CN102745792A - Arsenic-removing material of nano ferrimanganic composite oxide and preparation method thereof - Google Patents
Arsenic-removing material of nano ferrimanganic composite oxide and preparation method thereof Download PDFInfo
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Abstract
本发明涉及一种纳米铁锰复合氧化物的除砷材料，它是纳米铁锰复合氧化物，所含铁、锰和氧的原子比为4:3:(8~10)，其中锰为+4价，铁为+3价，所述除砷材料的BET比表面积为225~282m2/g，平均粒径为10~20nm。本发明方法制备得到的纳米铁锰复合氧化物具有较大的比表面积和良好的吸附性能，对水体中砷的去除速度快、效果好，不仅能吸附砷，还能将毒性大的三价砷氧化为毒性较小的五价砷，在除砷的同时具有解毒作用，既可以用于静态吸附方式，也可装入填充柱用动态吸附方式除砷。
The invention relates to an arsenic-removing material of nano-iron-manganese composite oxide, which is a nano-iron-manganese composite oxide containing iron, manganese and oxygen in an atomic ratio of 4:3:(8~10), wherein manganese is + 4 valence, iron is +3 valence, the BET specific surface area of the arsenic removal material is 225-282m 2 /g, and the average particle size is 10-20nm. The nano-iron-manganese composite oxide prepared by the method of the present invention has a large specific surface area and good adsorption performance, has a fast removal speed and a good effect on arsenic in water bodies, and can not only adsorb arsenic, but also remove highly toxic trivalent arsenic It is oxidized to pentavalent arsenic with less toxicity, and has detoxification effect while removing arsenic. It can be used in static adsorption method or loaded into a packed column to remove arsenic in dynamic adsorption method.
Description
技术领域 technical field
本发明属于水处理领域，具体涉及一种纳米铁锰复合氧化物的除砷材料及其制备方法。 The invention belongs to the field of water treatment, and in particular relates to an arsenic-removing material of nanometer iron-manganese composite oxide and a preparation method thereof.
背景技术 Background technique
当今，自然状态下水体中砷含量超过人类安全饮用标准的情况广泛存在。中国是世界上受砷污染最严重的国家之一。砷是很重要的污染饮用水的指标之一，我国最新颁布的生活饮用水标准中的砷限定值为10μg/L，如果按照饮用水砷含量卫生标准，我国有数千万人口的饮用水超过了该标准（我国地方性砷中毒基础研究工作进展《中国地方病学杂志》付松波，陈志，2006）。如果人类长期饮用砷含量超标的水会引起砷中毒，进而导致多种健康问题，例如皮肤颜色发生变化，脚掌和手掌皮肤会变硬，容易患上皮肤癌、膀胱癌、肺癌和肾病，以及脚和腿的血管病变、糖尿病、高血压和内分泌紊乱症，严重的会引起死亡。 Nowadays, the arsenic content in water bodies in the natural state exceeds the safe drinking standard for human beings. China is one of the countries most seriously polluted by arsenic in the world. Arsenic is one of the most important indicators of drinking water pollution. The limit value of arsenic in my country's latest drinking water standard is 10 μg/L. (Fu Songbo, Chen Zhi, 2006). If humans drink water with excessive arsenic content for a long time, it will cause arsenic poisoning, which will lead to a variety of health problems, such as changes in skin color, hard skin on the soles of the feet and palms, and are prone to skin cancer, bladder cancer, lung cancer and kidney disease, as well as feet. And leg vascular disease, diabetes, hypertension and endocrine disorders, serious can cause death.
水体中除砷方法有化学方法、物理方法、生物方法等。其中，吸附法成本低廉，简便易行，是最为常见、有效的方法。除砷的吸附材料有膨润土、硅藻土、椰壳、氧化铝、氧化铁等金属氧化矿物、水合氧化物等，其中铁氧化物对砷具有强吸附能力而最为广泛关注。砷以三价和五价状态存在于自然界地下水中，而三价砷的毒性是五价砷的毒性的60倍以上。 There are chemical methods, physical methods, biological methods, etc. to remove arsenic from water. Among them, the adsorption method is the most common and effective method because of its low cost and simplicity. Adsorption materials for arsenic removal include bentonite, diatomaceous earth, coconut shell, aluminum oxide, iron oxide and other metal oxide minerals, hydrated oxides, etc. Among them, iron oxide has a strong adsorption capacity for arsenic and has attracted the most attention. Arsenic exists in natural groundwater in trivalent and pentavalent states, and the toxicity of trivalent arsenic is more than 60 times that of pentavalent arsenic.
目前的吸附材料中，大多对五价砷有较好的去除效果，但对三价砷的去除能力较差。因此在除砷过程中氧化三价砷为五价砷，同步吸附除砷的方法既能起到降低砷的毒性，还能提高砷的去除效率。铁锰复合氧化物是一种合适的材料，其中的四价锰能将三价砷氧化为五价砷，三价铁对砷有较强的去除能力。此前的方法[ 曲久辉等人，Preparation and evaluation of a novel Fe-Mn binary oxide adsorbent for effective arsenite removal, Water Research, 2007:41(9) ]中利用高锰酸盐和亚铁盐发生氧化还原反应，共沉淀法制备得到了微米级的铁锰氧化物，但是亚铁盐在反应过程中容易发生氧化，操作条件不易控制，生成物产率较低。 Most of the current adsorption materials have a good removal effect on pentavalent arsenic, but poor removal ability on trivalent arsenic. Therefore, in the process of arsenic removal, trivalent arsenic is oxidized to pentavalent arsenic, and the method of simultaneous adsorption and removal of arsenic can not only reduce the toxicity of arsenic, but also improve the removal efficiency of arsenic. Iron-manganese composite oxide is a suitable material, in which tetravalent manganese can oxidize trivalent arsenic to pentavalent arsenic, and trivalent iron has a strong ability to remove arsenic. The previous method [ Qu Jiuhui et al., Preparation and evaluation of a novel Fe-Mn binary oxide adsorbent for effective arsenite removal, Water Research, 2007:41(9) ] used permanganate and ferrous salt to generate redox reaction, co-precipitation method to prepare micron-sized iron-manganese oxides, but the ferrous salt is prone to oxidation during the reaction process, the operating conditions are not easy to control, and the product yield is low.
发明内容 Contents of the invention
本发明所要解决的技术问题是针对上述现有技术中的不足，提供一种纳米铁锰复合氧化物的除砷材料及其制备方法，其除砷材料对水体中砷的去除速度快、效果好。 The technical problem to be solved by the present invention is to provide an arsenic-removing material of nano-iron-manganese composite oxide and its preparation method in view of the deficiencies in the above-mentioned prior art. .
为了解决上述技术问题，本发明采用的技术方案如下： In order to solve the problems of the technologies described above, the technical scheme adopted in the present invention is as follows:
一种纳米铁锰复合氧化物的除砷材料，它是纳米铁锰复合氧化物，所含铁、锰和氧的原子比为4:3:(8~10)，其中锰为+4价，铁为+3价。所述除砷材料的BET比表面积为225~282 A kind of arsenic-removing material of nano-iron-manganese composite oxide, which is nano-iron-manganese composite oxide, and the atomic ratio of iron, manganese and oxygen contained is 4:3:(8~10), wherein manganese is +4 valence, Iron is +3. The BET specific surface area of the described arsenic removal material is 225 ~ 282
m2/g，平均粒径为10~20 nm。 m 2 /g, the average particle size is 10~20 nm.
一种纳米铁锰复合氧化物的除砷材料的制备方法，它包括如下步骤： A preparation method of arsenic-removing material of nano-iron-manganese composite oxide, which comprises the following steps:
(1) 按照铁盐和高锰酸盐的摩尔比为4:3，在剧烈搅拌下将铁盐溶液雾化为液滴喷入高锰酸盐溶液，同时不断调节体系的pH值为8-10并保持稳定； (1) According to the molar ratio of iron salt and permanganate as 4:3, the iron salt solution is atomized into droplets and sprayed into the permanganate solution under vigorous stirring, while continuously adjusting the pH value of the system to 8- 10 and remain stable;
(2)待铁盐溶液喷入完毕后，然后置于电炉上加热至90-100℃，保持在此温度持续加热1~2小时，加热过程中用玻璃棒搅拌防止暴沸，静置老化6-12小时，将所得固体反应产物用去离子水洗涤至中性，干燥后碾碎过筛，再于300-500℃煅烧6-12小时，即可制备得到纳米铁锰复合氧化物的除砷材料。 (2) After the iron salt solution is sprayed in, place it on an electric furnace and heat it to 90-100°C, keep heating at this temperature for 1-2 hours, stir with a glass rod during the heating process to prevent bumping, and leave it to age for 6 -12 hours, the resulting solid reaction product is washed with deionized water until neutral, dried, crushed and sieved, and then calcined at 300-500°C for 6-12 hours to prepare the arsenic-removing nano-iron-manganese composite oxide Material.
按上述方案，所述铁盐溶液浓度小于0.20mol/L。 According to the above scheme, the concentration of the iron salt solution is less than 0.20mol/L.
按上述方案，所述高锰酸盐浓度小于0.15mol/L。 According to the above scheme, the concentration of the permanganate is less than 0.15mol/L.
按上述方案，所述调节体系pH的碱性调节剂为1-3 mol/L的氢氧化钠或氢氧化钾溶液。 According to the above scheme, the alkaline regulator of the pH adjustment system is 1-3 mol/L of sodium hydroxide or potassium hydroxide solution.
按上述方案，所述铁盐为氯化铁。 According to the above scheme, the iron salt is ferric chloride.
按上述方案，所述高锰酸盐为高锰酸钾或高锰酸钠。 According to the above scheme, the permanganate is potassium permanganate or sodium permanganate.
按上述方案，所述的干燥温度为105-120℃，干燥时间为5-10 小时。 According to the above scheme, the drying temperature is 105-120° C., and the drying time is 5-10 hours.
按上述方案，所述的剧烈搅拌是指搅拌转速为150-200转/分钟。 According to the above scheme, the vigorous stirring means that the stirring speed is 150-200 rpm.
本发明通过将氯化铁溶液雾化为液滴后以喷雾方式加入到高锰酸盐反应溶液中，使雾化的铁盐液滴与反应溶液充分接触，同时剧烈搅拌，增加反应系统的扰动，使铁盐溶液和高锰酸盐溶液反应形成颗粒细小的固体反应产物，并加热分解形成铁锰复合氧化物，其中的锰为+4价，铁为+3价，然后再经煅烧处理，可使反应固体产物颗粒减小，形成纳米铁锰复合氧化物的除砷材料。 In the present invention, the ferric chloride solution is atomized into droplets and then added to the permanganate reaction solution in a spraying manner, so that the atomized iron salt droplets are fully contacted with the reaction solution, and at the same time vigorously stirred to increase the disturbance of the reaction system , make iron salt solution and permanganate solution react to form fine particle solid reaction product, and heat and decompose to form iron-manganese composite oxide, in which manganese is +4 valence, iron is +3 valence, and then calcined, The reaction solid product particles can be reduced to form arsenic-removing materials of nano-iron-manganese composite oxides.
与现有技术相比，本发明的有益效果是： Compared with prior art, the beneficial effect of the present invention is:
1、本发明所述的纳米铁锰复合氧化物除砷材料具有较大的比表面积和良好的吸附性能，对水体中砷的去除速度快、效果好，不仅能吸附砷，还能将毒性大的三价砷氧化为毒性较小的五价砷，具有氧化解毒和吸附双重功能，对三价砷和五价砷等污染物具有优良的去除效果；2、本发明制备得到的除砷材料既可以用于静态吸附方式，也可装入填充柱用动态吸附方式，除砷操作条件简单，反应完全，制备过程简单可控、成本低廉，可大规模生产，便于推广应用； 3、本发明利用喷雾进入的三价铁盐与高锰酸盐充分混合反应后，再对生成的胶体进行加热而制得，该方法避免了过去反应过程中亚铁盐变质的情况，同时使得反应更充分；4、本发明的煅烧过程有利于铁锰复合氧化物尺寸进一步减小，比表面积增大。 1. The nano-iron-manganese composite oxide arsenic removal material of the present invention has a large specific surface area and good adsorption performance, and can remove arsenic in water quickly and effectively. It can not only adsorb arsenic, but also remove highly toxic The trivalent arsenic is oxidized to less toxic pentavalent arsenic, which has dual functions of oxidation, detoxification and adsorption, and has excellent removal effect on pollutants such as trivalent arsenic and pentavalent arsenic; 2. The arsenic removal material prepared by the present invention is both It can be used in static adsorption mode, and can also be loaded into a packed column for dynamic adsorption mode. The operating conditions for arsenic removal are simple, the reaction is complete, the preparation process is simple and controllable, and the cost is low. It can be produced on a large scale and is convenient for popularization and application; 3. The present invention utilizes After the ferric salt sprayed in and permanganate are fully mixed and reacted, the colloid formed is then heated. This method avoids the deterioration of ferrous salt in the past reaction process and makes the reaction more complete; 4 . The calcination process of the present invention is beneficial to the further reduction of the size of the iron-manganese composite oxide and the increase of the specific surface area.
附图说明 Description of drawings
图1为本发明实施例1所述的纳米铁锰复合氧化物的除砷材料的EDAX能谱图。 FIG. 1 is an EDAX energy spectrum diagram of the arsenic-removing material of the nano-iron-manganese composite oxide described in Example 1 of the present invention.
图2为本发明实施例1所述的纳米铁锰复合氧化物的除砷材料的BET测试图， Fig. 2 is the BET test chart of the arsenic-removing material of the nano-iron-manganese composite oxide described in Example 1 of the present invention,
图3为本发明实施例1所述的纳米铁锰复合氧化物的除砷材料的透射电子显微镜TEM图。 Fig. 3 is a transmission electron microscope TEM image of the arsenic-removing material of the nano-iron-manganese composite oxide described in Example 1 of the present invention.
图4为本发明实施例1所述纳米铁锰复合氧化物的除砷材料对三价砷和五价砷的除砷效果图。 Fig. 4 is a diagram showing the arsenic removal effect of trivalent arsenic and pentavalent arsenic by the arsenic removal material of the nano-iron-manganese composite oxide in Example 1 of the present invention.
图5为本发明实施例2所述的纳米铁锰复合氧化物的除砷材料的EDAX能谱图。 Fig. 5 is an EDAX energy spectrum diagram of the arsenic-removing material of the nano-iron-manganese composite oxide described in Example 2 of the present invention.
图6为本发明实施例2所述的纳米铁锰复合氧化物的除砷材料的BET测试图， Fig. 6 is the BET test diagram of the arsenic-removing material of the nano-iron-manganese composite oxide described in Example 2 of the present invention,
图7为本发明实施例2所述的纳米铁锰复合氧化物的除砷材料的透射电子显微镜TEM图。 Fig. 7 is a transmission electron microscope TEM image of the arsenic-removing material of the nano-iron-manganese composite oxide described in Example 2 of the present invention.
具体实施方式 Detailed ways
实施例1 Example 1
一种纳米铁锰复合氧化物的除砷材料，它是纳米铁锰复合氧化物，所含铁、锰和氧的原子比为4:3:10，其中锰为+4价，铁为+3价，所述除砷材料的BET比表面积为282 m2/g，平均粒径为20 nm。 An arsenic-removing material for nano-iron-manganese composite oxide, which is a nano-iron-manganese composite oxide containing iron, manganese and oxygen in an atomic ratio of 4:3:10, wherein manganese is +4, and iron is +3 The BET specific surface area of the arsenic-removing material is 282 m 2 /g, and the average particle diameter is 20 nm.
上述纳米铁锰复合氧化物的除砷材料，它的制备方法包括如下步骤： The arsenic-removing material of the above-mentioned nano-iron-manganese composite oxide, its preparation method comprises the following steps:
（1）称取9.48克KMnO4和21.62克FeCl3·6H2O分别溶解于500ml去离子水中，将上述氯化铁溶液雾化为液滴喷入KMnO4溶液中，采用1 mol/L的氢氧化钠调节体系pH值为8并使其保持稳定； (1) Weigh 9.48 grams of KMnO 4 and 21.62 grams of FeCl 3 6H 2 O and dissolve them in 500ml of deionized water respectively, atomize the above ferric chloride solution into droplets and spray them into the KMnO4 solution, using 1 mol/L hydrogen Sodium oxide regulates the pH value of the system to be 8 and keeps it stable;
（2）待FeCl3·6H2O溶液喷入完毕后，将上述溶液于电炉上加热至90℃，在此温度持续加热2小时，加热过程中有氯气产生，不断用玻璃棒搅拌防止暴沸；然后静置老化12小时，将所得固体反应产物用去离子水洗涤至中性，105℃干燥10 小时后，再于300℃中煅烧12小时，即获得纳米铁锰复合氧化物的除砷材料。 (2) After the FeCl 3 6H 2 O solution is sprayed in, heat the above solution on an electric furnace to 90°C, and continue heating at this temperature for 2 hours. Chlorine gas is generated during the heating process, and keep stirring with a glass rod to prevent bumping ; Then stand and age for 12 hours, wash the obtained solid reaction product with deionized water to neutrality, dry at 105°C for 10 hours, and then calcinate at 300°C for 12 hours to obtain the arsenic-removing material of nano-iron-manganese composite oxide .
该除砷材料的反应原理为：在加热条件下，高锰酸盐分解产生的氧与氯离子发生氧化还原反应，高锰酸根中的锰被还原为Mn（Ⅳ），同时生成了氯气，在反应体系的pH条件下，Fe（Ⅲ）生成的胶体在加热过程中发生分解。最终获得了成分均一的纳米铁锰复合氧化物。 The reaction principle of this arsenic removal material is: under heating conditions, the oxygen generated by the decomposition of permanganate undergoes a redox reaction with chlorine ions, and the manganese in the permanganate is reduced to Mn (IV), and chlorine gas is generated at the same time. Under the pH condition of the reaction system, the colloid formed by Fe(Ⅲ) decomposed during heating. Finally, a nano-iron-manganese composite oxide with uniform composition was obtained.
由图1可知：该纳米铁锰复合氧化物的除砷材料为复合氧化物，铁、锰和氧的原子比为4:3:10。 It can be seen from Figure 1 that the arsenic removal material of the nano-iron-manganese composite oxide is a composite oxide, and the atomic ratio of iron, manganese and oxygen is 4:3:10.
由图2可知，该纳米铁锰复合氧化物的除砷材料的BET比表面积为282 m2/g。 It can be seen from Fig. 2 that the BET specific surface area of the arsenic-removing material of the nano-iron-manganese composite oxide is 282 m 2 /g.
由图3可知，该纳米铁锰复合氧化物的除砷材料颗粒均匀，平均粒径为10~20nm。 It can be seen from Figure 3 that the arsenic-removing material particles of the nano-iron-manganese composite oxide are uniform, with an average particle size of 10-20 nm.
上述纳米铁锰复合氧化物的除砷材料的应用效果为： The application effect of the arsenic-removing material of the above-mentioned nano-iron-manganese composite oxide is:
在初始砷浓度为 2 mg/L、pH 7.0的水体中以1g/L的使用量加入该除砷材料，摇床200转/分钟震荡，并检测体系中三价砷的浓度随时间的变化，计算三价砷去除率，结果见图4。由图4可知：5分钟后，该除砷材料对水体中三价砷和五价砷的去除率可达到84.1%和 72.4%，15分钟后，该材料对水体中三价砷和五价砷的去除率可达到92.4%和 84.6%，1小时后，该材料对水体中三价砷和五价砷的去除率可达到96.3%和91.8%，3小时后对三价砷和五价砷的去除率可达到99.9%和 99.2%。 Add the arsenic-removing material at an amount of 1 g/L to water with an initial arsenic concentration of 2 mg/L and a pH of 7.0, shake the shaker at 200 rpm, and detect the changes in the concentration of trivalent arsenic in the system over time. The removal rate of trivalent arsenic was calculated, and the results are shown in Figure 4. It can be seen from Figure 4 that after 5 minutes, the removal rate of trivalent arsenic and pentavalent arsenic in the water body by the arsenic removal material can reach 84.1% and 72.4%, and after 15 minutes, the removal rate of the trivalent arsenic and pentavalent arsenic in the water body by this material The removal rate of the material can reach 92.4% and 84.6%. After 1 hour, the removal rate of trivalent arsenic and pentavalent arsenic in water can reach 96.3% and 91.8%. After 3 hours, the removal rate of trivalent arsenic and pentavalent arsenic The removal rate can reach 99.9% and 99.2%.
实施例2 Example 2
一种纳米铁锰复合氧化物的除砷材料，它是纳米铁锰复合氧化物，所含铁、锰和氧的原子比为4:3:8，其中锰为+4价，铁为+3价，所述除砷材料的BET比表面积为225 m2/g，平均粒径为10 nm。 A material for removing arsenic from nano-iron-manganese composite oxides, which is a nano-iron-manganese composite oxide containing iron, manganese and oxygen in an atomic ratio of 4:3:8, wherein manganese is +4, and iron is +3 The BET specific surface area of the arsenic-removing material is 225 m 2 /g, and the average particle size is 10 nm.
上述纳米铁锰复合氧化物的除砷材料，它的制备方法包括如下步骤： The arsenic-removing material of the above-mentioned nano-iron-manganese composite oxide, its preparation method comprises the following steps:
（1）称取11.76克NaMnO4·3H2O和21.62克FeCl3·6H2O分别溶解于500ml去离子水中，将氯化铁溶液雾化为液滴喷入NaMnO4溶液中，采用3mol/L的氢氧化钾调节体系pH值为10并使其保持稳定； (1) Weigh 11.76 grams of NaMnO 4 3H 2 O and 21.62 grams of FeCl 3 6H 2 O and dissolve them in 500ml of deionized water, atomize the ferric chloride solution into droplets and spray it into the NaMnO 4 solution, using 3mol/ The potassium hydroxide of L adjusts the pH value of the system to be 10 and keeps it stable;
（2）待FeCl3·6H2O溶液喷入完毕后，将上述溶液于电炉上加热至95℃，在此温度持续加热1小时，加热过程中用玻璃棒搅拌防止暴沸；然后静置老化6小时，将所得固体反应产物用去离子水洗至中性，120℃干燥5小时后，再于500℃中煅烧6小时，即获得纳米铁锰复合氧化物的除砷材料。反应原理与实例1类似，在此不再赘述。 (2) After the FeCl 3 6H 2 O solution is sprayed in, heat the above solution to 95°C on an electric furnace, and continue heating at this temperature for 1 hour. During the heating process, stir with a glass rod to prevent bumping; then stand for aging After 6 hours, the obtained solid reaction product was washed with deionized water until neutral, dried at 120°C for 5 hours, and then calcined at 500°C for 6 hours to obtain the arsenic-removing material of nano-iron-manganese composite oxide. The reaction principle is similar to Example 1 and will not be repeated here.
由图5可知：该纳米铁锰复合氧化物的除砷材料为复合氧化物，铁、锰和氧的原子比为4:3:8。由图6可知，该纳米铁锰复合氧化物的除砷材料的BET比表面积为240 m2/g。 It can be seen from Fig. 5 that the arsenic removal material of the nano-iron-manganese composite oxide is a composite oxide, and the atomic ratio of iron, manganese and oxygen is 4:3:8. It can be seen from Fig. 6 that the BET specific surface area of the arsenic-removing material of the nano-iron-manganese composite oxide is 240 m 2 /g.
由图7可知，该纳米铁锰复合氧化物的除砷材料颗粒均匀，粒径约为10~20nm。 It can be seen from Fig. 7 that the arsenic-removing material particles of the nano-iron-manganese composite oxide are uniform, and the particle size is about 10-20nm.
在初始砷浓度为 2 mg/L、pH 7.0的水体中以0.5 g/L的使用量加入该除砷材料，并检测体系中三价砷的浓度随时间的变化，计算三价砷去除率，3小时后，该材料对水体中三价砷和五价砷的去除率可达到98.5%和 96.2%。 Add the arsenic removal material at an amount of 0.5 g/L in water with an initial arsenic concentration of 2 mg/L and a pH of 7.0, and detect the change of the concentration of trivalent arsenic in the system with time, and calculate the removal rate of trivalent arsenic. After 3 hours, the removal rate of trivalent arsenic and pentavalent arsenic in water can reach 98.5% and 96.2%.
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