煤催化加氢气化研究进展

煤加氢气化制天然气技术具有工艺路径短、热效率高等优点,其应用基础研究备受关注。但煤中存在部分致密的芳香碳结构,加氢反应性较差,即使在苛刻的反应条件下(~1 000℃、~7 MPa H_2),仍难以转化。通过引入催化剂,进行煤催化加氢气化可在温和的反应条件下实现煤的碳转化率和CH_4收率的同步提高。论述了碱金属(K、Na等)、碱土金属(Ca)和过渡金属(Fe、Co、Ni等)催化剂对模型碳加氢气化的催化作用原理。探讨了反应温度、氢气压力、和碳结构对C-H_2催化反应的影响规律,分析了适用于原煤催化加氢气化的最佳催化剂及工艺条件,并从CH_4和轻质液体焦油等产物生成规律、煤中碳结构随着反应进行的衍变过程等角度,讨论了催化剂分别对煤加氢热解和热解半焦加氢气化的催化作用行为。提出了煤催化加氢气化联产CH_4和轻质液体焦油技术从基础走向应用的进一步研究建议。现有研究结果表明,过渡金属与碱土金属组成的二元催化剂(Fe/Co/Ni-Ca)对煤加氢气化的活性较高。过渡金属元素在反应过程中主要提供C-H_2反应所需的活性氢,并削弱C—C键的键能;碱土金属元素Ca主要促进Fe/Co/Ni的分散,防止其发生硫中毒失活,并增强Fe/Co/Ni与碳之间的相互作用。温度升高一方面为化学键断裂过程提供了更高能量,加速C-H_2反应,另一方面促进催化剂在煤结构中扩散,提升催化剂的供氢和断键效率。升高压力促进了活性氢的供应,同时CH_4浓度得到稀释,反应向生成CH_4的方向移动。以5%Co-1%Ca为催化剂,在850℃、3 MPa H_2反应条件下,30 min内可同时达到90.0%的碳转化率和77.3%的CH_4收率。Co-Ca催化剂在煤加氢热解过程中具有催化解聚和催化加氢的作用,提高焦油和CH_4收率,同时催化剂在煤加氢热解过程中对煤结构产生催化活化作用,使得生成的半焦具有较高的气化活性。煤催化加氢气化的机理研究目前仍处于推测阶段,另外,该技术气化剂、煤种的适应性,催化剂循环利用性能有待进一步阐明。     

氢气在无催化煤液化中的反应机理

采用平衡液相取样法气体溶解度测定装置测定了氢气在萘中的溶解规律,并采用间歇式微型反应釜研究了氢气在无催化煤液化中的反应机理.结果表明:1)氢气在萘中的溶解随着温度和压力的升高而增加,溶解速率先快后慢,在5min时达到最大溶解量的76.21%左右,直到30min达到平衡;2)在萘溶剂的无催化煤液化反应中,氢气的溶解不是控制步骤,溶解氢参与液化反应的速度才是控制步骤;3)在较短时间的萘溶剂无催化煤液化时,氢气在萘溶剂中的预溶解提高了无催化煤液化的总转化率,其主要原因是部分预溶氢提前活化,使得煤液化反应初期活性氢增加;4)在较长时间的萘溶剂无催化煤液化时,预溶氢对总转化率的提高很小,但促进了液化产物的进一步裂解加氢轻质化.     

亚临界H2O-CO体系中CO对褐煤改性增黏的影响

在亚临界H_2O-CO体系中开展了褐煤改性增黏研究,利用气相色谱(GC)、傅立叶变换红外光谱(FTIR)、~(13)C核磁共振(~(13)C-NMR)、热重分析(TG)和电子自旋共振(ESR)等方法,探索了CO对煤黏结性、结构特征和自由基变迁规律的影响,进而认识了CO对煤改性增黏的作用机制。结果表明:在CO初压为4.5 MPa时对褐煤进行改性,褐煤的黏结指数(G_(RI))可由0显著提高至91.35。CO通过水煤气变换反应(WGSR)向体系提供活性氢(H·),提高CO初压促进了H·的生成,有利于H·向煤分子结构内部扩散实现加氢。同时,在CO初压为4.5 MPa时,褐煤中的亚甲基、氧桥键和甲基侧链等会发生断裂,并生成大量自由基,提高了芳香片层的活动性,以促进褐煤中较小的芳香层片重排形成中等分子多环芳烃自由基,这些自由基可被体系中活性氢H·稳定而生成前沥青烯等黏结性物质,从而提高了煤的黏结性。     

循环供氢溶剂在神华煤直接液化工艺中的应用

在神华煤直接液化工艺中,为达到理想的反应深度,煤直接液化反应需要供氢性能良好的循环供氢溶剂、氢气、煤粉及催化剂等原料。其中,经过预加氢处理后的循环溶剂,具有良好的供氢性能,使得煤直接液化反应条件温和。在煤直接液化过程中,溶剂起着溶解煤粒、溶胀分散、稳定自由基、提供和传递转移活性氢、稀释液化产物等作用。当前,提高循环供氢溶剂自身的供氢和传递氢能力是煤直接液化新技术开发的重点之一。     

煤高温快速液化过程中的单原子与双原子氢转移机理

氢转移对煤的加氢液化至关重要,理解氢转移机理对于改善煤液化过程具有重要意义。在微型反应釜中通过考察氢气的溶解、溶剂类型以及不同类型催化剂对煤高温快速液化的影响,揭示了煤高温快速液化过程中单原子氢和双原子氢的转移机理。结果表明,在以四氢萘、氢气为条件的高温快速液化过程中,主要的活性氢来源于溶剂所提供的单原子;在以四氢萘、氮气为条件的高温快速液化过程中,不同催化剂对溶剂提供单原子氢的影响不同。在以四氢萘和萘、氢气为条件的高温快速液化过程中,双原子氢基本未参与液化反应,溶解并不是其参与液化反应的主要影响因素。以萘为溶剂、氢气气氛下的高温快速液化过程中,双原子氢参与反应需要一定的时间。在以萘或四氢萘、氢气为条件的高温快速液化过程中通过加入一定量的催化剂,可以促使双原子氢快速参与反应。     

煤直接液化循环溶剂加氢体系中元素的转化与迁移

为深入解析煤直接液化循环溶剂的加氢反应并进行过程优化,分别以内蒙古褐煤液化粗油和内蒙古长焰煤液化粗油为原料,在固定床连续装置中进行加氢实验,对加氢全流程的物料平衡和元素平衡进行测算,开展了加氢产物及催化加氢性能的分析评价。通过研究碳、氢、氮、硫、氧五大元素在原料和各加氢产物中含量的变化,分析了各元素在加氢过程中的转化与迁移。结果表明:煤液化循环溶剂加氢反应的油产率接近100%(质量分数,下同),气产率仅为0.5%,原料中不足0.2%的碳元素进入有机气体中,80%~90%的氢耗用于芳烃部分加氢饱和反应,原料中约95%的硫元素进入H_2S中,褐煤液化粗油中12.69%的氮以及长焰煤液化粗油中27.49%的氮向氨气迁移,循环溶剂加氢体系中废水产率仅为0.5%,硫化氢和氨气不足1.5%,可与煤炭液化其他单元同类废弃物汇集处理。     

洗选低阶块煤的清洁转化油气新技术

论述了褐煤、长焰煤、不黏煤和弱黏煤洗选块煤的清洁转化利用新技术——低阶煤两步连续气化方法;分析了该技术的特点和商业优势及环保设施。     

5-羟甲基糠醛催化氢化制备2,5-呋喃二甲醇的研究进展

2,5-呋喃二甲醇（BHMF）在合成树脂、药物等方面具有重要应用。随着化石资源的日益缩减,由可再生的生物质基平台分子5-羟甲基糠醛（HMF）催化制备BHMF引起人们的广泛关注。本文在总结了HMF及BHMF物化性质的基础上,介绍了HMF在分子氢、醇类、甲酸3种不同的氢供体中催化加氢制备BHMF的研究近况,总结了贵金属、非贵金属、双金属或多金属协同催化体系在该加氢反应中的应用进展,同时分析了反应过程中温度、时间、催化剂载体、反应溶剂种类及酸值等因素对HMF转化率及BHMF得率的影响。最后对HMF催化转化制备BHMF的研究前景进行了总结和展望,提出了使用醇类代替氢气作为氢供体,开发非贵金属及金属协同催化体系将是该选择性氢化反应的重要研究方向之一。     

滴流床反应器上α-甲基苯乙烯加氢影响因素分析

以α-甲基苯乙烯、氢气为原料在滴流床反应器中催化加氢合成异丙苯。本文主要考察反应温度、压力、循环量及进料α-MS的浓度、氢油比、催化剂、床层设计等因素对加氢反应的影响。结果表明,反应温度提高只在60～120℃范围内能够加快反应速率;压力在0.7～0.8 MPa时加氢反应速率最快,处理能力最大;氢油比的提高在保证原料与催化剂接触时间的前提下对反应有利;循环量及进料α-MS的浓度可以改变反应速率但是不能改变实际处理能力;催化剂的活性稳定是保证加氢效果的前提;床层设计的处理能力限制是造成目前加氢效果下降生产能力受限的主要原因。     

我国非炼焦煤在炼焦中的应用

介绍了我国无烟煤、贫煤、不黏煤和长焰煤等非炼焦煤的性质及在炼焦生产中的应用情况。利用非炼焦煤代替部分焦煤炼焦,成本优势十分明显,既可缓解焦煤资源不足的压力,还能优化我国煤炭资源的利用。     

烟煤粘结指数准确测定的影响因素分析

粘结指数的测定在煤质分析中是很重要的,它是判别煤的粘结性、结焦性的关键性指标。测定烟煤的粘结指数后,就能确定它的工艺类别,根据煤样粘结指数的高低,可以大致确定该煤的主要用途。     

单种强黏结性肥煤的配煤实验及黏结指数变化分析

将半焦、焦粉、主焦煤以不同的比例,配入新疆焦煤集团强黏结性肥煤中,进行黏结性实验,实验结果表明,焦煤和经低温干馏处理过的半焦在配入比例5%以内时,配合煤的黏结指数并未遵循低于最高黏结指数的一般规律;不同温度干馏的半焦其配合煤的黏结指数不同。通过实验验证,强黏结性的肥煤对无黏结性的半焦会产生非常强的黏结性,这对于动力煤的半焦的配煤炼焦具有一定的实践意义。     

Hydrogenation of oleochemicals at supercritical single-phase conditions: influence of hydrogen and substrate concentrations on the process

Fatty alcohols can be produced by catalytic hydrogenation of fatty acid methyl esters. This heterogeneous catalytic reaction is normally performed in a multi-phase system. In such a system, with a low hydrogen solubility in the liquid substrate and a large mass transport resistance, the hydrogen concentration at the catalyst is low and limits the reaction rate. To overcome this limitation, we have used the unique properties of supercritical fluids, properties which are in between those of liquids and gases, making them a very suitable medium for reactions. By adding propane to the reaction mixture of hydrogen and fatty acid methyl esters (C₁₈) we have created supercritical single-phase conditions. At these single-phase conditions the concentrations of all the reactants at the catalyst surface can be controlled, and an excess of hydrogen becomes possible. In this way, extremely rapid hydrogenation can be combined with a high product selectivity.

In our lab-scale experiments the catalyst performance was studied as a function of hydrogen concentration, substrate concentration and temperature. Complete conversion of the liquid substrate was reached in a few seconds. As long as single-phase conditions remain, we have, in our experiments, tested up to 15 wt.% substrate, vapor-phase like reaction rates can be maintained. However, at these high substrate concentrations, mass transport becomes important again.

Our results show that performing hydrogenation at supercritical single-phase conditions has a large potential for this and other catalytic processes where the hydrogen concentration at the catalyst is the limiting factor.     

炼焦煤对大颗粒惰性物质黏结能力的实验探讨

通过测定气肥煤、肥煤和焦煤对小颗粒惰性物质和大颗粒惰性物质黏结能力的强弱,得出:当惰性物质粒度<0.4 mm时,气肥煤和肥煤对其黏结性强于焦煤对其黏结性,而当惰性物质粒度>0.4 mm时,焦煤对其黏结性强于气肥煤和肥煤对其黏结性。可以认为,采用黏结指数G值来评价气肥煤和肥煤黏结性特征具有一定的局限性。     

配入低阶煤炼焦对焦炭性能影响的研究

选用焦煤、1/3焦煤、肥煤、瘦煤、长焰煤进行配煤,堆密度为0.7g/cm3和1.0g/cm3,采用2kg焦炉炼焦,对焦炭的冷态强度和热态性能分析检测,探讨了堆密度及低阶煤加入量对焦炭性能的影响,结果表明,配入低阶煤后,焦炭的冷态强度及热态性能变差,配比小于5%时,影响较小,适当提高原料煤堆密度,焦炭的冷态强度及热态性能得到改善。     

石油焦配煤炼焦试验研究

通过对石油焦的特性研究及配煤炼焦试验,考察其对配煤黏结性能及焦炭质量的影响,研究结果表明,添加石油焦会引起煤的黏结指数下降,加入石油焦配煤炼焦会降低焦炭灰分,提高焦炭硫分,降低焦炭冷强度,提高焦炭热强度。     

Generation of pitch-like products by the thermal dissolution of coal in heavy semicoking tar

The influence of hydrogenating upgrading of heavy semicoking tar from long-flame coal on its properties and composition is studied when it is used as the solvent in the thermal dissolution of bituminous gas coal (GZh coal). It was found that the concentration of oxygen-bearing compounds declines on catalytic hydrogenation of tar at 5 MPa and on combined treatment with two hydrogen donors: tetralin and the anthracene oil. After hydrogenating treatment, the heavy semicoking tar may be used as the solvent in the thermal dissolution of GZh coal so as to obtain pitch-like products.     

基于CPD模型的低阶煤催化解聚过程模拟分析

低阶煤催化解聚过程定量分析和放大需要合理描述该过程的宏观动力学模型,使用化学渗透脱挥发分（CPD）模型结合陕西长焰煤的催化解聚实验,对低阶煤催化解聚过程进行了定量分析。综合对催化剂作用机理的认识,结合催化解聚实验结果确定相应表观动力学参数,所得模拟结果与实验结果趋势一致、吻合良好,其较好地体现了不同热解过程差异,低温下催化解聚产物释放量较少,温度升高后产物量才会高于原煤热解。模型中催化剂对焦油产率的影响体现在复合速率常数、交联反应活化能上,随两者增大,焦油产率均增加;Fe基催化剂有助于促进侧链断裂,提高气体产率,Zn基催化剂可抑制交联反应,但交联反应活化能较大时,受热解温度限制,焦油量增加变缓。     

Kinetic investigations of the deactivation by coking of a noble metal catalyst in the catalytic hydrogenation of nitrobenzene using a catalytic wall reactor

The vapour phase hydrogenation of nitrobenzene to aniline is a highly exothermic reaction deactivated by coking of the palladium catalyst supported on -alumina carrier. For studying the deactivation of the catalyst a catalytic wall reactor was used in order to ensure isothermal reaction conditions for the kinetic measurements. Furthermore, the catalytic wall reactor allowed the determination of axial coke profiles by total carbon analysis of different wall segments. On the assumption that the main reaction and the deactivation of the catalyst can be assumed separable both the steady state and the unsteady state kinetics were studied. Nitrobenzene was identified as the relevant coke precursor whereas aniline has neither an influence on the main reaction nor on the deactivation. It could be shown that the hydrogenation of nitrobenzene to aniline follows a Langmuir–Hinshelwood mechanism considering the surface reaction of the adsorbed nitrobenzene molecule and one adsorbed hydrogen atom as the rate determining step. The differentiation of coke on the active sites and coke on the support must be taken into account to model the kinetics of coke formation with sufficient accuracy.     

Selectivity improvement in the SRC process

The selectivity for hydrodesulfurization over hydrogenation has been examined in a new short residence time catalytic two-stage SRC process, which has the potential of producing a low-sulfur solid SRC product to meet the newly proposed EPA new point source emission standards (NPSES). In the first stage of the process, residence time and hydrogen consumption are minimized through the use of an inexpensive mineral catalyst (SRC residue ash) that has been treated under a combustion environment to improve its selectivity for hydrodesulfurization over hydrogenation. The second stage of the process involves hydrotreating the filtered liquid product with a commercial Co-Mo-Al catalyst, before splitting into a solid SRC and solvent recycle by distillation. Several process variables — such as type of coal, catalyst, temperature, hydrogen partial pressure, and reaction time — have been examined to provide information on hydrogen consumption, product distribution, sulfur removal, SRC yield and solvent quality. The results show that the ash of SRC residue can be used to selectively catalyze desulfurization over hydrogenation in SRC processing. Selectivity for desulfurization in two stage hydrodesulfurization of coal is improved by using high reaction temperatures, short residence times, the ash of SRC residue as a first stage catalyst, and Co-Mo-Al as a second stage catalyst. Two stage catalytic SRC processing is more selective for hydrodesulfurization than catalytic or non-catalytic single stage SRC processing.