单层多孔石墨烯膜结构对C_(2)烃气体分离性能影响的分子动力学研究

利用分子动力学模拟研究了孔径、孔形状、官能团修饰对纳米多孔石墨烯膜分离C_(2)烃气体的效率和选择性的影响。结果表明:孔径为0.444~0.484 nm的石墨烯膜对乙烷的截留性能较好,乙烯的通过率较高;圆形孔石墨烯膜具有较高的气体通过效率,扁平孔石墨烯膜具有较高的气体分离的选择性;孔短径为0.510 nm、孔长径为1.164 nm的石墨烯膜对乙烷的截留性能较好,其乙烯通量较大;孔径为0.596 nm且孔口周围带有两个羧基的石墨烯膜对乙烯的截留性能较好,乙炔的通过率较高。所得模拟结果为设计高效、高选择性分离C_(2)烃气体的单层多孔石墨烯膜提供理论依据。

Co-Generation of C_2 Hydrocarbons and Synthesis Gases from Methane and Carbon Dioxide: a Thermodynamic Analysis

This paper deals with thermodynamic chemical equilibrium analysis using the method of direct minimization of Gibbs free energy for all possible CH4 and CO2 reactions. The effects of CO2/CH4 feed ratio, reaction temperature, and system pressure on equilibrium composition, conversion, selectivity and yield were studied. In addition, carbon and no carbon formation regions were also considered at various reaction temperatures and CO2/CH4 feed ratios in the reaction system at equilibrium. It was found that the reaction temperature above 1100 K and CO2/CH4 ratio=1 were favourable for synthesis gas production with H2/CO ratio unity, while carbon dioxide oxidative coupling of methane （CO2 OCM） reaction to produce ethane and ethylene is less favourable thermodynamically. Numerical results indicated that the no carbon formation region was at temperatures above 1000 K and CO2/CH4 ratio larger than 1.

C_(2)链烃在热解/气化中的碳链裂解机理及速率常数计算研究

链烃裂解在热解/气化过程中大量存在,其中,轻质链烃反应时间短并且存在多种反应路径,难以通过实验的方式对单一演变路径进行准确的检测和分析。本研究选用Gaussian及其配套软件对C_(2)系列链烃(包括乙烷、乙烯和乙炔)的反应位点进行了预测,并对上述链烃在H/OH/O自由基及水分子作用下的碳链裂解机理进行研究。结果表明,自由基对乙烷的C原子及H原子均可发起进攻,而对于乙烯和乙炔的进攻则主要集中在C原子。在上述三种自由基中,OH自由基对不饱和烃的裂解效果最佳,而H自由基对于饱和烃的裂解效果更好,该结果反映了实际过程中水蒸气对于C_(2)系列链烃化合物的碳链断裂具有积极作用。此外,对比乙烯和乙炔与OH自由基作用的最优路径可以发现,CH_(2)CH_(2)OH在低于1200 K的环境中比CH_(2)CHO更容易裂解,而在高于1200 K的环境中则是CH_(2)CHO裂解更易,从中可以推断出醛类基团对于温度变化的响应速率优于醇类基团。

Catalysis Conversion Methane into C_(2) Hydrocarbons via Electric Field Enhanced Plasma

In this paper the effect of catalyst and carrier in electric field enhanced plasma on methane conversion into C2 hydrocarbons was investigated. Methane coupling reaction was studied in the system of continuous flow reactor on Ni, MoO3, MnO2 catalysts and different ZSM-5 carriers. The per pass conversion of methane can be as high as 22%, the selectivity of ethylene can be as high as 23.8%, of acetylene 60.8%, of ethane 5.4% and of total C2 hydrocarbons was more than 90%. ZSM-5-25 was the better carrier and MnO2 was the better active component. The efficiency of energy was as high as 7.81%.

Conversion of Methane to C_2 Hydrocarbons via Cold Plasma Reaction

Direct conversion of methane to C_2 hydrocarbons via cold plasma reactionwith catalysts has been studied at room temperature and atmospheric pressure. Methane can beconverted into C_2 hydrocarbons in different selectivity depending on the form of the reactor, powerof plasma, flow rate of methane, ratio of N_2/CH_4 and nature of the catalysts. The selectivity toC_2 hydrocarbons can reach as high as 98.64%, and the conversion of methane as high as 60% and theyield of C_2 hydrocarbons as high as 50% are obtained. Coking can be minimized under the conditionsof: proper selection of the catalysts, appropriate high flow rate of inlet methane and suitableratio of N_2 to CH_4. The catalyst surface provides active sites for radical recombination.

基于浅冷油吸收法的C_(1)/C_(2)分离装置标定总结

介绍了某公司采用浅冷油吸收法干气回收技术新建的一套0.9 Mt/a C_(1)/C_(2)分离装置情况,并对装置性能标定结果进行了总结。根据不同干气原料的特点,将6股原料干气归类为不饱和干气、饱和干气和富烃干气,并以浅冷油吸收技术为核心,将上述3种类型的炼厂干气回收路线通过系统集成整合后分别得到富乙烯气、富乙烷气、轻烃和氢气等产品,有机衔接了炼油装置和下游化工装置。装置开工后运行稳定,负荷率在89%。装置性能标定结果表明:产品分布达到了指标要求,乙烯、乙烷回收率分别达到了91.91%和98.37%,均高于性能保证值。该装置工艺技术路线的选择和工程设计完全可行,对国内大规模复杂原料C_(1)/C_(2)分离装置具有很好的示范效果。

大型C_(2)、C_(3)低温储罐与LNG储罐换存可行性分析

随着LNG接收站建设的加快及其选址难度的增大,探讨将大型乙烷、乙烯、丙烷等C_(2)、C_(3)烃类低温储罐换存为LNG储罐的技术可行性很有必要。本文通过对C_(2)、C_(3)低温储罐与LNG储罐在材料标准、工艺设计、结构设计、施工与开车调试等方面的对比分析,探讨C_(2)、C_(3)低温储罐换存为LNG储罐的可行性。结果发现,C_(2)、C_(3)低温储罐与LNG储罐在主要设计建造标准、设计流程、外罐与保冷材料等方面具有共同点,而内罐材料、介质密度、温度等方面的差异,导致了工艺、结构、施工与开车调试等方面的不同;基于上述共同点与差异,认为C_(2)低温储罐换存为LNG储罐理论上可行,而C_(3)低温储罐由于内罐材料设计温度较高,不适合换存为LNG储罐。本文研究可为C_(2)、C_(3)低温储罐项目改造为LNG储罐项目提供一定的技术参考。

Gas diffusion in catalyst layer of flow cell for CO_(2) electroreduction toward C_(2+) products

The use of gas diffusion electrode(GDE)based flow cell can realize industrial-scale CO_(2) reduction reactions(CO_(2)RRs).Controlling local CO_(2) and CO intermediate diffusion plays a key role in CO_(2)RR toward multi-carbon(C_(2+))products.In this work,local CO_(2) and CO intermediate diffusion through the catalyst layer(CL)was investigated for improving CO_(2)RR toward C_(2+)products.The gas permeability tests and finite element simulation results indicated CL can balance the CO_(2) gas diffusion and residence time of the CO intermediate,leading to a sufficient CO concentration with a suitable CO_(2)/H_(2)O supply for high C_(2+)products.As a result,an excellent selectivity of C_(2+)products~79%at a high current density of 400 mA·cm^(-2) could be obtained on the optimal 500 nm Cu CL(Cu500).This work provides a new insight into the optimization of CO_(2)/H_(2)O supply and local CO concentration by controlling CL for C_(2+)products in CO_(2)RR flow cell.

Current status and technical challenges of C_(2)storage in coal seams and enhanced coalbed methane recovery:an overview

In the past two decades,research on C_(2)storage in coal seams and simultaneously enhanced coalbed methane recovery(ECBM)has attracted a lot of attention due to its win–win effect between greenhouse gas(C_(2))emission reduction and coalbed methane recovery enhancement.This paper presents an overview on the current status of research on C_(2)-ECBM in the past two decades,which involves C_(2)storage capacity evaluations,laboratory investigations,modelings and pilot tests.The current status shows that we have made great progress in the ECBM technology study,especially in the understanding of the ECBM mechanisms.However,there still have many technical challenges,such as the definition of unmineable coal seams for C_(2)storage capacity evaluation and storage site characterization,methods for C_(2)injectivity enhancement,etc.The low injectivity of coal seams and injectivity loss with C_(2)injection are the major technique challenges of ECBM.We also search several ways to promote the advancement of ECBM technology in the present stage,such as integrating ECBM with hydraulic fracturing,using a gas mixture instead of pure C_(2)for injection into coal seams and the application of ECBM to underground coal mines.

电子工业气体氧化亚氮中C_(2)烃杂质分离技术研究

采用氢火焰离子检测器气相色谱仪,通过前切割技术解决氧化亚氮对C_(2)烃的分析干扰,使用GDX-104色谱柱完成对氧化亚氮中乙烷、乙烯和乙炔的分离。

Methane Decomposition and C_2 Hydrocarbon Formation under the Condition of DC Discharge Plasma

The infrared emission spectra of methane, H, CH' and C_2 hydrocarbons in natural gas were measured. The processes of methane decomposition and formation of C_2 hydrocarbons were studied. The experiment shows that methane decomposition can be divided into three periods as the reaction proceeds. In the first period, a large number of free radicals were formed. While in the last period, the formation of C_2 hydrocarbons and the decrease of free radicals were observed. The time and conditions of methane decomposition and formation of C_2 hydrocarbons are different.

Boosting selective C_(2)H_(2)/CH_(4),C_(2)H_(4)/CH_(4) and CO_(2)/CH_(4) adsorption performance via 1,2,3-triazole functionalized triazine-based porous organic polymers

Nitrogen-rich porous organic polymers have shown great potentials in gas adsorption/separation,photocatalysis,electrochemistry,sensing and so on.Herein,1,2,3-triazole functionalized triazine-based porous organic polymers(TT-POPs)have been synthesized by the copper-catalyzed azide-alkyne cycloaddition(Cu-AAC)polymerization reactions of 1,3,5-tris(4-azidophenyl)-triazine with 1,4-diacetylene benzene and 1,3,5-triacetylenebenzene,respectively.The characterizations of N2 adsorption at 77 K show TTPOPs possess permanent porosity with BET surface areas of 666 m^(2)·g^(-1)(TT-POP-1)and 406 m^(2)·g^(-1)(TT-POP-2).The adsorption capacities of TT-POPs for CO_(2),CH4,C2H2 and C2H4,as well as the selective separation abilities of CO_(2)/N2,CO_(2)/CH_(4),C_(2)H_(2)/CH_(4) and C_(2)H_(4)/CH_(4) were evaluated.The gas selective separation ratio of TT-POPs was calculated by the ideal adsorbed solution theory(IAST)method,wherein the selective separation ratios of C_(2)H_(2)/CH_(4) and C_(2)H_(4)/CH_(4) of TT-POP-2 was 48.4 and 13.6(298 K,0.1 MPa),which is comparable to other adsorbents(5.6–120.6 for C_(2)H_(2)/CH_(4),10–26 for C_(2)H_(4)/CH_(4)).This work shows that the 1,2,3-triazole functionalized triazine-based porous organic polymer has a good application prospect in natural gas purification.

Calculating densities and viscosities of natural gas with a high content of C_(2+) to predict two-phase liquid-gas flow pattern

The paper is devoted to the two-phase flow simulation.The gas-condensate mixture flow in a horizontal pipe under high pressure is considered.The influence of the equation of state(EOS)choice for mixture properties modelling on the flow regime calculation results is studied for gas with high content of methane homologues.An analytical overview of the methods to predict the flow pattern is provided.Based on this analysis,two techniques are selected.For these techniques,values of density and viscosity for each phase are required.Density calculation for the gas phase is performed with Van der Waals based EOS.The propriate EOS is selected based on studies of calculation errors for test mixtures.Calculation of liquid phase density is done by means of Patela-Teja and Guo-Du equations,two different models are considered for viscosity estimation.The flow patterns of gas-condensate mixture in a range of temperatures and pressures are calculated and verified via probability map.The results of study allow to recommend the Brusilovsky EOS for calculation of densities for similar gas mixtures and make more rigorous flow regime evaluation.The probability map shows that for the chosen composition and parameters of media the flow pattern is mostly transitional between segregated and annular independent from EOS.

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

A review on Ti_(3)C_(2)T_(x)-based nanomaterials:synthesis and applications in gas and humidity sensors

Ti_(3)C_(2)T_(x),which is a novel two-dimensional(2 D)material,has received enormous interest in the field of sensor technology due to its large surface area,excellent electrical conductivity,and abundant active surface sites.In recent years,several Ti_(3)C_(2)T_(x)-based gases and humidity sensors have been developed and reported.In this review,we focus on the latest applications of Ti_(3)C_(2)T_(x)-based nanomaterials in gas and humidity sensors.First,the synthesis of Ti_(3)C_(2)T_(x) from the dangerous fluorine-containing etching process to the safe fluorine-free preparation method was discussed,and the structures of the Ti_(3)C_(2)T_(x) controlled by different delamination methods were also outlined.Subsequently,the functionalization of pristine Ti_(3)C_(2)T_(x) and composite strategies for enhancing its gas and humidity sensing performance were reviewed.In addition,the gas and humidity sensing mechanisms of sensors based on Ti_(3)C_(2)T_(x) were also summarized.Finally,the challenges and opportunities for the use of Ti_(3)C_(2)T_(x) gas and humidity sensors were discussed to provide guidance on the promising potential of Ti_(3)C_(2)T_(x) in this field.

Recent Advances in C_(2) Gases Separation and Purification by Metal-Organic Frameworks

Separation of C_(2) gases(C_(2)H_(2)/C_(2)H_(4),C_(2)H_(6)/C_(2)H_(4) and C_(2)H_(2)/CO_(2))mixtures is one of the most important and energy-demanding processes in chemical industry.Traditional separation methods(fine distillation separation and selective catalytic hydrogenation separation)have the shortages of high energy consumption and inefficient use of resources,affecting the achievement of peak carbon dioxide emissions and carbon neutrality targets.Separation based on adsorption is considered as one of the best ways to achieve low-energy separations.Therefore,it is of great importance to synthesize materials that enable the effective separation and purification of C_(2) gases under mild conditions.As an emerging class of porous materials,metal-organic frameworks(MOFs)show great promise in the field of gas separation and purification due to their ultra-high specific surface area,easily modifiable pore surfaces,structural designability and functionalization.Herein,we summarize recent research advances by use of MOFs sorbents for the separation and purification of C_(2) gases,including C_(2)H_(2)/C_(2)H_(4),C_(2)H_(6)/C_(2)H_(4) and C_(2)H_(2)/CO_(2).Relationship between structures and separation mechanism is also explored.Furthermore,challenges and possible research directions related to the further exploration are also discussed.

The generation and accumulation of natural gas from Yinan 2 gas pool in Kuqa Depression

By using the methods of hydrocarbon generation kinetics and carbon isotope kinetics, combined with geological background of natural gas pool formation, the generation and accumulation of natural gas from Yinan 2 gas pool was studied in Kuqa Depression of the Tarim Basin. Natural gas of Yinan 2 gas pool is mainly derived from Middle and Lower Jurassic coal-bearing source rocks, and generally belongs to long time-accumulated gas. It is suggested that Yinan 2 gas is chiefly accumulated in the last 5 Ma, its Ro ranges from 1.25% to 1.95%, and the loss rate of natural gas is about 25%-30%. This work not only complements and reduces the deficiency of formation model of natural gas pools which traditionally depends on the matching relationships between source rock, reservoir, cap rock, and trap, but also is a useful reference in the study of other gas pools.

SnO-SnO_(2) modified two-dimensional MXene Ti3C2Tx for acetone gas sensor working at room temperature

Acetone,as widely used reagents in industry and laboratories,are extremely harmful to the human.So the detection of acetone gas concentrations and leaks in special environments at room temperature is essential.Herein,the nanocomposite combining SnO-SnO_(2)(p-n junction)and Ti_(3)C_(2)T_(x) MXene was successfully synthesized by a one-step hydrothermal method.Because of the existence of a small amount of oxygen during the hydrothermal conditions,part of the p-type SnO was oxidized to n-type SnO_(2),forming in-situ p-n junctions on the surface of Sn O.The hamburger-like SnO-SnO_(2)/Ti_(3)C_(2)T_(x) sensor exhibited improved acetone gas sensing response of 12.1(R_(g)/R_(a))at room temperature,which were nearly 11 and 4 times higher than those of pristine Ti_(3)C_(2)T_(x) and pristine SnO-SnO_(2),respectively.Moreover,it expressed a short recovery time(9 s)and outstanding reproducibility.Because of the different work functions,the Schottky barrier was formed between the SnO and the Ti_(3)C_(2)T_(x) nanosheets,acting as a hole accumulation layer(HALs)between Ti_(3)C_(2)T_(x) and tin oxides.Herein,the sensing mechanism based on the formation of hetero-junctions and high conductivity of the metallic phase of Ti_(3)C_(2)T_(x) MXene in SnO-SnO_(2)/Ti_(3)C_(2)T_(x) sensors was discussed in detail.

Electrochemical CO_(2) reduction to C_(2+) products using Cu-based electrocatalysts:A review

With the disruptive carbon cycle being blamed for global warming,the plausible electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to form valuable C_(2+)hydrocarbons and feedstock is becoming a hot topic.Cu-based electrocatalysts have been proven to be excellent CO_(2)RR alternatives for high energy value-added products in this regard.However,the selectivity of CO_(2)RR to form C_(2+)products via Cu-based catalysts suffers from a high overpotential,slow reaction kinetics,and low selectivity.This review attempts to discuss various cutting-edge strategies for understanding catalytic design such as Cu-based catalyst surface engineering,tuning Cu bandgap via alloying,nanocatalysis,and the effect of the electrolyte and pH on catalyst morphology.The most recent advances in in situ spectroscopy and computational techniques are summarized to fully comprehend reaction mechanisms,structural transformation/degradation mechanisms,and crystal facet loss with subsequent effects on catalyst activity.Furthermore,approaches for tuning Cu interactions are discussed from four key perspectives:single-atom catalysts,interfacial engineering,metal-organic frameworks,and polymer-incorporated materials,which provide new insights into the selectivity of C_(2+)products.Finally,major challenges are outlined,and potential prospects for the rational design of catalysts for robust CO_(2)RR are proposed.The integration of catalytic design with mechanistic understanding is a step forward in the promising advancement of CO_(2)RR technology for industrial applications.

DFT calculation on p-xylene sensing mechanism of (C_(4)H_(9)NH_(3))_(2)PbI_(4) single crystal based on physisorption

P-xylene(p-C_(8)H_(10))is extremely harmful and dangerous to human health due to high toxicity and strong carcinogenicity.Exploring sensitive material to effectively detect p-xylene is of importance.In this paper,perovskite single crystal(C_(4)H_(9)NH_(3))_(2)PbI_(4) has been successfully synthesized via solution method.The obtained product was analyzed by single crystal X-ray diffraction.With the space group Pbca,orthorhombic(C_(4)H_(9)NH_(3))_(2)PbI_(4) layered perovskite structure consists of an extended two-dimensional network of corner-sharing PbI_(6) octahedron.Single layer perovskite sheets of distorted PbI_(6) octahedron alternated with protonated n-butylammonium cation bilayers,which offers many advantages and provides the possibility of forming a gas sensor device based on the change of resistances.Density functional theory(DFT)simulations regarding the adsorption energy revealed that this organicinorganic hybrid perovskite compound has excellent selectivity toward p-xylene compared with other gases including C_(2)H_(5)OH,C_(6)H_(6),CH_(2)Cl_(2),HCHO,CH_(3)COCH_(3) and C_(7)H_(8).The calculation of electron density,density of states and electron density difference showed the sensing mechanism of p-C_(8)H_(10) is mainly derived from physical adsorption-desorption in view of electron transfer.