锰氧化膜包覆沸石的制备及其处理含锰水特性研究

摘要/Abstract

摘要： 净水厂广泛采用石英砂或锰砂滤池,但在接触氧化法除锰过程中存在滤料吸附性能差、“锰质活性滤膜”成熟期长等问题。针对这一现象,以沸石为基质材料,高锰酸钾和硫酸锰生成锰氧化物沉积在沸石表面,制备锰氧化膜包覆沸石(MOMCZ),MOMCZ结合了沸石的吸附性能和锰氧化物的催化氧化特性。采用SEM、EDS、XPS、XRD、BET、Zeta电位等分析表征方法研究MOMCZ的表面形态、化学组成等特性,通过响应曲面模型分析MOMCZ对锰离子的吸附性能。结果表明:MOMCZ表面的锰氧化膜呈现立体复杂的网状结构,Mn元素存在形式及摩尔分数分别为Mn(Ⅲ)51.28%,Mn(Ⅳ)48.72%,锰氧化膜主要成分为Na_0.55Mn₂O₄(H₂O)_1.5;MOMCZ比表面积为38.76 m²/g,孔径分布集中在3～40 nm,等电点pH=2.36;MOMCZ吸附锰离子的四项影响因素关系顺序为:pH值＞负荷＞吸附时间＞吸附温度;通过模型优化发现当负荷为0.8 mg/g、pH=8.5、吸附温度为23.40 ℃、吸附时间为6.58 min时,锰离子去除率达到最大值70.82%;试验模型预测值和实际数据值相对误差均小于2.5%。MOMCZ吸附锰离子响应曲面模型拟合程度高、预测准确,具有较高的可行性和参考价值。

关键词: 沸石, 锰氧化膜, Na_0.55Mn₂O₄(H₂O)_1.5, 吸附, 响应曲面

Abstract: Quartz or manganese sand filters are widely used in water purification plants, however, there are problems such as poor adsorption performance of filter materials and a long time of “start-up period” in the process of contact oxidation manganese removal. In view of this phenomenon, manganese oxide membrane coated zeolite (MOMCZ) was prepared by using zeolite as the matrix material, and potassium permanganate and manganese sulfate were used to generate manganese oxide and then deposit on the surface of zeolite. MOMCZ was combined with the adsorption properties of zeolite and the catalytic oxidation characteristics of manganese oxide. SEM, EDS, XPS, XRD, BET, and Zeta potential analyses were used to observe surface morphology and chemical composite of MOMCZ. The response surface model was used to analyze the effect of adsorption performance of MOMCZ on manganese ions. The results show that manganese oxide membrane on surface of MOMCZ exhibits a three-dimensional complex network structure. The existing forms and molar ratio of Mn element are 51.28% for Mn (Ⅲ) and 48.72% for Mn (Ⅳ). Na_0.55Mn₂O₄(H₂O)_1.5 is the main component of manganese oxide membrane. The specific surface area of MOMCZ is 38.76 m²/g, and the pore size distribution is concentrated in the range of 3～40 nm and the isoelectric point pH value is 2.36. The order of four influencing factors for adsorption of manganese ions by MOMCZ is pH value> load> adsorption time> adsorption temperature. Through model optimization, it is found that the maximum manganese ion removal rate reaches 70.82% at the load of 0.8 mg/g, pH=8.5, adsorption temperature of 23.40 ℃, and adsorption time of 6.58 min. The relative error between the predicted values of experimental model and the actual data values is less than 2.5%. The response surface model of MOMCZ adsorption manganese ion has a high degree of fitting and accurate prediction, and has high feasibility and reference value.

Key words: zeolite, manganese oxide membrane, Na_0.55Mn₂O₄(H₂O)_1.5, adsorption, response surface

中图分类号:

金星, 傅金祥, 张黎, 何祥. 锰氧化膜包覆沸石的制备及其处理含锰水特性研究[J]. 硅酸盐通报, 2023, 42(9): 3295-3305.

JIN Xing, FU Jinxiang, ZHANG Li, HE Xiang. Preparation of Manganese Oxide Membrane Coated Zeolite and Characteristics of Treating Manganese Containing Water[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2023, 42(9): 3295-3305.

参考文献

[1] 胡文静, 班锦锦, 谢顺利, 等. 氧化锰基电催化材料的设计合成及其铝空气电池应用[J]. 硅酸盐通报, 2023, 42(2): 728-735+742.
HU W J, BAN J J, XIE S L, et al. Design and synthesis of manganese oxide-based electrocatalytic materials and application in aluminum air battery[J]. Bulletin of the Chinese Ceramic Society, 2023, 42(2): 728-735+742 (in Chinese).
[2] 刘倩, 郑小平, 张荣华, 等. 新型汽车用高强度中锰钢研究现状及发展趋势[J]. 材料导报, 2019, 33(7): 1215-1220.
LIU Q, ZHENG X P, ZHANG R H, et al. Medium manganese high strength steel for automotive application: status quo and prospects[J]. Materials Reports, 2019, 33(7): 1215-1220 (in Chinese).
[3] 余高, 陈芬, 张晓东, 等. 锰矿区周边农田土壤重金属污染特征、来源解析及风险评价[J/OL]. 环境科学, 2023: 1-17 [2023-04-02]. http://kns.cnki.net/kcms/detail/11.2062.O3.20230329.1458.004.html.
YU G, CHEN F, ZHANG X D, et al. Pollution characteristics, source analysis, and risk assessment of heavy metals in the surrounding farmlands of manganese mining area[J]. Environmental Science, 2023: 1-17 [2023-04-02]. http://kns.cnki.net/kcms/detail/11.2062.O3.20230329.1458.004.html (in Chinese).
[4] 纪银传. 二氧化氯预氧化原水中铁锰微污染的实践[J]. 净水技术, 2022, 41(9): 174-179+186.
JI Y C. Practice of chlorine dioxide pre-oxidation for iron and manganese micropollution removal in raw water[J]. Water Purification Technology, 2022, 41(9): 174-179+186 (in Chinese).
[5] 黄春霞, 黄立幸. 广西锰矿区重金属污染现状及治理对策研究综述[J]. 能源环境保护, 2021, 35(1): 1-5.
HUANG C X, HUANG L X. A review of pollution status and countermeasures of heavy metal pollution in Guangxi manganese mining areas[J]. Energy Environmental Protection, 2021, 35(1): 1-5 (in Chinese).
[6] 谭荣浩, 杨秀贞. 矿区水体中锰污染及其控制技术研究现状[J]. 化工管理, 2020(26): 113-114.
TAN R H, YANG X Z. Research status of manganese pollution in mining water and its control technology[J]. Chemical Enterprise Management, 2020(26): 113-114 (in Chinese).
[7] OULHOTE Y, MERGLER D, BARBEAU B, et al. Neurobehavioral function in school-age children exposed to manganese in drinking water[J]. Environmental Health Perspectives, 2014, 122(12): 1343-1350.
[8] HERNÁNDEZ B D, ESCAMILLA N C, MERGLER D, et al. Effects of manganese exposure on visuoperception and visual memory in schoolchildren[J]. NeuroToxicology, 2016, 57: 230-240.
[9] 王广军, 田质光, 李振东, 等. 职业性锰中毒与原发性帕金森病临床特点的比较[J]. 中国工业医学杂志, 2017, 30(5): 340-341.
WANG G J, TIAN Z G, LI Z D, et al. Clinical feature comparison between occupational manganese poisoning and idiopathic Parkinson's disease[J]. Chinese Journal of Industrial Medicine, 2017, 30(5): 340-341 (in Chinese).
[10] 袁雅姝, 陈正洋, 傅金祥, 等. 地下水源除铁锰滤池调试运行实践及思考[J]. 中国给水排水, 2020, 36(15): 35-40.
YUAN Y S, CHEN Z Y, FU J X, et al. Practice and consideration of commissioning and operation of iron and manganese removal filter treating groundwater in Liaozhong district of Shenyang city[J]. China Water & Wastewater, 2020, 36(15): 35-40 (in Chinese).
[11] 陈天意. 锰砂滤池处理高浓度铁锰及氨氮地下水pH影响研究[D]. 哈尔滨: 哈尔滨工业大学, 2014: 8-9.
CHEN T Y. Influence of pH on the performance of manganese filter for treating high concentration iron, manganese and ammonia contaminated underground water[D]. Harbin: Harbin Institute of Technology, 2014: 8-9 (in Chinese).
[12] 李圭白, 梁恒, 余华荣, 等. 锰质活性滤膜化学催化氧化除锰机理研究[J]. 给水排水, 2019, 55(5): 6-10+75.
LI G B, LIANG H, YU H R, et al. Research on manganese removal by chemical auto-catalytic oxidation mechanism involved in active manganese oxides film[J]. Water & Wastewater Engineering, 2019, 55(5): 6-10+75 (in Chinese).
[13] 孙成超. 高锰酸钾快速启动接触氧化除锰滤池及其处理效能[D]. 哈尔滨: 哈尔滨工业大学, 2019: 5-8.
SUN C C. Contact oxidation filter enchanced by potassium permanganate for manganese removal: quick start and performance of treatment[D]. Harbin: Harbin Institute of Technology, 2019: 5-8 (in Chinese).
[14] JOHNSON E B G, ARSHAD S E. Hydrothermally synthesized zeolites based on kaolinite: a review[J]. Applied Clay Science, 2014, 97/98: 215-221.
[15] 傅金祥, 张思佳, 金星, 等. 载锰氧化物活性沸石的制备及去除水中Mn(Ⅱ)试验研究[J]. 湿法冶金, 2022, 41(4): 359-365.
FU J X, ZHANG S J, JIN X, et al. Preparation of zeolite-loaded manganese oxides and removal of Mn²⁺ in water[J]. Hydrometallurgy of China, 2022, 41(4): 359-365 (in Chinese).
[16] 谭文渊. 天然沸石的改性与表征及其去除生活废水中LAS的应用研究[D]. 成都: 成都理工大学, 2016: 10-23.
TAN W Y. Application study on the modification and characterization of nature zeolite and removal of LAS in domestic wastewater[D]. Chengdu: Chengdu University of Technology, 2016: 10-23 (in Chinese).
[17] 白朗明, 冯亭龙, 姚利辉, 等. pH对预氧化沸石滤柱启动过程中除锰效率的影响[J]. 环境工程学报, 2023, 17(5): 1476-1486.
BAI L M, FENG T L, YAO L H, et al. Effect of pH on manganese removal efficiency during the start-up process of pre-oxidation zeolite filter column[J]. Chinese Journal of Environmental Engineering, 2023, 17(5): 1476-1486 (in Chinese).
[18] ZANIN E, SCAPINELLO J, DE OLIVEIRA M, et al. Adsorption of heavy metals from wastewater graphic industry using clinoptilolite zeolite as adsorbent[J]. Process Safety and Environmental Protection, 2017, 105: 194-200.
[19] 徐响, 孙丽萍, 董捷. 响应面法优化蜂胶超临界二氧化碳萃取工艺的研究[J]. 食品科学, 2009, 30(8): 86-89.
XU X, SUN L P, DONG J. Optimization of supercritical carbon dioxide extraction of effective components from propolis using response surface methodology[J]. Food Science, 2009, 30(8): 86-89 (in Chinese).
[20] WU H, LIU Z, SUN B B, et al. Experimental investigation on freeze-thaw durability of Portland cement pervious concrete (PCPC)[J]. Construction and Building Materials, 2016, 117: 63-71.
[21] 王选, 时元昆, 杨博, 等. 基于响应面方法的破损-安全结构可靠性拓扑优化[J/OL]. 力学学报, 2023: 1-11[2023-04-02]. https://kns.cnki.net/kcms/detail/11.2062.O3.20230329.1458.004.html.
WANG X, SHI Y K, YANG B, et al. Reliability-based topology optimization of fail-safe structures using response surface method[J/OL]. Chinese Journal of Theoretical and Applied Mechanics, 2023: 1-11[2023-04-02]. https://kns.cnki.net/kcms/detail/11.2062.O3.20230329.1458.004.html (in Chinese).
[22] 姜盛基, 王刚, 严亚萍, 等. 响应面法优化重金属螯合絮凝剂MAAPAM去除水中Cu(Ⅱ)[J]. 环境科学与技术, 2020, 43(11): 124-130.
JIANG S J, WANG G, YAN Y P, et al. Optimization of the removal condition of Cu(Ⅱ) from water with heavy metal chelating-flocculant MAAPAM by response surface methodology[J]. Environmental Science & Technology, 2020, 43(11): 124-130 (in Chinese).
[23] JOHN F M, WILLIAM F S, PETER E S, et al. Handbook of X-ray photoelectron spectroscopy[M]. EDEN PRAIRIE: Perkin-elmer corporation physical electronics division, 1992, 226-227.
[24] 李金成. 负载锰氧化物滤料对高锰地下水处理技术研究[D]. 青岛: 中国海洋大学, 2011.
LI J C. Removal of high content manganese from ground water with manganese oxide-coated filter[D]. Qingdao: Ocean University of China, 2011 (in Chinese).