技术领域technical field
本发明属于吸附剂技术领域，具体涉及一种用絮凝所产絮体制备重金属离子吸附剂的方法。The invention belongs to the technical field of adsorbents, and in particular relates to a method for preparing a heavy metal ion adsorbent by using flocs produced by flocculation.
背景技术Background technique
纺织业、印刷等行业的印染废水是工业废水中的一个主要污染源。当染料废水进入水体后，会和水中的生物相互作用，水中溶解氧减少导致水中有机物开始发生厌氧分解，因此污染水体环境；并且染料分子本身也会悬浮在水中，从而使水体透光率下降，是生物活性降低，从而削弱了水体的自净能力，使水质持续恶化。随着对环保的要求越来越高，如何绿色高效的去除工业废水，成为了目前研究的热点问题。Printing and dyeing wastewater from textile, printing and other industries is a major source of pollution in industrial wastewater. When the dye wastewater enters the water body, it will interact with the organisms in the water. The reduction of dissolved oxygen in the water causes the anaerobic decomposition of the organic matter in the water, thus polluting the water environment; and the dye molecules themselves will also be suspended in the water, thereby reducing the light transmittance of the water body. , is the reduction of biological activity, thereby weakening the self-purification ability of the water body and making the water quality continue to deteriorate. With the increasing requirements for environmental protection, how to remove industrial wastewater in a green and efficient manner has become a hot issue in current research.
羧甲基壳聚糖是壳聚糖的衍生物，是由壳聚糖在碱性条件下与氯乙酸反应制得的产物。羧甲基壳聚糖分子中含有大量的氨基和羧基官能团，对一些难降解的偶氮染料具有良好的絮凝效果。羧甲基壳聚糖具有良好的可再生性、环境友好性和生物相溶性，用羧甲基壳聚糖絮凝剂去除废水中偶氮染料后形成絮体，对于这些絮凝后的产物通常有再生和丢弃两种处理方法。将这些絮凝后的产物直接丢弃会对环境造成二次污染，可以对这些絮体进行再生或二次利用来减少对环境的二次污染。目前，对絮凝剂处理废水中偶氮染料所得絮体改性后二次利用的研究较少。Carboxymethyl chitosan is a derivative of chitosan, which is obtained by reacting chitosan with chloroacetic acid under alkaline conditions. Carboxymethyl chitosan molecules contain a large number of amino and carboxyl functional groups, which have good flocculation effect on some refractory azo dyes. Carboxymethyl chitosan has good regenerability, environmental friendliness and biocompatibility. After removing azo dyes in wastewater with carboxymethyl chitosan flocculant, flocs are formed, and these flocculated products are usually regenerated. and discard two processing methods. Directly discarding these flocculated products will cause secondary pollution to the environment, and these flocs can be regenerated or reused to reduce secondary pollution to the environment. At present, there are few studies on the secondary utilization of flocs obtained from flocculant treatment of azo dyes in wastewater after modification.
中国专利申请号CN200910205648.1，发明名称为“一种吸附废水中重金属离子和染料的吸附剂及其制备方法”，公开了一种以竹炭为基质负载壳聚糖、以海藻酸钠为交联剂，水浴加热后洗涤干燥，得到复合型天然高分子吸附剂的方法。其具有制备工艺简便等优点，但其在制备过程中需要在105~110℃温度下活化120~240 min，高温可能会对壳聚糖絮凝剂的结构和性能产生影响，并且该吸附剂通过正、负电荷同时吸引呈负电性和金属离子和呈正电性的染料，对目标污染物的吸附效果没有最大化。Chinese Patent Application No. CN200910205648.1, the name of the invention is "A kind of adsorbent for adsorbing heavy metal ions and dyes in wastewater and its preparation method", which discloses a kind of chitosan loaded with bamboo charcoal as a matrix and sodium alginate as a cross-linking agent A method for obtaining a composite natural polymer adsorbent after heating in a water bath, washing and drying. It has the advantages of simple preparation process, but it needs to be activated at a temperature of 105-110 °C for 120-240 min during the preparation process. High temperature may affect the structure and performance of chitosan flocculant, and the adsorbent passes , negative charges attract negatively charged and metal ions and positively charged dyes at the same time, and the adsorption effect of target pollutants is not maximized.
中国专利申请号CN200910205648.1，发明名称为“一种螯合脱色絮凝剂及其制备方法”，公开了一种先以环糊精、环氧氯丙烷和多亚乙基多胺为原料合成基本骨架,然后在碱存在下使二硫化碳与分子链上的活泼氨基或亚氨基反应生成螯合脱色絮凝剂的制备方法。其丰富了产物中羟基、氨基等官能团的数量，提高了对重金属的螯合捕集能力，但是其在制备过程中会使用到有毒且具有致癌作用的环氧氯丙烷。Chinese Patent Application No. CN200910205648.1, the name of the invention is "a chelating decolorizing flocculant and its preparation method", which discloses a kind of basic synthetic method using cyclodextrin, epichlorohydrin and polyethylene polyamine as raw materials. A method for preparing a chelating decolorizing flocculant by reacting carbon disulfide with an active amino group or imino group on the molecular chain in the presence of an alkali. It enriches the number of functional groups such as hydroxyl and amino groups in the product, and improves the chelation and capture ability of heavy metals, but epichlorohydrin, which is toxic and carcinogenic, is used in the preparation process.
因此，研发一种反应条件简单，具有良好的可再生性、环境友好性的重金属离子吸附剂的方法十分必要。Therefore, it is necessary to develop a method for a heavy metal ion adsorbent with simple reaction conditions, good reproducibility and environmental friendliness.
发明内容SUMMARY OF THE INVENTION
针对现有技术存在的上述不足，本发明提供一种反应过程简单、减少环境二次污染、产品性能稳定的用絮凝所产絮体制备重金属离子吸附剂的方法。In view of the above-mentioned deficiencies in the prior art, the present invention provides a method for preparing a heavy metal ion adsorbent from flocs produced by flocculation, which is simple in reaction process, reduces secondary environmental pollution, and has stable product performance.
为了实现上述目的，本发明采用的技术方案如下：In order to achieve the above object, the technical scheme adopted in the present invention is as follows:
该方法先用羧甲基化壳聚糖絮凝剂混凝处理偶氮染料废水，将羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体溶解于盛有磷酸盐缓冲溶液的反应器中；然后将1-乙基-（3-二甲基氨基丙基）碳酰二亚胺加入反应器中，搅拌至1-乙基-（3-二甲基氨基丙基）碳酰二亚胺完全溶解；再将N-羟基琥珀酰亚胺和羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体加入到反应器中，充分搅拌混匀；最后将反应器置于室温下避光反应；待反应完全后，用无水乙醇沉淀、洗涤并纯化，干燥后即得重金属离子吸附剂。In the method, azo dye wastewater is coagulated with carboxymethylated chitosan flocculant, and the flocs obtained by flocculating azo dye with carboxymethylated chitosan flocculant are dissolved in a reactor containing a phosphate buffer solution ; Then add 1-ethyl-(3-dimethylaminopropyl) carbodiimide to the reactor, stir to 1-ethyl-(3-dimethylaminopropyl) carbodiimide Completely dissolve; then add the flocs obtained by flocculating azo dyes with N-hydroxysuccinimide and carboxymethylated chitosan flocculant into the reactor, stir and mix well; finally, place the reactor at room temperature to avoid light Reaction; after the reaction is complete, use absolute ethanol to precipitate, wash and purify, and dry to obtain a heavy metal ion adsorbent.
具体包括以下步骤：Specifically include the following steps:
1）先用羧甲基化壳聚糖絮凝剂混凝处理偶氮染料废水，控制羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体中羧甲基化壳聚糖絮凝剂与偶氮染料质量比为1：0.6~1。1) First use carboxymethylated chitosan flocculant to coagulate azo dye wastewater, and control the carboxymethylated chitosan flocculant and azo dyes in the flocs obtained by flocculating azo dye with carboxymethylated chitosan flocculant. The nitrogen-dye mass ratio is 1:0.6~1.
2）将羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体溶解于盛有磷酸盐缓冲溶液的反应器中，控制絮体在磷酸盐缓冲溶液中的质量分数为0.7~1%，磷酸盐缓冲溶液的pH值为6~8。2) Dissolve the flocs obtained by flocculating the azo dyes with the carboxymethylated chitosan flocculant in a reactor containing a phosphate buffer solution, and control the mass fraction of the flocs in the phosphate buffer solution to be 0.7~1%, Phosphate buffer solution has a pH of 6-8.
3）然后将1-乙基-（3-二甲基氨基丙基）碳酰二亚胺加入反应器中，搅拌使其完全溶解，控制絮体和1-乙基-（3-二甲基氨基丙基）碳酰二亚胺在混合溶液中的质量比为1：0.125~0.175，充分搅拌混匀。3) Then add 1-ethyl-(3-dimethylaminopropyl) carbodiimide into the reactor, stir to dissolve it completely, control the floc and 1-ethyl-(3-dimethyl The mass ratio of aminopropyl) carbodiimide in the mixed solution is 1:0.125~0.175, and the mixture is fully stirred and mixed.
4）再将N-羟基琥珀酰亚胺和羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体加入到反应器中，控制N-羟基琥珀酰亚胺、1-乙基-（3-二甲基氨基丙基）碳酰二亚胺的质量比为1：0.7~1.1，第二次加入的絮体与第一次加入的絮体质量比为1：1~2。4) Then, the flocs obtained by flocculating azo dyes with N-hydroxysuccinimide and carboxymethylated chitosan flocculant were added into the reactor to control N-hydroxysuccinimide, 1-ethyl-(3 The mass ratio of -dimethylaminopropyl)carbodiimide is 1:0.7~1.1, and the mass ratio of the flocs added for the second time to the flocs added for the first time is 1:1~2.
5）将反应器置于温度在20~30℃的恒温水浴锅中避光反应20~24h。5) Place the reactor in a constant temperature water bath with a temperature of 20~30°C for 20~24h in the dark.
6）待反应完毕后，用无水乙醇沉洗涤2~3次，干燥后即得重金属离子吸附剂。6) After the reaction is completed, wash with anhydrous ethanol for 2 to 3 times, and dry to obtain a heavy metal ion adsorbent.
其中：步骤（1）中所述控制羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体中羧甲基化壳聚糖絮凝剂与偶氮染料质量比为1：0.6~1。当羧甲基化壳聚糖絮凝剂与偶氮染料质量比过低时不能形成有效絮体；当羧甲基化壳聚糖絮凝剂与偶氮染料质量比过高时不利于废弃物的高效回收利用。Wherein: the mass ratio of the carboxymethylated chitosan flocculant to the azo dye in the flocs obtained by controlling the carboxymethylated chitosan flocculant to flocculate the azo dye in step (1) is 1:0.6~1. When the mass ratio of carboxymethylated chitosan flocculant to azo dye is too low, effective flocs cannot be formed; when the mass ratio of carboxymethylated chitosan flocculant to azo dye is too high, it is not conducive to the high efficiency of waste. recycle and re-use.
步骤（2）中所述控制絮体在磷酸盐缓冲溶液中的质量分数为0.7~1%。当絮体质量分数过低时不能形成有效吸附剂；当絮体质量浓度过高时吸附剂比表面积大幅降低。The mass fraction of the control flocs in the phosphate buffer solution in step (2) is 0.7-1%. When the floc mass fraction is too low, no effective adsorbent can be formed; when the floc mass concentration is too high, the specific surface area of the adsorbent is greatly reduced.
步骤（2）中所述控制磷酸盐缓冲溶液的pH值在6~8。当pH过大时，基团-COOH与1-乙基-（3-二甲基氨基丙基）碳酰二亚胺中的C=N双键发生加成反应生成的中间产物1过少，导致最后反应时能参与反应的偶氮染料絮体会偏少，且反应速率较低；当pH过小时，氢离子的存在会与后续的重金属离子的吸附产生竞争。In step (2), the pH value of the phosphate buffer solution is controlled at 6-8. When the pH is too high, the intermediate product 1 generated by the addition reaction between the group -COOH and the C=N double bond in 1-ethyl-(3-dimethylaminopropyl)carbodiimide is too small, As a result, there are few azo dye flocs that can participate in the reaction in the final reaction, and the reaction rate is low; when the pH is too small, the presence of hydrogen ions will compete with the subsequent adsorption of heavy metal ions.
步骤（3）中所述控制絮体和1-乙基-（3-二甲基氨基丙基）碳酰二亚胺在混合溶液中的质量比为1：0.125~0.175；质量比高于1：0.125时，絮体中的-COOH加成反应不完全，生成的中间产物1过少，不利于后续取代反应的发生；质量比低于1：0.175时，1-乙基-（3-二甲基氨基丙基）碳酰二亚胺中C=N双键的量明显多于絮体中羧基基团所含的量，造成浪费。The mass ratio of the control floc and 1-ethyl-(3-dimethylaminopropyl)carbodiimide in the mixed solution is 1:0.125~0.175; the mass ratio is higher than 1 : 0.125, the addition reaction of -COOH in the floc is incomplete, and the resulting intermediate product 1 is too small, which is not conducive to the subsequent substitution reaction; when the mass ratio is lower than 1:0.175, 1-ethyl-(3-di The amount of C=N double bonds in methylaminopropyl) carbodiimide is significantly more than the amount of carboxyl groups in the flocs, causing waste.
步骤（4）中所述控制N-羟基琥珀酰亚胺、1-乙基-（3-二甲基氨基丙基）碳酰二亚胺的质量比为1：0.7~1.1；质量比高于1：0.7时，絮体与1-乙基-（3-二甲基氨基丙基）碳酰二亚胺生成的中间产物1与N-羟基琥珀酰亚胺发生取代反应时，与羧基连接的1-乙基-（3-二甲基氨基丙基）碳酰二亚胺无法完全被N-羟基琥珀酰亚胺取代，反应进行不完全，不利于后续反应的进行；质量比低于1：1.1时，N-羟基琥珀酰亚胺过量，不经济。In step (4), the mass ratio of N-hydroxysuccinimide and 1-ethyl-(3-dimethylaminopropyl)carbodiimide is controlled to be 1:0.7~1.1; the mass ratio is higher than At 1:0.7, when the intermediate product 1 generated by the floc and 1-ethyl-(3-dimethylaminopropyl) carbodiimide undergoes a substitution reaction with N-hydroxysuccinimide, the carboxy-linked 1-Ethyl-(3-dimethylaminopropyl)carbodiimide cannot be completely replaced by N-hydroxysuccinimide, and the reaction is incomplete, which is not conducive to the subsequent reaction; the mass ratio is lower than 1: At 1.1, N-hydroxysuccinimide is excessive and uneconomical.
步骤（4）中所述控制第二次加入的絮体与第一次加入的絮体的质量比为1：1~2；质量比高于1：1时，加入的絮体过多，导致第二次加入的絮体中所含的的能发生反应的基团明显多于第一次加入的絮体中所含的能参与反应的基团，产生浪费，同时还会降低反应的速率；质量比低于1：2时，会使得第一次加入的絮体不能全部发生反应，也会降低反应速率。In the step (4), the mass ratio of the flocs added for the second time and the flocs added for the first time is controlled to be 1:1~2; when the mass ratio is higher than 1:1, too many flocs are added, resulting in The flocs added for the second time contain significantly more reactive groups than the flocs added for the first time, resulting in waste and reducing the reaction rate; When the mass ratio is lower than 1:2, the flocs added for the first time cannot all react, and the reaction rate will also be reduced.
步骤（5）中所述控制反应温度在20~30℃。当反应温度过低时，反应速率较慢；当反应过高时，反应速率并未显著提升，且能耗较高。In step (5), the reaction temperature is controlled at 20-30°C. When the reaction temperature is too low, the reaction rate is slow; when the reaction is too high, the reaction rate is not significantly improved, and the energy consumption is high.
步骤（5）中所述控制反应时间为20~24h。当反应时间过短，反应并未进行完全；反应时间过长，能耗较高，不经济。The control reaction time described in step (5) is 20-24h. When the reaction time is too short, the reaction is not completed; if the reaction time is too long, the energy consumption is high, which is uneconomical.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1、本发明的制备方法简单，能耗较少，所得的吸附剂结合牢靠、稳定性好，所用原料为羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体，具有较好的经济效益和社会效益。1. The preparation method of the present invention is simple, the energy consumption is low, the obtained adsorbent has firm binding and good stability, and the raw material used is flocculation obtained by flocculating azo dyes with carboxymethylated chitosan flocculant, which has good economical efficiency. benefits and social benefits.
2、此方法制得的以絮凝所产絮体为原料制备的重金属离子吸附剂，除了具有常规的重金属离子吸附剂的吸附作用外，还能利用偶氮结构对某些重金属离子发挥更好的吸附效果，并且还解决了混凝后絮体再利用的问题，具有良好的社会效益和经济效益。2. The heavy metal ion adsorbent prepared by this method using the flocs produced by flocculation as the raw material, in addition to the adsorption effect of the conventional heavy metal ion adsorbent, can also use the azo structure to play a better role in some heavy metal ions. It has good adsorption effect, and also solves the problem of reuse of flocs after coagulation, and has good social and economic benefits.
具体实施方法Specific implementation method
下面结合具体实施例对本发明作进一步详细说明，实施例中如无特殊说明，采用的原料即为普通市售产品。The present invention will be described in further detail below in conjunction with specific embodiments. Unless otherwise specified in the embodiments, the raw materials used are common commercially available products.
实施例1：Example 1:
1）先用羧甲基化壳聚糖絮凝剂混凝处理偶氮染料废水，控制羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体中羧甲基化壳聚糖絮凝剂与偶氮染料质量比为1：0.6。1) First use carboxymethylated chitosan flocculant to coagulate azo dye wastewater, and control the carboxymethylated chitosan flocculant and azo dyes in the flocs obtained by flocculating azo dye with carboxymethylated chitosan flocculant. The nitrogen-dye mass ratio is 1:0.6.
2）将羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体溶解于盛有pH值为6的磷酸盐缓冲溶液的反应器中，控制絮体在磷酸盐缓冲溶液中的质量分数为0.7%。2) Dissolve the flocs obtained by flocculating azo dyes with carboxymethylated chitosan flocculant in a reactor containing a phosphate buffer solution with a pH value of 6, and control the mass fraction of the flocs in the phosphate buffer solution to be 0.7%.
3）然后将1-乙基-（3-二甲基氨基丙基）碳酰二亚胺加入反应器中，搅拌至1-乙基-（3-二甲基氨基丙基）碳酰二亚胺完全溶解，控制絮体和1-乙基-（3-二甲基氨基丙基）碳酰二亚胺在混合溶液中的质量比为1：0.125，充分搅拌混匀。3) Then add 1-ethyl-(3-dimethylaminopropyl)carbodiimide to the reactor and stir until 1-ethyl-(3-dimethylaminopropyl)carbodiimide The amine was completely dissolved, and the mass ratio of floc and 1-ethyl-(3-dimethylaminopropyl) carbodiimide in the mixed solution was controlled to be 1:0.125, and the mixture was fully stirred and mixed.
4）再将N-羟基琥珀酰亚胺和羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体加入到反应器中，控制N-羟基琥珀酰亚胺、1-乙基-（3-二甲基氨基丙基）碳酰二亚胺的质量比为1：0.7，第二次加入的絮体与第一次加入的絮体质量比为1：1。4) Then, the flocs obtained by flocculating azo dyes with N-hydroxysuccinimide and carboxymethylated chitosan flocculant were added into the reactor to control N-hydroxysuccinimide, 1-ethyl-(3 The mass ratio of -dimethylaminopropyl) carbodiimide is 1:0.7, and the mass ratio of the flocs added for the second time to the flocs added for the first time is 1:1.
5）将反应器置于温度在20℃的恒温水浴锅中避光反应20h。5) The reactor was placed in a constant temperature water bath with a temperature of 20°C for 20 hours in the dark.
6）待反应完毕后，用无水乙醇沉洗涤2~3次，干燥后即得重金属离子吸附剂。6) After the reaction is completed, wash with anhydrous ethanol for 2 to 3 times, and dry to obtain a heavy metal ion adsorbent.
实施例2：Example 2:
1）先用羧甲基化壳聚糖絮凝剂混凝处理偶氮染料废水，控制羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体中羧甲基化壳聚糖絮凝剂与偶氮染料质量比为1：0.8。1) First use carboxymethylated chitosan flocculant to coagulate azo dye wastewater, and control the carboxymethylated chitosan flocculant and azo dyes in the flocs obtained by flocculating azo dye with carboxymethylated chitosan flocculant. The nitrogen-dye mass ratio is 1:0.8.
2）将羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体溶解于盛有pH值为6的磷酸盐缓冲溶液的反应器中，控制絮体在磷酸盐缓冲溶液中的质量分数为0.7%。2) Dissolve the flocs obtained by flocculating azo dyes with carboxymethylated chitosan flocculant in a reactor containing a phosphate buffer solution with a pH value of 6, and control the mass fraction of the flocs in the phosphate buffer solution to be 0.7%.
3）然后将1-乙基-（3-二甲基氨基丙基）碳酰二亚胺加入反应器中，搅拌至1-乙基-（3-二甲基氨基丙基）碳酰二亚胺完全溶解，控制絮体和1-乙基-（3-二甲基氨基丙基）碳酰二亚胺在混合溶液中的质量比为1：0.15，充分搅拌混匀。3) Then add 1-ethyl-(3-dimethylaminopropyl)carbodiimide to the reactor and stir until 1-ethyl-(3-dimethylaminopropyl)carbodiimide The amine is completely dissolved, and the mass ratio of flocs and 1-ethyl-(3-dimethylaminopropyl) carbodiimide in the mixed solution is controlled to be 1:0.15, and the mixture is fully stirred and mixed.
4）再将N-羟基琥珀酰亚胺和羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体加入到反应器中，控制N-羟基琥珀酰亚胺、1-乙基-（3-二甲基氨基丙基）碳酰二亚胺的质量比为1：0.9，第二次加入的絮体与第一次加入的絮体质量比为1：1。4) Then, the flocs obtained by flocculating azo dyes with N-hydroxysuccinimide and carboxymethylated chitosan flocculant were added into the reactor to control N-hydroxysuccinimide, 1-ethyl-(3 The mass ratio of -dimethylaminopropyl) carbodiimide is 1:0.9, and the mass ratio of the flocs added for the second time to the flocs added for the first time is 1:1.
5）将反应器置于温度在20℃的恒温水浴锅中避光反应20h。5) The reactor was placed in a constant temperature water bath with a temperature of 20°C for 20 hours in the dark.
6）待反应完毕后，用无水乙醇沉洗涤2~3次，干燥后即得重金属离子吸附剂。6) After the reaction is completed, wash with anhydrous ethanol for 2 to 3 times, and dry to obtain a heavy metal ion adsorbent.
实施例3：Example 3:
1）将羧甲基化壳聚糖絮凝剂混凝处理偶氮染料废水，控制羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体中羧甲基化壳聚糖絮凝剂与偶氮染料质量比为1：1。1) Coagulate the carboxymethylated chitosan flocculant to treat the azo dye wastewater, and control the carboxymethylated chitosan flocculant and azo in the flocs obtained by flocculating the azo dye with the carboxymethylated chitosan flocculant. The dye mass ratio is 1:1.
2）将羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体溶解于盛有pH值为7的磷酸盐缓冲溶液的反应器中，控制絮体在磷酸盐缓冲溶液中的质量分数为0.85%。2) Dissolve the flocs obtained by flocculating azo dyes with carboxymethylated chitosan flocculant in a reactor containing a phosphate buffer solution with a pH value of 7, and control the mass fraction of the flocs in the phosphate buffer solution to be 0.85%.
3）然后将1-乙基-（3-二甲基氨基丙基）碳酰二亚胺加入反应器中，搅拌至1-乙基-（3-二甲基氨基丙基）碳酰二亚胺完全溶解，控制絮体和1-乙基-（3-二甲基氨基丙基）碳酰二亚胺在混合溶液中的质量比为1：0.125，充分搅拌混匀。3) Then add 1-ethyl-(3-dimethylaminopropyl)carbodiimide to the reactor and stir until 1-ethyl-(3-dimethylaminopropyl)carbodiimide The amine was completely dissolved, and the mass ratio of floc and 1-ethyl-(3-dimethylaminopropyl) carbodiimide in the mixed solution was controlled to be 1:0.125, and the mixture was fully stirred and mixed.
4）再将N-羟基琥珀酰亚胺和羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体加入到反应器中，控制N-羟基琥珀酰亚胺、1-乙基-（3-二甲基氨基丙基）碳酰二亚胺的质量比为1：0.7，第二次加入的絮体与第一次加入的絮体质量比为1：1.5。4) Then, the flocs obtained by flocculating azo dyes with N-hydroxysuccinimide and carboxymethylated chitosan flocculant were added into the reactor to control N-hydroxysuccinimide, 1-ethyl-(3 The mass ratio of -dimethylaminopropyl)carbodiimide is 1:0.7, and the mass ratio of the flocs added for the second time to the flocs added for the first time is 1:1.5.
5）将反应器置于温度在25℃的恒温水浴锅中避光反应22h。5) The reactor was placed in a constant temperature water bath with a temperature of 25°C for 22 hours in the dark.
6）待反应完毕后，用无水乙醇沉洗涤2~3次，干燥后即得重金属离子吸附剂。6) After the reaction is completed, wash with anhydrous ethanol for 2 to 3 times, and dry to obtain a heavy metal ion adsorbent.
实施例4：Example 4:
1）将羧甲基化壳聚糖絮凝剂混凝处理偶氮染料废水，控制羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体中羧甲基化壳聚糖絮凝剂与偶氮染料质量比为1：0.6。1) Coagulate the carboxymethylated chitosan flocculant to treat the azo dye wastewater, and control the carboxymethylated chitosan flocculant and azo in the flocs obtained by flocculating the azo dye with the carboxymethylated chitosan flocculant. The dye mass ratio is 1:0.6.
2）将羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体溶解于盛有pH值为7的磷酸盐缓冲溶液的反应器中，控制絮体在磷酸盐缓冲溶液中的质量分数为0.85%。2) Dissolve the flocs obtained by flocculating azo dyes with carboxymethylated chitosan flocculant in a reactor containing a phosphate buffer solution with a pH value of 7, and control the mass fraction of the flocs in the phosphate buffer solution to be 0.85%.
3）然后将1-乙基-（3-二甲基氨基丙基）碳酰二亚胺加入反应器中，搅拌至1-乙基-（3-二甲基氨基丙基）碳酰二亚胺完全溶解，控制絮体和1-乙基-（3-二甲基氨基丙基）碳酰二亚胺在混合溶液中的质量比为1：0.15，充分搅拌混匀。3) Then add 1-ethyl-(3-dimethylaminopropyl)carbodiimide to the reactor and stir until 1-ethyl-(3-dimethylaminopropyl)carbodiimide The amine is completely dissolved, and the mass ratio of flocs and 1-ethyl-(3-dimethylaminopropyl) carbodiimide in the mixed solution is controlled to be 1:0.15, and the mixture is fully stirred and mixed.
4）再将N-羟基琥珀酰亚胺和羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体加入到反应器中，控制N-羟基琥珀酰亚胺、1-乙基-（3-二甲基氨基丙基）碳酰二亚胺的质量比为1：0.9，第二次加入的絮体与第一次加入的絮体质量比为1：1。4) Then, the flocs obtained by flocculating azo dyes with N-hydroxysuccinimide and carboxymethylated chitosan flocculant were added into the reactor to control N-hydroxysuccinimide, 1-ethyl-(3 The mass ratio of -dimethylaminopropyl) carbodiimide is 1:0.9, and the mass ratio of the flocs added for the second time to the flocs added for the first time is 1:1.
5）将反应器置于温度在25℃的恒温水浴锅中避光反应22h。5) The reactor was placed in a constant temperature water bath with a temperature of 25°C for 22 hours in the dark.
6）待反应完毕后，用无水乙醇沉洗涤2~3次，干燥后即得重金属离子吸附剂。6) After the reaction is completed, wash with anhydrous ethanol for 2 to 3 times, and dry to obtain a heavy metal ion adsorbent.
实施例5：Example 5:
1）将羧甲基化壳聚糖絮凝剂混凝处理偶氮染料废水，控制羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体中羧甲基化壳聚糖絮凝剂与偶氮染料质量比为1：0.8。1) Coagulate the carboxymethylated chitosan flocculant to treat the azo dye wastewater, and control the carboxymethylated chitosan flocculant and azo in the flocs obtained by flocculating the azo dye with the carboxymethylated chitosan flocculant. The dye mass ratio is 1:0.8.
2）将羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体溶解于盛有pH值为8的磷酸盐缓冲溶液的反应器中，控制絮体在磷酸盐缓冲溶液中的质量分数为1%。2) Dissolve the flocs obtained by flocculating azo dyes with carboxymethylated chitosan flocculant in a reactor containing a phosphate buffer solution with a pH value of 8, and control the mass fraction of the flocs in the phosphate buffer solution to be 1%.
3）然后将1-乙基-（3-二甲基氨基丙基）碳酰二亚胺加入反应器中，搅拌至1-乙基-（3-二甲基氨基丙基）碳酰二亚胺完全溶解，控制絮体和1-乙基-（3-二甲基氨基丙基）碳酰二亚胺在混合溶液中的质量比为1：0.15，充分搅拌混匀。3) Then add 1-ethyl-(3-dimethylaminopropyl)carbodiimide to the reactor and stir until 1-ethyl-(3-dimethylaminopropyl)carbodiimide The amine is completely dissolved, and the mass ratio of flocs and 1-ethyl-(3-dimethylaminopropyl) carbodiimide in the mixed solution is controlled to be 1:0.15, and the mixture is fully stirred and mixed.
4）再将N-羟基琥珀酰亚胺和羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体加入到反应器中，控制N-羟基琥珀酰亚胺、1-乙基-（3-二甲基氨基丙基）碳酰二亚胺的质量比为1：0.9，第二次加入的絮体与第一次加入的絮体质量比为1：2。4) Then, the flocs obtained by flocculating azo dyes with N-hydroxysuccinimide and carboxymethylated chitosan flocculant were added into the reactor to control N-hydroxysuccinimide, 1-ethyl-(3 The mass ratio of -dimethylaminopropyl) carbodiimide is 1:0.9, and the mass ratio of the flocs added for the second time to the flocs added for the first time is 1:2.
5）将反应器置于温度在30℃的恒温水浴锅中避光反应24h。5) Place the reactor in a constant temperature water bath with a temperature of 30°C for 24 hours in the dark.
6）待反应完毕后，用无水乙醇沉洗涤2~3次，干燥后即得重金属离子吸附剂。6) After the reaction is completed, wash with anhydrous ethanol for 2 to 3 times, and dry to obtain a heavy metal ion adsorbent.
实施例6：Example 6:
1）将羧甲基化壳聚糖絮凝剂混凝处理偶氮染料废水，控制羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体中羧甲基化壳聚糖絮凝剂与偶氮染料质量比为1：1。1) Coagulate the carboxymethylated chitosan flocculant to treat the azo dye wastewater, and control the carboxymethylated chitosan flocculant and azo in the flocs obtained by flocculating the azo dye with the carboxymethylated chitosan flocculant. The dye mass ratio is 1:1.
2）将羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体溶解于盛有pH值为8的磷酸盐缓冲溶液的反应器中，控制絮体在磷酸盐缓冲溶液中的质量分数为1%。2) Dissolve the flocs obtained by flocculating azo dyes with carboxymethylated chitosan flocculant in a reactor containing a phosphate buffer solution with a pH value of 8, and control the mass fraction of the flocs in the phosphate buffer solution to be 1%.
3）然后将1-乙基-（3-二甲基氨基丙基）碳酰二亚胺加入反应器中，搅拌至1-乙基-（3-二甲基氨基丙基）碳酰二亚胺完全溶解，控制絮体和1-乙基-（3-二甲基氨基丙基）碳酰二亚胺在混合溶液中的质量比为1：0.175，充分搅拌混匀。3) Then add 1-ethyl-(3-dimethylaminopropyl)carbodiimide to the reactor and stir until 1-ethyl-(3-dimethylaminopropyl)carbodiimide The amine was completely dissolved, and the mass ratio of floc and 1-ethyl-(3-dimethylaminopropyl) carbodiimide in the mixed solution was controlled to be 1:0.175, and the mixture was fully stirred and mixed.
4）再将N-羟基琥珀酰亚胺和羧甲基化壳聚糖絮凝剂絮凝偶氮染料所得絮体加入到反应器中，控制N-羟基琥珀酰亚胺、1-乙基-（3-二甲基氨基丙基）碳酰二亚胺的质量比为1：1.1，第二次加入的絮体与第一次加入的絮体质量比为1：2。4) Then, the flocs obtained by flocculating azo dyes with N-hydroxysuccinimide and carboxymethylated chitosan flocculant were added into the reactor to control N-hydroxysuccinimide, 1-ethyl-(3 The mass ratio of -dimethylaminopropyl) carbodiimide is 1:1.1, and the mass ratio of the flocs added for the second time to the flocs added for the first time is 1:2.
5）将反应器置于温度在30℃的恒温水浴锅中避光反应24h。5) Place the reactor in a constant temperature water bath with a temperature of 30°C for 24 hours in the dark.
6）待反应完毕后，用无水乙醇沉洗涤2~3次，干燥后即得重金属离子吸附剂。6) After the reaction is completed, wash with anhydrous ethanol for 2 to 3 times, and dry to obtain a heavy metal ion adsorbent.
分别测定实施例1~6制得的以羧甲基化壳聚糖絮凝剂处理偶氮染料废水所得絮体为原料制备重金属离子吸附剂的相关性质，数据详见表1。The relevant properties of the heavy metal ion adsorbents prepared in Examples 1 to 6 were respectively measured using the flocs obtained from the treatment of azo dye wastewater with carboxymethylated chitosan flocculants as raw materials, and the data are shown in Table 1.
表1 重金属离子吸附剂特性
由上表1可以看出，本发明所得以羧甲基化壳聚糖絮凝剂处理废水中偶氮染料所得絮体为原料制备重金属离子吸附剂产品性能优异且稳定，比表面积大，其对含重金属离子废水去除效果较好，由此证明说明这是一套切实可行效果又优异的重金属离子吸附剂的制备方法。As can be seen from the above table 1, the present invention uses the flocs obtained from azo dyes in waste water treated by carboxymethylated chitosan flocculants as raw materials to prepare heavy metal ion adsorbent products with excellent performance and stability, and a large specific surface area. The removal effect of heavy metal ion wastewater is good, which proves that this is a practical and excellent preparation method of heavy metal ion adsorbent.
最后需要说明的是，本发明的上述实施例仅是为说明本发明所作的举例，而并非是对本发明实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其他不同形式的变化和变动。这里无法对所有的实施方式予以穷举。凡是属于本发明的技术方案所引申出的显而易见的变化或变动仍处于本发明的保护范围之列。Finally, it should be noted that the above-mentioned embodiments of the present invention are only examples for illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those of ordinary skill in the art, changes and modifications in other different forms can also be made on the basis of the above description. Not all implementations can be exhaustive here. Any obvious changes or changes derived from the technical solutions of the present invention are still within the protection scope of the present invention.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116637603A (en)* | 2023-07-03 | 2023-08-25 | 重庆工商大学 | A method for preparing porous adsorbent by coagulation produced flocs |
| CN116726886A (en)* | 2023-07-17 | 2023-09-12 | 重庆工商大学 | Method for improving regeneration performance of adsorbent prepared from coagulated sludge |
| CN117069215A (en)* | 2023-09-04 | 2023-11-17 | 江西师范大学 | A kind of sewage treatment flocculant and preparation method thereof |
| WO2024236274A1 (en)* | 2023-05-12 | 2024-11-21 | CQ Studio Limited | Material and method for forming a material |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010133734A1 (en)* | 2009-05-22 | 2010-11-25 | Universitat Politècnica De Catalunya | Use of biopolymer chitosan for the removal of colour from wastewater using a combined coagulation-flocculation and adsorption process |
| CN107814434A (en)* | 2017-10-12 | 2018-03-20 | 广州振清环保技术有限公司 | A kind of modified soluble chitosan flocculant and preparation method thereof |
| CN109456421A (en)* | 2018-10-30 | 2019-03-12 | 江南大学 | A kind of preparation of water soluble chitosan material and application method |
| CN114210311A (en)* | 2021-12-14 | 2022-03-22 | 中南大学 | A germanium adsorbent, preparation method, and method for recovering germanium |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010133734A1 (en)* | 2009-05-22 | 2010-11-25 | Universitat Politècnica De Catalunya | Use of biopolymer chitosan for the removal of colour from wastewater using a combined coagulation-flocculation and adsorption process |
| CN107814434A (en)* | 2017-10-12 | 2018-03-20 | 广州振清环保技术有限公司 | A kind of modified soluble chitosan flocculant and preparation method thereof |
| CN109456421A (en)* | 2018-10-30 | 2019-03-12 | 江南大学 | A kind of preparation of water soluble chitosan material and application method |
| CN114210311A (en)* | 2021-12-14 | 2022-03-22 | 中南大学 | A germanium adsorbent, preparation method, and method for recovering germanium |
| Title |
|---|
| NADIA H. ELSAYED等: "Preparation of chromium (III) ion-imprinted polymer based on azo dye functionalized chitosan", CARBOHYDRATE POLYMERS* |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024236274A1 (en)* | 2023-05-12 | 2024-11-21 | CQ Studio Limited | Material and method for forming a material |
| CN116637603A (en)* | 2023-07-03 | 2023-08-25 | 重庆工商大学 | A method for preparing porous adsorbent by coagulation produced flocs |
| CN116726886A (en)* | 2023-07-17 | 2023-09-12 | 重庆工商大学 | Method for improving regeneration performance of adsorbent prepared from coagulated sludge |
| CN117069215A (en)* | 2023-09-04 | 2023-11-17 | 江西师范大学 | A kind of sewage treatment flocculant and preparation method thereof |
| Publication | Publication Date | Title |
|---|---|---|
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