Theoretical analysis of hydrogen solubility in direct coal liquefaction solvents

The cyclic hydrogenation technology in a direct coal liquefaction process relies on the dissolved hydrogen of the solvent or oil participating in the hydrogenation reaction.Thus,a theoretical basis for process optimization and reactor design can be established by analyzing the solubility of hydrogen in liquefaction solvents.Experimental studies of hydrogen solubility in liquefaction solvents are challenging due to harsh reaction conditions and complex solvent compositions.In this study,the composition and content of liquefied solvents were analyzed.As model compounds,hexadecane,toluene,naphthalene,tetrahydronaphthalene,and phenanthrene were chosen to represent the liquefied solvents in chain alkanes and monocyclic,bicyclic,and tricyclic aromatic hydrocarbons.The solubility of hydrogen X(mol/mol)in pure solvent components and mixed solvents(alkanes and aromatics mixed in proportion to the chain alkanes+bicyclic aromatic hydrocarbons,bicyclic saturated aromatic hydrocarbons+bicyclic aromatic hydrocarbons,and bicyclic aromatic hydrocarbons+compounds containing het-eroatoms composed of mixed components)are determined using Aspen simulation at temperature and pressure conditions of 373–523 K and 2–10 MPa.The results demonstrated that at high temperatures and pressures,the solubility of hydrogen in the solvent increases with the increase in temperature and pressure,with the pressure having a greater impact.Further-more,the results revealed that hydrogen is more soluble in straight-chain alkanes than in other solvents,and the solubility of eicosanoids reaches a maximum of 0.296.The hydrogen solubility in aromatic ring compounds decreased gradually with an increase in the aromatic ring number.The influence of chain alkanes on the solubility of hydrogen predominates in a mixture of solvents with different mixing ratios of chain alkanes and aromatic hydrocarbons.The solubility of hydrogen in mixed aromatic solvents is less than that in the corresponding single solvents.Hydrogen is less soluble in solvent compounds containing heteroatoms than in compounds without heteroatoms.

Research on the maceral characteristics of Shenhua coal and efficient and directional direct coal liquefaction technology

In this research,molecular structure models were developed respectively for Shenhua coal vitrinite concentrates(SDV)and inertinite concentrates(SDI),on the basis of information on constitutional unit of Shenhau coal and elemental analysis results obtained from^(13)C-NMR analysis characterization,FTIR analysis characterization,X-ray diffraction XRD and XPS analysis characterization.It can be observed from characterization data and molecular structure models that the structure of SDV and SDI is dominated by aromatic hydrocarbon,with aromaticity of SDI higher than that of SDV;SDV mainly consists of small molecule basic structure unit,while SDI is largely made from macromolecular structure unit.Based on bond-level parameters of the molecular model,the research found through the autoclave experiment that vitrinite liquefaction process goes under thermodynamics control and inertinite liquefaction process under dynamics control.The research developed an efficient directional direct coal liquefaction technology based on the maceral characteristics of Shenhua coal,which can effectively improve oil yield and lower gas yield.

The relationship between the microstructures and catalytic behaviors of iron–oxygen precursors during direct coal liquefaction

A series of both unsupported and coal‐supported iron–oxygen compounds with gradual changes in microstructure were synthesized by a precipitation‐oxidation process at 20 to 70°C.The relationship between the microstructures and catalytic activities of these precursors during direct coal liquefaction was studied.The results show that the microstructure could be controlled through adjusting the synthesis temperature during the precipitation‐oxidation procedure,and that compounds synthesized at lower temperatures exhibit higher catalytic activity.As a result of their higher proportions ofγ‐FeOOH orα‐FeOOH crystalline phases,the unsupported iron–oxygen compounds synthesized at 20–30°C,which also had high specific surface areas and moisture levels,generate oil yields 4.5%–4.6%higher than those obtained with precursors synthesized at 70°C.It was also determined that higher oil yields were obtained when the catalytically‐active phase formed by the precursors during liquefaction(pyrrhotite,Fe1-xS)had smaller crystallites.Feed coal added as a carrier was found to efficiently disperse the active precursors,which in turn significantly improved the catalytic activity during coal liquefaction.

Study on reaction characteristics of phenolic hydroxyl in coal by using the model compound during direct coal liquefaction

The reaction characteristics of phenolic hydroxyl group were studied under the conditions of direct coal liquefaction. 2-naphthol was used as a coal model compound in this study. Under the conditions of with and without catalysts, a series of experiments were conducted at different temperatures, pressures and reaction time. Gas chromatography-mass spectrometry and gas chromatography were used to identify and quantify the reactants and products respectively. The conversion of 2-naphthol rises with the increase of reaction temperature, initial pressure and catalyst amount. The results indicated that tem- perature had a significant effect on 2-naphthol conversion, which promoted the dehydroxylation reaction. However, initial pressure had an important influence on the hydrogenation of 2-naphthol and naphthalene. The iron catalyst plays a significant role of cracking instead of hydrogenation. It is concluded that the harsh reaction conditions of high temperature, high pressure, and more catalyst are conducive to promoting dehydroxylation of 2-naphthol. The reaction mechanism was put forward based the experimental results, in which 2-tetralone was an intermediate.

Determination of the gas compositions for direct coal liquefaction by gas chromatography

Via multi-dimensional gas chromatography, configured with parallel dual-channel, double detectors, valves switching and back flushing, rapid analysis of the gas compositions consisting of C1-C5 hydrocarbons and permanent gases, such as CO2, H2S, H2, and CO, for direct coal liquefaction has been realized. With four packed chromatographic columns, which are Hayesep-Q pre-column, Hayesep-Q column, molecular sieve 5A column and one PLOT A1203 S capillary column, the gas compositions for direct coal liquefaction are analyzed qualitatively and quantitatively by the external standard method. The determination method has such advantages as excellent separation, simple operation, rapid analysis and accurate results.

Discharge characteristics of coal and extraction residue from direct coal liquefaction in partial fluidization silo

Gasification of extraction residue(ER) from direct coal liquefaction with pulverized coal is an efficient way for the utilization of carbonaceous wastes, which improve the overall efficiency of direct coal liquefaction technology. The discharge characteristics of ER mixing with pulverized coal is important paraments for its gasification process, which is seldom studied in the literature. In this study, the discharge characteristics of the pulverized coal(M1) as well as its mixture with ER(M2) were systematically investigated in an atmospheric pressure partial fluidization silo with different fluidization apparent velocity. It was observed that although M2 is a viscous powder with lower flowability than M1, the mass flow rate of M2 is 65% higher than M1 at the 3.7 mm·s-1apparent gas velocity. M2 exhibits the properties of Geldart A type powder, which improves the mass flow rate and stability of the discharged material. The mass flow rate of both M1 and M2 first increases and then slowly decreases with the increase of apparent gas velocity of the fluidizing air, which means the discharge process of M1 and M2 can be optimized by the apparent gas velocity.

Compatibility Evaluation between Direct Coal Liquefaction Residue and Bitumen

The compatibility between direct coal liquefaction residue(DCLR) and five kinds of pure bitumen(Shell-90,SK-90, ZSY-70, DM-70 and KLMY-50) was evaluated in this study. The rheological characteristics, glass transition temperatures(T_g), solubility parameters(SP) and SARA(saturates, aromatics, resins, and asphaltenes) fractions of DCLR,five kinds of pure bitumen and their blends(named as DCLR modified bitumen) were measured using the dynamic shear rheometer(DSR), differential scanning calorimetry(DSC), viscosity, and SARA tests, respectively. And the compatibility between DCLR and pure bitumen was characterized with three approaches, viz. the Cole-Cole plot,T_g, and the solubility parameter difference(SPD) method. Since each method has its own working mechanism, the compatibility ranking for the DCLR and five kinds of pure bitumen is slightly different according to the three approaches. However, the difference is pretty close and sometimes can be ignored. The general compatibility ranking decreases in the following order: Shell-90≈SK-90>DM-70≈ZSY-70>KLMY-50, which is affected by the asphaltenes content and the colloid index(I_c) value in the pure bitumen. Pure bitumen with lower asphaltenes content and colloid index(I_c) value has better compatibility with DCLR.

Regulation of radicals by hydrogen-donor solvent in direct coal liquefaction

Radicals are important intermediates in direct coal liquefaction.Certain radicals can cause the cleavage of chemical bonds.At high temperatures,radical fragments can be produced by the splitting of large organic molecules,which can break strong chemical bonds through the induction pyrolysis of radicals.The reaction between the formation and annihilation of coal radical fragments and the effect of hydrogen-donor solvents on the radical fragments are discussed in lignite hydrogenolysis.Using the hydroxyl and ether bonds as indicators,the effects of different radicals on the cleavage of chemical bond were investigated employing density functional theory calculations and lignite hydrogenolysis experiments.Results showed that the adjustment of the coal radical fragments could be made by the addition of hydrogendonor solvents.Results showed that the transition from coal radical fragment to H radical leads to the variation of product distribution.The synergistic mechanism of hydrogen supply and hydrogenolysis of hydrogen-donor solvent was proposed.

Micro Morphology of Soot Particles Sampled from High Pressure Jet Flames of Diesel from Direct Coal Liquefaction

Diesel from direct coal liquefaction(DDCL) is a new type of engine alternative energy. But its hydrocarbon composition and physicochemical properties are quite different from those of Petro diesel. In this study, a premixed constant volume combustion chamber(CVCC) system with soot particle sampling devices was built. The soot particles in the spray flame were sampled and photographed by thermophoresis probe and transmission electron microscope(TEM). An automatic processing code based on Matlab software was developed to process the TEM images and extract the micro morphology parameters of the soot particles. This study has systematically studied the effects of sampling location, injection pressure, ambient density and oxygen concentration on the micro morphology of soot particles. The ambient density refers to the initial gas density in the CVCC. The results showed that various morphologies and sizes of soot particles coexisted in the upstream of the spray flame. During the evolution of soot particles from upstream to downstream in the flame, the size of soot aggregates gradually decreased, while the maturity of soot aggregates increased. With the increase of injection pressure, ambient density and oxygen concentration, the average sizes of soot aggregates and primary soot particles decreased, but the fractal dimensions of soot aggregates increased gradually. Under the same combustion condition and in-flame sampling location, the average projection area, gyration radius and primary soot diameter of soot aggregates produced by DDCL were significantly lower than those of Petro diesel. The structure of soot particles from DDCL was more compact than that of Petro diesel.

Study on the corrosion of refractory materials by coal blended with the extraction residue of direct coal liquefaction in a simulated gasification atmosphere

Utilizing the extraction residue(ER)of direct coal liquefaction residue as a gasification feedstock has significant economic value.But the characteristic of high ash and iron in the ER would increase the risk of corrosion of the refractory materials and affect the long-term operation of the gasifier.In this work,corrosion experiments of molten slag derived from a mixture of 20 wt%ER and 80 wt%coal on a high-chromia refractory brick and SiC brick were carried out using a rotary-drum furnace in a simulated gasification atmosphere.The experimental results show that the viscosity of the poured slag is larger as compared to the initial ash sample at the same temperature,which suggests that the viscosity-temperature relationship of the poured slag should be used as the reference for the operation temperature of the gasifier to ensure that the slag can flow during operation.For a high-chromia refractory brick,iron oxides in molten slag could react with Cr_(2)O_(3) in the refractory matrix but,because the aggregate was not found to be damaged,the damage to the matrix structure was the key factor for causing the corrosion of the high-chromia refractory brick.Metallic iron was observed in the exposed SiC brick,which indicated that the reaction between the iron oxides in the slag and SiC occurred,forming metallic iron and SiO_(2).The corrosion of a SiC brick by molten slag depended mainly on the dissolution of Al_(2)O_(3) particles and the reaction between iron oxides in the molten slag and SiC particles.Therefore,the high iron content in coal ash had a serious influence on the corrosion of refractory materials.More efforts need to be made on coal blended with ER as a gasification feedstock in the future.

Co-pyrolysis characteristics and interaction route between low-rank coals and Shenhua coal direct liquefaction residue

To reasonably utilize the coal direct liquefaction residue(DLR), contrasting research on the co-pyrolysis between different low-rank coals and DLR was investigated using a TGA coupled with an FT-IR spectrophotometer and a fixed-bed reactor. GC–MS, FTIR, and XRD were used to explore the reaction mechanisms of the various co-pyrolysis processes. Based on the TGA results, it was confirmed that the tetrahydrofuran insoluble fraction of DLR helped to catalyze the conversion reaction of lignite. Also, the addition of DLR improved the yield of tar in the fixed-bed, with altering the composition of the tar. Moreover, a kinetic analysis during the co-pyrolysis was conducted using a distributed activation energy model. The co-pyrolysis reactions showed an approximate double-Gaussian distribution.

Direct-impact of sieving coal and gangue

Gangue from underground separation of coal can directly be used for filling mined out areas, saving transport capacity and reducing the amount of waste polluting the environment above the ground. We introduced a structure and operating principle of an underground direct-impact sieving device by which a separation experiment was carried out. By means of high speed conveyer belts, coal and gangue impacted the breaking board at high speeds ranging from 6 to 14 m/s. Given the differences of hardness between coal and gangue, after selective crushing, the gangue with the higher hardness was crushed less and coal with lower hardness crushed more, which could be separated by a 50 mm sieving plate. The material above the sieving plate was disposed of as gangue and the material below as coal. The results indicate that the crush ratio below the 50 mm sieving plate increases linearly with an increase in impact velocity and decays exponentially with an increase in hardness. Employing this equipment to separate coal and gangue, the hardness of coal f should be <2. This separation device provides relatively good effect in separating coal and gangue with a relatively wide difference of hardness.

Double-directional control bolt support technology and engineering application at large span Y-type intersections in deep coal mines

Under deep and complex geological conditions,severe deformation occurs at intersection points of Y-type roadways with large cross sections during engineering projects in coal mines,especially at junction arches.Based on in-situ investigations and theoretical studies,we have summarized typical forms of destruction and identified high stress and unrestricted support at both sides of junction arch as its main causes.In this study,we also presented double-directional control bolt support technology for a large Y-type span intersection,applied to deep intersection engineering in the Jiahe Coal Mine,which has proved effective.

INFLUENCE OF COAL SORT ON THE DIRECT REDUCTION OF HIGH-IRON-CONTENT RED MUD

The technology of coal-based direct reduction of high-ironcontent red mud is studied. The factors affecting this kind of direct reduction mainly are: coal sort, carbon amount, time, temperature and etc. has been investigated. It has been shown that an ide

The composition analysis of coal-derived light oil

The composition of coal-derived light oil (IBP-220℃) was separated into 5 fractions by atmospheric distillation and analyzed by gas chromatography/mass spec- trometry (GC/MS).The light oil was made at 0.1 t/d coal direct liquefaction bench scale unit (BSU) at China Coal Research Institute (CCRI).Six groups of organics,including acyclic hydrocarbon,alicyclic hydrocarbon,aromatics,phenols,polynuclear aromatics and heterocyclics,were found and 80 compounds were tentatively identified in total.Alicyclic hydrocarbon is the main component of the light oil compared to other groups whether in relative mass percentage or the number of compounds in group.The predominant oxy- gen-contained compound is phenols,and the nitrogen-containing compound is pyridine. No sulfur-containing compound is detected.

Prediction of coal structure using particle size characteristics of coalbed methane well cuttings

Severely deformed coal seams barely deliver satisfactory gas production. This research was undertaken to develop a new method to predict the positions of deformed coals for a horizontal CBM well. Firstly, the drilling cuttings of different structure coals were collected from a coal mine and compared. In light of the varying cuttings characteristics for different structure coals, the coal structure of the horizontally drilled coal seam was predicted. And the feasibility of this prediction method was discussed. The result shows that exogenetic fractures have an important influence on the deformation of coal seams. The hardness coefficient of coal decreases with the deformation degree in the order of primary structural, cataclastic and fragmented coal. And the expanding-ratio of gas drainage holes and the average particle size of cuttings increase with the increase of the deformation degree. The particle size distribution of coal cuttings for the three types of coals is distinctive from each other. Based on the particle size distribution of cuttings from X-2 well in a coal seam, six sections of fragmented coal which are unsuitable for perforating are predicted. This method may benefit the optimization of perforation and fracturing of a horizontal CBM well in the study area.

松软薄煤层条带消突下斜定向钻孔成孔护孔技术研究与应用

针对松软薄煤层煤巷条带消突长距离下斜钻孔,存在成孔难、易钻遇煤层顶底板、积水堵塞瓦斯抽采通道的难题,提出了氮气排渣下斜定向钻进成孔与护孔技术,采用高压氮气排渣、大功率气动螺杆钻具定向、“波浪式”轨迹控制和三层管护孔排水技术,在河南省平煤股份一矿开展现场试验,完成8个孔深超300 m下斜定向长钻孔,煤层钻遇率90%以上,全孔段下三层护排水管,平均下入深度302 m,支管平均抽采纯量1.66 m^(3)/min,平均瓦斯浓度17.5%。试验结果表明:该技术可有效解决松软薄煤层下斜钻孔长距离定向成孔、全孔段筛管护孔和排水的技术难题,提高了钻孔成孔深度和煤层钻遇率,实现了下斜孔全孔段护孔和排水,保障了瓦斯抽采效果,为松软薄煤层煤巷条带长距离消突提供技术保障,在类似地层条件具有广泛的应用推广价值。

非常规油气高质量发展战略方向优选

近10年来,化石能源多样化趋势明显,从常规油气领域向致密油/页岩油、致密气/页岩气、煤炭地下气化等非常规领域发展。油气藏类型增多,资源规模、品位、勘探开发难度及效益存在差异。要实现不同类型油气藏规模效益开发及绿色高质量发展,必须对化石能源未来发展方向和类型做出选择。分析国内外能源消费结构变化规律、现状及未来发展趋势,煤炭和石油一直保持主体地位,天然气占比逐年上升。对比研究不同类型化石能源单位体积能量密度、资源规模、开发成本、开发现状、技术成熟度等主要指标,结果显示煤炭地下气化具有能量密度最高、可采资源量最大、开采成本低等特点,在增加天然气供应、推动煤炭行业绿色低碳发展和助力实现碳中和方面拥有技术优势,可优选为非常规油气战略方向,为高质量发展开拓新路径。