神华煤直接液化工艺中硫元素的回收利用

神华煤直接液化原料煤中的硫元素和催化剂助剂中的硫元素在煤直接液化过程中大部分转化为H2S气体,并分散于中压气、干气、液化气和酸性水中。为满足产品质量和工艺技术指标要求,并回收循环利用硫元素,鄂尔多斯煤直接液化项目采用气体脱硫工艺回收中压气、干气、液化气中H2S气体,装置运行稳定,回收率分别为97.28%、99.92%和99.99%;采用污水汽提工艺分离收集酸性水中H2S气体,回收率达99.6%;脱硫回收和汽提收集到的含H2S酸性气混合后采用Claus硫磺回收工艺将H2S转化成硫磺,平均每年回收硫磺14 683.5 t,硫磺产品作为催化剂助剂供煤液化反应和加氢稳定反应注硫使用,从而实现硫元素循环利用,减少了环境污染。     

德国IGOR煤液化工艺及云南先锋褐煤液化

介绍了德国IGOR煤直接液化工艺和云南先锋褐煤在IGOR工艺200kg／d的PDU装置的试验结果．与其它煤直接液化工艺相比,IGOR工艺具有煤直接液化反应器的空速高、系统集成度高和油品质量好的特点．云南先锋褐煤在IGOR工艺200kg／d的PDU装置上的试验结果表明．先锋褐煤是适宜IGOR煤液化的煤种．得到的油收率为53％,油品中氮和硫的含量分别为2mg／kg和17mg／kg．煤液化油经过简单蒸馏可得到合格的0^#柴油,经过重整可得到合格的90^#无铅汽油．     

煤制油催化剂段降低含盐废水量的装置改进研究

本文主要介绍神华煤直接液化制备高效催化剂工艺现状,对催化剂制备过程产生的含盐废水(催化剂废水)来源进行了分析,研究通过催化剂制备工段的操作优化及装置改进,降低催化工段废水产生量。结果表明,在该改进装置条件下催化剂制备工段产生的含盐废水量每小时降低14.5 t。     

煤直接液化催化剂研究进展

我国煤炭储量丰富,煤液化制油技术是缓解我国一次能源结构中原油供应不足的措施。煤液化工艺的各种催化剂中,铁基催化剂以其高效、廉价及低污染而倍受青睐。非铁系催化剂有Sn和Zn水溶液、含碘的煤液化催化剂、碱金属氢氧化物或碳酸盐、Cr-Mo-Ⅷ族的加氢催化液化催化和硫转移剂等。概述了近年来煤液化技术在铁系催化剂研究、回收利用、制备工艺和预处理等方面的研究进展,综述了煤液化催化反应器研究状况。     

胜利褐煤液化油的常减压蒸馏及NMR分析

为更好地描述煤液化油的基本性质,用常减压蒸馏和H—NMR方法,对在反应温度450℃,反应压力19MPa,催化剂用量为铁／干煤-1．0％（质量分数）条件下,在0．1t／d煤直接液化连续实验装置上得到的内蒙古胜利褐煤液化轻、中、重油进行分析．由常减压蒸馏方法得到的蒸馏曲线用于描述液化油的馏程分布,H—NMR方法给出液化油的平均分子结构参数．轻油、中油和重油的缩合指数依次为0．96,0．91和0．78,分别相当于由一个、两个和大于两个芳香环所组成．     

合成气环境下的煤直接液化反应

我国煤炭资源丰富,一直是主要的能源和化工原料。随着国际市场原油价格的不断上涨,为了有效地利用煤炭资源,发展洁净煤技术,对煤直接液化的研究又重新成为热点。本文对新疆硫磺沟煤的液化性能进行了研究。在500ml间歇液化反应釜装置上,研究了氢初压、催化剂加入量、液化气氛等工艺参数对硫磺沟煤液化的影响。结果表明硫磺沟煤具有良好液化性能。硫磺沟煤直接液化最佳工艺条件反应温2液化气氛CO／H2为0．5时,硫磺沟煤的转化率和油产率与纯氢气氛条件下相当。添加O．5％的Ni后,油产率进一步提高。     

科技动态

<正> 我国天祝煤在日本0.1t/d NEDOL液化工艺连续装置上运转情况良好根据中日合作开发煤液化技术协议,双方对天祝煤在高压釜和在中国0.1t/d煤液化装置(反应器为釜式)试验研究的基础上,为了进一步验证天祝煤对日本开发的NEDOL液化工艺的适应性,同对取得与国外几种优质液化煤种的性能比较,双方商定在日本0.1t/d的BSU装置上进行了天祝煤加氢溶剂的一次通过和循环试验,试验取得预期的结果。     

甲烷气氛下铁基催化剂对低阶煤温和液化的影响

针对煤直接液化的高温高压苛刻反应条件和高昂的氢气成本问题,通过降低煤液化反应温度、压力和更换供氢气氛等方法来优化工艺过程。选用四种铁基催化剂研究低阶煤在甲烷气氛下温和液化的反应特性,研究结果表明：神华黑山长焰煤HS在温度350℃、初始压力3 MPa的甲烷气氛下液化产物为轻质气体、液化油和沥青质;以FeSO₄为催化剂时沥青质的产率最高达到8.03%,并将煤液化的转化率提升了6.10%;以FeS为催化剂时油气产率提升了3.48%;助剂硫元素的加入对煤液化反应总转化率的提升有着重要作用;Fe粉、Fe+S和FeS催化剂的加入有助于提升煤液化油中单环芳烃的含量。     

煤液化残渣中硫的迁移和转化研究现状及展望

为了解煤液化残渣利用过程中,硫化物迁移和转化规律,介绍了煤液化残渣中硫的来源及分布,总结了煤液化残渣在加氢液化、气化制氢、热解、燃烧等过程中硫化物的迁移和转化过程及影响因素,并对煤液化残渣中硫的迁移和转化的研究前景进行展望。结果表明,无机硫逐渐向有机硫转化,H2S是转化过程中的重要介质;H_2S、CS_2、SO_2等气态硫化物是煤液化残渣利用过程中的主要气态副产物;部分硫化物转化为大分子有机硫进入二次产品,影响产品质量和使用效果。为了合理有效地利用煤液化残渣,需寻找残渣中无机硫转化为单质硫或大分子有机硫的新方法,循环利用气体硫化物,开发新型煤液化催化剂,减少单质硫助剂使用量。     

煤直接液化催化剂中总可溶性铁含量分析方法研究

针对煤直接液化催化在煤直接液化工艺过程中的重要性和特殊性质,本论文通过研究煤直接液化催化剂中铁含量的分析过程和影响因素,包括样品取样量、盐酸的使用量、煮沸时间及固液分离方法,获取最佳的实验方案。研究发现,当盐酸量为25mL时,样品质量为0.250g,煮沸时间为5min时,选择抽滤法固液分离,分析效果最优,方法相对标准偏差（RSD,n=20）小于5%。该分析方法减少了分析过程中人为因素导致的结果重复性、再现性差等问题,对煤直接液化催化剂中铁含量的分析和煤直接液化催化剂质量控制有现实指导意义。     

日本褐煤直接液化工艺

日本的BCL工艺是目前世界上唯一针对褐煤开发并经过了工业性试验结果（PP）验证的褐煤液化工艺,是先进成熟的直接液化工艺之一。改进的BCL工艺,由于采用了多级反应模式、双组分煤浆溶剂、高效催化剂、在线加氢等技术,使工艺的油收率进一步提高。     

Catalytic effects of iron compounds and the role of sulfur in coal liquefaction and hydrogenolysis of SRC

Effective iron catalysts in coal liquefaction have been explored. Reduced Fe, Fe(CO)₅, and ferrocene have shown a considerably high catalytic activity in the liquefaction of Yallourn coal at 400°C. Degree of reduction has been shown to be one of the most important factors determining the catalytic activity of the iron catalyst. In the hydrogenolysis of SRC derived from Wandoan coal, water formed in situ has been shown to exhibit a negative effect due to reoxidation of the iron catalyst, but addition of elemental sulfur is greatly effective in preventing such deleterious influence of water. This can be interpreted on the basis of the sulfidation of reduced Fe by elemental sulfur, competing with reoxidation of the iron catalyst by water. In the systems with elemental sulfur, active and oxidation-proof pyrrhotite is formed, and the degree of reduction of the remaining iron oxide is maintained higher than that in the absence of elemental sulfur.     

隔膜压滤机在煤直接液化项目的应用及优化

针对神华煤直接液化项目运行初期催化剂制备装置中隔膜压滤机运行不稳定问题,通过分析催化系统的压滤结构、压滤机结构原理及使用情况,针对隔膜压滤机运行存在的问题对压滤系统进行改造,并对改造后效果进行分析。结果表明,滤板漏料、滤液外泄、拉板小车故障、翻板变形、滤布检查耗时过长等是影响隔膜压滤机稳定运行的主要因素,采用在压滤机止推板的接管上增大补偿器补偿量、增加闭式气水分离器、整平轨道和改造链轮轴承、采用多加支撑点、在隔膜滤板开孔安装检查滤液水龙头等方法对压滤系统进行改造。改造后,4台压滤机的故障次数减少,维修时间缩短,设备稳定运行能力加强,减少滤液流进滤饼仓。目前压滤机负荷已能够满足煤直接液化项目的生产负荷要求,催化剂装置运行稳定,基本满足了煤直接液化项目运行要求,取得良好的效果。     

煤炭直接液化油收率极限理论及其应用

首次建立了煤炭直接液化油收率极限理论,在指定的液化试验装置上,当催化剂、助催化剂和试验条件一定时,可以确定煤种的低限油收率和高限油收率,从而阐明了煤种进行直接液化主反应的限度,掌握煤种的低限油收率和高限油收率可以识别煤炭直接液化催化剂性能,最大限度地降低前沥青烯和沥青烯等液化反应中间产物的产率,就可以获得接近高限油收率的液化油收率。     

Study on industrial catalyst for bituminous coal liquefaction

The catalyst activities and the grinding characteristics of natural iron compounds and sulfides were investigated with the aim of preparing an industrial coal liquefaction catalyst for the NEDOL process large-scale plants. From the viewpoint of economy, since these plants are to be located at coal mining sites, it is economical to utilize a natural compound produced in the vicinity of plant site as the catalyst raw material. The coal liquefaction, using an electromagnetic agitation type autoclave, suggested that iron sulfide (pyrite) is the best raw material for the catalyst, because it contains higher iron and sulfur for producing pyrrhotite, an active component under the reacting conditions, and thereby, it needs no pollutant sulfur addition. However, taking into consideration the grinding characteristics, iron sulfide is not thought to have good grinding characteristics in a fine particle zone. Co-pulverization, using iron sulfide and coal, improves the grinding efficiency, the abrasion and the catalyst activities, so that the industrial catalyst preparation can be realized by means of the co-pulverization method.     

Catalytic activity of iron compounds for coal liquefaction

The catalytic activity of pyrite and synthesized -FeOOH in coal liquefaction was investigated using batch autoclaves with the aim of developing an industrial iron catalyst. The results indicate that the presence of H₂S helps gaseous hydrogen transferring and prevents deactivation so that the catalyst promotes hydrocracking of coal and hydrogenation of the products. The activity converges with excess H₂S and sulfur addition equivalent to an S/Fe molar ratio of 2.0 being reasonable for the activation. The active site is located on the outer surface, with finely divided catalysts exhibiting high activity. Both pulverized pyrite and synthesized -FeOOH are sufficiently fine as to exhibit high activity in the process. Pulverized pyrite is an industrially feasible iron catalyst for coal liquefaction process, because it is inexpensive and does not require sulfur addition.     

Scale formation in coal liquefaction reactor using FeS catalysts

The origin and formation behavior of scale in a coal liquefaction reactor, in which disposable catalysts such as red mud-sulfur were used, has been investigated by means of model experiments. The scale formed in the continuous coal liquefaction reactor which operated at a throughput of 0.1 t/d was analyzed with an electron probe microanalyzer (EPMA), scanning electron microscope (SEM), X-ray and scanning Auger electron microscope (SAM) techniques. It was observed in the model experiments that the scale formed on the surface of stainless steel (SUS-316) at temperatures higher than 250°C. The amount of scale formed was found to depend on the reaction temperature, the exposure time and the sulfur content of the catalyst. The scale formed in the continuous reactor collected on the walls of the tube, preheater and reactor. It was found that the scale was derived from two sources, the coal paste (catalyst, inorganic components in coal and unreacted coal) and the sulfidation of reactor materials.     

Hydrogenation of heavy liquids from a direct coal liquefaction residue for improved oil yield

For hydrogenation of heavy liquids in direct coal liquefaction residue (DCLR) within the direct coal liquefaction (DCL) process, heavy liquids in a DCLR derived from a bench-scale Shenhua DCL process using Shenhua coal are evaluated under two conditions. One simulates the coal liquefaction conditions of the Shenhua plant in the presence of a Fe-based Shenhua catalyst; the other one simulates the online hydrotreating conditions in the presence of a NiMo/Al₂O₃ catalyst. The results show that the heavy liquids of DCLR can be hydrogenated under these two conditions yielding less heavy products; hydrogenating the heavy liquids under the online hydrotreating conditions is more effective than that under the coal liquefaction conditions; the preasphaltene fraction is a main problem that yields non-soluble materials under these hydrogenation conditions. The results suggest that hydrogenation of toluene soluble and tetrahydrofuran soluble fractions of the DCLR under the coal liquefaction and online hydrotreating conditions is feasible, but their conversion to lighter products are inapparent under the coal liquefaction conditions, and elimination of the formation of tetrahydrofuran insoluble fraction in the online hydrotreator should be considered.     

Prediction of coal liquefaction reactivity by solid state 13C NMR spectral data

A method for the deconvolution of ¹³C NMR spectra of coals has been developed by using coal-like model compounds and various lithotypes separated from Yallourn brown coal which is rich in various types of oxygen-functional groups. The spectrum of coal was resolved into 24 peaks which were classified into nine types of carbon-functional group. This analytical method can be applied to all ranks of coal from lignite to anthracite. In addition, the liquefaction data of seven kinds of coal collected from five different countries were obtained by the operation of 1 t/d process support unit and 150 t/d pilot plant NEDOL process liquefaction plants. A good correlation was obtained for every reaction product between structural data derived from solid state ¹³C NMR spectra and liquefaction data of coals. This means that the yields of liquefaction products could be predicted from ¹³C NMR spectral data of coal.