煤基燃料油品特性与煤制油产业发展分析

基于最新汽油、柴油和航煤质量标准,结合我国市场对成品油需求走向,本文探讨了煤直接液化油、煤间接液化油、加氢煤焦油、煤油共炼产品、甲醇制汽油（MTG汽油）和聚甲氧基二甲醚（DMM_n）等煤基油品的馏分结构与性质,分析了它们对煤制油产业发展的影响。文章指出国家绿色可持续发展需要低硫、低烯烃、低芳烃和高抗爆性能的交通运输燃料,需要降低柴汽比,增产航空煤油。煤基油品的硫氮等有害物质含量低、清洁性很好。除了MTG汽油外,煤基油品的柴汽比过高,需要与石油产品协同发展以满足我国未来的成品油市场需求。费托合成工艺能够直接生产优质柴油和航空喷气燃料油组分,是煤制油产业发展的主要技术路线;煤直接液化工艺所产汽煤柴油馏分性质均不理想,需要持续改进提高;煤油共炼工艺在成品油质量方面弥补了煤直接液化工艺的不足,可作为一条新的煤制油途径。煤焦油加氢可以生产出质量指标达到或接近国Ⅵ标准的车用柴油调和组分,是一条高效利用煤炭加工过程副产品的煤制油技术路线。MTG汽油和DMM_n是优质汽油和柴油组分,能改善炼油企业成品油的柴汽比结构和交通运输燃料产品质量,应加大低成本工艺技术研发、扩大产能。     

煤直接液化油加氢改质生产清洁燃料研究

采用RGC-1/RNC-2/RCC-1催化剂组合,以煤直接液化油品为原料,在100万t/a加氢改质装置上进行加氢改质研究。结果表明,煤直接液化油的性质得到明显改善,绝大部分不饱和烃加氢饱和,加氢精制段对改善油品质量起主要作用,原料油中的S、N、O等几乎全部脱除;其柴油馏分S、N含量很低,凝点和冷滤点均低于-27℃,十六烷值约43,是国Ⅴ低凝点柴油的优质调和组分;石脑油馏分的S、N含量均小于1μg/g,芳潜含量高达68.8%,是优质的催化重整原料。     

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高速高、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作的0^#柴油,经过重整可得到合格的90^#无铅汽油。     

煤直接液化油航空煤油馏分的性质与组分分析

以煤直接液化油航空煤油馏分为原料,对其进行理化性质、硫/氮化合物分布、烃类组成分布及酚油含量的检测.结果表明,煤直接液化油航空煤油馏分部分指标不符合3号喷气燃料规范要求,如密度偏大、热值偏低、酸值偏高、硫/氮含量偏高和芳烃含量高,但煤直接液化油航空煤油馏分又具有高闪点、低冰点和富含环烷烃等突出优点.煤直接液化油航空煤油馏分的上述特性将使其通过加氢精制的方法获得合格的大比重喷气燃料.实验通过碱洗酸提方法富集酚,测得煤直接液化油航空煤油馏分中酚油约占26%左右,低级酚含量约占总酚量的72%.     

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．     

煤液化粗油提质加工工艺开发现状

评述了世界上最新的煤液化粗油提质加工工艺和催化剂。在这些工艺中，德国ＩＧＯＲ的技术水平最高。通常用在石油加氢裂化工艺中的商品催化剂也适用于煤液化粗油的提质加工，但由于煤液化粗油与石油在组成和性质上有差别，常需要做一些改进。     

分析技术在煤液化油分析中的应用

利用现代化分析仪器,如色谱、质谱、核磁共振等,对煤液化油的组成和结构进行分析,可以获得比较满意的分析结果。这不仅可以指导煤液化油的合理利用,优化煤液化油提质加氢工艺,而且对煤的结构、液化机理的阐明及液化工艺条件的选择等均有重要的意义。     

煤直接液化高附加值环烷基油开发应用

国家能源集团鄂尔多斯煤制油分公司是世界首套百万吨级煤直接液化工业示范装置,煤直接液化柴油环烷烃含量高,以煤直接液化柴油为原料,通过高压催化加氢,降低油品中的芳烃含量,可以成功生产出高附加值的W2-40、W2-60、W2-80、W2-100型轻质白油,提高煤直接液化产品附加值,拓展煤直接液化产业链,有效弥补我国环烷基油资源短缺的问题。     

我国煤直接液化技术的研究与开发

本文对我国煤直接液化技术的研究与开发状况进行了综述,包括煤种液化性能的评价、工艺条件的选择、催化剂的研究、液化油的提质等。对煤直接液化技术在我国的发展前景进行了预测。     

煤直接液化油多环烷烃择形开环及催化剂研究进展

由于煤直接液化柴油组分中直链烷烃含量低、环烷烃含量高,十六烷值偏低,限制了其作为优质柴油使用,而环烷烃选择性开环技术是提高柴油质量的重要手段。介绍了煤直接液化柴油的组成特性,总结了煤直接液化油双环芳烃、三环芳烃及多环烷烃选择性加氢开环的反应机理,阐述了择形开环催化剂氧化物类载体与分子筛类载体、非贵金属活性组分与贵金属活性组分的优缺点,最后展望了多环烷烃选择性开环催化剂的研究方向。     

Short contact-time liquefaction of subbituminous coal: Directions for improving coal conversion

This study was undertaken to find ways to solubilize subbituminous coal in high yield at short contact times. Short contact-time hydroliquefaction runs were carried out in a continuous unit using Belle Ayr subbituminous coal with a solvent rich in hydrogen-donor molecules derived from the Lummus ITSL process, and also with solvents lower in donor concentration derived from the SRC processes. Catalysis by pyrite, molybdenum and supported cobalt-molybdenum was also studied. It was found that pyrite and other hydrogenation catalysts enhanced solubilization and also increased production of distillate oil. Solvent quality seemed to have no effect on the solubilization of Belle Ayr coal. The availability of H₂S also appeared to have no effect. Provided that pyrite was present, reaction could be carried out at severities high enough to give insoluble organic matter yields equivalent to those obtained with bituminous coals (5–10 wt% daf coal). At equivalent levels of solubilization, however, hydrocarbon gas and distillate yields were invariably higher for the subbituminous coal. Implications for two-stage processing of Belle Ayr coal are discussed.     

Oil agglomeration as a pretreatment for coal liquefaction

Laboratory experiments demonstrated that a variety of distillate coal liquefaction recycle oils were satisfactory agents for cleaning Illinois no. 6 bituminous coal by oil agglomeration. Ash rejection up to 41% with 98% organic recovery was attained with conventionally cleaned coal, and ash rejection up to 67% with 90% organic recovery with run-of-mine coal. Agglomerates of > 1 mm average diameter were produced under a variety of conditions. Similar results were obtained in the scaled-up production of 268 kg of agglomerates. Oils with lower hydrogen aromaticities and higher hydrogen contents performed better than more aromatic oils. Fe, Ti and Mg were selectively enriched in the ash of the product coal, while Ca, Si, and Al were selectively rejected. The mineral pyrite was rejected only ≈ 30–40% as extensively as the bulk of the ashforming minerals. The coal cleaned by oil agglomeration performed similarly to the feed coal in batch donor liquefaction tests. In continuous hydroliquefaction tests, run-of-mine coal cleaned by oil agglomeration performed substantially better than coal cleaned to the same ash level by conventional means, because of the selective enrichment of catalytic iron minerals.     

Hydroliquefaction of Sulcis low-rank coal. 1. Conversion to low-sulphur fuel oil

A low-rank Italian coal was subjected to high-pressure and high-temperature hydroliquefaction with and without a hydrogenation catalyst. A low-sulphur oil was produced, showing properties similar to those of a standard fuel oil. The hydroliquefaction product may be used directly either as a fuel or as raw material for petrochemical processes. Sulcis coal displayed particular reactivity towards hydrogen, as shown also by comparison with a widely used North American coal.     

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。     

Coal-oil mixture from a synthetic oil obtained by hydroliquefaction of a South African coal

A coal-oil mixture (COM) was prepared from a South African coal and a synthetic oil derived from the same coal by hydroliquefaction. The settling and rheological properties of this mixture were compared with those of a mixture of the same coal with fuel oil. The synthetic oil mixture showed greater settling stability, comparable with that of a commercial COM containing additives. The increased stability may be related to polar compounds present in the oil and on the coal surface.     

Effects of coal cleaning on the short contact time liquefaction of Illinois No. 6 coal

This study was carried out to determine the effect of coal cleaning by oil agglomeration and sink-float methods on yields from short contact time liquefaction of Illinois No. 6 coal. The runs were made in a continuous unit using SRC-II distillates as process solvent. Measured yields included hydrogen (consumption), hydrocarbon gas, distillate oil, SRC (the pyridine-soluble portion of the residue) and insoluble organic matter, the pyridine-insoluble organic residue. The solubility of product SRC in hexane, toluene and pyridine was also determined. The principal finding was that coal cleaning by density methods reduced the yield of IOM obtained in subsequent liquefaction and this is attributed to the removal of inert components from the feed coal. In addition, cleaning which significantly reduced pyrite content of the feed coal also reduced the yield of distillate oil and tended to give a less soluble SRC during liquefaction. Deep cleaning by gravity methods gave the lowest IOM, but reduced pyrite content to the point where distillate oil was consumed rather than produced. Oil agglomeration reduced total ash to 50% of that in the run-of-mine coal, but left the pyrite level in the coal high. The relevance of these results to two-stage liquefaction is discussed.     

煤的一段加氢液化的催化剂

煤的一段加氢液化使用的催化剂有可弃性催化剂,铁和钼氧化物及溶于水或油的催化剂和浸渍催化剂,其中以Co-Mo/Al_2O_3,Ni-Mo/Al_2O_3和钼酸铵为最广泛;黄铁矿能促进煤向油的转化,但却降低了脱硫率:Fe(OH)3-MoO_3-S在较低和较高温度下都是一种较活泼的催化剂;SnMo混合物明显优于纯SnO_2或无助催化剂的MoO_3/Al_2O_3;硫化的Mo(CO)_6是一种性能很好的煤加氢液化催化剂。     

芴的提取精制研究进展

芴是重要的有机化工原料，多从煤焦油的洗油馏份中提出，也可从葸油中提出。芴的提取精制过程是先间歇蒸馏洗油馏份或蒽油馏份切取芴主馏份，再采用冷却结晶法或溶剂结晶法精制芴主馏份得到芴。     

Solubilization of Illinois bituminous coal: the critical importance of methylene group cleavage

The extent of solubilization of an Illinois bituminous coal achieved by hydroliquefaction at various temperatures with and without catalyst was determined. The coal was also solubilized by treatment in suspension in THF with potassium in the presence of naphthalene. The original coal was also extracted with THF without prior treatment. After removal of solvent the soluble fractions were examined by ¹H n.m.r. spectroscopy. It is concluded that there are two temperature regimes which affect coal conversion: in the 350–400 °C region, hydroliquefaction proceeds principally by ether cleavage; whereas in the 400–450 °C range, hydroliquefaction results in additional cleavage of methylene groups joining aromatic or heteroaromatic units. Comparison of solubilization by hydroliquefaction with solubilization achieved with potassium in THF seems to indicate the initial degradation of coal by both techniques proceeds by ether cleavage and that further degradation is achieved in both cases by attack at the methylene bridge. The n.m.r. studies on hydroliquefaction products indicate that Illinois bituminous coal is structurally quite homogeneous because the product composition is largely independent of the degree of solubilization. Thus, solubilization results from molecular weight degradation rather than from preferential-degradation to different structural units.     

中低温煤焦油蒸馏过程中金属元素的迁移规律

以中低温煤焦油轻油和重油为实验原料,采用常压蒸馏获得170~200℃、200~240℃、240~270℃、270~300℃、300~320℃、320~340℃、340~360℃和360~390℃煤焦油馏分油;利用配有油品加氧制冷进样系统的ICP-OES测定了21种微量元素在馏分油中的含量,考察了不同馏分油中元素的分布情况。研究表明：在原煤焦油中,未发现Ag、Mg、Mo、Na、Ni、Fe、Mn、Cr及Ti元素,含量较高的元素有Sn、P、Al、Pb、Si,其中Sn元素在轻油和重油中的含量分别为11.78μg/g和14.04μg/g;在所有馏分油中,未发现Al、Mo、Fe、Mn、Cr及Ti元素,含量比较高的元素有Si、Sn、Na、Zn、Pb,特别是Si、Na、Sn、Zn、Ni、Pb及B元素可以有效富集于馏分油中。可能的原因是Ca、Fe、Mg、Al等金属以不同的盐类形态存在,在煤焦油脱水及<170℃蒸馏过程中,这些金属盐类会被部分带出,导致其在馏分油中的含量未富集或未检出;通过关联金属元素在馏分油中的分布与其组成的关系,馏分油中元素的分布可能与酚类化合物、杂环化合物和蒸馏温度等相关。酚类化合物及杂环化合物可能与Ag、B、Cu、Mo、Sn、Na、Zn、Ca、Pb等金属形成络合物或卟啉配合物,蒸馏温度一方面可以破坏Sn、Cd、Pb、Zn、Cu、Ca、Pb等元素在馏分油中的结合力,另一方面也可以促进这些元素与馏分油中的含氧、含氮等化合物更好地发生化合反应,进而影响金属元素在馏分油中的含量分布。