电解水煤浆制氢技术研究进展

电解水煤浆制氢在能源消耗与产氢效率上都更优于电解水过程,并且在电解过程中可以同时达到对矿石能源净化的目的,是一种十分值得推广与发展的产氢新技术。本文在综述电解水煤浆技术现状及特点的基础上,阐述了电解水煤浆制氢技术的原理,并以此为理论基础概述了反应温度、电解质种类、样品预处理对电解水煤浆制氢的影响,综述了国内外电解水煤浆电极材料的研究进展,并对电解水煤浆技术的发展现状和存在的不足进行了分析与展望。指出电解水煤浆技术发展的重点方向为：降低电解水煤浆过程中的能量消耗,多使用可再生能源;深入研究反应机理,提高产氢效率,实现化学能与电能耦合向氢能的转变;改善电极的稳定性和耐腐蚀性,使电极更加耐久并降低电极成本;通过研究新型催化电极与催化剂来提高反应的效率。     

焦粉制备工艺技术的比较

利用粉焦作瘦化剂掺混到煤料中配煤炼焦,不仅解决了粉焦的销路问题,减少了环境污染,还可以节约大量瘦煤,达到能源的二次利用。概述了焦粉制备工艺技术在生产中的应用状况,分别介绍了干法、湿法、润磨、振动棒磨机和高压对辊粉磨机5种焦粉制备工艺流程,并对5种焦粉制备工艺与设备的优缺点进行了分析比较。     

Thermogravimetric study of coal and petroleum coke for co-gasification

As a preliminary study of gasification of coal and petroleum coke mixtures, thermogravimetric analyses were performed at various temperatures (1,100, 1,200, 1,300, and 1,400 °C) and the isothermal kinetics were analyzed and compared. The activation energies of coal, petroleum coke and coal/petroleum coke mixture were calculated by using both a shrinking core model and a modified volumetric model. The results showed that the activation energies for the anthracite and petroleum coke used in this study were 9.56 and 11.92 kcal/mol and reaction times were 15.8 and 27.0 min. In the case of mixed fuel, however, the activation energy (6.97 kcal/mol) and reaction time (17.0 min) were lower than the average value of the individual fuels, confirming that a synergistic effect was observed in the coprocessing of coal and petroleum coke. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

配合煤配比对焦炭综合热性质的影响

以企业生产实践为背景,研究在配合煤中增配肥煤和1/3焦煤对焦炭综合热性质的影响。对不同配比配合煤的性质指标进行检测,采用40 kg焦炉实施炼焦试验,并对炼制焦炭的传统国家标准热性质指标和利用自主研制装置测得的综合热性质指标进行测定。结果表明:增配肥煤和1/3焦煤,均会使配合煤的变质程度降低,挥发分含量升高,胶质体的黏结能力下降,但胶质体的量保持不变。配比变化引起的配合煤性质指标的变化没有显现在焦炭的传统国家标准热性质指标反应性CRI和反应后强度CSR上。以往的研究都是以CRI和CSR指标为目标量判断配合煤的配比是否合适,本研究除此之外还采用了自主提出的焦炭综合热性质指标。配合煤配比变化引起的焦炭的综合热性质指标变化比国家标准热性质CRI和CSR指标变化敏感,这可能与其反映了焦炭某些新的特征有关。基于焦炭综合热性质指标的变化规律,考虑到1/3焦煤具有经济性,生产上增配某些特定的1/3焦煤,可以同时达到提高焦炭质量和降低配煤成本的目的。     

富钙废渣配煤对焦炭溶损反应的影响

将1%富钙碱渣配入焦煤中制备焦炭,采用自制小型垂直固定床反应器研究了900~1200℃下所得焦炭的溶损反应过程. 结果表明,碳素溶损率小于15%时焦炭的溶损反应速率基本不变,碳素溶损率大于15%时溶损反应速率逐渐减小. 焦炭反应后的比表面积随碳素溶损率增加先增大后减小,在溶损率约为15%时最大. 配入富钙碱渣提高了焦炭的溶损反应速率,增大了焦炭的反应性,溶损温度越高,溶损速率增幅越大. 用随机孔模型描述了焦炭的溶损反应动力学过程,基础焦炭和添加1%碱渣的焦炭的溶损反应表观活化能分别为132.15和103.81 kJ/mol.     

1.5 MPa多喷嘴对置式水焦浆气化炉的模拟与优化

针对w（水焦浆）和氧焦比预测优化过程未采用严格反应机理模型,工艺参数的预测优化与实际生产存在较大偏差的情况,以UniSim Design流程模拟软件为工具,采用Gasifier反应器严格机理模型建立了1.5 MPa多喷嘴对置式水焦浆气化炉模型,并根据工业数据对水焦浆气化炉进行标定,标定结果相对误差小于2%,同时研究了氧焦比和w（水焦浆）对焦煤气化工艺参数的影响。结果表明：w（水焦浆）和氧焦比是影响水焦浆气化过程和粗煤气组成的关键因素,通过气化炉模型标定和优化分析,石油焦的氧焦比控制范围为0.95~1.10,为焦煤浆气化工艺生产实践指导提供了理论依据。     

Coal blend moisture—a boon or bane in cokemaking?

A by-product coke making plant is required to supply sufficient coke of good quality and adequate gas of high calorific value for the integrated steel plant to be a going concern. The one element that influences the handling of coal and impacts the operation and efficiency of the plant is moisture. Compared to other important properties of the coal blend, moisture can be easily manipulated. The coal moisture can be increased simply by adding water through hose pipes. Also, it can be reduced to 5–6 mass percent using Coal Moisture Control (CMC) and 2–4 mass percent using Dry-cleaned & Agglomerated Pre-compaction System (DAPS). Moisture content is one among the many variables affecting the bulk density of coal blend and those controlling the coke qualities and yield. Increase in moisture reduces coal grindability, coking pressure and internal gas pressure; helps in dust suppression during charging and hence reduces jamming of ascension pipes and hydraulic main. Batteries charging coals with high moisture content are not troubled with roof carbon deposits. It was observed that when moisture content in coal blend of SAIL-Bokaro Steel Plant increased to more than 8.50%, the calorific value of coke oven gas improved. In the working moisture range of 9–11%, the increase of the yield of coke oven gas per 1% of working moisture is 5.2 m³. Studies have shown, however, that the increase in moisture content of coal beyond 8% hampers strong coke formation. Pre-carbonization preheating process generally showed an increase in the proportion of 40–80 mm coke, compared with wet charges. For SAILBokaro coke ovens, driving out 1% moisture from coal blend requires 125 Mega-calories of heat/oven. With lesser moisture, the emission of NO _x in atmosphere will also be low. On using dry to low moisture coal blend, the swelling of coke mass increases leading to difficulty in oven pushings. Hence, an optimum level of moisture content of charge coal needs to be maintained for improving coke oven productivity, coke quality and operational smoothness. The coke oven managers all around the globe maintain this optimum level according to their requirement, the operating conditions, the quality of product and by products, the oven health & age and the ease of handling.     

QRD-2000型无回收焦炉的清洁生产分析

QRD-2000型无回收焦炉不走尾部治理的老路,从根本上杜绝了酚氰废水的排放,省去了大量化产废气对环境的危害。QRD-2000型无回收焦炉针对焦炉区的无组织排放,结合焦炉结构进行工艺改进,大大降低了无组织有害气体的排放量,优化了焦炉区操作环境,实现了焦化行业的清洁生产目标。     

试论煤炭高温电化学转化制甲醇的碳循环工业革命

论述了CO2在自然生态环境中的产生与循环以及碳元素化学反应平衡理论基础;分析了国内几大工业生产中碳的利用率与CO2排放量;针对节能减排,揭示了我国煤炭转化工艺技术存在的误区,从工艺流程、设备开发、资源优化配置等方面,阐述了粉煤气化同水电解氢制甲醇的CO2零排放工艺技术;提出了在我国建设大型煤制甲醇能源化工基地的战略方案。     

不同煤阶煤焦炭显微结构与热性质的研究

采用模拟焦炭反应性和反应后强度,研究了不同变质程度单种煤焦炭显微结构与热性质之间的关系。中等变质阶段的焦煤、肥煤和瘦煤所制焦炭有较高的各向异性,低变质程度的气煤、1/3焦煤以及高变质程度的贫煤所制焦炭各向异性程度较低。焦炭的热性质与焦炭的各向异性有很好的相关性,焦炭反应性随各向异性程度的增大而减小,反应后强度则随各向异性的增大而增大。     

低阶煤制备活性焦及其吸附性能研究

为解决煤化工废水处理难题,提高活性焦吸附性能,以5种典型低阶煤为原料,通过回转炉炭化和活化工序制备活性焦,研究活化温度、活化蒸气量和活化时间对活性焦吸附性能的影响,分析了不同活性焦对废水的吸附能力。结果表明:以褐煤为原料制备活性焦时,最佳活化温度为800℃,活化时间为3 h,活化蒸气量为1050 g;长焰煤最佳活化温度为850℃,活化时间为4 h,活化蒸气量为1200 g。在最佳条件下,褐煤活性焦的吸附值为36.32 mg/g,比长焰煤活性焦吸附值高10%。5种原煤制备的活性焦的比表面积与吸附值没有明显相关性。活性焦的孔容积越大,吸附值越高,造成不同活性焦吸附值差别的主要孔径为2~5 nm和5~20 nm。     

配煤添加高灰低硫及中灰中硫贫煤炼焦的研究

对高灰低硫(新元矿)、中灰中硫(平舒矿)贫煤进行煤质分析和炼焦特性研究,并结合配合煤种进行炼焦和生产验证试验。结果表明,新元矿和平舒矿贫煤适用于捣固工艺,在炼焦中起到瘦化剂的作用,同时能够降低配合煤及焦炭的硫分,改善焦炭的反应后强度。     

碱性膜电解水制氢技术现状与展望

开发清洁高效的可再生能源是未来能源转型的必然趋势。氢能作为一种绿色无污染的能源载体,可通过电解水技术实现氢能与电能的高效转化,有望作为风力、光伏发电的重要调节手段。碱性膜电解水制氢能够提高电流密度,增加能量转化效率,优于碱性水溶液电解水制氢;与此同时,可采用铁、镍等非贵金属制备催化剂,克服质子交换膜电解水制氢使用贵金属催化剂带来的设备昂贵、资源受限问题。本文综述了碱性膜电解制氢技术发展现状,重点围绕自支撑催化电极、耐碱腐蚀离子膜、有序结构膜电极开展讨论,包括催化剂制备策略,耐碱离子膜发展现状,以及有序化膜电极的应用优势,阐释电化学工程中的传质与反应耦合原理。本文为进一步研究开发高性能电化学关键材料提供了指导思路,推动电解水制氢技术的发展。     

电极上气泡分离行为及其强化技术研究进展

电解水作为大规模生产氢气的途径,增强电解水效率对于氢能源的生产具有十分重要的意义。而如何提高电解水工艺的电解效率是一个被广泛关注的问题。在电解过程中,电极两端产生的气体有三种去向：逸出电解槽、溶解于电解质中、附着在电极上。但在电解过程中,附着在电极上的气泡会严重影响电极与电解质之间的接触面积,直接降低了电解效率。降低气泡在电极上的停留时间能够有效增加电解质与电极的接触时间,提高产氢效率。本工作主要综述了近年来促进电解过程中极板上氢氧气泡从电极分离行为的研究,分别从极板属性、电流、溶液浓度和外加物理场这几个方面对气泡成核、生长、聚结和分离行为进行了具体的归纳总结,讨论了各种强化气泡分离方法的特点,并展望了未来的发展方向和路线,为未来的电解气泡脱离技术的研究提供参考。     

添加SiO2质钝化剂改善焦炭热性能试验

对添加SiO2质钝化剂改善焦炭热性能效果进行了小试、中试和工业化实验。研究结果表明,用SiO2质钝化剂5‰水溶液直接喷洒熄焦对CSR有较好的改善作用,对焦炭冷强度M40影响很小;SiO2质钝化剂粉末添加到配合煤中,大幅降低了焦炭的热性能,起了相反作用;正常熄焦后再添加钝化剂水溶液几乎没有改善效果。     

集成CO2高效利用的煤制乙二醇过程设计与系统分析

为减少传统煤制乙二醇过程资源利用效率低和CO₂排放量高等问题，提出了一种集成CO₂高效利用的煤制乙二醇过程，并对其进行了全流程建模及系统分析。与传统过程不同，新过程利用焦炉气来提高其资源利用率和能量效率，集成甲烷干重整与湿重整技术降低CO₂排放。在全流程建模的基础之上，对新工艺的关键操作参数进行了分析与优化。结果表明，焦炉气的最佳进料比和甲烷蒸汽重整反应的分配比为0.68和0.74。与传统过程相比，新工艺的CO₂排放降低了94.05％，同时?效率提高了15.17％。     

Electrolytic pretreatment of Illinois No. 6 coal

Electrolysis of Illinois No. 6 coal in acidic as well as basic electrolytes accomplishes significant amount of sulfur and ash removal under moderate reaction conditions. Electrolysis at 1.4 V vs. SCE (saturated calomel electrode) in 2 M NaCl + 9% HCl electrolyte accomplishes 62% sulfur removal and leaves behind a clean coal with the sulfur to heating value ratio of 1.44 lb S/million Btu (0.619 kg S/GJ) while coal slurry oxidation at 3.0 V vs. SCE results in 72% ash removal. Coal electrolysis in basic electrolytes accomplishes a clean residue with relatively low oxygen content. The sulfur to heating value ratio of 2.11 lb S/million Btu (0.907 kg S/GJ) is observed for coal electrolyzed in 2 M NaOH at 3.0 V vs. SCE. Impurity removal from coal is simultaneously accompanied by clean hydrogen gas production at the cathode at Faradaic coulometric efficiencies of over 95%. Hydrogen gas is produced by the depolarization of water by mineral impurities present in coal. A relatively small amount of H₂ is produced due to water splitting caused by the carbonaceous part of the coal. Model reaction pathways for coal cleaning are discussed. More work is in progress on the types of sulfur forms removed from coal.     

基于配煤和表面修饰改善褐煤成浆性的研究

为改善褐煤成浆性,使其满足水煤浆气化需求,利用石油焦配煤,煤油作为表面修饰剂,研究改性方式对褐煤成浆性的影响。结果表明：（1）石油焦具有较强的疏水性,添加石油焦配煤显著提高褐煤的成浆浓度,且成浆浓度与石油焦占干基固体颗粒质量分数α（α>10.0%）正相关;（2）添加占干基固体颗粒质量β的煤油表面修饰配煤混合颗粒可以增强颗粒疏水性,进一步提高煤焦浆浓度,黏度随β先减小后增大,β最佳值与α（α>10.0%）负相关;（3）添加微量石油焦（α<1.0%）煤油悬浮液修饰时,可以提高煤油修饰效果,降低煤焦浆黏度η,α最佳值与β正相关。     

A reaction kinetic study of CO<Subscript>2</Subscript> gasification of petroleum coke,coals and mixture

Characteristics of Char-CO₂ gasification were compared in the temperature range of 1,100–1,400 °C using a thermogravimetric analyzer (TGA) for petroleum coke, coal chars and mixed fuels (Petroleum coke/coal ratios: 0, 0.25, 0.5, 0.75, 1). The results showed that reaction time decreased with increasing gasification temperature, BET surface area and alkali index of coal. Mixed fuels composed of petroleum coke/coal exhibited reduced activation energies. Modified volumetric reaction model and shrinking core model might be suitably matched with experimental data depending on coal type and petroleum coke/coal ratio. Rate equations were suggested by selecting gas-solid reaction rate models for each sample that could simulate CO₂ gasification behavior.     

烧结配料过程焦粉最低配比计算方法

提出了一种烧结过程焦粉最低配比计算方法。首先针对不同烧结终点位置、料层厚度的料层等温线数据建立烧结料层侧面温度场BP神经网络(back propagation neural network,BPNN)模型;然后采用最小二乘支持向量机(least squares support vector machine,LS-SVM)算法建立烧结终点位置、料层厚度等烧结过程状态变量与料层蓄热所需能量之间的关系模型;通过对烧结过程中主要物理、化学反应的分析,计算得到了水分蒸发与碳酸盐分解过程需要热量;最后通过对碳转换形式进行分析,计算得到烧结配料过程焦粉最低配比。仿真实验和工业实际数值算例表明,提出的焦粉最低配比计算方法能有效地反映实际生产所需的最低焦粉配比,从而为烧结过程节能减排提供重要的数值依据。