技术领域technical field
本发明属于工业废水处理技术领域，具体涉及一种磁性活性炭纤维的制备方法及应用。The invention belongs to the technical field of industrial wastewater treatment, and in particular relates to a preparation method and application of magnetic activated carbon fibers.
背景技术Background technique
随着工业的快速发展，工业废水及人类生活污水的种类及数量快速增长。同时对水体污染也日益严重，其主要特点表现为排放量较大、组成复杂和污染严重，因此废水处理成为我国需要解决的问题之一。除此之外，工业废水中含有大量的对水体及人体有毒有害的污染物，若不经过处理直接排放，不仅会破坏水体生态环境，而且影响人类健康和安全。因此，关于工业废水的有效治理方法的研究已经受到人们的高度重视。目前，处理工业废水常用的方法主要有预处理、生物处理法、电凝聚法、光催化降解法及吸附法等。其中吸附法因能耗低、工艺简单、吸附效率高、处理量大、不会造成二次污染等特点而成为工业废水净化处理的较理想方法。活性炭纤维虽在污水处理中得到应用，但目前使用中存在颗粒过小的活性炭会通过筛孔流失的问题。With the rapid development of industry, the types and quantities of industrial wastewater and human domestic sewage are increasing rapidly. At the same time, the pollution of water bodies is also becoming more and more serious. Its main characteristics are large discharge, complex composition and serious pollution. Therefore, wastewater treatment has become one of the problems that need to be solved in our country. In addition, industrial wastewater contains a large amount of toxic and harmful pollutants to the water body and human body. If it is discharged directly without treatment, it will not only damage the ecological environment of the water body, but also affect human health and safety. Therefore, the research on effective treatment methods of industrial wastewater has been highly valued by people. At present, the commonly used methods for treating industrial wastewater mainly include pretreatment, biological treatment, electrocoagulation, photocatalytic degradation, and adsorption. Among them, the adsorption method has become an ideal method for industrial wastewater purification due to its low energy consumption, simple process, high adsorption efficiency, large treatment capacity, and no secondary pollution. Although activated carbon fibers are used in sewage treatment, there is a problem that activated carbon with too small particles will be lost through the sieve holes in current use.
从液相介质中对活性炭纤维进行回收，通常采用过滤与分离等传统方法，但这些方法经常会造成筛网堵塞或活性炭纤维流失，因此如何有效地回收活性炭纤维成为活性炭纤维应用领域需要解决的问题。活性炭纤维本身不具有磁性而且回收较困难,需要将磁性介质引入活性炭纤维，才能进行磁液分离。因此，磁性活性炭纤维的研制成为国内外研究的热点，目前应用最多的有污水处理和黄金回收以及废水处理等领域。The recovery of activated carbon fibers from liquid media usually adopts traditional methods such as filtration and separation, but these methods often cause screen blockage or loss of activated carbon fibers. Therefore, how to effectively recover activated carbon fibers has become a problem to be solved in the application field of activated carbon fibers. . Activated carbon fiber itself is not magnetic and difficult to recycle. It is necessary to introduce magnetic media into activated carbon fiber to perform magnetic liquid separation. Therefore, the research and development of magnetic activated carbon fibers has become a research hotspot at home and abroad, and the most widely used fields are sewage treatment, gold recovery, and wastewater treatment.
然而截至目前，尚未发现利用废旧有机棉制备磁性活性炭纤维的相关技术见诸报道。However, up to now, no related technology of using waste organic cotton to prepare magnetic activated carbon fibers has been reported.
发明内容Contents of the invention
本发明所要解决的技术问题在于针对上述现有技术的不足，提供一种磁性活性炭纤维的制备方法及应用。该方法采用废旧有机棉为原料，通过碳化和活化处理获得活性炭纤维，然后采用化学沉淀法制备磁性活性炭纤维，并将其用于染料废水中甲基橙的吸附，吸附效果好，大大节约了污水处理的成本。The technical problem to be solved by the present invention is to provide a preparation method and application of magnetic activated carbon fibers for the above-mentioned deficiencies in the prior art. The method uses waste organic cotton as raw material, obtains activated carbon fiber through carbonization and activation treatment, and then prepares magnetic activated carbon fiber by chemical precipitation method, and uses it for the adsorption of methyl orange in dye wastewater, the adsorption effect is good, and the sewage is greatly saved processing costs.
为解决上述问题，本发明采用的技术方案是：In order to solve the above problems, the technical solution adopted in the present invention is:
一种磁性活性炭纤维的制备方法，包括以下步骤：A preparation method of magnetic activated carbon fiber, comprising the following steps:
1)将有机棉蒸馏水洗后，自然干燥至恒重，再用丙酮浸渍以脱油除水；用蒸馏水洗净，再用氯化铵溶液浸渍，浸渍完成后烘干备用；1) After washing the organic cotton with distilled water, dry it naturally to constant weight, then impregnate it with acetone to remove oil and water; wash it with distilled water, then impregnate it with ammonium chloride solution, and dry it for later use after impregnation;
2)对烘干后的有机棉升温至650℃～700℃，进行炭化反应；在升温以及炭化过程中，通入N2保护；再以二氧化碳作为活化剂，在800℃～1000℃进行活化反应，制得活性炭纤维；2) Raise the temperature of the dried organic cotton to 650°C-700°C for carbonization reaction; during the heating and carbonization process, pass throughN2 for protection; then use carbon dioxide as an activator to carry out the activation reaction at 800°C-1000°C , to prepare activated carbon fibers;
3)取FeCl3·6H2O及FeCl2·4H2O溶解于水中，加入制得的活性炭纤维，活性炭纤维与溶液的固液比为10～15g/L；使之充分混合均匀，在70℃～90℃的超声波场中，缓慢逐滴加入氢氧化钠水溶液作为沉淀剂，进行化学共沉淀反应，反应后静置沉淀，移去上清液，将剩余悬浊液烘干，再反复冲洗至上清液呈中性，磁力回收烘干后制得的磁性活性碳纤维。3) Dissolve FeCl3 6H2 O and FeCl2 4H2 O in water, add the prepared activated carbon fiber, the solid-liquid ratio of activated carbon fiber to solution is 10-15g/L; In the ultrasonic field at ℃ ~ 90 ℃, slowly add aqueous sodium hydroxide solution drop by drop as a precipitating agent, carry out chemical co-precipitation reaction, after the reaction, let it stand for precipitation, remove the supernatant, dry the remaining suspension, and then rinse repeatedly Until the supernatant is neutral, the magnetic activated carbon fibers obtained after magnetic recovery and drying are recovered.
步骤1)中，氯化铵溶液的质量分数为10％，浸渍时间为3h～4h。In step 1), the mass fraction of the ammonium chloride solution is 10%, and the soaking time is 3h-4h.
步骤2)中，炭化反应升温速率为5-10℃/min，恒温后反应时间为50min～60min。In step 2), the heating rate of the carbonization reaction is 5-10°C/min, and the reaction time after constant temperature is 50min-60min.
步骤2)中，N2的通入流量为200mL/min～250mL/min。In step 2), the flow rate of N2 is 200mL/min-250mL/min.
步骤2)中，二氧化碳的通入流量为200mL/min～250mL/min；活化反应时间为20min～80min。In step 2), the flow rate of carbon dioxide is 200mL/min-250mL/min; the activation reaction time is 20min-80min.
步骤3)中，化学共沉淀反应时间为3h～4h。In step 3), the chemical co-precipitation reaction time is 3h-4h.
步骤3)中，FeCl3·6H2O及FeCl2·4H2O的加入量为：每升蒸馏水加入(18.75～31.25)g FeCl2·4H2O、(56.25～68.75)g FeCl3·6H2O。In step 3), the amount of FeCl3 6H2 O and FeCl2 4H2 O added is: (18.75-31.25) g FeCl2 4H2 O, (56.25-68.75) g FeCl3 6H per liter of distilled water2 O.
步骤3)中，氢氧化钠水溶液的浓度为5.0mol/L。In step 3), the concentration of the aqueous sodium hydroxide solution is 5.0mol/L.
磁性活性炭纤维在吸附染料废水中的应用。具体用于吸附染料废水中甲基橙，吸附甲基橙后通过外加磁场进行诱导分离。Application of magnetic activated carbon fiber in adsorption of dye wastewater. It is specifically used for the adsorption of methyl orange in dye wastewater, and after the adsorption of methyl orange, it is induced and separated by an external magnetic field.
本发明与现有技术相比具有以下优点：Compared with the prior art, the present invention has the following advantages:
本发明的方法所用活性炭纤维是由废旧有机棉在高温下碳化和活化所得，采用丙酮浸渍以脱油除水，再以氯化铵溶液浸渍预处理；高温下碳化活化，以二氧化碳作为活化剂，制得活性炭纤维，然后在超声波场中以化学沉淀法制备磁性活性炭纤维，并利用其吸附染料废水中的甲基橙，磁性活性炭纤维吸附甲基橙后可通过外加磁场进行诱导分离。磁性分离与传统的离心或过滤分离相比，操作更简单，效果更好，而且大大节约了污水处理的成本。The activated carbon fibers used in the method of the present invention are obtained by carbonizing and activating waste organic cotton at high temperature, impregnated with acetone to remove oil and water, and then impregnated with ammonium chloride solution for pretreatment; carbonized and activated at high temperature, using carbon dioxide as an activator, The activated carbon fiber is prepared, and then the magnetic activated carbon fiber is prepared by chemical precipitation in the ultrasonic field, and the methyl orange in the dye wastewater is absorbed by the magnetic activated carbon fiber. After the magnetic activated carbon fiber absorbs the methyl orange, it can be induced and separated by an external magnetic field. Compared with traditional centrifugation or filtration separation, magnetic separation is simpler to operate, better in effect, and greatly saves the cost of sewage treatment.
最终研究发现，此方法采用废旧有机棉为原料通过碳化和活化处理获得活性碳纤维，再通过化学沉淀法在超声场中制得磁性活性炭纤维，成功制得了磁性活性炭纤维。磁性活性炭纤维吸附效果好，而且在外加磁场中很容易回收，大大节约了污水处理的成本，降低了活性炭纤维的制备成本。吸附染料废水甲基橙吸附率达到96％，吸附性能良好。The final study found that this method uses waste organic cotton as raw material to obtain activated carbon fibers through carbonization and activation treatment, and then obtains magnetic activated carbon fibers in an ultrasonic field by chemical precipitation, and successfully produces magnetic activated carbon fibers. The magnetic activated carbon fiber has a good adsorption effect, and is easy to recover in an external magnetic field, which greatly saves the cost of sewage treatment and reduces the preparation cost of activated carbon fiber. The methyl orange adsorption rate of adsorption dye wastewater reaches 96%, and the adsorption performance is good.
附图说明Description of drawings
图1磁性活性炭纤维的XRD图；The XRD pattern of Fig. 1 magnetic activated carbon fiber;
图2磁性活性炭纤维的SEM图；Figure 2 SEM image of magnetic activated carbon fiber;
图3磁性活性炭纤维的红外光谱；The infrared spectrum of Fig. 3 magnetic activated carbon fiber;
图4为25℃时纯铁氧化物和磁性活性炭纤维的磁滞回线。Figure 4 is the hysteresis loop of pure iron oxide and magnetic activated carbon fiber at 25 °C.
具体实施方式detailed description
本发明的一种磁性活性炭纤维的制备方法，包括以下步骤：A kind of preparation method of magnetic activated carbon fiber of the present invention, comprises the following steps:
步骤一、将废旧有机棉蒸馏水洗后，自然干燥至恒重，再用丙酮浸渍以脱油除水，3h～4h后，用蒸馏水洗净，再用质量分数为10％的氯化铵溶液浸渍3h～4h，烘干备用；Step 1. After washing the waste organic cotton with distilled water, dry it naturally to constant weight, then impregnate it with acetone to remove oil and water. After 3h to 4h, wash it with distilled water, and then impregnate it with 10% ammonium chloride solution 3h～4h, dry for later use;
步骤二、废旧有机棉碳化：升温速率控制在5-10℃/min，在温度达到650℃～700℃后，炭化时间为50min～60min。在升温以及炭化过程中，一直通有惰性气体N2保护。N2的流量用阀门和气体流量计控制在200mL/min～250mL/min；选择二氧化碳作为活化剂，活化温度为800℃～1000℃，活化时间为20min～80min。用二氧化碳进行活化时，其流量用阀门和气体流量计控制在200mL/min～250mL/min。Step 2. Carbonization of waste organic cotton: the heating rate is controlled at 5-10°C/min, and after the temperature reaches 650°C-700°C, the carbonization time is 50min-60min. During the temperature rise and carbonization process, the inert gasN2 protection is always passed through. The flow ofN2 is controlled at 200mL/min to 250mL/min with a valve and a gas flow meter; carbon dioxide is selected as the activator, the activation temperature is 800°C to 1000°C, and the activation time is 20min to 80min. When carbon dioxide is used for activation, its flow rate is controlled at 200mL/min to 250mL/min with a valve and a gas flow meter.
步骤三、采用化学共沉淀法制备磁性活性炭纤维：分别取FeCl3·6H2O及FeCl2·4H2O溶解于烧杯中，每升蒸馏水加入(18.75～31.25)g FeCl2·4H2O、(56.25～68.75)gFeCl3·6H2O；加入活性炭纤维，活性炭纤维与溶液的固液比为10～15g/L，使之充分混合均匀，在70℃～90℃温度下，超声波分散搅拌的同时，缓慢逐滴加入40mL～60mL、5.0mol/L的氢氧化钠水溶液作为沉淀剂，反应3h～4h后将烧杯静置沉淀，移去上清液，将剩余悬浊液放入烘箱烘干，用超纯水将所得材料反复冲洗至上清液呈中性，磁力回收烘干后移入样品瓶中密封保存，即为制得的磁性活性碳纤维。Step 3. Prepare magnetic activated carbon fiber by chemical co-precipitation method: Dissolve FeCl3 6H2 O and FeCl2 4H2 O in a beaker, add (18.75-31.25) g FeCl2 4H2 O, (56.25～68.75)gFeCl3 6H2 O; add activated carbon fiber, the solid-liquid ratio of activated carbon fiber to the solution is 10～15g/L, make it fully mixed evenly, at 70℃～90℃, ultrasonic dispersion and stirring At the same time, slowly add 40mL ~ 60mL, 5.0mol/L sodium hydroxide aqueous solution drop by drop as a precipitant, react for 3h ~ 4h, let the beaker stand for precipitation, remove the supernatant, and put the remaining suspension in an oven for drying , the obtained material was washed repeatedly with ultrapure water until the supernatant was neutral, and after magnetic recovery and drying, it was transferred into a sample bottle and sealed for storage, which was the prepared magnetic activated carbon fiber.
下面结合实施例对本发明作进一步详细说明。The present invention is described in further detail below in conjunction with embodiment.
实施例1Example 1
本实施例利用废旧有机棉制备磁性活性炭纤维的方法包括以下步骤：The method that present embodiment utilizes waste and old organic cotton to prepare magnetic activated carbon fiber comprises the following steps:
步骤一、将废旧有机棉蒸馏水洗后，自然干燥至恒重，再用丙酮浸渍以脱油除水，3h后，用蒸馏水洗净，再用质量分数为10％的氯化铵溶液浸渍3h，烘干备用；Step 1. Wash the waste organic cotton with distilled water, dry it naturally to constant weight, then soak it with acetone to remove oil and water, wash it with distilled water after 3 hours, and then soak it with 10% ammonium chloride solution for 3 hours. drying spare;
步骤二、废旧有机棉碳化：升温速率控制在5-10℃/min，在温度达到650℃后，炭化时间为60min。在升温以及炭化过程中，一直通有惰性气体N2保护。N2的流量用阀门和气体流量计控制在250mL/min；选择二氧化碳作为活化剂，活化温度为800℃，活化时间为40min。用二氧化碳进行活化时，其流量用阀门和气体流量计控制在250mL/min。Step 2. Carbonization of waste organic cotton: the heating rate is controlled at 5-10°C/min, and the carbonization time is 60 minutes after the temperature reaches 650°C. During the temperature rise and carbonization process, the inert gasN2 protection is always passed through. The flow of N2 is controlled at 250mL/min with a valve and a gas flow meter; carbon dioxide is selected as the activator, the activation temperature is 800°C, and the activation time is 40min. When carbon dioxide is used for activation, its flow is controlled at 250mL/min with a valve and a gas flow meter.
步骤三、采用化学共沉淀法制备磁性活性炭纤维：分别取FeCl3·6H2O及FeCl2·4H2O溶解于烧杯中，每升蒸馏水加入18.75g FeCl2·4H2O、68.75g FeCl3·6H2O；加入1.50g活性炭纤维，使之充分混合均匀，在70℃温度下，超声波分散搅拌的同时，缓慢逐滴加入40mL、5.0mol/L的氢氧化钠水溶液作为沉淀剂，反应3h后将烧杯静置沉淀，移去上清液，将剩余悬浊液放入烘箱烘干，用超纯水将所得材料反复冲洗至上清液呈中性，磁力回收烘干后移入样品瓶中密封保存，即为制得的磁性活性碳纤维。Step 3. Prepare magnetic activated carbon fiber by chemical co-precipitation method: Dissolve FeCl3 6H2 O and FeCl2 4H2 O in a beaker, add 18.75g FeCl2 4H2 O and 68.75g FeCl3 per liter of distilled water 6H2 O; add 1.50g of activated carbon fiber, make it fully mixed, and at 70℃, while ultrasonically dispersing and stirring, slowly add 40mL, 5.0mol/L sodium hydroxide aqueous solution as a precipitant, and react for 3h Finally, let the beaker stand for precipitation, remove the supernatant, put the remaining suspension in an oven for drying, and repeatedly rinse the obtained material with ultrapure water until the supernatant is neutral, recover and dry it by magnetic force, and then transfer it to a sample bottle and seal it. Preservation is the prepared magnetic activated carbon fiber.
以分光光度法测得磁性活性炭纤维吸附染料废水中甲基橙的吸附率为96.3％。The adsorption rate of methyl orange in dye wastewater adsorbed by magnetic activated carbon fiber was 96.3% measured by spectrophotometry.
实施例2Example 2
本实施例利用废旧有机棉制备磁性活性炭纤维的方法包括以下步骤：The method that present embodiment utilizes waste and old organic cotton to prepare magnetic activated carbon fiber comprises the following steps:
步骤一、将废旧有机棉蒸馏水洗后，自然干燥至恒重，再用丙酮浸渍以脱油除水，4h后，用蒸馏水洗净，再用质量分数为10％的氯化铵溶液浸渍4h，烘干备用；Step 1. Wash the waste organic cotton with distilled water, dry it naturally to constant weight, then soak it with acetone to remove oil and water, wash it with distilled water after 4 hours, and then soak it with 10% ammonium chloride solution for 4 hours. drying spare;
步骤二、废旧有机棉碳化：升温速率控制在10℃/min，在温度达到650℃后，炭化时间为50min。在升温以及炭化过程中，一直通有惰性气体N2保护。N2的流量用阀门和气体流量计控制在250mL/min；选择二氧化碳作为活化剂，活化温度为800℃，活化时间为80min。用二氧化碳进行活化时，其流量用阀门和气体流量计控制在250mL/min。Step 2. Carbonization of waste organic cotton: the heating rate is controlled at 10°C/min, and the carbonization time is 50min after the temperature reaches 650°C. During the temperature rise and carbonization process, the inert gasN2 protection is always passed through. The flow of N2 is controlled at 250mL/min with a valve and a gas flow meter; carbon dioxide is selected as the activator, the activation temperature is 800°C, and the activation time is 80min. When carbon dioxide is used for activation, its flow is controlled at 250mL/min with a valve and a gas flow meter.
步骤三、采用化学共沉淀法制备磁性活性炭纤维：分别取FeCl3·6H2O及FeCl2·4H2O溶解于烧杯中，每升蒸馏水加入20.00g FeCl2·4H2O、56.25g FeCl3·6H2O；加入2.00g活性炭纤维，使之充分混合均匀，在90℃温度下，超声波分散搅拌的同时，缓慢逐滴加入60mL、5.0mol/L的氢氧化钠水溶液作为沉淀剂，反应4h后将烧杯静置沉淀，移去上清液，将剩余悬浊液放入烘箱烘干，用超纯水将所得材料反复冲洗至上清液呈中性，磁力回收烘干后移入样品瓶中密封保存，即为制得的磁性活性碳纤维。Step 3. Prepare magnetic activated carbon fiber by chemical co-precipitation method: Dissolve FeCl3 6H2 O and FeCl2 4H2 O in a beaker, add 20.00g FeCl2 4H2 O and 56.25g FeCl3 per liter of distilled water 6H2 O; add 2.00g of activated carbon fiber, make it fully mixed, and at 90°C, while ultrasonically dispersing and stirring, slowly add 60mL, 5.0mol/L sodium hydroxide aqueous solution as a precipitating agent, and react for 4h Finally, let the beaker stand for precipitation, remove the supernatant, put the remaining suspension in an oven for drying, and repeatedly rinse the obtained material with ultrapure water until the supernatant is neutral, recover and dry it by magnetic force, and then transfer it to a sample bottle and seal it. Preservation is the prepared magnetic activated carbon fiber.
以分光光度法测得磁性活性炭纤维吸附染料废水中甲基橙的吸附率为96.7％。The adsorption rate of methyl orange in dye wastewater adsorbed by magnetic activated carbon fiber was 96.7% measured by spectrophotometry.
实施例3Example 3
本实施例利用废旧有机棉制备磁性活性炭纤维的方法包括以下步骤：The method that present embodiment utilizes waste and old organic cotton to prepare magnetic activated carbon fiber comprises the following steps:
步骤一、将废旧有机棉蒸馏水洗后，自然干燥至恒重，再用丙酮浸渍以脱油除水，3h后，用蒸馏水洗净，再用质量分数为10％的氯化铵溶液浸渍4h，烘干备用；Step 1. Wash the waste organic cotton with distilled water, dry it naturally to constant weight, then soak it with acetone to remove oil and water. After 3 hours, wash it with distilled water, and then soak it with 10% ammonium chloride solution for 4 hours. drying spare;
步骤二、废旧有机棉碳化：升温速率控制在10℃/min，在温度达到650℃后，炭化时间为50min。在升温以及炭化过程中，一直通有惰性气体N2保护。N2的流量用阀门和气体流量计控制在250mL/min；选择二氧化碳作为活化剂，活化温度为800℃，活化时间为60min。用二氧化碳进行活化时，其流量用阀门和气体流量计控制在250mL/min。Step 2. Carbonization of waste organic cotton: the heating rate is controlled at 10°C/min, and the carbonization time is 50min after the temperature reaches 650°C. During the temperature rise and carbonization process, the inert gasN2 protection is always passed through. The flow of N2 is controlled at 250mL/min with a valve and a gas flow meter; carbon dioxide is selected as the activator, the activation temperature is 800°C, and the activation time is 60min. When carbon dioxide is used for activation, its flow is controlled at 250mL/min with a valve and a gas flow meter.
步骤三、采用化学共沉淀法制备磁性活性炭纤维：分别取FeCl3·6H2O及FeCl2·4H2O溶解于烧杯中，每升蒸馏水加入31.25g FeCl2·4H2O、60.00g FeCl3·6H2O；加入2.00g活性炭纤维，使之充分混合均匀，在80℃温度下，超声波分散搅拌的同时，缓慢逐滴加入50mL、5.0mol/L的氢氧化钠水溶液作为沉淀剂，反应4h后将烧杯静置沉淀，移去上清液，将剩余悬浊液放入烘箱烘干，用超纯水将所得材料反复冲洗至上清液呈中性，磁力回收烘干后移入样品瓶中密封保存，即为制得的磁性活性碳纤维。Step 3. Prepare magnetic activated carbon fiber by chemical co-precipitation method: Dissolve FeCl3 6H2 O and FeCl2 4H2 O in a beaker, add 31.25g FeCl2 4H2 O and 60.00g FeCl3 per liter of distilled water 6H2 O; add 2.00g of activated carbon fiber, make it fully mixed, at 80°C, while ultrasonically dispersing and stirring, slowly add 50mL, 5.0mol/L sodium hydroxide aqueous solution as a precipitant, and react for 4h Finally, let the beaker stand for precipitation, remove the supernatant, put the remaining suspension in an oven for drying, and repeatedly rinse the obtained material with ultrapure water until the supernatant is neutral, recover and dry it by magnetic force, and then transfer it to a sample bottle and seal it. Preservation is the prepared magnetic activated carbon fiber.
以分光光度法测得磁性活性炭纤维吸附染料废水中甲基橙的吸附率为97.2％。The adsorption rate of methyl orange in dye wastewater adsorbed by magnetic activated carbon fiber was 97.2% by spectrophotometry.
实施例4Example 4
本实施例利用废旧有机棉制备磁性活性炭纤维的方法包括以下步骤：步骤一、将废旧有机棉蒸馏水洗后，自然干燥至恒重，再用丙酮浸渍以脱油除水，3h后，用蒸馏水洗净，再用质量分数为10％的氯化铵溶液浸渍3h，烘干备用；In this embodiment, the method for preparing magnetic activated carbon fibers by using waste organic cotton includes the following steps: Step 1. After washing the waste organic cotton with distilled water, dry it naturally to constant weight, then soak it in acetone to remove oil and water, and after 3 hours, wash it with distilled water clean, and then soaked in ammonium chloride solution with a mass fraction of 10% for 3 hours, and dried for later use;
步骤二、废旧有机棉碳化：升温速率控制在10℃/min，在温度达到650℃后，炭化时间为50min。在升温以及炭化过程中，一直通有惰性气体N2保护。N2的流量用阀门和气体流量计控制在250mL/min；选择二氧化碳作为活化剂，活化温度为900℃，活化时间为70min。用二氧化碳进行活化时，其流量用阀门和气体流量计控制在250mL/min。Step 2. Carbonization of waste organic cotton: the heating rate is controlled at 10°C/min, and the carbonization time is 50min after the temperature reaches 650°C. During the temperature rise and carbonization process, the inert gasN2 protection is always passed through. The flow ofN2 is controlled at 250mL/min with a valve and a gas flow meter; carbon dioxide is selected as the activator, the activation temperature is 900°C, and the activation time is 70min. When carbon dioxide is used for activation, its flow is controlled at 250mL/min with a valve and a gas flow meter.
步骤三、采用化学共沉淀法制备磁性活性炭纤维：分别取FeCl3·6H2O及FeCl2·4H2O溶解于烧杯中，每升蒸馏水加入25.0g FeCl2·4H2O、62.5g FeCl3·6H2O；加入1.65g活性炭纤维，使之充分混合均匀，在80℃温度下，超声波分散搅拌的同时，缓慢逐滴加入60mL、5.0mol/L的氢氧化钠水溶液作为沉淀剂，反应3h后将烧杯静置沉淀，移去上清液，将剩余悬浊液放入烘箱烘干，用超纯水将所得材料反复冲洗至上清液呈中性，磁力回收烘干后移入样品瓶中密封保存，即为制得的磁性活性碳纤维。Step 3. Prepare magnetic activated carbon fiber by chemical co-precipitation method: Dissolve FeCl3 6H2 O and FeCl2 4H2 O in a beaker, add 25.0g FeCl2 4H2 O and 62.5g FeCl3 per liter of distilled water 6H2 O; add 1.65g of activated carbon fiber, make it fully mixed, and at 80°C, while ultrasonically dispersing and stirring, slowly add 60mL, 5.0mol/L sodium hydroxide aqueous solution as a precipitating agent, and react for 3h Finally, let the beaker stand for precipitation, remove the supernatant, put the remaining suspension in an oven for drying, and repeatedly rinse the obtained material with ultrapure water until the supernatant is neutral, recover and dry it by magnetic force, and then transfer it to a sample bottle and seal it. Preservation is the prepared magnetic activated carbon fiber.
以分光光度法测得磁性活性炭纤维吸附染料废水中甲基橙的吸附率为97.6％。The adsorption rate of methyl orange in dye wastewater adsorbed by magnetic activated carbon fiber was 97.6% measured by spectrophotometry.
下面对本发明的实施例制备的磁性活性炭纤维进行测试分析，分析如下：The magnetic activated carbon fiber prepared by the embodiment of the present invention is tested and analyzed below, and the analysis is as follows:
由图1可见，磁性活性炭纤维的XRD图，图中不仅有活性炭纤维的特征峰，也出现了铁氧化物(Fe3O4和γ-Fe2O3)的特征衍射峰，此即磁性活性炭纤维具有磁性的原因。但相比铁氧化物颗粒的衍射峰，磁性活性炭复合材料中铁氧化物和活性炭的衍射峰强度均有一定程度的减弱，这是由于单位质量的复合材料中铁氧化物和活性炭各自的含量减少所致，同时也说明了铁氧化物粒径较小。It can be seen from Figure 1 that in the XRD pattern of magnetic activated carbon fibers, not only the characteristic peaks of activated carbon fibers, but also the characteristic diffraction peaks of iron oxides (Fe3 O4 and γ-Fe2 O3 ), this is the magnetic activated carbon fiber. Fibers are magnetic. However, compared with the diffraction peaks of iron oxide particles, the intensity of the diffraction peaks of iron oxide and activated carbon in the magnetic activated carbon composite material weakens to a certain extent, which is due to the reduction of the respective contents of iron oxide and activated carbon in the composite material per unit mass. , which also shows that the iron oxide particle size is smaller.
如图2所示，磁性活性炭纤维的SEM图，可见磁性活性炭纤维的表面光滑，没有看见大的裂缝，这可能是活化时气体对微晶晶棱氧化刻蚀的不明显，说明微晶的尺寸小，这和XRD检测结果相吻合。纤维表面还可以看见一些白色的斑点，这可能是负载在上面的四氧化三铁。As shown in Figure 2, the SEM image of the magnetic activated carbon fiber shows that the surface of the magnetic activated carbon fiber is smooth and no large cracks are seen. This may be due to the inconspicuous oxidation and etching of the microcrystalline crystal ribs by the gas during activation, indicating that the size of the microcrystalline Small, which is consistent with the XRD detection results. Some white spots can also be seen on the surface of the fiber, which may be the ferric oxide loaded on it.
由图3可知，1257cm-1处的吸收峰归属为C-C结构吸收峰.在2720cm-1左右的微弱吸收峰是由C-H伸缩振动引起的，同时1466cm-1处的吸收峰为C-H的弯曲振动，说明产物表面残留有CH3或CH2，但吸收强度较弱。It can be seen from Figure 3 that the absorption peak at 1257cm-1 belongs to the absorption peak of the CC structure. The weak absorption peak at around 2720cm-1 is caused by the stretching vibration of CH, while the absorption peak at 1466cm-1 is the bending vibration of CH, It shows that CH3 or CH2 remains on the surface of the product, but the absorption intensity is weak.
由图4可见，磁化状态从出发随着磁场强度的增加，磁化强度慢慢增强，即沿线逐渐上升，直至与轴平行，此时外加磁场的最大强度为磁饱和强度，再逐渐减小外加磁场。磁性活性炭和铁氧化物均随着外加磁场强度的增加不断增大，磁化强度逐渐增强直至达到饱和磁化状态，当外加磁场达到±20000Oe时，化学沉淀法制备的铁氧化物的饱和磁化强度为72.06emu/g，而磁性炭的饱和磁化强度为22.34emu/g，活性炭和更小尺寸的磁性纳米粒子的存在导致了磁性活性炭的饱和磁化强度比铁氧化物的小。样品都有一定的剩磁和矫顽力，这是由于在制备过程中，磁性纳米颗粒部分团聚所致。但样品的剩磁和矫顽力均很小，在使用时也未发生磁聚集现象，这样的磁性质意味着在选择了适宜的外加磁场和磁场梯度时，磁性活性炭较易与水分离。It can be seen from Figure 4 that the magnetization state increases gradually with the increase of the magnetic field strength from the starting point, that is, it gradually increases along the line until it is parallel to the axis. . Magnetic activated carbon and iron oxide both increase with the increase of the applied magnetic field strength, and the magnetization gradually increases until reaching the saturation magnetization state. When the external magnetic field reaches ±20000Oe, the saturation magnetization of the iron oxide prepared by chemical precipitation method is 72.06 emu/g, while the saturation magnetization of magnetic carbon is 22.34 emu/g, the presence of activated carbon and magnetic nanoparticles of smaller size results in a smaller saturation magnetization of magnetic activated carbon than that of iron oxide. The samples all have certain remanence and coercive force, which is due to the partial agglomeration of magnetic nanoparticles during the preparation process. However, the remanence and coercive force of the sample are very small, and no magnetic aggregation phenomenon occurs during use. Such magnetic properties mean that when an appropriate external magnetic field and magnetic field gradient are selected, magnetic activated carbon is easier to separate from water.
以上所述，仅是本发明的较佳实施例，并非对本发明作任何限制。凡是根据发明技术实质对以上实施例所作的任何简单修改、变更以及等效变化，均仍属于本发明技术方案的保护范围内。The above descriptions are only preferred embodiments of the present invention, and do not limit the present invention in any way. All simple modifications, changes and equivalent changes made to the above embodiments according to the technical essence of the invention still belong to the protection scope of the technical solution of the invention.
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| CN201710642379.XACN107376838A (en) | 2017-07-31 | 2017-07-31 | A kind of preparation method and application of magnetic active carbon fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108865433A (en)* | 2018-05-29 | 2018-11-23 | 江苏大学 | A kind of discoloration method of propolis alcohol steep solution |
| CN110680807A (en)* | 2019-08-01 | 2020-01-14 | 广东健信制药股份有限公司 | Preparation method of propyl gallate for injection |
| CN111232975A (en)* | 2020-02-17 | 2020-06-05 | 西南大学 | Activated carbon material for super capacitor and preparation method and application thereof |
| CN112875699A (en)* | 2021-02-07 | 2021-06-01 | 西安科技大学 | Preparation method and application of special steel slag-based biomass activated carbon |
| CN113694886A (en)* | 2021-07-28 | 2021-11-26 | 广东建科创新技术研究院有限公司 | Magnetic adsorption material with Fenton oxidation catalysis function and preparation method and application thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101940910A (en)* | 2010-10-22 | 2011-01-12 | 福州大学 | Magnetic separation type composite adsorbing material and preparation method thereof |
| CN104047071A (en)* | 2014-07-07 | 2014-09-17 | 扬州大学 | Preparation method for magnetic active carbon fibers |
| CN106540656A (en)* | 2016-09-22 | 2017-03-29 | 华东交通大学 | A kind of preparation method of magnetic Fe3O4-based magnetic shell carbon novel adsorbent |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101940910A (en)* | 2010-10-22 | 2011-01-12 | 福州大学 | Magnetic separation type composite adsorbing material and preparation method thereof |
| CN104047071A (en)* | 2014-07-07 | 2014-09-17 | 扬州大学 | Preparation method for magnetic active carbon fibers |
| CN106540656A (en)* | 2016-09-22 | 2017-03-29 | 华东交通大学 | A kind of preparation method of magnetic Fe3O4-based magnetic shell carbon novel adsorbent |
| Title |
|---|
| 杨建利等: "废旧有机丝制备活性炭纤维的研究", 《煤炭转化》* |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108865433A (en)* | 2018-05-29 | 2018-11-23 | 江苏大学 | A kind of discoloration method of propolis alcohol steep solution |
| CN110680807A (en)* | 2019-08-01 | 2020-01-14 | 广东健信制药股份有限公司 | Preparation method of propyl gallate for injection |
| CN110680807B (en)* | 2019-08-01 | 2021-07-13 | 广东健信制药股份有限公司 | Preparation method of propyl gallate for injection |
| CN111232975A (en)* | 2020-02-17 | 2020-06-05 | 西南大学 | Activated carbon material for super capacitor and preparation method and application thereof |
| CN111232975B (en)* | 2020-02-17 | 2021-01-08 | 西南大学 | Activated carbon material for supercapacitor, preparation method and application thereof |
| CN112875699A (en)* | 2021-02-07 | 2021-06-01 | 西安科技大学 | Preparation method and application of special steel slag-based biomass activated carbon |
| CN113694886A (en)* | 2021-07-28 | 2021-11-26 | 广东建科创新技术研究院有限公司 | Magnetic adsorption material with Fenton oxidation catalysis function and preparation method and application thereof |
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