The effect of hydrotreatment of liquefied heavy oil on direct coal liquefaction (DCL) was studied by hydrogenating the liquefied heavy oil (initial boiling point greater than 320 degrees C) in a 30 ml continuous hydrogenation apparatus at operating conditions of pressure (P) 13-19 MPa, temperature (T) 360-400 degrees C, liquid space velocity (LHSV) 0.6-1.4 h(-1). After hydrogenation, the properties and hydrocarbon composition of liquefied heavy oil were regulated, leading to the enhancement of hydrogen donating ability and 5.6% increase in oil yield of DCL as compared with non-hydrogenated raw oil. Based on the results, a new method of preparing recycle solvent for direct coal liquefaction by mixing hydrogenated heavy oil and un-hydrogenated middle oil in a suitable proportion was proposed, which has been verified to be effective and efficient to increase oil yield. (C) 2017 Elsevier Ltd. All rights reserved.

To study the performance and reaction kinetics of direct coal liquefaction for Shenhua Shangwan coal bituminous coal, experiments were carried out in a 0.01 t·d?1 continuous tubular facility using the hydrogenated anthracene and wash oil as solvent and FeOOH as catalyst in the range of residence time 7—110 min, reaction temperature 435—465℃. The results showed that, as the coal pyrolysis and a series of hydrogenation proceed, coal and PAA yields continue to decrease, heavy liquefied product gradually transformed to light liquefied product. When the reaction temperature is 455℃, residence time of 90 min, the coal conversion reached 90.41% (mass) and oil yield 61.28% (mass) respectively, and with the reaction conditions were further harsh, the oil yield will decrease. Based on the reaction characteristics of Shenhua Shangwan coal and its data from experiments, 11 lumps reaction kinetics model was build and BFGS optimization algorithm was adopted to get reaction kinetics parameters. The kinetics model better predicted the reaction behavior of direct coal liquefaction of Shangwan coal in isothermal stage.

高等反应工程是化学工艺二级学科硕士研究生的核心课程和学位课程.课程讲授多重反应体系动力学、催化剂失活反应动力学、气固相催化反应器数学模型、气-液-固三相催化反应器数学模型等内容.课程教学中突出运用数学模型方法进行案例分析.课后布置催化反应器数学模拟的大作业,让学生分组完成,并进行汇报和交流.课程教改取得了良好的效果.

采用管式反应器实验装置进行催化裂化柴油(LCO)液相加氢反应.在单反应管模式下,考察了反应压力、混氢量、空速、温度对加氢反应的影响及混氢量对催化剂床层热点温度的影响;在双反应管串联模式(中间补氢)下,考察了不同混氢量对加氢反应的影响.结果表明,单反应管催化裂化柴油液相加氢反应较为适宜的条件为压力6.5 MPa、混氢量(质量分数)0.56％、空速2.0h-1、温度360℃;管式反应器液相加氢的催化剂床层热点温差在10～20℃之间,热点温度出现在床层高度的15％～30％范围,最为合适的补氢点应在热点温度高峰出现下落趋势处.采用双反应管串联装置进行催化裂化柴油液相加氢反应,可使脱硫率、脱氮率均达到90％以上.

Direct coal liquefaction in the heating stage of Shenhua Shendong bituminous coal was carried out in a 0.01 t/d continuous tubular facility with iron catalyst and hydrogenated anthracene and wash oil as solvent at a residence time (t) of 3.56.5 min and a reaction temperature (T) of 340-450 degrees C. The results show that when t = 3.5 min and T = 340 degrees C, a cracking reaction of coal occurs, while the oil yield was almost zero. As the residence time and temperature each increase, coal conversion and product yield exhibit different change patterns. Especially when t = 6.5 min and T = 450 degrees C: under these conditions, the coal conversion and oil yield reached 83.67 and 52.27 wt?%, respectively. To investigate the liquefaction kinetics, a 8-lump reaction kinetic model which follow first-order irreversible reactions (r = k(i) dC/dt) was developed to estimate the rate constants. The results indicated that the model is perfectly valid for the heating stage, and the yield of oil and gas were mainly from coal other than preasphaltene (PAA).

To study the direct coal liquefaction in the isothermal stage of Shenhua Shendong bituminous coal, the direct coal liquefaction with an iron-based catalyst was carried out in a 0.01 ton/day continuous tubular facility in the temperature range of 445-465 degrees C, with hydrogenated anthracene and wash oil as the solvent. An eight-lump kinetic model of the isothermal stage was proposed, and the kinetic parameters were estimated. The result showed that, in the isothermal stage, the oil was mainly obtained from pre-asphaltene and asphaltene (PAA) rather than from coal directly. The model was valid for the isothermal stage of direct coal liquefaction.

According to the characteristics of FCC diesel, a technology of liquid-phase hydrodesulfurization of the diesel in tubular reactors was proposed and lab-scale experiments were carried out. A kinetic model for the hydrodesulfurization process was developed and verified. The model was utilized to predict the sulfur content of products under different operating conditions. The effects of temperature, space velocity, pressure, and hydrogen concentration on the desulfurization rate were investigated.

The equilibrium solubility of hydrogen in seven diesel oils,namely straight run diesel oil,FCC diesel oil,coking diesel oil,etc.,were measured using saturation method in the temperature range of 323.15-573.15 K and in the pressure range of 1-8 MPa. A correlation between the hydrocarbon composition of the diesel oils and the hydrogen solubility in the diesel oils was established to calculate the equilibrium solubility. The correlation coefficients were obtained according to the experimental data. The correlation was verified with different kinds of diesel oils at high temperature. The result showed that all the relative deviations between the calculated data and experimental data were less than 5.0%,and the correlation could be used to calculate the equilibrium solubility of hydrogen in different kinds of diesel oils in the wide ranges of temperature and pressure.

Base on the technology of a domestic refinery for FCC diesel liquid-phase hydrogenation in the pipe reactor, a small scale experiment was carried out using RS-2000 as catalyst under the conditions of reaction pressure of 6.5 MPa, reaction temperature of 623.15 K, and initial hydrogen content of 0.42% (mass fraction). A kinetic model for the process was established by the experimental results and model parameters were observed. The simulation results by software MATLAB were in good agreement with the experimental results. The model was also applied to simulate the process of multi-points hydrogen supply under the test reaction conditions. The results indicated that the points of hydrogen supplied and the amount of hydrogen added by each point had a great impact on the reaction results, which could provide references for further study.

To predict distributions of different gas component in heating-up stage of coal direct liquefaction, regression analysis on a great deal of experimental data of coal direct liquefaction under different reaction temperature and different residence time was carried out. Correlation models were developed to study the correlate between gas component and reaction conditions, lumped product components. The corresponding regression model parameters were obtained, and the correlation models were optimized by SPSS software. The relative error between experiment and simulation of CH4, C2H6, C3H8, C4, CO, CO2 and H2S were 1.1%, 1.0%, 6.0%, 9.8%, 9.3%, 0.5% and 0.4%, respectively, which indicated that the simulated results agreed with the experimental results.

Single-event microkinetic（SEMK） model of the catalytic cracking of methylcyclohexane admixed with 1-octene over REUSY zeolites at 693 K—753 K in the absence of coke formation is enhanced. To keep consistency with the wellknown carbenium ion chemistry, hydride transfer forming and consuming allylic carbenium ions in the aromatization of cycloparaffins are further investigated and differentiated. The reversibility of endocyclic β-scission and cyclization reactions is refined by accounting explicitly for the reacting olefins and resulting cycloparaffins in the corresponding thermodynamics. 24 activation energies for the reactions involved in the cracking of cycloparaffins are obtained by the regression of 15 sets of experimental data upon taking the resulting 37 main cracking products, i. e., responses into account. The enhanced SEMK model can adequately describe the catalytic behavior of 37 main products with conversion and temperature.

Based on six lumped kinetic model, this paper used the BFGS optimization algorithm to obtain kinetic constant of heating-up and isothermal stage of direct coal liquefaction process, and through regression of experimental data to get specific product composition for separation unit of direct coal liquefaction. Then the Aspen Plus user model of direct coal liquefaction was developed and integrated with the Aspen Plus software to achieve an entire process simulation of direct coal liquefaction process in Aspen Plus platform which can make the best use of its powerful databases and simulation calculation ability of separation processes. The calculation value of gas liquid equilibrium in high temperature and low temperature separators for reaction products agreed well with the experiment data. The entire process simulation in Aspen Plus platform can provide technical support for the optimization of direct coal liquefaction reaction and separation conditions.

With phenanthrene and hydrogen as raw materials, the hydrogenation of phenanthrene was tested over CoMo/Al2O3 catalyst in a fixed-bed microreactor. Effects of temperature, pressure and space velocity on the reactions were systematically investigated. On the basis of the equilibrium constants calculated by thermodynamic method and kinetic equation derived by the adsorption theory of Langmuir-Hinshelwood-Hougen-Watson, the rate constants, activation energy, and adsorption constants were estimated by the Broyden-Fletcher-Goldfarb-Shanno optimization method, and the different reaction networks were compared and screened. In this study, the result showed the path from 9,10-dihydrophenathrene to tetrahydrophenathrene could be neglected, and the path from 9,10-dihydrophenathrene to 1,10-octahydrophenanthrene could not be excluded.

The hydrogenation of 2-methylphenanthrene was studied by group contributions and cor-responding state methods to investigate the physicochemical properties of compounds involved.The Gibbs free energy change,equilibrium constants and enthalpy changes of each step of the reaction net-work at different temperatures were calculated based on the physicochemical properties obtained.The calculations of the product compositions and hydrogen consumptions under different pressures and tem-peratures according to the equilibrium constants were conducted.The calculation results show that all step reactions are exothermic,their equilibrium constants decrease as the reaction temperature increa-ses.High temperature and low pressure are beneficial for the production of intermediate 2-methyl-9,10-dihydro-phenanthrene and for the reduction of total hydrogen consumption.

In an experiment,researchers refined the 145-230℃ fraction of the coal-to-olefin process using dimethylsulfoxide as solvent and synthesized lubricant base oil with the refined olefin using AlCl3 as catalyst and normal octane as solvent by means of solvent polymerization.The experiment examined the effect of tem perature,reaction time and catalyst percent on polymerization.The experimental results showed that when the catalyst percent was 2.25%,reaction lasted for 2 hours and the reaction temperature was 110 ℃,the yield of PAO base oil could reach 84.36%.At 100℃,the dynamic viscosity of the base oil was 8.606mm2/s,the viscosity index reached 147,the flash point was 237℃ and the pour point was-55℃.These researchers compared the PAO base oil produced with olefin made from coal and that produced with traditional pure olefin(1-decene) in terms of yield and main properties and the results showed that all properties of olefin made from coal,except yield and flash point,which were lower,were equal to those of 1-decene.Therefore,olefin made from coal is a fully qualified alternative to the conventional feedstock used for synthesizing low-viscosity PAO base oil.The research results can be used to guide the method of using olefin made from coal to synthesize lubricant base oil.

A kinetic model of MTO process over the SAPO-34 catalyst considering the effect of water and coke deposition has been proposed. The model takes into account three steps of the MTO reaction in which the products cover 5 lumped components. The water in the feed not only reduces the concentration of methanol but also alleviates the deactivation of SAPO-34 catalyst. The kinetic parameters have been estimated by the least square method. It has been proved that the calculated values in the kinetic model are in good agreement with the experimental values.

Thermodynamic models for 10 reactions in methanol to olefins (MTO) was established based on the reaction mechanisms. The thermodynamic calculation for the MTO process was carried out by the four parameters method, and the relationships of the enthalpy changes, Gibbs free energy changes and equilibrium constant changes with temperature were obtained. The thermodynamics of the MTO process were also studied by means of the Aspen Plus software. The effects of temperature, pressure and water content on the reactions were investigated according to the thermodynamic calculation. It was showed that most of the reactions in the MTO process were strong exothermic reactions and all the reactions could occur spontaneously. The results calculated by the four parameters method was in accordance with the results simulated by the Aspen Plus software. High temperature is beneficial to the formation of light olefins and the ratio of ethylene to propylene in the products can be adjusted by controlling the temperature. The pressure and water content have less effect on the reactions than that of temperature. High pressure and high water content are unfavourable to the formation of light olefins.

Hydride transfer(htr)is generally recognized as one of the most important elementary reactions in catalytic cracking.Using Single Event Micro Kinetics(SEMK)in the assessment of the catalytic cracking of aliphatics,the autocatalytic character of hydride transfer was addressed at the molecular level.The results showed that the presence of 1-octene in the feedstock resulted in the enhanced acid site coverage,in particular at lower feed conversions and,consequently,in higher hydride transfer rates.Irrespective of the co-feeding of olefins,hydride transfer rates towards tertiary carbenium ions were almost 5 orders of magnitude higher than those towards secondary ones.The investigation of the Cracking Mechanism Ratio(CMR)and the reaction cycle Chain Length(CL)reveals that both CMR and CL adopt similar values when a pure paraffin feed is processed.However,while CMR was strongly affected by the addition of olefins in the feedstock,CL remained practically constant.