范素兵, 吕俊敏, 马玉龙, 杨小风. Cu修饰成型13X分子筛对水中四环素的吸附行为[J]. 环境化学, 2018, 37(12): 2721-2729
FAN Subing, LV Junmin, MA Yulong, YANG Xiaofeng. Adsorption behavior of modified shaped 13X zeolite for removing tetracycline in aqueous solution[J]. Environmental Chemistry, 2018, 37(12): 2721-2729

范素兵, 吕俊敏, 马玉龙, 杨小风
宁夏大学省部共建煤炭高效利用与绿色化工国家重点实验室, 宁夏大学化学化工学院, 银川, 750021
关键词:    13X成型分子筛    四环素    吸附行为    再生   
Adsorption behavior of modified shaped 13X zeolite for removing tetracycline in aqueous solution
FAN Subing, LV Junmin, MA Yulong, YANG Xiaofeng
State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering;College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan, 750021, China
To remove of organic pollutant tetracycline (TC) in water, Cu(Ⅱ) modified shaped zeolite (Cu-13X(s)) as an adsorbent was prepared and investigated to understand its adsorption behaviour for TC and regenerability. Results showed that the crystal topology, morphology and Si/Al ratio of Cu-13X(s) almost remained unchanged in comparison to 13X. The adsorption kinetics fitted pseudo-second-order model. For high concentrations of tetracycline, intra-particle diffusion was the rate-determining step, but not the only one. The adsorption isotherms were described well by the Langmuir model, and the process was exothermic and entropically unfavorable. After repeated adsorption-regeneration for 4 times, Cu-13X(s) still possessed constant removal efficiency, indicating excellent regenerability.
Key words:    shaped 13X zeolite    tetracycline    adsorption behavior    regenerability   
收稿日期: 2018-08-23
基金项目: 国家自然科学基金(21467023)和宁夏高校科学研究项目(NGY2016005,NGY2017001)资助.
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[1] 李伟明, 鲍艳宇, 周启星.四环素类抗生素降解途径及其主要降解产物研究进展[J]. 应用生态学报,2012,23(8):2300-2308. LI W M, BAO Y Y, ZHOU Q X. Degradation pathways and main degradation products of tetracycline antibiotics:Research progress[J]. Chinese Journal of Applied Ecology, 2012, 23(8):2300-2308(in Chinese).
[2] DAGHRIR R, DROGUI P. Tetracycline antibiotics in the environment:A review[J]. Environmental Chemistry Letters, 2013, 11:209-227.
[3] ZHOU Q, ZHANG M C, SHUANG C D, et al. Preparation of a novel magnetic powder resin for the rapid removal of tetracycline in the aquatic environment[J]. Chinese Chemical Letters, 2012, 23:745-748.
[4] 戴江栋.多级孔碳基材料的可控制备及其高效分离抗生素行为和机理研究[D]. 镇江:江苏大学,2016. DAI J D. Controlled preparation of porous carbon-based materials and study on behavior and mechanism of high-efficiency antibiotic separation[D]. Zhenjiang:Jiangsu University, 2016(in Chinese).
[5] LI R P, ZHANG Y, LEE C C, et al. Hydrophilic interaction chromatography separation mechanisms of tetracyclines on amino-bonded silica column[J]. Journal of Separation Science, 2011, 34:1508-1516.
[6] XIE X J, ZHOU Q X, HE Z C, et al. Physiological and potential genetic toxicity of chlortetracycline as an emerging pollutant in wheat (Triticum aestivum L.)[J]. Environmental Toxicology and Chemistry, 2010, 29:922-928.
[7] PENA A, PAULO M, SILVA L J G, et al. Tetracycline antibiotics in hospital and municipal wastewaters:A pilot study in Portugal[J]. Analytical and Bioanalytical Chemistry, 2010, 396:2929-2936.
[8] DEBLONDE T, COSSU-LEGUILLE C, HARTEMANN P. Emerging pollutants in wastewater:A review of the literature[J]. International Journal of Hygiene and Environmental Health, 2011, 214:442-448.
[9] LIU M M, HOU L A, YU S L, et al. MCM-41 impregnated with A zeolite precursor:Synthesis, characterization and tetracycline antibiotics removal from aqueous solution[J]. Chemical Engineering Journal, 2013, 223:678-687.
[10] 刘莉莉, 郭倩倩, 陈鑫, 等. 城市污水处理厂四环素抗性菌的筛选及其抗性基因分析[J]. 环境科学学报,2017,37(11):4039-4046. LIU L L, GUO Q Q, CHEN X, et al. Isolation of tetracycline resistant bacteria and the analysis of its antibiotic resistance genes from municipal wastewater treatment plant[J]. Acta Scientiae Circumstantiae, 2017,37(11):4039-4046(in Chinese).
[11] LARSSON D G J, FICK J. Transparency throughout the production chain-a way to reduce pollution from the manufacturing of pharmaceuticals[J]. Regulatory Toxicology and Pharmacology, 2009, 53:161-163.
[12] 俞幼萍, 高品, 刘保江, 等. 新型光-类芬顿催化剂纳米Fe VO4的制备及其对盐酸四环素的降解性能[J]. 环境工程学报,2017,11(1):401-407. YU Y P, GAO P, LIU B J, et al. Preparation and degradation properties toward tetracycline hydrochloride of a new photo-Fenton-like catalyst nano Fe VO4[J], Chinese Journal of Environmental Engineering, 2017, 11(1):401-407(in Chinese).
[13] HOMEM V, SANTOS L. Degradation and removal methods of antibiotics from aqueous matrices-a review[J]. Journal of Environmental Management, 2011, 92:2304-2347.
[14] 王丽琼, 王凯, 马玉龙. 改性蒙脱石吸附制药废水中残留四环素的研究[J]. 环境科学与技术,2017,40(8):197-201. WANG L Q, WANG K, MA Y L. Study on adsorption of residual tetracycline in pharmaceutical wastewater using modified montmorillonite[J], Environmental Science & Technology, 2017,40(8):197-201(in Chinese).
[15] KOYUNCU I, ARIKAN O A, WIESNER M R, et al. Removal of hormones and antibiotics by nanofiltration membranes[J]. Journal of Membrane Science, 2008, 309:94-101.
[16] MIYATA M, IHARA I, YOSHID G, et al. Electrochemical oxidation of tetracycline antibiotics using a Ti/TiO2 anode for wastewater treatment of animal husbandry[J]. Water Science and Technology, 2011, 63:456-461.
[17] WANG Y, ZHANG H, CHEN L, et al. Ozonation combined with ultrasound for the degradation of tetracycline in a rectangular air-lift reactor[J]. Separation and Purification Technology, 2012, 84:138-146.
[18] 郭照冰, 周飞, 张超智, 等.水中四环素的超声辐照降解[J]. 环境化学,2012,31(8):1215-1221. GUO Z B, ZHOU F, ZHANG C Z, et al. Degradation of tetracycline in aqueous solution by ultrasonic irradiation[J]. Environmental Chemistry, 2012, 31(8):1215-1221(in Chinese).
[19] YAGUB M T, SEN T K, AFROZE. S, et al. Dye and its removal from aqueous solution by adsorption:A review[J]. Advances in Colloid and Interface Science, 2014, 209:172-184.
[20] 邢淑建, 臧甲忠, 刘伟, 等.分子筛吸附剂的工业应用研究进展[J]. 无机盐工业,2009,41(3):13-16. XING S J, ZANG J Z, LIU W, et al. Progresson industrial application of molecular sieve adsorbents[J]. Inorganic Chemicals Industry, 2009, 41(3):13-16(in Chinese).
[21] LIU X P, WANG R. Effective removal of hydrogen sulfide using 4A molecular sieve zeolite synthesized from attapulgite[J]. Journal of Hazardous Materials, 2017, 326:157-164.
[22] MABEL V M, CALLEJAS R L, GEHR R. Heavy metal removal with Mexican clinoptilolitemulti-component ionic exchange[J]. Water Research, 2001, 35(2):373-378.
[23] 全姗姗, 朱玉婵, 任占海, 等.改性MCM-41分子筛对阴离子偶氮染料的吸附作用机理[J]. 化工进展,2016,35(1):320-326. QUAN S S, ZHU Y C, REN Z H, et al. Adsorption performance of anionic azo dye by the modified MCM-41 mesoporous molecular sieve[J]. Chemical Industry and Engineering Progress, 2016, 35(1):320-326(in Chinese).
[24] 江明明, 朱孟府, 邓橙, 等. LiX沸石分子筛的铈离子改性研究[J]. 应用化工,2017,46(2):332-334. JIANG M M, ZHU M F, DENG C, et al. Modification of Li X zeolite molecular sieve via cerium ions[J]. Applied Chemical Industry, 2017, 46(2):332-334(in Chinese).
[25] 张志芳, 杨丽娜, 白金, 等. 介孔炭-HY分子筛复合型脱硫吸附剂的制备与性能[J]. 硅酸盐学报,2017,54(4):579-584. ZHANG Z F, YANG L N, BAI J, et al. Preparation and Performance of OMC-HY Composite Desulfurization Adsorbent[J]. Journal of the Chinese Ceramic Society, 2017, 54(4):579-584(in Chinese).
[26] 潘兴朋, 吴相英, 杜君, 等.碱处理Beta分子筛吸附脱硫动力学[J]. 化工学报,2016,67(9):3747-3754. PAN X P, WU X Y, DU J, et al. Kinetics of adsorptive desulfurization over alkaline-treated Beta zeolite[J]. CIESC Journal, 2016, 67(9):3747-3754(in Chinese).
[27] 荚德安.土壤中四环素与铜的吸附行为及其影响因素研究[D]. 南京:南京林业大学, 2008. JIA D A, Study of adsorption of tetracycline and copper in soils and impact of factors on their adsorption[D]. Nanjing:Nanjing Forestry University, 2008(in Chinese).
[28] JIA D A, ZHOU D M, WANG Y J, et al. Adsorption and cosorption of Cu(Ⅱ) and tetracycline on two soils with different characteristics[J]. Geoderma, 2008, 146:224-230.
[29] LIAN F, SONG Z G, LIU Z Q, et al. Mechanistic understanding of tetracyclinesorption on waste tire powder and its chars as affected by Cu2+ and pH[J]. Environmental Pollution, 2013, 178:264-270.
[30] LV J M, MA Y L, CHANG X, et al. Removal and removing mechanism of tetracycline residue from aqueous solution by using Cu-13X[J]. Chemical Engineering Journal, 2015, 273:247-253.
[31] RAJI C, ANIRUDHAN T S. Batch Cr(Ⅵ) removal by polyacrylamide-graftee sawdust:kinetics and thermodynamics[J]. Water Research, 1998, 32(12):3772-3780.
[32] KHAN A A, SINGH R P. Adsorption thermodynamics of carbofuran on Sn(Ⅳ) arsenosilicate in H+, Na+ and Ca2+ forms[J]. Colloids and Surfaces, 1987, 24:33-42.