废汞触媒中汞的浸出及其再生活性炭的吸附性能
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摘要
对电石法生产聚氯乙烯产生的废汞触媒进行浸出及再生活性炭的研究,以6 mol·L~(-1)HCl溶液作为浸出剂,在浸出反应温度为65℃、浸出反应时间为90 min和液固比为15∶1的实验条件下得到Hg~(2+)的优化浸出率为61.25%。采用扫描电镜(SEM)、Brunauer-Emmet-Tller(BET)比表面积等方法分析再生活性炭特征。结果表明焙烧废汞触媒浸出渣热再生活性炭是可行的,焙烧最佳工艺条件为:焙烧温度850℃,焙烧时间90 min。得到的焙烧产物亚甲基蓝吸附值为120.5 mg·g~(-1),BET表面积为704.25 m~2·g~(-1),平均孔径为3.28 nm。再生前后的汞含量与从1.067%降至0.351%,再生后能再次作为汞触媒生产的催化剂载体材料,同时减缓固废堆积过程中汞流失造成的一系列环境问题。
Leaching and activated carbon regeneration from waste mercury catalyst produced during polyvinyl chloride preparation by calcium carbide process were studied. When 6 mol·L~(-1) HCl was used as a leaching agent, the optimum leaching rate of Hg~(2+)was 61.25% under the conditions of reaction temperature of 65 ℃,reaction time of 90 min and liquid-solid ratio of 15∶1. Scanning electron microscopy(SEM), Brunauer-EmmetTller(BET) surface area and other analysis methods were used to identify the characteristics of regenerated activated carbon, which indicated that it is feasible to regenerate activated carbon by roasting waste mercury catalyst. The optimum roasting conditions were as following: 850 ℃ for roasting temperature and 90 min for roasting duration. The methylene blue adsorption value, specific surface area and average pore size of the roasted product were 120.5 mg·g~(-1), 704.25 m~2·g~(-1) and 3.28 nm, respectively. Mercury content in waste mercury catalyst decreased from 1.067% to 0.351% after regeneration. The regenerated activated carbon can be used as catalyst carrier material for mercury catalyst production again, and also alleviate a series of environmental problems caused by mercury loss during solid waste accumulation process.
Leaching and activated carbon regeneration from waste mercury catalyst produced during polyvinyl chloride preparation by calcium carbide process were studied. When 6 mol·L~(-1) HCl was used as a leaching agent, the optimum leaching rate of Hg~(2+)was 61.25% under the conditions of reaction temperature of 65 ℃,reaction time of 90 min and liquid-solid ratio of 15∶1. Scanning electron microscopy(SEM), Brunauer-EmmetTller(BET) surface area and other analysis methods were used to identify the characteristics of regenerated activated carbon, which indicated that it is feasible to regenerate activated carbon by roasting waste mercury catalyst. The optimum roasting conditions were as following: 850 ℃ for roasting temperature and 90 min for roasting duration. The methylene blue adsorption value, specific surface area and average pore size of the roasted product were 120.5 mg·g~(-1), 704.25 m~2·g~(-1) and 3.28 nm, respectively. Mercury content in waste mercury catalyst decreased from 1.067% to 0.351% after regeneration. The regenerated activated carbon can be used as catalyst carrier material for mercury catalyst production again, and also alleviate a series of environmental problems caused by mercury loss during solid waste accumulation process.
引文
[1]薛之化.电石法聚氯乙烯生产中的汞污染治理[J].中国氯碱, 2011(2):25-31.
[2] LIU C,PENG J H,MA A Y,et al. Study on non-isothermal kinetics of the thermal desorption ofmercury from spent mercuric chloride catalyst[J]. Journal of Hazardous Materials, 2017, 322:325-333.
[3]曾华星,胡奔流,张银玲.我国含汞废物的再生利用[J].有色冶金设计与研究, 2012, 33(3):40-42.
[4]任亚峰.基于机械化学法的PVC行业废汞触媒稳定化固化技术及应用研究[D].北京:中国科学院大学,2017.
[5]李全胜,张萍.电石法PVC汞减排措施的建议[J].聚氯乙烯, 2014, 42(10):41-45.
[6]陈绍杨,王里奥,王惠俊,等.汞矿区周边土壤和溪流底泥对汞的吸附解吸特征[J].环境工程学报, 2017,11(3):1913-1919.
[7]陈杰,刘洁,李顺奇,等.几种硫化物对紫色土汞的稳定化效果及优化稳定条件[J].环境工程学报, 2018, 12(3):893-903.
[8]唐美如,黄振山,喻珊,等.反硝化菌对烟气汞吸附特性研究[J].环境科学学报, 2013, 38(9):3503-3513.
[9] LIU C,PENG J H,ZHANG L B,et al. Mercury adsorption from aqueous solution by regenerated activatedcarbon produced from depleted mercury-containing catalyst bymicrowave-assisted decontamination[J]. Journal of Cleaner Production, 2018,196:109-121.
[10] YANG X,XIAO B Z,GUANG Q L,et al. Study on the effects of carrier and modifier on mercury adsorption behavior over halides modified sorbents using temperature programmed desorption method[J]. Fuel Processing Technology, 2018, 178:293-300.
[11]张亚雄.我国氯化汞触媒生产和废氯化汞触媒回收利用技术进展[J].聚氯乙烯, 2008, 36(10):24-27.
[12]王小艳,王小昌,李国栋.废汞触媒回收技术的实验室研究[J].聚氯乙烯, 2017, 45(8):33-35.
[13]王小昌,李国栋,李春华.电石法聚氯乙烯行业汞资源的高效循环利用[J].聚氯乙烯, 2017, 45(12):36-38.
[14]佚名.控氧干馏法回收废触媒中HgCl2及再生汞触媒的新工艺及设备[C]//中国石油和化学工业协会. 2010全国石油和化学工业节能环保技术、设备交流会.成都, 2010.
[15]王玉晶,臧文超,赵静,等.我国电石法生产聚氯乙烯行业汞排放清单[J].化工环保, 2016, 36(5):772-576.
[16]邱运仁,闫升.一种回收利用废汞触媒的方法:CN103803638A[P]. 2014-05-21.
[17]于光认,张昊,陈晓春.一种湿法回收含汞触媒中汞的新技术:CN104451154A[P]. 2015-03-25.
[18]朱建新,任亚峰.一种以硫为添加剂机械球磨无害化处理废汞触媒的方法:CN104438285A[P]. 2015-03-25.
[19]陈扬,张正洁,冯钦忠,等.从废汞触媒多组分中环保回收汞和活性炭的设备及回收方法:201410741444.0[P]. 2015-02-25.
[20]李宝磊,陈刚,张正洁. PVC生产行业含汞废物特性分析与处置对策[J].化工环保, 2018, 38(5):514-518.
[21]左卫元,仝海娟,史兵方.改性活性炭对废水中铬离子的吸附[J].环境工程学报, 2015, 9(1):45-50.
[22]何慧军,杨春平,罗联胜,等.改性污泥活性炭对水中镉离子的吸附性能[J].环境工程学报, 2012, 6(11):4034-4040.
[23]张本镔,刘运权,叶跃元.活性炭制备及其活化机理研究进展[J].现代化工, 2014, 34(3):34-39.
[24]吴东强,马培勇,胡淞,等.污泥-锯末混合ZnCl2活化制备活性炭[J].过程工程学报, 2018, 18(4):792-798.
[25] GUO D S,SHI Q T,HE B B,et al. Different solvents for the regeneration of the exhausted activatedcarbon used in the treatment of coking wastewater[J]. Journal of Hazardous Materials, 2011, 186:1788-1793.
[26] REBECCA V M,GEOFFREY W S. The electrochemical regeneration of granular activated carbons:A review[J]. Journal of Hazardous Materials, 2018, 355:34-49.
[27] FOO K Y,HAMEED B H. Microwave-assisted regeneration of activated carbon[J]. Bioresource Technology, 2012, 119:234-240.
[28] MAISA E G,MOUSA H A,MUFTAH H E,et al. Bio-regeneration of activated carbon:A comprehensive review[J]. Separation and Puri?cation Technology, 2018, 197:345-359.
[29]张亚雄.氯氧化法再生氯化汞触媒及尾气综合利用的研究[J].中国有色冶金, 2014, 49(1):41-45.
[30]田祎,邢奕,刘景洋,等.氯化汞触媒的汞挥发速率[J].北京科技大学学报, 2012, 34(8):939-942.
[31]王珏,马战宇,吴勤波,等.双硫腙法研究废电池中汞的分布及浸出[J].环境污染与防治, 2005, 27(5):343-345.
[32]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.木质活性炭试验方法亚甲基蓝吸附值的测定:GB/T 12496.10-1999[S].北京:中国标准出版社, 1999.
[33]刘亚纳,周鸣,汤红妍,等.亚甲基蓝在污泥活性炭上的吸附[J].环境工程学报, 2012, 6(7):2339-2344.
[34]曾淦宁,周鸿艳,艾宁.高比表面积铜藻基活性炭的制备及工艺优化[J].环境科学学报, 2013, 33(8):2209-2217.
[35]毛振华.一种废汞触媒回收工艺及装置:201310671649.1[P]. 2014-04-02.
[2] LIU C,PENG J H,MA A Y,et al. Study on non-isothermal kinetics of the thermal desorption ofmercury from spent mercuric chloride catalyst[J]. Journal of Hazardous Materials, 2017, 322:325-333.
[3]曾华星,胡奔流,张银玲.我国含汞废物的再生利用[J].有色冶金设计与研究, 2012, 33(3):40-42.
[4]任亚峰.基于机械化学法的PVC行业废汞触媒稳定化固化技术及应用研究[D].北京:中国科学院大学,2017.
[5]李全胜,张萍.电石法PVC汞减排措施的建议[J].聚氯乙烯, 2014, 42(10):41-45.
[6]陈绍杨,王里奥,王惠俊,等.汞矿区周边土壤和溪流底泥对汞的吸附解吸特征[J].环境工程学报, 2017,11(3):1913-1919.
[7]陈杰,刘洁,李顺奇,等.几种硫化物对紫色土汞的稳定化效果及优化稳定条件[J].环境工程学报, 2018, 12(3):893-903.
[8]唐美如,黄振山,喻珊,等.反硝化菌对烟气汞吸附特性研究[J].环境科学学报, 2013, 38(9):3503-3513.
[9] LIU C,PENG J H,ZHANG L B,et al. Mercury adsorption from aqueous solution by regenerated activatedcarbon produced from depleted mercury-containing catalyst bymicrowave-assisted decontamination[J]. Journal of Cleaner Production, 2018,196:109-121.
[10] YANG X,XIAO B Z,GUANG Q L,et al. Study on the effects of carrier and modifier on mercury adsorption behavior over halides modified sorbents using temperature programmed desorption method[J]. Fuel Processing Technology, 2018, 178:293-300.
[11]张亚雄.我国氯化汞触媒生产和废氯化汞触媒回收利用技术进展[J].聚氯乙烯, 2008, 36(10):24-27.
[12]王小艳,王小昌,李国栋.废汞触媒回收技术的实验室研究[J].聚氯乙烯, 2017, 45(8):33-35.
[13]王小昌,李国栋,李春华.电石法聚氯乙烯行业汞资源的高效循环利用[J].聚氯乙烯, 2017, 45(12):36-38.
[14]佚名.控氧干馏法回收废触媒中HgCl2及再生汞触媒的新工艺及设备[C]//中国石油和化学工业协会. 2010全国石油和化学工业节能环保技术、设备交流会.成都, 2010.
[15]王玉晶,臧文超,赵静,等.我国电石法生产聚氯乙烯行业汞排放清单[J].化工环保, 2016, 36(5):772-576.
[16]邱运仁,闫升.一种回收利用废汞触媒的方法:CN103803638A[P]. 2014-05-21.
[17]于光认,张昊,陈晓春.一种湿法回收含汞触媒中汞的新技术:CN104451154A[P]. 2015-03-25.
[18]朱建新,任亚峰.一种以硫为添加剂机械球磨无害化处理废汞触媒的方法:CN104438285A[P]. 2015-03-25.
[19]陈扬,张正洁,冯钦忠,等.从废汞触媒多组分中环保回收汞和活性炭的设备及回收方法:201410741444.0[P]. 2015-02-25.
[20]李宝磊,陈刚,张正洁. PVC生产行业含汞废物特性分析与处置对策[J].化工环保, 2018, 38(5):514-518.
[21]左卫元,仝海娟,史兵方.改性活性炭对废水中铬离子的吸附[J].环境工程学报, 2015, 9(1):45-50.
[22]何慧军,杨春平,罗联胜,等.改性污泥活性炭对水中镉离子的吸附性能[J].环境工程学报, 2012, 6(11):4034-4040.
[23]张本镔,刘运权,叶跃元.活性炭制备及其活化机理研究进展[J].现代化工, 2014, 34(3):34-39.
[24]吴东强,马培勇,胡淞,等.污泥-锯末混合ZnCl2活化制备活性炭[J].过程工程学报, 2018, 18(4):792-798.
[25] GUO D S,SHI Q T,HE B B,et al. Different solvents for the regeneration of the exhausted activatedcarbon used in the treatment of coking wastewater[J]. Journal of Hazardous Materials, 2011, 186:1788-1793.
[26] REBECCA V M,GEOFFREY W S. The electrochemical regeneration of granular activated carbons:A review[J]. Journal of Hazardous Materials, 2018, 355:34-49.
[27] FOO K Y,HAMEED B H. Microwave-assisted regeneration of activated carbon[J]. Bioresource Technology, 2012, 119:234-240.
[28] MAISA E G,MOUSA H A,MUFTAH H E,et al. Bio-regeneration of activated carbon:A comprehensive review[J]. Separation and Puri?cation Technology, 2018, 197:345-359.
[29]张亚雄.氯氧化法再生氯化汞触媒及尾气综合利用的研究[J].中国有色冶金, 2014, 49(1):41-45.
[30]田祎,邢奕,刘景洋,等.氯化汞触媒的汞挥发速率[J].北京科技大学学报, 2012, 34(8):939-942.
[31]王珏,马战宇,吴勤波,等.双硫腙法研究废电池中汞的分布及浸出[J].环境污染与防治, 2005, 27(5):343-345.
[32]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.木质活性炭试验方法亚甲基蓝吸附值的测定:GB/T 12496.10-1999[S].北京:中国标准出版社, 1999.
[33]刘亚纳,周鸣,汤红妍,等.亚甲基蓝在污泥活性炭上的吸附[J].环境工程学报, 2012, 6(7):2339-2344.
[34]曾淦宁,周鸿艳,艾宁.高比表面积铜藻基活性炭的制备及工艺优化[J].环境科学学报, 2013, 33(8):2209-2217.
[35]毛振华.一种废汞触媒回收工艺及装置:201310671649.1[P]. 2014-04-02.
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