon monolithic composite material:
称取一根直径20mm，高度为50mm的200目堇青石蜂窝陶瓷(约10.00g)放入20ml磷酸和焦磷酸混合水溶液(浓度分别为3.00M/L和1.00M/L)中浸泡30分钟，取出后烘干。将负载磷酸和焦磷酸的蜂窝陶瓷放入反应釜中。移取1.50g吡咯、1.00g 2-甲基吡咯、0.50g 3-甲基吡咯(即吡咯、2-甲基吡咯、3-甲基吡咯按质量比3:2:1进行混合)至玻璃瓶中，将玻璃瓶一并放入反应釜中。把反应釜放入200℃烘箱中反应6小时，取出后再次放入20ml磷酸和焦磷酸混合水溶液(浓度分别为3.00M/L和1.00M/L)中浸泡30分钟，取出后烘干。然后在氮气氛围下600℃焙烧90分钟，得到蜂窝陶瓷-多孔炭整体式复合材料，重约10.95g。Weigh a 200-mesh cordierite honeycomb ceramic (about 10.00g) with a diameter of 20mm and a height of 50mm and soak it in 20ml of phosphoric acid and pyrophosphoric acid mixed aqueous solution (concentrations are 3.00M/L and 1.00M/L respectively) for 30 minutes, Take out and tumble dry. Put the honeycomb ceramics loaded with phosphoric acid and pyrophosphoric acid into the reaction kettle. Pipette 1.50g pyrrole, 1.00g 2-methylpyrrole, 0.50g 3-methylpyrrole (that is, mix pyrrole, 2-methylpyrrole, and 3-methylpyrrole in a mass ratio of 3:2:1) into a glass bottle Put the glass bottle into the reaction kettle together. Put the reaction kettle in an oven at 200°C for 6 hours, take it out and put it in 20ml of phosphoric acid and pyrophosphoric acid mixed aqueous solution (concentrations are 3.00M/L and 1.00M/L respectively) to soak for 30 minutes, take it out and dry it. Then it was calcined at 600° C. for 90 minutes under a nitrogen atmosphere to obtain a honeycomb ceramic-porous carbon monolithic composite material, weighing about 10.95 g.
(2)蜂窝陶瓷-多孔炭-有机胺整体式复合材料的制备：(2) Preparation of honeycomb ceramic-porous carbon-organic amine monolithic composite material:
将蜂窝陶瓷-多孔炭整体式复合材料放入到含有0.50g四乙烯五胺、0.25g五乙烯六胺和0.25g聚乙烯亚胺(即四乙烯五胺、五乙烯六胺和聚乙烯亚胺按质量比2:1:1进行混合)的25mL甲醇混合溶液中，超声5分钟，然后放入真空干燥箱中除去溶剂，得到重约11.95g蜂窝陶瓷-多孔炭-有机胺整体式复合材料，即为二氧化碳吸附剂。Put the honeycomb ceramics-porous carbon monolithic composite into a mixture containing 0.50g tetraethylenepentamine, 0.25g pentaethylenehexamine and 0.25g polyethyleneimine (i.e. tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine Mix by mass ratio 2:1:1) in 25mL methanol mixed solution, ultrasonic 5 minutes, then put into the vacuum oven and remove solvent, obtain the cellular ceramics-porous carbon-organic amine monolithic composite material weighing about 11.95g, It is carbon dioxide adsorbent.
(3)臭氧催化分解性能测试：(3) Ozone catalytic decomposition performance test:
催化剂性能测试与实施例1相同，臭氧催化分解性能见表1。The catalyst performance test is the same as in Example 1, and the catalytic decomposition performance of ozone is shown in Table 1.
(4)吸附剂性能测试：(4) Adsorbent performance test:
吸附剂性能测试与实施例1相同，二氧化碳吸附反应性能见表2。The performance test of the adsorbent is the same as in Example 1, and the carbon dioxide adsorption reaction performance is shown in Table 2.
实施例3Example 3
(1)蜂窝陶瓷-多孔炭整体式复合材料的制备：(1) Preparation of honeycomb ceramic-porous carbon monolithic composite material:
称取一根直径20mm，高度为50mm的300目堇青石蜂窝陶瓷(约10.00g)放入20ml磷酸和焦磷酸混合水溶液(浓度分别为2.00M/L和2.00M/L)中浸泡30分钟，取出后烘干。将负载磷酸和焦磷酸的蜂窝陶瓷放入反应釜中。移取2.00g吡咯、0.50g 2-甲基吡咯、0.50g 3-甲基吡咯(即吡咯、2-甲基吡咯、3-甲基吡咯按质量比4:1:1进行混合)至玻璃瓶中，将玻璃瓶一并放入反应釜中。把反应釜放入180℃烘箱中反应6小时，取出后再次放入20ml磷酸和焦磷酸混合水溶液(浓度分别为2.00M/L和2.00M/L)中浸泡30分钟，取出后烘干。然后在氮气氛围下700℃焙烧90分钟，得到蜂窝陶瓷-多孔炭整体式复合材料，重约10.80g。Weigh a 300-mesh cordierite honeycomb ceramic (about 10.00g) with a diameter of 20mm and a height of 50mm and put it into 20ml of a mixed aqueous solution of phosphoric acid and pyrophosphoric acid (concentrations are 2.00M/L and 2.00M/L respectively) and soak for 30 minutes. Take out and tumble dry. Put the honeycomb ceramics loaded with phosphoric acid and pyrophosphoric acid into the reaction kettle. Pipette 2.00g pyrrole, 0.50g 2-methylpyrrole, 0.50g 3-methylpyrrole (that is, pyrrole, 2-methylpyrrole, 3-methylpyrrole are mixed according to the mass ratio of 4:1:1) to the glass bottle Put the glass bottle into the reaction kettle together. Put the reaction kettle in an oven at 180°C for 6 hours, take it out and put it into 20ml of phosphoric acid and pyrophosphoric acid mixed aqueous solution (concentrations are 2.00M/L and 2.00M/L respectively) to soak for 30 minutes, take it out and dry it. Then it was calcined at 700° C. for 90 minutes under a nitrogen atmosphere to obtain a honeycomb ceramic-porous carbon monolithic composite material, weighing about 10.80 g.
(2)蜂窝陶瓷-多孔炭-有机胺整体式复合材料的制备：(2) Preparation of honeycomb ceramic-porous carbon-organic amine monolithic composite material:
将蜂窝陶瓷-多孔炭整体式复合材料放入到含有0.40g四乙烯五胺、0.30g五乙烯六胺和0.10g聚乙烯亚胺(即四乙烯五胺、五乙烯六胺和聚乙烯亚胺按质量比4:3:1进行混合)的25mL甲醇混合溶液中，超声5分钟，然后放入真空干燥箱中除去溶剂，得到重约11.60g蜂窝陶瓷-多孔炭-有机胺整体式复合材料，即为二氧化碳吸附剂。Put the honeycomb ceramics-porous carbon monolithic composite into a mixture containing 0.40g tetraethylenepentamine, 0.30g pentaethylenehexamine and 0.10g polyethyleneimine (i.e. tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine Mix by mass ratio 4:3:1) in 25mL methanol mixed solution, ultrasonic 5 minutes, then put into the vacuum drying box and remove solvent, obtain the honeycomb ceramics-porous carbon-organic amine monolithic composite material weighing about 11.60g, It is carbon dioxide adsorbent.
(3)臭氧催化分解性能测试：(3) Ozone catalytic decomposition performance test:
催化剂性能测试与实施例1相同，臭氧催化分解性能见表1。The catalyst performance test is the same as in Example 1, and the catalytic decomposition performance of ozone is shown in Table 1.
(4)吸附剂性能测试：(4) Adsorbent performance test:
吸附剂性能测试与实施例1相同，二氧化碳吸附反应性能见表2。The performance test of the adsorbent is the same as in Example 1, and the carbon dioxide adsorption reaction performance is shown in Table 2.
实施例4Example 4
(1)蜂窝陶瓷-多孔炭复合材料的制备：(1) Preparation of honeycomb ceramic-porous carbon composite material:
称取一根直径20mm，高度为50mm的200目堇青石蜂窝陶瓷(约10.00g)放入20ml磷酸和焦磷酸混合水溶液(浓度分别为1.00M/L和5.00M/L)中浸泡30分钟，取出后烘干。将负载磷酸和焦磷酸的蜂窝陶瓷放入反应釜中。移取3.00g吡咯、1.00g 2-甲基吡咯、1.00g 3-甲基吡咯(即吡咯、2-甲基吡咯、3-甲基吡咯按质量比3:1:1进行混合)至玻璃瓶中，将玻璃瓶一并放入反应釜中。把反应釜放入180℃烘箱中反应6小时，取出后再次放入20ml磷酸和焦磷酸混合水溶液(浓度分别为1.00M/L和5.00M/L)中浸泡30分钟，取出后烘干。然后在氮气氛围下700℃焙烧90分钟，得到蜂窝陶瓷-多孔炭整体式复合材料，重约11.20g。Weigh a 200-mesh cordierite honeycomb ceramic (about 10.00g) with a diameter of 20mm and a height of 50mm and soak it in 20ml of phosphoric acid and pyrophosphoric acid mixed aqueous solution (concentrations are 1.00M/L and 5.00M/L respectively) for 30 minutes, Take out and tumble dry. Put the honeycomb ceramics loaded with phosphoric acid and pyrophosphoric acid into the reaction kettle. Pipette 3.00g pyrrole, 1.00g 2-methylpyrrole, 1.00g 3-methylpyrrole (that is, pyrrole, 2-methylpyrrole, 3-methylpyrrole are mixed according to the mass ratio of 3:1:1) to the glass bottle Put the glass bottle into the reaction kettle together. Put the reaction kettle in an oven at 180°C for 6 hours, take it out and put it in 20ml of phosphoric acid and pyrophosphoric acid mixed aqueous solution (concentrations are 1.00M/L and 5.00M/L respectively) to soak for 30 minutes, take it out and dry it. Then it was calcined at 700° C. for 90 minutes under a nitrogen atmosphere to obtain a honeycomb ceramic-porous carbon monolithic composite material, weighing about 11.20 g.
(2)蜂窝陶瓷-多孔炭-有机胺整体式复合材料的制备：(2) Preparation of honeycomb ceramic-porous carbon-organic amine monolithic composite material:
将蜂窝陶瓷-多孔炭整体式复合材料放入到含有0.40g四乙烯五胺、0.60g五乙烯六胺和0.20g聚乙烯亚胺(即四乙烯五胺、五乙烯六胺和聚乙烯亚胺按质量比2:3:1进行混合)的25mL甲醇混合溶液中，超声5分钟，然后放入真空干燥箱中除去溶剂，得到重约12.40g蜂窝陶瓷-多孔炭-有机胺整体式复合材料，即为二氧化碳吸附剂。Put the honeycomb ceramics-porous carbon monolithic composite into a mixture containing 0.40g tetraethylenepentamine, 0.60g pentaethylenehexamine and 0.20g polyethyleneimine (i.e. tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine Mix by mass ratio 2:3:1) in 25mL methanol mixed solution, ultrasonic 5 minutes, then put into the vacuum drying box and remove solvent, obtain the honeycomb ceramics-porous carbon-organic amine monolithic composite material weighing about 12.40g, It is carbon dioxide adsorbent.
(3)臭氧催化分解性能测试：(3) Ozone catalytic decomposition performance test:
催化剂性能测试与实施例1相同，臭氧催化分解性能见表1。The catalyst performance test is the same as in Example 1, and the catalytic decomposition performance of ozone is shown in Table 1.
(4)吸附剂性能测试：(4) Adsorbent performance test:
吸附剂性能测试与实施例1相同，二氧化碳吸附反应性能见表2。The performance test of the adsorbent is the same as in Example 1, and the carbon dioxide adsorption reaction performance is shown in Table 2.
实施例5Example 5
(1)蜂窝陶瓷-多孔炭整体式复合材料的制备：(1) Preparation of honeycomb ceramic-porous carbon monolithic composite material:
称取一根直径20mm，高度为50mm的200目堇青石蜂窝陶瓷(约10.00g，见图1a)放入20ml磷酸和焦磷酸混合水溶液(浓度分别为1.00M/L和5.00M/L)中浸泡30分钟，取出后烘干。将负载磷酸和焦磷酸的蜂窝陶瓷放入反应釜中。移取1.00g吡咯、2.00g 2-甲基吡咯、3.00g 3-甲基吡咯(即吡咯、2-甲基吡咯、3-甲基吡咯按质量比1:2:3进行混合)至玻璃瓶中，将玻璃瓶一并放入反应釜中。把反应釜放入190℃烘箱中反应6小时，取出后再次放入20ml磷酸和焦磷酸混合水溶液(浓度分别为1.00M/L和5.00M/L)中浸泡30分钟，取出后烘干。然后在氮气氛围下800℃焙烧90分钟，得到蜂窝陶瓷-多孔炭整体式复合材料，如图1b所示，重约11.00g。Weigh a 200-mesh cordierite honeycomb ceramic (about 10.00g, see Figure 1a) with a diameter of 20mm and a height of 50mm into 20ml of a mixed aqueous solution of phosphoric acid and pyrophosphoric acid (concentrations are 1.00M/L and 5.00M/L, respectively) Soak for 30 minutes, take it out and dry it. Put the honeycomb ceramics loaded with phosphoric acid and pyrophosphoric acid into the reaction kettle. Pipette 1.00g pyrrole, 2.00g 2-methylpyrrole, 3.00g 3-methylpyrrole (that is, pyrrole, 2-methylpyrrole, 3-methylpyrrole are mixed according to the mass ratio of 1:2:3) to the glass bottle Put the glass bottle into the reaction kettle together. Put the reaction kettle in an oven at 190°C for 6 hours, take it out, put it into 20ml of phosphoric acid and pyrophosphoric acid mixed aqueous solution (concentrations are 1.00M/L and 5.00M/L respectively) and soak for 30 minutes, take it out and dry it. Then it was calcined at 800°C for 90 minutes under a nitrogen atmosphere to obtain a honeycomb ceramic-porous carbon monolithic composite material, as shown in Figure 1b, weighing about 11.00g.
(2)蜂窝陶瓷-多孔炭-有机胺整体式复合材料的制备：(2) Preparation of honeycomb ceramic-porous carbon-organic amine monolithic composite material:
将蜂窝陶瓷-多孔炭整体式复合材料放入到含有0.10g四乙烯五胺、0.20g五乙烯六胺和0.70g聚乙烯亚胺(即四乙烯五胺、五乙烯六胺和聚乙烯亚胺按质量比1:2:7进行混合)的25mL甲醇混合溶液中，超声5分钟，然后放入真空干燥箱中除去溶剂，得到重约12.00g蜂窝陶瓷-多孔炭-有机胺整体式复合材料，即为二氧化碳吸附剂。Put the honeycomb ceramics-porous carbon monolithic composite into a mixture containing 0.10g tetraethylenepentamine, 0.20g pentaethylenehexamine and 0.70g polyethyleneimine (i.e. tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine Mix by mass ratio 1:2:7) in 25mL methanol mixed solution, ultrasonic 5 minutes, then put into the vacuum drying box and remove solvent, obtain the honeycomb ceramics-porous carbon-organic amine monolithic composite material weighing about 12.00g, It is carbon dioxide adsorbent.
(3)臭氧催化分解性能测试：(3) Ozone catalytic decomposition performance test:
催化剂性能测试与实施例1相同，臭氧催化分解稳定性见图3，臭氧催化分解性能见表1。The catalyst performance test is the same as that in Example 1. The ozone catalytic decomposition stability is shown in FIG. 3 , and the ozone catalytic decomposition performance is shown in Table 1.
(4)吸附剂性能测试：(4) Adsorbent performance test:
吸附剂性能测试与实施例1相同，二氧化碳穿透曲线见图4，二氧化碳吸附反应性能见表2。The performance test of the adsorbent is the same as in Example 1. The carbon dioxide breakthrough curve is shown in FIG. 4 , and the carbon dioxide adsorption reaction performance is shown in Table 2.
实施例6Example 6
(1)蜂窝陶瓷-多孔炭整体式复合材料的制备：(1) Preparation of honeycomb ceramic-porous carbon monolithic composite material:
称取一根直径20mm，高度为50mm的200目堇青石蜂窝陶瓷(约10.00g)放入20ml磷酸和焦磷酸混合水溶液(浓度分别为1.00M/L和5.00M/L)中浸泡30分钟，取出后烘干。将负载磷酸和焦磷酸的蜂窝陶瓷放入反应釜中。移取1.00g吡咯、2.00g 2-甲基吡咯、3.00g 3-甲基吡咯(即吡咯、2-甲基吡咯、3-甲基吡咯按质量比3:1:1进行混合)至玻璃瓶中，将玻璃瓶一并放入反应釜中。把反应釜放入190℃烘箱中反应6小时，取出后再次放入20ml磷酸和焦磷酸混合水溶液(浓度分别为1.00M/L和5.00M/L)中浸泡30分钟，取出后烘干。然后在氮气氛围下800℃焙烧90分钟，得到蜂窝陶瓷-多孔炭整体式复合材料，重约11.00g。Weigh a 200-mesh cordierite honeycomb ceramic (about 10.00g) with a diameter of 20mm and a height of 50mm and soak it in 20ml of phosphoric acid and pyrophosphoric acid mixed aqueous solution (concentrations are 1.00M/L and 5.00M/L respectively) for 30 minutes, Take out and tumble dry. Put the honeycomb ceramics loaded with phosphoric acid and pyrophosphoric acid into the reaction kettle. Pipette 1.00g pyrrole, 2.00g 2-methylpyrrole, 3.00g 3-methylpyrrole (that is, mix pyrrole, 2-methylpyrrole, and 3-methylpyrrole in a mass ratio of 3:1:1) into a glass bottle Put the glass bottle into the reaction kettle together. Put the reaction kettle in an oven at 190°C for 6 hours, take it out, put it into 20ml of phosphoric acid and pyrophosphoric acid mixed aqueous solution (concentrations are 1.00M/L and 5.00M/L respectively) and soak for 30 minutes, take it out and dry it. Then it was calcined at 800° C. for 90 minutes under a nitrogen atmosphere to obtain a honeycomb ceramic-porous carbon monolithic composite material, weighing about 11.00 g.
(2)蜂窝陶瓷-多孔炭-有机胺整体式复合材料的制备：(2) Preparation of honeycomb ceramic-porous carbon-organic amine monolithic composite material:
将蜂窝陶瓷-多孔炭整体式复合材料放入到含有0.10g四乙烯五胺、0.20g五乙烯六胺和0.70g聚乙烯亚胺(即四乙烯五胺、五乙烯六胺和聚乙烯亚胺按质量比2:3:1进行混合)的25mL甲醇混合溶液中，超声5分钟，然后放入真空干燥箱中除去溶剂，得到重约12.00g蜂窝陶瓷-多孔炭-有机胺整体式复合材料，即为二氧化碳吸附剂。Put the honeycomb ceramics-porous carbon monolithic composite into a mixture containing 0.10g tetraethylenepentamine, 0.20g pentaethylenehexamine and 0.70g polyethyleneimine (i.e. tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine Mix by mass ratio 2:3:1) in 25mL methanol mixed solution, ultrasonic 5 minutes, then put into the vacuum drying box and remove solvent, obtain the honeycomb ceramics-porous carbon-organic amine monolithic composite material weighing about 12.00g, It is carbon dioxide adsorbent.
(3)臭氧催化分解性能测试：(3) Ozone catalytic decomposition performance test:
催化剂性能测试与实施例1相同，臭氧催化分解性能见表1。The catalyst performance test is the same as in Example 1, and the catalytic decomposition performance of ozone is shown in Table 1.
(4)吸附剂性能测试：(4) Adsorbent performance test:
吸附剂性能测试与实施例1相同，二氧化碳吸附反应性能见表2。The performance test of the adsorbent is the same as in Example 1, and the carbon dioxide adsorption reaction performance is shown in Table 2.
实施例7Example 7
(1)蜂窝陶瓷-多孔炭整体式复合材料的制备：(1) Preparation of honeycomb ceramic-porous carbon monolithic composite material:
称取一根直径20mm，高度为50mm的200目堇青石蜂窝陶瓷(约10.00g)放入20ml磷酸和焦磷酸混合水溶液(浓度分别为1.00M/L和5.00M/L)中浸泡30分钟，取出后烘干。将负载磷酸和焦磷酸的蜂窝陶瓷放入反应釜中。移取6.00g 3-甲基吡咯至玻璃瓶中，将玻璃瓶一并放入反应釜中。把反应釜放入190℃烘箱中反应6小时，取出后再次放入20ml磷酸和焦磷酸混合水溶液(浓度分别为1.00M/L和5.00M/L)中浸泡30分钟，取出后烘干。然后在氮气氛围下900℃焙烧90分钟，得到蜂窝陶瓷-多孔炭整体式复合材料，重约10.80g。Weigh a 200-mesh cordierite honeycomb ceramic (about 10.00g) with a diameter of 20mm and a height of 50mm and soak it in 20ml of phosphoric acid and pyrophosphoric acid mixed aqueous solution (concentrations are 1.00M/L and 5.00M/L respectively) for 30 minutes, Take out and tumble dry. Put the honeycomb ceramics loaded with phosphoric acid and pyrophosphoric acid into the reaction kettle. Pipette 6.00g of 3-methylpyrrole into a glass bottle, and put the glass bottle into the reaction kettle together. Put the reaction kettle in an oven at 190°C for 6 hours, take it out, put it into 20ml of phosphoric acid and pyrophosphoric acid mixed aqueous solution (concentrations are 1.00M/L and 5.00M/L respectively) and soak for 30 minutes, take it out and dry it. Then it was calcined at 900° C. for 90 minutes under a nitrogen atmosphere to obtain a honeycomb ceramic-porous carbon monolithic composite material, weighing about 10.80 g.
(2)蜂窝陶瓷-多孔炭-有机胺整体式复合材料的制备：(2) Preparation of honeycomb ceramic-porous carbon-organic amine monolithic composite material:
将蜂窝陶瓷-多孔炭整体式复合材料放入到含有0.80g聚乙烯亚胺的25mL甲醇混合溶液中，超声5分钟，然后放入真空干燥箱中除去溶剂，得到重约11.60g蜂窝陶瓷-多孔炭-有机胺整体式复合材料，即为二氧化碳吸附剂。Put the honeycomb ceramic-porous carbon integral composite material into 25mL methanol mixed solution containing 0.80g polyethyleneimine, ultrasonic for 5 minutes, and then put it in a vacuum drying oven to remove the solvent, and obtain a honeycomb ceramic-porous carbon composite weighing about 11.60g The carbon-organic amine integral composite material is a carbon dioxide adsorbent.
(3)臭氧催化分解性能测试：(3) Ozone catalytic decomposition performance test:
催化剂性能测试与实施例1相同，臭氧催化分解性能见表1。The catalyst performance test is the same as in Example 1, and the catalytic decomposition performance of ozone is shown in Table 1.
(4)吸附剂性能测试：(4) Adsorbent performance test:
吸附剂性能测试与实施例1相同，二氧化碳吸附反应性能见表2。The performance test of the adsorbent is the same as in Example 1, and the carbon dioxide adsorption reaction performance is shown in Table 2.
实施例8Example 8
(1)蜂窝陶瓷-多孔炭整体式复合材料的制备：(1) Preparation of honeycomb ceramic-porous carbon monolithic composite material:
称取一根直径20mm，高度为50mm的200目堇青石蜂窝陶瓷(约10.00g)放入20ml磷酸和焦磷酸混合水溶液(浓度分别为1.00M/L和5.00M/L)中浸泡30分钟，取出后烘干。将负载磷酸和焦磷酸的蜂窝陶瓷放入反应釜中。移取4.00g吡咯、0.50g 2-甲基吡咯、0.50g 3-甲基吡咯(即吡咯、2-甲基吡咯、3-甲基吡咯按质量比8:1:1进行混合)至玻璃瓶中，将玻璃瓶一并放入反应釜中。把反应釜放入190℃烘箱中反应6小时，取出后再次放入20ml磷酸和焦磷酸混合水溶液(浓度分别为1.00M/L和5.00M/L)中浸泡30分钟，取出后烘干。然后在氮气氛围下900℃焙烧90分钟，得到蜂窝陶瓷-多孔炭整体式复合材料，重约11.10g。Weigh a 200-mesh cordierite honeycomb ceramic (about 10.00g) with a diameter of 20mm and a height of 50mm and soak it in 20ml of phosphoric acid and pyrophosphoric acid mixed aqueous solution (concentrations are 1.00M/L and 5.00M/L respectively) for 30 minutes, Take out and tumble dry. Put the honeycomb ceramics loaded with phosphoric acid and pyrophosphoric acid into the reaction kettle. Pipette 4.00g pyrrole, 0.50g 2-methylpyrrole, 0.50g 3-methylpyrrole (that is, mix pyrrole, 2-methylpyrrole, and 3-methylpyrrole in a mass ratio of 8:1:1) to a glass bottle Put the glass bottle into the reaction kettle together. Put the reaction kettle in an oven at 190°C for 6 hours, take it out, put it into 20ml of phosphoric acid and pyrophosphoric acid mixed aqueous solution (concentrations are 1.00M/L and 5.00M/L respectively) and soak for 30 minutes, take it out and dry it. Then it was calcined at 900° C. for 90 minutes under a nitrogen atmosphere to obtain a honeycomb ceramic-porous carbon monolithic composite material, weighing about 11.10 g.
(2)蜂窝陶瓷-多孔炭-有机胺整体式复合材料的制备：(2) Preparation of honeycomb ceramic-porous carbon-organic amine monolithic composite material:
将蜂窝陶瓷-多孔炭整体式复合材料放入到含有0.50g四乙烯五胺、0.50g五乙烯六胺和0.10g聚乙烯亚胺(即四乙烯五胺、五乙烯六胺和聚乙烯亚胺按质量比5:5:1进行混合)的25mL甲醇混合溶液中，超声5分钟，然后放入真空干燥箱中除去溶剂，得到重约12.20g蜂窝陶瓷-多孔炭-有机胺整体式复合材料，即为二氧化碳吸附剂。Put the honeycomb ceramics-porous carbon monolithic composite into a mixture containing 0.50g tetraethylenepentamine, 0.50g pentaethylenehexamine and 0.10g polyethyleneimine (that is, tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine Mix by mass ratio 5:5:1) in 25mL methanol mixed solution, ultrasonic 5 minutes, then put into the vacuum drying box and remove solvent, obtain the honeycomb ceramics-porous carbon-organic amine monolithic composite material weighing about 12.20g, It is carbon dioxide adsorbent.
(3)臭氧催化分解性能测试：(3) Ozone catalytic decomposition performance test:
催化剂性能测试与实施例1相同，臭氧催化分解性能见表1。The catalyst performance test is the same as in Example 1, and the catalytic decomposition performance of ozone is shown in Table 1.
(4)吸附剂性能测试：(4) Adsorbent performance test:
吸附剂性能测试与实施例1相同，二氧化碳吸附反应性能见表2。The performance test of the adsorbent is the same as in Example 1, and the carbon dioxide adsorption reaction performance is shown in Table 2.
实施例9Example 9
(1)蜂窝陶瓷-多孔炭整体式复合材料的制备：(1) Preparation of honeycomb ceramic-porous carbon monolithic composite material:
称取一根直径20mm，高度为50mm的200目堇青石蜂窝陶瓷(约10.00g)放入20ml磷酸水溶液(浓度分别为4.00M/L)中浸泡30分钟，取出后烘干。将负载磷酸的蜂窝陶瓷放入反应釜中。移取5.00g吡咯至玻璃瓶中，将玻璃瓶一并放入反应釜中。把反应釜放入190℃烘箱中反应6小时，取出后再次放入20ml磷酸水溶液(浓度分别为4.00M/L)中浸泡30分钟，取出后烘干。然后在氮气氛围下800℃焙烧90分钟，得到蜂窝陶瓷-多孔炭整体式复合材料，重约11.10g。Weigh a 200-mesh cordierite honeycomb ceramic (about 10.00g) with a diameter of 20mm and a height of 50mm, put it into 20ml of phosphoric acid aqueous solution (concentrations of 4.00M/L respectively) and soak for 30 minutes, take it out and dry it. Put the honeycomb ceramics loaded with phosphoric acid into the reaction kettle. Pipette 5.00 g of pyrrole into a glass bottle, and put the glass bottle into the reaction kettle together. Put the reaction kettle into an oven at 190°C for 6 hours, take it out and put it in 20ml phosphoric acid aqueous solution (4.00M/L concentration) for 30 minutes, take it out and dry it. Then, it was calcined at 800° C. for 90 minutes under a nitrogen atmosphere to obtain a honeycomb ceramic-porous carbon monolithic composite material, weighing about 11.10 g.
(2)蜂窝陶瓷-多孔炭-有机胺整体式复合材料的制备：(2) Preparation of honeycomb ceramic-porous carbon-organic amine monolithic composite material:
将蜂窝陶瓷-多孔炭整体式复合材料放入到含有1.10g四乙烯五胺的25mL甲醇混合溶液中，超声5分钟，然后放入真空干燥箱中除去溶剂，得到重约12.20g蜂窝陶瓷-多孔炭-有机胺整体式复合材料，即为二氧化碳吸附剂。Put the honeycomb ceramic-porous carbon integral composite material into 25mL methanol mixed solution containing 1.10g tetraethylenepentamine, ultrasonicate for 5 minutes, then put it in a vacuum drying oven to remove the solvent, and obtain a honeycomb ceramic-porous carbon composite weighing about 12.20g The carbon-organic amine integral composite material is a carbon dioxide adsorbent.
(3)臭氧催化分解性能测试：(3) Ozone catalytic decomposition performance test:
催化剂性能测试与实施例1相同，臭氧催化分解性能见表1。The catalyst performance test is the same as in Example 1, and the catalytic decomposition performance of ozone is shown in Table 1.
(4)吸附剂性能测试：(4) Adsorbent performance test:
吸附剂性能测试与实施例1相同，二氧化碳吸附反应性能见表2。The performance test of the adsorbent is the same as in Example 1, and the carbon dioxide adsorption reaction performance is shown in Table 2.
实施例10Example 10
(1)蜂窝陶瓷-多孔炭整体式复合材料的制备：(1) Preparation of honeycomb ceramic-porous carbon monolithic composite material:
称取一根直径20mm，高度为50mm的200目堇青石蜂窝陶瓷(约10.00g)放入20ml焦磷酸水溶液(浓度为5.00M/L)中浸泡30分钟，取出后烘干。将负载焦磷酸的蜂窝陶瓷放入反应釜中。移取5.00g 2-甲基吡咯至玻璃瓶中，将玻璃瓶一并放入反应釜中。把反应釜放入190℃烘箱中反应6小时，取出后再次放入20ml焦磷酸混合溶液(浓度为5.00M/L)中浸泡30分钟，取出后烘干。然后在氮气氛围下900℃焙烧90分钟，得到蜂窝陶瓷-多孔炭整体式复合材料，重约10.90g。Weigh a 200-mesh cordierite honeycomb ceramic (about 10.00 g) with a diameter of 20 mm and a height of 50 mm, put it into 20 ml of pyrophosphoric acid aqueous solution (concentration of 5.00 M/L) and soak for 30 minutes, take it out and dry it. Put the honeycomb ceramics loaded with pyrophosphoric acid into the reaction kettle. Pipette 5.00 g of 2-methylpyrrole into a glass bottle, and put the glass bottle into the reaction kettle together. Put the reaction kettle in an oven at 190°C for 6 hours, take it out and put it in 20ml pyrophosphoric acid mixed solution (concentration: 5.00M/L) to soak for 30 minutes, take it out and dry it. Then it was calcined at 900° C. for 90 minutes under a nitrogen atmosphere to obtain a honeycomb ceramic-porous carbon monolithic composite material, weighing about 10.90 g.
(2)蜂窝陶瓷-多孔炭-有机胺整体式复合材料的制备：(2) Preparation of honeycomb ceramic-porous carbon-organic amine monolithic composite material:
将蜂窝陶瓷-多孔炭整体式复合材料放入到含有0.90g五乙烯六胺的25mL甲醇混合溶液中，超声5分钟，然后放入真空干燥箱中除去溶剂，得到重约11.80g蜂窝陶瓷-多孔炭-有机胺整体式复合材料，即为二氧化碳吸附剂。Put the honeycomb ceramic-porous carbon integral composite material into 25mL methanol mixed solution containing 0.90g pentaethylene hexamine, ultrasonicate for 5 minutes, then put it in a vacuum drying oven to remove the solvent, and obtain a honeycomb ceramic-porous carbon composite weighing about 11.80g The carbon-organic amine integral composite material is a carbon dioxide adsorbent.
(3)臭氧催化分解性能测试：(3) Ozone catalytic decomposition performance test:
催化剂性能测试与实施例1相同，臭氧催化分解性能见表1。The catalyst performance test is the same as in Example 1, and the catalytic decomposition performance of ozone is shown in Table 1.
(4)吸附剂性能测试：(4) Adsorbent performance test:
吸附剂性能测试与实施例1相同，二氧化碳吸附反应性能见表2。The performance test of the adsorbent is the same as in Example 1, and the carbon dioxide adsorption reaction performance is shown in Table 2.
对比例1Comparative example 1
(1)蜂窝陶瓷-多孔炭整体式复合材料的制备：(1) Preparation of honeycomb ceramic-porous carbon monolithic composite material:
称取一根直径20mm，高度为50mm的200目堇青石蜂窝陶瓷(约10.00g)，表面不负载磷酸或者焦磷酸，直接放入反应釜中。移取1.00g吡咯、2.00g 2-甲基吡咯、3.00g 3-甲基吡咯(即吡咯、2-甲基吡咯、3-甲基吡咯按质量比1:2:3进行混合)至玻璃瓶中，将玻璃瓶一并放入反应釜中。把反应釜放入190℃烘箱中反应6小时，取出后放入20ml磷酸和焦磷酸混合溶液(浓度分别为1.00M/L和5.00M/L)中浸泡30分钟，取出后烘干。然后在氮气氛围下800℃焙烧90分钟，得到蜂窝陶瓷-多孔炭整体式复合材料，重约10.20g。Weigh a 200-mesh cordierite honeycomb ceramic (about 10.00 g) with a diameter of 20 mm and a height of 50 mm, without phosphoric acid or pyrophosphoric acid on the surface, and put it directly into the reaction kettle. Pipette 1.00g pyrrole, 2.00g 2-methylpyrrole, 3.00g 3-methylpyrrole (that is, pyrrole, 2-methylpyrrole, 3-methylpyrrole are mixed according to the mass ratio of 1:2:3) to the glass bottle Put the glass bottle into the reaction kettle together. Put the reaction kettle in an oven at 190°C for 6 hours, take it out and soak it in 20ml of phosphoric acid and pyrophosphoric acid mixed solution (concentrations are 1.00M/L and 5.00M/L respectively) for 30 minutes, take it out and dry it. Then, it was calcined at 800° C. for 90 minutes under a nitrogen atmosphere to obtain a honeycomb ceramic-porous carbon monolithic composite material, weighing about 10.20 g.
(2)蜂窝陶瓷-多孔炭-有机胺整体式复合材料的制备：(2) Preparation of honeycomb ceramic-porous carbon-organic amine monolithic composite material:
将蜂窝陶瓷-多孔炭整体式复合材料放入到含有0.10g四乙烯五胺、0.05g五乙烯六胺和0.05g聚乙烯亚胺(即四乙烯五胺、五乙烯六胺和聚乙烯亚胺按质量比2:1:1进行混合)的25mL甲醇混合溶液中，超声5分钟，然后放入真空干燥箱中除去溶剂，得到重约10.40g蜂窝陶瓷-多孔炭-有机胺整体式复合材料，即为二氧化碳吸附剂。Put the honeycomb ceramics-porous carbon monolithic composite into a mixture containing 0.10g tetraethylenepentamine, 0.05g pentaethylenehexamine and 0.05g polyethyleneimine (i.e. tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine Mix by mass ratio 2:1:1) in 25mL methanol mixed solution, ultrasonic 5 minutes, then put into the vacuum oven and remove solvent, obtain the cellular ceramics-porous carbon-organic amine monolithic composite material weighing about 10.40g, It is carbon dioxide adsorbent.
(3)臭氧催化分解性能测试：(3) Ozone catalytic decomposition performance test:
催化剂性能测试与实施例5相同，臭氧催化分解性能见表3。The catalyst performance test is the same as in Example 5, and the catalytic decomposition performance of ozone is shown in Table 3.
(4)吸附剂性能测试：(4) Adsorbent performance test:
吸附剂性能测试与实施例5相同，二氧化碳吸附反应性能见表4。The performance test of the adsorbent is the same as in Example 5, and the carbon dioxide adsorption reaction performance is shown in Table 4.
对比例2Comparative example 2
(1)蜂窝陶瓷-多孔炭整体式复合材料的制备：(1) Preparation of honeycomb ceramic-porous carbon monolithic composite material:
称取一根直径20mm，高度为50mm的200目堇青石蜂窝陶瓷(约10.00g)放入20ml磷酸和焦磷酸混合溶液(浓度分别为1.00M/L和5.00M/L)中浸泡30分钟，取出后烘干。将负载磷酸的蜂窝陶瓷放入反应釜中。移取1.00g吡咯、2.00g 2-甲基吡咯、3.00g 3-甲基吡咯(即吡咯、2-甲基吡咯、3-甲基吡咯按质量比1:2:3进行混合)至玻璃瓶中，将玻璃瓶一并放入反应釜中。把反应釜放入190℃烘箱中反应6小时，取出后直接在氮气氛围下800℃焙烧90分钟，得到蜂窝陶瓷-多孔炭整体式复合材料，重约11.30g。Weigh a 200-mesh cordierite honeycomb ceramic (about 10.00g) with a diameter of 20mm and a height of 50mm and put it into 20ml of phosphoric acid and pyrophosphoric acid mixed solution (concentrations are 1.00M/L and 5.00M/L respectively) and soak for 30 minutes. Take out and tumble dry. Put the honeycomb ceramics loaded with phosphoric acid into the reaction kettle. Pipette 1.00g pyrrole, 2.00g 2-methylpyrrole, 3.00g 3-methylpyrrole (that is, pyrrole, 2-methylpyrrole, 3-methylpyrrole are mixed according to the mass ratio of 1:2:3) to the glass bottle Put the glass bottle into the reaction kettle together. Put the reaction kettle into an oven at 190°C for 6 hours, take it out, and bake it directly at 800°C for 90 minutes under nitrogen atmosphere to obtain a honeycomb ceramic-porous carbon monolithic composite material, weighing about 11.30g.
(2)蜂窝陶瓷-多孔炭-有机胺整体式复合材料的制备：(2) Preparation of honeycomb ceramic-porous carbon-organic amine monolithic composite material:
将蜂窝陶瓷-多孔炭整体式复合材料放入到含有0.30g四乙烯五胺、0.05g五乙烯六胺和0.05g聚乙烯亚胺(即四乙烯五胺、五乙烯六胺和聚乙烯亚胺按质量比2:1:1进行混合)的25mL甲醇混合溶液中，超声5分钟，然后放入真空干燥箱中除去溶剂，得到重约12.60g蜂窝陶瓷-多孔炭-有机胺整体式复合材料，即为二氧化碳吸附剂。Put the honeycomb ceramic-porous carbon monolithic composite material into a mixture containing 0.30g tetraethylenepentamine, 0.05g pentaethylenehexamine and 0.05g polyethyleneimine (that is, tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine Mix by mass ratio 2:1:1) in 25mL methanol mixed solution, ultrasonic 5 minutes, then put into the vacuum oven and remove solvent, obtain the cellular ceramics-porous carbon-organic amine monolithic composite material weighing about 12.60g, It is carbon dioxide adsorbent.
(3)臭氧催化分解性能测试：(3) Ozone catalytic decomposition performance test:
催化剂性能测试与实施例5相同，臭氧催化分解性能见表3。The catalyst performance test is the same as in Example 5, and the catalytic decomposition performance of ozone is shown in Table 3.
(4)吸附剂性能测试：(4) Adsorbent performance test:
吸附剂性能测试与实施例5相同，二氧化碳吸附反应性能见表4。The performance test of the adsorbent is the same as in Example 5, and the carbon dioxide adsorption reaction performance is shown in Table 4.
对比例3Comparative example 3
(1)蜂窝陶瓷-多孔炭整体式复合材料的制备：(1) Preparation of honeycomb ceramic-porous carbon monolithic composite material:
称取一根直径20mm，高度为50mm的200目堇青石蜂窝陶瓷(约10.00g)放入20ml焦磷酸溶液(浓度分别为5.0M/L)中浸泡30分钟，取出后烘干。将负载磷酸的蜂窝陶瓷放入反应釜中。移取1.00g吡咯、2.00g 2-甲基吡咯、3.00g 3-甲基吡咯(即吡咯、2-甲基吡咯、3-甲基吡咯按质量比1:2:3进行混合)至玻璃瓶中，将玻璃瓶一并放入反应釜中。把反应釜放入190℃烘箱中反应6小时，取出后再次放入20ml焦磷酸溶液(浓度为5.0M/L)中浸泡30分钟，取出后烘干。然后在氮气氛围下800℃焙烧90分钟，得到蜂窝陶瓷-多孔炭整体式复合材料，重约10.80g。Weigh a 200-mesh cordierite honeycomb ceramic (about 10.00 g) with a diameter of 20 mm and a height of 50 mm, put it into 20 ml of pyrophosphoric acid solution (5.0 M/L concentration) and soak for 30 minutes, take it out and dry it. Put the honeycomb ceramics loaded with phosphoric acid into the reaction kettle. Pipette 1.00g pyrrole, 2.00g 2-methylpyrrole, 3.00g 3-methylpyrrole (that is, pyrrole, 2-methylpyrrole, 3-methylpyrrole are mixed according to the mass ratio of 1:2:3) to the glass bottle Put the glass bottle into the reaction kettle together. Put the reaction kettle in an oven at 190°C for 6 hours, take it out and put it in 20ml of pyrophosphoric acid solution (concentration: 5.0M/L) to soak for 30 minutes, take it out and dry it. Then it was calcined at 800° C. for 90 minutes under a nitrogen atmosphere to obtain a honeycomb ceramic-porous carbon monolithic composite material, weighing about 10.80 g.
(2)蜂窝陶瓷-多孔炭-有机胺整体式复合材料的制备：(2) Preparation of honeycomb ceramic-porous carbon-organic amine monolithic composite material:
将蜂窝陶瓷-多孔炭整体式复合材料放入到含有0.40g四乙烯五胺、0.20g五乙烯六胺和0.20g聚乙烯亚胺(即四乙烯五胺、五乙烯六胺和聚乙烯亚胺按质量比2:1:1进行混合)的25mL甲醇混合溶液中，超声5分钟，然后放入真空干燥箱中除去溶剂，得到重约11.60g蜂窝陶瓷-多孔炭-有机胺整体式复合材料，即为二氧化碳吸附剂。Put the honeycomb ceramics-porous carbon monolithic composite into a mixture containing 0.40g tetraethylenepentamine, 0.20g pentaethylenehexamine and 0.20g polyethyleneimine (that is, tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine Mix by mass ratio 2:1:1) in 25mL methanol mixed solution, ultrasonic 5 minutes, then put into the vacuum oven and remove solvent, obtain the honeycomb ceramics-porous carbon-organic amine monolithic composite material weighing about 11.60g, It is carbon dioxide adsorbent.
(3)臭氧催化分解性能测试：(3) Ozone catalytic decomposition performance test:
催化剂性能测试与实施例5相同，臭氧催化分解性能见表3。The catalyst performance test is the same as in Example 5, and the catalytic decomposition performance of ozone is shown in Table 3.
(4)吸附剂性能测试：(4) Adsorbent performance test:
吸附剂性能测试与实施例5相同，二氧化碳吸附反应性能见表4。The performance test of the adsorbent is the same as in Example 5, and the carbon dioxide adsorption reaction performance is shown in Table 4.
对比例4Comparative example 4
(1)蜂窝陶瓷-多孔炭整体式复合材料的制备：(1) Preparation of honeycomb ceramic-porous carbon monolithic composite material:
称取一根直径20mm，高度为50mm的200目堇青石蜂窝陶瓷(约10.00g)放入20ml磷酸溶液(浓度为1.00M/L)中浸泡30分钟，取出后烘干。将负载磷酸的蜂窝陶瓷放入反应釜中。移取1.00g吡咯、2.00g 2-甲基吡咯、3.00g 3-甲基吡咯(即吡咯、2-甲基吡咯、3-甲基吡咯按质量比1:2:3进行混合)至玻璃瓶中，将玻璃瓶一并放入反应釜中。把反应釜放入190℃烘箱中反应6小时，取出后再次放入20ml磷酸溶液(浓度为1.00M/L)中浸泡30分钟，取出后烘干。然后在氮气氛围下800℃焙烧90分钟，得到蜂窝陶瓷-多孔炭整体式复合材料，重约10.70g。Weigh a 200-mesh cordierite honeycomb ceramic (about 10.00 g) with a diameter of 20 mm and a height of 50 mm, put it into 20 ml of phosphoric acid solution (concentration of 1.00 M/L) and soak it for 30 minutes, take it out and dry it. Put the honeycomb ceramics loaded with phosphoric acid into the reaction kettle. Pipette 1.00g pyrrole, 2.00g 2-methylpyrrole, 3.00g 3-methylpyrrole (that is, pyrrole, 2-methylpyrrole, 3-methylpyrrole are mixed according to the mass ratio of 1:2:3) to the glass bottle Put the glass bottle into the reaction kettle together. Put the reaction kettle in an oven at 190°C for 6 hours, take it out and put it in 20ml phosphoric acid solution (concentration: 1.00M/L) for 30 minutes, take it out and dry it. Then it was calcined at 800° C. for 90 minutes under a nitrogen atmosphere to obtain a honeycomb ceramic-porous carbon monolithic composite material, weighing about 10.70 g.
(2)蜂窝陶瓷-多孔炭-有机胺整体式复合材料的制备：(2) Preparation of honeycomb ceramic-porous carbon-organic amine monolithic composite material:
将蜂窝陶瓷-多孔炭整体式复合材料放入到含有0.10g四乙烯五胺、0.20g五乙烯六胺和0.40g聚乙烯亚胺(即四乙烯五胺、五乙烯六胺和聚乙烯亚胺按质量比1:2:4进行混合)的25mL甲醇混合溶液中，超声5分钟，然后放入真空干燥箱中除去溶剂，得到重约11.40g蜂窝陶瓷-多孔炭-有机胺整体式复合材料，即为二氧化碳吸附剂。Put the honeycomb ceramics-porous carbon monolithic composite into a mixture containing 0.10g tetraethylenepentamine, 0.20g pentaethylenehexamine and 0.40g polyethyleneimine (i.e. tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine Mix by mass ratio 1:2:4) in 25mL methanol mixed solution, ultrasonic 5 minutes, then put into the vacuum oven and remove solvent, obtain the honeycomb ceramics-porous carbon-organic amine monolithic composite material weighing about 11.40g, It is carbon dioxide adsorbent.
(3)臭氧催化分解性能测试：(3) Ozone catalytic decomposition performance test:
催化剂性能测试与实施例5相同，臭氧催化分解性能见表3。The catalyst performance test is the same as in Example 5, and the catalytic decomposition performance of ozone is shown in Table 3.
(4)吸附剂性能测试：(4) Adsorbent performance test:
吸附剂性能测试与实施例5相同，二氧化碳吸附反应性能见表4。The performance test of the adsorbent is the same as in Example 5, and the carbon dioxide adsorption reaction performance is shown in Table 4.
对比例5Comparative example 5
(1)蜂窝陶瓷-多孔炭整体式复合材料的制备：(1) Preparation of honeycomb ceramic-porous carbon monolithic composite material:
称取一根直径20mm，高度为50mm的200目堇青石蜂窝陶瓷(约10.00g)放入20ml磷酸和焦磷酸混合溶液(浓度分别为1.00M/L和5.00M/L)中浸泡30分钟，取出后烘干。将负载磷酸的蜂窝陶瓷放入反应釜中。移取1.00g吡咯、2.00g 2-甲基吡咯、3.00g 3-甲基吡咯(即吡咯、2-甲基吡咯、3-甲基吡咯按质量比1:2:3进行混合)至玻璃瓶中，将玻璃瓶一并放入反应釜中。把反应釜放入190℃烘箱中反应6小时，取出后再次放入20ml磷酸和焦磷酸混合溶液(浓度分别为1.00M/L和5.00M/L)中浸泡30分钟，取出后烘干。然后在氮气氛围下1200℃焙烧90分钟，得到蜂窝陶瓷-多孔炭整体式复合材料，重约10.50g。Weigh a 200-mesh cordierite honeycomb ceramic (about 10.00g) with a diameter of 20mm and a height of 50mm and put it into 20ml of phosphoric acid and pyrophosphoric acid mixed solution (concentrations are 1.00M/L and 5.00M/L respectively) and soak for 30 minutes. Take out and tumble dry. Put the honeycomb ceramics loaded with phosphoric acid into the reaction kettle. Pipette 1.00g pyrrole, 2.00g 2-methylpyrrole, 3.00g 3-methylpyrrole (that is, pyrrole, 2-methylpyrrole, 3-methylpyrrole are mixed according to the mass ratio of 1:2:3) to the glass bottle Put the glass bottle into the reaction kettle together. Put the reaction kettle in an oven at 190°C for 6 hours, take it out and put it into 20ml of phosphoric acid and pyrophosphoric acid mixed solution (concentrations are 1.00M/L and 5.00M/L respectively) to soak for 30 minutes, take it out and dry it. Then it was calcined at 1200° C. for 90 minutes under a nitrogen atmosphere to obtain a honeycomb ceramic-porous carbon monolithic composite material, weighing about 10.50 g.
(2)蜂窝陶瓷-多孔炭-有机胺整体式复合材料的制备：(2) Preparation of honeycomb ceramic-porous carbon-organic amine monolithic composite material:
将蜂窝陶瓷-多孔炭整体式复合材料放入到含有0.10g四乙烯五胺、0.20g五乙烯六胺和0.20g聚乙烯亚胺(即四乙烯五胺、五乙烯六胺和聚乙烯亚胺按质量比1:2:2进行混合)的25mL甲醇混合溶液中，超声5分钟，然后放入真空干燥箱中除去溶剂，得到重约11.00g蜂窝陶瓷-多孔炭-有机胺整体式复合材料，即为二氧化碳吸附剂。Put the honeycomb ceramics-porous carbon monolithic composite into a mixture containing 0.10g tetraethylenepentamine, 0.20g pentaethylenehexamine and 0.20g polyethyleneimine (i.e. tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine Mix by mass ratio 1:2:2) in 25mL methanol mixed solution, ultrasonic 5 minutes, then put into the vacuum drying box and remove solvent, obtain the honeycomb ceramics-porous carbon-organic amine monolithic composite material weighing about 11.00g, It is carbon dioxide adsorbent.
(3)臭氧催化分解性能测试：(3) Ozone catalytic decomposition performance test:
催化剂性能测试与实施例1相同，臭氧催化分解性能见表1。The catalyst performance test is the same as in Example 1, and the catalytic decomposition performance of ozone is shown in Table 1.
(4)吸附剂性能测试：(4) Adsorbent performance test:
吸附剂性能测试与实施例1相同，二氧化碳吸附反应性能见表2。The performance test of the adsorbent is the same as in Example 1, and the carbon dioxide adsorption reaction performance is shown in Table 2.
对比例6Comparative example 6
(1)蜂窝陶瓷-多孔炭整体式复合材料的制备：(1) Preparation of honeycomb ceramic-porous carbon monolithic composite material:
称取一根直径20mm，高度为50mm的200目堇青石蜂窝陶瓷(约10.00g)放入20ml磷酸和焦磷酸混合溶液(浓度分别为1.00M/L和5.00M/L)中浸泡30分钟，取出后烘干。将负载磷酸的蜂窝陶瓷放入反应釜中。移取3.00g 2-甲基吡咯、3.00g 3-甲基吡咯(即2-甲基吡咯、3-甲基吡咯按质量比1:1进行混合)至玻璃瓶中，将玻璃瓶一并放入反应釜中。把反应釜放入190℃烘箱中反应6小时，取出后再次放入20ml磷酸和焦磷酸混合溶液(浓度分别为1.00M/L和5.00M/L)中浸泡30分钟，取出后烘干。然后在氮气氛围下800℃焙烧90分钟，得到蜂窝陶瓷-多孔炭整体式复合材料，重约10.60g。Weigh a 200-mesh cordierite honeycomb ceramic (about 10.00g) with a diameter of 20mm and a height of 50mm and put it into 20ml of phosphoric acid and pyrophosphoric acid mixed solution (concentrations are 1.00M/L and 5.00M/L respectively) and soak for 30 minutes. Take out and tumble dry. Put the honeycomb ceramics loaded with phosphoric acid into the reaction kettle. Pipette 3.00g 2-methylpyrrole and 3.00g 3-methylpyrrole (that is, 2-methylpyrrole and 3-methylpyrrole are mixed at a mass ratio of 1:1) into glass bottles, and put the glass bottles together into the reactor. Put the reaction kettle in an oven at 190°C for 6 hours, take it out and put it into 20ml of phosphoric acid and pyrophosphoric acid mixed solution (concentrations are 1.00M/L and 5.00M/L respectively) to soak for 30 minutes, take it out and dry it. Then it was calcined at 800° C. for 90 minutes under a nitrogen atmosphere to obtain a honeycomb ceramic-porous carbon monolithic composite material, weighing about 10.60 g.
(2)蜂窝陶瓷-多孔炭-有机胺整体式复合材料的制备：(2) Preparation of honeycomb ceramic-porous carbon-organic amine monolithic composite material:
将蜂窝陶瓷-多孔炭整体式复合材料放入到含有0.30g五乙烯六胺和0.3g聚乙烯亚胺(即五乙烯六胺和聚乙烯亚胺按质量比1:1进行混合)的25mL甲醇混合溶液中，超声5分钟，然后放入真空干燥箱中除去溶剂，得到重约11.20g蜂窝陶瓷-多孔炭-有机胺整体式复合材料，即为二氧化碳吸附剂。Put the honeycomb ceramic-porous carbon integral composite material into 25mL methanol containing 0.30g pentaethylene hexamine and 0.3g polyethyleneimine (that is, pentaethylene hexamine and polyethyleneimine are mixed at a mass ratio of 1:1). The mixed solution was ultrasonicated for 5 minutes, and then placed in a vacuum drying oven to remove the solvent to obtain a honeycomb ceramic-porous carbon-organic amine monolithic composite material weighing about 11.20 g, which is a carbon dioxide adsorbent.
(3)臭氧催化分解性能测试：(3) Ozone catalytic decomposition performance test:
催化剂性能测试与实施例1相同，臭氧催化分解性能见表1。The catalyst performance test is the same as in Example 1, and the catalytic decomposition performance of ozone is shown in Table 1.
(4)吸附剂性能测试：(4) Adsorbent performance test:
吸附剂性能测试与实施例1相同，二氧化碳吸附反应性能见表2。The performance test of the adsorbent is the same as in Example 1, and the carbon dioxide adsorption reaction performance is shown in Table 2.
表1：实施例1-10中蜂窝陶瓷-多孔炭对臭氧催化分解反应的反应性能(以催化连续反应10.5h时臭氧的转化率表示，即已被转化的臭氧浓度除以转化前的臭氧浓度)Table 1: Response performance of honeycomb ceramics-porous carbon to ozone catalytic decomposition reaction in Examples 1-10 (represented by the conversion rate of ozone when the catalytic continuous reaction is 10.5h, that is, the ozone concentration that has been converted is divided by the ozone concentration before conversion )
从表1可见，实施例1-8的蜂窝陶瓷-多孔炭整体式复合材料催化剂都表现出较好的臭氧催化分解性能，且由于蜂窝陶瓷的孔状结构，催化剂可以一次使用多块，解决了压力降问题。特别是实施实例5的催化效率最高，在室温下一块催化剂的臭氧分解转化率为60.13％，两块催化剂转化率为80.08％，三块催化转化率为91.46％。从表3对比实施例1-4可见，若蜂窝陶瓷-多孔炭整体式复合材料的制备过程中，不适用磷酸和焦磷酸的混合溶液或者只是用其中一种，所制备的蜂窝陶瓷-多孔炭整体式复合材料的催化剂催化性能均有下降；从对比实施例5可以看出，太高的碳化温度(即由原来的800℃碳化改为1200℃碳化)，所制备的催化剂催化性能也下降；从对比实施例6可以看出，若只选择吡咯、2-甲基吡咯和3-甲基吡咯中的一种，所制备的蜂窝陶瓷-多孔炭整体式复合材料的催化性能也有所下降。As can be seen from Table 1, the honeycomb ceramics-porous carbon monolithic composite catalysts of Examples 1-8 all show good ozone catalytic decomposition performance, and due to the porous structure of the honeycomb ceramics, the catalyst can be used in multiple pieces at a time, solving the problem of Pressure drop problem. Especially the catalytic efficiency of implementation example 5 is the highest. At room temperature, the ozonolysis conversion rate of one catalyst is 60.13%, the conversion rate of two catalysts is 80.08%, and the conversion rate of three catalysts is 91.46%. As can be seen from Table 3 Comparative Examples 1-4, if in the preparation process of the honeycomb ceramic-porous carbon monolithic composite material, the mixed solution of phosphoric acid and pyrophosphoric acid is not applicable or only one of them is used, the prepared honeycomb ceramic-porous carbon The catalytic performance of the catalyst of the monolithic composite material all declines; as can be seen from Comparative Example 5, too high carbonization temperature (that is, changed from the original 800 ° C carbonization to 1200 ° C carbonization), the prepared catalyst catalytic performance also declines; It can be seen from Comparative Example 6 that if only one of pyrrole, 2-methylpyrrole and 3-methylpyrrole is selected, the catalytic performance of the prepared honeycomb ceramic-porous carbon monolithic composite material also decreases.
表2：实施例1-10中吸附剂的二氧化碳吸附性能(以单位质量吸附剂的二氧化碳吸附量来表示，单位为mmol/g。具体算法为二氧化碳吸附量除以(多孔炭和有机胺的质量之和)，蜂窝陶瓷作为载体，其质量不计算在吸附剂总质量内。)Table 2: The carbon dioxide adsorption performance of adsorbent in embodiment 1-10 (represent with the carbon dioxide adsorption capacity of unit mass adsorbent, unit is mmol/g. Concrete algorithm is carbon dioxide adsorption divided by (the quality of porous carbon and organic amine sum), the honeycomb ceramics are used as the carrier, and its mass is not included in the total mass of the adsorbent.)
从表2可见，实施例1-8的蜂窝陶瓷-多孔炭整体式复合材料负载有机胺后都表现出较好的二氧化碳吸附性能，且由于蜂窝陶瓷的孔状结构，吸附剂可以一次使用多块，解决了压力降问题。特别是实施实例5的二氧化碳吸附性能最高，在室温下一块吸附剂的二氧化碳吸附性能为3.09mmol/g，两块吸附剂的二氧化碳吸附性能为2.61mmol/g，三块吸附剂的二氧化碳吸附能力为2.30mmol/g。从表4对比实施例1-4可见，若蜂窝陶瓷-多孔炭整体式复合材料的制备过程中，不适用磷酸和焦磷酸的混合溶液或者只是用其中一种，所制备的蜂窝陶瓷-多孔炭整体式复合材料的催化剂催化性能均有下降；从对比实施例5可以看出，太高的碳化温度(即由原来的800℃碳化改为1200℃碳化)，所制备的催化剂催化性能也下降；从对比实施例6可以看出，若只选择吡咯、2-甲基吡咯和3-甲基吡咯三种中的两种，所制备的蜂窝陶瓷-多孔炭整体式复合材料的催化性能也有所下降。It can be seen from Table 2 that the honeycomb ceramics-porous carbon monolithic composites of Examples 1-8 all show good carbon dioxide adsorption performance after loading organic amines, and due to the porous structure of the honeycomb ceramics, the adsorbent can be used in multiple pieces at a time. , to solve the pressure drop problem. Especially the carbon dioxide adsorption performance of implementation example 5 is the highest, and the carbon dioxide adsorption performance of one adsorbent at room temperature is 3.09mmol/g, and the carbon dioxide adsorption performance of two adsorbents is 2.61mmol/g, and the carbon dioxide adsorption capacity of three adsorbents is 2.30 mmol/g. As can be seen from Table 4 Comparative Examples 1-4, if in the preparation process of the honeycomb ceramic-porous carbon monolithic composite material, the mixed solution of phosphoric acid and pyrophosphoric acid is not applicable or only one of them is used, the prepared honeycomb ceramic-porous carbon The catalytic performance of the catalyst of the monolithic composite material all declines; as can be seen from Comparative Example 5, too high carbonization temperature (that is, changed from the original 800 ° C carbonization to 1200 ° C carbonization), the prepared catalyst catalytic performance also declines; As can be seen from Comparative Example 6, if only two of pyrrole, 2-methylpyrrole and 3-methylpyrrole are selected, the catalytic performance of the prepared honeycomb ceramic-porous carbon monolithic composite material also decreases .
表3：实施例5、对比实施例1-6中对臭氧催化分解反应的反应性能(以催化连续反应10.5h时臭氧的转化率表示，即已被转化的臭氧浓度除以转化前的臭氧浓度)Table 3: Response performance to ozone catalytic decomposition reaction in
表4：实施例5、对比实施例1-6中对比二氧化碳吸附性能(以单位质量吸附剂的二氧化碳吸附量来表示，单位为mmol/g。具体算法为二氧化碳吸附量除以(多孔炭和有机胺的质量之和)，蜂窝陶瓷作为载体，其质量不计算在吸附剂总质量内。)Table 4: Contrasting carbon dioxide adsorption performance in
下面对附图1-6作进一步分析说明：Accompanying drawing 1-6 is done further analysis explanation below:
图1中，图1a所示为本发明所用到的蜂窝陶瓷原材料，颜色为浅黄色；图1b所示为实施例5所制得的蜂窝陶瓷-多孔炭整体式复合材料，颜色为黑色；表明由实施例5可以非常方便的在蜂窝陶瓷上生成一层多孔炭薄膜，且两者接触紧密，不容易脱落。Among Fig. 1, Fig. 1 a shows that the honeycomb ceramic raw material that the present invention is used, and color is light yellow; Fig. 1 b shows that the honeycomb ceramic-porous carbon monolithic composite material that
图2中，图2a为实施例5所用到的蜂窝陶瓷原材料剖面的扫描电子显微镜照片，可以看出蜂窝陶瓷结构为孔洞状材料；图2b分别为实施例5所制备的蜂窝陶瓷-多孔炭整体式复合材料剖面的扫描电子显微镜照片，从复合材料的扫描剖面图可以看出，在蜂窝陶瓷(图2b中下侧处为蜂窝陶瓷的剖面)的表面非常成功地生成了一层多孔炭薄膜(图2b中上侧处为多孔炭的剖面)，且两者接触紧密，不容易脱落。Among Fig. 2, Fig. 2 a is the scanning electron microscope photo of the honeycomb ceramic raw material section used in
图3为实施例5所制备的蜂窝陶瓷-多孔炭整体式复合材料剖面的透射电子显微镜照片，可以看出通过实例5非常成功的在蜂窝陶瓷生成一层多孔炭薄膜，且两者接触非常紧密，不容易脱落。Fig. 3 is the transmission electron micrograph of the section of the honeycomb ceramics-porous carbon monolithic composite material prepared in Example 5. It can be seen that a layer of porous carbon film is very successfully generated in the honeycomb ceramics by Example 5, and the two are in very close contact , not easy to fall off.
图4中，图谱a为蜂窝陶瓷原材料的X射线光电子能谱图，图谱b为实施例5所制备的蜂窝陶瓷-多孔炭整体式复合材料的X射线光电子能谱图，两者变比蜂窝陶瓷表面增加了N、C、P等元素，因此可以推测出，在蜂窝陶瓷表面生成了N、P掺杂的多孔炭材料。Among Fig. 4, graph a is the X-ray photoelectron spectrum figure of honeycomb ceramic raw material, and graph b is the X-ray photoelectron spectrum figure of the honeycomb ceramics-porous carbon monolithic composite material prepared in
图5中，图谱a、b、c分别为使用1块、2块和3块由实施例5所制备的蜂窝陶瓷-多孔炭整体式复合材料催化剂对臭氧的去除稳定性对比图；可以看出由于催化剂呈现多孔结构，不容易堵塞，因此即时增加催化剂的量，也不会产生压力降问题，解决了粉末样品的压力降问题。其中，使用3块催化剂的初始催化活性为99.9％，在反应30小时后，臭氧催化转化率仍然保持在86.9％。因而，Among Fig. 5, collection of illustrations a, b, c are the removal stability comparison charts to ozone of using 1, 2 and 3 honeycomb ceramics-porous carbon monolithic composite catalysts prepared by
图6中，图谱a、b、c分别为使用1块、2块和3块由实施例5所制备的一块、两块和三块蜂窝陶瓷-多孔炭-有机胺整体式复合材料吸附剂对二氧化碳吸附性能的穿透曲线图；可以看出由于吸附剂呈现多孔结构，不容易堵塞，因此即时增加吸附剂的量，也不会产生压力降问题，解决了粉末样品的压力降问题。由图5的穿透曲线可以计算出，使用一块吸附剂，吸附剂的单位吸附量为3.09mmol/g，用两块吸附剂，吸附剂的单位吸附量为2.61mmol/g，用三块吸附剂，吸附剂的单位吸附量为2.30mmol/g。In Fig. 6, graphs a, b, c are one, two and three honeycomb ceramics-porous carbon-organic amine monolithic composite adsorbent pairs prepared by Example 5 using 1, 2 and 3 respectively. The breakthrough curve of carbon dioxide adsorption performance; it can be seen that because the adsorbent has a porous structure, it is not easy to block, so even if the amount of adsorbent is increased, the pressure drop problem will not occur, and the pressure drop problem of the powder sample is solved. It can be calculated from the breakthrough curve in Figure 5 that if one piece of adsorbent is used, the unit adsorption capacity of the adsorbent is 3.09mmol/g; if two adsorbents are used, the unit adsorption capacity of the adsorbent is 2.61mmol/g; agent, and the unit adsorption capacity of the adsorbent is 2.30mmol/g.
综上，所述蜂窝陶瓷-多孔炭整体式催化剂对臭氧的催化分解氧化活性较高并具有较好的稳定性，而且这种催化剂制作工艺简单、重现性好且能够解决催化剂大规模应用所带来的的压力降问题。而所述蜂窝陶瓷-多孔炭-有机胺整体式复合材料作为吸附剂表现出较高的二氧化碳吸附性能，而且这种吸附剂制作工艺简单、重现性好且能够解决实际工业中吸附剂大规模应用所带来的压力降问题。In summary, the honeycomb ceramic-porous carbon monolithic catalyst has high catalytic decomposition and oxidation activity for ozone and good stability, and the catalyst has a simple manufacturing process, good reproducibility, and can solve the problem of large-scale application of the catalyst. The resulting pressure drop problem. However, the honeycomb ceramic-porous carbon-organic amine monolithic composite material shows high carbon dioxide adsorption performance as an adsorbent, and this adsorbent has a simple manufacturing process, good reproducibility, and can solve the problem of large-scale adsorption of adsorbents in the actual industry. The pressure drop problem caused by the application.
上述具体实施例只是用来解释说明本发明，而并非是对本发明进行限制，在本发明构思和权利要求保护范围内对本发明做出的任何不付出创造性劳动的改变和替换，皆落入本发明专利的保护范围。The above-mentioned specific embodiments are only used to explain the present invention, rather than to limit the present invention. Any changes and replacements made to the present invention without creative labor within the scope of the present invention and the protection scope of the claims all fall into the scope of the present invention. The scope of patent protection.
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