大气压旋转螺旋状电极辉光放电等离子体催化甲烷偶联

采用新研制的具有旋转螺旋状电极的大气压辉光放电等离子体反应器催化甲烷偶联制碳二烃. 实验采用铜电极和不锈钢电极分别考察了输入电场峰值电压和甲烷、氢气进料流量等参数对甲烷转化率和碳二烃收率、选择性的影响. 在长时间连续反应无明显积碳的情况下, 最佳试验结果是电极材料为金属铜, 进料流量为60 mL•min^-1, V(CH₄ )/V(H₂)=1的条件下, 输入电场峰值电压为2.3 kV时, 甲烷转化率为70.64%, 碳二烃单程收率及其选择性分别为69.85%和 99.14%.     

常压辉光放电等离子体转化CH4制C2烃的研究

采用新型的旋转电极辉光放电反应器, 在常温常压下对辉光等离子体作用下的甲烷转化制C₂烃进行了研究. 在氢气共存条件下, 考察了反应器电极的结构、材料, 输入电场峰值电压和反应物流率等参数对甲烷转化率和C₂烃单程收率及其选择性的影响规律, 同时比较了不同反应器的能量效率. 结果表明: 在本实验条件下, 金属铜材料好于不锈钢, 螺旋形结构优于三排圆盘结构. CH₄转化率和C₂烃选择性和收率均随输入电场峰值电压的升高而增大, 随反应物流量的增加而减小. 从CH₄转化率、C₂烃的收率和选择性的指标来评价这些反应器, 采用旋转螺旋状铜电极反应器时最好, 当反应物流量为60 mL/min时, 甲烷最高转化率为77.31%, 对应的C₂烃收率和选择性分别为75.66%和97.88%; 当能量密度为800 kJ/mol时, 能效最高为13.5%.     

常压辉光放电等离子体转化CH4制C2烃的研究

采用新型的旋转电极辉光放电反应器, 在常温常压下对辉光等离子体作用下的甲烷转化制C₂烃进行了研究. 在氢气共存条件下, 考察了反应器电极的结构、材料, 输入电场峰值电压和反应物流率等参数对甲烷转化率和C₂烃单程收率及其选择性的影响规律, 同时比较了不同反应器的能量效率. 结果表明: 在本实验条件下, 金属铜材料好于不锈钢, 螺旋形结构优于三排圆盘结构. CH₄转化率和C₂烃选择性和收率均随输入电场峰值电压的升高而增大, 随反应物流量的增加而减小. 从CH₄转化率、C₂烃的收率和选择性的指标来评价这些反应器, 采用旋转螺旋状铜电极反应器时最好, 当反应物流量为60 mL/min时, 甲烷最高转化率为77.31%, 对应的C₂烃收率和选择性分别为75.66%和97.88%; 当能量密度为800 kJ/mol时, 能效最高为13.5%.     

介质阻挡放电等离子体催化天然气偶联制C2烃

在常压、室温的介质阻挡放电连续流动反应器中, 对介质阻挡放电等离子体作用下天然气偶联反应制C₂烃进行了研究. 考察了放电频率、放电的电极结构、放电电压、放电的电极数目、氢气、甲烷进料流量和催化剂等参数对甲烷转化率和产物(碳二烃和碳三烃)的选择性影响规律, 同时探讨了反应过程. 结果表明合适的工艺条件为: 电源频率20 kHz, 电极结构为两个电极上都覆盖绝缘介质的b型, 放电电压20~40 kV, 进料流量20~60 mL·min^-1, H₂/CH₄为1/4; 甲烷的转化率随电压的升高而增大, 随甲烷进料流量的增大而减小, 碳二烃的选择性随电压的升高而减小, 随甲烷进料流量的增大而增大. 甲烷的转化率可达45%, 碳二烃选择性可达76%, 产品(碳二烃和碳三烃)的总选择性接近100%; 连续反应100 h无积碳; 催化剂可改善产品碳二烃的选择性; 碳二烃和碳三烃的生成主要是通过自由基和甲烷分子反应获得的.     

电场增强催化甲烷合成碳二烃催化剂影响研究

本研究提出了在常温、常压电场增强等离子体条件下甲烷直接转化合成碳二烃的洁净工艺 ,在不同的放电电压、放电功率、甲烷进料流量和不同的催化剂作用下 ,甲烷能够以不同的转化率和选择性转变为碳二烃。对影响甲烷转化率和碳二烃选择性的因素 :放电电压、放电功率、甲烷进料流量和催化剂进行了研究 ,对催化剂性能进行了比较 ,并探讨了反应机理。结果表明 ,适宜的工艺条件 :放电电压 2 0kV～ 4 0kV ;输入功率 :2 0W～ 4 0W ;合适的甲烷进料流量 :30mL/min～ 70mL/min。在该条件下 ,碳二烃的选择性可以达到 95 % ;催化剂对甲烷转化率的影响顺序为MnO2 /Al2 O3 >Ni/Al2 O3 >MoO3 /Al2 O3 >Ni/NaY >Pd/ZSM 5 >Ni/H4Mg2 Si3 O4>Ni/ZSM 5 >Co/ZSM 5 >无催化剂。     

多尖端旋转电极辉光放电甲烷偶联研究

石油资源的日趋短缺使人们对世界大储量能源天然气的开发利用越来越重视.甲烷(CH4)是天然气的主要成份.由于CH4分子具有很高的稳定性,用CH4直接偶联制C2烃(乙烷、乙烯、乙炔)在热力学上十分不利,采用常规催化手段一直未取得突破性进展\[1\],而辉光放电等冷等离子体对于CH4偶联是一种非常有效的方法,近年来已成为物理化学跨学科前沿研究热点.在本研究领域中,利用脉冲电晕等离子体结合催化剂进行甲烷转化[2],其等离子体在空间分布上是非连续的,活性较低,反应区较小,甲烷的转化率及C2烃收率必然是有限的;利用微波诱导甲烷在催化剂上转化制C2烃[3],由于温度很高,能量密度太大,很容易使甲烷完全裂解,生成大量积碳,C2烃的收率也较低;利用介质阻挡放电使CH4偶联[4],能耗太大,能量利用率很低.因此,冷等离子体CH4偶联实现工业化的课题就是要在提高CH4转化率及C2烃收率的同时降低能耗,以提高能量利用率.     

滑动弧放电等离子体分解甲醇制氢

对常温常压下滑动弧放电等离子体直接分解甲醇进行了研究,探讨了载气流量、甲醇浓度、电极间距、输入电压和气化室温度等实验参数的影响。结果表明,不同操作条件导致甲醇转化率由51%升高到81.7%,氢气和一氧化碳的选择性之比基本保持一个固定值。除了氢气和一氧化碳,产物中还检测到了少量的甲烷和C₂不饱和烃以及痕量二氧化碳。不同于传统的甲醇热分解机理,提出了滑动弧放电等离子体甲醇分解的制氢路径。     

正压、低温脉冲微波等离子体裂解天然气直接转化 制C2烃的研究

利用脉冲微波强化、扩展丝光等离子体反应装置,在常压和正压条件下,对低温脉冲微波等离子体裂解甲烷和氢气混合气制C2烃的反应进行了研究。考察了压力、微波功率、脉冲通/断时间以及氢气/甲烷比例、流量等参数对反应的影响。结果表明,在脉冲微波的作用下,常规高压放电形成的在空间呈非连续分布的丝状等离子体被强化和扩展成为连续分布的伞状等离子体,等离子体利用率和活性均得以大幅度提高;利用这种低温等离子体可以获得高的甲烷转化率,而且产物纯净,只有乙烯和乙炔;通过改变压力,还可能调节产物中C2H2/C2H4的物质的量比值,当气体总流量为300mL/min、物质的量比n(H2)/n(CH4)=2:1、压力为0.13MPa、微波峰值功率为120W、脉冲通/断比=400/400ms时,甲烷转化率可达59.2%,C2烃单程收率可达52%,其中乙炔单程收率达42.7%。     

微波等离子体下甲烷偶联制乙炔的研究

通过优化设计矩形波导谐振腔微波化学反应器,可以大幅提高微波等离子体下甲烷转化率（最高为93．7％）、C2烃收率（最高为91．0％）和乙炔收率（最高为88．6％）．且优化后,在实验的压强范围内,甲烷转化率和C2烃收率较为稳定,C2烃主要是乙炔,其选择性都在90％以上．生成乙炔的能量产率和时空产率也都比较高．利用发射光谱法对微波等离子体下甲烷偶联制乙炔的反应进行了诊断研究,在300nm～750nm波长范围内激发态物种有：CH,C2,H2,Hα-根据反应产物和激发态物种从化学反应热力学和动力学上对反应机理进行了初步探索．     

丙烯和氧等离子体直接气相合成环氧丙烷

在室温和大气压下,在针板式反应器中,通过脉冲电晕放电等离子体对分子氧和丙烯直接合成环氧丙烷的活化作用,考察了放电电极间距、电晕放电脉冲电压以及电晕放电重复频率参数对丙烯转化率、环氧丙烷产率和其选择性的影响,反应物及各产物通过在线色谱法进行分析.实验结果表明,在室温和大气压下,用脉冲电晕等离子体法可转化丙烯和氧气直接生成环氧丙烷,适当调节上述各参数可提高环氧丙烷的收率.当反应气总流速为200mL/min,极间距为4mm,脉冲放电电压为18kV,放电频率为120Hz时,环氧丙烷的收率、丙烯的转化率及环氧丙烷的选择性分别为5.15%,19.15%和26.89%.     

Conversion of natural gas to C_2 hydrocarbons via cold plasma technology

The plasma technology served as a tool in unconventional catalysis has been used in natural gas conversion,because the traditional catalytic methane oxidative coupling reaction must be performed at high temperature on account of the stability of methane molecule.The focus of this research is to develop a process of converting methane to C2 hydrocarbons with non-equilibrium plasma technology at room temperature and atmospheric pressure.It was found that methane conversion increased and the selectivity of C2 hydrocarbons decreased with the voltage.The optimum input voltage range was 40-80 V corresponding to high yield of C2 hydrocarbons.Methane conversion decreased and the selectivity of C2 hydrocarbons increased with the inlet flow rate of methane.The proper methane flow rate was 20-40 ml/min (corresponding residence time 10-20 s).The experimental results show that methane conversion was 47% and the selectivity of C2 hydrocarbons was 40% under the proper condition using atmospheric DBD cold plasma technology.It was found that the breakdown voltage of methane VB was determined by the type of electrode and the discharge gap width in this glow discharge reactor.The breakdown voltage of methane VB,min derived from the Paschen law equation was established.     

Conversion of natural gas to C2 hydrocarbons via cold plasma technology

The plasma technology served as a tool in unconventional catalysis has been used in natural gas conversion, because the traditional catalytic methane oxidative coupling reaction must be performed at high temperature on account of the stability of methane molecule. The focus of this research is to develop a process of converting methane to C2 hydrocarbons with non-equilibrium plasma technology at room temperature and atmospheric pressure. It was found that methane conversion increased and the selectivity of C2 hydrocarbons decreased with the voltage. The optimum input voltage range was 40-80 V corresponding to high yield of C2 hydrocarbons. Methane conversion decreased and the selectivity of C2 hydrocarbons increased with the inlet flow rate of methane. The proper methane flow rate was 20-40 ml/min (corresponding residence time 10-20 s). The experimental results show that methane conversion was 47% and the selectivity of C2 hydrocarbons was 40% under the proper condition using atmospheric DBD cold plasma technology. It was found that the breakdown voltage of methane VB was determined by the type of electrode and the discharge gap width in this glow discharge reactor. The breakdown voltage of methane VB,min derived from the Paschen law equation was established.     

Conversion of natural gas to C_2 hydrocarbons through dielectric-barrier discharge plasma catalysis

The experiments are carried out in the system of continuous flow reactors with dielectric-barrier discharge (DBD) for studies on the conversion of natural gas to C2 hydrocarbons through plasma catalysis under the atmosphere pressure and room temperature. The influence of discharge frequency, structure of electrode, discharge voltage, number of electrode, ratio of H2/CH4, flow rate and catalyst on conversion of methane and selectivity of C2 hydrocarbons are investigated. At the same time, the reaction process is investigated. Higher conversion of methane and selectivity of C2 hydrocarbons are achieved and deposited carbons are eliminated by proper choice of parameters. The appropriate operation parameters in dielectric-barrier discharge plasma field are that the supply voltage is 20-40 kV (8.4-40 W), the frequency of power supply is 20 kHz, the structure of (b) electrode is suitable, and the flow of methane is 20-60 ml · min-1. The conversion of methane can reach 45%, the selectivity of C2 hydrocarbons i     

Conversion of Methane to C2 Hydrocarbons via Cold Plasma Reaction

Direct conversion of methane to C2 hydrocarbons via cold plasma reaction with catalysts has been studied at room temperature and atmospheric pressure. Methane can be converted into C2 hydrocarbons in different selectivity depending on the form of the reactor, power of plasma, flow rate of methane, ratio of N2/CH4 and nature of the catalysts. The selectivity to C2 hydrocarbons can reach as high as 98.64%, and the conversion of methane as high as 60% and the yield of C2 hydrocarbons as high as 50% are obtained. Coking can be minimized under the conditions of: proper selection of the catalysts, appropriate high flow rate of inlet methane and suitable ratio of N2 to CH4. The catalyst surface provides active sites for radical recombination.     

OXIDATIVE COUPLING OF METHANE OVER Mn_2O_3-Na_2WO_4/SiO_2 CATALYST IN THE ABSENCE OF DILUTE GAS

The oxidative coupling of methane over Mn2O3-Na2WO4/SiO2 catalyst has been investigated in the absence of dilute gas. 16.4% of C2 yield and 80.4% of the selectivity to C2 hydrocarbons were obtained at CH4/O2 = 8.5/1.5. The effect of flow rate on the selectivity to C2 hydrocarbons and CH4 conversion was different under the reaction condition of different ratio of CH4 to oxygen. The flow rate had a more remarkable effect on the selectivity at the lower ratio of methane to oxygen. The addition of steam into the reaction gas can increase C2 yield to some extent, but that of HC1 decrease the selectivity to C2 hydrocarbons.     

用无声放电转化甲烷和二氧化碳同时制备合成气与烃

在低温常压条件下,研究了在无声放电反应器中以A型分子筛为催化剂从甲烷和二氧化碳合成烃和合成气,实现了在无声放电反应器中同时合成烃和合成气。实验在原料气流量200－600ml/min、原料气甲烷和二氧化碳摩尔比1／1－3／1及输入功率100－500W的范围内进行。研究结果表明,低原料气流量有利于甲烷和二氧化碳的转化,而高原料气流量有利于烃的生成;原料气甲烷和二氧化碳摩尔比对制得合成气的H2／CO摩尔比的影响最显著;甲烷和二氧化碳转化率及合成气和烃的产率均随输入功率的增加而提高。而所研究的范围内,当原料气流理为200ml/min、甲烷和二氧化碳摩尔比为1／1、输入功率为500S时,甲烷和二氧化碳转化率达到最高值,分别为64％和39％。以此法制备的合成气的H2／CO摩尔可以在很宽的范围内变化,本研究合成气H2／CO摩尔比的变化范围是0.7-3.1。     

脉冲电晕放电下的甲烷氧化偶联反应(英文)

研究了在常温,常压及惰性气体稀释的条件下,用脉冲电晕放电进行的甲烷氧化偶联（OCM）反应。在各种实验条件下,产物CZ烃由一6o／o乙烯,－70rk乙烷和一87％乙炔组成。甲烷的转化率及CZ烃的生成速率依赖于反应气中甲烷与氧气的比值,它们的流速及直流电源的电压等n通过调节这些实验条件,甲烷转化为C4烃的转化率可得到优化,在45kV高压,30ml。／min的流速下（反应气体组成为95％CHn与50／0O2）,CZ烃的最高选择性可达85O／O。当反应气体组成为80％CH4和20O／oOZ时,甲烷的最高转化率达23％。在间歇式反应器中,甲烷转化率随反应时间增长而提高,反应75分钟时甲烷转化率达7lO／O,而CZ烃的产物分布,尤其是乙炔的含量随反应时间增长而明显降低,这些实验结果支持了文献中提出的ZCH4～CZH6—CZH4～CZHZ～CO／COZ反应历程。