O2介质阻挡放电微等离子体制备O3

介质阻挡放电(DBD)是工业生产臭氧(O₃)最有效的方法。研究以O₂为原料气采用DBD微等离子体放电制备O₃,研究了放电间距、放电长度、放电功率以及停留时间对产生O₃的影响。此外,通过向正弦AC等离子体电源中叠加调制脉冲,探讨了脉冲占空比与调制频率对O₃生成的影响。结果表明：O₃浓度与DBD反应器的放电间距呈负相关,与O₂的停留时间呈正相关,放电功率及有效放电长度对O₃浓度的影响呈现火山形变化趋势。综合考虑O₃浓度及能量产率确定了适宜的参数。与普通正弦交流电源相比,在其基础上叠加脉冲调制电源有利于O₃的产生,而能量产率与占空比呈正相关,与调制频率呈负相关,据此确定了合适的占空比与调制频率。     

联合发射光谱与动力学计算的非热等离子体重整CO2-CH4机理

非平衡等离子体重整CO₂-CH₄制合成气是实现2种温室气体资源化利用的新兴技术途径。综合采用发射光谱分析、反应动力学计算和连续质谱对常温常压介质阻挡放电(DBD)非热等离子体重整CO₂-CH₄反应途径进行探索。比功率S_EI为52 J/cm³时,可得到CH₄和CO₂转化率最大分别为22.8%和9.4%。稳态气相产物连续质谱在线分析表明,C₂H₄为C₂烃生成重要中间体,CH₄比例越高C₂烃生成量越大,且按C₂H₆2H₄2H₂顺序升高。发射光谱检测到·CH、·C₂自由基和CO、CO■特征谱线,·CH相对强度随比功率增加明显降低,CO■相对强...     

非平衡碘负离子转化二氧化碳

以直流脉冲负高压电晕放电形式,通过加入电子亲和能较高的碘气,在完全电负性离子体条件下资源化处理CO₂。考察了进气流量、高压放电频率和原料摩尔比对CO₂转化率的影响。结果表明:70℃时,利用碘负离子成功将CO₂还原生成了CI₄,其产率随着CO₂流量的增加而减少。当进气流量0.06 L·min^-1、放电频率9.608 kHz,n(I₂)/n(CO₂)为2.5时,CO₂转化率在碘负离子作用下达到88.71%。另外,对碘负离子和CO₂还原反应机理进行了初步探讨。     

旋转弧等离子体转化油脂制合成气

废弃油脂不仅造成严重的环境污染,而且容易引发各种社会问题,因此加快对废弃油脂的综合利用势在必行。本文以大豆油作为废弃油脂替代物,在自制炬/反应器中开展旋转弧等离子体转化油脂制合成气研究,系统考察了水/大豆油质量比、输入功率和磁感应强度对大豆油转化过程的影响。研究结果表明,气体产物主要为CO、H₂、CO₂与烃类,CO与H₂最高可占气体总量的91.0%(体积)以上。水/大豆油质量比主要影响产物组成和能量转化效率,对碳气相转化率和合成气收率影响较小。增加输入功率,碳气相转化率可提高至98.5%,能量转化效率在17.9 kW时达到最大值72.9%。实验考察范围内磁感应强度对大豆油转化效果的影响很小,但可以起到保护阳极的作用。     

介质阻挡放电等离子体脱除硫化氢的能效优化研究

为提高介质阻挡放电(DBD)系统降解H2S的能量利用效率,以同轴DBD反应系统为对象,从谐振特性和功率特性两方面研究了DBD放电系统的电气参数和反应器几何参数对反应器能量输入和H2S脱除效果的影响。研究发现,放电频率与负载电压之间的谐振特性直接影响H2S脱除效率,在谐振频率点脱除效率最大。谐振频率的大小受负载电压和反应器几何参数的影响,其原因可以归结于介质层等效电容的变化。DBD放电有效功率与放电频率、负载电压和反应器几何参数间存在量化规律P=A·L·f·Vn,且在相同的负载电压下,谐振频率点的能量输入效率ηP最大。其他条件不变的情况下,放电区域长度越大,H2S脱除效率越高;放电气隙的大小存在最优值,本文中最优的放电气隙为5 mm。     

二氧化碳协助强化对二甲苯氧化的连续过程实验与模拟

利用连续实验装置考察了气相CO₂浓度和反应温度对PX氧化反应的影响,并通过反应器建模对连续实验过程进行了模拟计算。研究结果表明,当气相CO₂浓度介于40%～60%时,CO₂能显著提高反应器出口PX转化率以及主产物收率,并且可以降低液相中主要杂质的含量;温度高于192℃后对反应器出口指标的影响比低温时明显。本文建立的全混流反应器模型能够预测气相CO₂含量以及温度等不同反应条件下氧化反应器出口的PX转化率、主产物收率以及液相主要杂质随停留时间的变化。相关研究结果可为当前工业PX氧化过程效率提高以及节能降耗提供新的思路。     

介质阻挡放电等离子体反应器降解盐酸四环素

采用介质阻挡放电等离子体反应器降解盐酸四环素（TC）,研究了输入功率、放电间距、气体流量、初始浓度等参数对盐酸四环素降解效果的影响,结果表明当输入功率为1.3 W,放电间距为2.5 mm,气体流量为150 ml·min^-1,初始浓度为100 mg·L^-1时降解效果最好,放电处理30 min盐酸四环素的降解率达到92%。动力学研究表明盐酸四环素的降解过程符合拟二级动力学方程。检测了降解过程中生成的中间产物,提出了盐酸四环素的降解路径与机理。     

铁基氧载体化学链CO2重整CH4方法制备合成气

提出一种铁基氧载体（Fe₃O₄/FeO）化学链CO₂重整CH₄方法制备合成气。为评价该系统的性能,采用Aspen Plus软件对其进行过程模拟和热力学分析。以CH₄转化率、CO₂转化率、能源利用效率和产气氢碳比（H₂/CO）为评价指标,得到系统的优化运行条件,并研究各操作参数（包括各反应器的温度和压力、氧载体甲烷比和CO₂甲烷比）对系统性能的影响。结果表明：当系统处于优化工况时,得到CH₄转化率为97.91%、CO₂转化率为32.76%、能源利用效率为93.77%及产气氢碳比为0.93。该系统能有效利用CO₂和CH₄这两种温室气体获得较低氢碳比的合成气,利于二甲醚的高效合成。     

介质阻挡放电常压低温等离子体转化甲烷制C2及高碳烃的研究

对介质阻挡放电(DBD)反应器用于甲烷常压低温等离子体转化过程,分别就停留时间、输入功率、内电极材料及温度、介质厚度等对反应的影响进行了研究。实验结果表明,甲烷转化率随停留时间、输入功率的增加而增加,但增加的幅度逐渐减小。内电极材料对反应积炭有很大的影响。紫铜和紫铜(镀银)材料能够有效地抑制积炭的产生,从而可以增加反应寿命,还对甲烷转化率有很大的影响。较低的内电极温度可以抑制积炭,但是甲烷转化率有所降低,同时液态高碳烃选择性增加。在甲烷流量较低时介质厚度对反应的影响很小,但随着甲烷流量的提高会逐渐增大,并且介质厚度越小,甲烷转化率越高。     

木屑炭高温CO2气化特性研究

在高温固定床反应器中,以木屑炭为原料,进行木屑炭CO₂气化的特性研究。考察了气化温度和CO₂流量对燃气各组分体积分数、热值、固体产率、产气率的影响。结果表明：随着气化温度从750 ℃升高到950 ℃,CO体积分数明显增加,CO₂体积分数明显减少,燃气热值增加较明显,而从950 ℃升高到1 050 ℃时,燃气热值增加趋势减缓。CO₂作为气化介质,随着其流量增加,固体产率减少,气体产率增加,燃气组分中CO₂体积分数明显增加,CO体积分数先增加后减少,燃气热值先增大后减小。CO₂流量为15 mL/（min·g）时,燃气热值最大。气化温度950 ℃、CO₂流量15 mL/（min·g）为较佳的气化条件,此时气化制备的气体中CO体积分数为51.51%,CO₂体积分数为37.99%,燃气热值为8.03 MJ/m³,产气率为0.78 L/g。     

Improved performance of non-thermal plasma reactor during decomposition of trichloroethylene: Optimization of the reactor geometry and introduction of catalytic electrode

The decomposition of trichloroethylene (TCE) by non-thermal plasma was investigated in a dielectric barrier discharge (DBD) reactor with a copper rod inner electrode and compared with a plasma-catalytic reactor. The particularity of the plasma-catalytic reactor is the inner electrode made of sintered metal fibers (SMF) coated by transition metal oxides. In order to optimize the geometry of the plasma reactor, the efficiency of TCE removal was compared for different discharge gap lengths in the range of 1–5 mm. Shorter gap lengths (1–3 mm) appear to be more advantageous with respect to TCE conversion. In this case TCE conversion varies between 67% and 100% for input energy densities in the range of 80–480 J/l, while for the 5 mm discharge gap the conversion was lower (53–97%) for similar values of the input energy. As a result of TCE oxidation carbon monoxide and carbon dioxide were detected in the effluent gas. Their selectivity was rather low, in the range 14–24% for CO₂ and 11–23% for CO, and was not influenced by the gap length. Several other chlorinated organic compounds were detected as reaction products.

When using MnOx/SMF catalysts as the inner electrode of the DBD reactor, the TCE conversion was significantly enhanced, reaching 95% at 150 J/l input energy. The selectivity to CO₂ showed a major increase as compared to the case without catalysts, reaching 58% for input energies above 550 J/l.     

Hydrogen production from methanol through dielectric barrier discharge

The hydrogen fuel cell is a promising option as a future energy resource and the production of hydrogen is mainly depended on fossil fuels now. In this paper, methanol reforming to produce H₂ through dielectric-barrier discharge (DBD) plasma reaction was studied. Effects of the power supply parameters, reactor parameters and process conditions on conversion of methanol and distribution of products were investigated. The best reaction conditions were following: input power (45 W), material of inner electrode (stainless steel), discharge gap (3.40 mm), length of reaction zone (90.00 mm), dielectric thickness (1.25 mm), and methanol content (37.65%). The highest conversion of methanol and the yield of H₂ were 82.38% and 27.43%, respectively.     

Dielectric barrier micro-plasma reactor with segmented outer electrode for decomposition of pure CO2

Four coaxial cylinder dielectric barrier discharge micro-plasma reactors were designed for the non-catalytic decomposition of pure CO₂ into CO and O₂ at low temperature and ambient pressure. The influence of segmented outer electrodes on the electrical characteristics and the reaction performance was investigated. Experimental results indicated that the introduction of segmented outer electrodes can significantly promote the decomposition of CO₂. Encouragingly, the highest conversion of 13.1% was obtained at an applied voltage of 18 kV, which was a substantial increase of 39.4% compared to the traditional device. Compared with other types of dielectric barrier discharge plasma reactors, the proposed segmented outer electrode micro-plasma reactor can give a higher CO₂ conversion and acceptable energy efficiency. The increase in conversion can be attributed mainly to the enhanced corona discharge caused by the fringe effect at electrode edges, the increase in energy density and the increase in the number of micro-discharges. In addition, detailed electrical characterization was performed to reveal some trends in the electrical behavior of proposed reactors.     

低温等离子体除苯过程中臭氧的演变与作用

大气污染物中,挥发性有机化合物(VOCs)已超越NOx和SO_2成为排放量最高的气态污染物,对人体健康和环境的影响已引起广泛关注。相比传统去除VOCs的技术,低温等离子体法具有高效率、低能耗、易操作等优势,但有产生臭氧(O_3)等副产物的问题。本研究选择苯作为VOCs的代表污染物,采用线管式介质阻挡放电反应器,考察电压、电流等放电参数对苯去除率、副产物臭氧浓度和CO_2选择性的影响,重点分析臭氧的演变、机理及其作用。结果表明,影响臭氧浓度的直接因素是输入功率:随着输入功率的上升,苯去除率逐渐上升,臭氧浓度先上升后下降。其原因在于高功率下生成更多低能电子,使得臭氧分解为氧气。等离子体产生的臭氧无法直接氧化苯,但可以氧化苯的中间产物CO完全转化为CO_2。     

Characterization and reactivity of pure TiO2–SO4 SCR catalyst: influence of SO4 content

The kinetics of the reaction of NO, N₂O and CO₂ with activated carbon without catalyst and impregnated with a precursor salt of vanadium (ammonium monovanadate) was investigated. The conversion of NO, N₂O and CO₂ was studied (450–900°C) using a TGA apparatus and a fixed bed reactor. The reactor effluents were analysed using a GC/MS on line. The addition of vanadium increased carbon reactivity and adsorption at lower temperatures. For NO and N₂O conversion the main products obtained were N₂, N₂O, CO and CO₂ but for CO₂ conversion only CO was detected. In situ XRD was a useful tool for interpreting catalyst behaviour and identifying phases present during reaction conditions. The catalytic effect of vanadium can be explained by the occurrence of redox processes in which the catalyst is reduced to lower oxidation states such as V₂O₅/V₆O₁₃.     

甲醇合成催化剂的工艺参数优化及反应机理探讨

对自主研制的甲醇合成催化剂进行工艺参数优化,同时根据实验结果对合成气条件下甲醇合成的反应机理进行探讨。实验采用16通道反应器,考察反应温度和接触时间对合成甲醇反应速率的影响,确定适宜的催化剂工艺条件。结果表明,在较长接触时间下,随着温度的升高,CO转化率、H_2转化率和甲醇相对含量先升高后降低,CO_2转化率降低。在较低温度下,CO_2转化率随接触时间延长基本不变,表明甲醇中碳元素主要来自于CO,而CO_2浓度处于水汽变换反应与加氢形成甲醇反应之间的平衡状态。     

Chemical Effects of CO2 Concentration on Soot Formation in Jet-stirred/Plug-flow Reactor

Soot formation was investigated numerically with CO2 addition in a jet-stirred/plug-flow reactor （JSR/PFR） C2H4/OJN2 reactor （C/O ratio of 2.2） at atmospheric pressure. An updated Kazakov mechanism empha- sizes the effect of the O2/CO2 atmosphere instead of an O2/N2 one in the premixed flame. The soot formation was taken into account in the JSR/PFR for C2H4/O2/N2. The effects of CO2 addition on soot formation in different C2H4/O2/CO2/N2 atmospheres were studied, with special emphasis on the chemical effect. The simulation shows that the endothermic reaction CO2 ＋ H - CO ＋ OH is responsible of the reduction of hydrocarbon intermediates in the CO2 added combustion through the supplementary formation of hydroxyl radicals. The competition of CO2 for H radical through the above forward reaction with the single most important chain branching reaction H ＋ O2, ＇ O ＋ OH reduces significantly the fuel burning rate. The chemical effects of CO2 cause a significant increase in residence time and mole fractions of CO and OH, significant decreases in some intermediates （H, C2H2）, polycyclic aromatic hydrocarbons （PAHs, C6H6 and CI6H10, etc.） and soot volume fraction. The CO2 addition will leads to a decrease by only about 5% to 20% of the maximum mole fractions of some C3 to Clo hydrocarbon intermediates. The sensitivity analysis and reaction-path analysis results show that C2H4 reaction path and products are altered due to the CO2 addition.     

ZSM-5催化剂与低温等离子体协同转化H2S-CO2制合成气

将H₂S和CO₂混合酸气一步转化制合成气,既实现了二者无害化处理,又生产出合成气,是一条理想的废气资源化利用新路线。由于分子结构稳定,在常规条件下因受热力学平衡限制,二者转化率极低。而在低温等离子体中,H₂S和CO₂可被激发为高活性物种来参与反应。研究了具有不同Si/Al摩尔比的ZSM-5催化剂与低温等离子体结合实现H₂S-CO₂一步高选择性制合成气,显著提高了H₂S-CO₂转化性能。考察了ZSM-5催化剂中Si/Al比和低温等离子体放电条件等对反应的影响。其中,当Si/Al比为80时表现出最优催化性能,最高H₂和CO产率分别达到56.1%和10.0%。对常规条件和低温等离子体氛围下的不同ZSM-5催化剂上CO₂、H₂S、CO、H₂等化学吸脱附行为进行了对比研究,发现低温等离子体促进了催化剂对CO₂、H₂及CO分子的吸附活化,进而明显提升了H₂S和CO₂转化。