微波等离子体下一氧化碳氢化制乙炔反应中产物的选择性研究(英文)

采用微波等离子体技术研究了一氧化碳氢化制乙炔反应的产物选择性。对影响乙炔选择性的几个因素,如微波输入功率、反应物的比例和体系压力进行了研究。乙炔的选择性随着微波输入功率的增加,反应物比例和体系压力的降低而增大。在最佳条件下,乙炔的选择性可达到９５．８７％,甲烷选择性的变化规律和乙炔相反,乙烯和乙烷的选择性很低。等离子体中的电子温度（或能量）和密度采用了静电悬浮双探针诊断,电子密度和能量受微波输入功率和体系压力的影响。在反应中,电子能量决定化学反应是否进行,电子密度决定产物的组成。根据自由基反应理论解释了乙炔选择性在Ｈ２＋ＣＯ等离子体化学反应中随影响因素的变化规律。     

甲烷在微波等离子体下直接转化成C2烃

研究了非平衡微波等离子体中影响甲烷脱氢转化的几个因素，如功率、ＣＨ４／Ｈ２比和体系压力。在最佳条件下，甲烷转化率和乙炔的选择性分别达到７７．４６％和７４．０４％。     

用气相色谱仪测定变压器油中气体

本文采用多柱自动切换气相色谱仪和真空全脱气装置对变压器和互感器用油中的气体进行了系统的分析，除可测定油中的氢、甲烷、乙炔、乙烯、乙烷、二氧化碳和一氧化碳等气体外，还可根据不同需要测定氮、氧以及Ｃ３和Ｃ４烃的含量。本方法已用于诊断变压器和互感器内部变化及故障。     

非平衡等离子体下乙烷脱氢反应的研究

在低温常压下,对脉冲电晕等离子体应用于乙烷脱氢反应进行了研究。考察了等离子体注入功率和添加气对反应的影响,并探讨了等离子体条件下乙烷脱氢反应的机理。研究结果表明：乙烷在脉冲电晕等离子体中可发生转化反应,主要产物是乙炔。乙烷转化率和乙炔收率随等离子提功率增加不断提高。添加气二氧化碳的加入提高了乙烷转化率,当体系中CO2浓度为50％时乙炔收率达到峰值。向反应体系中添加氢不仅促进了乙烷的转化,提高了乙炔选择性,且抑制了积碳的形成。     

羰基硫对FT合成气液相产物的影响

在５２４Ｋ，２．３１ＭＰａ，１８４５ｈ＾－１，Ｈ２／ＣＯ＝２．１的条件下考察了合成气中ＣＯＳ对下合成催化剂活性及产物分布的影响，结果表明，随着催化剂中硫含量的增加，尾气中ＣＯ２，ＣＨ４，含量减少，ＣＯ含量增加，催化剂中毒后，甲烷选择明显提高，Ｃ５重量百分含量降低，气态Ｃ２～Ｃ４烃增加了产物向低碳烃方向移动。油相和水相的产物分析结果表明，催化剂中毒后，气物中含氧化合物增加，液态烃中烯烃减少，正构烷烃     

微波激发甲烷气相裂解

乙炔、乙烯是重要的有机合成原料,利用甲烷生产乙炔、乙烯一直受到人们的关注。近年来已有用激光裂解甲烷得到乙炔的报道,但激光器价格昂贵,消耗电能也较高。我们对微波激发甲烷裂解反应的静态体系进行了实验研究,用自制的反应系统与检测质谱仪联机,测得气相裂解反应主要产物为乙炔、乙烯,其中乙炔含量可达66％。通过对产物组成与气体初始压力、激发时间,微波功率关系的研究,找到最佳实验条件。本方     

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%。     

反应器型式对甲烷低温等离子体转化制C2烃的影响

就不同反应器对甲烷常压低温等离子体转化制C2烃的影响进行了研究。结果表明，相同的甲烷停留时间和相同甲烷流率下，反应器A和B中反应的主要产物是乙炔，乙烯和乙烷的含量较少，积炭量较多；而反应器C和D中反应的主要产物为乙烷和丙烷，乙烯和乙炔含量较少，积炭量很少。反应积炭对反应器A中甲烷转化率影响很大，对于产物选择性影响不大，而对反应器C中的反应影响较小。根据产物分布可知，在反应器A和B中，由于电子具有很高的能量和密度，甲烷主要解离为碳原子；而在反应器C及D中，由于电子能量和密度较低，甲烷主要解离为CH3自由基。     

几种烃化合物在氮热等离子体中的热解

研究了数种烃包括液态苯和甲苯以及气态的四甲烷，乙烯及乙炔在氮热等离子体中的热解行为，结果发现，所有烃人合物在氮等离子体中均发生强烈的分解反应，生成大量炭黑和气体。气体产物中的主要成分是氢，乙炔和丙炔腈，在液态烃苯和甲苯的热解产物中不含有甲烷及乙烯等小分子烃，乙炔的浓度与丙炔腈的含量有关，丙炔腈的含量高时，乙炔的浓度低，反之亦然，所制得的炭黑粒细小，粒度分布范围产窄，具有较强的吸附性能，其确值为１４     

微波场对固态氧离子导体上的甲烷氧化偶联的影响

研究了微波场下甲烷在具有δ－Ｂｉ２Ｏ３结构的固态氧离子导体上氧化偶联反应行为。与常规加热条件下的反应结果相比较，微波辐射下的反应有上特点：（１）在达到相同甲烷转化率时，微波辐照下所需床层温度要远低于常规加热条件下所需床层温度；（２）微波辐照下，甲烷氧化偶联产物中Ｃ２烃的选择性普遍较高，在低温区尤为突出。微波场下甲烷偶联产物乙烷、乙烯的再氧化得到一定程度的抑制，致使微波场下的甲烷氧化偶联反应通常有较     

Selective ethane conversion into aromatic hydrocarbons over Zn-ZSM-11 zeolite

The conversion of ethane into aromatic compounds at 550°C and atmospheric pressure over Zn-ZSM-11 zeolite (Si/Al=17; 2.5 wt.% of Zn as counter ion) has been studied in a flow reactor at different partial pressures of ethane. The observed products at different ethane conversion levels were formed through a variety of processes including ethane dehydrogenation, producing ethylene as the only primary unstable product. Ethylene underwent very rapid reactions through carbenium ion intermediates, producing aromatic hydrocarbons and C1-C4 hydrocarbons as secondary products.     

Production of acetylene by a microwave catalytic reaction of water and carbon

The feasibility of producing hydrocarbons in a microwave induced catalytic reaction of carbon and water was successfully demonstrated. The major reaction products are acetylene, methane, ethylene and ethane. Other significant products include propylene, propyne, cyclopropane, carbon dioxide and carbon monoxide. Relative product yields and their distribution depend on a number of experimental variables, such as irradiation time, incident microwave power, water/carbon ratio and the characteristics of the microwave pulse train. At short irradiation times and low incident power only C₁ — C₂ products were observed, their rates of formation being an exponential function of the incident microwave power. High incident power led to the formation of C₃ to C₆ hydrocarbons at the expense of acetylene. Initial addition of methane and carbon dioxide to the reaction mixture increased the yield of acetylene, whereas addition of methanol to water resulted in a sharp increase in the amounts of both methane and acetylene. Mechanisms are considered to account for these observations.     

电场增强等离子催化反应由天然气合成碳二烃

本研究借助电场作用通过交流或直流等离子催化反应在常压、低下将天然气（甲烷）直接转一烃。甲烷被等离子场激活后直接和催化剂活性位作用生成乙烷、乙烯等碳二烃，由气相色谱在线分析其组成。考察了反应条件和催化剂的影响。得到了本实验较适宜反应条件下的碳二烃选择性在９０％以上的结果。     

The conversion of natural gas to higher hydrocarbons using a microwave plasma and catalysts

Methane, the major constituent of natural gas, had been converted to higher hydrocarbons by a microwave plasma. The yield of C2+ products increased from 29.2% to 42.2% with increasing the plasma power and decreasing the flow rate of methane. When the catalysts were used in the plasma reactor, the selectivities of ethylene and acetylene increased while the yield of C2+ remained constant. Among the various catalysts used, the Fe catalyst showed the highest ethylene selectivity of 30%. When we introduced the actual natural gas, more C2+ products were obtained (46%). This is due to the ethane and propane in the natural gas. When an electric field inductance for evolving the high plasma was applied, a high yield in C2+ products of 63.7% was obtained for the Pd-Ni bimetal catalyst.     

Wet Conversion of Methane and Carbon Dioxide in a DBD Reactor

The influence of water on the plasma assisted conversion of methane and carbon dioxide in a dielectric barrier discharge (DBD) plug flow reactor was studied. The plasma at atmospheric pressure was ignited by a power supply at a frequency of 13.56?MHz. Product formation was studied at a power range between 35 and 70?W. The concentrations of the three gases were altered and diluted with helium to 3?%. FTIR spectroscopy and mass spectroscopy were applied to analyze the inlet and the product streams. The main product of this process are hydrogen, carbon monoxide and ethane. Ethene, ethine, methanol and formaldehyde are generated beside the main products in this DBD in lower concentrations. The conversion of methane, the ratio of the synthesis gas components (n(H₂):n(CO)), and the yield of oxygenated hydrocarbons and hydrogen increases by adding water. The total consumed energy reaches lower values for small amounts of water. Additional water does not influence the generated amount of C2 hydrocarbons and of CO, but decreases the carbon dioxide conversion.     

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。     

Activation of methane in microwave plasmas at high pressure

Methane is converted to C2 products in a microwave plasma under pressure up to 400 torr at maximum plasma power of 100 W. Steam is introduced with methane into the plasma zone in order to suppress coke formation. Major products are C2 hydrocarbons. Small amounts of benzene are also formed. Very small amounts of some unusual highly unsaturated hydrocarbons are also formed. Oxygenated products are CO and CO₂. The conversion and yields are related to experimental variables by an empirical second order linear model. The conversion of methane ranges from 10 to 60%. The yield of C2 products ranges from 5 to 68%. The major C2 product is acetylene.     

A high-power X-band pulsed microwave induced catalytic decomposition of methane with integral acoustic measurements

A high-power microsecond pulsed microwave system operating in the X-band region was used for the catalytic conversion of methane. Microwave microsecond pulses at repetition rates of 50 and 80 Hz were used to initiate chemical reactions. The Microwave-Induced Acoustic technique was employed in combination with gas chromatography for on-line detection of chemical products. Methane was converted to C₂ and C₃ hydrocarbons. The selectivity of ethane in hydrocarbon products can be >90 %. The contribution of hydrogen evolution and carbon deposition has been shown to be important. A comparison between previous experiments performed with millisecond pulse durations is given.     

Microwve induced catalytic reactions of carbon dioxide and water: mimicry of photosynthesis

In an attempt to emulate the highly successful photosynthetic recycling of CO₂ to form energetically useful fuels in nature this study investigates the microwave induced reaction of carbon dioxide and water in a continuous flow system using a supported nickel catalyst and 2.45 GHz microwave radiation with an average incident power of 2.2 kW. The major reaction products were methane, ethane, methanol, acetone, C₃ and C₄ alcohols. The yields of methane, C₃ and C₄ alcohols reached maximum values after 30 s of irradiation, while the yields of ethane, methanol and acetone were proportional to the irradiation time within the investigated range.