添加煤灰及混合氧化物对石油焦CO2高温气化反应的影响

以化学组成相近的燃烧煤灰、气化煤灰和混合氧化物为添加剂,分别通过干混法和湿混法加入石油焦中,并借助热重分析仪在1200-1400 ℃下进行CO₂气化实验,研究高温下煤灰掺混方式、含量及物相组成对石油焦CO₂气化的影响,并使用混合氧化物替代实际煤灰研究其对石油焦的高温气化催化作用。结果表明,石油焦气化反应速率随煤灰添加量的增加而提升;气化温度为1200、1300 ℃时,使用干混法和气化煤灰对石油焦的气化促进作用较弱;但气化温度为1400 ℃时,改变煤灰和石油焦的掺混方式及其中活性金属存在方式,对石油焦气化反应几乎没有影响。这是高温下煤灰熔融,导致液态熔体与石油焦表面接触良好、活性金属自由度高以及传质阻力增加共同作用的结果。此时混合氧化物的催化指数与混合物中铁钙含量具有线性关系,即添加高铁钙含量的煤灰可以促进石油焦CO₂气化反应。     

稻秆焦炭热解和CO2气化过程中碱金属和碱土金属的迁移

研究了稻秆焦炭中碱金属与碱土金属（AAEMs）在N₂热解和CO₂气化气氛下的迁移过程。通过对不同热处理时间的固相样品分析,得到了两种气氛下AAEMs的迁移规律,并讨论了CO₂气化气氛对AAEMs迁移的影响机理。在两种气氛下,K的释放比例都随热处理时间延长先快速增加,然后缓慢增加,而Ca和Mg的释放比例都很低。气化前期K的释放比例高于热解,气化后期K的释放比例与热解几乎相同。热解时,焦炭中酸溶K和Ca的比例先降低然后维持稳定,而酸溶Mg的比例几乎不变。气化时,酸溶K的比例先缓慢降低,然后迅速降低;酸溶Ca和Mg的比例则先增加后迅速降低。气化前期,酸溶AAEMs的比例要高于热解相同时间的焦炭样品;气化后期,酸溶AAEMs的比例则明显低于热解焦炭样品。CO₂通过与焦炭有机结构反应,促进了char-K的释放,提高了K的释放比例,也促进了难溶的有机结合的AAEMs分解为酸溶AAEMs;在焦炭气化后期,焦炭中的Si会与AAEMs反应生成难溶硅酸盐。     

Sulfur evolution from coal combustion in O2/CO2 mixture

O₂/CO₂ coal combustion technology is considered as one of the most promising technologies for CO₂ sequestration due to its economical advantages and technical feasibility. It is significant to study the sulfur transfer behavior of coal in O₂/CO₂ atmosphere for organizing combustion properly and controlling SO₂ emission effectively. To clarify the effect of atmosphere on the sulfur transfer behavior, thermogravimetry coupled with Fourier Transform Infrared (TG-FTIR) system was employed to study the formation behavior of sulfur-containing gas species from Xuzhou bituminous coal pyrolysis in CO₂ atmosphere compared with that in N₂ atmosphere. Also the SO₂ formation behaviors during Xuzhou bituminous coal combustion in O₂/N₂ and O₂/CO₂ atmospheres were investigated. Results show that COS is preferentially formed during the coal pyrolysis process in CO₂ atmosphere rather than in N₂ atmosphere. When temperature is above 1000 K, sulfate in the CO₂ atmosphere begins to decompose due to the reduction effect of CO, which comes from the CO₂ gasification. During coal combustion process, replacing N₂ with CO₂ enhances the SO₂ releasing rate. SO₂ emission increases first and then decreases as O₂ fraction increases in the O₂/CO₂ mixture. XPS result of the ash after combustion indicates that higher O₂ concentration elevates the sulfur retention ability of the mineral matter in the coal.     

Experimental and kinetic investigation of the pyrolysis,combustion, and gasification of deoiled asphalt

The pyrolysis, combustion, and gasification behaviors of deoiled asphalt were studied by a thermogravimetric analyzer and the kinetics were also analyzed using a multi-stage first-order integral model. All the experiments were conducted at non-isothermal conditions with heating rates range of 10–40 K min^?1 under N₂ (pyrolysis), air (combustion), or CO₂ (gasification) atmosphere, respectively. The results showed that, for pyrolysis, the reaction mainly occurred between 498 and 798 K and could be divided into two stages: the first was caused by the volatilization of small molecules and the second probably due to the cracking reactions. For combustion, the mass loss process could be divided into three stages: the devolatilization and oxidation first, the ignition and combustion of the volatiles second, and finally the combustion of the formed char. Under CO₂ atmosphere, the mass loss behavior was similar with that of the N₂ atmosphere at lower temperatures, but when the temperature was higher than 1,233 K, the gasification reaction obviously happened. The results of kinetic investigation showed that the multi-stage first-order integral method agreed well with the above experiments.     

Thermogravimetric analysis of gasification reactivity of coal chars with steam and CO2 at moderate temperatures

Comparative study on the gasification reactivity of the three types of Chinese coal chars with steam and CO₂ at 850–1050 °C was conducted by isothermal thermogravimetric analysis. The effects of coal rank, pore structure, ash behavior, and gasification temperature on the gasification reactivity of coal chars were investigated. It is found that the gasification reactivity difference between different coal chars changes with reaction degree and gasification temperature, and has no immediate connection with coal rank and initial pore structure. Ash behavior plays an important role in the char reactivity, and changes with gasification temperature and reaction degree due to the variation in the compositions and relative amount. The influence of pore structure is more noticeable during a relatively moderate reaction process. The relative reactivity ratio of steam to CO₂ gasification generally decreases with the increasing temperature, and is related with the catalytic effect of inherent minerals. The characteristic parameters of the chars were analyzed, finding that the value of half reaction specific rate is approximate to the average specific rate under the same conditions. The nth-order distributed activation energy model is proposed to describe the coal char gasification process, and the results show that the activation energy increases with the increasing carbon conversion.     

应用TG-FTIR联用研究催化剂对煤热解的影响

用TG-FTIR联用技术研究了碱金属、碱土金属和过渡金属对宝日希勒褐煤和包头烟煤热解的催化作用和挥发分析出的影响。结果表明，各种催化剂对褐煤和烟煤热解的催化效果分别为Ni>Fe~Ca>K和Ca~Fe>Ni>K，K2CO3对煤的热解没有明显的催化作用。催化剂使褐煤和烟煤热解转化率增加的最大值分别为10.1％和6.4％。烟煤热解生成的CH4比褐煤的多，不同的催化剂使煤热解挥发产物CO2、H2O、CH4和CO增加的幅度不一样，催化效果与温度和煤的变质程度有关。     

内在矿物对高灰褐煤CO_2气化的影响研究

利用分选结合逐级酸洗的方法制备出不同灰含量和矿物组成的褐煤煤样,使用沉降管反应器(DTR)和热重分析仪(TGA)研究内在矿物在1 000-1 200℃对褐煤CO_2气化的影响。结果表明,内在矿物对褐煤CO_2气化具有促进作用,且促进机制具有温度敏感性。低温时(1 000℃),内在矿物可通过增加初生半焦微晶结构的无序度,间接提高气化碳转化率。高温时(1 100-1 200℃),内在矿物通过催化煤焦气化,直接促进气化碳转化率的上升。碱性指数不适用于表征本研究的褐煤内在矿物的催化作用。Ca是内在矿物中影响整体催化能力的主要成分,而且羧酸盐形式的Ca是其中的活性组分。不同的催化机制是导致煤焦中钙的催化活性因其化学形式而异的根本原因。羧酸盐形式的Ca可降低煤焦气化反应的活化能,而CaO则提高反应的表观频率因子。     

CO2 gasification of woody biomass chars: The influence of K and Si on char reactivity

Although the influence of metallic and alkaline elements on biomass char reactivity is well known, a quantitative assessment of this catalytic effect is hard to obtain because of the chemical and textural complexity of biomass. The effect of K and Si on the CO₂ gasification reactivity of a biomass char was studied using thermogravimetric analysis. A beech sample was pyrolyzed at 800 °C and then impregnated with known amounts of silicon or potassium allowing to obtain a wide range of K/Si ratios. The reactivity of the impregnated samples was studied under a CO₂ (20% vol.) atmosphere. The results show that at low conversion ratios, the char reactivity depends on its textural properties, with strong diffusional limitations. When conversion reaches 60%, the presence of a catalyst (K) and an inhibitor (Si) becomes the major parameter influencing reactivity. From these experiments, a general trend was obtained between K/Si ratio and reactivity as a function of conversion.     

Continuous high-temperature fluidized bed pyrolysis of coal in complex atmospheres: Product distribution and pyrolysis gas

This study is devoted to investigating the continuous coal pyrolysis in a laboratory fluidized bed reactor that fed coal and discharged char continuously at temperatures of 750–980 °C and in N₂-base atmospheres containing O₂, H₂, CO, CH₄ and CO₂ at varied contents. The results showed that the designed continuous pyrolysis test provided a clear understanding of the coal pyrolysis behavior in various complex atmospheres free of and with O₂. The effect of adding H₂, CO, CH₄ or CO₂ into the atmosphere on the tar yield was related to the O₂ content in the atmosphere. Without O₂ in the atmosphere, adding H₂ and CO₂ decreased the pyrolysis tar yield, but the tar yield was conversely higher with raising the CO and CH₄ contents in the atmosphere. In O₂-containing atmospheres, the influence from varying the atmospheric gas composition on the product distribution and pyrolysis gas composition was closely related to the oxidation or gasification reactions occurring to char, tar and the tested gas.     

Coal pyrolysis in a fluidized bed reactor simulating the process conditions of coal topping in CFB boiler

Simulating the conditions of pyrolytic topping in a fluidized bed reactor integrated into a CFB boiler, the study was devoted to the reaction fundamentals of coal pyrolysis in terms of the production characteristics of pyrolysis oil in fluidized bed reactors, including pyrolysis oil yield, required reaction time and the chemical species presented in the pyrolysis oil. The results demonstrated that the maximal pyrolysis oil yield occurred on conditions of 873 K, with a reaction time of 3 min and in a reaction atmosphere gas simulating the composition of pyrolysis gas. Adding H₂ and CO₂ into the reaction atmosphere decreased the pyrolysis oil yield, while the oil yield increased with increasing the CO and CH₄ contents in the atmosphere. TG-FTIR analysis was conducted to reveal the effects of reaction atmosphere on the chemical species present in the pyrolysis oil. The results clarified that the pyrolysis oil yield reached its maximum when the simulated pyrolysis gas was the reaction atmosphere, but there were slightly fewer volatile matters in the pyrolysis oil than the oil generated in the N₂ atmosphere. All of these results are expected not only to reveal the composition characteristics of the pyrolysis oil from different conditions of the coal topping process but also to optimize the pyrolysis conditions in terms of maximizing the light pyrolysis oil yield and quality.     

烟煤焦在H2O和CO2气氛下的结构演变与气化反应性关联

本研究以烟煤在1000 ℃热解所制得的焦样为研究对象,考察了其在H₂O、CO₂及两者混合气氛下的结构演变,以及气化反应性的影响。为了探究焦样在气化过程中的结构演变,利用氮吸附、SEM和拉曼光谱等表征手段分析不同碳转化率下的焦样结构。结果表明,H₂O气氛对焦样结构的演变明显不同于CO₂气氛,揭示了焦样在两种气氛下的反应路径不同。因结构演变的不同,随碳转化率的增加,焦样在两种气氛下表现出不同的气化反应性能。在CO₂气氛下,焦样的气化反应速率随碳转化率的增加而逐渐降低,与H₂O气氛存在下变化趋势相反。在H₂O和CO₂共气化条件下,煤焦在H₂O和CO₂混合气氛下的反应速率高于单气氛下的反应速率的计算值,表现出一定的协同作用。这是因为焦样与H₂O反应能够产生较大的比表面积,为焦样与CO₂反应提供更多的反应场所,促进了焦样与CO₂的反应。     

High-pressure gasification reactivity of biomass chars produced at different temperatures

The knowledge of biomass char gasification kinetics is of considerable importance in the design of advanced biomass gasifiers, some of which operate at high pressures. In the present work the effects of pyrolysis temperature, total pressure and CO₂ concentration on the gasification of biomass chars have been studied using the thermogravimetric approach. The chars were obtained by pyrolysis in a drop tube furnace reactor at temperatures of 1000 and 1400 °C. The gasification tests were carried out in a pressurized thermogravimetric analyser (PTGA) at different temperatures, pressures and CO₂ concentrations. The reactivity measurements were conducted under the kinetically controlled regime, and three nth-order kinetic models as well as the Langmuir–Hinshelwood model were applied to determine the kinetic parameters.     

H2气氛下褐煤快速热解过程中CH4逸出规律的分析

在带有输送煤样的管式反应器上进行了霍林河褐煤加压快速氢解实验,分析了H₂对煤/半焦的化学键断裂和对CH₄生成规律的影响。在加压快速氢解条件下,CH₄产率随着热解温度升高、压力的增大而增大;在50% H₂气氛下,操作压力为1.0 MPa、温度为900 ℃时,CH₄产率为8.08%,达到最大,较N₂气氛下的提高了72.5%。H₂或H·自由基诱发了芳环的开裂、侧链、脂肪链和醚键的断裂,促进了煤热解。CH₄产率的增加主要是由于外部供H的结果;热解温度低于700 ℃时,H₂对煤结构中活性基团的作用促进了煤热解,导致了CH₄产率的增加;而热解温度高于700 ℃后,煤/半焦加氢气化促进了CH₄产率的增加。     

Thermodynamic equilibrium study of mineral elements evaporation in O2/CO2 recycle combustion

The facility for the analysis of chemical thermodynamics method (F*A*C*T) based on the Gibbs energy minimization principle, was used to characterize the evaporation of mineral elements of coal in O₂/CO₂ recycle combustion. The effects of atmosphere and temperature on the speciation of mineral species were discussed. The results show that Na(K)Cl(g), FeO(g), and SiO(g) are the dominant gaseous species of the mineral elements. The dominant species of mineral elements in flue gases depend on both the combustion conditions (reducing or oxidizing) and the atmosphere. In O₂/CO₂ mixture combustion, the evaporation rate of mineral elements is much lower than that in air combustion, especially under reducing atmosphere. The total evaporation of mineral elements in O₂/CO₂ atmosphere and air combustion under reducing conditions is 4.46% and 9.65% respectively, up to the temperature of 2400 K. The calculation values are consistent with the experiment values. The decrease in the mineral element evaporation is helpful to suppress the tendency to form fine particle matter and the tendency of initial ash deposition.     

Investigation of the evolved gases from Sulcis coal during pyrolysis under N2 and H2 atmospheres

The evolution of gases and volatiles during Sulcis coal pyrolysis under different atmospheres (N₂ and H₂) was investigated to obtaining a clean feedstock of combustion/gasification for electric power generation. Raw coal samples were slowly heated in temperature programmed mode up to 800 °C at ambient pressure using a laboratory-scale quartz furnace coupled to a Fourier transform infrared spectrometer (FTIR) for evolved gas analysis. Under both pyrolysis and hydropyrolysis conditions the evolution of gases started at temperature as low as 100 °C and was mainly composed by CO and CO₂ as gaseous products. With increasing temperature SO₂, COS, and light aliphatic gases (CH₄ and C₂H₄) were also released. The release of SO₂ took place up to 300 °C regardless of the pyrolysis atmosphere, whilst the COS emissions were affected by the surrounding environment. Carbon oxide, CO₂, and CH₄ continuously evolved up to 800 °C, showing similar release pathways in both N₂ and H₂ atmospheres. Trace of HCNO was detected at low pyrolysis temperature solely in pure H₂ stream. Finally, the solid residues of pyrolysis (chars) were subjected to reaction with H₂ to produce CH₄ at 800 °C under 5.0 MPa pressure. The chars reactivity was found to be dependent on pyrolysis atmosphere, being the carbon conversions of 36% and 16% for charN₂ and charH₂, respectively.     

微型流化床反应分析仪中原位/非原位煤焦气化动力学研究

利用新开发的微型流化床反应分析仪(micro-fluidized bed reaction analysis, MFBRA) 考察了义马烟煤半焦的原位以及两种非原位半焦气化行为并测定了其动力学参数,其中,原位半焦气化是指煤热解温度和气氛与半焦气化过程一致,非原位半焦1气化是指煤在Ar气氛下热解,热态条件下直接在CO₂气氛下气化;非原位半焦2气化是指煤在Ar气氛下热解,冷却收集后再在CO₂气氛下气化。研究发现,原位半焦具有最大的比表面积和最小的平均孔径,石墨化程度最弱,且对CO₂的化学吸附能力最强,表面活性位点最多。在最小化气体扩散的实验条件下,原位半焦气化反应的反应速率明显比非原位半焦气化反应快,且求取的活化能数据较小。实验揭示了原位半焦和非原位半焦结构和反应性的差异,也证明了MFBRA对原位等温气化反应的适用性。     

Syngas Production from Lignite Coal Using K2CO3 Catalytic Steam Gasification with Controlled Heating Rate in Pyrolysis Step

Gasification uses steam increases H2 content in the syngas. Kinetics of gasification process can be improved by using K₂CO₃ catalyst. Controlled heating rate in pyrolysis step determines the pore size of charcoal that affects yield gas and H₂ and CO content in the syngas. In previous research, pyrolisis step was performed without considering heating rate in pyrolysis step. This experiment was performed by catalytic steam gasification using lignite char from pyrolysis with controlled heating rate intended to produce maximum yield of syngas with mole ratio of H₂/CO ≈ 2. Slow heating rate (3 °C/min) until 850 °C in the pyrolysis step has resulted in largest surface area of char. This study was performed by feeding Indonesian lignite char particles and K₂CO₃ catalyst into a fixed bed reactor with variation of steam/char mole ratio (2.2; 2.9; 4.0) and gasification temperature (750 °C, 825 °C, and 900 °C). Highest ratio of H₂/CO (1.682) was obtained at 750 °C and steam/char ratio 2.2. Largest gas yield obtained from this study was 0.504 mol/g of char at 900 °C and steam/char ratio 2.9. Optimum condition for syngas production was at 750 °C and steam/char mole ratio 2.2 with gas yield 0.353 mol/g of char and H₂/CO ratio 1.682.     

Pressurized CO<Subscript>2</Subscript>-enhanced gasification of coal

Carbon dioxide was considered as a co-gasifying agent in a coal gasification reactor. The work presented herein describes the simulation results for the process and the experimental data on coal char gasification with CO₂ addition as the rate-controlling step for the entire process. To study the potentially beneficial effect of the introduction of CO₂ into the gasification system, several simulations were conducted using the commercial process simulation software ChemCAD 6.3^®. The results of a Gibbs equilibrium reactor were evaluated. The Boudouard reaction is a critical path for the development of this process, and the kinetics were studied experimentally. Four chars derived from the pyrolysis of Polish coals of different origins were selected for the experiments. The kinetic characteristics of this system were examined using a custom-designed pressurized fixed-bed reactor. To determine the effect of pressure on the gasification rate, several preliminary studies on the gasification of coal chars were performed isothermally at the temperature of 950 °C and pressures of 1, 10, and 20 bars. In contrast to the thermodynamic calculations, the experimental data revealed that increasing the CO₂ pressure leads to a higher reaction rate for medium-rank coal chars and low-rank lignite coal char, resulting in higher efficiency for carbon monoxide production. The pressure influences the reactivity more strongly when varied from 1 to 10 bars; a further increase in pressure affects the rate almost insignificantly. The observed behavior representing the changes in carbon conversion degree during gasification is satisfactorily described by the grain model.     

Fe对胜利褐煤焦结构和气化反应性能的影响

酸洗褐煤负载不同含量的Fe催化剂在固定床反应器上进行热解,然后采用FT-IR、Raman spectra、TPD和TG研究Fe催化剂对煤焦官能团、碳微晶结构、表面活性位和气化反应性的影响。FT-IR结果表明,催化热解作用下煤焦中-OH、-CH₃、-CH₂活性官能团数量增加。Raman光谱测试结果显示,随着Fe含量的增加,I_G/I_all由0.095减少到0.087,I_D3/I_all由0.090增加至0.097,表明在Fe催化作用下部分大芳香环结构转变为小芳香环结构。TPD实验结果表明,活性位数量随着煤焦中Fe含量升高而不断增加。在3%含Fe量时煤焦活性位数量随着吸附温度的升高而增加,800 ℃后煤焦表面活性位数量开始降低。750 ℃条件下CO₂吸附量随着吸附时间的延长而增加,45 min后煤焦达到饱和吸附状态。煤焦-水蒸气等温气化实验表明,煤焦气化反应性与活性位数量有密切的关系,Fe催化剂主要通过增加煤焦表面活性位数量提高煤焦气化反应性。     

An experimental investigation into the gasification reactivity and structure of agricultural waste chars

The gasification reactivity as well as physical and chemical structure of chars generated from two kinds of agricultural waste (i.e. corn straw and wheat straw) were studied to better understand the role of lower pyrolysis temperatures and lower heating rates on the gasification characteristics of agricultural waste chars. Char samples were generated in a one-stage quartz fixed-bed reactor. The carbon dioxide (CO₂) gasification reactivity of chars was measured by thermogravimetric (TGA) analysis. Scanning electron microscopy (SEM) analysis, surface area (BET) analysis, Fourier transform infrared spectroscopy (FTIR) analysis and X-ray diffractometry (XRD) analysis were employed to determine the effect of operating conditions on the char structure. Char gasification reactivities decreased with increasing pyrolysis temperatures. The char particles generated under high pyrolysis temperatures had many smaller pores with thinner cell walls, larger surface areas, and some melting. Results indicated that many functional groups’ bands decreased and even disappeared with an increasing pyrolysis temperature. The chars’ microcrystalline became larger at high pyrolysis temperatures. The reactivity of wheat straw char is higher than corn straw char. The difference in the gasification reactivity of agricultural waste chars generated at different pyrolysis temperatures correlated well with the effect of pyrolysis temperatures on the agricultural waste char structure.