煤加压富氢热解及半焦气化特性研究

为研究加压固定床气化过程中热解区和气化区的反应,模拟固定床富氢气氛热解与半焦气化过程,利用加压富氢热解装置考察了压力、加热终温以及富氢比例对煤热解的影响,分析了各因素对热解影响的机理,以富氢气氛热解半焦为原料,通过加压热重分析仪进行试验研究,研究不同温度和不同热解半焦原料的条件下碳转化率与CO_2反应速率随时间的变化规律,分析富氢比例对气化反应活性的影响。结果表明:常压富氢气氛热解试验中,随着富氢比例的升高,提供大量H,H浓度增大,煤在热解过程中自由基会不断与H结合生成稳定组分,其中包括大量小分子的挥发物以及部分焦油析出,使半焦中挥发分降低0.69%,半焦收率降低4.8%;加压条件下半焦收率较高,半焦收率随压力的增大变化幅度不大,且没有明显规律,挥发分总体逐渐降低,但变化较小;随着终温的升高,挥发分析出量逐渐升高,伴随着挥发分析出,富氢氛围中的H将与自由基结合生成小分子结构而逸出,半焦收率与挥发分均逐渐降低;增加富氢比例能提高半焦的成熟程度,富氢比例由0增加到35%,H浓度增大,煤中小分子可迅速加氢生成挥发物,同时大分子也会加氢变为稳定结构,半焦挥发分降低了1.46%,半焦收率降低了2.50%;富氢热解能明显促进CO和CH_4的生成,在35%H_2时产量分别达到91.2和63.8 mL/g。由气化特性试验可知:提高气化反应温度,有助于提高富氢半焦与CO_2的气化反应性;富氢气氛与惰性气氛下热解半焦的气化反应活性相近,表明加氢热解能够提高焦油产率与焦油品质,同时对半焦的气化活性影响不大。     

热解气催化活化促进石河子烟煤热解的研究

采用等体积浸渍法制备了Fe/MgO,Co/MgO和Ni/MgO催化剂,利用固定床反应器对石河子烟煤在热解气气氛下的催化热解行为进行了研究,考察热解气在催化剂作用下对煤热解焦油产率、半焦产率、轻重油比例以及焦油族组成的影响,并与相同条件下N2气氛和热解气气氛热解特性进行了对比分析.结果表明,三种催化剂对煤在热解气中的热解都有促进作用,其中Ni/MgO催化剂对提高焦油产率最明显.在气体流量为400mL/min,热解温度为550℃,Ni/MgO为催化剂的条件下,焦油产率为7.33%,与相同条件下在N2气氛和热解气气氛下热解相比,焦油产率分别提高了78%和42%.而Co/MgO催化剂对提高轻油的作用较明显.这表明热解气催化活化对煤热解有较好的促进作用,可抑制缩聚反应,提高焦油的产率和改善焦油的品质.     

气氛及甲烷催化活化对流化床煤热解的影响

为了提高煤热解焦油的产率和品质,在小型流化床实验台上分别考察了N_2,N_2+H_2,CH_4+N_2,CH_4+H_2等气氛及前置Ni/Al_2O_3催化剂对流化床煤热解的影响,结果表明:H_2气氛会减少半焦产率,增加焦油产率;CH_4气氛在800℃时反而会增加半焦产率,同时高温下CH_4的分解对焦油产率的增加有促进作用,相比于N_2气氛,焦油产率提高了35.8%;CH_4+H_2气氛下半焦焦油产率的总体趋势同H_2气氛下相同.还原性气氛有利于焦油的轻质化:H_2,CH_4+N_2,CH_4+H_2气氛下800℃时,轻质焦油的占比分别较N_2气氛提高了29.1%,15.2%,24%.在CH_4+N_2和CH_4+H_2气氛下,采用前置Ni/Al_2O_3催化剂后,焦油产率都得到不同程度的提升.CH_4+N_2气氛下600℃时,催化剂可以使焦油产率较无催化剂时提高40%;CH_4+H_2气氛下800℃时,催化剂对CH_4的催化效果更好,热解气中CH_4含量明显减少,而焦油产率较无催化剂时提高了37%.Ni/Al_2O_3催化剂可以进一步提高焦油的品质,并且有利于焦油中芳香烃的生成.     

反应气氛对碳酸钾催化煤加压热解特性的影响

以内蒙古不连沟次烟煤为原料,在加压热解装置中考察了530℃,3.5MPa条件下热解气氛(N_2+H_2,N_2+H_2O和N_2+H_2O+H_2)对碳酸钾催化剂催化煤热解产物产率及性质的影响.结果表明:碳酸钾的分解以及碳酸钾催化剂促进煤中含氧官能团的断裂,导致大量CO_2的产生;与N_2气氛下催化热解相比,N_2+H_2和N_2+H_2O气氛促进了焦油和CH_4的生成;在N_2+H_2O+H_2气氛下热解,焦油产率进一步增至7.62%,CH_4产率增至2.06%;相同气氛下有/无催化剂的热解实验结果表明,H_2对碳酸钾催化剂的催化作用影响较小,H_2O气氛下碳酸钾能促进碳水气化反应的进行;实验考察范围内,气氛的改变对热解半焦的比表面积及其气化反应特性的影响较小.     

热解气催化活化促进烟煤热解探讨

使用Fe/MgO、Co/MgO、Ni/MgO三种催化剂,在热解气条件下对烟煤热解效果进行研究,得出以下结论 :Fe/MgO、Co/MgO、Ni/MgO三种催化剂可活化热解气的分解反应,很好的提高焦油产率,尤其Ni/MgO在提高焦油产率上效果最为显著,在550℃的热解温度下,达到了7.32%的焦油产油率。由此可知,热解气催化活化可很好的促进烟煤热解,增加油产率的同时,促进焦油品质的改善。     

钙元素对褐煤热解和气化特性的影响

综述了钙元素对褐煤热解和气化特性的影响,讨论了钙元素对热解产物中挥发分、焦油产率和气体产物分布的影响,以及对褐煤半焦气化的催化作用。结果表明,与酸洗煤相比,热解过程中,钙元素降低焦油产率,提高半焦产率;气化过程中,钙元素的植入提高褐煤半焦的反应活性,缩短了反应时间。高温时钙元素主要以氧化态的形式存在,低温时则不断与半焦基体键合而参与交联反应,少部分挥发。     

枣庄褐煤催化热解特性研究

在格金反应器上对一种枣庄褐煤添加镍基催化剂(Ni(NO₃)₂·6H₂O)进行催化热解,并对其添加催化剂前后热解产物焦油、半焦和气体等通过全二维气相色谱质谱联用仪(GC×GC-MS)、热重分析仪(TGA)、拉曼光谱仪和气相色谱仪(GC)等进行表征分析。催化热解产物分析结果表明,相较于原煤,添加镍基催化剂后半焦收率降低,焦油收率提高,其中半焦收率由82.72%降低到81.51%,焦油收率由8.21%增加到10.06%。焦油馏分分析结果表明,添加镍基催化剂后焦油品质提高,其中沥青含量由18.29%降低到13.88%,蒽油含量由9.39%增加到12.87%。拉曼光谱分析结果表明,添加镍基催化剂后半焦中3～5个芳环的芳香烃结构含量增加,六元以上芳香烃结构含量降低。综上分析结果推测出镍基催化剂在煤热解过程中促使煤大分子结构上连接稠环芳香结构(3～5个芳环)的脂肪桥键断裂,断键后的稠环芳香结构被CH₃·或H·稳定下来生成焦油或半焦。     

铁基催化剂对煤加氢热解和半焦结构的影响

应用固定床反应器研究了铁基催化剂Fe2O3、Fe S、Fe（NO3）3对伊犁南台子煤催化加氢热解产物分布和半焦结构的的影响。结果表明：添加铁基催化剂后,加氢热解中气产率增加最大为17.78个百分点,半焦产率下降最大为21.41个百分点。利用BET法对半焦进行了结构分析,结果发现,添加Fe（NO3）3后所制得的半焦的比表面积和总孔体积分别为不添加催化剂所制得的半焦的6倍和1.7倍。从TG和DTG图中发现,加入铁基催化剂后,半焦活性增加,其中Fe（NO3）3的作用最明显,热失重速率最大,说明半焦活性较大。     

半焦基催化剂裂解煤热解产物提高油气品质

利用上段热解下段催化的两段固定床反应器,针对府谷煤研究了半焦和半焦负载Co催化剂对煤热解产物的催化裂解效果。结果表明,半焦和半焦负载钴对热解产物催化裂解后,热解气收率增加,焦油收率降低,但焦油中沸点低于360℃的轻质组分含量提高,轻质焦油收率基本保持不变或略有增加。与煤在600℃直接热解相比,在热解和催化温度均为600℃,采用煤样质量20%的半焦为催化剂时焦油中轻质组分质量含量提高了约25%,轻质组分收率基本不变,热解气体积收率增加了31.2%;在热解温度600℃,催化温度500℃时,采用煤样质量5%的半焦负载钴催化剂,焦油中轻质组分质量收率和含量分别提高了约8.8%和28.8%,热解气体积收率增加了21.5%。煤热解产物的二次催化裂解的总体效果是将焦油中重质组分转化为轻质焦油和热解气。     

喷动-载流床中Co/ZSM-5分子筛催化剂对煤热解的催化作用

在喷动-载流床中考察了Co/ZSM-5分子筛催化剂对煤热解气、液、固产物产率及组成变化的影响,分析了催化剂失活的原因及催化剂的再生使用寿命. 结果表明,在550~600℃的热解温度范围内,Co/ZSM-5分子筛催化剂提高煤热解总转化率达70%以上. 而在650℃时,煤热解正己烷可溶物产率最大,其中酚类、脂肪烃类和芳香烃类的产率比无催化剂时分别增加203%, 51%和78%. 因积碳失活的Co/ZSM-5分子筛催化剂经过500℃焙烧后再生使用6次,活性下降不到5%. Co/ZSM-5分子筛催化剂的结构表征结果说明,Co进入了ZSM-5分子筛骨架. Co的催化加氢活性促进了H·与煤热解焦油片断的结合,减少了焦油聚合成大分子的几率,从而提高了煤热解油品的产率和品质.     

Scanning electron microscopic study on the catalytic gasification of coal

The behaviour of nickel catalyst during coal gasification of Leopold coal (West Germany) was examined by means of scanning electron microscopy. Microscopic observations of the same field were made several times as the reaction proceeded. In addition to the uncatalysed gasification, the nickel-catalysed gasification was clearly observed under the microscope. With steam gasification, catalysts moved very actively, and they seemed to accelerate the gasification mainly by pitting holes into the char. The topological changes on char surfaces by hydrogasification were not so pronounced. The function of catalyst may not be restricted to the pit formation, for it seems to accelerate the gasification over all of the char surface. Because of the high hydrogasification temperature, agglomeration of catalyst takes place to a considerable extent. Finely dispersed nickel catalysts were observed when the coal had been pretreated with liquid ammonia. The catalytic activity of these fine particles was so large that the char beneath them was gasified rapidly.     

煤催化气化技术的研究现状与展望

煤催化气化由于可以大幅度降低操作条件,实现定向转化,目前正受到国内外重视。本文综述了碱金属、碱土金属、过渡金属催化剂与复合催化剂在煤催化气化过程中的活性、优缺点、反应机理等。对影响煤催化气化的各类因素如煤阶、矿物质、催化剂添加方式、添加量、气化条件等进行了分析。介绍了当前催化气化工业化进程以及合成天然气甲烷和催化气化制氢两种工艺。当前研究的难点是兼顾催化剂的效率与经济性,煤催化气化未来将以开发高活性、易回收且廉价的催化剂为研究方向。     

Sulfur poisoning in the nickel catalyzed gasification of activated carbon in hydrogen

The effect of hydrogen sulfide on the catalytic activity of nickel has been investigated in the hydrogasification of activated carbon. The low-temperature gasification activity in the range of 400–700° C was seriously suppressed when hydrogen sulfide was added to the hydrogen stream. The carbon conversion in this temperature region was approx. 75,50,20 and 0 % for hydrogen sulfide concentration of 0,20,50 and 100 ppm. respectively. A similar deactivation was observed even in pure hydrogen if the catalyst had been previously treated with hydrogen sulfide. On the other hand, the retardation effect was much smaller in the temperature region higher than 900° C. and the original activity was easily reproduced when the catalyst was exposed to pure hydrogen. The sulfur problems in the catalytic gasification of activated carbon are discussed in connection with the gasification of coal.     

The catalytic steam gasification of one Australian and three Japanese coals using potassium and sodium carbonates

The catalytic steam gasification of four different coals using potassium and sodium carbonates as catalysts was carried out in a semi-flow type fixed-bed reactor. The coal was gasified with or without the catalyst under a steam—argon atmosphere at a heating rate of 50°C/s at 700–800°C. The catalytic activity of carbonates for gasification was remarkable for Japanese high-volatile coals (Miike and Takashima coals), and moderate for Australian medium-volatile coal (New Lithgow coal); however, the carbonates had little effect on gasification of Japanese lignite (Taiheiyo coal). It is assumed that Miike and Takashima coals soften and melt during the heating process to make the contact between char and catalyst better. New Lithgow and Taiheiyo coals do not have this property. Gasification was promoted significantly at lower temperatures when the catalyst was used. In both catalyzed and uncatalyzed runs the main products were hydrogen and carbon dioxide; the reaction temperature did not affect the composition of the gases much. A water—gas shift reaction occurred during gasification resulting in a large amount of carbon dioxide under a large excess of steam flow.     

准东煤水热提质及废液催化气化特性研究

准东煤的碱金属(特别是Na、Ca)含量高,直接作为动力煤燃烧会导致严重的锅炉沾污、结渣。采用水热提质方法能够有效脱除煤中碱金属,同时还可改善煤质的理化特性,但水热提质也会产生大量废液,并导致有机质损失,原料的能量利用率低,限制了该方法的应用。针对上述问题,将水热提质技术与废液气化技术进行耦合,在水热反应釜和自制的两段式反应装置上开展了准东煤水热提质改性及衍生废液催化气化的试验研究,探究了提质后三相产物的分布特性及废液的催化气化特性。结果表明,随着水热温度的升高,煤样的固体回收率降低,废液中总有机碳(TOC)和气体产物显著增大,但至少有97.8%的碳元素分布在固相产物中。废液催化气化产生了富含CH_4、H_2的可燃气,最高占比达到70%。Ni/C催化剂中Ni元素对废液的气化起催化作用,催化效率随着水热温度、气化温度的升高而升高,随液时空速的升高而降低。优选的催化气化试验条件:Ni/C催化剂、水热温度为300℃、催化气化温度为350℃和液时空速为150 h-1。总之,水热提质-废液催化气化联用技术既可以实现煤质的改性,又回收了废液中的能量,能够为准东煤的清洁、高效利用提供新的思路。     

煤催化气化催化剂发展现状及研究展望

煤与气化剂(如水蒸气、CO2、H2和O2)之间的气化反应最有效的催化剂主要为碱金属、碱土金属以及过渡金属的盐类,根据其组成,详细论述了煤催化气化催化剂的特性。据研究,在气化反应中碱金属催化剂如Na、K等易与煤中矿物质如Si或Al反应致使催化剂失活,同时过渡金属易被煤中S毒化,这在一定程度上制约了煤催化气化工业化进程。论述了煤催化气化催化剂的研究方向,认为开发新型高效、低廉且易回收催化剂是有必要的。     

Gasification of coal impregnated with catalyst during pulverization: effect of catalyst type and reactant gas on the gasification of Shin-Yubari coal

Shin-Yubari coal was impregnated with several catalysts of different chemical types during pulverization. The resultant system was more homogeneous and reactive than systems prepared by impregnation of coarse coal. The relative activities of the catalysts were determined as a function of gasification temperature, catalyst loading and gasifying agent. The activity sequence in steam was K ? Ba ? Ni ? Fe ? coal ash. Each catalyst had a unique reaction profile. For example, using steam the specific rate or the rate per remaining fixed-carbon weight decreased with time for the iron-catalysed reaction, whereas it increased for the potassium-catalysed reaction. A similar order of activity was observed in carbon dioxide, but a different sequence was noted for the hydrogenation reaction. Transition metal catalysts were the most active. The hydrogenation reaction profiles were different from the oxidation profiles.     

Gasification of carbon deposited on supported Ni-Cu catalysts

The activity of supported Ni-Cu alloy catalysts in the gasification of carbon was studied for a range of copper concentrations. Deposits formed from the decomposition of methane under constant and well-defined conditions were gasified by hydrogen and hydrogen-steam mixtures. The kinetics of hydrogasification were determined under such conditions that the reaction rates did not depend on the extent of carbon burn-off. Comparison of the different catalysts indicates that, similarly to previous results for the decomposition, an ensemble of surface nickel atoms plays a role in the gasification.     

Neuere technische Verfahren in der Kohlechemie

New technical processes in coal chemistry . The most important commercial basic processes of primary coal conversion are carbonisation, gasification, and hydrogenation. Some 450 mio t/a of coal are converted by coking in horizontal slot type ovens to 350 mio t/a of metallurgical coke for the reduction of iron ore in blast furnaces, coke oven gas, and some 20 mio t/a of coke oven benzole and coal tar as raw material for aromatics. The coke ovens are being developed to high-capacity coking reactors. New second generation processes for the gasification of coal and lignite have advanced to an industrial scale. A vapor-phase hydrocracking refining step has been integrated within the further developed process for the catalytic liquid-phase hydrogenation of coal. Plasma pyrolysis of high-volatile bituminous coal investigated on a semi-industrial scale yields acetylene. Pressure hydropyrolysis of coal currently being tested on a pilot plant scale generates high-aromatic liquid products. New processes for the upgrading of such liquids have been developed above all for aromatics from coal tar, e. g. for the production of naphthalene derivatives, and the conversion of polycyclic aromatic hydrocarbons into the technical carbon products carbon black, electrographite, carbon electrodes, and carbon fibres.     

纳米金催化剂的制备及其对肉桂醛选择性加氢的催化性能

以多壁碳纳米管和椰壳活性炭为载体,分别采用溶胶固载法和等体积浸渍法制备负载型纳米金催化剂。采用N_2吸附-脱附、XRD、TEM和XPS等对碳载体和纳米金催化剂样品进行表征,并研究纳米金催化剂在肉桂醛选择性加氢反应中的催化性能。结果表明,HNO_3-H_2SO_4预处理可以增加碳载体表面的含氧基团和含氮基团,在肉桂醛加氢反应中,溶胶固载法得到的更小尺寸的纳米金催化剂对C=C双键加氢选择性高,等体积浸渍法制备的纳米金催化剂对C=O双键加氢选择性高,椰壳活性炭为载体催化剂的C=C加氢催化活性优于多壁碳纳米管。