外加气体对等离子体降解CF2ClBr的影响

用等离子体处理难降解大气污染是近国内外产活跃的领域,选用化学方法难解的ＣＦ２ＣｌＢｒ为对象,研究了Ｈｅ,Ｎ２,Ｏ２及空气对等离子体降解ＣＦ２ＣｌＢｒ的影响,实现了ＣＦ２ＣｌＢｒ的常压降解,外加气体为Ｈｅ,Ｎ２时ＣＦ２ＣｌＢｒ的降解情况与纯ＣＦ２ＣｌＢｒ的降解基本相同,外加气体为Ｏ２,空气时的主要降解产物为ＣＦ２Ｏ,Ｂｒ２,Ｃｌ２,外加气体对降糖的影响大小Ｈｅ〈Ｎ２〈Ｏ２空气。     

CF2ClBr的火花等离子体降解

对用等离子体降解ＣＦ２ＣｌＢｒ进行了初步研究,产物主要用气相色谱分析。在ＣＦ２ＣｌＢｒ的强为２．６７×１０＾３Ｐａ时获得了９０％左右的解离率,主要降解产为ＣＦ３Ｃｌ,Ｂｒ２,ＣＦ４,ＣＦ２Ｃｌ２。另外,从热力学上对产物进行了解释,得出了产总是朝使体系更稳定的方向生成的结论。     

Decomposition of CF3CI by corona discharge

In this paper pulsed corona discharge is shown to be effective for the decomposition of CF₃Cl(Freon-13).The pressure of CF₃Cl was 2.67×10³Pa,after discharged for 2 min,39.5% of CF₃Cl was decomposed.The products were mainly CF₄,Cl₂ and CF₂Cl₂.The yield increased by adding O₂ or air.Under the same conditions,more than 94% decomposition yield was obtained if 5.32×10³Pa O₂ or air was added.The composition of products became CF₂O,Cl₂ and CF₄.While the partial pressure of O₂ or air reached 1 arm,the decomposition yield decreased to 54.5% and 48. 5% respectively.     

CF2ClBr在短紫外光照射下光解离过程的研究

以低压汞为激发光源,气相色谱和红外光谱为主要分析手段,研究了气态ＣＦ２ＣｌＢｒ在１８５ｎｍ紫外光照射下的光解离过程及其人在Ｏ２存在下的光氧化机理,发现ＣＦ２ＣｌＢｒ在１８５ｎｍ紫外光照射下的主要产物ＣＦ２Ｂｒ２ＣＦ２Ｃｌ２和Ｃｌ２,Ｂｒ２,而当Ｏ２存在时,主要光解产物为ＣＦ２Ｏ,在本实验条件下,纯ＣＦ２ＣｌＢｒ极限分解率约为２６％,在ＣＦ２ＣｌＢｒ－Ｏ２体系中,ＣＦ２ＣｌＢｒ的解离为一级反应,速率     

烷烃条件下CF2ClBr的紫外光解离机理研究

以气相色谱、红外光谱为主要分析手段,对气态ＣＦ２ＣｌＢｒ在ＣＲ２ＣｌＢｒ－Ｃ６Ｈ１２体系中的紫外光解离进行了研究,结果表明,在２５３．７ｎｍ紫外光照射下,该体系的主要光解产物为ＨＣＶＦ２Ｃｌ、ＨＢｒ以及Ｃ６Ｈ１２的聚合物,体系中ＣＦ２ＣｌＢｒ的解离近似精同缀反应,解离反应的速率常数为２．８７７×１０＾－６ｓ＾－１表观量子产率约０．１,基于此,对该光解反应的机理做了分析。     

Decomposition of CFC and Halon waste gases in normal-pressure plasma reactors

１ＩｎｔｒｏｄｕｃｔｉｏｎＳｉｎｃｅｔｈｅ１９７０ｓ，ｔｈｅＣＦＣｓａｎｄＨａｌｏｎｓｅｍｉｔｅｄｂｙｈｕｍａｎｈａｖｅｂｅｅｎｗｉｄｅｌｙｔｈｏｕｇｈｔａｓｓｕｂｓｔａｎｃｅｓｗｈｉｃｈｍａｙｃａｕｓｅｏｚｏｎｅｄｅｐｌｅｔｉｏｎｉｎｓｔｒａｔｏ...     

低温等离子体降解哈隆类物质中的竞争反应

利用低温等离子体技术对哈隆类物质 CF₂ClBr和 CF₃Br进行了降解反应研究 ,发现无氧条件下某些降解产物的量随放电时间不同而出现波动 ,表明降解过程中存在竞争反应 ;而氧气过量条件下不存在竞争反应 ,其主要产物为 CF₂O等 .对低气压下 CF₂ClBr和 CF₃Br在低温等离子体空间中的气相反应机理进行讨论 ,为实现低温等离子体降解污染物提供了理论依据 .     

脉冲电晕法藕合Ca(OH)2固体吸收处理四氯乙烯废气研究

采用线-筒式脉冲电晕反应器对四氯乙烯去除效果进行了研究.结果表明,四氯乙烯去除率随电压的增大而增大.在氮气中加入氧气,四氯乙烯降解效果低于纯氮气下的降解效果.四氯乙烯在氮气下的主要气相产物为Cl_2和少量的CCl_4.当氧气加入后,四氯乙烯主要降解为CO_2、CO、COCl_2、O_3和C_2Cl_4O.为了去除有害中间产物,在反应器中加入Ca(OH)_2固体吸收剂,这明显提高了有害中间产物的去除,存在水汽及含Ca(OH)_2固体吸收剂时并未检测到COCl_2、O_3和有害中间产物C_2Cl_4O,但水汽不利于四氯乙烯去除.     

电化学氧化PFOA阳极材料筛选及其机制研究

全氟辛酸(PFOA)具有环境持久性及内分泌干扰性,传统的生物降解及高级氧化法对PFOA的去除效果微弱.本研究采用电化学氧化法降解PFOA,选取BDD(掺硼金刚石电极)、Pt、Ti、Ti/RuO2、Ti/RuO2-IrO2、Ti/In2O3、Ti/SnO2-Sb2O5-IrO2、Ti/SnO2-Sb2O5-RhO2、Ti/SnO2-Sb2O5、Ti/SnO2-Sb2O5-CeO2和Ti/SnO2-Sb2O5-Bi2O3这11种阳极材料为备选电极.采用线性扫描伏安法测试析氧电位(OEP),评价11种电极对PFOA的降解效果和脱氟效果,并采用超声-电化学协同方法间接证明PFOA分子在电极表面的直接电子转移是降解反应的第一步.Ti/SnO2-Sb2O5-Bi2O3、Ti/SnO2-Sb2O5-CeO2、Ti/SnO2-Sb2O5和BDD对PFOA有较好的电氧化效果,降解率分别是89.8%、89.8%、93.3%和98.0%.Pt、Ti/SnO2-Sb2O5-RhO2、Ti/SnO2-Sb2O5-IrO2和Ti/In2O3对PFOA的电氧化效果微弱,降解率分别是2.1%、2.3%、12.5%和3.1%.而Ti、Ti/RuO2和Ti/RuO2-IrO2对PFOA没有电氧化能力.PFOA分子经过电极表面的直接电化学氧化发生脱羧反应,后经过逐步脱掉CF2单元的循环生成短链的全氟羧酸类化合物C6F13COO-、C5F11COO-、C4F9COO-和C3F7COO-.     

放电条件下SF5CF3的分解反应

SF₅CF₃是近年被发现的具有强红外辐射强迫、长寿命的新温室气体.本文利用火花放电技术模拟研究了放电条件下SF₅CF₃的去除机理.结果表明,SF₅CF₃在放电过程中将被分解并生成多种含硫、氟、氧和碳的化合物.H₂O的存在能够降低SF₅CF₃的分解速率,但降低的量与H₂O的分压无关. 在有H₂O存在的条件下,当体系总压约为31kPa时,闪电过程中SF₅CF₃的分解速率常数分别为0.011s^-.同时,SF₅CF₃的分解率随着体系的总压上升而呈指数下降.基于实验结果,对SF₅CF₃在放电过程中的反应途径作了探讨,并估算实际大气中放电的一种形式--闪电所引起的SF₅CF₃的分解量为53.6 kg·a^-.     

在氧化和还原氛围下脉冲电晕法降解二硫化碳废气

采用线-筒式脉冲电晕反应器对二硫化碳(CS2)模拟废气的去除效果进行了实验研究.实验以氩气为载气,考察了氧气和氢气对CS2去除效果的影响.结果表明CS2的去除率随脉冲电压升高而增大;氧气能够促进CS2的氧化分解,CS2去除率可达97%;有氧气存在时,CS2的最终氧化分解产物为CO、CO2、COS和SO2;当添加氢气时,反应产物主要为H2S和CH4.当反应器内筒表面加Ca(OH)2吸收剂时,CS2去除率有小幅度提高,同时气体产物中未检测到SO2和H2S,表明CS2的分解产物SO2和H2S气体被反应器中的Ca(OH)2吸收.实验还发现水汽的存在不利于CS2的氧化分解     

Decomposition of trifluoromethane in a dielectric barrier discharge non-thermal plasma reactor

The decomposition of trifluoromethane (CHF₃) was carried out using non-thermal plasma generated in a dielectric barrier discharge (DBD) reactor. The effects of reactor temperature, electric power, initial concentration and oxygen content were examined. The DBD reactor was able to completely destroy CHF₃ with alumina beads as a packing material. The decomposition efficiency increased with increasing electric power and reactor temperature. The destruction of CHF₃ gradually increased with the addition of O₂ up to 2%, but further increase in the oxygen content led to a decrease in the decomposition efficiency. The degradation pathways were explained with the identified by-products. The main by-products from CHF₃ were found to be COF₂, CF₄, CO₂ and CO although the COF₂ and CF₄ disappeared when the plasma were combined with alumina catalyst.     

等离子体场内CeO2催化降解甲醇的表面活性氧物种来源与作用研究

利用水热法制备了3种不同形貌(纳米棒、纳米颗粒、纳米立方体)的CeO_2催化剂,并通过比表面积测试(BET)、扫描电子显微镜(SEM)、拉曼光谱分析(Raman)、O_2程序升温脱附(O_2-TPD)手段表征其物理化学性质,结果发现,CeO_2纳米棒的表面氧空位和氧物种最多.等离子体与催化协同降解甲醇性能评价实验结果显示,CeO_2纳米棒展现出最好的催化性能.进一步设计实验(甲醇-TPD、不同气氛常温催化、催化剂内后置比较、O_3催化氧化)推测在等离子体场内CeO_2表面活性氧物种来源及其作用.结果表明:①在等离子体场内参与CeO_2表面催化反应的活性氧物种有两个来源,一是催化剂本身存在的表面氧物种,二是等离子体区域产生的短寿命物种及长寿命物种(主要是O_3),其中,O_3分解产生的活性氧物种是提高催化性能的主要因素.②不同形貌CeO_2由于表面氧空位含量不同,导致O_3在催化剂上分解产生的活性氧物种的量不同,最终影响等离子体催化性能.     

Experimental study of NO2 reduction in N2/Ar and O2/Ar mixtures by pulsed corona discharge

Non-thermal plasma technology has been regarded as a promising alternative technology for NOx removal. The understanding of NO2 reduction characteristics is extremely important since NO2 reduction could lower the total NO oxidation rate in the plasma atmosphere. In this study, NO2 reduction was experimentally investigated using a non-thermal plasma reactor driven by a pulsed power supply for different simulated gas compositions and operating parameters. The NO2 reduction was promoted by increasing the specific energy density （SED）, and the highest conversion rates were 33.7%, 42.1% and 25.7% for Ar, N2/Ar and O2/Ar, respectively. For a given SED, the NO2 conversion rate had the order N2/Ar 〉 Ar 〉 02/Ar. The highest energy yield of 3.31 g/kWh was obtained in N2/Ar plasma and decreased with increasing SED; the same trends were also found in the other two gas compositions. The conversion rate decreased with increasing initial NO2 concentration. Furthermore, the presence of N2 or O2 led to different reaction pathways for NO2 conversion due to the formation of different dominating reactive radicals.     

Co-adsorption of gaseous benzene, toluene, ethylbenzene, m-xylene (BTEX) and SO2 on recyclable Fe3O4 nanoparticles at 0-101% relative humidities

We herein used Fe3O4 nanoparticles(NPs) as an adsorption interface for the concurrent removal of gaseous benzene, toluene, ethylbenzene and m-xylene(BTEX) and sulfur dioxide(SO2), at different relative humidities(RH). X-ray diffraction, Brunauer–Emmett–Teller, and transmission electron microscopy were deployed for nanoparticle surface characterization.Mono-dispersed Fe3O4(Fe2O3·Fe O) NPs synthesized with oleic acid(OA) as surfactant, and uncoated poly-dispersed Fe3O4 NPs demonstrated comparable removal efficiencies.Adsorption experiments of BTEX on NPs were measured using gas chromatography equipped with flame ionization detection, which indicated high removal efficiencies(up to(95 ± 2)%) under dry conditions. The humidity effect and competitive adsorption were investigated using toluene as a model compound. It was observed that the removal efficiencies decreased as a function of the increase in RH, yet, under our experimental conditions, we observed(40 ± 4)% toluene removal at supersaturation for Fe3O4 NPs, and toluene removal of(83 ± 4)% to(59 ± 6)%, for OA-Fe3O4 NPs. In the presence of SO2, the toluene uptake was reduced under dry conditions to(89 ± 2)% and(75 ± 1)% for the uncoated and coated NPs, respectively, depicting competitive adsorption. At RH 100%,competitive adsorption reduced the removal efficiency to(27 ± 1)% for uncoated NPs whereas OA-Fe3O4 NPs exhibited moderate efficiency loss of(55 ± 2)% at supersaturation.Results point to heterogeneous water coverage on the NP surface. The magnetic property of magnetite facilitated the recovery of both types of NPs, without the loss in efficiency when recycled and reused.     

UV/H2O2光化学氧化降解对氯苯酚废水的反应动力学

研究了UV/H₂O₂体系降解对氯苯酚废水的过程及动力学结果表明,反应降解速率与双氧水加入量、污染物初始浓度及载气种类有关.在双氧水理论投加量一半的情况下,通入氧气或空气,总酚的降解率可达到96%,COD_Cr去除率接近50%.反应体系加入载气,显著影响污染物的去除率.在本实验中,总酚降解为拟一级反应.     

O(1D)与CF3Cl的反应研究

研究ＣＦ₃Ｃｌ－Ｏ₃体系在２５３．７ｎｍ 紫外光照射下所引发的Ｏ（¹Ｄ）与ＣＦ₃Ｃｌ的反应．Ｏ（¹Ｄ）与ＣＦ₃Ｃｌ的反应最终产物为ＣＦ₂Ｏ、Ｆ₂、Ｃｌ₂,并讨论了Ｏ（¹Ｄ）与ＣＦ₃Ｃｌ的反应机理．研究表明,在本实验条件的２５３．７ｎｍ 紫外光作用下,ＣＦ₃Ｃｌ自身不发生解离,同时Ｏ（³Ｐ）不与ＣＦ₃Ｃｌ发生反应．此外外加气体（氮气、氧气）对Ｏ（¹Ｄ）与ＣＦ₃Ｃｌ的反应有较强的淬灭作用     

ECD氧气诱导法分析大气中痕量HCFC-22

HCFC-22(CHClF₂)是CFC-12的主要替代物,它在大气中的体积分数仅为10^-12级.而且对ECD检测器响应灵敏度很低.本文经过低温浓缩进样后采用氧气诱导法来增强ECD对它的分析灵敏度,载气中氧气的体积分数为0.54%时,信噪比最大,此时ECD灵敏度增强约500倍.结合该条件下ECD温度选择、程序升温和载气流量的研究,建立了高灵敏度ECD气相色谱测定大气中HCFC-22浓度的实用分析方法.     

Numerical evaluation of the effectiveness of NO2 and N2O5 generation during the NO ozonation process

Wet scrubbing combined with ozone oxidation has become a promising technology for simultaneous removal of SO₂ and NO_x in exhaust gas. In this paper, a new 20-species, 76-step detailed kinetic mechanism was proposed between O₃ and NO_x. The concentration of N₂O₅ was measured using an in-situ IR spectrometer. The numerical evaluation results kept good pace with both the public experiment results and our experiment results. Key reaction parameters for the generation of NO₂ and N₂O₅ during the NO ozonation process were investigated by a numerical simulation method. The effect of temperature on producing NO₂ was found to be negligible. To produce NO₂, the optimal residence time was 1.25 sec and the molar ratio of O₃/NO about 1. For the generation of N₂O₅, the residence time should be about 8 sec while the temperature of the exhaust gas should be strictly controlled and the molar ratio of O₃/NO about 1.75. This study provided detailed investigations on the reaction parameters of ozonation of NO_x by a numerical simulation method, and the results obtained should be helpful for the design and optimization of ozone oxidation combined with the wet flue gas desulfurization methods (WFGD) method for the removal of NO_x.     

纳米Fe3 O4-H2 O2 非均相Fenton反应催化氧化邻苯二酚

由四氧化三铁(Fe3O4)-过氧化氢(H2O2)构成的非均相Fenton体系主要利用H2O2分解产生的羟基自由基氧化去除难降解有机污染物.研究了邻苯二酚在纳米Fe3O4-H2O2构成的非均相Fenton体系中的催化氧化特征,同时对实验室制备的纳米级Fe3O4和商品微米级Fe3O4两种催化剂的催化活性进行比较,并考察了H2O2初始浓度对邻苯二酚的催化氧化的影响.结果表明,自制纳米Fe3O4-H2O2体系较商品Fe3O4-H2O2体系,能更快速地去除溶液中的邻苯二酚和总有机碳(TOC),邻苯二酚的去除率接近100%,同时能迅速催化H2O2分解.邻苯二酚的催化氧化反应遵循准一级反应动力学方程,H2O2的分解反应能用三级反应动力学方程较好拟合.此外,反应过程中铁释放低于0.3 mg.L-1,不足以启动均相Fenton反应,反应机制为由界面反应控制的非均相反应机制.