微波诱导改性活性炭催化降解邻苯二甲酸二甲酯
|
摘要
通过HNO_3、H_2O_2、NaOH对活性炭进行浸渍改性,采用BET、SEM、Boehm、FT-IR对改性前后的活性炭进行表征,研究了改性前后的活性炭在不同反应体系对DMP的降解效果和动力学,探讨了微波诱导改性前后的活性炭催化降解DMP的机理。结果表明,3种改性活性炭的BET比表面积、总孔容、微孔孔容和平均孔径均有所增加。HNO_3、H_2O_2改性后表面酸性基团增加、碱性基团减少,而NaOH改性呈现相反的理化特征变化。活性炭理化特征的变化可能与化学改性剂溶液的酸碱性、氧化还原性有关。微波诱导改性前后的活性炭催化体系对DMP的降解率大于单独吸附或单纯微波辐射体系,且均符合一级反应动力学。在微波诱导改性前后的活性炭催化体系中,改性前后的活性炭通过表面吸附-微波诱导氧化协同作用极大地提高了对DMP的降解率。
The activated carbon was modified by HNO_3, H_2O_2 and NaOH immersion, respectively. The original and modified activated carbons were characterized by using BET, SEM, Boehm and FT-IR. The degradation effects and kinetics of dimethyl phthalate(DMP) by the original and modified activated carbons in different reaction systems were studied. The DMP degradation mechanism by microwave-induced catalytic oxidation with modified activated carbon was also discussed. The results showed that BET surface area, total pore volume,micropore volume and average pore diameter of all the modified activated carbons increased. For HNO_3 and H_2O_2 modified activated carbon, its surface acidic functional groups increased, while its surface alkaline functional groups decreased. For NaOH modified activated carbon, an opposite change occurred on its physicochemical properties. Such changes might be associated with the acidity/alkaline and oxidizability/reducibility of chemical modifier solutions. The DMP degradation rates of the microwave-induced catalytic oxidation system with the original or modified activated carbon were higher than that of adsorption alone or microwave irradiation alone, and their degradation processes all followed the first-order reaction kinetics. The reaction mechanism showed that the DMP degradation rates could be greatly improved by the synergistic effect of surface adsorption and microwave-induced oxidation.
The activated carbon was modified by HNO_3, H_2O_2 and NaOH immersion, respectively. The original and modified activated carbons were characterized by using BET, SEM, Boehm and FT-IR. The degradation effects and kinetics of dimethyl phthalate(DMP) by the original and modified activated carbons in different reaction systems were studied. The DMP degradation mechanism by microwave-induced catalytic oxidation with modified activated carbon was also discussed. The results showed that BET surface area, total pore volume,micropore volume and average pore diameter of all the modified activated carbons increased. For HNO_3 and H_2O_2 modified activated carbon, its surface acidic functional groups increased, while its surface alkaline functional groups decreased. For NaOH modified activated carbon, an opposite change occurred on its physicochemical properties. Such changes might be associated with the acidity/alkaline and oxidizability/reducibility of chemical modifier solutions. The DMP degradation rates of the microwave-induced catalytic oxidation system with the original or modified activated carbon were higher than that of adsorption alone or microwave irradiation alone, and their degradation processes all followed the first-order reaction kinetics. The reaction mechanism showed that the DMP degradation rates could be greatly improved by the synergistic effect of surface adsorption and microwave-induced oxidation.
引文
[1]路俊玲,彭宇科,陈旭,等.包埋法固定化对邻苯二甲酸酯降解菌功能的影响[J].南京大学学报(自然科学版),2017,53(2):309-315.
[2]李章良,黄建辉,肖尚忠,等.活性炭负载Fe3+催化H2O2氧化邻苯二甲酸二甲酯[J].环境工程学报,2014,8(3):827-833.
[3]翟斌,王朝万,张巍,等.环境介质中邻苯二甲酸酯类化合物的环境行为及生态风险研究进展[J].环境与健康杂志,2016,33(11):1030-1034.
[4]LIU Y,GUAN Y T,YANG Z H,et al.Toxicity of seven phthalate esters to embryonic development of the abalone Halitosis diverticular supertexta[J].Ecotoxicology,2018,18(3):293-303.
[5]张可,关允,格桑,等.低温邻苯二甲酸二甲酯降解菌STX-2和STX-5的分离、鉴定及降解特性[J].环境污染与防治,2017,39(1):16-20.
[6]郭静波,陈微,姜丽杰,等.邻苯二甲酸二丁酯生物降解研究进展[J].应用与环境生物学报,2014,20(6):1104-1110.
[7]黄荣新,赖后伟,林伟仲,等.不同活性炭对PAEs的吸附特性研究[J].中国给水排水,2017,33(17):81-83.
[8]WANG W L,WU Q Y,WANG C,et al.Health risk assessment of phthalate esters(PAEs)in drinking water sources of China[J].Environmental Science and Pollution Research,2015,22(5):3620-3630.
[9]胡晓宇,张克荣,孙俊红,等.中国环境中邻苯二甲酸酯类化合物污染的研究[J].中国卫生检验杂志,2003,13(1):9-14.
[10]MATSUMOTO M,HIRATA-KOIZUMI M,EMA M.Potential adverse effects of phthalate esters on human health:A review of recent studies on reproduction[J].Regulatory Toxicology and Pharmacology,2008,50(1):37-49.
[11]彭轶瑶,陶娟,冯靖雯,等.微波诱导催化氧化六方软锰矿降解四环素[J].人工晶体学报,2014,43(7):1651-1656.
[12]冯文煊,施文健,刘剑青,等.微波技术在污水处理中的研究进展和应用[J].环境污染与防治,2014,36(1):73-79.
[13]WANG N,WANG P.Study and application status of microwave in organic wastewater treatment:A review[J].Chemical Engineering Journal,2016,283:193-214.
[14]TAI H S,JOU C J G.Application of granular activated carbon packed-bed reactor in microwave radiation field to treat phenol[J].Chemosphere,1999,38(11):2667-2680.
[15]张洪卫,徐瑶,刘丹妮,等.硝酸改性活性炭催化微波诱导降解水中结晶紫的方法研究[J].工业水处理,2013,33(6):36-39.
[16]施向荣,丁洁莲,赵浩,等.改性氧化铝微波诱导催化氧化处理高浓度苯酚废水的研究[J].环境工程学报,2011,5(7):1468-1472.
[17]BOEHM H P.Surface oxides on carbon and their analysis:a critical assessment[J].Carbon,2002,40(2):145-149.
[18]张晓光,房俊卓,胡奇林.煤基活性炭轻度氧化改性的研究[J].化学世界,2008,49(4):210-212.
[19]方智,许国根,朱光威.碳纳米管对偏二甲肼的吸附性能分析[J].环境工程学报,2009,3(4):703-706.
[20]MIKHALOVSKY S V,ZAITSEV Y P.Catalytic properties of activated carbons I.Gas-phase oxidation of hydrogen sulphide[J].Carbon,1997,35(9):1367-1374.
[21]王金成,薛大明,全燮,等.活性艳蓝KN-R染料溶液微波催化脱色研究[J].大连理工大学学报,2001,41(5):545-548.
[22]周汇,买文宁,肖珊.微波诱导改性活性炭催化处理低浓度抗生素废水[J].环境化学,2012,31(10):1631-1636.
[23]李娜,李小明,杨麒,等.微波/活性炭强化过硫酸盐氧化处理垃圾渗滤液研究[J].中国环境科学,2014,34(1):91-96.
[24]吴慧英,施周,陈积义,等.活性炭-微波辐射法去除苯酚的机理研究[J].环境工程学报,2009,3(1):67-71.
[25]谢红艳,林亲铁,刘志,等.微波强化Cu/Fe3O4/活性炭-过硫酸钠催化氧化邻苯二甲酸二丁酯的研究[J].环境污染与防治,2017,39(8):851-855.
[2]李章良,黄建辉,肖尚忠,等.活性炭负载Fe3+催化H2O2氧化邻苯二甲酸二甲酯[J].环境工程学报,2014,8(3):827-833.
[3]翟斌,王朝万,张巍,等.环境介质中邻苯二甲酸酯类化合物的环境行为及生态风险研究进展[J].环境与健康杂志,2016,33(11):1030-1034.
[4]LIU Y,GUAN Y T,YANG Z H,et al.Toxicity of seven phthalate esters to embryonic development of the abalone Halitosis diverticular supertexta[J].Ecotoxicology,2018,18(3):293-303.
[5]张可,关允,格桑,等.低温邻苯二甲酸二甲酯降解菌STX-2和STX-5的分离、鉴定及降解特性[J].环境污染与防治,2017,39(1):16-20.
[6]郭静波,陈微,姜丽杰,等.邻苯二甲酸二丁酯生物降解研究进展[J].应用与环境生物学报,2014,20(6):1104-1110.
[7]黄荣新,赖后伟,林伟仲,等.不同活性炭对PAEs的吸附特性研究[J].中国给水排水,2017,33(17):81-83.
[8]WANG W L,WU Q Y,WANG C,et al.Health risk assessment of phthalate esters(PAEs)in drinking water sources of China[J].Environmental Science and Pollution Research,2015,22(5):3620-3630.
[9]胡晓宇,张克荣,孙俊红,等.中国环境中邻苯二甲酸酯类化合物污染的研究[J].中国卫生检验杂志,2003,13(1):9-14.
[10]MATSUMOTO M,HIRATA-KOIZUMI M,EMA M.Potential adverse effects of phthalate esters on human health:A review of recent studies on reproduction[J].Regulatory Toxicology and Pharmacology,2008,50(1):37-49.
[11]彭轶瑶,陶娟,冯靖雯,等.微波诱导催化氧化六方软锰矿降解四环素[J].人工晶体学报,2014,43(7):1651-1656.
[12]冯文煊,施文健,刘剑青,等.微波技术在污水处理中的研究进展和应用[J].环境污染与防治,2014,36(1):73-79.
[13]WANG N,WANG P.Study and application status of microwave in organic wastewater treatment:A review[J].Chemical Engineering Journal,2016,283:193-214.
[14]TAI H S,JOU C J G.Application of granular activated carbon packed-bed reactor in microwave radiation field to treat phenol[J].Chemosphere,1999,38(11):2667-2680.
[15]张洪卫,徐瑶,刘丹妮,等.硝酸改性活性炭催化微波诱导降解水中结晶紫的方法研究[J].工业水处理,2013,33(6):36-39.
[16]施向荣,丁洁莲,赵浩,等.改性氧化铝微波诱导催化氧化处理高浓度苯酚废水的研究[J].环境工程学报,2011,5(7):1468-1472.
[17]BOEHM H P.Surface oxides on carbon and their analysis:a critical assessment[J].Carbon,2002,40(2):145-149.
[18]张晓光,房俊卓,胡奇林.煤基活性炭轻度氧化改性的研究[J].化学世界,2008,49(4):210-212.
[19]方智,许国根,朱光威.碳纳米管对偏二甲肼的吸附性能分析[J].环境工程学报,2009,3(4):703-706.
[20]MIKHALOVSKY S V,ZAITSEV Y P.Catalytic properties of activated carbons I.Gas-phase oxidation of hydrogen sulphide[J].Carbon,1997,35(9):1367-1374.
[21]王金成,薛大明,全燮,等.活性艳蓝KN-R染料溶液微波催化脱色研究[J].大连理工大学学报,2001,41(5):545-548.
[22]周汇,买文宁,肖珊.微波诱导改性活性炭催化处理低浓度抗生素废水[J].环境化学,2012,31(10):1631-1636.
[23]李娜,李小明,杨麒,等.微波/活性炭强化过硫酸盐氧化处理垃圾渗滤液研究[J].中国环境科学,2014,34(1):91-96.
[24]吴慧英,施周,陈积义,等.活性炭-微波辐射法去除苯酚的机理研究[J].环境工程学报,2009,3(1):67-71.
[25]谢红艳,林亲铁,刘志,等.微波强化Cu/Fe3O4/活性炭-过硫酸钠催化氧化邻苯二甲酸二丁酯的研究[J].环境污染与防治,2017,39(8):851-855.