酒糟与煤焦在CO2气氛下的共气化特性

利用固定床反应器研究了酒糟和煤焦在CO2气氛下的共气化特性,考察了实验样品的孔隙结构、表面元素组成及灰分矿物组成. 结果表明,酒糟和煤焦在CO2气氛下共气化过程中存在协同作用,产气中除CO2外,主要产生CO, H2和CH4气体,且在酒糟掺混比例为80%时浓度最高. 气化反应温度和酒糟掺混比例是影响共气化反应的主要因素,酒糟掺混比例相同时,900?1100℃范围内随温度升高,共气化反应活性提高;温度相同时,20%?80%范围内随酒糟掺混比例增加,共气化反应活性增大. 酒糟含69.47%挥发分,且在气化过程中产生大量孔隙及酒糟和煤焦中分别含K和Ca元素对共气化反应起催化作用,是共气化反应活性提高的主要原因.     

一种褐煤热解煤焦的CO2气化反应特性

针对褐煤的热解-部分气化-残炭燃烧梯级利用工艺,以宁夏石沟驿褐煤为原料,采用水平管式炉在700℃～950℃温度范围内分别制备快速和慢速热解煤焦,考察了煤焦微晶结构和比表面积随制焦条件的变化.利用热重-质谱联用技术研究煤焦CO2气化反应特性,并采用不同评价指标对煤焦气化活性进行了表征.结果表明:气化温度每升高50℃,煤焦CO2气化反应速率增加50％以上;热解温度升高,虽然煤焦微晶结构的有序化程度加深,比表面积减小,但煤焦CO2气化反应活性主要受气化温度影响;快速热解煤焦的CO2气化反应活性高于慢速热解煤焦,二者的差异随着气化温度升高而增大;表征煤焦CO2气化活性的平均比气化速率和反应性指数存在线性关系.     

神木煤焦与流化床气化带出细粉的CO2气化特性

为了研究煤焦与流化床气化带出细粉的CO_2气化特性,采用热重分析仪考察了不同气化温度和CO_2分压对神木煤焦与细粉气化行为的影响。结果表明,固定CO_2分压提高气化温度或固定气化温度提高CO_2分压都能加快神木煤焦和细粉气化反应的进行,缩短达到一定碳转化率所需时间;神木煤焦和细粉的反应速率随碳转化率的增大均先快速增大到最大值,而后缓慢降低;神木煤焦和细粉的CO_2气化反应活化能均随碳转化率的升高而增大,在相同的碳转化率下,神木煤细粉的反应活化能大于神木煤焦。与神木煤焦相比,神木煤细粉的CO_2气化反应活性较低。     

水/二氧化碳气氛下酒糟催化气化反应特性的研究

在固定床气化装置中,以赤泥为催化剂、水/二氧化碳为气化剂对酒糟进行气化实验。研究了赤泥添加量、气化温度和V（水）/V（二氧化碳）对酒糟气化活性的影响,并对水/二氧化碳共气化协同机理进行了探讨。结果表明：当赤泥添加量为20%（质量分数）时气化活性最佳;升高气化温度有利于提高气化反应活性;随着V（水）/V（二氧化碳）的增大,合成气产量、n（氢气）/n（一氧化碳）均增加,分别达到270.7 mmol/g和6.67;在水/二氧化碳混合气氛下共气化反应产生了明显的协同效应,协同因子在60%水-40%二氧化碳（体积分数）时达到峰值。拉曼光谱、扫描电子显微镜及比表面积分析表明：水/二氧化碳混合气氛下酒糟焦无定形碳和非晶碳结构的破坏程度比在纯水或二氧化碳中更严重,验证了二氧化碳和水在酒糟气化中存在协同效应;二氧化碳更容易在酒糟焦表面发生气化反应,形成大量微孔使其比表面积增加;水炭渗透力较强有利于形成中孔;在水/二氧化碳混合气氛下,二氧化碳与水产生的交互作用促进了孔结构的发育,使酒糟焦的微孔发展为中孔和大孔并促使气化反应向酒糟颗粒内部发展,这是协同效应产生的主要原因。     

煤焦结构及其气化反应影响因素的研究进展

简述了国内外研究中煤焦结构的研究方法,对煤焦结构研究现状进行了综述,讨论了煤焦气化剂、灰分、温度、压力、升温速率、制焦时间、变质程度和显微组分含量等这些气化反应的影响因素。因此,在气化过程中,煤焦的气化反应活性不但要考虑原煤的性质,还要综合考虑气化剂、温度、压力、升温速率、制焦时间,尤其是温度和压力在气化过程中的影响。掌握了煤焦结构的研究方法和影响气化反应的因素可以更好的对煤进行清洁利用和转化。     

白酒酒糟与污水污泥共气化制氢反应特性及协同性分析

利用固定床为反应器、水蒸气为气化剂进行了污水污泥（SS）和白酒酒糟（SDG）的气化实验，通过分析二者的掺混比和反应温度对二者气化特性的影响，推导了二者共气化的协同作用及协同机理。结果表明，污水污泥比白酒酒糟气化反应活性更强，白酒酒糟比污水污泥合成气选择性更高，二者在气化中存在互补作用。污水污泥与白酒酒糟共气化时，随着共混物中白酒酒糟比例的提高，氢气含量逐渐提高、一氧化碳含量逐渐降低；提高反应温度和增大污水污泥比例，可以提升气化反应的活性。当反应温度为800℃、污水污泥与白酒酒糟的质量比为1∶1时，污水污泥与白酒酒糟共气化具有最大的协同因子（1.36）。污水污泥和白酒酒糟中的钾和钙对气化反应产生了协同催化效果，催化机理为钾和钙的氧化还原循环。     

煤焦氧化对其结构和气化行为的影响

采用固定床反应器对煤焦进行部分氧化处理,然后测定氧化后煤焦在水蒸气和CO2中的气化行为,并用SEM,XRD和N2/CO2吸附对煤焦结构进行表征.结果表明,煤焦低温氧化处理可以显著改善煤焦的孔隙结构,大幅增加比表面积,降低煤焦的有序化和石墨化程度,从而提高其气化活性;并且随氧化程度( burnout)增加,煤焦气化活性不断增加.随氧化温度升高(＞600℃),氧化过程逐渐过渡到扩散控制,O2主要在煤焦外表面反应,因而氧化几乎不会改变煤焦的结构,表面积略有增加,对其后续气化活性无明显影响.     

煤和生物质共气化协同效应的初步研究

采用等温热重法对神木煤焦、稻草焦、高梁秆焦和松木屑焦以及煤焦和生物质焦的混合物进行了CO2气化研究。结果表明,煤焦和生物质焦反应活性由大到小的顺序为松木屑焦〉高粱秆焦〉稻草焦〉神木煤焦,煤焦和稻草焦及高梁焦共气化存在明显的协同效应;煤焦和松木屑焦的共气化没有观察到协同效应;当煤焦和脱灰后的稻草焦、高梁焦进行共气化时,协同效应消失。在处理量是8kg／h的流化床实验装置上,比较了煤单独气化和煤与三种生物质共气化的气化结果,发现气化过程中,碳转化率的顺序与物料的气化反应性一致,协同效应不明显。     

煤与生物质共气化制甲烷实验研究

以烟煤和高粱秸秆为研究对象,在小型加压固定床反应器上考察了压力3.5MPa及温度700℃条件下制焦方式、煤/生物质混合比和气固接触时间对煤与生物质共气化制取富甲烷气体过程中水蒸气气化反应和甲烷化反应的影响.结果表明,对于水蒸气气化反应,煤焦和生物质焦共气化时不能观察到明显的协同作用;对于甲烷化反应,高粱秸秆焦的甲烷化反应活性高于煤焦的甲烷化反应活性,当对高粱秸秆水洗后,高粱秸秆焦的甲烷化反应活性降低至与煤焦的甲烷化反应活性相当,分析表明,水洗后高粱秸秆焦碱金属钾的含量显著降低,说明高粱秸秆焦中碱金属钾的存在是高粱秸秆焦甲烷化反应活性较高的主要原因.增加气固接触时间,有利于提高甲烷产率.     

脱矿物质对铁镍催化煤焦—CO2气化反应性的影响

在先锋褐煤的原煤、脱矿物质煤中掺加一定量的金属Fe、Ni、Ca的硝酸盐,在固定床管式碳化炉上,600℃制焦。XRD技术测试了煤焦中金属元素的存在形态,程序升温法测定了上述煤焦的CO_2气化反应活性。结果表明,Si对Fe催化煤焦—CO_2气化反应没有影响,而Ca对Fe、Ni的催化行为有促进作用,原因在于Ca元素有助于Fe物种的还原和Ni物种在煤焦表面的分散,而Si元素以SiO_2的形式分散在煤焦中,未与Fe形成不溶体,因而不影响Fe的催化作用。     

Studies in char gasification—IV: Multi-stage char gasifier

A detailed analysis of a gasifier with two and three stages is made. It is shown that a multi-stage gasifier is superior to a single stage gasifier from the point of view of net carbon conversion as well as methane mole fraction in the product gases.     

Hydrodesulphurization of char

Treatment of coal char with acid removes ash constituents, primarily calcium and iron compounds. Removal of these constituents reduces much of the back reaction of char with hydrogen sulphide, produced during the treatment of char with hydrogen at elevated temperatures, thus reducing the hydrogen-to-char ratio needed to effect desulphurization. The combination of an acid wash and the use of a char prepared by flash pyrolysis gives a hydrodesulphurization reaction which has a favourable ‘equilibrium’ and fast kinetics¹.     

Co-gasification behavior of meat and bone meal char and coal char

The co-gasification behavior of meat and bone meal (MBM) char and two types of coal (Jincheng anthracite (JC) and Huolinhe lignite (HLH)) char was investigated using a thermogravimetric analyzer (TGA). The effects of coal type, mineral matter in MBM, gasification temperatures and contacting conditions between MBM char and coal char on the gasification behavior were studied. The results show that the gasification behavior of MBM char and HLH char can be well described by ash diffusion controlled shrinking core model, while that of JC char can be described by chemical reaction controlled shrinking core model. The co-gasification rate of MBM/JC chars at 950 °C is approximately 1.5 times faster than that calculated from independent behavior. The mineral matter in MBM may play as a catalyst during co-gasification. However, the analogous effect observed in the blends of HLH/MBM chars is smaller, suggesting that the coal types play a great role. Furthermore, as the gasification temperature increased from 850 to 1000 °C, the maximum synergistic effect is observed at 900 °C. The lower temperature is not conducive to transferring the mineral matters of MBM to the coal char, while the higher temperature makes Na and Ca react with minerals of coal, leading to a loss of catalytic activity.     

Attrition of char agglomerates

A 15.2 cm diameter fluidized bed system with single- and multiple-jet distributors was designed and constructed to study the attrition behavior and mechanism of Kentucky No. 9 char from IGT's U-GAS fluidized bed gasifier. The effects of the jet and auxiliary gas velocities, the number of jets, the bed height, and the roughness of the fluidized bed wall on the attrition of char particles were studied. Particle shape variation during attrition was calculated by comparing our experimental data on pressure drop for a packed bed with the Ergun equation prediction. A mathematical procedure was developed to translate the size distribution variation of particles in the fluidized bed to the attrition rate expression.     

Effect of char gasification reaction order on bounding solutions for char combustion

The rate of oxidation and surface temperature of a char particle during combustion is determined by the combined action of reactions of carbon with oxygen and CO₂ at the surface and carbon monoxide with O₂ in the gas phase. Limiting values for the rates and temperature were determined by Amundson et al. assuming that the CO₂ and CCO₂ reactions were first order with respect to the gas reactant concentration. Results are presented here for the cases in which the CO₂ reaction is zeroth order and the CCO₂ reaction is both first and zero order to bound the reaction orders found in practice. Allowance for zeroth order kinetics is found to have a profound effect on the shape of the bounding solutions for burning rates and temperatures, most notably by showing that diffusion-limited combustion can occur at much lower temperatur than would be predicted using first order kinetics.     

Noncatalytic coal char gasification

A simple particle model is used to interpret differential thermogravimetric data taken on the gasification of coal/char with CO₂, H₂ and H₂O. The model takes into account the major physical factors which influence the gasification rate, viz., the changing magnitudes of surface area, porosity, activation energy and effective diffusivity during gasification. Specific reaction rate constants based on surface area and activation energies are extracted from the data. Practical criteria for regimes of reaction rate and diffusion control and for particle isothermality are developed. For isothermal particles at low classical Thiele moduli, the data can be correlated with only one parameter, which has a simple physical interpretation.     

Steam gasification reactivity of char from rapid pyrolysis of bio-oil/char slurry

A slurry of bio-oil and char originating from wood pyrolysis is a promising gasifier feed-stock because of its high energy density. When such a slurry is injected into a high temperature gasifier it undergoes a rapid pyrolysis yielding a char which then reacts with steam. The char produced by pyrolysis of an 80 wt% bio-oil/20 wt% char mixture at heating rates of 100-10,000 °C/s was subjected to steam gasification in a thermogravimetric analyzer. The original wood char from the bio-oil production was also tested. Gasification was conducted with 10-50 mol% steam at temperatures from 800 to 1200 °C. Reactivity of the slurry chars increased with pyrolysis heating rate, but was lower than that of the original chars. Kinetic parameters were established for a power-law rate model of the steam-char reaction, and compared to values from the literature. At temperatures over 1000 °C, the gasification rates appeared to be affected by diffusional resistance.     

生物质炭吸附及其与O3耦合处理生物质废水

针对我国生物质废水污染问题,建立生物质炭吸附、生物质炭/O3耦合处理生物质废水的工艺,并与O3氧化工艺比较。生物质炭吸附处理生物质废水的工艺中,研究了生物质炭吸附生物质废水中的有机物的吸附平衡曲线,考察了吸附时间、生物质炭投加量、不同炭种对COD脱除率的影响。生物质炭吸附生物质废水中的有机物的吸附平衡曲线符合Langmuir方程,吸附平衡常数为8.833×10-5 L/mg,饱和吸附容量为1.136×106 mg/g;20℃下,生物质炭的投加量为20g/100mL废水,吸附15min,废水相COD值可从12496mg/L降至761mg/L,有机物脱除率可达93.9%。单独O3降解及先O3降解后生物质炭吸附的两步法工艺不适合生物质废水的处理,生物质炭/O3协同的一锅法处理废水效果最佳,在生物质用量仅为1g/100mL废水,臭氧流速为150mL/min,处理时间20min时,COD脱除率高于90%。     

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.     

Fluidized bed char combustion kinetic models

The effect of the kinetics of the heterogeneous reaction between the char and oxygen, and the importance of the subsequent homogeneous oxidation of carbon monoxide oil the performance of an atmospheric fluidized bed combustor have been examined by a comparative analysis of three models. Numerical calculations illustrating the effect of operating variables such as bed temperature, fuel and sorbent particle feed size and excess air were performed for values of the parameters which are pertinent to the design of large scale utility boilers. It is found that the kinetic models predict existence of multiple steady states over a wide range of operating conditions and values of model parameters. The model predictions of combustion efficiency, carbon loading and CO concentrations are in qualitative agreement with experimental data reported in the literature.