煤催化气化过程中钾催化剂回收的实验研究

对内蒙平庄煤-蒸汽催化气化过程残渣中KOH催化剂的回收进行了实验研究,考察了时间、温度、水渣比和洗涤次数等条件对钾催化剂回收率的影响。实验结果表明,水蒸气催化气化过程中,催化剂的流失可忽略不计。水洗法回收可溶钾占总钾量的80%,回收所得催化剂的有效成分为K2CO3和KOH,占总回收钾量的90%以上。钾收率随时间的增长而快速提高,一般洗涤4 h即可达到预期的收率;升高温度和增大水渣比能明显提高催化剂的收率;水洗洗涤3次,能回收90%左右的可溶钾。     

A study on the direct catalytic steam gasification of coal for the bench-scale system

Various techniques have been developed to increase the efficiency of coal gasification. The use of a catalyst in the catalytic-steam gasification process lowers the activation energy required for the coal gasification reaction. Catalytic-steam gasification uses steam rather than oxygen as the oxidant and can lead to an increased H₂/CO ratio. The purpose of this study was to evaluate the composition of syngas produced under various reaction conditions and the effects of these conditions on the catalyst performance in the gasification reaction. Simultaneous evaluation of the kinetic parameters was undertaken through a lab-scale experiment using Indonesian low rank coals and a bench-scale catalytic-steam gasifier design. The composition of the syngas and the reaction characteristics obtained in the lab- and bench-scale experiments employing the catalytic gasification reactor were compared. The optimal conditions for syngas production were empirically derived using lab-scale catalytic-steam gasification. Scale-up of a bench-scale catalytic-steam gasifier was based on the lab-scale results based on the similarities between the two systems. The results indicated that when the catalytic-steam gasification reaction was optimized by applying the K₂CO₃ catalyst to low rank coal, a higher hydrogen yield could be produced compared to the conventional gasification process, even at low temperature.     

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。     

Scanning electron microscopy of coal macerals

Individual macerals separated from some United Kingdom coals of Carboniferous age and bituminous rank were examined by scanning electron microscopy. In each case a specific morphology characteristic of the macerals studied could be recognized. Collinite (a member of the vitrinite maceral group) was recognizable in all samples by its angular shape and characteristic fracture patterns, the particles (30–200 μm) frequently showing striated or laminated surfaces. Sporinite particles had no well defined shape and were associated with more detrital material than were the other macerals studied. This detritus was shown by conventional light microscopy to be the maceral micrinite. Fusinite was remarkable in having a ‘chunky’ needle form, with lengths of up to 200 μm.     

添加剂对催化气化工艺中煤灰结渣性及气化性能影响研究

煤催化气化工艺中碱金属催化剂的引入加剧了气化炉的结渣，直接影响了流化床气化炉的正常操作。煤灰的烧结特性是流化床气化炉结渣的主要影响因素之一。通过自制的压差法烧结温度测定实验装置，并结合XRD 等分析表征及Factsage热力学软件模拟计算，考察了不同添加剂对煤灰烧结特性及气化性能的影响，并从矿物学角度探讨了添加剂对煤灰结渣特性及气化工艺的影响。结果表明，添加硅铝系添加剂可提高煤灰的烧结温度；相比硅系添加剂，添加高铝系添加剂对改善煤灰的烧结温度效果更明显；高铝系添加剂可作为一种高效的阻熔剂，但因在气化过程中容易同催化剂反应，导致催化剂催化性能降低，对煤的气化活性及催化剂回收率产生不利影响；添加氧化钙添加剂，煤的灰熔温度及烧结温度均增加，随氧化钙含量增加，灰熔点及烧结温度均升高，且对气化活性及催化剂回收率有良性作用；氧化钙可作为改善煤种结渣性的添加剂用于催化气化工艺中，需根据煤种性质及工艺特点确定适宜的添加量。     

Effect of catalyst on coal char structure and its role in catalytic coal gasification

The structure of the coal chars with and without catalyst was characterized using X-ray diffraction and laser Raman techniques. The catalyst changes the structure of the organic unit in coal char. The mechanism by which the catalyst affects the structure of coal char in pyrolysis was investigated by X-ray photoelectron spectroscopy. For the first time, the direct evidence of electron transfer in catalyst–coal interactions was obtained, and a K-Char intermediate forms. This makes it easier for H₂O to attack the K-Char intermediate, thus increasing the gasification reactivity of coal char.     

煤气化过程中钙催化作用的研究进展

煤的催化气化在国内外已被广泛研究, Ca作为一种对煤气化反应具有催化作用的碱土金属催化剂也受到许多研究者的关注。本文总结了可作为煤气化反应催化剂的Ca的类型, 论述了Ca催化煤气化反应的机理, 分析了影响Ca催化作用的主要因素, 指出当Ca与其他物质共同作为煤气化反应的催化剂时, 往往可以产生协同效应, 更有效地催化煤气化反应的进行。同时提出了今后在Ca催化煤气化反应方面所应进行的研究内容, 认为进一步探讨Ca在煤气化反应过程中发生的催化机理, 开发使用廉价的石灰石、熟石灰, 并且与其他物质, 尤其是纸浆黑液共同作为煤气化反应的催化剂很有必要。     

Exxon catalytic coal gasification process: Fundamentals to flowsheets

This Paper reviews basic features of the reaction kinetics of potassium-catalysed coal gasification and describes how small-scale data were used for the conceptual design of large fluidized-bed gasifiers. It shows how potassium was chosen from among the alkali metals, the importance of the methanation reaction, and of steam conversion.     

Studies on catalytic gasification of coal chars. Part 1. Development of pores during gasification

Chars prepared from three coals were impregnated with nickel catalyst and gasified with hydrogen at 850°C and 10 atm. The surface area and porosity of gasified residues at several conversions were measured. Blair Athol char, which had a relatively large surface area, showed a unique gasification pattern, i.e., the rate increased with time until a maximum was attained. Catalytic gasification resulted in an increase in the volume of macropores of a given diameter range, which was characteristic of the catalyst system used. In non-catalytic gasification and in cases when activity of the catalyst was low, mainly pores smaller than 6 nm were enlarged. Possible explanations of the acceleration of the rate are discussed and some consequences of the porosity measurements for this explanation are indicated. As the macropores are enlarged during catalytic gasification, the kinetic pattern could be modified when intraparticle diffusion comes into play.     

The kinetic study of catalytic low-rank coal gasification under CO2 atmosphere using MVRM

In this study, we carried out a kinetic investigation and analysis of the syngas produced by low-rank coal gasification. We conducted a proximate and ultimate analysis of six types of coals in order to measure the amount of sulfur and ash. The coal was then analyzed using a thermo gravimetric analyzer (TGA) to select a suitable sample. The selected Samhwa coal sample was mixed with catalysts. Samples mixed with catalysts were used to determine the activation energy under CO₂ atmosphere using the modified volume reaction model (MVRM). An analysis of the resulting syngas was performed using gas chromatography (GC).     

Modeling of catalytic gasification kinetics of coal char and carbon

Calcium- and potassium-catalyzed gasification reactions of coal char and carbon by CO₂ are conducted, and the common theoretical kinetic models for gas-carbon (or char) reaction are reviewed. The obtained experimental reactivities as a function of conversion are compared with those calculated based on the random pore model (RPM), and great deviations are found at low or high conversion levels as predicted by theory. Namely, calcium-catalyzed gasification shows enhanced reactivity at low conversion levels of <0.4, whereas potassium-catalyzed gasification indicated a peculiarity that the reactivity increases with conversion. CO₂ chemisorption analysis received satisfactory successes in both interpreting catalytic effects and correlating the gasification reactivity with irreversible CO₂ chemical uptakes (CCU_ir) of char and carbon at 300 °C. In details, calcium and potassium additions led to significant increases in CCU_ir and correspondent high reactivities of the char and carbon. Furthermore, CCU_ir of char and carbon decreased with conversion for calcium-catalyzed reaction but increased for potassium-catalyzed one, corresponded to the tendency of their reactivity. The RPM is extended and applied to these catalytic gasification systems. It is found that the extended RPM predicts the experimental reactivity satisfactorily. The most important finding of this paper is that the empirical constants in the extended RPM correlate well with catalyst loadings on coal.     

府谷煤CO2催化气化反应性的研究

加入适宜的催化剂可以提高气化反应速率,降低起始气化温度。为了研究不同阴离子（SO₄^2-、CO₃^2-、Cl^-）盐对府谷煤热失重过程的影响,利用热重分析仪对负载了8种催化剂（K₂CO₃、K₂SO₄、KCl;Na₂CO₃、Na₂SO₄、NaCl;FeSO₄、FeCl₂）的煤样进行了CO₂气化实验,其中每克府谷煤的K⁺、Na⁺、Fe²⁺负载量分别为0.001mol。同时采用升温动力学模型进行了数据拟合。实验结果表明：催化剂对煤与CO₂的低温热解并无明显的催化作用,而在高温气化阶段催化效果显著。对于钾盐和钠盐催化剂,当阳离子相同时,其催化活性顺序为：CO₃^2->SO₄^2->Cl^-。对于铁盐催化剂,FeSO₄的催化活性优于FeCl₂。动力学结果发现：负载催化剂煤样的活化能大小符合上述实验规律,分布在169～232.6kJ/mol之间,相比原煤（267.9kJ/mol）都有一定程度的降低。     

臭氧催化氧化技术深度处理煤气废水的实验研究

经生化法处理后的煤气废水,COD、总氰化合物、色度没有达到排放标准。通过实验研究了臭氧催化氧化技术对煤气废水的处理效果,并考察了反应时间、pH、催化剂对臭氧氧化效果的影响。实验结果表明,当反应时间>30 min、pH在9~12,臭氧有较高的氧化效率;当反应时间为30 min、pH=9时,煤气废水COD的去除率达到65.3%。TS-2型催化剂的使用使煤气废水COD去除率提高到66.9%,增加了1.6%。达到最佳时的反应时间降低了5 min。     

焦渣吸附-催化氧化法处理鲁奇炉煤气废水研究

对褐煤焦渣吸附、Fenton试剂氧化联合处理鲁奇炉煤气废水作了研究,分别考察了焦渣、H2O2、Fe2+投加量以及pH值、温度、时间等因素对COD去除率的影响,确定了最佳处理条件。实验结果表明,可使废水的COD值由1 880 mg/L降至90 mg/L,去除率达到95.16%,符合国家一级排放标准。同时,采用吸附-氧化法联合处理,不仅降低了直接使用Fenton试剂氧化的处理成本,而且为焦渣开辟了新的用途。     

Numerical study on the coal gasification characteristics in an entrained flow coal gasifier

The coal gasification process of a slurry feed type, entrained-flow coal gasifier was numerically predicted in this paper. By dividing the complicated coal gasification process into several simplified stages such as slurry evaporation, coal devolatilization and two-phase reactions coupled with turbulent flow and two-phase heat transfer, a comprehensive numerical model was constructed to simulate the coal gasification process. The k– turbulence model was used for the gas phase flow while the Random-Trajectory model was applied to describe the behavior of the coal slurry particles. The unreacted-core shrinking model and modified Eddy break-up (EBU) model, were used to simulate the heterogeneous and homogeneous reactions, respectively. The simulation results obtained the detailed information about the flow field, temperature and species concentration distributions inside the gasifier. Meanwhile, the simulation results were compared with the experimental data as a function of O₂/coal ratio. It illustrated that the calculated carbon conversions agreed with the measured ones and that the measured quality of the syngas was better than the calculated one when the O₂/coal ratio increases. This result was related with the total heat loss through the gasifier and uncertain kinetics for the heterogeneous reactions.     

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。     

煤催化气化工艺中内蒙王家塔烟煤灰烧结温度的影响因素分析

煤催化气化工艺中碱金属催化剂的引入加剧了气化炉的结渣,直接影响了流化床气化炉结渣的正常操作。煤灰的烧结特性是流化床气化炉结渣的主要影响因素之一,通过摸索工艺条件使煤气化在烧结温度以下运行,可有效避免流化床气化炉内出现结渣问题。利用压差法测定烧结温度,结合灰渣的XRD分析结果系统研究了钾基碱金属催化剂的添加量、操作压力、反应气氛对王家塔烟煤低温灰化煤灰烧结温度的影响。结果表明,碳酸钾催化剂的添加明显降低了煤的灰熔点及烧结温度。0.1～3.5 MPa下,烧结温度随压力增大而降低,而且压力对烧结温度的影响在高压区更为明显,具体影响规律与煤种灰成分及钾基碱金属催化剂的添加有关。空气、CO₂氧化性气氛下的烧结温度较高,N₂惰性气氛下次之,还原性气氛下较低,而蒸汽的加入显著降低了烧结温度。烧结温度的变化与不同气氛下铁离子存在状态及钾的存在形态密切相关。蒸汽气氛下,钾更多以KOH等低熔点化合物形态存在,而且含钾物相在蒸汽气氛下更容易同煤灰中的硅铝、铁钙等矿物质反应,生成低共融点化合物,致使灰熔点及烧结温度大幅下降。     

串行流化床煤气化试验

针对串行流化床煤气化技术特点,以水蒸气为气化剂,在串行流化床试验装置上进行煤气化特性的试验研究,考察了气化反应器温度、蒸汽煤比对煤气组成、热值、冷煤气效率和碳转化率的影响。结果表明,燃烧反应器内燃烧烟气不会串混至气化反应器,该煤气化技术能够稳定连续地从气化反应器获得不含N₂的高品质合成气。随着气化反应器温度的升高、蒸汽煤比的增加,煤气热值和冷煤气效率均会提高,但对碳转化率影响有所不同。在试验阶段获得的最高煤气热值为6.9 MJ&#8226;m^-3,冷煤气效率为68％,碳转化率为92％。