【作者】 晋日亚；

【导师】 胡双启；

【作者基本信息】 中北大学 ， 武器系统与运用工程， 2008， 博士

【摘要】 研究针对微生物的高效杀菌剂是遏制生物武器杀伤威力的有效对策。气体ClO₂因具有优异的高效广谱杀菌性能且有毒副产物含量较低而倍受青睐。本文从高纯度气体ClO₂的生成方法、反应动力学以及ClO₂对微生物的杀菌效果等方面进行了研究。（1）高纯度气体ClO₂生成技术及ClO₂浓度、纯度检测技术研究提出了NaClO₃—NaClO₂组合法生成高纯度气体ClO₂的新工艺。HCl与NaClO₃在主反应器内反应，生成的Cl₂和ClO₂混合气体通过NaClO₂的固定床，将Cl₂进一步转化为ClO₂气体，最终产物气中ClO₂／Cl₂≈60／1，ClO₂纯度达到98．19％。制备了快速测试ClO₂浓度的标准比色卡及配套测试卡，所得测试卡测试ClO₂溶液浓度的范围为5～1000mg／L，测试误差在10％以内。（2）高纯度气体ClO₂反应动力学研究提出了HCl与NaClO₃反应可能存在的假设机理，并进行了验证。通过理论上对亚氯酸钠与氯气发生气固反应的微观分析，建立了NaClO₂与Cl₂发生气固反应的固定床——等效粒子模型并进行表征，得出了NaClO₃—NaClO₂组合工艺生成高纯度气体ClO₂的反应动力学模型。（3）气体二氧化氯爆炸特性和爆炸机理研究首次在20L的柱状爆炸罐内研究了气体ClO₂的爆炸特性，考查了气体ClO₂的爆炸极限及浓度对爆炸压力、爆炸诱导时间的影响。得出了气体ClO₂的爆炸下限为9．5％（体积比），爆炸上限为100％；气体ClO₂的爆炸压力随浓度的增加而增大，最大爆炸压力出现的诱导时间随着气体ClO₂浓度的增加而缩短。提出了气体ClO₂的爆炸属于分解爆炸，其爆炸机理是涉及到中间稳定物——Cl₂O₃的特殊衰减支链分解爆炸机理，Cl₂O₃是引发、促进支链反应的主要因素。（4）高纯度气体ClO₂生成系统装置研究利用安全原理设计了高纯气体ClO₂反应器，ClO₂发生量达到了1．5kg／次以上，NaClO₂转化率达到93．7％、NaClO₃转化率达到95．5％时，气体ClO₂的产率最高达到97．3％，纯度达到了98．55％以上。NaClO₃—NaClO₂组合工艺生成高纯度的气体ClO₂，控制反应时间在30～45min左右较好。理论产量与实际产量二者的偏差在6．2％以内；超出此时间范围，实际产量与动力学计算结果的偏差会越来越大。（5）气体ClO₂的应用研究a高纯度气体ClO₂对葡萄的杀菌保鲜研究研究了气体ClO₂对葡萄表面致病菌——葡萄球菌、大肠杆菌、李斯特单增菌和腐生酵母菌的杀菌效果。得出了气体ClO₂浓度增加和杀菌时间的延长，可以使杀菌效果很快的提高，在气体ClO₂杀菌浓度为25mg/L、杀菌时间12min、杀菌温度25℃的较佳条件下，金黄色葡萄球菌、李斯特单增菌和腐生酵母菌均减少了6．4log量级以上，而大肠杆菌达到5．76log量级。ClO₂的作用浓度和杀菌时间存在协同增效的作用。气体ClO₂对葡萄的保鲜效果研究表明，常温下采用浓度为30ml／m³的气体ClO₂处理葡萄效果最好。ClO₂可以迅速有效地阻止蛋氨酸的分解，消除乙烯等物质并杀灭腐败菌，从而延缓果蔬变质过程，减少营养成分损失，起到长期保鲜的作用。b二氧化氯消毒城市生活废水研究研究表明，污水中粪大肠菌的灭菌效果随着ClO₂浓度和作用时间的增加而增加，得出了ClO₂消毒城市污水的投药浓度为5 mg／L、杀菌时间为20min的最佳条件，粪大肠菌杀菌率达到99．99％的去除率极限。处理后的出水中未检出CHCl₃，CCl₄的含量虽然随ClO₂浓度不同而有所区别，但是含量很少且差别不大。研究结果证实ClO₂消毒水体形成卤代烃类明显低于普通含氯消毒剂，将ClO₂用于污水消毒增强了回用污水的环境安全性。更多还原

【Abstract】 It is the most effective countermove to exploit the highly active germicidal agentagainst the lethality of biological weapon.ClO₂ gas has attracted attention in the views ofbroad spectrum and highly active bactericidal ability and few or none poisonous byproducts.In this paper,the formative technology of high-purity ClO₂ gas,kinetics of its reaction andbactericidal effect were studied.（1） Study on the generation of high-purity ClO₂ gas and the determination of itsconcentration and purityA new technology used the NaClO₃-NaClO₂ compound mode to generated ClO₂ gas wasset forth.The reaction of HCl and NaClO₃ was proceed in main reactor,and,the generatedgaseous mixture containing Cl₂ and ClO₂ enter into the fixed bed reactor loaded NaClO₂granule,where Cl₂ was inverted into ClO₂,and the ClO₂/Cl₂ is 60/1 approximately in the endproducts,the purity of ClO₂ was up to 98.19%.The colorimetric card and test cardcorresponding to concentration of ClO₂ rapid determination were prepared,and the errorpercentage was less than 10% in test specification 5～1000mg/L.（2） The kinetics of the formation reaction of high-purity ClO₂ gasThe mechanics hypothesis about chemical reaction of HCl and NaClO₃ was set forth,andbeen verified furtherly.The fixed bed and equivalent particle model was established bymicrostructure analysis of gas-solid reaction of NaClO₂ and Cl₂,and the reaction kineticsmodel,using NaClO₃-NaClO₂ compound technology to generate high-purity ClO₂ gas wasobtained.（3） The explosion characteristics and mechanics of ClO₂ gasIt was the first time for the explosion characteristics of ClO₂ gas was studied in acylindrical exploder with a shell capacity of 20 liters.The impact of concentration toexplosion limit,explosion pressure and induction time were determinated.The experimentalresults indicated that the lower concentration limit for the explosive decomposition ofchlorine dioxide gas was 9.5% （[ClO₂]/[air]）,the upper concentration limit was 100%,and thepressure of explosion increased with increasing concentration of ClO₂ gas,the induction time（the time from the moment of sparking to explosion） to attain the maximum pressure of explosion was shorten with increasing concentration of ClO₂ gas.The explosion reaction styleof ClO₂ is decomposition,the reaction mechanism of ClO₂ is of a degenerate chain-branchingtype involving the formation of a stable intermediate Cl₂O₃,and it is the major factor toinitiating and accelerating branched chain reaction.（4） System device for generating high-purity ClO₂ gasFollowing the principle of safety,the reactor to generated high-purity ClO₂ gas wasprepared.The production capacity of ClO₂ gas attained 1.5kg/batch,the percent conversion ofNaClO₂ and NaClO₃ were up to 93.7% and 95.5% respectively,the productive rate of ClO₂gas attained 97.3%,its purity was more than 98.55%.The optimum reaction time range wasfrom 30 to 45 minutes,the deviation of ClO₂ yield between theoretically,and,actually,was nomore than 6.2%,but the deviation of actual output to computing result by dynamics methodbecame more and more when the reaction time exceed the optimum range.（5） Research on the application of ClO₂ gasa Effect of ClO₂ gas on bactericidal and keep fresh on grapeThe regularity of sterilization to Staphylococcus Aureus,Escherichia Coli 0157.H7,Listeria Monocytogenes and Saprophytic Yeast on grape surface with ClO₂ gas were studiedin this paper.The result showed that the bactericidal effect was markedly increased alongwith the concentration increased of ClO₂ gas and the bactericidal time in the experiment range.When the ClO₂ gas concentration 25mgl^-1,bactericidal time 12min and temperature 25℃,Staphylococcus Aureus,Listeria Monocytogenes and Saprophytic Yeast decreased more than6.41og,but the decrease of Escherichia Coli 0157:H7 attained 5.761og.There exist synergismeffect between the bactericidal time and ClO₂ concentration.The result also showed that itwas best condition for grape to keep fresh when the concentration of ClO₂ gas is 30ml/m³,ClO₂ gas can inhibit effectively methionine catabolic process decrease,the generating ofethene when killing the Saprospira on the surface of fruit and vegetable,so it is useful todelay metamorphic process,reduce nutritional ingredient loss,and keep the fruit andvegetable fresh for a long time.b The municipal wastewater disposal by ClO₂The result showed that the sterilizing effect to bacillus coli was increasing with theconcentration of ClO₂ and the treating duration increasing,the optimum were ClO₂concentration 5mg/L and bactericidal time 20min,the bactericidal ratio to bacillus coli was99.99%,which is limit bactericidal limit.After wastewater disposal,the CHCl₃ had not been detected in the water,the content of ClC₄ existed difference in some degree with the differentClO₂ concentration,but the real content is lower.The results indicate that the content ofhalogenated hydrocarbon are less than other common chlorine disinfectors after wastewaterare disposed by ClO₂,therefore,environment security is enhanced by using the ClO₂ gas tosterilized recycle-water.更多还原