NH_3-H_2O_2气雾对氰化氢气体的消毒
|
摘要
采用NH_3-H_2O_2气雾对1 m3密闭试验舱内氰化氢气体进行消毒,采用单因素试验研究H_2O_2和NH_3质量浓度对消毒率和消毒反应速率的影响规律。结果表明,NH_3-H_2O_2气雾对HCN的消毒符合一级反应动力学特征,NH_3质量浓度对消毒反应速率有一定影响,但当NH_3质量浓度增加至20 mg/m3以上时,对反应速率几乎没有影响; H_2O_2质量浓度对消毒反应速率有显著影响,反应速率随H_2O_2质量浓度的提高明显增大。NH_3-H_2O_2气雾消毒剂的最佳配方为H_2O_2的质量浓度为120 mg/m3、NH_3的质量浓度为20 mg/m3,在此条件下对HCN进行消毒,在28 min时HCN的残余质量浓度为0. 92 mg/m3,可以达到GBZ 2. 1—2007《工作场所有害因素职业接触限值第1部分:化学有害因素》中有关HCN最高容许质量浓度MAC值(1 mg/m3)的规定。分析消毒机理为H_2O_2首先将HCN氧化为氰酸(HCNO),氰酸不稳定,在NH_3和水的作用下可以水解成碳酸铵,也可以进一步被氧化形成CO2和N2。
The paper is inclined to use NH_3-H_2O_2 vapor to decontaminate HCN gas in an airtight testing chamber with a capacity of 1 m3. For this purpose,we have made efforts to generate HCN gas by adding sulfuric acid to KCN powder in the chamber and make the mass concentration of HCN stabilized within 35 min. As a matter of fact,NH_3-H_2O_2 vapor can be efficiently used to decontaminate such chemical warfare agents,such as sarin,sulfur mustard,soman and VX,in the enclosed space. NH_3 is introduced into the chamber by a standard cylinder gas. At the same time,H_2O_2 vapor generator can also be switched on to start up the decontamination process. What is more,a HCN gas sensor can still be adopted to monitor the mass concentration online.Besides,it is also necessary to investigate the impacts of the mass concentrations of H_2O_2 and NH_3 on the decontamination efficiency and the reaction kinetics. Thus,as a result,the decontamination reaction of HCN with NH_3-H_2O_2 vapor can be found following the first order reaction,whereas the mass concentration of NH_3 may also have some extent of effects on the decontamination reaction rate. However,the reaction rate constant tends to keep almost unchanged when the mass concentration of NH_3 in-creases to over 20 mg/m3. Or rather,the mass concentration of H_2O_2 can have a considerable positive effect on the reaction rate.And,in correspondence with the experimental results,an optimal formulation of NH_3-H_2O_2 vapor can be screened out,so as to make the massconcentrations of H_2O_2 and NH_3 equal to 120 mg/m3 and 20 mg/m3,respectively. And,if possible,in the optimalized condition,the residual mass concentration of HCN would like to get reduced to 0. 92 mg/m3 just for 28 min,which can meet the maximum allowable concentration( MAC) rate of 1 mg/m3,as prescribed in the "Occupational exposure limits for the hazardous agents in the workplace Part 1: chemical hazardous agents"( GBZ 2. 1—2007) in China national standard of the occupational health. Based on the products detection and literature reports,the decontamination mechanism has been stated as follows: HCN is oxidized by H_2O_2 to HCNO firstly. But HCNO is so instable that it can be hydrolyzed to ammonium carbonate with the participation of NH_3 and H2 O,either or further oxidized to CO2 and N2.
The paper is inclined to use NH_3-H_2O_2 vapor to decontaminate HCN gas in an airtight testing chamber with a capacity of 1 m3. For this purpose,we have made efforts to generate HCN gas by adding sulfuric acid to KCN powder in the chamber and make the mass concentration of HCN stabilized within 35 min. As a matter of fact,NH_3-H_2O_2 vapor can be efficiently used to decontaminate such chemical warfare agents,such as sarin,sulfur mustard,soman and VX,in the enclosed space. NH_3 is introduced into the chamber by a standard cylinder gas. At the same time,H_2O_2 vapor generator can also be switched on to start up the decontamination process. What is more,a HCN gas sensor can still be adopted to monitor the mass concentration online.Besides,it is also necessary to investigate the impacts of the mass concentrations of H_2O_2 and NH_3 on the decontamination efficiency and the reaction kinetics. Thus,as a result,the decontamination reaction of HCN with NH_3-H_2O_2 vapor can be found following the first order reaction,whereas the mass concentration of NH_3 may also have some extent of effects on the decontamination reaction rate. However,the reaction rate constant tends to keep almost unchanged when the mass concentration of NH_3 in-creases to over 20 mg/m3. Or rather,the mass concentration of H_2O_2 can have a considerable positive effect on the reaction rate.And,in correspondence with the experimental results,an optimal formulation of NH_3-H_2O_2 vapor can be screened out,so as to make the massconcentrations of H_2O_2 and NH_3 equal to 120 mg/m3 and 20 mg/m3,respectively. And,if possible,in the optimalized condition,the residual mass concentration of HCN would like to get reduced to 0. 92 mg/m3 just for 28 min,which can meet the maximum allowable concentration( MAC) rate of 1 mg/m3,as prescribed in the "Occupational exposure limits for the hazardous agents in the workplace Part 1: chemical hazardous agents"( GBZ 2. 1—2007) in China national standard of the occupational health. Based on the products detection and literature reports,the decontamination mechanism has been stated as follows: HCN is oxidized by H_2O_2 to HCNO firstly. But HCNO is so instable that it can be hydrolyzed to ammonium carbonate with the participation of NH_3 and H2 O,either or further oxidized to CO2 and N2.
引文
[1] ENSERINK M. UN taps special labs to investigate syrianattack[J]. Science,2013,341(6150):1050-1051.
[2] GAO Wanglai. China’s battle with abandoned chemicalweapons[J]. The RUSI Journal,2017,162(4):8-16.
[3] SOUZA B M,SOUZA B S,GUIMARAES T M,et al. Re-moval of recalcitrant organic matter content in wastewater bymeans of AOPs aiming industrial water reuse[J]. Environ-mental Science and Pollution Research, 2016, 23:22947-22956.
[4] RANI M,SHANKER U. Degradation of traditional and newemerging pesticides in water by nanomaterials:recent trendsand future recommendations[J]. International Journal ofEnvironmental Science and Technology,2017,14:1-34.
[5] WAGNER G W,PROCELL L R,SORRICK D C,et al.All-weather hydrogen peroxide-based decontamination ofCBRN contaminants[J]. Industrial&Engineering Chem-istry Research,2010,49:3099-3105.
[6] Research and Development Office of US EPA,NationalHomeland Security Research Center. Building decon-tamination alternatives[M]. XI Hailing(习海玲),HAN Shitong(韩世同),ZHOU Wen(周文),et al.trans. Beijing:National Defense Industry Press,2012:17.
[7] WOOD J P,CALFEE M W,CLAYTON M,et al. Evalu-ation of peracetic acid fog for the inactivation of Bacillusanthracis spore surrogates in a large decontaminationchamber[J]. Journal of Hazardous Materials,2013,250/251:61-67.
[8] BOYCE J M. Modern technologies for improving cleaningand disinfection of environmental surfaces in hospitals[J]. Antimicrobial Resistance and Infection Control,2016,5:10.
[9] RUTALA W A,WEBER D J. Disinfectants used for envi-ronmental disinfection and new room decontaminationtechnology[J]. American Journal of Infection Control,2013,41:S36-S41.
[10] WAGNER G W. Hydrogen peroxide-based decontamina-tion of chemical warfare agents[J]. Main Group Chemis-try,2010,28:257-263.
[11] WAGNER G W,SORRICK D C,PROCELL L R,et al.Decontamination of VX,GD,and HD on a surface usingmodified vaporized hydrogen peroxide[J]. Langmuir,2007,23:1178-1186.
[12] WAGNER G W. Decontamination of chemical warfare a-gents using household chemicals[J]. Industrial&Engi-neering Chemistry Research,2011,50:12285-12287.
[13] XIA Zhiqiang(夏志强). Parts of chemistry,biology,radioactivity and nuclear events happened in recent 30years[J]. Development of Foreign Chemical Defense(国外防化科技动态),2018(3):19-2.
[14] WANG Z,XI H,KONG L,et al. Solubility and selec-tive oxidation of 2-chloroethyl ethyl sulfide in imidazole-based ionic liquids[J]. Journal of Molecular CatalysisA:Chemical,2017,430:1-8.
[15] XU Pengcheng(徐鹏程). Discussion on polymerizationand prevention of hydrogen cyanide[J]. Inner MongoliaPetrochemical(内蒙古石油化工),2016,(4):53-54.
[16] LIU Na(刘娜),NING Ping(宁平),LI Kai(李凯),etal. Research progress in catalytic hydrolysis of HCN,COS and CS2and synergetic purification of hydrolysates[J]. Chemical Industry and Engineering Progress(化工进展),2018,37(1):301-310.
[17] LI Y,YANG H,ZHANG Y,et al. Catalytic decomposi-tion of HCN on copper manganese oxide at low tempera-tures:performance and mechanism[J]. Chemical Engi-neering Journal,2018,346:621-629.
[18] WANG X,CHENG J,WANG X,et al. Mn based cata-lysts for driving high performance of HCN catalytic oxida-tion to N2under micro-oxygen and low temperature con-ditions[J]. Chemical Engineering Journal,2018,333:402-413.
[2] GAO Wanglai. China’s battle with abandoned chemicalweapons[J]. The RUSI Journal,2017,162(4):8-16.
[3] SOUZA B M,SOUZA B S,GUIMARAES T M,et al. Re-moval of recalcitrant organic matter content in wastewater bymeans of AOPs aiming industrial water reuse[J]. Environ-mental Science and Pollution Research, 2016, 23:22947-22956.
[4] RANI M,SHANKER U. Degradation of traditional and newemerging pesticides in water by nanomaterials:recent trendsand future recommendations[J]. International Journal ofEnvironmental Science and Technology,2017,14:1-34.
[5] WAGNER G W,PROCELL L R,SORRICK D C,et al.All-weather hydrogen peroxide-based decontamination ofCBRN contaminants[J]. Industrial&Engineering Chem-istry Research,2010,49:3099-3105.
[6] Research and Development Office of US EPA,NationalHomeland Security Research Center. Building decon-tamination alternatives[M]. XI Hailing(习海玲),HAN Shitong(韩世同),ZHOU Wen(周文),et al.trans. Beijing:National Defense Industry Press,2012:17.
[7] WOOD J P,CALFEE M W,CLAYTON M,et al. Evalu-ation of peracetic acid fog for the inactivation of Bacillusanthracis spore surrogates in a large decontaminationchamber[J]. Journal of Hazardous Materials,2013,250/251:61-67.
[8] BOYCE J M. Modern technologies for improving cleaningand disinfection of environmental surfaces in hospitals[J]. Antimicrobial Resistance and Infection Control,2016,5:10.
[9] RUTALA W A,WEBER D J. Disinfectants used for envi-ronmental disinfection and new room decontaminationtechnology[J]. American Journal of Infection Control,2013,41:S36-S41.
[10] WAGNER G W. Hydrogen peroxide-based decontamina-tion of chemical warfare agents[J]. Main Group Chemis-try,2010,28:257-263.
[11] WAGNER G W,SORRICK D C,PROCELL L R,et al.Decontamination of VX,GD,and HD on a surface usingmodified vaporized hydrogen peroxide[J]. Langmuir,2007,23:1178-1186.
[12] WAGNER G W. Decontamination of chemical warfare a-gents using household chemicals[J]. Industrial&Engi-neering Chemistry Research,2011,50:12285-12287.
[13] XIA Zhiqiang(夏志强). Parts of chemistry,biology,radioactivity and nuclear events happened in recent 30years[J]. Development of Foreign Chemical Defense(国外防化科技动态),2018(3):19-2.
[14] WANG Z,XI H,KONG L,et al. Solubility and selec-tive oxidation of 2-chloroethyl ethyl sulfide in imidazole-based ionic liquids[J]. Journal of Molecular CatalysisA:Chemical,2017,430:1-8.
[15] XU Pengcheng(徐鹏程). Discussion on polymerizationand prevention of hydrogen cyanide[J]. Inner MongoliaPetrochemical(内蒙古石油化工),2016,(4):53-54.
[16] LIU Na(刘娜),NING Ping(宁平),LI Kai(李凯),etal. Research progress in catalytic hydrolysis of HCN,COS and CS2and synergetic purification of hydrolysates[J]. Chemical Industry and Engineering Progress(化工进展),2018,37(1):301-310.
[17] LI Y,YANG H,ZHANG Y,et al. Catalytic decomposi-tion of HCN on copper manganese oxide at low tempera-tures:performance and mechanism[J]. Chemical Engi-neering Journal,2018,346:621-629.
[18] WANG X,CHENG J,WANG X,et al. Mn based cata-lysts for driving high performance of HCN catalytic oxida-tion to N2under micro-oxygen and low temperature con-ditions[J]. Chemical Engineering Journal,2018,333:402-413.
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |