煤液化用煤种的选择研究

影响煤加氢液化反应的因素很多,不同的煤对氢敏感度不一样,有的容易加氢,有的不容易加氢.显然容易加氢的煤在经济上就比较划算.在煤的工业分析、元素分析和煤岩相显微组分含量分析的基础上,简要讨论了原料煤对煤液化的影响.在煤的组成和物理性质等与液化特征之间建立良好的对应关系,总结出适合煤液化用煤种的一些特性.     

两种西部煤的化学结构及加氢液化性能

为探究西部煤的加氢液化反应性能,对新疆淖毛湖煤和内蒙古不连沟煤在间歇高压反应釜中进行了加氢液化实验,借助固体13 C-NMR和FTIR分析手段,对比研究了不同类型碳和官能团在两种煤及反应中间产物沥青质(PAA)中的分布.结果发现:淖毛湖煤的转化率和油产率分别为96.33%和47.86%,明显高于不连沟煤的转化率(76.18%)和油产率(23.44%).煤中脂肪碳和芳香碳所占比例是造成加氢液化反应转化率差异的主要因素,脂肪类和芳香类官能团的含量与反应性的关系分别呈正相关和负相关;液化油产率与原料煤中亚甲基碳和次甲基碳含量有关;与原煤相比,沥青质中的脂肪碳比例减少而芳香碳比例增加,说明脂肪碳是加氢过程中发生裂解加氢的主要活性结构.     

影响神华煤直接液化性能的因素及分析

对影响神华煤直接液化性能的8个因素进行分析可知,各因素对煤液化反应具有不同的影响;在工业生产中,对影响液化生成油液固分离因素分析可知,液固分离效果对液化油产率有很重要的影响.同时对影响因素进行分析并提出了优化装置操作的调整措施,为实际生产调整操作、装置稳定运行以及进一步确定合适的工艺条件提供一定的参考,为提高装置的生产效率和煤直接液化技术逐渐走向成熟打下基础.最后提出了煤直接加氢液化产业化的关键不仅仅是工艺技术问题,其设备运行的可靠性也不可忽视.     

煤直接液化溶剂研究进展

分析了煤加氢液化的反应机理,发现溶剂在加氢液化过程中起着非常重要的作用。重点讨论了溶剂在反应过程中的热溶解作用以及供氢和传递氢作用,介绍了目前煤直接液化工业生产中溶剂的常用分类,最后指出开发新型溶剂,对缓和煤加氢液化条件和改善生产工艺具有重要意义。     

新疆淖毛湖煤加氢液化特性及液化产物中氢的分布规律

以新疆淖毛湖煤和四氢萘为原料,在2L高压釜中进行加氢液化实验,开展新疆淖毛湖煤直接液化过程调控研究,考查了温度、压力、时间及催化剂对氢耗、气产率、转化率、油产率和沥青类物质产率的影响规律,探讨了复杂多相体系液化产物中氢的分布规律,揭示了煤直接加氢液化反应与氢分布规律的内在联系.结果表明:在420℃,15MPa和60min的反应条件下,淖毛湖煤的转化率为94%,油产率为65%,是适宜直接液化的优良煤种;氢较均匀地分布在淖毛湖煤加氢液化的轻质产物(水、150℃馏分油、150℃～260℃馏分油和260℃～350℃馏分油)中,在350℃重质馏分油中分布最高,接近30%;氢在液化产物中的分布与加氢液化反应效果呈现出正相关特征.     

煤直接液化循环溶剂加氢稳定试验研究

在300 m L加氢试验装置上进行加氢稳定试验,考察了反应压力对煤直接液化循环溶剂性质的影响,并通过0.5 L高压釜煤液化试验,考察了煤在不同加氢深度循环溶剂中的液化效果。结果表明,随着溶剂加氢反应压力的升高,循环溶剂密度、黏度及氮含量递减,氢碳原子比及供氢指数递增,循环溶剂性质得到改善,供氢性能得到提高,从而促进煤的转化率和油收率提高。当加氢反应压力由12.5 MPa升至19.3 MPa时,煤的转化率从87.21%提高到88.40%,液化油收率从51.62%提高到55.58%。     

兖州煤的催化加氢及其重质产物的分离和表征

煤在温和条件下的内化加氢是煤直接液化和煤温和热解领域的重要内容,是由煤生产液体煤料和化学产品的重要手段。从兖州煤的加氢反应入手,研究了加氢条件与产物产率的关系,考察了不同溶剂对产物萃取物数量和质量的影响,从族组成的角度分析了重质产物与优质道路沥青的异同,为以煤直接液化重质产物为原料生产优化道路沥青作了探索性研究。研究表明：在一定反应和分离条件下,通过兖州煤催化加氢可制得与进口和国产优质道路沥青族组     

煤的超临界抽提

这一方法的优点在于抽提时不需氢,同时容易从煤溶液中分离半焦。美国政府和私营工业正努力发展环境规定容许的从煤制燃料和化学品的方法。这些方法包括加氢液化、加氢裂解和气化。它们已发展了数十年但仍然遇到不少     

煤直接液化油催化加氢脱硫脱氮的研究

S、N的脱除是煤直接液化油加工的重要方面,为了更好的对煤液化油进行加工利用,系统分析了目前煤液化油加氢脱硫脱氮的研究。主要从油品组分、实验室反应条件和工艺以及动力学4个方面进行了介绍。结果发现:石油行业中关于含硫氮化合物的分析手段(如GC-AED、GC-PFPD)可以进一步与煤液化油的脱硫脱氮实验研究结合起来,这有利于液化油中S、N的脱除;目前关于液化油加氢工艺条件的研究数据公开不多,反应动力学方面的研究缺乏充足的数据支持,由于催化剂对工艺的影响研究较少,但催化剂技术已有了很大发展,可以考虑将新型催化剂引入反应中。     

煤直接液化低分油加氢脱硫脱氮反应动力学研究

为了进一步了解煤直接液化油中硫氮化合物的形态和性质,采用石油研究中的先进分析手段GC-PFPD和GC-NCD,对煤直接液化低分油进行了分析,获得了详细的硫氮化合物组成含量。结果发现:煤直接液化低分油中含有大量的杂环化合物,S主要以苯并噻吩类和二苯并噻吩类化合物存在,N主要以五元环化合物形式存在。在高压釜中进行了催化剂添加量和不同温度条件下的加氢实验,对总硫总氮的加氢反应动力学进行了研究。通过计算得到了高压釜煤液化油加氢脱硫反应的一级反应动力学模型,且通过模型计算的S含量与反应实测的S含量相对误差仅为7.8%;对实验得到的震荡式高压釜中煤液化油加氢脱氮反应的一级反应动力学模型进行验证,发现相对误差也仅为0.97%。     

煤焦油加氢技术概述

文章主要对煤焦油加氢技术从反应原理、工艺过程、运行实例进行了探讨。对煤焦油加氢的反应原理进行了重点描述;对目前已研发出的中低温煤焦油加氢技术进行了汇总;对国内现行的煤焦油加氢运行实例进行了罗列;最后对煤焦油加氢技术的发展趋势与前景进行了展望。     

中低温煤焦油加氢技术及产业发展分析

介绍了我国中低温煤焦油的生产及加工现状,对中低温煤焦油通过加氢制取汽、柴油的技术路线和工艺流程进行了分析,并着重分析了加氢过程中芳烃加氢反应的控制问题。最后对中低温煤焦油加氢的产业发展进行了相关分析,并提出发展建议。     

Coal liquefaction by the hydrogen produced from methanol

Methanol was used as an in-situ hydrogen source, following its decomposition over ZnO-Cr₂O₃, for the hydrogenation of coal. The reaction was carried out in a high pressure autoclave at ≈400–440 °C, in the presence of different hydrogenation catalysts. Stabilized nickel, stabilized Co and Ni-Cr-Cu catalysts gave excellent results. The maximum conversion was 100% for pyridine, 94.4% for benzene and 66.2% for straight-chain hexane.     

Coal hydrogenation under short-term reaction conditions

The results of the hydrogenation of coal from the Zashulanskoe deposit in the Chita oblast under conditions of a short reaction time (no longer than 10 min) are given. It was found that, to reach a 78–80% degree of coal conversion under the conditions of high-speed heating (∼200 K/min), the reaction time can be no longer than 10 min (the coal: paste-forming agent ratio = 50: 50), which corresponds to a feed space velocity of 2.5–3.0 kg l⁻¹·h⁻¹. This value, which determines the process productivity of coal hydrogenation, is higher by a factor of 3–3.5 than that under analogous conditions used in second generation processes, which were developed in the 1990s.     

中、低温煤焦油加氢技术进展

概述了我国中、低温煤焦油的性质及加氢工艺,对中、低温煤焦油通过加氢制取汽、柴油的技术路线及存在问题进行了分析,并对几种主要的中低温煤焦油加氢技术进行了对比分析。最后对中低温煤焦油加氢技术提出了几点发展建议,以期为我国煤焦油加氢技术的发展提供参考。     

Coal liquefaction by in-situ hydrogen generation.: 1. Zinc-water-coal reaction

Liquefaction of coal was carried out in a zinc—water—solvent system to give a product with high concentration of pyridine and benzene solubles. In this system the metal reacts with water to produce the corresponding metal oxide and hydrogen. This hydrogen was used for in-situ hydrogenation of coal. The effects of reaction time, temperature, type of solvent, the quantity of metal used and the rank of coal were investigated. The solvent has a very marked effect on the conversion of coal to benzene-soluble materials, especially at short reaction times. A maximum benzene conversion of 96% for Taiheiyo coal was obtained when it was treated at 445 °C for 1 h using wash oil as solvent. With regard to the influence of coal rank it was found that low rank coals were more reactive than high rank coals. The amount of preasphaltene is only slightly influenced by coal rank but depends on the temperature and the type of solvent used.     

高温煤焦油的应用现状分析

文章针对我国高温煤焦油的应用现状进行了调研,对目前高温煤焦油加工应用的三个主要方面：直接应用,提取化学品和加氢做了详细阐述。通过对高温煤焦油不同应用方向的工艺,技术及应用现状的分析,提出了国内高温煤焦油产业存在的一些问题。     

Coal hydrogenation: Quality of start-up solvents and partially process-derived recycle solvents

The performance of three sets of start-up solvents and one set of partially process-derived recycle solvents was studied in small autoclave coal hydrogenation tests. The start-up solvents were obtained by catalytically hydrotreating anthracene oils or creosote oils. It is shown that this preparation procedure converts polynuclear aromatics and two-ring aromatics to hydroaromatics and, ultimately, to alicyclics. Coal conversions using start-up solvents are found to reach a maximum at intermediate degrees of solvent hydrogenation which is believed to correspond to a maximal abundance of hydroaromatic solvent hydrogen donors. A solvent hydrogen donor index (SHDI), simply derived from ¹H n.m.r. spectral data, was devised and is found to successfully correlate coal conversions obtained using different start-up solvents, especially where N₂ gas rather than H₂ gas is employed in the autoclave tests. A set of partially process-derived recycle solvents were produced in multiple cycle continuous coal hydrogenation experiments. These were tested under relatively severe hydrogenation conditions in the presence of hydrogen gas, using the small autoclave unit. Substantial donation of solvent hydrogen was found to occur and coal conversions to hexane — and toluene-soluble products are found to be a smooth function of the solvent hydrogen donor index. It is concluded that the hydrogen donor capacity of a solvent is a major factor governing coal conversion, especially when the demand for solvent hydrogen is high. The SHDI parameter is useful in rationalizing the behaviour of start-up solvents. Also, at least in the first few cycles of a continuous two stage coal hydrogenation process, the SHDI parameter allows solvent quality to be monitored, and consequently optimized.     

煤制乙醇技术的研究及开发应用进展

介绍了以煤为原料生产燃料乙醇的4条工艺技术路线:合成气化学催化法、合成气厌氧发酵法、醋酸直接加氢法和醋酸酯化加氢法的反应机理、技术特点及最新进展,并且对各条路线的优势和劣势进行了对比,认为煤制乙醇将成为我国能源化工产业的重要组成部分。