Reviews of clean coal conversion technology in China:Situations & challenges

It is important to develop the advanced coal to chemicals industry(ACCI)against a backdrop of coal-based energy structures,excessive imported oil and natural gas,and strict environmental constraints in China.In this study,the technology and industry of China’s ACCI are reviewed to explain the effect of using coal to replace oil and natural gas,and the corresponding resource and environmental burdens that this will create.Development trends in technology and industry are also proposed to explore future scenarios.The review shows that although excellent progress has been made on an industrial scale,demonstrative level,and in terms of technology and equipment,the lack of strategic understanding,severe external constraints,partly underdeveloped technologies,and weak foundations must be immediately addressed.Therefore,it is necessary to clarify the importance that the ACCI has on the energy revolution and energy system.Based on technological innovation,a variety of external factors should be considered as a whole with emphasis on filling the knowledge gap of theoretical foundations and industry standards to support high-quality development for ACCI.

Pyrolysis Mechanisms of Quinoline and Isoquinoline with Density Functional Theory

The pyrolysis mechanisms of quinoline and isoquinoline were investigated using the density functional theory of quantum chemistry,including eight reaction paths and a common tautomeric intermediate 1-indene imine.It is concluded that the conformational tautomerism of the intermediate decides the pyrolysis products(C6H6,HC≡C—C≡N,C6H5C≡N and HC≡CH)to be the same,and also decides the total disappearance rates of the reactants to be the same,for both original reactants quinoline and isoquinoline during the pyrolysis reaction.The results indicate that the intramolecular hydrogen migration is an important reaction step,which often appears in the paths of the pyrolysis mechanism.The activation energies of the rate determining steps are obtained.The calculated results are in good agreement with the experimental results.

The newly-assisted catalytic mechanism of surface hydroxyl species performed as the promoter in syngas-to-C2 species on the Cu-based bimetallic catalysts

In the conversion process of syngas-to-C_(2)species,the OH species are inevitably produced accompanying the production of key intermediates CH_(x)(x=1-3),traditionally,the function of surface OH species is generally accepted as the hydrogenating reactive species.This work for the first time proposed and confirmed the assisted catalytic mechanism of surface OH species that performed as the promoter for syngas-to-C_(2)species on Cu-based catalysts.DFT and microkinetic modeling results reveal that the produced OH species accompanying the intermediates CH_(x)production on the MCu(M=Co,Fe,Rh)catalysts can stably exist to form OH/MCu catalysts,on which the presence of surface OH species as the promoter not only presented better activity and selectivity toward CH_(x)(x=1-3)compared to MCu catalysts,but also significantly suppressed CH_(3)OH production,providing enough CH_(x)sources to favor the production of C_(2)hydrocarbons and oxygenates.Correspondingly,the electronic properties analysis revealed the essential relationship between the electronic feature of OH/MCu catalysts and catalytic performance,attributing to the unique electronic micro-environment of the catalysts under the interaction of surface OH species.This new mechanism is called as OH-assisted catalytic mechanism,which may be applied in the reaction systems related to the generation of OH species.

Formation mechanism of methane during coal evolution:A density functional theory study

The formation mechanism of methane （CH4） during coal evolution has been investigated by density functional theory （DFT） of quantum chemistry. Thermogenic gas, which is generated during the thermal evolution of medium rank coal, is the main source of coalbed methane （CBM）. Ethylbenzene （A） and 6,7-dimethyl-5,6,7,8-tetrahydro-1-hydroxynaphthalene （B） have been used as model compounds to study the pyrolysis mechanism of highly volatile bituminous coal （R）, according to the similarity of bond orders and bond lengths. All possible paths are designed for each model. It can be concluded that the activation energies for H-assisted paths are lower than others in the process of methane formation; an H radical attacking on β-C to yield CH4 is the dominant path for the formation of CH4 from highly volatile bituminous coal. In addition, the calculated results also reveal that the positions on which H radical attacks and to which intramolecular H migrates have effects on methyl cleavage.

Methodology for Design of Reactive Distillation Column and Kinetics for Isoamylene Etherification Catalysed by Amberlyst 35

Isoamylene from the Fischer-Tropsch syncrude can be transformed to valuable fuel oxygenate additives through an equilibrium limited etherification reaction with methanol. A reactive distillation process is established to increase isoamylene conversion. Facing the challenge of improving product purity at the same time, an equilibrium stage model based design methodology is proposed and illustrated step-by-step for converting the Fischer-Tropsch C_5 olefins to tert-amyl methyl ether(TAME) process by using Aspen Plus. Under the guide of the proposed methodology, the design leads to a TAME product purity of higher than 95% and an isoamylene conversion of higher than 90%. The etherification kinetics over Amberlyst 35 is also studied within a temperature range of 60 ℃ to 75 ℃ to shed more light on the feasibility of process development. The methodology provides an effective reactive distillation column design to achieve the target reactant conversion and product purity simultaneously.

Syngas to ethanol on MoCu(211)surface:Effect of promoter Mo on C-O bond breaking and C-C bond formation

The mechanism of syngas to ethanol on MoCu(211)surface has been researched by density functional theory(DFT)calculation,and the effects of Mo as a promoter on C-O bond breaking and C-C bond formation have been discussed.Calculations show that Cu-Mo atoms constitute the active sites on MoCu(211)surface after Mo atom being served as a promoter of Cu catalyst.Compared with Cu(211),MoCu(211)has two improvements.Firstly,CH_(3) is the most advantageous monomer on the MoCu(211)surface,which provides abundant CH_(3) intermediate for syngas to ethanol.Secondly,the C-C bond is formed mainly by inserting CHO into the abundant CH_(3),and the generated CH_(3)CHO through multiple steps of hydrogenation to generate C_(2)H_(5)OH.The key of the promoter Mo on the MoCu(211)surface also has been verified by the analysis of its electronic properties.Differential charge density shows that the massive electron transfer from Mo to Cu,projected density of states(pDOS)shows that the electron transfer from Mo to Cu makes the d-band center of MoCu(211)nearer to the Fermi level,these indicate that the MoCu(211)catalytic capacity increased.The addition of Mo in the Cu-based catalyst not only can effectively solve the problem of C-O bond breaking,but also promote C-C bond formation.About the influence of Mo content on C-O bond breaking and C-C bond formation,compared with MoCu(211),the DFT results and the d-band center of Mo_(2)Cu(211)show that the increase of Mo content could not promote the synergistic effect of Cu/Mo on the generation of ethanol more effectively.

Synthesis of HTLcs modified by K_(3)PO_(4) for side chain alkylation of toluene with methanol

A series of calcined HTLcs catalysts were prepared and modified with potassium phosphate by impregnation method to clarify the influence of catalyst alkalinity on the side chain alkylation of toluene with methanol for synthesis of ethylbenzene and styrene.The catalysts were characterized by X-ray diffraction(XRD),N_(2)physical adsorption-desorption,Fourier-transform infrared spectroscopy(FT-IR),Scanning electron microscopy(SEM),X-ray photoelectron spectrometry(XPS),NH_(3)temperature-programmed desorption(NH_(3)-TPD)and CO_(2)temperature-programmed desorption(CO_(2)-TPD).It was found that the selectivity of styrene was highest(39.25%)when the K_(3)PO_(4)loading was 7.5 wt%.And the total yield of styrene and ethylbenzene could reach 65.08%with 10 wt%K_(3)PO_(4)loading.This might due to the fact that the addition of K_(3)PO_(4)could adjust the acid and basic sites of catalysts.In addition,appropriate strength and amount of basic sites were favorable to producing more styrene.

The carbon isotopic compositions of Non-methane Hydrocarbons in atmosphere

Carbon isotopic compositions of atmospheric Non-methane Hydrocarbons(NMHCs) in the urban areas of Taiyuan and Lanzhou in summer were reported and the sources of NMHCs are discussed.Carbon isotopic ratios(δ 13C) of vehicle exhaust,coal-combustion exhaust,fuel volatiles and cooking exhaust were also measured with thermal desorption-gas chromatography-isotope ratio-mass spectrometry(TD-GC-IR-MS).δ 13C values of NMHCs in the urban areas of Lanzhou and Taiyuan range from-32.3‰ to-22.3‰ and from-32.8‰ to-18.1‰.δ 13C values of vehicle exhaust,coal-combustion exhaust,fuel volatiles and cooking exhaust are-32.6‰―-21.7‰,-24.5‰―-22.3‰,-32.5‰―-27.4‰ and-31.6‰―-24.5‰,respectively.The data indicate that vehicle exhaust and cooking exhaust make a significant contribution to the atmospheric NMHCs.Therefore,to reduce emissions of vehicle exhaust and cook-ing exhaust is critical for controlling atmospheric NMHCs pollution in summer.

苯为前驱体的稠环芳烃的自由基反应机理的量子化学研究(英文)

The free-radical growth mechanisms for the formation of polycyclic arenes (PCAs) were constructed based on the block unit of benzene, and were calculated by the quantum chemistry PM3 method. Two kinds of reaction paths are proposed and discussed. The calculation results show that the formation of PCAs is only controlled by the elimination of H atom from benzene, and the corresponding activation energy is 307.60 kJ·mol-1. H2 is only the ef-fluent gas in our proposed reaction mechanism, and the calculation results are in accord with the experimental facts.