CO2 gasification rate analysis of coal char in entrained flow coal gasifier

Coal chars of four coal types were gasified with carbon dioxide using a PDTF or TGA at high temperature and pressure. Test conditions of temperature and partial pressure of the gasifying agent were determined to simulate the conditions in air-blown or oxygen-blown entrained flow coal gasifiers. Coal chars were produced by rapid pyrolysis of pulverized bituminous coals using a DTF with a nitrogen gas flow at 1670 K. In gasification tests with the PDTF, gasification temperatures were 1670 K or below and partial pressures of carbon dioxide were 0.7 MPa or below. Carbon monoxide of 0.6 MPa or below was supplied for the gasification tests with the TGA.As a result, coal types showed a large difference in the char gasification rate with carbon dioxide, and this difference remained large without decreasing even in the high-temperature area when the gasification rate was controlled by pore diffusion the same as in entrained flow gasifiers. Inhibition of the gasification reaction by carbon monoxide was also observed. Reaction rate equations of both the nth order and Langmuir-Hinshelwood type were applied to the char gasification reaction with the random pore model and the effectiveness factor, and the applicability of these rate equations to air-blown and oxygen-blown entrained flow gasifiers evaluated. Gasification rate equations and kinetic parameters applicable to a pore diffusion zone at high temperature were obtained for each coal.     

滴管炉内不同煤阶煤焦水蒸气气化反应特性

在滴管炉内对煤焦与水蒸气气化反应进行了实验研究,考察了煤阶、气化温度、水蒸气与进料煤焦质量比（气焦比）对气化气体产物释放特性以及煤焦转化率的影响。实验温度为1100、1200、1300和1400℃,气焦比分别为0.4：1、0.6：1和1：1。研究发现：滴管炉内不同煤焦的水蒸气气化气体产物以H₂含量最高,CH₄含量最低。不同煤阶热解焦、气化温度以及气焦比的变化影响滴管炉内水蒸气气化产物气体组成和转化率的高低。随气化温度的升高,神府煤焦和北宿煤焦气化气体产物中H₂和CO产率不断增大,H₂/CO的比值则逐渐减小,碳转化率有不断增加的趋势。在气化温度大于1200℃的条件下,当气焦比从0.4：1增至0.6：1,神府煤焦和北宿煤焦的碳转化率变化幅度不大（5%以内）;当气焦比从0.6：1增至1：1,北宿煤焦的碳转化率略微降低,而神府煤焦的碳转化率增幅则在15%以上。     

Comparison of steam-gasification characteristics of coal char and petroleum coke char in drop tube furnace

The steam-gasification reaction characteristics of coal and petroleum coke (PC) were studied in the drop tube fur-nace (DTF). The effects of various factors such as types of carbonaceous material, gasification temperature (1100–1400 °C) and mass ratio of steam to char (0.4:1, 0.6:1 and 1:1 separately) on gasification gas or solid products were investigated. The results showed that for al carbonaceous materials studied, H2 content exhibited the larg-est part of gasification gaseous products and CH4 had the smal est part. For the two petroleum cokes, CO2 content was higher than CO, which was similar to Zun-yi char. When the steam/char ratio was constant, the carbon con-version of both Shen-fu and PC chars increased with increasing temperature. When the gasification temperature was constant, the carbon conversions of al char samples increased with increasing steam/char ratio. For al the steam/char ratios, compared to water gas shift reaction, char-H2O and char-CO2 reaction were further from the thermodynamic equilibrium due to a much lower char gasification rate than that of water gas shift reaction rate. Therefore, kinetic effects may play a more important role in a char gasification step than thermodynamic ef-fects when the gasification reaction of char was held in DTF. The calculating method for the equilibrium shift in this study wil be a worth reference for analysis of the gaseous components in industrial gasifier. The reactivity of residual cokes decreased and the crystal layer (L002/d002) numbers of residual cokes increased with increasing gasification temperature. Therefore, L002/d002, the carbon crystallite structure parameter, can be used to evaluate the reactivity of residual cokes.     

Enhanced catalysis of K2CO3 for steam gasification of coal char by using Ca(OH)2 in char preparation

A novel approach has been proposed for mitigating the potassium deactivation in the K₂CO₃-catalyzed steam gasification of coal char by addition of Ca(OH)₂ in the char preparation. It was experimentally found that the Ca(OH)₂-added char had higher reactivity for the catalytic gasification than the raw char. Ca(OH)₂ played a role in suppressing the interactions of K₂CO₃ with acidic minerals in coal during the gasification and also probably in forming more active oxygenated intermediate on the char surface. The distribution of gaseous products was examined during the catalytic gasification. An oxygen transfer and intermediate hybrid mechanism is applied for understanding of the rate and selectivity of the catalytic gasification.     

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.     

Gasification of an Indonesian subbituminous coal in a pilot-scale coal gasification system

Indonesian Roto Middle subbituminous coal was gasified in a pilot-scale dry-feeding gasification system and the produced syngas was purified with hot gas filtering and by low temperature desulfurization to the quality that can be utilized as a feedstock for chemical conversion. Roto middle coal produced syngas that has a typical composition of 36–38% CO, 14–16% H₂, and 5–8% CO₂. Particulates in syngas were 99.8% removed by metal filters at the operating temperature condition of 200–250°C. Sulfur containing compounds of H₂S and COS in syngas were also desulfurized in the Fe chelate system to yield less than 0.5 ppm level. The full stream gasification and syngas purifying system has been successfully operated and thus can provide clean syngas for the research on the conversion of syngas to chemicals like DME and on the future IGFC using fuel cells. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Coal char combustion under a CO2-rich atmosphere: Implications for pulverized coal injection in a blast furnace

Pulverized coal injection (PCI) is employed in blast furnace tuyeres attempting to maximize the injection rate without increasing the amount of unburned char inside the stack of the blast furnace. When coal is injected with air through the injection lance, the resolidified char will burn in an atmosphere with a progressively lower oxygen content and higher CO₂ concentration. In this study an experimental approach was followed to separate the combustion process into two distinct devolatilization and combustion steps. Initially coal was injected into a drop tube furnace (DTF) operating at 1300 °C in an atmosphere with a low oxygen concentration to ensure the combustion of volatiles and prevent the formation of soot. Then the char was refired into the DTF at the same temperature under two different atmospheres O₂/N₂ (typical combustion) and O₂/CO₂ (oxy-combustion) with the same oxygen concentration. Coal injection was also performed under a higher oxygen concentration in atmospheres typical for both combustion and oxy-combustion. The fuels tested comprised a petroleum coke and coals currently used for PCI injection ranging from high volatile to low volatile bituminous rank. Thermogravimetric analyses and microscopy techniques were used to establish the reactivity and appearance of the chars.     

Experimental studies on gasification of the Shenmu coal char with CO2 at elevated pressures

The gasification rates of Shenmu coal chars with CO₂ were experimentally studied with a pressurized thermo- gravimetric analyzer (PTGA). Shenmu coal is a typical Chinese coal, and the coal char was prepared by a fixed-bed reactor in nitrogen at 900 °C. The experiments were carried out in the dynamic heating segments from 750 °C to 1,000 °C, and the reaction pressure increased from 0.1MPa to 3.1MPa with pure CO₂. The external diffusion resistances were minimized by increasing the flow rates and decreasing the thickness of sample layer before the test, to ensure the reactions were under kinetic control. The results show that the gasification rates increase proportionally to the 0.1 power of the CO₂ partial pressure. The unreacted-core shrinking model was applied to predict the reaction rate by changing the molar fraction of CO₂ at 0.6Mpa and 1.6Mpa total pressures, which showed a good match with experimental data. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

高温烟气中煤焦气化行为

针对高温烟气中煤焦的气化行为,本文采用FactSage 6.1计算了煤焦在高温烟气下的高温反应特性,并利用热重分析仪分析了煤焦气化行为。通过沉降炉实验进一步研究了不同温度、气体配比、粒径条件下气体产物的动态析出特性,同时计算了评价指标α、β、LHV值。结果表明：随着温度的升高,气体产物H₂和CO的含量增加,β、α、LHV值增大,CH₄和CO₂的含量下降。在温度为1200℃时,β、α值分别由CO₂/CO比为10∶70时的10.80%、5.21%增加到CO₂/CO比为50∶30时的24.71%、41.06%。同时,随着CO₂/CO比值的增大,高温烟气对煤焦气化反应抑制减弱。通过对比反应温度和粒径对煤焦气化反应的影响,得出反应温度远大于粒径对煤焦气化反应的影响。通过实验验证了向高温烟气中喷吹煤焦制备高品质可燃气体方法的可行性。     

Reactivity and structural change of coal char during steam gasification

This study is intended to clarify the relationship among the reactivity of coal char with steam, structural change in residual carbon, and ash behavior. Steam gasification of various coal chars and demineralized chars was carried out in a fixed-bed reactor. After gasification, the reacted char was analyzed using laser raman spectroscope (LRS), and scanning electron microscope, energy dispersive X-ray spectroscope (SEM/EDX) mapping. Results of SEM images and EDX-mappings revealed that novel parallel analysis of cross correlation between EDX-mapping and LRS-mapping was found to be very effective for the comprehensive evaluation of ash behavior and carbonaceous structure. As the gasification reaction proceeds, the reactivity of the char was varied; existence of Si and Al seemed to suffocate the char reactivity.     

MODELLING OF THE INTERACTION OF NITROGEN DIOXIDE WITH ACTIVATED CARBON II. KINETICS OF REACTION WITH PORE EVOLUTION

Adsorption of nitrogen dioxide on activated carbon is found to be followed by reaction with the carbon surface at temperatures higher than 373 K. The dynamics of the nitrogen dioxide reaction with the carbon are measured gravimetrically over the temperature range 423-623 K. At small particle sizes (0.014 cm radius) the overall gasification kinetics are controlled by the surface reaction step, and are first order in nitrogen dioxide concentration. Using the random pore model to describe the evolution of reaction surface with porosity, the experimental data are fitted by a kinetic control gasification model, giving an activation energy of 86.2 kJ/mole.     

Gasification reaction kinetics on biomass char obtained as a by-product of gasification in an entrained-flow gasifier with steam and oxygen at 900-1000 °C

The purpose of this study was to investigate the gasification kinetics of biomass char, such as the wood portion of Japanese cedar char (JC), Japanese cedar bark char (JB), a mixture of hardwood char (MH) and Japanese lawngrass char (JL), each of which was obtained as a by-product of gasification in an entrained-flow type gasifier with steam and oxygen at 900-1000 °C. Biomass char was gasified in a drop tube furnace (DTF), in which gasification conditions such as temperature (T_g), gasifying agent (CO₂ or H₂O), and its partial pressure (P_g) were controlled over a wide range, with accompanying measurement of gasification properties such as gasification reaction ratio (X), gasification reaction rate (R_g), change of particle size and change of surface area. Surfaces were also observed with a scanning electric microscope (SEM). By analyzing various relationships, we concluded that the random pore model was the most suitable for the biomass char gasification reaction because of surface porosity, constant particle size and specific surface area profile, as well as the coincidence of R_g, as experimentally obtained from Arrhenius expression, and the value is calculated using the random pore model. The order of R_g was from 10⁻² to 10⁻¹ s⁻¹, when T_g = 1000 °C and P_g = 0.05 MPa, and was proportional to the power of P_g in the range of 0.2-0.22 regardless of gasifying agent. Reactivity order was MH > JC > (JB, JL) and was roughly dependent on the concentration of alkali metals in biomass feedstock ash and the O/C (the molar ratio of oxygen to carbon) in biomass char.     

Effect of pyrolysis pressure and heating rate on radiata pine char structure and apparent gasification reactivity

The knowledge of biomass char gasification kinetics has considerable importance in the design of advanced biomass gasifiers, some of which operate at high pressure. The char gasification kinetics themselves are influenced by char structure. In this study, the effects of pyrolysis pressure and heating rate on the char structure were investigated using scanning electron microscopy (SEM) analysis, digital cinematography, and surface area analysis. Char samples were prepared at pressures between 1 and 20 bar, temperatures ranging from 800 to 1000 °C, and heating rates between 20 and 500 °C/s. Our results indicate that pyrolysis conditions have a notable impact on the biomass char morphology. Pyrolysis pressure, in particular, was found to influence the size and the shape of char particles while high heating rates led to plastic deformation of particles (i.e. melting) resulting in smooth surfaces and large cavities. The global gasification reactivities of char samples were also determined using thermogravimetric analysis (TGA) technique. Char reactivities were found to increase with increasing pyrolysis heating rates and decreasing pyrolysis pressure.     

Modelling of combustion characteristics of high ash coal char particles at high pressure: Shrinking reactive core model

Combustion of a single-particle high ash coal char at elevated pressure has been analyzed. A fully transient shrinking reactive core model incorporating a simple mechanistic kinetic scheme is used to study the combustion characteristics of high ash coal char. The model includes heat and mass transfer phenomena, reaction kinetics and intra-particle details. Finite volume method (FVM) has been used to solve partial differential equations representing fully transient conservation equations. The char combustion model predicts the mass-loss profile and burnout time of the char particle at different temperature and oxygen concentration. The computed results are found to agree well with the published experimental findings of pressurized combustion of high ash coal char. The effects of bulk temperature, total pressure and initial particle size on combustion characteristic and burnout time have been examined through model simulation.     

微型流化床反应分析及其对煤焦气化动力学的应用

在概述最新研发的微型流化床反应分析(micro-fluidized bed reaction analysis,MFBRA)方法与应用的基础上,应用该方法进一步研究了半焦-CO₂、半焦-水蒸气等温气化反应动力学,并与热重分析(thermogravimetric analyzer,TGA)求取的气化反应动力学数据比较。在最小化气体扩散的实验条件下,利用MFBRA和TGA测定求算的半焦-CO₂、半焦-水蒸气气化反应在受反应动力学控制的低温段的活化能非常接近,说明了MFBRA对等温气化反应分析的适用性和可靠性。实验研究还发现:半焦-CO₂、半焦-水蒸气气化反应在MFBRA中受反应动力学控制的温度范围较在TGA中明显宽,且在具有明显扩散影响的高温段通过MFBRA测定的半焦-CO₂气化反应表观活化能明显大于利用TGA测定的值,表明在MFBRA中受到的气体扩散抑制效应较小。     

Characterization of porous structure of coal char from a single devolatilized coal particle: Coal combustion in a fluidized bed

The combustion characteristics of coal char are highly dependent on initial pore structure of devolatilized char as well as on the structural evolution during the combustion of char. The development of pore structure also throws light on the mechanism of the combustion process. In the present work evolution of pore structure of partially burnt coal char of Indian origin has been investigated experimentally in a batch-fluidized bed and analyzed. The BET surface area, micropore surface area and porosity of char at various levels of carbon burn-off have been determined. Experimental specific surface area has been found to agree well with theoretical prediction using random pore model. Modified random pore model is used to determine the active surface area. Char combustion mechanism based on shrinking unreacted core and shrinking reacted core models are delineated during the course of reaction at various bed temperatures. This is substantiated with the proportional representation of ash and carbon matrix in scanning electron microscope images. It is also concluded that in the present investigation the mean pore size is much smaller and hence the Knudsen diffusion predominates. Analysis based on similar experimental observations and models for pore structure evolution to investigate char combustion reaction regime has not been reported in literature.     

煤焦燃烧特性及反应活性探究

中国褐煤资源丰富,然而由于褐煤自身特点使其应用受到了极大的限制。针对中国褐煤应用最广的途径———燃烧,借助热重分析仪对不同热解终温的褐煤半焦及热解终温为1273 K的褐煤半焦与原煤的混合燃料的燃烧特性进行了分析。并利用Coats-Redfern法进行了燃烧动力学的分析,通过求得的表观活化能表征煤焦的燃烧反应活性。研究发现：热解终温越高,煤焦的燃烧特性越差;掺混褐煤有助于提高其半焦的燃烧特性,而掺混燃料的燃烧稳定性几乎和原煤无差别,且随着掺混比例的增加,混合燃料的活化能逐渐增大,越不易点燃,掺混半焦对燃料的燃烧特性和反应活性都有影响。相同制备条件下的烟煤半焦和褐煤半焦的燃烧动力学参数尤其是活化能相差很大,可见煤焦的燃烧反应活性与煤种有关。     

Catalytic effect of Na–Fe on NO–char reaction and NO emission during coal char combustion

The catalytic reduction of NO over coal-derived chars and the catalytic effect of Na–Fe on NO emission during char combustion were investigated in a quartz fixed bed reactor. The catalytic characteristics of Na and Fe in the NO–char reaction were studied and compared in detail. The results show that the catalytic activity of Na depends greatly on its loading amount, while the activity of Fe is more sensitive to temperature. Na–Fe composite catalysts were also prepared with chars as support. Synergistic effect was found both in the reduction of NO and the char combustion. The Na–Fe composite catalysts exhibit significantly higher catalytic activity than the mono-metallic catalysts with the same metal loading amount. It is intriguing to note that the effectiveness of the catalysts on reducing NO emission during char combustion is in the same order as that in the NO–char reaction, i.e. the chars with catalysts not only have high activity in NO–char reaction but also emit less NO during their combustion.     

Mineral reaction and morphology change during gasification of coal in CO2 at elevated temperatures

Studies of the gasification of char in CO₂ at elevated temperatures are necessary for the development of IGCC technology. Experiments at high heating rates and elevated temperatures revealed that the temperature dependence of gasification reactivity was very different for low compared with high temperature ranges. To elucidate these mechanisms, the reaction of mineral matter and the change in morphology during gasification of a char at elevated temperatures were examined by char characterisation. CO₂ gasification experiments showed a large difference in gasification rate for chars prepared at higher temperatures compared to those prepared at lower temperatures. Changes in char particle morphology and mineral matter during gasification are also quite different. At higher carbonisation temperatures, mineral reactions during pyrolysis, which occurs in addition to ash fusion, appear to be one of the factors accounting for these differences. Certainly, a change of mechanism is involved. Graphite enrichment may also contribute to the decrease in char reactivity.     

Gasification reactivity of charcoal with CO2. Part II: Metal catalysis as a function of conversion

The catalytic influence of major metal species found with waste wood (Na, K, Ca, Mg, Zn, Pb, Cu) was studied during the gasification of nitrate salt impregnated charcoal with CO₂ at 800°C in the kinetically controlled regime. In contrast with literature, the respective reaction rate data were analysed over the entire carbon conversion (X) range by using extended kinetic relations to quantify catalyst metal-specific reaction rate contributions not accounted for by the original random pore model of Bhatia and Perlmutter. The kinetic analysis provided valuable insights in the underlying mechanisms. With alkali nitrate impregnated charcoal, it is demonstrated that the often found reaction rate maximum around X∼0.7 may merely reflect increasing catalytic activity resulting from alkali accumulation in the charcoal, superimposed on structural changes in the charcoal micropore domain. Impregnated earth-alkali nitrates revealed substantial activity as well, but only during the early gasification stage (X<0.2), hereby, underlining their sintering propensity in combination with the localised deposition of the earth-alkaline nitrate salt in the former wood cells by the impregnation procedure. Added heavy metal nitrates revealed no activity, apart from lowering the charcoal reactivity over the entire conversion range by ca. 15% compared with the untreated charcoal, suggesting inhibition by covering, hence, blocking of otherwise accessible active charcoal surface sites and/or by deactivation of neighbouring indigenous alkali due to immobilisation at the heavy metal oxide surfaces formed during pyrolysis. The extended kinetic relation reproduced all of our reaction rate data well over the entire gasification stage, hereby, supporting the superposition of micropore domain and catalyst specific effects.