中温煤焦油与新疆黑山煤共处理的研究

在0.5L搅拌式高压釜上开展了中温煤焦油与新疆黑山煤共处理的实验研究,考察了中温煤焦油添加量对新疆黑山煤制浆性能和液化结果的影响,探索中温煤焦油加工利用新途径.结果表明,添加中温煤焦油增加了油煤浆输送时的黏度,在油煤浆浓度为42%时,中温煤焦油添加量不高于18%.与新疆黑山煤单独液化相比,中温煤焦油与新疆黑山煤共处理具有氢耗、气产率、转化率和油产率高的特点;添加适量的中温煤焦油对新疆黑山煤液化具有正协同效应,添加量大于20%时反而对煤转化不利;最佳添加量为5%,与煤单独处理的结果相比,转化率高1.6%,油产率高1.1%;添加量大于20%时,油收率下降.因此,添加适量的中温煤焦油与新疆黑山煤共处理,既可提高煤的转化率和油收率,又可加工利用中温煤焦油,提高煤直接液化的经济效益.     

秸秆与兖州煤共液化反应条件的研究

在高压反应釜内,以四氢萘为供氢溶剂,Fe2O3＋S为催化剂,研究了温度、反应时间、初始氢压、配比对兖州煤与秸秆共液化的影响。结果表明,提高反应温度,转化率、油产率增加;延长反应时间对转化率、油产率的影响较小;升高初始氢压,转化率、油产率刚开始增加,6 MPa以后增幅趋缓;在m（秸秆）∶m（兖州煤）=0.5∶9.5时,共液化的油产率为60.45%,比兖州煤单独液化的油产率提高了4.17%;在m（兖州煤）∶m（秸秆）=9.5∶0.5,440℃,8 MPa,90 min的条件下,共液化转化率和油产率达到最大,分别为83.58%和63.1%。     

甘肃省发展煤液化的前景分析

煤炭液化工艺技术已发展成熟,投入商业化是今后的发展方向;从社会效益与经济效益分析,煤炭液化前景看好;甘肃省适宜液化的煤炭资源较丰富,大有煤与天祝煤配煤液化油产率极高,进行产业化开发十分必要。     

煤直接液化工艺技术的发展

<正> 一、前言 1980年以来,煤直接液化工艺发展的主要方向是由煤制取液体运输燃料油,提高馏分油产率和质量以及氢的利用率,其目的是降低生产成本,改善煤直接液化的经济性。在美国和加拿大政府资助下,经过近十年的基础研究和工艺试验,开发出两段煤直接液化和煤油共炼工艺技术。现在煤直接液化的粗油生产成本已降到38.75美元/桶(相当于原油价格32.9美元/桶),煤油共炼工艺生产的液化油成本为25～30美元/桶。预计,若将现有各种技术成果应用于工业生产,煤液化油成本还可以下降16％。美国能源部根据实际可能性,提出在1995年由煤直接液化生产的     

新疆淖毛湖煤直接液化反应行为研究

为研究新疆淖毛湖煤直接液化反应特性和产品分布规律,在0.5 L间歇式高压釜中,以四氢萘为溶剂,纳米氧化铁为催化剂及S为助剂,考察了不同反应温度、反应时间条件对煤转化率和液化产物收率的影响。结果表明:淖毛湖煤易液化,在反应器温度刚加热到425℃时,煤转化率和液化油收率已分别达到96.6%、56.68%;随着反应温度的升高以及反应时间的延长,煤转化率、氢耗、气体产率、油收率逐渐增加,而沥青类物质产率下降,水产率基本保持不变;当反应温度进一步增加以及反应时间继续延长,轻质油将会发生裂解,导致气体产率进一步增加,而油收率有所降低。当反应温度为455℃、反应时间为80 min时,煤转化率达到99.6%,油、沥青和气体收率分别为73.42%、1.64%、16.61%,氢耗为4.85%。基于液化试验结果,建立了5集总的反应动力学模型,采用优化算法获得动力学模型参数,煤转化率、沥青类物质和油气收率的模拟值和试验值的相对误差分别为0.5%、1.0%、8.0%。     

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.     

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.     

超声波辐射下溶胀改善煤液化性能的研究

以山东兖州局的北宿煤 ( BS)、兴隆庄煤 ( XLZ)、枣庄局的柴里煤 ( CL)等为研究用煤 ,首先在自然条件下使用吡啶溶剂进行原煤样的溶胀 ,然后利用超声波仪 ,在 40 k Hz和 5 0 0 W辐射功率和室温的条件下 ,进行超声波辐射作用下的吡啶溶剂溶胀 .经过对脱除溶剂后溶胀煤的加氢液化实验、低温干馏焦油产率测定、挥发分产率测定及体积溶胀率的测定 ,结果表明该三种原煤具有良好的可溶胀性能 ,溶胀煤均具有良好的加氢液化性能 .在 H2 冷态压力 8.2 MPa,40 0℃ ,Fe SO4·7H2 O和升华 S作催化剂、反应 1 .5 h的液化实验条件下 ,自然溶胀煤的液化油产率比原煤增加 1 2%～ 2 5 % ,北宿溶胀煤的液化油产率达到 69.76% .辐射溶胀后的溶胀煤与自然溶胀煤比较 ,在如上所述同样的液化条件下 ,兴隆庄煤的液化油产率增加了 2 2 % ,并且煤的总转化率也增加了 .实验数据表明 ,对于以提高煤加氢液化反应活性为目的的研究 ,当超声波辐射的频率和功率一定时 ,辐射时间对于改善煤样加氢液化的性能存在着最适宜值 ,这一最适宜值与煤的变质程度有直接关系 .     

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。     

煤直接液化油中硫氮化合物的类型分布

为研究煤直接液化油中硫氮化合物的类型分布,根据煤直接液化油的特点,采用GC-PFPD和GC-NCD方法分别优化煤直接液化油中硫氮化合物的分析条件,获得了煤直接液化油中硫、氮化合物的组成及含量。结果表明,煤直接液化油中硫主要以苯并噻吩类和二苯并噻吩类化合物存在,两者占原料油中总硫含量的90%以上,是煤直接液化油加工脱硫的主要对象;煤直接液化油中氮主要以五元杂环含氮化合物形式存在,占比32%,主要代表物质是吲哚类和咔唑类化合物,两者占原料中总氮含量的50%左右,是煤直接液化油加工脱氮的主要对象。     

煤炭直接液化技术研究

我国煤炭直接液化技术研究已达到国际先进水平．兖州、天祝、神府烟煤和先锋．沈北、东胜褐煤都是较好的直接液化原料煤。煤直接液化的馏分油最适宜生产高辛烷值汽油、优质喷气燃料和催化重整制取芳烃原料油．两段催化液化由1t无水无灰煤生产5bb1馏分油．煤油共炼与直接液化相比较，简化了工艺过程，改进了馏分油产率和质量。我国煤直接工艺发展方向是煤油共炼或两段催化液化工艺。     

溶胀煤制备及煤加氢液化性能的研究

在自然和微波条件下,对五彩湾煤进行溶胀处理,进行煤质、电镜、热解、煤的结构-化学指数分类、加氢液化产率和液化残渣热解的分析。实验结果表明:五彩湾煤自然溶胀煤样和微波溶胀煤样的层状和裂纹显著增加,失重量明显增大。煤加氢液化测试结果表明,在氢初压6.0 MPa、溶煤比1.75:1、反应温度450℃和反应时间60 min条件下,气产率由原煤的9.7%,降低到两种溶胀煤均在3.4%左右;油产率由原煤的55.2%,提高到自然溶胀煤的70.1%和微波溶胀煤的74.0%;转化率由原煤的76.8%,增加到自然溶胀煤的82.1%和微波溶胀煤的84.8%。可见,经过溶胀处理,煤加氢液化效果显著。     

Study on coal liquefaction characteristics of Chinese coals

The New Energy and Industrial Technology Development Organization (NEDO) has implemented the collaborative research work with China Coal Research Institute (CCRI) on the liquefaction of Chinese coals for about 20 years. A total of 53 runs in a 0.1 t/d bench scale coal liquefaction plant installed at the CCRI were made on 27 kinds of coal selected among coals existing throughout China. The bench plant was operated in a direct hydrogenation (DH) mode and NEDOL mode. In the DH mode, 25 MPa of reaction pressure was employed with decrystallized anthracene oil used as the solvent, while 17 MPa of reaction pressure was employed and hydrogenated solvent was used in the NEDOL mode. This study confirmed that the NEDOL mode, which uses comparatively mild in liquefaction conditions, can liquefy each coal with the high oil yield more efficiently, and is capable of liquefying about 60% of inertinite in high inertinite coals.     

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。     

Effects of solvent and iron-compounds on the liquefaction of brown coal

Hydrogen-donor solvents such as hydrophenanthrene are the most effective aromatic solvents for the liquefaction of brown coal. The hydrogen-donating ability of the solvent is more important for brown coals than for bituminous coals, because the thermal decomposition and subsequent recombination of the structure of the brown coals occurs rapidly. Three-ring aromatic hydrocarbons are more effective solvents than two-ring aromatics, and polar compounds are less effective solvents with brown coals than with bituminous coals. The thermal treatment of brown coal, accompanied by carbon dioxide evolution at temperatures > 300°C, in the presence of hydrogen-donating solvent did not affect the subsequent liquefaction reaction. However, thermal treatment in the absence of solvent strongly suppressed the liquefaction reaction, suggesting that the carbonization reaction occurred after the decarboxylation reaction in the absence of hydrogen donor. To study the effect of various iron compounds, brown coal and its THF-soluble fraction were hydrogenated at 450°C in the presence of ferrocene or iron oxide. The conversion of coal and the yield of degradation products are increased by the addition of the iron compounds, particularly ferrocene, and the yield of carbonaceous materials is decreased.     

依兰煤液化过程中天然矿物催化剂影响的研究

研究了黑龙江依兰煤在加氢液化反应过程中,4种天然含铁矿物的液化催化活性.试验结果表明,黑龙江西林铅锌矿的黄铁矿在依兰煤的加氢液化过程中,催化活性最高,萃取油收率达到68%,蒸馏油收率达到58%.     

Solvolytic liquefaction of coals with a series of solvents

Solvolytic liquefaction of coals of different rank was studied with a variety of solvents at 370–390 °C under nitrogen in order to elucidate the role of solvent in coal liquefaction of this kind and to find a suitable solvent for the highest yields of liquefaction. The yield was found to depend strongly upon the nature of the coal as well as the solvent under these conditions. Pyrene and a SRC-BS pitch were excellent solvents for Miike coal, which was fusible with high fluidity at these temperatures. However, the former was less efficient for Itmann and Taiheiyō coals which were fusible at a higher temperature and non-fusible, respectively. The mechanism of solvolytic liquefaction is discussed, including nature of coal and solvent at reaction temperatures, in order to understand the properties required for high yields with non-fusible coals in solvolytic liquefaction. It is found that for liquefaction with a high yield if the coal is non-fusible, solvolytic reaction should take place between solvent and coal, so giving a liquid phase of low viscosity at the reaction temperature. The solvolytic reaction may be one of hydrogen transfer when SRC-BS is used as the solvent.     

Hydrogen transferring liquefaction of some bituminous coals with hydrogenated fluoranthene under high temperature-short contact time conditions

Hydrogen transferring liquefaction using hydrogenated fluoranthene at high temperatures was very effective for three Japanese bituminous coals, with a total yield of oil and asphaltene > 85 wt%. The high temperature-short contact time conditions (480 °C for 10 min or 510 °C for 2.5 min) resulted in a total yield of > 90 wt% from the coal of lowest rank, with low consumption of hydrogenated fluoranthene. The oil yields were as high as 75 and 68 wt% at 480 °C and 510 °C, respectively. In contrast, the lower temperature of 450 °C appeared more effective in diminishing preasphaltene formation with the highest rank coal providing oil and asphaltene yields of 47 and 38 wt%, respectively. Longer times or higher temperature increased the oil yield but without reducing the preasphaltene. Higher temperature was found favourable for the formation of asphaltene of lower molecular weight. The reactivity of butiminous coals of different rank is discussed from the viewpoint of their structure.     

Effect of pre-swelling of coal on its solvent extraction and liquefaction properties

Effects of pre-swelling of coal on solvent extraction and liquefaction properties were studied with Shenhua coal. It was found that pre-swelling treatments of the coal in three solvents, i.e., toluene (TOL), N-methyl-2-pyrrolidinone (NMP) and tetralin (THN) increased its extraction yield and liquefaction conversion, and differed the liquefied product distributions. The pre-swollen coals after removing the swelling solvents showed increased conversion in liquefaction compared with that of the swollen coals in the presence of swelling solvents. It was also found that the yields of (oil + gas) in liquefaction of the pre-swollen coals with NMP and TOL dramatically decreased in the presence of swelling solvent. TG and FTIR analyses of the raw coal, the swollen coals and the liquefied products were carried out in order to investigate the mechanism governing the effects of pre-swelling treatment on coal extraction and liquefaction. The results showed that the swelling pre-treatment could disrupt some non-covalent interactions of the coal molecules, relax its network structure and loosened the coal structure. It would thus benefit diffusion of a hydrogen donor solvent into the coal structure during liquefaction, and also enhance the hydrogen donating ability of the hydrogen-rich species derived from the coal.