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.

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.

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.

Mechanisms and characteristics of mesocarbon microbeads prepared by co-carbonization of coal tar pitch and direct coal liquefaction residue

DCLR-P was prepared by direct coal liquefaction residue (DCLR) with ash removal.In the present experiments,mesocarbon microbeads (MCMBs) were prepared by co-carbonization of coal tar pitch (CTP) and DCLR-P.With the increase of DCLR-P content,the yield of MCMBs increased from 47.8% to 56.8%.At the same time,the particle sizes distribution of MCMBs was narrowed,resulting in the decrease of D9o/D10 ratio from 154.88 to 6.53.The results showed that DCLR-P had a positive effect on the preparation of MCMBs.1H-NMR,FTIR,SEM and XRD were used to analyze the mechanisms and characteristics of MCMBs prepared by co-carbonization of CTP and DCLR-P.The results showed that the Proton Donor Quality Index (PDQI) of DCLR-P was 13.32,significantly higher than that of CTP (0.83).This indicated that DCLR-P had more naphthenic structure than CTP,which leads to hydrogen transferring in polycondensation reaction.The aliphatic structure of DCLR-P can improve the solubility and fusibility of mesophase,thereby making the structure of MCMBs more structured.The microstructure of the graphitized MCMBs had a substantially parallel carbon layer useful for its electrical performance.The performance of graphitized MCMBs as a negative electrode material for Li-ion batteries was tested.The particle sizes,tap density,specific surface area and initial charge-discharge efficiency of graphitized MCMBs met the requirements of CMB-I in GB/T-24533-2009.However,the initial discharge capacity of graphitized MCMB was only 296.3 mA h g-1 due to the low degree of graphitization of MCMBs.

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.

Spatio-temporal variation and propagation direction of coal fire in Jharia Coalfield,India by satellite-based multi-temporal night-time land surface temperature imaging

In this paper,the spatio-temporal variation and propagation direction of coal fire were studied in the Jharia Coalfield(JCF),India during 2006–2015 through satellite-based night-time land surface temperature(LST)imaging.The LST was retrieved from Advanced Spaceborne Thermal Emission and Reflection Radiometer(ASTER)night-time thermal-infrared data by a robust split-window algorithm based on scene-specific regression coefficients,band-specific hybrid emissivity,and night-time atmospheric transmittance.The LST-profile-based coal fire detection algorithm was formulated through statistical analysis of the LST values along multiple transects across diverse coal fire locations in the JCF in order to compute date-specific threshold temperatures for separating thermally-anomalous and background pixels.This algorithm efficiently separates surface fire,subsurface fire,and thermally-anomalous transitional pixels.During the observation period,it was noticed that the coal fire area increased significantly,which resulted from new coal fire at many places owing to extensive opencast-mining operations.It was observed that the fire propagation occurred primarily along the dip direction of the coal seams.At places,lateral-propagation of limited spatial extent was also observed along the strike direction possibly due to spatial continuity of the coal seams along strike.Moreover,the opencast-mining activities carried out during 2009–2015 and the structurally weak planes facilitated the fire propagation.

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.

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.

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

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.

In-situ gas contents of a multi-section coal seam in Sydney basin for coal and gas outburst management

The gas content is crucial for evaluating coal and gas outburst potential in underground coal mining. This study focuses on investigating the in-situ coal seam gas content and gas sorption capacity in a representative coal seam with multiple sections (A1, A2, and A3) in the Sydney basin, where the CO_(2) composition exceeds 90%. The fast direct desorption method and associated devices were described in detail and employed to measure the in-situ gas components (Q_(1), Q_(2), and Q_(3)) of the coal seam. The results show that in-situ total gas content (Q_(T)) ranges from 9.48 m^(3)/t for the A2 section to 14.80 m^(3)/t for the A3 section, surpassing the Level 2 outburst threshold limit value, thereby necessitating gas drainage measures. Among the gas components, Q_(2) demonstrates the highest contribution to Q_(T), ranging between 55% and 70%. Furthermore, high-pressure isothermal gas sorption experiments were conducted on coal samples from each seam section to explore their gas sorption capacity. The Langmuir model accurately characterizes CO_(2) sorption behavior, with ft coefcients (R^(2)) greater than 0.99. Strong positive correlations are observed between in-situ gas content and Langmuir volume, as well as between residual gas content (Q_(3)) and sorption hysteresis. Notably, the A3 seam section is proved to have a higher outburst propensity due to its higher Q_(1) and Q_(2) gas contents, lower sorption hysteresis, and reduced coal toughness f value. The insights derived from the study can contribute to the development of efective gas management strategies and enhance the safety and efciency of coal mining operations.

极近距离煤层开采无煤柱自成巷控制方法研究

极近距离煤层传统长壁开采,受上层遗留煤柱和采空区垮落等因素的影响,下煤层开采过程中应力环境复杂、矿压显现剧烈,易诱发巷道围岩大变形。为解决上述问题,提出了极近距离条件下巷道定向切顶–约束高强支护无煤柱自成巷控制方法。通过顶板定向预裂切顶,主动改变顶板悬臂结构,切断采空区向巷道顶板的应力传递。充分利用矿山压力和岩体碎胀特性,取消煤柱留设,结合高强支护加强巷道顶板整体性,共同实现切顶自成巷。建立了极近距离煤层开采覆岩结构模型,计算了下煤层切顶自成巷巷旁支护阻力。以典型极近距离煤层为工程背景,开展了不同开采方法的数值试验对比研究,结果表明,提出的自成巷控制方法使巷道围岩应力降低59.8%,巷道顶板变形减少70.8%,并明确了极近距离煤层开采无煤柱自成巷控制机理。在此基础上,开展了典型极近距离煤层工程设计及现场应用研究,结果表明该方法有效降低了矿压显现程度,保证了自成巷的安全稳定控制。

ML-QSPR方法预测煤基液体的燃料性能

煤基液体混合物如煤焦油、煤直接液化油的分子结构描述和性质预测是开发煤基液体产品高值化工艺和技术的重要基础。由于煤基液体主要由C、H、O、N、S元素构成数量庞杂、芳环结构各异的混合物,因此,使用Python中的RDKit工具包,利用简化分子线性输入规范(Simplified Molecular Input Line Entry System,SMILES)语言构建煤基液体中物质分子描述符,描述符包含样品元素信息、环数与环结构信息、原子数及分子量信息等共计115个分子描述符。对比人工信息提取方法,将所构建的分子描述符能够体现煤基液体分子结构碎片、分子量及原子个数信息等作为机器学习的特征输入变量,用于建立预测煤基液体的燃料性能的分子机器学习-定量结构性质关系方法 (ML-QSPR),实现对燃料低位热值(LHV)、液体密度(ρ)、闪点(FP)、十六烷值(CN)4个关键燃料性能参数的快速预测。模型验证分析表明LHV、ρ、FP模型的R^(2)分别为0.996、0.988、0.987;CN预测中加入混合物数据进行预测,R^(2)=0.959。与已公开报道的预测LHV、ρ、FP、CN性质方法对比,笔者提出ML-QSPR方法在预测4个关键燃料性能参数准确度方面有提升,在获取结果速度方面有显著优势。利用ML-QSPR模型预测得到的煤基液体制特种燃料性能参数数据库中的信息,分析增加不同族组分物质的碳原子数量时4个燃料性能参数的演变趋势,发现LHV、ρ、FP、CN四个燃料性能参数均受碳数(n)影响显著。由于LHV主要由n决定,不同族组分物质的LHV差距小;而不同族组分物质的ρ、FP和CN性质差距明显。此外,本研究训练好的模型可用于预测新的分子,为新型燃料分子设计提供参考;ML-QSPR方法作为迁移学习模型可在今后用于煤基液体其他场景相关理化性质的分析。

煤液化固渣萃余物的组成结构及铁催化剂活性相回收

为解决大规模煤直接液化催化剂铁源供应问题,同时实现煤液化固渣萃余物的无害化分质利用,从固渣萃余物中回收铁催化剂的角度进行研究,探索采用物理磁选法进行铁催化剂富集回收的可行性。首先采用粒度分析、XRF、XRD、SEM、TG、SEM-EDX等表征手段对固渣萃余物进行全面的物化性质表征,确定铁催化剂的质量分数和存在形态。由分析可知,工业装置固渣萃余物主要由未反应煤中的炭及残炭、挥发分及灰分组成,其粒度均匀且没有团聚,其中铁元素质量分数为5.96%,铁物种仍以具有顺磁性的Fe1-xS活性相存在,被未反应煤、残余沥青掺杂、包裹,与各种元素Ca、Si、Al、O等均匀混杂分布在萃余物中。在此基础上,选用4种型式的磁选设备在不同磁场强度下进行磁选富集,并将富集后的样品作为催化剂用于煤直接液化反应,考察其直接液化反应性能。试验结果表明,湿式立环脉动高梯度磁选机一方面将所产生的高梯度磁场力作用于磁性催化剂细粉,同时脉动流体力在一定程度上消除了非磁性颗粒的机械夹杂。在清水作为分散介质及洗涤介质下,更有效地实现了固渣萃余物中铁催化剂细粉的精细分离。在640000 A/m外加磁场强度下,含铁催化剂物料富集率为10.48%,铁元素质量分数可达11.37%,高压釜萃取油产率为41.96%,与无催化剂时相比高7.17%,比固渣萃余物提高8.99%,可掺混至新鲜催化剂中实现有效回用,部分解决催化剂铁源短缺的问题。

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。