技术领域technical field
本发明属于水处理剂领域，特别涉及一种碳纳米管复合TiO2绿色深度水处理剂的制备方法。The invention belongs to the field of water treatment agents, in particular to a preparation method of a carbon nanotube compositeTiO2 green deep water treatment agent.
背景技术Background technique
全球仅约10％的水是直接为人类所用。最大的份额，70％用于农业，剩余的20％为工业用。中国的排污约为全球的20％，而它只得到全球的5％的新鲜水。因此，解决污染问题已列入议事日程。在纺织印染、皮革、造纸行业加工过程中，大量使用了污染环境和对人体有害的助剂，这些助剂大多以液体的形态排放而污染环境，生物降解性差，毒性大，游离甲醛含量高，重金属离子的含量超标。其中，印染湿整理更是无可争议地成为水污染大户。从上浆开始到退浆、水洗、练漂、丝光，然后染色印花、可能还需涂层，按此流程每道工序都涉及水洗，而每道工序每千克材料需20L耗水。结果是湿整理过程中每千克原棉的用水量加起来多达200L。当一件标准的男式衬衣定制后在商店橱窗展示时，超过2000L水在生产加工它时被用掉了(布料：纯棉，125g/m)。Only about 10% of the world's water is directly used by humans. The largest share, 70%, is used in agriculture, and the remaining 20% is used in industry. China's sewage is about 20% of the world's, but it only gets 5% of the world's fresh water. Therefore, solving the pollution problem is on the agenda. In the process of textile printing and dyeing, leather, and paper-making industries, a large number of additives that pollute the environment and are harmful to the human body are used. Most of these additives are discharged in the form of liquid and pollute the environment. They have poor biodegradability, high toxicity, and high free formaldehyde content. The content of heavy metal ions exceeds the standard. Among them, printing and dyeing wet finishing is indisputably a major water polluter. From sizing to desizing, washing, bleaching, mercerizing, dyeing and printing, and possibly coating, each process involves washing, and each process requires 20L of water per kilogram of material. The result is up to 200 liters of water per kilogram of raw cotton added up during wet finishing. When a standard men's shirt is customized and displayed in the store window, more than 2000L of water is used in the production and processing of it (fabric: pure cotton, 125g/m2).
目前使用的处理废水的方法主要有：物理分离法、生物降解法、化学分解法，但这些方法都存在一定的局限性，不利于可持续发展。因而，人们开始致力于开发高效、低能耗、适用范围广和有深度氧化能力的污染物清除技术。近年来，很多学者将TiO2用于光催化降解水中有机污染物，将TiO2负载到碳纳米管上，制备高效的光催化剂成为当前研究的热点。The methods currently used to treat wastewater mainly include: physical separation, biodegradation, and chemical decomposition, but these methods have certain limitations and are not conducive to sustainable development. Therefore, people began to devote themselves to the development of pollutant removal technology with high efficiency, low energy consumption, wide application range and deep oxidation ability. In recent years, many scholars have used TiO2 for photocatalytic degradation of organic pollutants in water, and loading TiO2 on carbon nanotubes to prepare efficient photocatalysts has become a current research hotspot.
发明内容Contents of the invention
本发明所要解决的技术问题是提供一种碳纳米管复合TiO2绿色深度水处理剂的制备方法，该方法操作简单，成本低廉，对设备的要求低；水处理剂适用于各种废水的深度处理，环保无二次污染。The technical problem to be solved by the present invention is to provide a preparation method of carbon nanotube compositeTiO2 green deep water treatment agent, the method is simple to operate, low in cost, and has low requirements on equipment; the water treatment agent is suitable for the depth of various waste water Treatment, environmental protection and no secondary pollution.
本发明的一种碳纳米管复合TiO2绿色深度水处理剂的制备方法，包括：A kind of carbon nanotube compositeTiO of the present invention The preparation method of green depth water treatment agent comprises:
(1)将碳纳米管在H2SO4和HNO3混合液中室温超声反应30～60min，水洗到中性，室温真空烘干，得到羧基化碳纳米管；然后将羧基化碳纳米管分散到过量二乙烯三胺中，加入2-(7-偶氮苯并三氮唑)-N,N,N',N'-四甲基脲六氟磷酸酯，40～50℃反应5～6h，乙醇洗涤，室温真空烘干，得到氨基化碳纳米管；然后将氨基化碳纳米管超声分散到水和丙酮的混合液中，调节pH值为5～6，冰水浴滴加2,4,6-三氟-5-氯嘧啶，调节pH值为6～6.5，20～30℃超声反应24～48h，乙醇洗涤，水洗，室温真空烘干，辐照(在222nm准分子紫外光源下辐照3min)得到反应型碳纳米管；(1) Ultrasonically react the carbon nanotubes in a mixture of H2 SO4 and HNO3 at room temperature for 30-60 minutes, wash with water until neutral, and dry in vacuum at room temperature to obtain carboxylated carbon nanotubes; then disperse the carboxylated carbon nanotubes Add 2-(7-azobenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate to excess diethylenetriamine, react at 40~50℃ for 5~6h , washed with ethanol, and vacuum-dried at room temperature to obtain aminated carbon nanotubes; then ultrasonically disperse the aminated carbon nanotubes into a mixture of water and acetone, adjust the pH value to 5-6, add 2,4, 6-trifluoro-5-chloropyrimidine, adjust the pH value to 6-6.5, ultrasonically react at 20-30°C for 24-48 hours, wash with ethanol, wash with water, dry in vacuum at room temperature, and irradiate (irradiate under 222nm excimer ultraviolet light source 3min) to obtain reactive carbon nanotubes;
(2)将纳米TiO2P25、稳定剂、模板剂和步骤(1)中的反应型碳纳米管加入到磷酸盐缓冲液中，搅拌30～60min，形成悬浊液；其中，纳米TiO2P25与反应型碳纳米管的质量比为1:5～1:20；(2) Add nano-TiO2 P25, stabilizer, template and reactive carbon nanotubes in step (1) into phosphate buffer, stir for 30-60 min to form a suspension; wherein, nano-TiO2 P25 The mass ratio of reactive carbon nanotubes is 1:5 to 1:20;
(3)用碱性溶液调节pH值为5～6，加热至80～100℃回流6～24h并过滤，得到碳纳米管复合TiO2绿色深度水处理剂。(3) Adjust the pH value to 5-6 with an alkaline solution, heat to 80-100° C. to reflux for 6-24 hours and filter to obtain a carbon nanotube composite TiO2 green advanced water treatment agent.
所述步骤(1)中的碳纳米管与H2SO4和HNO3混合液的比例为10～20g:4L；其中，H2SO4和HNO3的体积比为1:1～5:1。The ratio of carbon nanotubes to H2 SO4 and HNO3 mixture in the step (1) is 10-20g:4L; wherein, the volume ratio of H2 SO4 and HNO3 is 1:1-5:1 .
所述步骤(1)中的羧基化碳纳米管与2-(7-偶氮苯并三氮唑)-N,N,N',N'-四甲基脲六氟磷酸的质量比为5～8:0.1～0.6。The mass ratio of the carboxylated carbon nanotubes in the step (1) to 2-(7-azobenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphoric acid is 5 ~8:0.1~0.6.
所述步骤(1)中的氨基化碳纳米管与水和丙酮的混合液的比例为4～4.5g:1L；其中，水和丙酮的体积比为3:1～5:1。The ratio of the aminated carbon nanotube to the mixture of water and acetone in the step (1) is 4-4.5g:1L; wherein, the volume ratio of water and acetone is 3:1-5:1.
所述步骤(1)中的氨基化碳纳米管与2,4,6-三氟-5-氯嘧啶的质量比为4～4.5:4～6。The mass ratio of the aminated carbon nanotubes to 2,4,6-trifluoro-5-chloropyrimidine in the step (1) is 4-4.5:4-6.
所述步骤(1)中采用碳酸钠溶液调节pH值。In the step (1), sodium carbonate solution is used to adjust the pH value.
所述步骤(2)中的纳米TiO2P25浓度为0.01～0.2mol/L。The nano TiO2 P25 concentration in the step (2) is 0.01-0.2 mol/L.
所述步骤(2)中的稳定剂为乙二胺四乙酸二钠、乙二胺四乙酸四钠、葡萄糖酸钠、丁烷四羧酸中的一种；稳定剂浓度为0.01～0.1mol/L。The stabilizer in the step (2) is one of disodium edetate, tetrasodium edetate, sodium gluconate, butane tetracarboxylic acid; the concentration of stabilizer is 0.01～0.1mol/ L.
所述步骤(2)中的模板剂为质量比1：3的三嵌段聚醚P123和三嵌段共聚物F127的混合物；模板剂浓度为0.01～0.1mol/L。The template in the step (2) is a mixture of tri-block polyether P123 and tri-block copolymer F127 with a mass ratio of 1:3; the template concentration is 0.01-0.1 mol/L.
所述步骤(2)中的磷酸盐缓冲液由浓度0.025～0.05mol/L磷酸二氢钠和0.05～0.1mol/L磷酸氢钠组成。The phosphate buffer in the step (2) is composed of 0.025-0.05 mol/L sodium dihydrogen phosphate and 0.05-0.1 mol/L sodium hydrogen phosphate.
所述步骤(3)中的碱性溶液为浓度0.5mol/L～1.5mol/L的氢氧化钠或氢氧化钾的水溶液。The alkaline solution in the step (3) is an aqueous solution of sodium hydroxide or potassium hydroxide with a concentration of 0.5mol/L˜1.5mol/L.
碳纳米管作为一种多孔物质，具有特殊的层间特性，可在其表面负载纳米TiO2P25微粒，制备成负载型催化剂。这种负载型光催化剂可以提高光催化剂的分散性，利于回收重复利用。As a kind of porous substance, carbon nanotube has special interlayer characteristics, and nano TiO2 P25 particles can be loaded on its surface to prepare a supported catalyst. The supported photocatalyst can improve the dispersibility of the photocatalyst, which is beneficial to recycling and reuse.
本发明利用碳纳米管的多孔、吸附能力强、与水易分离等特点和纳米TiO2P25的光催化活性结合起来，将纳米TiO2成功地负载到碳纳米管上，制备成可以悬浮于废水中而又可以顺利与水分离的高催化活性的可见光光催化材料，并且将其应用于废水的深度处理，可以实现对水中高浓度有机污染物氧化去除，而不是转移到其他地方，是一个环保型的工艺技术。The present invention combines the characteristics of carbon nanotubes such as porosity, strong adsorption capacity, and easy separation from water with the photocatalytic activity of nano-TiO2 P25 to successfully load nano-TiO2 on carbon nanotubes and prepare them to be suspended in wastewater A visible-light photocatalytic material with high catalytic activity that can be separated from water smoothly, and applied to the advanced treatment of wastewater, can realize the oxidation and removal of high-concentration organic pollutants in water instead of transferring them to other places, which is an environmental protection type of technology.
有益效果Beneficial effect
(1)本发明成本低廉，制备方法简单，对设备的要求低，可操作性好；(1) The present invention has low cost, simple preparation method, low requirement on equipment, and good operability;
(2)本发明的水处理剂可以去除水中高浓度有机污染物，适用于各种废水的深度处理，环保无二次污染，且具有抗菌、除臭、可以吸附其他重金属离子等优点；(2) The water treatment agent of the present invention can remove high-concentration organic pollutants in water, is suitable for advanced treatment of various waste water, is environmentally friendly without secondary pollution, and has the advantages of antibacterial, deodorizing, and can adsorb other heavy metal ions;
(3)本发明的水处理剂可以克服现有铋基水处理剂的不足，水处理效果好，可以循环使用。(3) The water treatment agent of the present invention can overcome the deficiency of the existing bismuth-based water treatment agent, has good water treatment effect and can be recycled.
具体实施方式Detailed ways
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
实施例1Example 1
(1)将10g碳纳米管在4L体积比为1:1的H2SO4和HNO4混合液中室温超声反应30min，水洗到中性，室温真空烘干48h，得到5g羧基化碳纳米管；然后将上述5g羧基化碳纳米管分散到过量二乙烯三胺中，加入100mg 2-(7-偶氮苯并三氮唑)-N,N,N',N'-四甲基脲六氟磷酸酯，40℃反应5h，乙醇洗涤，室温真空烘干48h，得到4g氨基化碳纳米管；最后将4g氨基化碳纳米管超声分散在1L体积比为3：1的水和丙酮的混合液中，用碳酸钠溶液调节pH值为5，冰水浴滴加4g 2,4,6-三氟-5-氯嘧啶，用碳酸钠溶液调节pH值为6，20℃超声反应24h，乙醇洗涤，水洗，室温真空烘干48h，在222nm准分子紫外光源下辐照3min得到反应型碳纳米管；(1) 10 g of carbon nanotubes were ultrasonically reacted at room temperature for 30 min in 4 L of H2 SO4 and HNO4 mixed solution with a volume ratio of 1:1, washed with water until neutral, and vacuum-dried at room temperature for 48 h to obtain 5 g of carboxylated carbon nanotubes ; Then the above-mentioned 5g carboxylated carbon nanotubes were dispersed in excess diethylenetriamine, and 100mg 2-(7-azobenzotriazole)-N,N,N',N'-tetramethylurea hexa Fluorophosphate, reacted at 40°C for 5 hours, washed with ethanol, and dried in vacuum at room temperature for 48 hours to obtain 4g of aminated carbon nanotubes; finally, 4g of aminated carbon nanotubes were ultrasonically dispersed in 1L of a mixture of water and acetone with a volume ratio of 3:1 In the solution, use sodium carbonate solution to adjust the pH value to 5, add 4 g of 2,4,6-trifluoro-5-chloropyrimidine dropwise in an ice-water bath, use sodium carbonate solution to adjust the pH value to 6, perform ultrasonic reaction at 20°C for 24 hours, and wash with ethanol , washed with water, vacuum-dried at room temperature for 48 hours, and irradiated under a 222nm excimer ultraviolet light source for 3 minutes to obtain reactive carbon nanotubes;
(2)将纳米TiO2P25、乙二胺四乙酸二钠、质量比为1：3的三嵌段聚醚P123和三嵌段共聚物F127的混合物和上述步骤(1)中反应型碳纳米管加入到浓度为0.025mol/L磷酸二氢钠和0.05mol/L磷酸氢钠组成的缓冲液中，搅拌30min，形成悬浊液；其中纳米TiO2P25的浓度为0.01mol/L、稳定剂的浓度为0.01mol/L、模板剂的浓度为0.05mol/L。(2) the mixture of nanometer TiO2 P25, disodium edetate, mass ratio of triblock polyether P123 and triblock copolymer F127 of 1:3 and the reactive carbon nanometer in the above step (1) Add the tube into the buffer solution composed of 0.025mol/L sodium dihydrogen phosphate and 0.05mol/L sodium hydrogen phosphate, stir for 30min to form a suspension; the concentration of nano-TiO2 P25 is 0.01mol/L, stabilizer The concentration of the template agent is 0.01mol/L, and the concentration of the template is 0.05mol/L.
(3)用浓度0.5mol/L的氢氧化钠水溶液调节上述悬浊液的pH值为5，加热80℃下，回流6h，过滤，得反应产物；其中纳米TiO2P25与碳纳米管的质量比为1:5。(3) Adjust the pH value of the above-mentioned suspension to 5 with an aqueous solution of sodium hydroxide with a concentration of 0.5mol/L, heat at 80°C, reflux for 6h, and filter to obtain a reaction product; wherein the mass of nano-TiO2 P25 and carbon nanotube The ratio is 1:5.
实施例2Example 2
(1)将10g碳纳米管在4L体积比为3:1的H2SO4和HNO4混合液中室温超声反应45min，水洗到中性，室温真空烘干54h，得到6.5g羧基化碳纳米管；然后将上述5g羧基化碳纳米管分散到过量二乙烯三胺中，加入300mg 2-(7-偶氮苯并三氮唑)-N,N,N',N'-四甲基脲六氟磷酸酯，45℃反应5h，乙醇洗涤，室温真空烘干48h，得到4.2g氨基化碳纳米管；最后将4.2g氨基化碳纳米管超声分散在1L体积比为4:1的水和丙酮的混合液中，用碳酸钠溶液调节pH值为5.5，冰水浴滴加5g 2,4,6-三氟-5-氯嘧啶，用碳酸钠溶液调节pH值为6.2，25℃超声反应36h，乙醇洗涤，水洗，室温真空烘干48h，在222nm准分子紫外光源下辐照3min得到反应型碳纳米管；(1) 10 g of carbon nanotubes were ultrasonically reacted at room temperature for 45 min in 4 L of H2 SO4 and HNO4 mixed solution with a volume ratio of 3:1, washed with water until neutral, and vacuum-dried at room temperature for 54 h to obtain 6.5 g of carboxylated carbon nanotubes. tube; then the above 5g carboxylated carbon nanotubes were dispersed into excess diethylenetriamine, and 300mg 2-(7-azobenzotriazole)-N,N,N',N'-tetramethylurea was added Hexafluorophosphate, reacted at 45°C for 5 hours, washed with ethanol, and dried in vacuum at room temperature for 48 hours to obtain 4.2 g of aminated carbon nanotubes; finally, ultrasonically dispersed 4.2 g of aminated carbon nanotubes in 1 L of water with a volume ratio of 4:1 and In the mixed solution of acetone, use sodium carbonate solution to adjust the pH value to 5.5, add 5g of 2,4,6-trifluoro-5-chloropyrimidine dropwise in an ice-water bath, use sodium carbonate solution to adjust the pH value to 6.2, and conduct ultrasonic reaction at 25°C for 36 hours , washed with ethanol, washed with water, dried in vacuum at room temperature for 48 hours, and irradiated for 3 minutes under a 222nm excimer ultraviolet light source to obtain reactive carbon nanotubes;
(2)将纳米TiO2P25、葡萄糖酸钠、质量比为1：3的三嵌段聚醚P123和三嵌段共聚物F127的混合物和上述步骤(1)中反应型碳纳米管加入到浓度为0.03mol/L磷酸二氢钠和0.05mol/L磷酸氢钠组成的缓冲液中，搅拌45min，形成悬浊液；其中纳米TiO2P25的浓度为0.01mol/L、稳定剂的浓度为0.03mol/L、模板剂的浓度为0.07mol/L。(2) the mixture of nano-TiO2 P25, sodium gluconate, mass ratio of three-block polyether P123 and three-block copolymer F127 and the above-mentioned steps (1) are added to the concentration In a buffer composed of 0.03mol/L sodium dihydrogen phosphate and 0.05mol/L sodium hydrogen phosphate, stir for 45 minutes to form a suspension; the concentration of nano-TiO2 P25 is 0.01mol/L, and the concentration of stabilizer is 0.03 mol/L, the concentration of template agent is 0.07mol/L.
(3)用浓度0.5mol/L的氢氧化钠水溶液调节上述悬浊液的pH值为7，加热90℃下，回流16h，过滤，得反应产物；其中纳米TiO2P25与碳纳米管的质量比为1:15。(3) Adjust the pH value of the above-mentioned suspension to 7 with an aqueous solution of sodium hydroxide with a concentration of 0.5mol/L, heat at 90°C, reflux for 16 hours, and filter to obtain a reaction product; wherein the mass of nano-TiO2 P25 and carbon nanotubes The ratio is 1:15.
实施例3Example 3
(1)将10g碳纳米管在4L体积比为5:1的H2SO4和HNO4混合液中室温超声反应60min，水洗到中性，室温真空烘干60h，得到8g羧基化碳纳米管；然后将上述8g羧基化碳纳米管分散到过量二乙烯三胺中，加入600mg 2-(7-偶氮苯并三氮唑)-N,N,N',N'-四甲基脲六氟磷酸酯，50℃反应5h，乙醇洗涤，室温真空烘干48h，得到4.5g氨基化碳纳米管；最后将4.5g氨基化碳纳米管超声分散在1L体积比为5:1的水和丙酮的混合液中，用碳酸钠溶液调节pH值为6，冰水浴滴加6g 2,4,6-三氟-5-氯嘧啶，用碳酸钠溶液调节pH值为6.5，30℃超声反应48h，乙醇洗涤，水洗，室温真空烘干48h，在222nm准分子紫外光源下辐照3min得到反应型碳纳米管；(1) 10 g of carbon nanotubes were ultrasonically reacted at room temperature for 60 min in 4 L of H2 SO4 and HNO4 mixed solution with a volume ratio of 5:1, washed with water until neutral, and vacuum-dried at room temperature for 60 h to obtain 8 g of carboxylated carbon nanotubes ; Then the above-mentioned 8g carboxylated carbon nanotubes were dispersed in excess diethylenetriamine, and 600mg 2-(7-azobenzotriazole)-N,N,N',N'-tetramethylurea hexa Fluorophosphate, reacted at 50°C for 5h, washed with ethanol, and dried in vacuum at room temperature for 48h to obtain 4.5g of aminated carbon nanotubes; finally, 4.5g of aminated carbon nanotubes were ultrasonically dispersed in 1L of water and acetone with a volume ratio of 5:1 In the mixed solution, adjust the pH value to 6 with sodium carbonate solution, add 6 g of 2,4,6-trifluoro-5-chloropyrimidine dropwise in an ice-water bath, adjust the pH value to 6.5 with sodium carbonate solution, and perform ultrasonic reaction at 30°C for 48 hours. Washing with ethanol, washing with water, vacuum drying at room temperature for 48 hours, and irradiating for 3 minutes under a 222nm excimer ultraviolet light source to obtain reactive carbon nanotubes;
(2)将纳米TiO2P25、丁烷四羧酸、质量比为1：3的三嵌段聚醚P123和三嵌段共聚物F127的混合物和上述步骤(1)中反应型碳纳米管加入到浓度为0.05mol/L磷酸二氢钠和0.1mol/L磷酸氢钠组成的缓冲液中，搅拌60min，形成悬浊液；其中纳米TiO2P25的浓度0.15mol/L、稳定剂的浓度为0.05mol/L、模板剂的浓度为0.1mol/L。(2) Nano TiO2 P25, butane tetracarboxylic acid, a mixture of three-block polyether P123 and three-block copolymer F127 with a mass ratio of 1:3 and the reactive carbon nanotubes in the above step (1) are added Into the buffer solution that concentration is 0.05mol/L sodium dihydrogen phosphate and 0.1mol/L sodium hydrogen phosphate, stir 60min, form suspension liquid; Wherein the concentration of nanometer TiO2 P25 0.15mol/L, the concentration of stabilizing agent is 0.05mol/L, template concentration is 0.1mol/L.
(3)用浓度1.5mol/L的氢氧化钾水溶液调节上述悬浊液的pH值为9，加热100℃下，回流24h，过滤，得反应产物；其中纳米TiO2P25与碳纳米管的质量比为1:20。(3) Adjust the pH value of the above-mentioned suspension to 9 with an aqueous potassium hydroxide solution with a concentration of 1.5 mol/L, heat at 100° C., reflux for 24 hours, and filter to obtain a reaction product; wherein the mass of nano-TiO2 P25 and carbon nanotubes The ratio is 1:20.
以同一时间取样的印染厂的印染废水为处理对象，在废水中分别加入不同浓度的实施例1～3所得的水处理剂，经过6小时日光照射后，水处理剂对印染废水的脱色率如下表所示：Taking the printing and dyeing wastewater of the printing and dyeing factory sampled at the same time as the treatment object, adding different concentrations of the water treatment agents obtained in Examples 1 to 3 to the wastewater, after 6 hours of sunlight, the decolorization rate of the water treatment agent on the printing and dyeing wastewater is as follows As shown in the table:
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