煤焦加压气化反应性研究

利用加压热分析仪,测定了义马煤焦的CO2气化反应性。结果表明:随温度的提高,义马煤焦的反应性和反应速度呈增加趋势,与前期研究常压下的情况一致;压力对气化反应的促进作用不明显,且温度对气化过程的影响大于压力;反应速率在初始阶段最大,随后逐渐减小。经过动力学计算表明:反应速率与温度的关系符合Arrhen ius定律;反应级数随温度增加而减小,近似于线性关系;煤焦活化能大约为60.02 kJ/mol。     

Reaction kinetics of gasification of black liquor char

CO₂ gasification of black liquor char, prepared from kraft spent pulping liquor is studied thermogravimetrically up to 775°C. The gasification rate is described by Langmuir-Hinshelwood type kinetics and activation energy is similar to that found for alkali metal impregnated porous carbons. However the rate is about 20 times larger than that of coal char mixed with 10-20% Na₂ CO₃. CO inhibition is relatively small and the rate is first order in carbon up to 80% conversion. The behavior is explained by a fine and three-dimensional dispersion of sodium salts in the char. The rate is insensitive to pulping conditions over the range of industrial practice.     

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。     

浅谈煤气化技术进展及选择

阐述了研究和开发煤气化技术的重要意义，详细介绍了目前国内外主流煤气化技术的进展及应用，比较了各种煤气化技术的优缺点，并对如何选择煤气化技术提出了自己的看法。     

K2CO3-catalysed steam gasification of supercritical extracted chars

The K₂C0₃-catalysed steam gasification of coal chars, obtained by the Supercritical Gas Extraction (SGE) process, is studied. Kinetics experiments used a gravimetric technique at atmospheric pressure and at temperatures ranging from 700 to 800 °C. It was found that K₂C0₃ is an effective catalyst for steam gasification of solvent extracted residue. The catalytic effect was similar to that observed for gasification of the unextracted parent coal. The gasification-time curves exhibited a sigmoid shape, which reduced to a single master curve for the various reaction temperatures studied and fitted well the predictions of the random capillary model. Activation energies, calculated using this model, varied from 155 to 173 kJ mol^?1 for the various chars studied.     

典型煤气化技术概述

我国煤炭资源丰富,能源消费以煤炭为主。煤炭气化是煤高效洁净利用的关键技术。分别对固定床、流化床及气流床气化工艺进行了简介,列举了典型的煤气化技术,分析了各自的工艺特点,并对其应用现状进行了综述。     

Reaction kinetics and internal diffusion of Zhundong char gasification with CO2

Mass transfer usually affects the rate of chemical reactions in coal.The effect of internal diffusion on char gasification with CO₂ in the temperature range from 1123 K to 1273 K was investigated via thermo-gravimetric analysis and assessment of char morphology features.The results revealed that the effect of internal diffusion on the initial reaction rate was more significant with an increase of particle size,due to the concentration gradient of the gasification agent within the solid particles.In the early stage of gasification,the generation of new micropores and the opening of closed pores led to an increase in specific surface area.As the reaction proceeded,the openings were gradually expanded and the specific surface area continued to increase.However,with further reaction,disappearance of edge pores,melting and collapse of the pore structure led to a decrease in specific surface area.The intrinsic activation energy and reaction order based on the nth-order model were 157.67 kJ?mol^?1 and 0.36,respectively.Thus,temperature zones corresponding to chemical reaction and diffusion control were identified.Moreover,the calculated effectiveness factor provided a quantitative estimation of internal diffusion in the initial stage.     

德士古煤气化工艺CO2排放分析

煤化工是高耗能高CO₂排放的工业,利用热力学分析方法对其工艺过程中能量利用情况进行分析,可以有效地发现工艺的能量利用缺陷和节能潜力,为过程的节能优化改造提供依据.目前热力学分析方法主要包括能量衡算法和(火用)分析法,本文在对传统热力学方法进行分析和评价的基础上,指出了已有方法的不足,提出了新的熵(火用)分析相结合的分析方法,并以德士古煤气化工艺为例,分别使用传统的能量衡算法、(火用)分析法和本文提出的熵(火用)结合分析法对工艺过程的能量利用情况进行了分析,获得了工艺过程中内各模块的能量、熵增和(火用)损分布.在此基础上,将(火用)损与工艺过程中CO₂排放量建立联系,经过计算得到了工艺过程中各个设备对应的CO₂排放分布和(火用)损系数,得出气化炉是工艺过程中主要的节能位置.这种能量与CO₂排放的关联能为工艺过程的节能减排提供理论依据.     

Kinetics of gasification of Douglas Fir and Cottonwood chars by carbon dioxide

Arrhenius kinetic parameters have been determined for the CO₂ gasification of chars (heat treatment at 1000 °C) prepared from well-characterized samples of a hardwood, a softwood and a Montana lignite. The effects of pre-pyrolysis addition of inorganic salts of the alkali, alkaline earth and transition metal groups to the wood samples have also been determined. The reactivities of the chars of the cottonwood and lignite samples exceeded that of Douglas fir char by a factor of four to seven between 700 and 900 °C. The reactivity of the wood char was related to the inorganic content of the sample. There was very little difference in the reactivity of chars prepared from the hardwood and the softwood after treatment with similar quantities of inorganic salts. The inorganic content of the lignite char was more than five times greater than that of cottonwood char, but its reactivity was similar. The carbonates of sodium and potassium were equally effective gasification catalysts. The transition metal salts were the most effective catalysts initially, but they lost their activity well before the gasification was complete. The data indicate that treatment of wood with aqueous salts results in replacement of some of the natural minerals by ion exchange, and that these exchangeable ions play a major role in controlling reactivity of the chars.     

Flax straw char‐CO2 gasification kinetics and its inhibition studies with CO

Char gasification has been studied in different ways with different feedstock; however, the fundamental studies about the variation of char reactivity with different combination of parameters are still required in order to design the biomass char gasification process in large scale unit. In this work, char from flax straw pyrolysis was used for gasification with different partial pressure of CO₂, different temperature and particle size. Results showed that 375‐µm particle sizes of char has higher reactivity compared to other particle sizes and the inhibition effect was also less at 375‐µm particle size. Kinetic parameters varied for gasification reaction with different particle sizes and the average activation energy was 196 kJ/mol and the order of the reaction was approximately 1. Inhibition studies with the addition of CO in the gasifying agent proved that CO molecules interfere significantly and reduced the reactivity. ANOVA test showed that the temperature plays a vital role in char reactivity. The particle sizes of 375 and 800 µm along with the CO₂ partial pressure of 0.35 bars are the best combination for achieving the maximum reactivity. © 2012 Canadian Society for Chemical Engineering     

Reactive intermediate in the alkali-carbonate-catalysed gasification of coal char

Based on results from a variety of experimental measurements, a detailed mechanism is postulated for the action of the inorganic catalyst in char gasification. In this mechanism, a catalyst such as potassium carbonate in contact with char undergoes a chemical and physical transformation to form a molten potassium oxide film that covers the char surface. This film serves as an oxygen transfer medium between the gaseous reactant (H₂O or CO₂) and the char. At the catalyst/char interface, an oxidation-reduction reaction occurs and the anions in the catalyst react with the oxidized char to form a phenolate-type functional group that subsequently splits out CO. The anions are replenished by reaction between the oxidizing gas (H₂O or CO₂) and the oxide at the gas/catalyst interface. Net transport of oxygen from gas to char occurs by diffusion of the species in the molten catalyst film.     

Intrinsic kinetics and external diffusion of catalytic steam gasification of fine coal char particles under pressurized and fluidized conditions

Catalytic steam gasification of fine coal char particles was carried out using a self-made laboratory reactor to determine the intrinsic kinetics and external diffusion under varying pressures (0.1-0.5 MPa) and superficial gas flow velocities (GF Vs) of 13.8- 68.8 cm· s^-1. In order to estimate the in-situ gas release rate at a low GFV, the transported effect of effluent gas on the temporal gasification rate pattern was simulated by the Fluent computation and verified experimentally. The external mass transfer coefficients(kmam) and the effectiveness factors were determined at lower GF Vs, based on the intrinsic gasification rate obtained at a high GFV of 55.0 cm·s^-1. The kmamwas found to be almost invariable in a wider carbon conversion of 0.2-0.7. The variations of kmam at a median carbon conversion with GFV, temperature and pressure were found to follow a modified Chilton-Colburn correlation:Sh=0.311Re^2.83Sc1/3(P/P0)^-2.07 (0.04相似文献   

Rate retardation phenomenon during gasification of Wandoan coal char

During the course of coal gasification, the rate per unit weight of remaining char often decreases as the coal conversion increases. The present study has tried to elucidate the reason why this rate retardation occurs. Possible reasons can be roughly divided into two categories; one due to the change of the mineral matter in char, and one related to the variation of carbon structure. Char samples at different conversion levels were prepared from raw and demineralized Wandoan coal. Their reactivities and other properties were examined, and their relationship was considered. The principal reason for the rate retardation in the present case was attributed to the loss of catalytic activity of mineral matter as the conversion increases.     

Catalytic gasification of chars

The gasification of pure and cobalt-doped chars obtained by carbonization of wood sawdust is compared. The catalytic action of cobalt affects both the kinetics of char gasification and the texture of the resulting porous carbons.     

CO2 gasification of wood charcoals derived from vacuum and atmospheric pyrolysis

The gasification of biomass derived char obtained via vacuum and atmospheric pyrolysis of Populus tremuloides has been studied in the ranges of 725–960°C and 0.1 to 6 MPa. CO₂ was used as the oxidizing gas. The results show that char reactivity is influenced by the preheating rates and that pressure effects are significant between 850°C and 950°C. A correlation based on the expression: df/dt = k₀{exp(-E/RT)}(1 - f)^af^βP^yCO₂ was used to fit the experimental data. In general, vacuum pyrolysis derived char showed a higher reactivity than atmospheric pyrolysis chars. An explanation based on a higher oxygen content of the vacuum pyrolysis char is suggested.     

煤焦二氧化碳气化动力学研究(Ⅰ) 等温热重法

在常压热天平上以等温法来研究神府煤焦 - CO2 气化反应 ,并用多种方法来求算动力学参数 ,实验结果表明 :随气化反应温度增加 ,煤焦炭转化率明显增加 ;不同反应温度下 ,煤焦 - CO2气化反应在 1 2 0 0℃以下为动力学控制阶段 ,1 2 0 0℃以上逐步过渡到扩散控制 ,表观活化能急剧降低     

Coal pyrolysis and gasification in a fluidized bed thermogravimetric analyzer

The kinetics and modelling of coal gasification were studied in the newly developed fluidized bed thermogravimetric analyzer. The total weight loss obtained from the fluidized bed reactor and the total gas product are in general agreement. The presented model for the micro‐fluidized bed reactor encompasses the kinetics of coal pyrolysis as well as the gasification reactions. For coal pyrolysis, the resulting activation energies for the individual gases were 34.7 to 59.8 kcal/mol. These values are 19 to 21 % lower than those found in the literature for similar coals. This decrease of the activation energies of the endothermic pyrolysis reactions is attributed to a gradient of temperature of 185 to 209 °C. The obtained activation energy for the CO shift reaction is 46.6 kcal/mol, increasing by 20 % from the one used in the literature. This increase of the activation energy of such a mildly exothermic reaction represents an equivalent of 170 °C gradient of temperature. The effects of temperature on the yield and the composition of the gas product are studied. Experimental results and equilibrium data are also compared. The model shows reasonably good agreement with the experimental results, except for the water gas shift reaction.

     

基于等转化率法的煤焦-CO_2气化动力学研究

为获得可靠的煤焦-CO_2气化反应动力学参数,采用Flunm-Wall-Ozawa(FWO)等转化率法进行煤焦-CO_2气化动力学研究。在3个不同升温速率下进行了煤焦-CO_2气化热重试验,计算不同碳转化率下的反应活化能,用主曲线法分析了气化机理模型,并采用拟合法对等转化率法的结果进行验证。结果表明,气化主反应区不同碳转化率下(α为0.2~0.8)活化能的变化较小,为(228.25±5.22)k J/mol。煤焦-CO_2气化反应为均相模型,该模型标准曲线与试验曲线重合度较好,并符合目前常用的煤气化动力学模型。拟合法计算的活化能仅与等转化率法相差0.74 k J/mol,说明等转化率法研究煤焦-CO_2动力学可行。