神华上湾煤恒温阶段直接液化反应动力学

为考察神华上湾煤的直接液化性能及反应动力学,以加氢蒽油-洗油混合油作为溶剂、负载型FeOOH作为催化剂,在0.01 t·d^-1煤直接液化连续实验装置上考察了不同反应温度（435~465℃）、不同停留时间（7~110 min）下液化产品组成的演变规律。研究发现,随着煤的裂解及加氢反应的进行,煤及沥青类物质（PAA）收率不断减小,重质液化产物逐步向轻质液化产物转化。当反应温度为455℃、停留时间为90 min时,煤转化率为90.41%（质量分数（,油收率为61.28%（质量分数（。随着反应条件进一步苛刻,油收率下降。基于上湾煤直接液化反应特性及其产物收率变化规律建立了11集总煤直接液化反应动力学候选模型,以BFGS优化算法对实验数据搜索、选优,确定了动力学模型参数。检验结果表明所建立的动力学模型可用于恒温阶段直接液化行为的模拟计算。     

煤焦CO_2气化的热重分析研究（Ⅱ）程序升温热重研究

用程序升温热重法（Ｔｅｍｐｅｒａｔｕｒｅ－ｐｒｏｇｒａｍｍｅｄＴｈｅｒｍｏｇｒａｖｉｍｅｔｒｙ）对内蒙扎赍诺尔煤（ＺＬ）、陕西神府煤（ＳＦ）、山西阳泉煤（ＹＱ）的８００℃半焦进行ＣＯ_２气化研究，对表征煤焦反应性的参数变化进行了分析讨论和动力学计算，并与等温法的结果相比较，结果表明：ＤＴＧ参数是对煤焦气化反应的动态扫描，由此得出的煤焦活性顺序和动力学参数值，与等温法的研究结果不同，这种差异是由于不同的分析方法和煤焦不同的岩相组成造成的。     

煤焦CO2气化的热重分析研究：（II）程序升温热重研究

用程序升温热重法（Ｔｅｍｐｅｒａｔｕｒｅ－ＰｒｏｇｒａｍｍｅｄＴｈｅｒｍｏｇｒａｖｉｍｅｔｒｙ）对内蒙扎贲诺尔煤（ＺＬ），陕西神府煤（ＳＦ），山西阳泉煤（ＹＱ）的８００℃半焦进行ＣＯ２气化研究，对表征煤焦反应性的参数变化进行了分析讨论和动力学计算，并与等温法的结果相比较，结果表明：ＤＴＧ参数是对煤焦气化反应的动态扫描，由此得出的煤焦活性顺序和动力学参数值，与等温法的研究结果不同，这种差异是由于不同     

滴管炉技术特点及其研制进展

阐述了进行煤反应动力学研究的必要性和实验研究的重要性,分析了一种重要的实验室用装置滴管炉在煤反应动力学研究方面的特点,总结了当前国内外滴管炉的研制进展,认为其具有广泛的应用前景。     

生物质与煤共热解气化行为特性及动力学研究（摘要）

在现有实验室条件下,全面分析了6种形式的生物质与煤共热解过程,考察其中的协同反应效应,利用分布活化能法（DAEM）研究生物质与煤的共热解动力学特性,得出共热解动力学相关参数,为实现生物质与煤高效协同共热解反应寻找更为有效的途径。主要内容和研究成果归纳如下：     

DAEM和Coats-Redfern积分法研究煤半焦燃烧动力学的比较

利用恒温和程序升温热重技术研究了神木煤半焦的燃烧动力学,采用DAEM（分布活化能模型）和Coats-Redfern积分法对其进行了动力学分析,比较了二者在处理程序升温半焦燃烧反应动力学的差异,同时还对恒温及程序升温的燃烧动力学进行了分析.结果表明,在恒温燃烧和程序升温燃烧过程中,随着燃烧反应的进行,比燃烧速率逐渐增加,所得半焦燃烧的活化能有不同的变化趋势.DAEM和Coats-Redfern 积分法因所用方法的不同而使结果有所差异.而恒温燃烧时由于所用燃烧温度较低,可以最大限度地消除外扩散的影响,使所得动力学参数更接近半焦燃烧的本征动力学参数.     

程序升温热重法研究活性焦气化反应特性

在管式炉上以较高炭化温度（1000℃以上）制备煤焦,并在较低温度（850℃）下用水蒸气活化而制得活性焦。采用程序升温热重法对高炭化温度下制得活性焦的CO2气化反应特性进行了研究,并利用组合升温速率法对其动力学参数进行了计算。从对碳转化率曲线、气化速率曲线的分析和比较来看：随着制焦温度的升高和煤阶的增加,活性焦的活性逐渐下降;活化之后的煤焦比未活化煤焦的气化反应活性更好。动力学参数的计算结果符合上述结论。     

神华煤高压釜加氢液化等温反应的动力学研究

在高压釜中对神华液化示范工程用煤进行了450℃等温加氢液化动力学研究,提出了液化反应网络,建立了相应的动力学模型,通过实验求出各反应速率常数.结果表明,在等温反应阶段,可按液化反应动力学性质将煤划分为易转化和难转化两种煤组分;易转化煤组分生成各产物的反应速率顺序为沥青烯组分＞油＞气态产物,其生成沥青烯组分的速率常数是难转化煤组分转化的12.56倍;反应后期沥青烯组分转化为油的速率是油产率增加的主要控制因素.     

煤分子中-HCOH-初期氧化反应机理研究

根据煤分子中α位带羟基的次甲基键（—HCOH-）活性基团与O2反应的可能路径,计算确定出反应物及产物和稳定中间体的平衡构型,运用DFT方法对可能的反应路径推测（—HCOH-）活性基团煤分子初期氧化生成水和二氧化碳的反应过程,并通过计算热力学和动力学得出反应焓变、吉布斯自由能和活化能等重要参数,得到α位带羟基的次甲基键的活性及热效应,从而为煤氧复合微观反应机理的研究提供理论依据．     

煤中黄铁矿的电化学脱硫及动力学研究

为了降低煤的脱硫费用和提高脱硫效率，以硫酸为介质，以硫酸锰为脱硫催化剂，在以石墨为电极的无隔膜电解池中研究了煤的电化学催化脱硫。研究表明，在特定的电解电位下，煤中无机硫脱硫率随着锰离子的浓度增加，煤浆浓度的降低和电解温度的提高而提高。进而对这些数据进行了动力学分析。结果表明：煤中黄铁矿脱硫速率与煤中活性黄铁矿（易接近）和惰性黄铁矿（难接近）及脱硫反应有关，脱硫模型符合Langmuir-Hinshelwood近似，脱硫表观活化能为10.44kJ/mol。     

SOME ASPECTS OF DESIGN OF COMMERCIAL REACTORS FOR DIRECT COAL LIQUEFACTION

In recent years, a number of direct coal liquefaction processes have been developed. All processes use a slurry type reactor. Although for lab-scale reactors of large length-to-diameter ratio the use of highly sophisticated slurry reactor model may be justified, simple considerations can meaningfully elucidate the behavior of industrial reactors. A simple analysis shows that the coal liquefaction is controlled by intrinsic kinetics. Both gas and slurry phases can be assumed to be completely backmixed in large diameter reactors. A simple analysis of the thermal behavior revealed multiplicity for a fairly wide range of operating conditions. In most cases, the intermediate unstable steady state is close to the temperature observed in adiabatic coal liquefaction reactors (with and without quench). Due to the unstable character of the operation, point pathological phenomena like runaway may be possible and a close feedback control of the commercial reactor may be required.     

甲醇制烯烃反应动力学及反应器模型研究进展

甲醇制烯烃（MTO）工艺是现代煤化工领域的研究热点,MTO反应动力学及其反应器模型研究是高效反应器开发和工业装置操作优化的基础。本文综述了甲醇制烯烃反应动力学研究进展,详细论述了机理型动力学模型、八集总动力学模型、五集总动力学模型,指出集总动力学模型适用于描述MTO反应过程,如何考虑水、积炭等因素的影响是MTO动力学研究的难点和关键。结合现有动力学模型,评述了MTO反应过程在工业规模的固定床反应器、提升管反应器、循环流化床反应器、湍动流化床反应器中产物分布和转化率模拟情况,结果表明：循环流化床反应器和湍动流化床反应器适合MTO工业过程。最后指出,甲醇制烯烃反应动力学下一步研究方应集中于工业规模流化床反应器气固两相流动模拟,以及与动力学模型结合获得准确预测工业反应结果的MTO反应器模型。     

Design of laboratory reactors for the measurement of catalytic carbon and coal gasification kinetics

A great deal of conflicting experimental kinetics results have appeared for catalytic carbon and coal gasification by water and carbon dioxide. The reason for this can in large part be attributed to inhibition of these reactions by their products and the influence of this product inhibition on the measured kinetics in different laboratory reactor systems. The measurement of differential rates and the determination of true kinetic values requires the use of feed streams with an excess of water and hydrogen for the catalytic CH₂O reaction and an excess of carbon dioxide and carbon monoxide for the catalytic CCO₂ reaction. Recommendations are put forward for the design of laboratory reactors for the measurement of catalytic carbon and coal gasification kinetics.     

Application of catalysts to coal gasification processes. Incentives and perspectives

There are several processes used for coal gasification, but these have three characteristic types of reactors — moving-bed, fluidized-bed and entrained phase. Design and comparison of different processes and reactors is possible if kinetic data relevant to technical performance of processes are available. The state of reaction kinetics of the non-catalysed and catalysed steam-carbon reaction as the basic coal gasification reaction is discussed. Catalysts only have effects on gasification rates in the temperature range of chemical reaction or pore diffusion control. Furthermore the increase in reaction rates by catalysts can also be reached without using catalysts. Therefore the application of catalysts seems not to be attractive in conventional gasification processes because the advantages (less coal and oxygen consumption and lower heat losses) are compensated by their disadvantages (additional costs, side effects). Only such processes in which a temperature increase is limited for different reasons does the application of catalysts have significant advantages. Such processes are the allothermal gasification using nuclear heat and processes leading to synthetic natural gas (SNG).     

Kinetik der Kohlen-Pyrolyse als Grundlage für die Auslegung technischer Reaktoren

Kinetics of coal pyrolysis as a foundation for the design of technical reactors . The pyrolysis of coal is understood to mean its thermal decomposition at temperatures above 300°C, affording tar and char. It is the basic process underlying coking and the starting reaction of combustion, gasification, and hydrogenation. In addition, pyrolysis offers a means of converting coal into gases and liquids in a ?third way”? besides gasification and hydrogenation. In order to establish a basis for the design of relevant technical reactors, the kinetics of coal pyrolysis has been investigated as a function of temperature and rate of heating and recently of pressure under inert gases and hydrogen. In particular, the rates of formation and the yields of liquid and gaseous products and the alteration of the solid matter have been examined under pressures ranging from 1 to 100 bar and at rates of heating between 0.05 and 1 000 K/s. It is shown how product formation can be controlled by these parameters and how the experimental data can be applied to reactor design.     

ISOTHERMAL AXIAL DISPERSION REACTORS IN COAL LIQUEFACTION HYDROPROCESSING

The purpose of this study is to provide a better understanding of reactors for hydroprocessing of liquid-solid mixtures, and to assist in the design and scale-up of large scale reactors from the information obtained from small scale experimental units. The paper describes a linear, isothermal, cocurrent upflow tubular reactor model with axial dispersion. The model is applied to coal liquefaction, assuming that the complex liquefaction kinetics can be represented by five lumped components-six first order reactions, and that the three phase (coal-solvent-gas) flow can be approximated by a two phase (slurry-gas)flow.     

ISOTHERMAL AXIAL DISPERSION REACTORS IN COAL LIQUEFACTION HYDROPROCESSING

The purpose of this study is to provide a better understanding of reactors for hydroprocessing of liquid-solid mixtures, and to assist in the design and scale-up of large scale reactors from the information obtained from small scale experimental units. The paper describes a linear, isothermal, cocurrent upflow tubular reactor model with axial dispersion. The model is applied to coal liquefaction, assuming that the complex liquefaction kinetics can be represented by five lumped components-six first order reactions, and that the three phase (coal-solvent-gas) flow can be approximated by a two phase (slurry-gas)flow.     

多相光催化反应器数学模型研究进展

本文介绍了当前多相光催化反应体系中反应动力学模型以及反应器数模研究领域内的主要方法及成果。反应动力学方面依据反应机理和动力学方程进行了说明 ;反应器模型则按学术团体各自不同的研究思路及方法分别概述 ,并依照反应器内部的各相的情况作了分类 ,扼要介绍了辐射能分布方程。对未来此领域的研究方向作了展望。     

重氮盐水解制酚反应器的分析研究

结合重氮盐水解制酚反应机理及动力学,从化学反应工程的角度出发,对现有重氮盐水解制酚的反应器进行了简单阐述,讨论了现有水解反应器的优点及其局限性,并对其今后研究发展趋势进行了展望。     

Kinetics of swelling and plasticity of coal during rapid pressurized pyrolysis and hydropyrolysis

The change of vitrain and durain particles from three high volatile bituminous coals pyrolysed in a wire net apparatus has been filmed with a high speed camera. Results are given on swelling kinetics and plasticity data for a particle of size up to 1 mm, with pressures up to 10 M Pa of hydrogen and rates of heating, 55–900 K s⁻¹ in a helium atmosphere. Also, a correlation between swelling and tar formation is established, which can be used for predicting the change of coal particles in coal conversion reactors.