技术领域Technical field
本发明属于工业固体废弃物的资源化处置技术领域，尤其涉及一种氮掺杂化工污泥基活性炭及其制备方法与应用。The invention belongs to the technical field of resource disposal of industrial solid waste, and in particular relates to a nitrogen-doped chemical sludge-based activated carbon and its preparation method and application.
背景技术Background technique
化工污泥是污水处理厂用无机混凝剂(絮凝剂)进行化学废水处理后沉淀出来的物质。统计显示，每年有4000万吨化工污泥在化工厂和化学废水处理厂排放，且排放增长率超过10％。虽然污泥占化工废水量的比例不到1％，但统计显示，每年用于污水污泥解毒和处理的费用至少有几十亿。由于化工企业排放的污水中含有的成分复杂，净化难度大，污水中约70％以上的重金属元素仍然被排放转移到化工污泥中，化工污泥的资源化和无害化处理日益得到重视。目前，化工污泥处置利用方式主要有以下几种：Chemical sludge is a substance that precipitates after chemical wastewater treatment using inorganic coagulants (flocculants) in sewage treatment plants. Statistics show that 40 million tons of chemical sludge are discharged from chemical plants and chemical wastewater treatment plants every year, and the discharge growth rate exceeds 10%. Although sludge accounts for less than 1% of chemical wastewater, statistics show that the cost of detoxifying and treating sewage sludge is at least several billion every year. Since the sewage discharged by chemical enterprises contains complex components and is difficult to purify, more than 70% of the heavy metal elements in the sewage are still discharged and transferred into chemical sludge. The resource utilization and harmless treatment of chemical sludge have received increasing attention. At present, the main methods of chemical sludge disposal and utilization are as follows:
(1)卫生填埋，污泥的卫生填埋法是最常见的，因为它简单且处理成本低。然而，如果垃圾填埋场建造或操作不当，会带来交叉污染的风险，含有污染物的液体和气体会在填埋过程中从污泥中逸出，液体会渗入地下水层，污染地下水；气体如甲烷会进入到空气中，如遇明火会造成爆炸和火灾等危险灾害，对人类造成巨大的伤害。(1) Sanitary landfill. The sanitary landfill method of sludge is the most common because it is simple and has low disposal cost. However, if the landfill is improperly constructed or operated, it will bring the risk of cross-contamination. Liquids and gases containing pollutants will escape from the sludge during the landfill process, and the liquids will seep into the groundwater layer and contaminate the groundwater; gases For example, methane will enter the air, and if it encounters an open flame, it will cause dangerous disasters such as explosions and fires, causing huge harm to humans.
(2)高温焚烧，此技术是处理化工污泥的最完整和有效的方法之一，含水率较低的化工污泥可直接进行焚烧；含水率较高的化工污泥需经过干燥后再送进焚烧炉焚烧。使用高温焚烧法处理污泥，能够消灭原始化工污泥中的有害细菌并大大减少化工污泥的处理量，同时，燃烧污泥产生的热量可用于供暖或发电，从而回收热能。但是，在采用焚烧法处理污泥时，需要使用相关器械将化工污泥中的水分甩干，同时需要占用很大的场地来晾干污泥中残留的水分，因此其运行成本较高，操作费用高。另外，污泥的燃烧会产生如二氧化硫等大量的有害气体，这些有害气体释放到空气中会对环境造成二次污染。(2) High-temperature incineration. This technology is one of the most complete and effective methods for treating chemical sludge. Chemical sludge with a lower moisture content can be directly incinerated; chemical sludge with a higher moisture content needs to be dried before being sent Burn in the incinerator. The use of high-temperature incineration to treat sludge can eliminate harmful bacteria in the original chemical sludge and greatly reduce the amount of chemical sludge to be processed. At the same time, the heat generated by burning the sludge can be used for heating or power generation, thereby recovering heat energy. However, when using the incineration method to treat sludge, it is necessary to use relevant equipment to dry the water in the chemical sludge. At the same time, a large space is needed to dry the remaining water in the sludge. Therefore, its operating cost is high and the operation costly. In addition, the combustion of sludge will produce a large amount of harmful gases such as sulfur dioxide. The release of these harmful gases into the air will cause secondary pollution to the environment.
(3)土地利用，由于化工污泥富含氮、磷、钾等营养元素和微量元素，同时还包括重金属和病原微生物，这些营养物质不仅为植物生长提供了必要的养分，还可以改善土壤结构，提高土壤肥力。此外，污泥本身粘性和吸收性较强，还可以增加土壤的持水能力，防止土壤侵蚀。然而污泥中含有大量害虫卵和有害微生物，以及高浓度的重金属，如果不进行无害化处置而直接进行土地利用，将会导致对水体和土壤的污染。(3) Land use, because chemical sludge is rich in nutrients and trace elements such as nitrogen, phosphorus, and potassium, as well as heavy metals and pathogenic microorganisms. These nutrients not only provide necessary nutrients for plant growth, but can also improve soil structure. , improve soil fertility. In addition, sludge itself is highly sticky and absorbent, which can also increase the water-holding capacity of the soil and prevent soil erosion. However, the sludge contains a large number of pest eggs and harmful microorganisms, as well as high concentrations of heavy metals. If it is directly used for land use without harmless disposal, it will lead to pollution of water bodies and soil.
(4)其他资源化利用主要包括化工污泥堆肥、化工污泥烧制建材、化工污泥制吸附剂、化工污泥热解制油、化工污泥厌氧消化制沼气、化工污泥合成燃料等，但往往均存在利用过程复杂的缺点，难以大规模推广。(4) Other resource utilization mainly includes chemical sludge composting, chemical sludge burning for building materials, chemical sludge to produce adsorbents, chemical sludge pyrolysis to produce oil, chemical sludge anaerobic digestion to produce biogas, and chemical sludge to synthesize fuel. etc., but they often have the disadvantage of complicated utilization process and are difficult to promote on a large scale.
随着人类工农业活动的发展和化石燃料的大量使用，每年二氧化碳的排放量已经超标，并且仍在逐年增加，对于二氧化碳的吸附处理主要有膜分离法、吸附法，吸附法因其具有无腐蚀、低能耗、操作简单、自动化程度高等特点，为实现对混合气中二氧化碳的高效吸附分离提供了一条新途径。用于吸附法的活性炭通常采用物理活化或化学活化法进行制备，生产活性炭的物理活化过程是一个简单、环保和燃料消耗少的生产过程，但由于它依赖于碳原子的消耗来形成孔隙结构，活化需要更长的时间，并且单位时间所制得的活性炭产量少，耗费成本高；化学活化由于会用到强酸、强碱等化学试剂，在反应过程中可能会对相关设备造成破坏，同时反应过程中排放的废水需要经过繁琐的处理工艺以达到污水排放标准，否则将会对环境造成很大的污染。With the development of human industrial and agricultural activities and the extensive use of fossil fuels, annual carbon dioxide emissions have exceeded standards and are still increasing year by year. The main methods for adsorbing carbon dioxide include membrane separation and adsorption. The adsorption method is non-corrosive due to its non-corrosive properties. , low energy consumption, simple operation, high degree of automation and other characteristics, it provides a new way to achieve efficient adsorption and separation of carbon dioxide in the mixed gas. Activated carbon used for adsorption methods is usually prepared by physical activation or chemical activation. The physical activation process to produce activated carbon is a simple, environmentally friendly and fuel-consuming production process, but because it relies on the consumption of carbon atoms to form a pore structure, Activation takes longer, and the output of activated carbon per unit time is small and the cost is high; chemical activation uses chemical reagents such as strong acid and strong alkali, which may cause damage to related equipment during the reaction process. The wastewater discharged during the process needs to go through tedious treatment processes to meet the sewage discharge standards, otherwise it will cause great pollution to the environment.
为解决化工污泥资源化处理难、化石燃料燃烧产生的CO2超标的问题，本发明提出了一种新型化工污泥基活性炭及其制备方法，并将其进一步用于二氧化碳的吸附中。In order to solve the problems of difficulty in recycling chemical sludge and excessiveCO2 produced by fossil fuel combustion, the present invention proposes a new type of chemical sludge-based activated carbon and its preparation method, and further uses it for the adsorption of carbon dioxide.
发明内容Contents of the invention
为解决上述技术问题，本发明提出了一种氮掺杂化工污泥基活性炭及其制备方法与应用，以化工污泥为主要原料，开发具有发达中、微孔结构，高效吸附CO2的污泥基活性炭。将化工污泥与一定的生物质碳源材料进行复合，为化工污泥的无害化处置提供一种新的解决方案，减轻有害固体废弃物污泥引起的环境污染，又可以利用活性炭高效吸附化石燃料排放的大量CO2，减缓地球温室效应。In order to solve the above technical problems, the present invention proposes a nitrogen-doped chemical sludge-based activated carbon and its preparation method and application. Using chemical sludge as the main raw material, the invention develops a sewage activated carbon with a developed meso- and microporous structure and efficient CO2 adsorption. Mud-based activated carbon. Compounding chemical sludge with certain biomass carbon source materials provides a new solution for the harmless disposal of chemical sludge, reduces environmental pollution caused by hazardous solid waste sludge, and can use activated carbon to efficiently adsorb The large amount of CO2 emitted by fossil fuels slows down the global greenhouse effect.
为实现上述目的，本发明提供了以下技术方案：In order to achieve the above objects, the present invention provides the following technical solutions:
本发明的技术方案之一：一种氮掺杂化工污泥基活性炭的制备方法，包括以下步骤：One of the technical solutions of the present invention: a preparation method of nitrogen-doped chemical sludge-based activated carbon, including the following steps:
将污泥干燥、研磨后预炭化处理，将预炭化处理后的污泥用硝酸、去离子水洗涤，烘干后得到预处理化工污泥，将所述预处理化工污泥与生物质原料混合，用氢氧化钾溶液浸渍，浸渍结束后炭化活化，水洗、干燥得到化工污泥基活性炭，将所述化工污泥基活性炭与有机胺溶液混合，加热回流后干燥，得到所述氮掺杂化工污泥基活性炭。The sludge is dried and ground and then pre-carbonized. The pre-carbonized sludge is washed with nitric acid and deionized water, and dried to obtain pre-treated chemical sludge. The pre-treated chemical sludge is mixed with biomass raw materials. , impregnated with potassium hydroxide solution, carbonized and activated after impregnation, washed with water, and dried to obtain chemical sludge-based activated carbon. The chemical sludge-based activated carbon was mixed with an organic amine solution, heated to reflux and dried to obtain the nitrogen-doped chemical Sludge-based activated carbon.
更具的步骤：将脱水污泥在105℃下干燥，研磨过200目筛，之后放入马弗炉中预炭化处理，将预炭化处理后的污泥用硝酸、去离子水洗涤至中性，烘干后得到预处理化工污泥，将所述预处理化工污泥与生物质原料混合，磁力搅拌器搅拌并用氢氧化钾溶液浸渍，浸渍结束后用去离子水洗涤至溶液为中性，装入坩埚放烘箱中105℃干燥24h，之后放入马弗炉中炭化活化，炭化活化结束后用去离子水洗涤至溶液为中性，放入烘箱105℃温度下干燥12h，冷却后置于粉碎机中粉碎至过200目筛，得到化工污泥基活性炭，将所述化工污泥基活性炭与有机胺溶液混合，置于水浴锅中加热回流后至乙醇完全挥发，之后放入干燥箱中105℃干燥2h，得到所述氮掺杂化工污泥基活性炭。More steps: dry the dewatered sludge at 105°C, grind it through a 200-mesh sieve, and then put it into a muffle furnace for pre-carbonization. Wash the pre-carbonized sludge with nitric acid and deionized water until it is neutral. , after drying, the pretreated chemical sludge is obtained. The pretreated chemical sludge is mixed with biomass raw materials, stirred with a magnetic stirrer and impregnated with potassium hydroxide solution. After the impregnation is completed, it is washed with deionized water until the solution is neutral. Put it into a crucible and dry it in an oven at 105°C for 24 hours, then put it into a muffle furnace for carbonization and activation. After carbonization and activation, wash it with deionized water until the solution is neutral, put it in an oven and dry it at 105°C for 12 hours, cool it and place it in the oven. Crush it in a pulverizer until it passes through a 200-mesh sieve to obtain chemical sludge-based activated carbon. Mix the chemical sludge-based activated carbon with an organic amine solution, place it in a water bath and heat to reflux until the ethanol completely evaporates, and then put it into a drying box. Dry at 105°C for 2 hours to obtain the nitrogen-doped chemical sludge-based activated carbon.
进一步地，预炭化处理过程中通氮气，氮气流量为210mL/min，升温速率为5℃/min，升温至300℃。Further, during the pre-carbonization process, nitrogen gas was passed, the nitrogen flow rate was 210 mL/min, the heating rate was 5°C/min, and the temperature was raised to 300°C.
进一步地，所述预处理化工污泥与生物质原料的质量比为4∶1。原始化工污泥中的C含量较少，而生物质原料花生壳中有机成分含量较高，灰分含量较少，且其本身的孔隙结构也比较发达，将其掺杂进化工污泥中共同炭化，可极大地提高活性炭中有机组分的含量，同时增加其孔隙结构和比表面积，从而提高活性炭的吸附性能。Further, the mass ratio of the pretreated chemical sludge to biomass raw material is 4:1. The C content in the original chemical sludge is less, while the biomass raw material peanut shells have a higher organic component content, less ash content, and its own pore structure is relatively developed. It is doped into the chemical sludge and jointly carbonized. , can greatly increase the content of organic components in activated carbon, while increasing its pore structure and specific surface area, thereby improving the adsorption performance of activated carbon.
进一步地，用硝酸洗涤可以除去活性炭表面残留的杂质，进一步提高化工污泥基活性炭的吸附能力。若不用硝酸洗涤或洗涤次数太少，会导致K元素不能被清洗干净，氢氧化钾继续发挥扩孔作用，破坏活性炭原有的结构特征，同时灰分等无机物杂质附着在化工污泥基活性炭的表面，抑制孔隙吸附。另外，经表面酸处理后的活性炭表面引入了-COOH，-OH活性官能团，有利于进一步拓宽孔道，增大比表面积，提高吸附性能。Furthermore, washing with nitric acid can remove residual impurities on the surface of activated carbon, further improving the adsorption capacity of chemical sludge-based activated carbon. If nitric acid is not used for washing or the washing times are too few, the K element will not be cleaned, and the potassium hydroxide will continue to play a pore-expanding role, destroying the original structural characteristics of the activated carbon. At the same time, inorganic impurities such as ash will adhere to the chemical sludge-based activated carbon. surface, inhibiting pore adsorption. In addition, -COOH and -OH active functional groups are introduced into the surface of activated carbon after surface acid treatment, which is beneficial to further widening the pore channels, increasing the specific surface area, and improving the adsorption performance.
进一步地，所述生物质原料为花生壳，需将花生壳研磨过筛。Further, the biomass raw material is peanut shells, and the peanut shells need to be ground and screened.
进一步地，所述氢氧化钾溶液的浓度为1M-3M，浸渍时间为24h，氢氧化钾溶液的用量无限制，只需没过预处理化工污泥与生物质原料混合料即可。但浸渍时间不宜过长，以免活性炭孔道发生坍塌和颗粒破碎的现象。Further, the concentration of the potassium hydroxide solution is 1M-3M, the soaking time is 24 hours, and the amount of potassium hydroxide solution is not limited, as long as the pretreated chemical sludge and biomass raw material mixture is used. However, the impregnation time should not be too long to avoid collapse of the activated carbon channels and particle breakage.
进一步地，所述炭化活化的温度为600℃-700℃，升温速率为5℃/min，保温时间为1-3h。Further, the carbonization activation temperature is 600°C-700°C, the heating rate is 5°C/min, and the heat preservation time is 1-3h.
进一步地，所述有机胺溶液与化工污泥基活性炭的料液比为50mL∶1g。Further, the material-to-liquid ratio of the organic amine solution and chemical sludge-based activated carbon is 50 mL:1g.
进一步地，所述有机胺溶液的质量浓度为10％-30％，所述有机胺溶液包括乙二胺溶液(EDA)、二乙烯三胺溶液(DETA)、三聚氰胺溶液、N,N-二甲基双丙烯酰胺溶液中的一种或多种。有机胺可以调控化工污泥基活性炭孔道结构，有效提高其孔道表面负载的氨基量，改善对CO2的选择性吸附。经过有机胺改性剂对活性炭改性，引入了大量N原子并与活性炭上本就存在的基团结合形成碱性官能团，增加活性炭表面粒子与CO2的吸附位点，使其饱和吸附量大大增加。其具体机理为有机胺调控的活性炭中有附着在其孔道表面的不饱和氮原子，氮原子在与CO2接触时会发生反应，生成氨基甲酸酯、碳酸盐、碳酸氢盐，从而提高CO2吸附量和吸附速率。Further, the mass concentration of the organic amine solution is 10%-30%, and the organic amine solution includes ethylenediamine solution (EDA), diethylenetriamine solution (DETA), melamine solution, N,N-dimethyl One or more of the base bisacrylamide solutions. Organic amines can regulate the pore structure of chemical sludge-based activated carbon, effectively increase the amount of amino groups loaded on the surface of the pores, and improve the selective adsorption ofCO2 . After the activated carbon is modified with an organic amine modifier, a large number of N atoms are introduced and combined with the existing groups on the activated carbon to form basic functional groups, which increases the adsorption sites between the surface particles of the activated carbon and CO2 , greatly increasing the saturated adsorption capacity. Increase. The specific mechanism is that the activated carbon regulated by organic amines has unsaturated nitrogen atoms attached to the surface of its pores. The nitrogen atoms will react when in contact with CO2 to generate carbamates, carbonates, and bicarbonates, thereby improving CO2 adsorption capacity and adsorption rate.
更进一步地，所述有机胺溶液为将有机胺溶解在乙醇中得到，使有机胺溶液的质量浓度为10％-30％。Furthermore, the organic amine solution is obtained by dissolving the organic amine in ethanol, so that the mass concentration of the organic amine solution is 10%-30%.
进一步地，加热回流的温度为80℃，时间为3h。Further, the heating reflux temperature was 80°C and the time was 3 hours.
本发明的技术方案之二：一种上述制备方法制备得到的氮掺杂化工污泥基活性炭。The second technical solution of the present invention: a nitrogen-doped chemical sludge-based activated carbon prepared by the above preparation method.
本发明的技术方案之三：上述氮掺杂化工污泥基活性炭在吸附CO2中的应用。The third technical solution of the present invention: the application of the above nitrogen-doped chemical sludge-based activated carbon in adsorbing CO2 .
与现有技术相比，本发明具有如下优点和技术效果：Compared with the existing technology, the present invention has the following advantages and technical effects:
(1)本发明采用KOH活化、酸洗、炭化、有机胺改性等步骤制备得到氮掺杂化工污泥基活性炭，通过KOH活化可显著拓宽活性炭的孔容结构，同时KOH处理后的化工污泥，其重金属含量显著降低，解决了污泥引起的环境污染；另外，酸洗可以除去活性炭孔隙内部残留的K原子和灰分，以防止杂质堵塞孔道；用有机胺改性后，活性炭孔道内负载了大量氨基官能团，极大的增加了活性炭对CO2的吸附选择性。(1) The present invention adopts KOH activation, pickling, carbonization, organic amine modification and other steps to prepare nitrogen-doped chemical sludge-based activated carbon. The pore volume structure of the activated carbon can be significantly broadened through KOH activation. At the same time, the chemical sludge after KOH treatment can Sludge, its heavy metal content is significantly reduced, solving the environmental pollution caused by sludge; in addition, pickling can remove residual K atoms and ash inside the activated carbon pores to prevent impurities from clogging the pores; after modification with organic amines, the activated carbon pores are loaded A large number of amino functional groups greatly increase the adsorption selectivity of activated carbon forCO2 .
(2)本发明制备的氮掺杂化工污泥基活性炭能够有效对CO2进行吸附。用有机胺改性后的活性炭具有更高的比表面积，可达500m2/g以上，孔隙表面N原子负载量增多，明显增加了对CO2的吸附位点，提高了对化石燃料排放的大量CO2的选择性吸附，减缓地球温室效应。(2) The nitrogen-doped chemical sludge-based activated carbon prepared by the present invention can effectively adsorbCO2 . Activated carbon modified with organic amine has a higher specific surface area, which can reach more than500m2 /g. The N atom loading on the pore surface increases, which significantly increases the adsorption sites forCO2 and improves the large amount of fossil fuel emissions. Selective adsorption of CO2 slows down the global greenhouse effect.
(3)本发明氮掺杂化工污泥基活性炭的制备方法简单，条件温和，适合大规模推广应用。(3) The preparation method of nitrogen-doped chemical sludge-based activated carbon of the present invention is simple, the conditions are mild, and it is suitable for large-scale promotion and application.
附图说明Description of drawings
构成本申请的一部分的附图用来提供对本申请的进一步理解，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。在附图中：The drawings that form a part of this application are used to provide a further understanding of this application. The illustrative embodiments and descriptions of this application are used to explain this application and do not constitute an improper limitation of this application. In the attached picture:
图1为实施例1制备得到的化工污泥-花生壳活性炭与对比例1制备得到的化工污泥活性炭的吸附-脱附等温线图；Figure 1 is an adsorption-desorption isotherm diagram of the chemical sludge-peanut shell activated carbon prepared in Example 1 and the chemical sludge activated carbon prepared in Comparative Example 1;
图2为初始化工污泥的扫描电镜图；Figure 2 is a scanning electron microscope image of the initial chemical sludge;
图3为实施例1制备的KOH浸渍污泥基活性炭的扫描电镜图；Figure 3 is a scanning electron microscope image of the KOH-impregnated sludge-based activated carbon prepared in Example 1;
图4为实施例1制备的炭化污泥基活性炭的扫描电镜图(5μm)；Figure 4 is a scanning electron microscope image (5 μm) of the carbonized sludge-based activated carbon prepared in Example 1;
图5为实施例1制备的炭化污泥基活性炭的扫描电镜图(2μm)；Figure 5 is a scanning electron microscope image (2 μm) of the carbonized sludge-based activated carbon prepared in Example 1;
图6为实施例1制备的化工污泥基活性炭(原始活性炭)和氮掺杂化工污泥基活性炭(乙二胺)、实施例2制备的氮掺杂化工污泥基活性炭(DETA)以及实施例3制备的氮掺杂化工污泥基活性炭(N,N-二甲基双丙烯酰胺)的傅里叶红外光谱(FT-IR)分析结果；Figure 6 shows the chemical sludge-based activated carbon (original activated carbon) and nitrogen-doped chemical sludge-based activated carbon (ethylenediamine) prepared in Example 1, the nitrogen-doped chemical sludge-based activated carbon (DETA) prepared in Example 2, and the implementation Fourier transform infrared spectroscopy (FT-IR) analysis results of nitrogen-doped chemical sludge-based activated carbon (N,N-dimethylbisacrylamide) prepared in Example 3;
图7为实施例1所用原始样本(初始化工污泥)的TGA-DTA热重曲线图；Figure 7 is a TGA-DTA thermogravimetric curve diagram of the original sample (initial chemical sludge) used in Example 1;
图8为CO2吸附装置流程图，其中1-C-1压缩空气钢瓶，2-C-2压缩空气钢瓶，3,4-流量计，5-压力进料罐，6-反应器，7-冷却器，8-液体产品罐，9-气体产品罐；Figure 8 is the flow chart of the CO2 adsorption device, including 1-C-1 compressed air cylinder, 2-C-2 compressed air cylinder, 3, 4-flow meter, 5-pressure feed tank, 6-reactor, 7- Cooler, 8-liquid product tank, 9-gas product tank;
图9为实施例4制备的氮掺杂化工污泥基活性炭(三聚氰胺掺杂)的SEM图；Figure 9 is an SEM image of the nitrogen-doped chemical sludge-based activated carbon (melamine doped) prepared in Example 4;
图10为实施例4制备的氮掺杂化工污泥基活性炭(三聚氰胺掺杂)以及化工污泥基活性炭(原始活性炭)在25℃、101KPa条件下的CO2吸附等温线；Figure 10 is the CO2 adsorption isotherm of the nitrogen-doped chemical sludge-based activated carbon (melamine doped) and chemical sludge-based activated carbon (original activated carbon) prepared in Example 4 under the conditions of 25°C and 101KPa;
图11为实施例1制备的化工污泥基活性炭(原始活性炭)和氮掺杂化工污泥基活性炭(乙二胺)以及实施例4制备的氮掺杂化工污泥基活性炭(三聚氰胺)的CO2吸附等温线；Figure 11 shows the CO of chemical sludge-based activated carbon (original activated carbon) and nitrogen-doped chemical sludge-based activated carbon (ethylenediamine) prepared in Example 1 and nitrogen-doped chemical sludge-based activated carbon (melamine) prepared in Example 4.2 Adsorption isotherm;
图12为实施例4(20％)、实施例5(10％)和实施例6(30％)制备的氮掺杂化工污泥基活性炭的CO2吸附等温线；Figure 12 is the CO2 adsorption isotherm of the nitrogen-doped chemical sludge-based activated carbon prepared in Example 4 (20%), Example 5 (10%) and Example 6 (30%);
图13为实施例4(20％)、实施例5(10％)和实施例6(30％)制备的氮掺杂化工污泥基活性炭对CO2最大吸附量对比图。Figure 13 is a comparison chart of the maximum adsorption capacity of CO2 by the nitrogen-doped chemical sludge-based activated carbon prepared in Example 4 (20%), Example 5 (10%) and Example 6 (30%).
具体实施方式Detailed ways
现详细说明本发明的多种示例性实施方式，该详细说明不应认为是对本发明的限制，而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。Various exemplary embodiments of the invention will now be described in detail. This detailed description should not be construed as limitations of the invention, but rather as a more detailed description of certain aspects, features and embodiments of the invention.
应理解本发明中所述的术语仅仅是为描述特别的实施方式，并非用于限制本发明。另外，对于本发明中的数值范围，应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。It should be understood that the terms used in the present invention are only used to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges in the present invention, it should be understood that every intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or value intermediate within a stated range and any other stated value or value intermediate within a stated range is also included within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded from the range.
除非另有说明，否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料，但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入，用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时，以本说明书的内容为准。Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only the preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and/or materials in connection with which the documents relate. In the event of conflict with any incorporated document, the contents of this specification shall prevail.
在不背离本发明的范围或精神的情况下，可对本发明说明书的具体实施方式做多种改进和变化，这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见得的。本发明说明书和实施例仅是示例性的。It will be apparent to those skilled in the art that various modifications and changes can be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to the skilled person from the description of the invention. The specification and examples of the present invention are exemplary only.
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等，均为开放性的用语，即意指包含但不限于。The words "includes", "includes", "has", "contains", etc. used in this article are all open terms, which mean including but not limited to.
本发明实施例所用化工污泥采集自江苏省淮安清江化工有限公司，从化工厂排放的污水中采集沉淀的脱水污泥，剔除其中的木棍、石头等杂物后，其中的一部分立刻放到冰箱中为原始样本(初始化工污泥)；另外一部分放在阴凉避光处，自然晾干后放入搅碎机中搅碎，过200目筛备用。花生壳采集自江苏省淮安市淮阴区棉花镇。The chemical sludge used in the embodiments of the present invention was collected from Huaian Qingjiang Chemical Co., Ltd. in Jiangsu Province. The precipitated dewatered sludge was collected from the sewage discharged from the chemical plant. After removing sticks, stones and other debris, part of it was immediately placed in the refrigerator. The middle part is the original sample (initial chemical sludge); the other part is placed in a cool and dark place, dried naturally, then put into a grinder and crushed, passed through a 200-mesh sieve and set aside. Peanut shells were collected from Mianmian Town, Huaiyin District, Huai'an City, Jiangsu Province.
本发明实施例所用各化学试剂均为市售购买得到，详细信息见表1。All chemical reagents used in the examples of the present invention are commercially available. See Table 1 for detailed information.
表1化学试剂购买信息Table 1 Chemical reagent purchase information
本发明实施例中所用有机胺的分子结构信息见表2。The molecular structure information of the organic amines used in the examples of the present invention is shown in Table 2.
表2有机胺分子结构Table 2 Molecular structure of organic amines
本发明实验过程所用到的仪器设备信息见表3。Information on the instruments and equipment used in the experimental process of the present invention is shown in Table 3.
表3仪器设备信息Table 3 Instrument and equipment information
以下通过实施例对本发明的技术方案做进一步说明。The technical solutions of the present invention will be further described below through examples.
实施例1Example 1
将脱水化工污泥在105℃下干燥，研磨过200目筛，之后放入马弗炉中，通入流量为210mL/min的氮气进行预炭化处理，预炭化处理的升温速率为5℃/min，升温至300℃，将预炭化处理后的污泥用4M的硝酸洗涤，之后用去离子水洗涤至中性，烘干后得到预处理化工污泥；Dry the dehydrated chemical sludge at 105°C, grind it through a 200-mesh sieve, and then put it into a muffle furnace. Nitrogen gas with a flow rate of 210 mL/min is introduced for pre-carbonization. The temperature rise rate of the pre-carbonization treatment is 5°C/min. , raise the temperature to 300°C, wash the pre-carbonized sludge with 4M nitric acid, then wash it with deionized water until neutral, and dry it to obtain the pre-treated chemical sludge;
将预处理化工污泥与生物质原料(在120℃下干燥，研磨至100目的花生壳)按照质量比为4∶1混合，在磁力搅拌器搅拌下用浓度为2M的氢氧化钾溶液浸渍24h得到KOH浸渍污泥基活性炭，用去离子水将KOH浸渍污泥基活性炭洗涤至溶液为中性，装入坩埚放烘箱中105℃干燥24h，之后放入马弗炉中，以5℃/min的升温速率升温至700℃进行炭化活化，保温2h，炭化活化结束后得到炭化污泥基活性炭，之后用去离子水洗涤至溶液为中性，放入烘箱105℃温度下干燥12h，冷却后置于粉碎机中粉碎至过200目筛，得到化工污泥基活性炭(化工污泥-花生壳活性炭)；Mix the pretreated chemical sludge and biomass raw materials (dried at 120°C and ground to 100 mesh peanut shells) at a mass ratio of 4:1, and soaked with a 2M potassium hydroxide solution for 24 hours under stirring with a magnetic stirrer. Obtain KOH-impregnated sludge-based activated carbon. Use deionized water to wash the KOH-impregnated sludge-based activated carbon until the solution is neutral. Put it into a crucible and dry it in an oven at 105°C for 24 hours. Then put it into a muffle furnace and dry it at 5°C/min. The heating rate is raised to 700°C for carbonization activation, and the temperature is kept for 2 hours. After the carbonization activation is completed, the carbonized sludge-based activated carbon is obtained, and then washed with deionized water until the solution is neutral, placed in an oven to dry at 105°C for 12 hours, cooled and then placed Crush it in a pulverizer until it passes through a 200-mesh sieve to obtain chemical sludge-based activated carbon (chemical sludge-peanut shell activated carbon);
将乙二胺(EDA)溶解在50mL乙醇中得到质量浓度为20％的有机胺溶液，之后加入1g化工污泥基活性炭，置于水浴锅中，在80℃下加热回流3h后至乙醇完全挥发，之后放入干燥箱中105℃干燥2h，得到氮掺杂化工污泥基活性炭。Dissolve ethylenediamine (EDA) in 50 mL of ethanol to obtain an organic amine solution with a mass concentration of 20%. Then add 1g of chemical sludge-based activated carbon, place it in a water bath, and heat and reflux at 80°C for 3 hours until the ethanol is completely evaporated. , and then placed in a drying box to dry at 105°C for 2 hours to obtain nitrogen-doped chemical sludge-based activated carbon.
实施例2Example 2
同实施例1，区别仅在于将乙二胺(EDA)等质量替换为二乙烯三胺(DETA)。Same as Example 1, the only difference is that the equivalent mass of ethylenediamine (EDA) is replaced by diethylenetriamine (DETA).
实施例3Example 3
同实施例1，区别仅在于将乙二胺(EDA)等质量替换为N,N-二甲基双丙烯酰胺。Same as Example 1, the only difference is that the equivalent mass of ethylenediamine (EDA) is replaced by N,N-dimethylbisacrylamide.
实施例4Example 4
同实施例1，区别仅在于将乙二胺(EDA)等质量替换为三聚氰胺。Same as Example 1, the only difference is that the mass of ethylenediamine (EDA) is replaced by melamine.
实施例5Example 5
同实施例4，区别仅在于将三聚氰胺溶解在50mL乙醇中得到质量浓度为10％的有机胺溶液。The same as Example 4, except that the melamine was dissolved in 50 mL of ethanol to obtain an organic amine solution with a mass concentration of 10%.
实施例6Example 6
同实施例4，区别仅在于将三聚氰胺溶解在50mL乙醇中得到质量浓度为30％的有机胺溶液。The same as Example 4, except that the melamine was dissolved in 50 mL of ethanol to obtain an organic amine solution with a mass concentration of 30%.
对比例1(化工污泥单独制成的活性炭，不加入生物质原料)Comparative Example 1 (Activated carbon made from chemical sludge alone, without adding biomass raw materials)
将脱水化工污泥在105℃下干燥，研磨过200目筛，之后放入马弗炉中，通入流量为210mL/min的氮气进行预炭化处理，预炭化处理的升温速率为5℃/min，升温至300℃，将预炭化处理后的污泥用4M硝酸洗涤，之后用去离子水洗涤至中性，烘干后得到预处理化工污泥；Dry the dehydrated chemical sludge at 105°C, grind it through a 200-mesh sieve, and then put it into a muffle furnace. Nitrogen gas with a flow rate of 210 mL/min is introduced for pre-carbonization. The temperature rise rate of the pre-carbonization treatment is 5°C/min. , raise the temperature to 300°C, wash the pre-carbonized sludge with 4M nitric acid, then wash it with deionized water until neutral, and dry it to obtain the pre-treated chemical sludge;
将预处理化工污泥用浓度为2M的氢氧化钾溶液浸渍24h，浸渍结束后用去离子水洗涤至溶液为中性，装入坩埚放烘箱中105℃干燥24h，之后放入马弗炉中，以5℃/min的升温速率升温至700℃进行炭化活化，保温2h，炭化活化结束后用去离子水洗涤至溶液为中性，放入烘箱105℃温度下干燥12h，冷却后置于粉碎机中粉碎至过200目筛，得到化工污泥活性炭。Soak the pretreated chemical sludge with a potassium hydroxide solution with a concentration of 2M for 24 hours. After the soaking is completed, wash it with deionized water until the solution is neutral. Put it into a crucible and dry it in an oven at 105°C for 24 hours, and then put it into a muffle furnace. , increase the temperature to 700°C at a heating rate of 5°C/min for carbonization activation, and keep it for 2 hours. After the carbonization activation is completed, wash it with deionized water until the solution becomes neutral, place it in an oven and dry it at 105°C for 12 hours, cool it and then grind it. It is crushed in the machine until it passes through a 200-mesh sieve to obtain chemical sludge activated carbon.
对比例2(未经硝酸处理)Comparative Example 2 (without nitric acid treatment)
同实施例1，区别仅在于，预处理化工污泥的制备过程如下：将脱水化工污泥在105℃下干燥，研磨过200目筛，之后放入马弗炉中，通入流量为210mL/min的氮气进行预炭化处理，预炭化处理的升温速率为5℃/min，升温至300℃，得到预处理化工污泥；其他制备过程同实施例1。Same as Example 1, the only difference is that the preparation process of pretreated chemical sludge is as follows: dry the dehydrated chemical sludge at 105°C, grind it through a 200 mesh sieve, and then put it into a muffle furnace with a flow rate of 210 mL/ min of nitrogen for pre-carbonization treatment, the temperature rise rate of the pre-carbonization treatment is 5°C/min, and the temperature is raised to 300°C to obtain pretreated chemical sludge; other preparation processes are the same as in Example 1.
性能测试Performance Testing
一、比表面积及孔隙结构测定1. Determination of specific surface area and pore structure
使用SA 3100比表面积及孔径分析仪来检测样品(实施例1制备得到的化工污泥-花生壳活性炭与对比例1制备得到的化工污泥活性炭)的N2吸附-脱附等温线。测试前现将样品放在300℃下真空脱气2h，使活性炭样品中的水分完全蒸发，之后将样品放置在77.6K下对氮气进行吸附脱附测定。Use the SA 3100 specific surface area and pore size analyzer to detect the N2 adsorption-desorption isotherms of the samples (chemical sludge-peanut shell activated carbon prepared in Example 1 and chemical sludge activated carbon prepared in Comparative Example 1). Before the test, the sample was placed at 300°C for vacuum degassing for 2 hours to completely evaporate the water in the activated carbon sample. The sample was then placed at 77.6K for nitrogen adsorption and desorption measurement.
实施例1制备得到的化工污泥-花生壳活性炭与对比例1制备得到的化工污泥活性炭的吸附-脱附等温线图见图1，由图1可以看出，实施例1制备的活性炭的吸附等温线与标准曲线比较，不规则性较明显，较接近于第I类，图中曲线在相对压力0.6到0.8间N2吸附量趋于饱和，说明在活性炭内部可能存在着大量的中微孔。比较对比例1使用污泥直接炭化制成的活性炭和用花生壳掺杂后而制成的活性炭(实施例1)，可以看出，化工污泥单独制成的活性炭最大吸附量仅有150cm3/g左右，经生物质原料掺杂后，最大吸附量达到600cm3/g。因此，用生物质原料(花生壳)掺杂化工污泥可明显提高活性炭的吸附量。这是由于原始化工污泥中的C含量较少，而花生壳中有机成分含量较高，灰分含量较少，且其本身的孔隙结构也比较发达，将其掺杂进化工污泥中共同炭化，可极大的提高活性炭中有机组分的含量，同时增加其孔隙结构和比表面积，从而提高活性炭的吸附性能。The adsorption-desorption isotherm diagram of the chemical sludge-peanut shell activated carbon prepared in Example 1 and the chemical sludge activated carbon prepared in Comparative Example 1 is shown in Figure 1. It can be seen from Figure 1 that the activated carbon prepared in Example 1 has Comparing the adsorption isotherm with the standard curve, the irregularity is more obvious, which is closer to type I. The curve in the figure tends to be saturated withN2 adsorption capacity between the relative pressure of 0.6 and 0.8, indicating that there may be a large number of medium and microorganisms inside the activated carbon. hole. Comparing the activated carbon made by direct carbonization of sludge in Comparative Example 1 and the activated carbon made by doping peanut shells (Example 1), it can be seen that the maximum adsorption capacity of activated carbon made from chemical sludge alone is only 150cm3 /g, after doping with biomass raw materials, the maximum adsorption capacity reaches 600cm3 /g. Therefore, doping chemical sludge with biomass raw material (peanut shell) can significantly increase the adsorption capacity of activated carbon. This is because the C content in the original chemical sludge is less, while the peanut shell has a higher organic component content, less ash content, and its own pore structure is relatively developed. It is doped into the chemical sludge and jointly carbonized. , can greatly increase the content of organic components in activated carbon, while increasing its pore structure and specific surface area, thereby improving the adsorption performance of activated carbon.
采用BET(Brunauer-Emmett-Teller)和Langmuir模型计算比表面积；采用介孔孔径分布BJH(Barett-Toyner-Halenda)法和微孔孔径分布HK(Horvath-Kawazoe)法计算孔体积。对实施例1制备得到的化工污泥-花生壳活性炭与对比例1制备得到的化工污泥活性炭进行孔结构的测定，结果见表4。The BET (Brunauer-Emmett-Teller) and Langmuir models were used to calculate the specific surface area; the mesopore pore size distribution BJH (Barett-Toyner-Halenda) method and micropore pore size distribution HK (Horvath-Kawazoe) method were used to calculate the pore volume. The pore structure of the chemical sludge-peanut shell activated carbon prepared in Example 1 and the chemical sludge activated carbon prepared in Comparative Example 1 was measured. The results are shown in Table 4.
表4实施例1与对比例1活性炭孔结构测定结果Table 4 Example 1 and Comparative Example 1 Activated Carbon Pore Structure Measurement Results
由表4可以看出，本发明实施例1的化工污泥-花生壳活性炭的比表面积增大，总孔孔容也增大。而对比例1中未掺杂生物质原料的化工污泥制成的活性炭比表面积较小，而实施例1中生物质原料(花生壳)掺杂后活性炭的单点表面积增加了37.31％，BET表面积增加了36.89％，Langmuir表面积增加了27.01％，中孔和微孔容积也有较大程度的增加。由此可知，用生物质原料与化工污泥混合制成的活性炭在保持活性炭结构不变的情况下，可增加活性炭内部总孔容积，明显提高其比表面积。It can be seen from Table 4 that the specific surface area of the chemical sludge-peanut shell activated carbon in Example 1 of the present invention increases, and the total pore volume also increases. In Comparative Example 1, the activated carbon made from chemical sludge without biomass raw materials has a smaller specific surface area, while in Example 1, the single-point surface area of activated carbon after doping biomass raw materials (peanut shells) increased by 37.31%, BET The surface area increased by 36.89%, the Langmuir surface area increased by 27.01%, and the mesopore and micropore volumes also increased to a large extent. It can be seen that activated carbon made by mixing biomass raw materials and chemical sludge can increase the total pore volume inside the activated carbon and significantly increase its specific surface area while keeping the activated carbon structure unchanged.
二、微观形貌表征2. Microscopic morphology characterization
使用FEG450场发射扫描电子显微镜来观察分析微观形貌特征。观察对象为初始化工污泥、实施例1制备的KOH浸渍污泥基活性炭、实施例1制备的炭化污泥基活性炭，其中初始化工污泥的扫描电镜图见图2，实施例1制备的KOH浸渍污泥基活性炭的扫描电镜图见图3，实施例1制备的炭化污泥基活性炭的扫描电镜图见图4(5μm)和图5(2μm)。A FEG450 field emission scanning electron microscope was used to observe and analyze the micromorphological characteristics. The objects of observation are the initial chemical sludge, the KOH impregnated sludge-based activated carbon prepared in Example 1, and the carbonized sludge-based activated carbon prepared in Example 1. The scanning electron microscope picture of the initial chemical sludge is shown in Figure 2, and the KOH prepared in Example 1 The scanning electron microscope image of the impregnated sludge-based activated carbon is shown in Figure 3, and the scanning electron microscope image of the carbonized sludge-based activated carbon prepared in Example 1 is shown in Figure 4 (5 μm) and Figure 5 (2 μm).
由图2-图5可以看出，初始化工污泥(图2)的孔隙结构为块状，几乎无明显微孔道，表面有圆形颗粒，为化工污泥内存有的重金属元素。由图3可以看出，使用KOH作为活化剂，可以使活化后的活性炭微孔数量明显增多，表面非常粗糙，多为颗粒状，说明碱性活性剂可有效拓宽活性炭孔容结构。而经高温炭化后的化工污泥(图4和图5)呈现不规则的多孔结构，孔隙分散，大小不一，且其表面有少量颗粒状结构，表面粗糙，具有丰富的孔隙结构，说明经过合理的高温炭化操作，可以对活性炭有显著的扩孔作用。It can be seen from Figures 2 to 5 that the pore structure of the initial chemical sludge (Figure 2) is massive, with almost no obvious micropores, and round particles on the surface, which are heavy metal elements present in the chemical sludge. It can be seen from Figure 3 that using KOH as the activator can significantly increase the number of micropores in the activated carbon after activation, and the surface is very rough and mostly granular, indicating that the alkaline activator can effectively broaden the pore volume structure of the activated carbon. The chemical sludge after high-temperature carbonization (Figure 4 and Figure 5) shows an irregular porous structure with dispersed pores of different sizes, and a small amount of granular structure on the surface. The surface is rough and has a rich pore structure, indicating that after Reasonable high-temperature carbonization operation can significantly expand the pores of activated carbon.
三、傅里叶红外光谱分析3. Fourier transform infrared spectroscopy analysis
使用Nicolet iS50 FT-IR傅里叶变换红外光谱仪来测定。使用KBr压片方法，将所需要的试样和纯的KBr粉体混合，用压片法将其压平，再放到红外光谱仪中进行测定，分析表征结果显示，在谱图曲线的1010cm-1处有明显的-C-O伸缩振动峰。经酸处理后的样品(实施例1)吸收峰较未经酸处理样品(对比例2)的吸收峰更宽更显著，究其原因，这可能是由于样品在硝酸处理过程中部分基团被氧化导致产生更多C-O-C的伸缩振动产生。位于2100cm-1处的吸收峰为伸缩振动峰，此吸收峰强度较弱。3400cm-1附近处的特征峰为O-H伸缩振动峰，这是O-H基团之间氢键作用，经酸处理后，3400cm-1处的特征峰更加明显，说明表面酸处理增加了活性炭表面的O-H基团。另外，经硝酸氧化后，活性炭在1600cm-1左右处的吸收峰更加明显，这可能是羧基COOH中C＝O的伸缩振动产生的吸收峰。此外，光谱图在700-860cm-1处的峰与化工污泥中重金属元素的存在有关。因此，化工污泥基活性炭的表面具有丰富的C-O键和O-H键，且经表面酸处理后的活性炭表面引入了-COOH，-OH活性官能团，有利于进一步拓宽孔道，增大比表面积，提高吸附性能。Measured using Nicolet iS50 FT-IR Fourier transform infrared spectrometer. Use the KBr tableting method to mix the required sample with pure KBr powder, flatten it using the tableting method, and then place it in an infrared spectrometer for measurement. The analysis and characterization results show that at 1010cm- of the spectrum curve There is an obvious -CO stretching vibration peak at1 place. The absorption peak of the sample after acid treatment (Example 1) is broader and more significant than the absorption peak of the sample without acid treatment (Comparative Example 2). The reason may be that some groups of the sample were removed during the nitric acid treatment process. Oxidation leads to the production of stretching vibrations that produce more COC. The absorption peak located at 2100cm-1 is a stretching vibration peak, and the intensity of this absorption peak is weak. The characteristic peak near 3400cm-1 is the OH stretching vibration peak, which is the hydrogen bonding effect between OH groups. After acid treatment, the characteristic peak at 3400cm-1 is more obvious, indicating that surface acid treatment increases OH on the surface of activated carbon. group. In addition, after nitric acid oxidation, the absorption peak of activated carbon at around 1600cm-1 is more obvious, which may be the absorption peak generated by the stretching vibration of C=O in carboxyl COOH. In addition, the peaks in the spectrum at 700-860 cm-1 are related to the presence of heavy metal elements in chemical sludge. Therefore, the surface of chemical sludge-based activated carbon is rich in CO bonds and OH bonds, and -COOH and -OH active functional groups are introduced into the surface of activated carbon after surface acid treatment, which is beneficial to further widening the pore channels, increasing the specific surface area, and improving adsorption performance.
(2)将实施例1制备的化工污泥基活性炭(原始活性炭)和氮掺杂化工污泥基活性炭(乙二胺)、实施例2制备的氮掺杂化工污泥基活性炭(DETA)以及实施例3制备的氮掺杂化工污泥基活性炭(N,N-二甲基双丙烯酰胺)进行傅里叶红外光谱(FT-IR)分析，其分析表征的结果见图6。(2) Combine the chemical sludge-based activated carbon (original activated carbon) and nitrogen-doped chemical sludge-based activated carbon (ethylenediamine) prepared in Example 1, the nitrogen-doped chemical sludge-based activated carbon (DETA) prepared in Example 2, and The nitrogen-doped chemical sludge-based activated carbon (N,N-dimethylbisacrylamide) prepared in Example 3 was analyzed by Fourier transform infrared spectroscopy (FT-IR). The results of the analysis and characterization are shown in Figure 6.
由图6可以看出，相比于原始活性炭，用DETA改性后的活性炭在1600cm-1左右处的吸收峰减弱，说明用有机胺DETA调控活性炭时，其表面的-COOH已经与有机胺发生化学反应。而用乙二胺改性的活性炭在1600cm-1处的吸收峰同样减弱，且在1520cm-1，690cm-1处产生新的吸收峰，这是NH基团的弯曲和伸缩振动峰。另外，N,N-二甲基双丙烯酰胺改性的活性炭在1660cm-1，1520cm-1，985cm-1处分别产生了新的吸收峰。酰胺基团主要有三个吸收峰，在乙二胺和N,N-二甲基双丙烯酰胺的红外光谱图都可以找到。由此可知，用有机胺调控化工污泥基活性炭可有效提高其孔道表面负载的氨基量，改善对CO2的选择性吸附。As can be seen from Figure 6, compared with the original activated carbon, the absorption peak of the activated carbon modified with DETA at about 1600 cm-1 is weakened, indicating that when the organic amine DETA is used to regulate the activated carbon, the -COOH on its surface has reacted with the organic amine. chemical reaction. The absorption peak of activated carbon modified with ethylenediamine at 1600cm-1 also weakens, and new absorption peaks are generated at 1520cm-1 and 690cm-1 , which are the bending and stretching vibration peaks of the NH group. In addition, N,N-dimethylbisacrylamide-modified activated carbon produced new absorption peaks at 1660cm-1 , 1520cm-1 , and 985cm-1 respectively. The amide group has three main absorption peaks, which can be found in the infrared spectra of ethylenediamine and N,N-dimethylbisacrylamide. It can be seen that using organic amines to regulate chemical sludge-based activated carbon can effectively increase the amount of amino groups loaded on the surface of its pores and improve the selective adsorption ofCO2 .
四、热重分析4. Thermogravimetric analysis
使用TGA/SDTA85le热重分析仪，在惰性气体(N2)保护下测得活性炭的质量与温度或时间之间的关系，并分析样品的热稳定性能。Use TGA/SDTA85le thermogravimetric analyzer to measure the relationship between the mass of activated carbon and temperature or time under the protection of inert gas (N2 ), and analyze the thermal stability performance of the sample.
实施例1所用原始样本(初始化工污泥)的TGA-DTA热重曲线图见图7，由图7可以看出，初始化工污泥在整个过程可以分为三个失重阶段：第一阶段是从室温(约20.94℃)到191.09℃左右，DTA曲线先下降后上升，初始化工污泥内部为吸热过程，这个失重过程可能是由初始化工污泥本身内部的游离水和空气中的其他杂质气体被吸收蒸发，以及在初始化工污泥烘干过程中表面吸附水分的蒸发而引起的，此过程失重率为7.64％；第二阶段是从191.09℃到361.03℃，DTA曲线上升缓慢，这可能仍然是初始化工污泥内部水分及和杂质气体被持续蒸发，同时其表面某些不稳定物质开始分解，此过程失重率为2.35％；第三阶段是从361.03℃到660.34℃左右，DTA曲线先上升后下降，且TG曲线迅速下降，这表明在此阶段失重较大，失重率达到20.26％，这是由于初始化工污泥表面的不稳定组分已经被分解，内部挥发性物质生成。当化工污泥经炭化活化后，其内部为放热过程，内部饱和时，变为吸热过程，因此，在450℃左右活化时，DTA可达到最大值。The TGA-DTA thermogravimetric curve of the original sample (initial chemical sludge) used in Example 1 is shown in Figure 7. It can be seen from Figure 7 that the entire process of the initial chemical sludge can be divided into three weight loss stages: the first stage is From room temperature (about 20.94℃) to about 191.09℃, the DTA curve first drops and then rises. The interior of the initial chemical sludge is an endothermic process. This weight loss process may be caused by the free water inside the initial chemical sludge itself and other impurities in the air. It is caused by the absorption and evaporation of gas and the evaporation of surface adsorbed water during the initial chemical sludge drying process. The weight loss rate in this process is 7.64%; the second stage is from 191.09℃ to 361.03℃, and the DTA curve rises slowly, which may The internal moisture and impurity gases of the initial chemical sludge are still evaporated continuously, and at the same time, some unstable substances on the surface begin to decompose. The weight loss rate in this process is 2.35%; the third stage is from about 361.03℃ to 660.34℃, and the DTA curve first It rises and then drops, and the TG curve drops rapidly, which shows that the weight loss is relatively large at this stage, and the weight loss rate reaches 20.26%. This is because the unstable components on the surface of the initial chemical sludge have been decomposed and internal volatile substances are generated. When chemical sludge is activated by carbonization, its interior is an exothermic process. When the interior is saturated, it becomes an endothermic process. Therefore, when activated at around 450°C, DTA can reach its maximum value.
实施例1所用原始样本(初始化工污泥)的热分析数据结果见表5，由表5可以看出，整个失重过程分为三个阶段，其中最大的失重率为20.26％，原始样本(初始化工污泥)的最佳的热解温度为452.80℃。The thermal analysis data results of the original sample (initialized chemical sludge) used in Example 1 are shown in Table 5. It can be seen from Table 5 that the entire weight loss process is divided into three stages, in which the maximum weight loss rate is 20.26%. The original sample (initialized The optimal pyrolysis temperature of industrial sludge is 452.80℃.
表5实施例1所用原始样本(初始化工污泥)的热分析数据Table 5 Thermal analysis data of the original sample (initial chemical sludge) used in Example 1
五、ICP分析5. ICP analysis
使用ICP光谱仪测定样品中重金属元素的含量，取10g样品放入马弗炉中650℃灼烧2h，待炉内温度低于200℃时取出，冷却至室温后，将两份样品各放入1mol/L浓硫酸中浸渍12h后经过滤，取滤液，倒入样品管中，放入ICP光谱仪测定。Use an ICP spectrometer to measure the content of heavy metal elements in the sample. Put 10g of the sample into a muffle furnace and burn it at 650°C for 2 hours. Take it out when the temperature in the furnace is lower than 200°C. After cooling to room temperature, put 1 mol of each of the two samples into /L concentrated sulfuric acid for 12 hours and then filtered. Take the filtrate, pour it into a sample tube, and put it into an ICP spectrometer for measurement.
分析对象为：初始化工污泥以及实施例1制备得到的KOH浸渍污泥基活性炭。The analysis objects are: initial chemical sludge and KOH impregnated sludge-based activated carbon prepared in Example 1.
分析结果见表6。The analysis results are shown in Table 6.
表6 KOH处理前后污泥的重金属含量对比Table 6 Comparison of heavy metal content in sludge before and after KOH treatment
由表6可以看出，初始化工污泥组成复杂，其中含有多种有害重金属，直接排放会对环境和人类健康造成极大伤害，而经KOH溶液处理后的污泥样品各金属元素含量有了显著的降低，说明原化工污泥在经过适当的碱处理后可大大降低其重金属污染的问题，同时还可利用此方法通过活化和炭化两步骤制备活性炭，实现“固废资源化”，减少固体废弃物对环境造成的污染。It can be seen from Table 6 that the initial chemical sludge has a complex composition and contains a variety of harmful heavy metals. Direct discharge will cause great harm to the environment and human health. However, the content of each metal element in the sludge sample treated with KOH solution has improved. The significant reduction shows that the heavy metal pollution problem of raw chemical sludge can be greatly reduced after appropriate alkali treatment. At the same time, this method can also be used to prepare activated carbon through the two steps of activation and carbonization to achieve "solid waste resource utilization" and reduce solid waste. Environmental pollution caused by waste.
六、吸附性能分析6. Adsorption performance analysis
图8为CO2吸附装置流程图，其中1-C-1压缩空气钢瓶，2-C-2压缩空气钢瓶，3,4-流量计，5-压力进料罐，6-反应器，7-冷却器，8-液体产品罐，9-气体产品罐。将制备好的氮掺杂污泥基活性炭放置于高压容量法气体吸附仪上，打开压缩空气钢瓶C-1、C-2的阀门，通入模拟烟气(体积分数为9％的CO2，平衡气为氮气)，烟气通过压力进料罐进行缓冲，并设定其出口压力为101KPa，然后将其送入气体吸附仪(HPA-200)进行吸附，操作温度为室温25℃，吸附后的气体经冷却器冷却后进气体产品罐9保存。Figure 8 is the flow chart of the CO2 adsorption device, including 1-C-1 compressed air cylinder, 2-C-2 compressed air cylinder, 3, 4-flow meter, 5-pressure feed tank, 6-reactor, 7- Cooler, 8-liquid product tank, 9-gas product tank. Place the prepared nitrogen-doped sludge-based activated carbon on a high-pressure volumetric gas adsorption instrument, open the valves of compressed air cylinders C-1 and C-2, and introduce simulated flue gas (CO2 with a volume fraction of 9%, The balance gas is nitrogen), the flue gas is buffered through a pressure feed tank, and its outlet pressure is set to 101KPa, and then sent to the gas adsorption instrument (HPA-200) for adsorption. The operating temperature is room temperature 25°C. After adsorption The gas is cooled by the cooler and then enters the gas product tank 9 for storage.
实施例4制备的氮掺杂化工污泥基活性炭(三聚氰胺掺杂)的SEM图见图9。The SEM image of the nitrogen-doped chemical sludge-based activated carbon (melamine doped) prepared in Example 4 is shown in Figure 9.
实施例4制备的氮掺杂化工污泥基活性炭(三聚氰胺掺杂)以及化工污泥基活性炭(原始活性炭)在25℃、101KPa条件下的CO2吸附等温线见图10。The CO2 adsorption isotherms of the nitrogen-doped chemical sludge-based activated carbon (melamine doped) and chemical sludge-based activated carbon (original activated carbon) prepared in Example 4 under the conditions of 25°C and 101KPa are shown in Figure 10.
图9与图3相比，经胺改性后的活性炭，其孔隙表面N原子负载量增多，增加了对CO2的吸附位点，原因可能在于，对于比表面较小的活性炭，由于孔隙体积较小，用有机胺改性时可能会造成活性炭孔道的堵塞，活性炭表面碱性位点难以与CO2分子接触，CO2的吸附量大大减少。因此，有机胺调控的活性炭的CO2吸附机制与载体的种类和结构大大相关，载体结构不同，吸附机制也有所差异。Compared with Figure 3, Figure 9 shows that the amine-modified activated carbon has an increased N atom loading on the pore surface, which increases the adsorption sites for CO2. The reason may be that for activated carbon with a smaller specific surface, due to the pore volume Smaller, when modified with organic amines, the activated carbon pores may be blocked. The alkaline sites on the surface of the activated carbon are difficult to contact withCO2 molecules, and the adsorption capacity ofCO2 is greatly reduced. Therefore, the CO2 adsorption mechanism of activated carbon regulated by organic amines is greatly related to the type and structure of the carrier. Different carrier structures have different adsorption mechanisms.
由图10可知，掺氮后的化工污泥基活性炭的吸附等温线呈现I型等温线，随着压力的增加，活性炭对CO2的吸附量迅速增加，而后达到一个稳定值，活性炭样品中有大量的微孔结构。同时，通过比较可以发现，有机胺改性后的活性炭的CO2吸附量明显高于原始活性炭，这是由于原始活性炭内部孔隙结构发达，主要依靠与CO2之间较弱的引力实现物理吸附过程，此过程吸附效率低且对目标气体混合物无靶向性。经过有机胺改性剂对活性炭改性，所得的样品引入了大量N原子并与活性炭上本就存在的基团结合形成碱性官能团，增加活性炭表面粒子与CO2的吸附位点，使其饱和吸附量大大增加。其具体机理为有机胺调控的活性炭中有附着在其孔道表面的不饱和氮原子，氮原子在与CO2接触时会发生反应，生成氨基甲酸酯、碳酸盐、碳酸氢盐，从而提高CO2吸附量和吸附速率。由此可见，在活性炭载体上用有机胺修饰，增加活性炭表面的碱性官能团，能实现物理与化学的综合吸附过程，从而有效提高化工污泥基活性炭对CO2的吸附性能。It can be seen from Figure 10 that the adsorption isotherm of chemical sludge-based activated carbon after nitrogen doping presents a type I isotherm. As the pressure increases, the adsorption capacity of CO2 by activated carbon increases rapidly, and then reaches a stable value. There are A large number of microporous structures. At the same time, it can be found through comparison that the CO2 adsorption capacity of the organic amine-modified activated carbon is significantly higher than that of the original activated carbon. This is due to the well-developed internal pore structure of the original activated carbon, which mainly relies on the weak attraction with CO2 to achieve the physical adsorption process. , this process has low adsorption efficiency and is not targeted to the target gas mixture. After modifying the activated carbon with an organic amine modifier, the resulting sample introduces a large number of N atoms and combines with the existing groups on the activated carbon to form basic functional groups, which increases the adsorption sites of activated carbon surface particles and CO2 , making it saturated. The adsorption capacity is greatly increased. The specific mechanism is that the activated carbon regulated by organic amines has unsaturated nitrogen atoms attached to the surface of its pores. The nitrogen atoms will react when in contact with CO2 to generate carbamates, carbonates, and bicarbonates, thereby improving CO2 adsorption capacity and adsorption rate. It can be seen that modifying the activated carbon carrier with organic amines and increasing the basic functional groups on the surface of the activated carbon can achieve a comprehensive physical and chemical adsorption process, thereby effectively improving the adsorption performance of chemical sludge-based activated carbon forCO2 .
实施例1制备的化工污泥基活性炭(原始活性炭)和氮掺杂化工污泥基活性炭(乙二胺)以及实施例4制备的氮掺杂化工污泥基活性炭(三聚氰胺)的CO2吸附等温线见图11。CO2 adsorption isotherms of chemical sludge-based activated carbon (original activated carbon) and nitrogen-doped chemical sludge-based activated carbon (ethylenediamine) prepared in Example 1 and nitrogen-doped chemical sludge-based activated carbon (melamine) prepared in Example 4 See Figure 11 for the line.
由图11可以看出，不同种类的有机胺活性炭样品表现出相同的吸附过程，在相对压力为0.4左右时达到吸附饱和点，同属于I类吸附等温线。但在相同的相对压力下，不同有机胺调控的活性炭对CO2的吸附量并不相同。这是由于不同种有机胺的分子结构式不同，其烃基数量也不同，在一定程度上会影响有机胺中的氨基在活性炭表面的负载位点的数量，从而影响了活性炭的吸附性能。从图中可以看出，有机胺分子链的长度越长，活性炭对CO2的吸附量越多。其中，原始活性炭的饱和吸附量为10cm3左右，乙二胺改性活性炭饱和吸附量为30cm3左右，三聚氰胺改性活性炭的饱和吸附量可达60cm3。为比较不同种有机胺对化工污泥基活性炭吸附CO2性能的影响，表2列出了图中几种有机胺的相关信息。由表2可知，三聚氰胺的氮含量最高，且其化学结构式较复杂，通过对比不同种有机胺调控的活性炭样品对CO2的吸附量可知，在相同有机胺负载量的情况下，三聚氰胺相较于其他有机胺吸附效率更高。原因可能是：有机胺改性剂的氮含量和分子链长度有差异，三聚氰胺的分子量高于乙二胺(EDA)和二乙烯三胺(DETA)，在活性炭载体上，三聚氰胺不仅可以使N原子附着在活性炭表面，同时可以拓宽活性炭的孔隙结构，增大比表面积，开发出了大孔容的微孔结构，提高CO2吸附性能。虽然N,N-二甲基双丙烯酰胺的分子量大于三聚氰胺，但是其氮含量较低，在相同的负载量条件下，N,N-二甲基双丙烯酰胺仅能提供少量的氨基数量，对于活性炭载体表面的碱性官能团数量减少，CO2的吸附位点减少，因此吸附效率降低。As can be seen from Figure 11, different types of organic amine activated carbon samples show the same adsorption process, reaching the adsorption saturation point when the relative pressure is about 0.4, and they all belong to type I adsorption isotherms. However, under the same relative pressure, the adsorption capacity of activated carbon controlled by different organic amines on CO2 is not the same. This is because different organic amines have different molecular structural formulas and different numbers of hydrocarbon groups, which to a certain extent will affect the number of loading sites of the amino groups in the organic amines on the surface of activated carbon, thus affecting the adsorption performance of activated carbon. It can be seen from the figure that the longer the length of the organic amine molecular chain, the moreCO2 adsorbed by activated carbon. Among them, the saturated adsorption capacity of original activated carbon is about 10cm3 , the saturated adsorption capacity of ethylenediamine-modified activated carbon is about 30cm3 , and the saturated adsorption capacity of melamine-modified activated carbon can reach 60cm3 . In order to compare the effects of different organic amines on theCO2 adsorption performance of chemical sludge-based activated carbon, Table 2 lists the relevant information of several organic amines in the figure. As can be seen from Table 2, melamine has the highest nitrogen content and its chemical structural formula is relatively complex. By comparing the adsorption capacity of activated carbon samples regulated by different organic amines for CO2 , it can be seen that under the same organic amine loading, melamine is compared with Other organic amines adsorb more efficiently. The reason may be: the nitrogen content and molecular chain length of the organic amine modifier are different. The molecular weight of melamine is higher than that of ethylenediamine (EDA) and diethylenetriamine (DETA). On the activated carbon carrier, melamine can not only make N atoms Attached to the surface of activated carbon, it can also broaden the pore structure of activated carbon, increase the specific surface area, develop a microporous structure with large pore volume, and improve the CO2 adsorption performance. Although the molecular weight of N,N-dimethylbisacrylamide is larger than that of melamine, its nitrogen content is lower. Under the same loading conditions, N,N-dimethylbisacrylamide can only provide a small amount of amino groups. The number of basic functional groups on the surface of the activated carbon carrier is reduced, and the adsorption sites forCO2 are reduced, so the adsorption efficiency is reduced.
同时，有机胺负载的方法也对活性炭吸附性能有很大影响，物理浸渍法负载的活性炭对CO2的吸附量稍好于现有技术中的化学嫁接法，这是由于物理浸渍法是通过范德华力来实现有机胺与活性炭的结合，氨基材料负载在活性炭的孔道内壁，其负载位点多，制备效率高。由于化工污泥中成分比较复杂，官能团种类繁多，与氨基产生化学反应的官能团比较少，嫁接率较低，从而导致引入的碱性官能团数量少，最终制得的活性炭CO2吸附性能低。At the same time, the method of loading organic amines also has a great impact on the adsorption performance of activated carbon. The adsorption capacity of activated carbon supported by the physical impregnation method for CO2 is slightly better than the chemical grafting method in the prior art. This is because the physical impregnation method uses van der Waals. To realize the combination of organic amine and activated carbon, the amino material is loaded on the inner wall of the pore channel of the activated carbon. It has many loading sites and high preparation efficiency. Due to the complex composition of chemical sludge and the wide variety of functional groups, there are relatively few functional groups that react chemically with amino groups, and the grafting rate is low. This results in a small number of basic functional groups introduced, and the final activated carbon has low CO2 adsorption performance.
实施例4(20％)、实施例5(10％)和实施例6(30％)制备的氮掺杂化工污泥基活性炭的CO2吸附等温线见图12，最大吸附量对比图见图13。TheCO2 adsorption isotherms of the nitrogen-doped chemical sludge-based activated carbon prepared in Example 4 (20%), Example 5 (10%) and Example 6 (30%) are shown in Figure 12, and the maximum adsorption capacity comparison chart is shown in Figure 12 13.
由图12和图13可以看出，CO2在化工污泥基活性炭上的穿透时间较短，即在较短时间内可达到吸附平衡状态，这表明经有机胺调控后的活性炭主要通过活性炭表面负载的碱性官能团与，CO2发生化学反应而起的吸附作用，活性炭本身对，CO2的吸附量较小。但同时经过多次的吸附-脱附实验可以看出，附着在活性炭表面的氨基会发生脱离流失现象，导致后期吸附仍以活性炭物理吸附为主，所以其选择性低，吸附量下降。由图可知，活性炭对，CO2的吸附量随着三聚氰胺负载量的增加而逐渐增加，当三聚氰胺的负载量达到20％时，活性炭具有最高的吸附量，此时活性炭对CO2的吸附量为60cm3/g。当增加有机胺的负载量达到30％时，活性炭对CO2的吸附量减少至39cm3/g。其原因是适当增加有机胺在活性炭上的负载量，可以在一定程度上拓宽孔道，增大活性炭比表面积，增加N原子在活性炭孔道内的负载位点，从而可以增加CO2的吸附位点，提高饱和吸附量。但是如果有机胺浓度过高，会使得活性炭表面形成一层有机胺膜，增加了CO2向活性炭孔道内部扩散的阻力，化学吸附速率减慢，附着在活性炭表面的氨基利用率下降，最终导致活性炭吸附效率下降。另外，当有机胺负载量超过40％时，大量有粘度的有机胺溶液包裹活性炭表面，内壁孔隙由于大量的氨基及其他官能团存在，造成孔道堵塞，活性炭的孔隙结构一定程度发生了改变，导致吸附剂制备过程难度增加，且对CO2的吸附效率大大降低。It can be seen from Figure 12 and Figure 13 that the penetration time ofCO2 on chemical sludge-based activated carbon is short, that is, the adsorption equilibrium state can be reached in a relatively short time, which indicates that the activated carbon regulated by organic amines mainly passes through the activated carbon. The alkaline functional groups loaded on the surface chemically react with CO2 to form an adsorption effect. The activated carbon itself has a small adsorption capacity for CO2 . However, after many adsorption-desorption experiments, it can be seen that the amino groups attached to the surface of activated carbon will detach and lose. As a result, the later adsorption is still dominated by physical adsorption of activated carbon, so its selectivity is low and the adsorption capacity decreases. It can be seen from the figure that the adsorption capacity of CO2 by activated carbon gradually increases with the increase of melamine loading. When the melamine loading reaches 20%, activated carbon has the highest adsorption capacity. At this time, the adsorption capacity of CO2 by activated carbon is 60cm3 /g. When the loading of organic amines is increased to 30%, the adsorption capacity ofCO2 by activated carbon decreases to39cm3 /g. The reason is that appropriately increasing the loading amount of organic amines on activated carbon can broaden the pore channels to a certain extent, increase the specific surface area of activated carbon, and increase the loading sites of N atoms in the activated carbon pore channels, thereby increasing the adsorption sites for CO2 . Increase the saturated adsorption capacity. However, if the concentration of organic amines is too high, an organic amine film will be formed on the surface of the activated carbon, which increases the resistance ofCO2 to diffuse into the activated carbon pores, slows down the chemical adsorption rate, and decreases the utilization rate of the amino groups attached to the surface of the activated carbon, ultimately resulting in the loss of activated carbon. Adsorption efficiency decreases. In addition, when the organic amine loading exceeds 40%, a large amount of viscous organic amine solution wraps the surface of the activated carbon. Due to the presence of a large number of amino groups and other functional groups in the inner wall pores, the pores are blocked, and the pore structure of the activated carbon is changed to a certain extent, leading to adsorption The preparation process of the agent becomes more difficult, and the adsorption efficiency of CO2 is greatly reduced.
以上，仅为本申请较佳的具体实施方式，但本申请的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本申请的保护范围之内。因此，本申请的保护范围应该以权利要求的保护范围为准。The above are only preferred specific implementations of the present application, but the protection scope of the present application is not limited thereto. Any person familiar with the technical field can easily think of changes or substitutions within the technical scope disclosed in the present application. All are covered by the protection scope of this application. Therefore, the protection scope of this application should be subject to the protection scope of the claims.
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