Production of High-Density Jet and Diesel Fuels by Hydrogenation of Highly Aromatic Fractions

Physicochemical characteristics and hydrocarbon composition of highly aromatic wastes (light gas oil from catalytic cracking, pyrolysis tar, coal tar, coal gasification tar) as a feedstock for producing high-density jet fuels are considered. The hydrogenation reactions of polycyclic aromatic hydrocarbons, including mixtures of hydrocarbons with different numbers of rings, are described. Catalysts for hydrogenation of highly aromatic waste to obtain fuel fractions are considered. Particular attention is paid to catalyst deactivation in the course of processing of this feedstock. A separate section deals with the choice and implementation of procedures for processing highly aromatic feedstock to obtain jet and diesel fuels.     

Production of Oil by Hydrogenation of Coal

A survey of coal hydrogenation processes revealed that, despite a wealth of experience gathered in Germany up to 1945 some of which served as a basis for further work in the USA, there is at present no process available anywhere in the world for the commercial production of oil from coal. Approaches suitable for further development are the noncatalytic one-step limited hydrogenation and catalytic hydrogenation. Under the most favorable conditions production of oil from coal should become technically feasible some time between the early and mid-1980's. In view of the price of heavy fuel oil the commercial prerequisites for production of synthetic fuel oil from coal are presumably fulfilled only in those countries with low coal prices.     

神府煤与胜利减压渣油共处理反应特性的研究

用共振搅拌反应器研究了神府煤与胜利减压渣油共处理液化的过程,在430 ℃、460 ℃、490 ℃;3 min～18 min,考察了煤的转化率。结果表明,煤油共处理的最佳反应温度为460 ℃,最佳反应时间为15 min,最高转化率为48.56％,反应过程可分为三个阶段：快速裂解加氢阶段、慢速裂解加氢阶段和缩聚反应阶段。采取了胜利减压渣油加氢处理、添加蒽油、煤油共处理三种措施所得苯可溶物作溶剂,结果表明,胜利减压渣油∶蒽＝1∶1作供氢溶剂时煤转化率有较大提高,达到54.11％;加氢处理后的胜利减压渣油供氢效果也不佳;用煤油共处理所得苯可溶物作供氢溶剂在460 ℃、 6 min时达最高转化率 65.33％。     

From Solar Energy to Fuels: Recent Advances in Light‐Driven C1 Chemistry

Catalytic C₁ chemistry based on the activation/conversion of synthesis gas (CO+H₂), methane, carbon dioxide, and methanol offers great potential for the sustainable development of hydrocarbon fuels to replace oil, coal, and natural gas. Traditional thermal catalytic processes used for C₁ transformations require high temperatures and pressures, thereby carrying a significant carbon footprint. In comparison, solar‐driven C₁ catalysis offers a greener and more sustainable pathway for manufacturing fuels and other commodity chemicals, although conversion efficiencies are currently too low to justify industry investment. In this Review, we highlight recent advances and milestones in light‐driven C₁ chemistry, including solar Fischer–Tropsch synthesis, the water‐gas‐shift reaction, CO₂ hydrogenation, as well as methane and methanol conversion reactions. Particular emphasis is placed on the rational design of catalysts, structure–reactivity relationships, as well as reaction mechanisms. Strategies for scaling up solar‐driven C₁ processes are also discussed.     

氢气压力对煤加氢反应影响的热重-气相色谱实验研究

采用加压热重分析仪和气相色谱仪联用的方法研究了府谷烟煤和海拉尔褐煤加氢反应过程中的失重规律和主要气体产物析出规律,升温速率15℃/min,压力0.1~5.0MPa,反应终温1000℃。实验结果表明,煤粉加氢反应主要分为初始干燥脱气、热分解及挥发分加氢,半焦加氢气化和焦炭加氢气化四个阶段。氢气压力的提高促进了挥发分自由基的加氢反应,抑制了含氧官能团脱除形成碳氧化物。在热分解及挥发分加氢阶段,府谷烟煤失重速率随氢气压力的升高而减小,氢气压力对海拉尔褐煤失重速率的影响不大。在半焦加氢气化阶段,CH₄生成速率随氢气压力的升高而增大,当氢气压力较高时(3~5MPa),海拉尔褐煤CH₄生成速率随氢气压力的升高不再增大。海拉尔褐煤O_daf较高,其半焦中含氧官能团提供的活性位较多。府谷烟煤H/C原子比较高,能提供更多的内部氢。府谷烟煤和海拉尔褐煤焦炭加氢反应动力学参数分别为k₀=2.38×10⁷ (min^-1·MPa^-1),E=231kJ/mol,n=1和k₀=2.64×10³ (min^-1·MPa^-0.736),E=127kJ/mol,n=0.736。     

Thermal characteristics of the combustion process of biomass and sewage sludge

The combustion of two kinds of biomass and sewage sludge was studied. The biomass fuels were wood biomass (pellets) and agriculture biomass (oat). The sewage sludge came from waste water treatment plant. The biomass and sludge percentage in blends with coal were 10 %. The studied materials were characterised in terms of their proximate and ultimate analysis and calorific value. The composition of the ash of the studied fuels was also carried out. The behaviour of studied fuels was investigated by thermogravimetric analysis (TG, DTG and DTA). The samples were heated from an ambient temperature up to 1,000 °C at a constant three rates: 10, 40 and 100 °C min^?1 in 40 mL min^?1 air flow. TG, DTG and DTA analysis showed differences between coal, biomass fuels and sewage sludge. 10 % addition of studied fuels to the mixture with coal changed its combustion profile in the case of sewage sludge addition. The combustion characteristics of fuel mixtures showed, respectively, qualitative summarise behaviour based on single fuels. Evolved gaseous products from the decomposition of studied samples were identified. This study showed that thermogravimetric analysis connected with mass spectrometry is useful techniques to investigate the combustion and co-combustion of biomass fuels, and sewage sludge, together with coal. Non-isothermal kinetic analysis was used to evaluate the Arrhenius activation energy and the pre-exponential factor. The kinetic parameters were calculated using Kissinger–Akahira–Sunose model.     

煤化工工艺技术评述与展望Ⅳ．煤间接液化技术

评述了国内外煤间接液化合成液体燃料开发趋势和工业化状况,从催化剂研制,F－T合成反应器开发,合成油工艺路线,工艺软件开发,工艺集成优化和技术经济分析等方面进行了讨论,指出发展洁净高效煤基合成液体燃料工业过程是解决我国燃油短缺的根本途径,并对我国煤制油工业化开发工作和示范厂建立提出一些建议和展望。     

合成高密度烃类燃料研究进展

本文对合成高密度烃类燃料的进展进行了总结,分别对多环烃类燃料、高张力笼状烃类燃料和添加纳米级微粒的燃料进行了评述.以烃类物质为原料,通过聚合、加氢、异构等工艺合成的多环高密度燃料拥有较高的能量密度和较佳的稳定性能,是目前高密度燃 料的发展重点.高张力笼状烃类燃料和添加纳米级微粒的燃料拥有更大的密度(一般大于1g/ cm3)和燃烧热值,是极具发展前景的新一代燃料。     

Ash-free coal as fuel for direct carbon fuel cell

This work describes the performance of the direct carbon fuel cell (DCFC) fuelled by ash-free coal. Employing coal in the DCFC might be problematic, mainly because of the ash deposition after the cell reactions. In the study, the carbonaceous ash-free component of coal is obtained, which is then evaluated as the DCFC fuel and compared with raw coal, active carbon, carbon black, and graphite. The electrolyte-supported SOFC structure is adapted to build the DCFC. The DCFC based on the ash-free coal fuel exhibits good performance with regard to the maximum power density, day-by-day measurements, and durability at continuous run. When the carbon fuels are internally gasified to H₂ and CO, the power density is generally much improved, compared to N₂ pyrolysis environment. The power generation is most likely related to the concentration of pyrolyzed gases as well as the electrochemical reactivity of the solid carbon.     

灰污热流探针模拟锅炉受热面灰沉积的研究

基于傅里叶导热定律,设计了一简单实用的灰污热流探针,以神木煤、黄陵煤、新汶水煤浆和新汶黑液水煤浆为研究对象,在0.25MW热态实验炉上用灰污热流探针模拟了灰沉积过程,研究了四种燃料灰沉积过程中的热流变化特性和灰沉积机理。结果表明,灰污探针能很好地模拟不同燃料的灰污形成过程,模拟结果与实际情况相吻合;灰粒的沉积速率和吸收热流的衰减速率主要取决于燃料本身特性,同时也受烟气温度的影响;通过对探针上灰污的表观物理特性、微观结构、元素构成和矿物相的分析,发现四种燃料的灰沉积机理是不同的,黑液水煤浆灰污中Na、K含量较高,主要物相为熔融温度很低的富Na霞石和无水芒硝,黄陵煤灰污含有较高的Fe、Ca、S,而水煤浆燃烧时Fe的沉积和富集是灰污形成的主要因素;四种实验燃料中,黑液水煤浆和黄陵煤的结渣趋势强于神木煤和水煤浆。     

铁基催化剂在COx加氢制高附加值烃反应中的应用

化石燃料的广泛使用导致大气中CO₂的排放量急剧增加,进而引起全球变暖和海洋酸化等一系列问题.CO加氢(费托合成)反应是利用非石油来源的原料生产液体燃料和化学品的一种重要途径.同时,利用可再生的H₂将CO₂转化为高附加值的产品有利于减少对化石燃料的依赖,减轻由于大气中CO₂浓度过高带来的负面影响.开发新型、高效、稳定的催化剂是费托合成和CO₂加氢制高附加值烃的关键因素之一.Fe基、Co基和Ru基催化剂是费托合成中常用的催化剂.而在CO₂加氢反应中,Co基和Ru基催化剂上主要发生甲烷化反应,几乎没有长链烃生成.Fe基催化剂在费托合成和CO₂加氢反应中均表现出优异的催化生成长链烃性能.同时,Fe储量丰富和价格便宜的特点也促进Fe基催化剂在两个反应中的广泛应用.一般认为,在Fe基催化剂上CO₂通过逆水煤气变换反应生成CO,CO通过费托合成反应继续加氢生成烃类.因此,CO₂加氢反应和费托合成反应有相似之处,同时也有较大的区别.本文从活性相、助剂和载体的角度综述了各组分在Fe基催化剂催化CO/CO₂加氢反应中的作用,总结了其中的区别与联系.催化剂在反应中会发生复杂的相变过程,形成多种铁物种;其中,碳化铁(χ-Fe₅C₂,ε-Fe₂C,Fe₇C₃和θ-Fe₃C)在费托合成反应中是C-C偶联的活性相,但对于θ-Fe₃C现还存在一些争议.在CO₂加氢反应中Fe₃O₄催化逆水煤气变换反应,碳化铁催化CO加氢反应.金属助剂对CO/CO₂加氢反应的促进作用较为相似,在两个反应中碱金属的促进作用最为明显.费托合成反应对载体有较强的适应性,而CO₂加氢反应对载体敏感性较强,Al₂O₃,ZrO₂和碳材料载体效果较好.本文还总结了近些年来基于对活性相、助剂和载体的深入理解设计制备的一些新型催化剂及其在费托合成和CO₂加氢反应中的应用,包括具有新颖结构的催化剂、金属-有机骨架衍生催化剂以及与沸石分子筛结合的双功能催化剂.最后,还分析了目前Fe基催化剂在费托合成和CO₂加氢反应应用中所面临的问题和挑战,并对未来的发展趋势进行了展望.     

铁基催化剂在COx加氢制高附加值烃反应中的应用

化石燃料的广泛使用导致大气中CO₂的排放量急剧增加,进而引起全球变暖和海洋酸化等一系列问题.CO加氢(费托合成)反应是利用非石油来源的原料生产液体燃料和化学品的一种重要途径.同时,利用可再生的H₂将CO₂转化为高附加值的产品有利于减少对化石燃料的依赖,减轻由于大气中CO₂浓度过高带来的负面影响.开发新型、高效、稳定的催化剂是费托合成和CO₂加氢制高附加值烃的关键因素之一.Fe基、Co基和Ru基催化剂是费托合成中常用的催化剂.而在CO₂加氢反应中,Co基和Ru基催化剂上主要发生甲烷化反应,几乎没有长链烃生成.Fe基催化剂在费托合成和CO₂加氢反应中均表现出优异的催化生成长链烃性能.同时,Fe储量丰富和价格便宜的特点也促进Fe基催化剂在两个反应中的广泛应用.一般认为,在Fe基催化剂上CO₂通过逆水煤气变换反应生成CO,CO通过费托合成反应继续加氢生成烃类.因此,CO₂加氢反应和费托合成反应有相似之处,同时也有较大的区别.本文从活性相、助剂和载体的角度综述了各组分在Fe基催化剂催化CO/CO₂加氢反应中的作用,总结了其中的区别与联系.催化剂在反应中会发生复杂的相变过程,形成多种铁物种;其中,碳化铁(χ-Fe₅C₂,ε-Fe₂C,Fe₇C₃和θ-Fe₃C)在费托合成反应中是C-C偶联的活性相,但对于θ-Fe₃C现还存在一些争议.在CO₂加氢反应中Fe₃O₄催化逆水煤气变换反应,碳化铁催化CO加氢反应.金属助剂对CO/CO₂加氢反应的促进作用较为相似,在两个反应中碱金属的促进作用最为明显.费托合成反应对载体有较强的适应性,而CO₂加氢反应对载体敏感性较强,Al₂O₃,ZrO₂和碳材料载体效果较好.本文还总结了近些年来基于对活性相、助剂和载体的深入理解设计制备的一些新型催化剂及其在费托合成和CO₂加氢反应中的应用,包括具有新颖结构的催化剂、金属-有机骨架衍生催化剂以及与沸石分子筛结合的双功能催化剂.最后,还分析了目前Fe基催化剂在费托合成和CO₂加氢反应应用中所面临的问题和挑战,并对未来的发展趋势进行了展望.     

Hydrogen-transfer conversion of furfural into levulinate esters as potential biofuel feedstock

Furfural is directly converted to levulinate esters(isopropyl levulinate and furan-2-ylmethyl-levulinate) as potential biofuel feedstocks, through a combined catalytic strategy. Nb_2O_5-ZrO_2 mixed oxide microspheres are used as bifunctional catalysts for hydrogen-transfer hydrogenation and acid-catalyzed alcoholysis in isopropanol. Bifunctional catalysts improve sustainability of furfural conversion through process intensification. Hydrogen transfer hydrogenation from isopropanol avoids dangerous hydrogen gas, and abates process and environmental costs. Isopropyl levulinate and furan-2-ylmethyl-levulinate are the main products that can be applied as blending components in biodiesel or hydrocarbon fuels.     

Catalytic conversion of lignocellulosic biomass to fine chemicals and fuels

Lignocellulosic biomass is the most abundant and bio-renewable resource with great potential for sustainable production of chemicals and fuels. This critical review provides insights into the state-of the-art accomplishments in the chemocatalytic technologies to generate fuels and value-added chemicals from lignocellulosic biomass, with an emphasis on its major component, cellulose. Catalytic hydrolysis, solvolysis, liquefaction, pyrolysis, gasification, hydrogenolysis and hydrogenation are the major processes presently studied. Regarding catalytic hydrolysis, the acid catalysts cover inorganic or organic acids and various solid acids such as sulfonated carbon, zeolites, heteropolyacids and oxides. Liquefaction and fast pyrolysis of cellulose are primarily conducted over catalysts with proper acidity/basicity. Gasification is typically conducted over supported noble metal catalysts. Reaction conditions, solvents and catalysts are the prime factors that affect the yield and composition of the target products. Most of processes yield a complex mixture, leading to problematic upgrading and separation. An emerging technique is to integrate hydrolysis, liquefaction or pyrolysis with hydrogenation over multifunctional solid catalysts to convert lignocellulosic biomass to value-added fine chemicals and bio-hydrocarbon fuels. And the promising catalysts might be supported transition metal catalysts and zeolite-related materials. There still exist technological barriers that need to be overcome (229 references).     

金属-有机骨架衍生催化剂在二氧化碳加氢和费托合成反应中的应用

CO₂加氢和费托合成反应是C1化学中重要的研究领域,CO₂加氢制备高附加值化学品和燃料有助于降低大气中CO₂浓度,减轻化石燃料消耗的压力;费托合成反应是以非石油资源为原料生产液体燃料和化学品的重要路径。 开发新型、高效、稳定的催化剂是CO₂加氢和费托合成反应的关键点之一。 利用金属-有机骨架(Metal-Organic Frameworks,MOFs)材料的特点制备的MOFs衍生催化剂在CO₂加氢和费托合成反应中具有较好的应用前景。 本文综述了CO₂加氢和费托合成反应中MOFs衍生催化剂的制备方法,以及催化剂在各反应中的催化性能,并对目前所存在的问题以及今后的发展进行了总结和展望。     

Thermal reactions of polyethylene with coal (TG/DSC approach)

Thermal reactions of polyethylene with coal were studied. Coal used exhibited an endothermal effect in the temperature range of 425-495°C with a flat maximum (about 460°C). In contrast, polyethylene alone was decomposed in the temperature range of 420-540°C (mainly of 485-540°C) with the significant DSC maximum at 510°C. In the presence of coal this maximum shifted to lower temperature (483°C), therefore, coal promoted the decomposition of polyethylene. As decomposition of polyethylene yields alkenes and alkadienes, the thermal reaction of polyethylene with coal under low temperature conditions can be described as two-stage process in which the first stage includes the decomposition of polyethylene giving unsaturated hydrocarbons and the second stage adsorption and hydrogenation of these products (mainly by coal hydrogen) on the inner surfaces of semicoke and coal.     

面向CO2电化学转化的铜基催化剂研究进展

Burning of fossil fuels increases CO₂ concentration in the atmosphere, resulting in a series of climate- and environment-related concerns such as global warming, sea-level rise, and melting of glaciers. Therefore, utilization of renewable energy to reduce the CO₂ concentration, in order to realize a sustainable development, is urgent. Capturing and utilizing CO₂, a greenhouse gas, can not only address these concerns but also alleviate the current scenario of energy shortage. Thermal catalytic CO₂ hydrogenation offers various pathways with high conversion efficiencies to produce fuels and industrial chemicals including CO, HCOOH, CH₃OH, and CH₄. However, CO₂ is chemically inert due to the highly stable C＝O bond. Thus, harsh reaction conditions such as high temperature and pressure are required for CO₂ hydrogenation.     

Trace impurities in Canadian oil-sands,coals and petroleum products and their fate during extraction,up-grading and combustion

National energy programs for the next two decades entail increased total consumption of fossil fuels in general and, in particular of portable fuels extracted from oil sands and shales and from lower quality coals. Improved fuel-upgrading and combustion technologies are recognized to be vital for minimizing environmental degradation caused by continental and global acid-rain precipitation from fossil-fuel impurities. A further consideration, however, is the fate of those trace-element co-contaminants of acid-rain such as heavy metals, which are present at lower concentrations (10⁻⁴–10⁻⁷) but may also be of environmental significance when 10⁷ to 10⁹ tons·y⁻¹ are utilized on several continents. In this laboratory, INAA procedures have been adapted for the determination of 25–30 trace impurities in a variety of fuels and extracts including: S, V and Al, As, Ba, Br, Ca, Ce, Cl, Co, Cr, Dy, Eu, Fe, Hf, K, La, Mn, Na, Rb, Sb, Sc, Sm, Th, Ti, U. Samples were obtained of typical Canadian pumped crudes, and from several Canadian oil-sands and coal deposits (mostly bituminous and subbituminous) both in their natural states and after stages of extraction and upgrading. Also analyzed were fuels derived from them and the residues resulting from their refining and combustion. InAA of all fossil fuel extracts including light oils, viscous bitumen and such organic fluids could be performed under the same conditions as the parent substances: crude oils, oil-sands and coals, without any special sample preparation. Although no standard samples are routinely required because of the 1–2% long-term flux stability of the reactor, accuracy checks were performed periodically by reference to NBS-1632A standard coal and atomic absorption standard dilute solutions. Results obtained for the NBS coal SRM and the BAM flyash sample (1978) are also given. A wide range of trace impurities determined in the Canadian fossil fuels included some of those which are of particular significance in Canadian coals and their ashes (a STM standard ashing method). The ‘inorganic’ traces can also be grouped according to their fate during static combustion at 750°C. The research reported here was supported with funds from a Natural Sciences and Engineering Research Council of Canada Strategic energy grant (G 0017), 1978–80, “Trace Contaminants of Environmental Importance in Present and Future Fossil Fuels”.     

二氧化碳多相催化加氢制C2及以上烃类和醇的研究进展

通过可再生能源得到的氢气将二氧化碳转化为高附加值的燃料和化学品,对于缓解全球变暖、改善生态环境和解决化石资源日益枯竭的难题具有重要的意义。通过加氢反应合成碳氢化合物,尤其是C₂₊烃类和含氧化合物愈来愈引起大家的研究兴趣。设计制备兼具二氧化碳活化和碳-碳键耦合的多功能催化剂仍然是一较大的挑战。本文总结了二氧化碳加氢合成长链烷烃、低碳烯烃、高级醇的最新研究进展,探讨了二氧化碳加氢所涉及的相关反应的热力学和动力学、反应机理和反应路径,并对现阶段报道的多相催化剂进行了归纳和分析,最后指出未来在二氧化碳加氢的多相催化过程中所面临的问题和发展方向。     

CO2 Hydrogenation Catalyzed by Graphene-Based Materials

In the context of an increased interest in the abatement of CO₂ emissions generated by industrial activities, CO₂ hydrogenation processes show an important potential to be used for the production of valuable compounds (methane, methanol, formic acid, light olefins, aromatics, syngas and/or synthetic fuels), with important benefits for the decarbonization of the energy sector. However, in order to increase the efficiency of the CO₂ hydrogenation processes, the selection of active and selective catalysts is of utmost importance. In this context, the interest in graphene-based materials as catalysts for CO₂ hydrogenation has significantly increased in the last years. The aim of the present paper is to review and discuss the results published until now on graphene-based materials (graphene oxide, reduced graphene oxide, or N-dopped graphenes) used as metal-free catalysts or as catalytic support for the thermocatalytic hydrogenation of CO₂. The reactions discussed in this paper are CO₂ methanation, CO₂ hydrogenation to methanol, CO₂ transformation into formic acid, CO₂ hydrogenation to high hydrocarbons, and syngas production from CO₂. The discussions will focus on the effect of the support on the catalytic process, the involvement of the graphene-based support in the reaction mechanism, or the explanation of the graphene intervention in the hydrogenation process. Most of the papers emphasized the graphene’s role in dispersing and stabilizing the metal and/or oxide nanoparticles or in preventing the metal oxidation, but further investigations are needed to elucidate the actual role of graphenes and to propose reaction mechanisms.