全氟温室气体SF_6、NF_3的降解途径探索
摘要
随着全球变暖的现象引起人们越来越多的关注,等离子体工业排放出来的SF_6和NF_3等全氟温室气体走进了学者们的视野。很多学者对它们在大气中浓度的增加表示忧虑。它们寿命长达几千年,是迄今发现辐射强迫最强的气体。已有研究表明,大气中O·,OH·等氧化性自由基都不与SF_6、NF_3反应,造成它们在大气层中不断积累。
已报道文献中研究降解全氟化合物的技术主要有燃烧法、催化转化法和等离子体技术(火花放电、微波、电弧放电)。但以上技术由于燃烧温度高、催化剂易失活、电极易腐蚀等缺点而难以被应用于工业中;且上述研究面临最大的难题是处理过程中会生成各种含F、O的有毒气体,使得后续处理变得很困难。
本文首次提出利用紫外光降解SF_6和NF_3及去除其有毒副产物的技术——紫外光缓释法。其机理是天然橡胶在紫外光照下缓慢释放的还原性自由基攻击SF_6和NF_3分子,使之发生脱氟反应:然后含氟自由基通过聚合沉积到橡胶表面。还原性自由基生成速率受到控制,因此灯管表面无结焦。通过实验证明紫外光缓释法在原理上可行,且具有良好的经济和环境效益。
首先,本文探索了紫外光缓释法降解SF_6和NF_3的方法和条件,提出了相应的反应机理。SF_6和NF_3在与缓释自由基(CRR)的反应后被有效地去除。气相中没有检测到有毒含氟产物。F加合到聚异戊二烯的骨架当中;S元素则掺杂到橡胶的表面。Ar气氛中SF_6和NF_3的光化学反应呈现准一级反应动力学的特征,准一级反应速率常数分别为5.16×10~(-5)s~(-1)及1.53×10~(-4)s~(-1)。3h内SF_6和NF_3的降解率分别达到了40%和80%。通过研究反应可能的途径和反应结果,我们提出了“CRR”反应初步机理的框图。进一步,我们研究了空气中O_2和H_2O对缓释法降解SF_6和NF_3的影响。
其次,本文研究了介质阻挡放电处理SF_6和NF_3的方法和大气中主要成分的分压大小对其降解率的影响。在实验的浓度范围内,SF_6(<0.054mol/m~3)和NF_3(<0.54mol/m~3)均能在60S的时间内达到80%以上的降解率。介质阻挡放电等离子体处理效率与总气压有关,SF_6和NF_3分压不变时,在反应器中稀释气体分压越大,SF_6和NF_3的降解率越小。气相的主要产物为SiF_4;但是随着氧气含量的增加会产生SO_2F_2、SOF_4、N_2O、NO、NOF等有毒物质,使得产物的处理更加困难。
As global warming draws increasing attention, SF_6 and NF_3, which are being potently released by Plasma industry into atmosphere, make some scientists anxious about the outcome. Becuause the F-containing species can exist in atmosphere for thousands of years and they are the most efficient absorber of Infrared radiation. Oxidative radicals as O and OM can not react with SF_6 and NF_3, this cause their stable accumulation in the atmosphere.
The degradation of SF_6 had been achieved utilizing combustion, chemical-thermal catalysis and plasma methods. Yet these technologies suffer either from high energy consumption, catalyzer poisoning or from the yield of especially toxic byproducts. Therefore an economically feasible approach that can eliminate SF_6 molecules effectively and generate less toxic products needs to be developed.
In this paper we developed a novel method to degrade SF_6 and NF_3 utilizing the reductive radicals excited by UV light on surface of polyisoprene(PI) and according machenism was put forward as the "Controlled Release of Radicals"(CRR) process. The reductive radicals attack Fluorine in SF_6 and NF_3 and thus defluorinate them, F-containing radicals then collide with each other to polymerize on surface of PI. Because the release of radicals was controlled, the lamp surface was not fouled. We proved that the "CRR" can be an economical and environmental favourable treatment of SF_6 and NF_3.
Efficient removel of SF_6 and NF_3 was achieved by "CRR" process. Degradation and Removal Efficiency (DRE) of SF_6 and NF_3 reached 40% and 80% respectively after 3 hours of irradiation. No poisonious fluoride was detected in the products. Fluorine and Sulfur was adducted or doped onto PI's surface. In argon atmosphere, the degradation curve of SF_6 and NF_3 exihibits characteristics of psydo-first order reactions, and their rate constant was calculated to be 5.16×10~(-5)s~(-1) and 1.53×10~(-4) s~(-1) respectively. Further, we studied how contents in air (O_2 and H_2O) affect the degradation of SF_6 and NF_3.
Then, we applied Dielectric Barrier Discharge (DBD) to degrade SF_6 and NF_3. In our experiment, SF_6 (<0.054mol/m~3) and NF_3(<0.54mol/m~3) were both able to be decomposed to less than 20% in 60 seconds. However, the DRE decreased as total pressure in DBD increased. Main product in gas phase was SiF_4. But after oxgen was introduced into the system, it helped to generate other gaseous harzadous products such as SO_2F_2、SOF_4、N_2O、NO and NOF.
已报道文献中研究降解全氟化合物的技术主要有燃烧法、催化转化法和等离子体技术(火花放电、微波、电弧放电)。但以上技术由于燃烧温度高、催化剂易失活、电极易腐蚀等缺点而难以被应用于工业中;且上述研究面临最大的难题是处理过程中会生成各种含F、O的有毒气体,使得后续处理变得很困难。
本文首次提出利用紫外光降解SF_6和NF_3及去除其有毒副产物的技术——紫外光缓释法。其机理是天然橡胶在紫外光照下缓慢释放的还原性自由基攻击SF_6和NF_3分子,使之发生脱氟反应:然后含氟自由基通过聚合沉积到橡胶表面。还原性自由基生成速率受到控制,因此灯管表面无结焦。通过实验证明紫外光缓释法在原理上可行,且具有良好的经济和环境效益。
首先,本文探索了紫外光缓释法降解SF_6和NF_3的方法和条件,提出了相应的反应机理。SF_6和NF_3在与缓释自由基(CRR)的反应后被有效地去除。气相中没有检测到有毒含氟产物。F加合到聚异戊二烯的骨架当中;S元素则掺杂到橡胶的表面。Ar气氛中SF_6和NF_3的光化学反应呈现准一级反应动力学的特征,准一级反应速率常数分别为5.16×10~(-5)s~(-1)及1.53×10~(-4)s~(-1)。3h内SF_6和NF_3的降解率分别达到了40%和80%。通过研究反应可能的途径和反应结果,我们提出了“CRR”反应初步机理的框图。进一步,我们研究了空气中O_2和H_2O对缓释法降解SF_6和NF_3的影响。
其次,本文研究了介质阻挡放电处理SF_6和NF_3的方法和大气中主要成分的分压大小对其降解率的影响。在实验的浓度范围内,SF_6(<0.054mol/m~3)和NF_3(<0.54mol/m~3)均能在60S的时间内达到80%以上的降解率。介质阻挡放电等离子体处理效率与总气压有关,SF_6和NF_3分压不变时,在反应器中稀释气体分压越大,SF_6和NF_3的降解率越小。气相的主要产物为SiF_4;但是随着氧气含量的增加会产生SO_2F_2、SOF_4、N_2O、NO、NOF等有毒物质,使得产物的处理更加困难。
As global warming draws increasing attention, SF_6 and NF_3, which are being potently released by Plasma industry into atmosphere, make some scientists anxious about the outcome. Becuause the F-containing species can exist in atmosphere for thousands of years and they are the most efficient absorber of Infrared radiation. Oxidative radicals as O and OM can not react with SF_6 and NF_3, this cause their stable accumulation in the atmosphere.
The degradation of SF_6 had been achieved utilizing combustion, chemical-thermal catalysis and plasma methods. Yet these technologies suffer either from high energy consumption, catalyzer poisoning or from the yield of especially toxic byproducts. Therefore an economically feasible approach that can eliminate SF_6 molecules effectively and generate less toxic products needs to be developed.
In this paper we developed a novel method to degrade SF_6 and NF_3 utilizing the reductive radicals excited by UV light on surface of polyisoprene(PI) and according machenism was put forward as the "Controlled Release of Radicals"(CRR) process. The reductive radicals attack Fluorine in SF_6 and NF_3 and thus defluorinate them, F-containing radicals then collide with each other to polymerize on surface of PI. Because the release of radicals was controlled, the lamp surface was not fouled. We proved that the "CRR" can be an economical and environmental favourable treatment of SF_6 and NF_3.
Efficient removel of SF_6 and NF_3 was achieved by "CRR" process. Degradation and Removal Efficiency (DRE) of SF_6 and NF_3 reached 40% and 80% respectively after 3 hours of irradiation. No poisonious fluoride was detected in the products. Fluorine and Sulfur was adducted or doped onto PI's surface. In argon atmosphere, the degradation curve of SF_6 and NF_3 exihibits characteristics of psydo-first order reactions, and their rate constant was calculated to be 5.16×10~(-5)s~(-1) and 1.53×10~(-4) s~(-1) respectively. Further, we studied how contents in air (O_2 and H_2O) affect the degradation of SF_6 and NF_3.
Then, we applied Dielectric Barrier Discharge (DBD) to degrade SF_6 and NF_3. In our experiment, SF_6 (<0.054mol/m~3) and NF_3(<0.54mol/m~3) were both able to be decomposed to less than 20% in 60 seconds. However, the DRE decreased as total pressure in DBD increased. Main product in gas phase was SiF_4. But after oxgen was introduced into the system, it helped to generate other gaseous harzadous products such as SO_2F_2、SOF_4、N_2O、NO and NOF.
引文
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