技术领域Technical field
本发明属于有机废气吸附技术领域，特别涉及一种耐高温活性炭复合吸附剂及其制备方法和其在VOCs吸附中的应用。The invention belongs to the technical field of organic waste gas adsorption, and particularly relates to a high-temperature resistant activated carbon composite adsorbent, a preparation method thereof and its application in VOCs adsorption.
背景技术Background technique
在第二次工业革命以后，随着化石燃料等的开发和利用，挥发性有机化合物(VOCs)的产生不断增加，对自然环境和人类的身体健康产生了巨大的影响。现代VOCs的主要来源于特殊化学品生产、橡胶和轮胎的生产、石油炼制、石油化工氧化工艺、塑料生产等等。工业生产中排放的VOCs中芳烃类、醇类、酯类等作为工业溶剂广泛使用，因而排放量巨大。挥发性有机物对人体的影响主要表现在感官效应和超敏感效应，包括感官刺激，感觉干燥，刺激眼黏膜、鼻黏膜、呼吸道和皮肤等，挥发性有机化合物很容易通过血液到大脑，从而导致中枢神经系统受到抑制，使人产生头痛、乏力、昏昏欲睡和不舒服的感觉：醇、芳烃和醛能刺激黏膜和上呼吸道：很多挥发性有机化合物如苯、甲氯乙烯、三氯乙烷、三氯乙烯和甲醛等被证明是致癌物或可疑致癌物。VOCs的种类很多，其中多数有毒、有恶臭，部分有致癌性：在光照下可引发光化学烟雾：卤代烃类还会破坏臭氧层。After the second industrial revolution, with the development and utilization of fossil fuels, the production of volatile organic compounds (VOCs) continued to increase, which had a huge impact on the natural environment and human health. Modern VOCs mainly come from the production of special chemicals, rubber and tire production, petroleum refining, petrochemical oxidation processes, plastic production, etc. Among the VOCs emitted in industrial production, aromatic hydrocarbons, alcohols, esters, etc. are widely used as industrial solvents, so the emissions are huge. The impact of volatile organic compounds on the human body is mainly manifested in sensory effects and hypersensitivity effects, including sensory stimulation, dryness, irritation of eye mucosa, nasal mucosa, respiratory tract and skin, etc. Volatile organic compounds can easily pass through the blood to the brain, causing central nervous system damage. The nervous system is suppressed, causing headaches, fatigue, drowsiness and uncomfortable feelings: alcohols, aromatic hydrocarbons and aldehydes can irritate mucous membranes and upper respiratory tract: many volatile organic compounds such as benzene, methyl chloride and trichloroethane , trichlorethylene and formaldehyde have been proven to be carcinogens or suspected carcinogens. There are many types of VOCs, most of which are toxic and smelly, and some are carcinogenic: they can cause photochemical smog when exposed to light: halogenated hydrocarbons can also destroy the ozone layer.
对于VOCs的处理，吸附浓缩法是处理有机废气的有效处理方法。该处理方法对VOCs其中的一些有回收利用价值的有机气体。它利用多孔的固体介质能吸附气体中有害成分这一性质来达到净化目的。对于如何达到处理效果，吸附剂的选择起到了重要作用，吸附剂种类多种多样，活性炭是工业吸附剂中最常用的。对于各种吸附剂的发展从未停止过脚步。For the treatment of VOCs, adsorption concentration method is an effective treatment method for organic waste gas. This treatment method recovers some of the VOCs, some of which are valuable organic gases. It uses the property of porous solid media to adsorb harmful components in gases to achieve purification purposes. The choice of adsorbent plays an important role in how to achieve the treatment effect. There are many types of adsorbents, and activated carbon is the most commonly used industrial adsorbent. The development of various adsorbents has never stopped.
活性炭有成本低、操作简单、比表面积大、孔隙多吸附能力强、稳定性好、且能再生等优点。在废水处理、催化、除臭、废气及有害气体的治理、气体回收等领域都有着广泛的应用。活性炭具有像石墨晶粒却无规则地排列的微晶。在活化过程中微晶间产生了形状不同、大小不一的空隙。由于这些孔隙，特别是微孔提供了巨大的表面积。使得活性炭具有良好的吸附效果。但活性炭也具有一些缺点。它不适用高浓度的有机废气，活性炭热稳定性差，不适用与高温有机废气的回收。在高温时活性炭的结构以及吸附性能容易受破坏。SiO2的热稳定性好，且表面结合性能良好，但其吸附能力较弱。因此该复合吸附剂的就是基于活性炭以及SiO2各自优点结合而成的。Activated carbon has the advantages of low cost, simple operation, large specific surface area, multiple pores, strong adsorption capacity, good stability, and can be regenerated. It is widely used in wastewater treatment, catalysis, deodorization, waste gas and harmful gas treatment, gas recovery and other fields. Activated carbon has microcrystals that resemble graphite grains but are arranged irregularly. During the activation process, gaps of different shapes and sizes are generated between the crystallites. Because of these pores, especially micropores provide a huge surface area. The activated carbon has good adsorption effect. But activated carbon also has some disadvantages. It is not suitable for high-concentration organic waste gas. The thermal stability of activated carbon is poor, and it is not suitable for the recovery of high-temperature organic waste gas. The structure and adsorption performance of activated carbon are easily damaged at high temperatures. SiO2 has good thermal stability and good surface binding properties, but its adsorption capacity is weak. Therefore, this composite adsorbent is based on the combination of the advantages of activated carbon and SiO2 .
将活性炭与SiO2材料复合以达到耐高温复合型活性炭成为新型研究。研究发现，将活性炭与介孔SiO2材料复合具有更大的表面积，还具有更高的自燃温度和更好的吸附性能，这让炭-硅复合材料更适用与工程应用。Compounding activated carbon with SiO2 materials to achieve high temperature resistance composite activated carbon has become a new type of research. Research has found that combining activated carbon with mesoporous SiO2 materials has a larger surface area, higher auto-ignition temperature and better adsorption performance, which makes carbon-silicon composite materials more suitable for engineering applications.
CN201711214656.3提供一种高效耐高温型活性炭吸附剂，所述吸附剂的原料包括活性炭和脂肪酶液，所述活性炭与脂肪酶液的质量比为1：10-20；所述脂肪酶液为恶臭假单胞杆菌、荧光假单胞杆菌和反硝化细菌三者混合发酵培养时所分泌产生的脂肪酶液。本发明中采用的脂肪酶液为恶臭假单胞杆菌、荧光假单胞杆菌和反硝化细菌在添加了工业废水的培养基上混合发酵所分泌的脂肪酶液，这种脂肪酶液能够适应在培养基中工业废水的环境，适用于高温条件，且在高温条件下依然能够保持很高的活性，具有稳定性，这种脂肪酶液自身对于重金属离子和有机物都具有非常好的吸附效果；将具有这些特性的脂肪酶液与活性炭进行协同配合所制得的活性炭吸附剂具有优异的耐高温性。其缺点就是适用范围较窄，使用后的再生性能较差。CN201711214656.3 provides a high-efficiency and high-temperature-resistant activated carbon adsorbent. The raw materials of the adsorbent include activated carbon and lipase liquid. The mass ratio of the activated carbon to lipase liquid is 1:10-20; the lipase liquid is Lipase liquid secreted by mixed fermentation culture of Pseudomonas putida, Pseudomonas fluorescens and denitrifying bacteria. The lipase liquid used in the present invention is a lipase liquid secreted by mixed fermentation of Pseudomonas putida, Pseudomonas fluorescens and denitrifying bacteria on a culture medium added with industrial wastewater. This lipase liquid can be adapted to The environment of industrial wastewater in the culture medium is suitable for high temperature conditions, and it can still maintain high activity and stability under high temperature conditions. This lipase liquid itself has a very good adsorption effect on heavy metal ions and organic matter; The activated carbon adsorbent prepared by synergistically combining lipase liquid with these characteristics and activated carbon has excellent high temperature resistance. Its disadvantage is that its application range is narrow and its regeneration performance after use is poor.
CN201810022498.XCN201810022498.X本发明涉及一种不易着火的活性炭复合材料及其制备方法和用途。所述活性炭复合材料包括活性炭和无机导热颗粒；所述无机导热颗粒包括SiC颗粒和/或BN颗粒。本发明通过在活性炭中添加SiC颗粒和/或BN颗粒，将整个材料的体相温度显著均匀化，提高材料内部热传导和热扩散效率，从而大大提高活性炭的复合材料的耐燃稳定性；相较于现有技术，本发明活性炭复合材料的优势还在于不会造成活性炭的孔道被阻塞，大幅提高活性炭吸附性能稳定性。缺点就是C/SiC复合材料难以被稳定地去除加工，制备费用较高。CN201810022498. The activated carbon composite material includes activated carbon and inorganic thermally conductive particles; the inorganic thermally conductive particles include SiC particles and/or BN particles. By adding SiC particles and/or BN particles to the activated carbon, the present invention significantly homogenizes the bulk temperature of the entire material, improves the internal heat conduction and thermal diffusion efficiency of the material, thereby greatly improving the flame resistance stability of the activated carbon composite material; compared with According to the existing technology, the advantage of the activated carbon composite material of the present invention is that it will not cause the pores of the activated carbon to be blocked and greatly improve the stability of the adsorption performance of the activated carbon. The disadvantage is that C/SiC composite materials are difficult to remove and process stably, and the preparation cost is high.
发明内容Contents of the invention
针对现有的技术问题，本发明的目的在于提供一种活性炭@SiO2复合吸附剂的制备方法及其在VOCs吸附中的应用，解决在活性炭吸附VOCs时的耐热性较差引发自燃和抗水性能较差等问题。In view of the existing technical problems, the purpose of the present invention is to provide a preparation method of activated carbon @SiO2 composite adsorbent and its application in VOCs adsorption, so as to solve the problem of spontaneous combustion and resistance caused by poor heat resistance of activated carbon when adsorbing VOCs. Problems such as poor water performance.
为解决现有技术问题，本发明采用的技术方案为：In order to solve the existing technical problems, the technical solutions adopted by the present invention are:
一种耐高温活性炭复合吸附剂，由疏水改性的介孔SiO2和活性炭按0.1-0.3:1的质量比构成，具有多级孔结构，包括孔径范围为5-8nm的介孔SiO2和0.8-2nm的微孔活性炭。A high-temperature resistant activated carbon composite adsorbent, consisting of hydrophobically modified mesoporous SiO2 and activated carbon in a mass ratio of 0.1-0.3:1, with a multi-level pore structure, including mesoporous SiO2 and pore diameters ranging from 5 to 8 nm. 0.8-2nm microporous activated carbon.
一种耐高温活性炭复合吸附剂的制备方法，包括以下步骤：A method for preparing a high-temperature resistant activated carbon composite adsorbent, including the following steps:
步骤1，以100:50:1的比例配制乙醇、蒸馏水、氨水的混合溶液，调节pH至9-11，将5wt%正硅酸乙酯和2wt%模板剂滴加至混合液中，磁力搅拌作用下进行反应；Step 1: Prepare a mixed solution of ethanol, distilled water, and ammonia in a ratio of 100:50:1, adjust the pH to 9-11, add 5wt% ethyl orthosilicate and 2wt% template agent dropwise into the mixed solution, and stir magnetically. react under action;
步骤2，将步骤1得到的产物用乙醇和蒸馏水洗涤干净，然后进行干燥和煅烧，得到SiO2小球;Step 2: Wash the product obtained in Step 1 with ethanol and distilled water, then dry and calcine to obtain SiO2 pellets;
步骤3，将步骤2中得到的SiO2小球和去离子水按体积比1:4加入三口烧瓶中，搅拌均匀后在搅拌的条件下滴加等体积的硅烷偶联剂三甲基氯硅烷（TMCS）水解液，升温进行回流反应，将样品洗涤干燥，得到疏水改性的SiO2小球；Step 3: Add the SiO2 pellets and deionized water obtained in Step 2 into the three-necked flask at a volume ratio of 1:4, stir evenly, and then add an equal volume of silane coupling agent trimethylsilyl chloride dropwise while stirring. (TMCS) hydrolyzate, raise the temperature to perform reflux reaction, wash and dry the sample to obtain hydrophobically modified SiO2 beads;
步骤4，将胶黏剂、疏水改性的SiO2小球和活性炭粉末混合形成分散系，三者的质量比为0.12:0.1-0.3:1，干燥后得到目标产品。Step 4: Mix the adhesive, hydrophobically modified SiO2 beads and activated carbon powder to form a dispersion. The mass ratio of the three is 0.12:0.1-0.3:1. After drying, the target product is obtained.
所述步骤1中的模板剂为十六烷基三甲基溴化铵(CTAB)。The template agent in step 1 is cetyltrimethylammonium bromide (CTAB).
所述步骤2中煅烧条件为550℃下恒温3h。The calcination conditions in step 2 are constant temperature at 550°C for 3 hours.
所述步骤3中硅烷偶联剂三甲基氯硅烷（TMCS）是在异丙醇和醋酸调节pH值为4-5的条件下，搅拌至溶液清澈而完成水解。In step 3, the silane coupling agent trimethylchlorosilane (TMCS) is hydrolyzed by stirring until the solution is clear and the pH value is adjusted to 4-5 with isopropyl alcohol and acetic acid.
所述步骤4中的胶黏剂为羧甲基纤维素(CMC)。The adhesive in step 4 is carboxymethylcellulose (CMC).
一种耐高温活性炭复合吸附剂的应用，用于VOCs的吸附。The application of a high-temperature resistant activated carbon composite adsorbent for the adsorption of VOCs.
有益效果：Beneficial effects:
与现有技术相比，本发明具有如下优势：采用不燃和热稳定性高的介孔SiO2小球对活性炭进行进行掺杂复合，改善活性炭的耐热性能。一是通过介孔SiO2小球掺杂，避免活性炭吸附VOCs时发生自燃现象；二是介孔SiO2小球与微孔活性炭形成具有多级孔结构的复合材料，改善活性炭的吸附性能；三是由于SiO2小球经过疏水改性，因此复合材料在吸附VOCs时具有良好的抗水性能。Compared with the existing technology, the present invention has the following advantages: mesoporous SiO2 pellets with non-combustibility and high thermal stability are used to dope and compound the activated carbon to improve the heat resistance of the activated carbon. The first is to avoid spontaneous combustion when activated carbon adsorbs VOCs by doping mesoporous SiO2 beads; the second is to form a composite material with a hierarchical pore structure between mesoporous SiO2 beads and microporous activated carbon to improve the adsorption performance of activated carbon; third It is because the SiO2 beads have been hydrophobically modified, so the composite material has good water resistance when adsorbing VOCs.
附图说明Description of drawings
图1为本发明的制备工艺流程图。Figure 1 is a flow chart of the preparation process of the present invention.
具体实施方式Detailed ways
下面结合附图和具体实施例对本发明作进一步描述。The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.
实施例1Example 1
如图1所示，一种耐高温活性炭复合吸附剂的制备方法，包括以下步骤：As shown in Figure 1, a method for preparing a high-temperature resistant activated carbon composite adsorbent includes the following steps:
（1）以100:50:1的比例配制乙醇、蒸馏水、氨水的混合溶液，调节pH，将5wt%正硅酸乙酯和2wt%模板剂十六烷基三甲基溴化铵(CTAB)滴加至混合液中，磁力搅拌作用下进行反应；(1) Prepare a mixed solution of ethanol, distilled water, and ammonia in a ratio of 100:50:1, adjust the pH, and mix 5wt% ethyl orthosilicate and 2wt% template agent cetyltrimethylammonium bromide (CTAB) Add dropwise to the mixed solution and react under magnetic stirring;
（2）将反应得到的固体沉淀用乙醇和蒸馏水洗涤干净，然后进行干燥，在550℃下恒温煅烧3h，得到SiO2小球；(2) Wash the solid precipitate obtained by the reaction with ethanol and distilled water, then dry it, and calcine at a constant temperature of 550°C for 3 hours to obtain SiO2 pellets;
（3）将步骤2中得到的SiO2小球和去离子水加入三口烧瓶中，搅拌至均匀；将硅烷偶联剂三甲基氯硅烷（TMCS）在异丙醇和醋酸调节pH值（4-5）的条件下搅拌至溶液清澈而完成水解，然后在搅拌的条件下滴加TMCS的水解液，升温进行回流反应，而后将样品洗涤干燥，得到疏水改性的SiO2小球；(3) Add the SiO2 pellets and deionized water obtained in step 2 into the three-necked flask and stir until uniform; add the silane coupling agent trimethylchlorosilane (TMCS) in isopropyl alcohol and acetic acid to adjust the pH value (4- 5) Stir until the solution is clear to complete the hydrolysis, then add the TMCS hydrolyzate dropwise under stirring conditions, raise the temperature to perform a reflux reaction, and then wash and dry the sample to obtain hydrophobically modified SiO2 pellets;
（4）将胶黏剂羧甲基纤维素(CMC)、疏水性SiO2小球以及活性炭粉末混合形成分散系，疏水改性的介孔SiO2小球与活性炭粉末的比例为0.1，干燥后得到活性炭复合吸附剂，标记为M-SiO2@AC-0.1。(4) Mix the adhesive carboxymethyl cellulose (CMC), hydrophobic SiO2 beads and activated carbon powder to form a dispersion. The ratio of hydrophobically modified mesoporous SiO2 beads to activated carbon powder is 0.1. After drying An activated carbon composite adsorbent was obtained, labeled M-SiO2 @AC-0.1.
实施例2Example 2
一种耐高温活性炭复合吸附剂的制备方法，包括以下步骤：A method for preparing a high-temperature resistant activated carbon composite adsorbent, including the following steps:
（1）以100:50:1的比例配制乙醇、蒸馏水、氨水的混合溶液，调节pH，将5wt%正硅酸乙酯和2wt%模板剂十六烷基三甲基溴化铵(CTAB)滴加至混合液中，磁力搅拌作用下进行反应；(1) Prepare a mixed solution of ethanol, distilled water, and ammonia in a ratio of 100:50:1, adjust the pH, and mix 5wt% ethyl orthosilicate and 2wt% template agent cetyltrimethylammonium bromide (CTAB) Add dropwise to the mixed solution and react under magnetic stirring;
（2）将反应得到的固体沉淀用乙醇和蒸馏水洗涤干净，然后进行干燥，在550℃下恒温煅烧3h，得到SiO2小球；(2) Wash the solid precipitate obtained by the reaction with ethanol and distilled water, then dry it, and calcine at a constant temperature of 550°C for 3 hours to obtain SiO2 pellets;
（3）将步骤2中得到的SiO2小球和去离子水加入三口烧瓶中，搅拌至均匀；将硅烷偶联剂三甲基氯硅烷（TMCS）在异丙醇和醋酸调节pH值（4-5）的条件下搅拌至溶液清澈而完成水解，然后在搅拌的条件下滴加TMCS的水解液，升温进行回流反应，而后将样品洗涤干燥，得到疏水改性的SiO2小球；(3) Add the SiO2 pellets and deionized water obtained in step 2 into the three-necked flask and stir until uniform; add the silane coupling agent trimethylchlorosilane (TMCS) in isopropyl alcohol and acetic acid to adjust the pH value (4- 5) Stir until the solution is clear to complete the hydrolysis, then add the TMCS hydrolyzate dropwise under stirring conditions, raise the temperature to perform a reflux reaction, and then wash and dry the sample to obtain hydrophobically modified SiO2 pellets;
（4）将胶黏剂羧甲基纤维素(CMC)、疏水性SiO2小球以及活性炭粉末混合形成分散系，疏水改性的介孔SiO2小球与活性炭粉末的比例为0.2，干燥后得到活性炭复合吸附剂，标记为M-SiO2@AC-0.2。(4) Mix the adhesive carboxymethyl cellulose (CMC), hydrophobic SiO2 beads and activated carbon powder to form a dispersion. The ratio of hydrophobically modified mesoporous SiO2 beads to activated carbon powder is 0.2. After drying An activated carbon composite adsorbent was obtained, labeled M-SiO2 @AC-0.2.
实施例3Example 3
一种耐高温活性炭复合吸附剂的制备方法，包括以下步骤：A method for preparing a high-temperature resistant activated carbon composite adsorbent, including the following steps:
（1）以100:50:1的比例配制乙醇、蒸馏水、氨水的混合溶液，调节pH，将5wt%正硅酸乙酯和2wt%模板剂十六烷基三甲基溴化铵(CTAB)滴加至混合液中，磁力搅拌作用下进行反应；(1) Prepare a mixed solution of ethanol, distilled water, and ammonia in a ratio of 100:50:1, adjust the pH, and mix 5wt% ethyl orthosilicate and 2wt% template agent cetyltrimethylammonium bromide (CTAB) Add dropwise to the mixed solution and react under magnetic stirring;
（2）将反应得到的固体沉淀用乙醇和蒸馏水洗涤干净，然后进行干燥，在550℃下恒温煅烧3h，得到SiO2小球；(2) Wash the solid precipitate obtained by the reaction with ethanol and distilled water, then dry it, and calcine at a constant temperature of 550°C for 3 hours to obtain SiO2 pellets;
（3）将步骤2中得到的SiO2小球和去离子水加入三口烧瓶中，搅拌至均匀；将硅烷偶联剂三甲基氯硅烷（TMCS）在异丙醇和醋酸调节pH值（4-5）的条件下搅拌至溶液清澈而完成水解，然后在搅拌的条件下滴加TMCS的水解液，升温进行回流反应，而后将样品洗涤干燥，得到疏水改性的SiO2小球；(3) Add the SiO2 pellets and deionized water obtained in step 2 into the three-necked flask and stir until uniform; add the silane coupling agent trimethylchlorosilane (TMCS) in isopropyl alcohol and acetic acid to adjust the pH value (4- 5) Stir until the solution is clear to complete the hydrolysis, then add the TMCS hydrolyzate dropwise under stirring conditions, raise the temperature to perform a reflux reaction, and then wash and dry the sample to obtain hydrophobically modified SiO2 pellets;
（4）将胶黏剂羧甲基纤维素(CMC)、疏水性SiO2小球以及活性炭粉末混合形成分散系，疏水改性的介孔SiO2小球与活性炭粉末的比例为0.3，干燥后得到活性炭复合吸附剂，标记为M-SiO2@AC-0.3。(4) Mix the adhesive carboxymethyl cellulose (CMC), hydrophobic SiO2 beads and activated carbon powder to form a dispersion. The ratio of hydrophobically modified mesoporous SiO2 beads to activated carbon powder is 0.3. After drying An activated carbon composite adsorbent was obtained, labeled M-SiO2 @AC-0.3.
对比例1Comparative example 1
（1）以100:50:1的比例配制乙醇、蒸馏水、氨水的混合溶液，调节pH，将正硅酸乙酯滴加至混合液中，磁力搅拌作用下进行反应；(1) Prepare a mixed solution of ethanol, distilled water, and ammonia in a ratio of 100:50:1, adjust the pH, add ethyl orthosilicate dropwise into the mixed solution, and carry out the reaction under magnetic stirring;
（2）将反应得到的固体沉淀用乙醇和蒸馏水洗涤干净，然后进行干燥，在550℃下恒温煅烧3h，得到SiO2小球；(2) Wash the solid precipitate obtained by the reaction with ethanol and distilled water, then dry it, and calcine at a constant temperature of 550°C for 3 hours to obtain SiO2 pellets;
（3）将步骤2中得到的SiO2小球和去离子水加入三口烧瓶中，搅拌至均匀；将硅烷偶联剂三甲基氯硅烷（TMCS）在异丙醇和醋酸调节pH值（4-5）的条件下搅拌至溶液清澈而完成水解，然后在搅拌的条件下滴加TMCS的水解液，升温进行回流反应，而后将样品洗涤干燥，得到疏水改性的SiO2小球；(3) Add the SiO2 pellets and deionized water obtained in step 2 into the three-necked flask and stir until uniform; add the silane coupling agent trimethylchlorosilane (TMCS) in isopropyl alcohol and acetic acid to adjust the pH value (4- 5) Stir until the solution is clear to complete the hydrolysis, then add the TMCS hydrolyzate dropwise under stirring conditions, raise the temperature to perform a reflux reaction, and then wash and dry the sample to obtain hydrophobically modified SiO2 pellets;
（4）将胶黏剂羧甲基纤维素(CMC)、疏水性SiO2小球以及活性炭粉末混合形成分散系，疏水改性的SiO2小球与活性炭粉末的比例为0.1，干燥后得到活性炭复合吸附剂，标记为SiO2@AC-0.1。(4) Mix the adhesive carboxymethyl cellulose (CMC), hydrophobic SiO2 beads and activated carbon powder to form a dispersion. The ratio of hydrophobically modified SiO2 beads to activated carbon powder is 0.1. After drying, the activated carbon is obtained Composite adsorbent, labeled SiO2 @AC-0.1.
对比例2Comparative example 2
（1）以100:50:1的比例配制乙醇、蒸馏水、氨水的混合溶液，调节pH，将正硅酸乙酯滴加至混合液中，磁力搅拌作用下进行反应；(1) Prepare a mixed solution of ethanol, distilled water, and ammonia in a ratio of 100:50:1, adjust the pH, add ethyl orthosilicate dropwise into the mixed solution, and carry out the reaction under magnetic stirring;
（2）将反应得到的固体沉淀用乙醇和蒸馏水洗涤干净，然后进行干燥，在550℃下恒温煅烧3h，得到SiO2小球；(2) Wash the solid precipitate obtained by the reaction with ethanol and distilled water, then dry it, and calcine at a constant temperature of 550°C for 3 hours to obtain SiO2 pellets;
（3）将步骤2中得到的SiO2小球和去离子水加入三口烧瓶中，搅拌至均匀；将硅烷偶联剂三甲基氯硅烷（TMCS）在异丙醇和醋酸调节pH值（4-5）的条件下搅拌至溶液清澈而完成水解，然后在搅拌的条件下滴加TMCS的水解液，升温进行回流反应，而后将样品洗涤干燥，得到疏水改性的SiO2小球；(3) Add the SiO2 pellets and deionized water obtained in step 2 into the three-necked flask and stir until uniform; add the silane coupling agent trimethylchlorosilane (TMCS) in isopropyl alcohol and acetic acid to adjust the pH value (4- 5) Stir until the solution is clear to complete the hydrolysis, then add the TMCS hydrolyzate dropwise under stirring conditions, raise the temperature to perform a reflux reaction, and then wash and dry the sample to obtain hydrophobically modified SiO2 pellets;
（4）将胶黏剂羧甲基纤维素(CMC)、疏水性SiO2小球以及活性炭粉末混合形成分散系，疏水改性的SiO2小球与活性炭粉末的比例为0.2，干燥后得到活性炭复合吸附剂，标记为SiO2@AC-0.2。(4) Mix the adhesive carboxymethylcellulose (CMC), hydrophobic SiO2 beads and activated carbon powder to form a dispersion. The ratio of hydrophobically modified SiO2 beads to activated carbon powder is 0.2. After drying, activated carbon is obtained Composite adsorbent, labeled SiO2 @AC-0.2.
对比例3Comparative example 3
（1）以100:50:1的比例配制乙醇、蒸馏水、氨水的混合溶液，调节pH，将正硅酸乙酯滴加至混合液中，磁力搅拌作用下进行反应；(1) Prepare a mixed solution of ethanol, distilled water, and ammonia in a ratio of 100:50:1, adjust the pH, add ethyl orthosilicate dropwise into the mixed solution, and carry out the reaction under magnetic stirring;
（2）将反应得到的固体沉淀用乙醇和蒸馏水洗涤干净，然后进行干燥，在550℃下恒温煅烧3h，得到SiO2小球；(2) Wash the solid precipitate obtained by the reaction with ethanol and distilled water, then dry it, and calcine at a constant temperature of 550°C for 3 hours to obtain SiO2 pellets;
（3）将步骤2中得到的SiO2小球和去离子水加入三口烧瓶中，搅拌至均匀；将硅烷偶联剂三甲基氯硅烷（TMCS）在异丙醇和醋酸调节pH值（4-5）的条件下搅拌至溶液清澈而完成水解，然后在搅拌的条件下滴加TMCS的水解液，升温进行回流反应，而后将样品洗涤干燥，得到疏水改性的SiO2小球；(3) Add the SiO2 pellets and deionized water obtained in step 2 into the three-necked flask and stir until uniform; add the silane coupling agent trimethylchlorosilane (TMCS) in isopropyl alcohol and acetic acid to adjust the pH value (4- 5) Stir until the solution is clear to complete the hydrolysis, then add the TMCS hydrolyzate dropwise under stirring conditions, raise the temperature to perform a reflux reaction, and then wash and dry the sample to obtain hydrophobically modified SiO2 pellets;
（4）将胶黏剂羧甲基纤维素(CMC)、疏水性SiO2小球以及活性炭粉末混合形成分散系，疏水改性的SiO2小球与活性炭粉末的比例为0.3，干燥后得到活性炭复合吸附剂，标记为SiO2@AC-0.3。(4) Mix the adhesive carboxymethyl cellulose (CMC), hydrophobic SiO2 beads and activated carbon powder to form a dispersion. The ratio of hydrophobically modified SiO2 beads to activated carbon powder is 0.3. After drying, the activated carbon is obtained Composite adsorbent, labeled SiO2 @AC-0.3.
采用氮物理吸附在液氮条件下测试上述活性碳粉末和不同方法制备的活性炭复合吸附剂的N2吸脱附等温线，比表面积和孔体积，采用重量法测试20℃下丙酮吸附量，采用热重分析仪测试吸附剂的起始热失重温度，测试结果如表1所示：Nitrogen physical adsorption was used to test the N2 adsorption and desorption isotherms, specific surface area and pore volume of the above-mentioned activated carbon powder and activated carbon composite adsorbents prepared by different methods under liquid nitrogen conditions. The gravimetric method was used to test the acetone adsorption capacity at 20°C. A thermogravimetric analyzer was used to test the initial thermal weight loss temperature of the adsorbent. The test results are shown in Table 1:
表1 活性碳粉末和不同方法制备的活性炭复合吸附剂的比表面积、总孔体积、丙酮吸附量及起始热失重温度Table 1 Specific surface area, total pore volume, acetone adsorption capacity and initial thermal weight loss temperature of activated carbon powder and activated carbon composite adsorbents prepared by different methods
由表1可见，原始活性炭粉末AC-raw的比表面积和总孔体积分别为837 m2/g，为0.72 m3/g，丙酮吸附量为3.27 mmol/g。采用介孔SiO2小球对其进行改性后得到的M-SiO2@AC-X系列样品的比表面积、总孔体积和起始热失重温度均随着介孔SiO2小球掺杂量的增加而升高，这是由于介孔SiO2小球的比表面积、总孔体积和起始热失重温度高于活性炭；然而，M-SiO2@AC-X系列样品的丙酮吸附量随着介孔SiO2小球掺杂量的增加先升高后降低，可能是由于适量的介孔SiO2小球掺杂到微孔活性炭中可以促进丙酮吸附，而过量的介孔结构则会影响丙酮的吸附。As can be seen from Table 1, the specific surface area and total pore volume of the original activated carbon powder AC-raw are 837 m2 /g and 0.72 m3 /g respectively, and the acetone adsorption capacity is 3.27 mmol/g. The specific surface area, total pore volume and initial thermal weight losstemperature of the M-SiO 2@ AC-X series samples modified with mesoporous SiO 2 beads all increase with the doping amount of mesoporous SiO2 beads. This is due to the fact that the specific surface area, total pore volume and initial thermal weight loss temperature of mesoporous SiO2 beads are higher than those of activated carbon; however, the acetone adsorption capacity of M-SiO2 @AC-X series samples increases with The increase in the doping amount of mesoporous SiO2 beads first increases and then decreases. This may be because an appropriate amount of mesoporous SiO2 beads doped into microporous activated carbon can promote the adsorption of acetone, while the excessive mesoporous structure will affect the adsorption of acetone. adsorption.
采用不具有介孔结构的SiO2小球对活性炭粉末进行改性后得到的SiO2@AC-X系列样品的起始热失重温度随着SiO2小球掺杂量的增加而升高。然而，比表面积、总孔体积和丙酮吸附量均随着SiO2小球掺杂量的增加而下降，这是由于SiO2小球的比表面积、总孔体积和丙酮吸附量均低于活性炭。The initial thermal weight loss temperature of the SiO2 @AC-X series samples obtained by modifying activated carbon powder with SiO2 beads without mesoporous structure increases with the increase in the doping amount of SiO2 beads. However, the specific surface area, total pore volume, and acetone adsorption capacity all decrease with the increase in the doping amount of SiO2 beads. This is because the specific surface area, total pore volume, and acetone adsorption capacity of SiO2 beads are lower than those of activated carbon.
综上所述，SiO2小球具有较高的热稳定性和不燃性能，因此SiO2小球掺杂可以提高活性炭吸附剂的热稳定性，改善了活性炭吸附丙酮时易发生自燃和爆炸的问题。采用适量的介孔SiO2小球掺杂，可以提高活性炭的丙酮吸附量，最佳掺杂量为20%。In summary, SiO2 beads have high thermal stability and non-flammable properties. Therefore, the doping of SiO2 beads can improve the thermal stability of activated carbon adsorbents and improve the problem of spontaneous combustion and explosion when activated carbon adsorbs acetone. . Doping with an appropriate amount of mesoporous SiO2 beads can increase the acetone adsorption capacity of activated carbon, and the optimal doping amount is 20%.
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