焦炉煤气非催化部分氧化制合成气实验研究与数值模拟

在带有单孔喷嘴石英管反应器实验的基础上,对焦炉煤气非催化部分氧化工艺制合成气进行了研究,分析了O_2/GAS比对合成气各组分含量的影响,反应器中反应过程和温度分布及出口产品组成.实验结果表明CH4转化率随O_2/GAS比增大而增大,O_2/GAS比调节到0.22～0.26时,CH_4转化率达到95%～97%,此时合成气CH_4含量低于1%.利用CFD软件平台对转化反应器进行了数值模拟.模拟结果显示,流量一定时出口气体组分H_2与CH4分别随着进气氧气与焦炉煤气体积流量比值的增加而减少.CO和CO_2分别随着比值的增加而增加.出口气体有效组分摩尔分数随进气流量的变化不是非常明显.在壁面温度为1 100 K时转化效果最好.     

煤与天然气气流床共气化制合成气试验研究

为提高煤、天然气资源综合利用效率,优化合成气成分,进行了煤与天然气气流床共气化技术研究。介绍了煤与天然气气流床共气化的试验装置及工艺流程,考察了气化温度、压力、水煤浆浓度、CH4与煤比对共气化反应的影响。结果表明,气化温度和CH4与煤比是共气化反应的主要影响因素,较高的气化温度对共气化反应有利,气化温度为1 350℃时,共气化指标较好,有效气体积分数大于90%;随着CH4与煤比的增大,合成气n(H2)/n(CO)增高。CH4与煤比为0.9 m3/kg时,合成气中n(H2)/n(CO)约1.2。根据后续合成工艺要求,通过调节气化温度和CH4与煤比,可获得n(H2)/n(CO)在0.8~2.0的合成气。     

煤种对煤与天然气共气化过程的影响

以移动床为反应器,进行煤与天然气共气化热态模拟实验,对无烟煤、瘦煤、肥煤与焦炭进行了对比研究,考察了煤种在不同喷吹参数H2O/CH4/O2时对高温火焰区温度、合成气有效成分H2+CO和H2/CO、以及CH4与水蒸汽转化率的影响. 结果表明,相对于焦炭,煤为原料时,高温火焰区温度略高,粗合成气有效成分H2+CO体积含量较高,且H2/CO更接近于热力学平衡值. 通过不同煤种的实验,可以直接制备H2/CO在1~2之间可调、有效成分H2+CO体积含量大于92%、残留CH4小于2%的粗合成气,CH4转化率超过90%,水蒸汽转化率高达75%. 煤种中高灰分含量有利于煤与天然气共气化过程.     

煤与重质油共气化热态模拟实验

以固定床为反应器,焦炭和胜利常压渣油为原料,进行煤与重质油共气化热态模拟实验,考察了不同操作参数对出口气体成分及结焦生成物的影响。结果表明:当m(氧气)∶m(水蒸气)∶m(渣油)为0.3∶1.0∶1.0、裂解温度为800℃、停留时间小于0.5 s时,烯烃(C2H4 C3H6)、烷烃(CH4 C2H6)和合成气(H2 CO)的体积分数分别为24%、28%和37%。应用扫描电镜观察了焦炭介质表面上结焦生成物的形貌,发现通氧气后结焦生成物残留量较少。热态模拟实验结果进一步表明,煤与重质油共气化可以制备低碳烯烃,同时联产合成气,且能有效地解决重质油裂解造成的结焦问题。     

昭通褐煤半焦气化特性的研究

以O2/水蒸气作为气化剂,对褐煤半焦气化过程进行实验研究.结果表明,随着气化温度的提高,在生成的煤气组成中CO和H2含量增加,而CO2和CH4的含量减少,煤气热值和合成气产率均增加;在温度一定时,随着氧气流量的增加,煤气中CO含量和H2含量先增加然后逐渐减少,CO2含量增加,CH4含量减少,煤气热值和合成气产率均存在一个最大值.     

气化剂参数对流化床生物质气化指标影响的模型研究

以典型生物质资源麦秆为原料,采用流化床气化方法,通过建立热力学平衡模型,计算并分析气化剂参数对气化指标的影响,理论优化了以蒸汽+空气为气化剂时的气化指标,得出了空气中氧气浓度的增加能够显著提高气化指标,降低消耗;气化剂预热温度的增加可以增加气化炉操作温度,降低气化过程无用的热负荷,降低消耗;空气中氧气浓度和蒸汽/空气质量比与气化反应温度近似成线性关系,即氧气浓度增加,气化炉温度增加,蒸汽/空气质量比增加,气化炉温度降低;蒸汽/空气质量比能够调节气化炉反应温度和气体组成,当该值在0.05时,气化温度为1 270 K,合成气中CO+H2+CH4体积分数为25.7%,气化指标较好。     

移动床煤与天然气共气化制备合成气的工艺技术

煤与天然气共气化是基于天然气蒸汽转化和煤气化工艺耦合的一种新工艺.阐述了煤与天然气共气化制合成气的技术原理.实验研究表明合成气最佳出口温度为1000 ℃,氧气、水蒸气和天然气在同一位置进入反应器能有效降低火焰区温度;理论计算得到的合成气有效气体浓度（CO+H₂）大于95%.实验研究和理论计算结果都表明,煤与天然气共气化可以直接得到H₂/CO在1.0～1.5之间可以调节的合成气.     

淮南煤气化工艺过程模拟

采用Aspen Plus软件对淮南煤气化进行了稳态流程模拟研究,结果表明:O2流量的增大导致气化温度快速升高;合成气中CO、H2以及有效合成气(CO+H2)的体积分率随O2流量的增加呈先增大后减小的趋势;CO2和H2O的变化趋势则相反。氧煤比在0.03~0.17kg/kg区域内,有效气体积分率均大于60%;且在氧煤比为0.1kg/kg时,有效合成气体积分率达到最大值64.2%。氧煤比在0.06~0.14kg/kg区域内,汽氧比的增大会导致气化温度随之减小,并直接影响合成气组分。合成气中,CO、H2、CH4以及有效合成气(CO+H2)的体积分率随汽氧比的增大而降低;H2O和CO2体积分率则随之增大。     

基于Gibbs自由能最小化原理模拟固体燃料-氧气气化反应

采用Gibbs自由能最小化原理考察了气流床中不同固体燃料-氧气的气化特性以探索固体燃料-氧气气化规律。考察了气流床中不同固体燃料(H和C物质的量比(H/C比)为0~1.6,O和C物质的量比(O/C比)为0.1~0.8)在氧气气氛下完全气化时所能达到的平衡温度、合成气组成、气化炉有效能效率及所需当量氧气比。结果表明:固体燃料H/C比一定时,低O/C比下,H2和CO含量保持恒定,H2O和CO2含量较少;高O/C比下完全气化所需当量氧气比迅速降低,平衡温度降至700℃(O/C比大于0.6),气化炉有效能效率也呈现下降趋势,H2和CO含量减少,CO2和H2O含量增加。固体燃料O/C比一定时,随着H/C比增加,平衡温度迅速降低(O/C比小于0.6),气化炉有效能效率也随之减少,CO含量减少,H2,CO2和H2O含量增加。     

焦炉煤气转化反应器的数值模拟

通过对焦炉煤气和纯氧在双孔喷嘴石英管反应器内发生非预混燃烧的过程进行实验研究和数值模拟,得到了反应器内温度分布、流场、浓度分布和反应产品气(合成气)中H2/CO比.模拟结果显示,反应主要在靠近氧气入口的区域内发生,反应器壁温对反应结果有非常重要的影响.实验结果和模拟结果比较,表明温度和流场吻合得很好,组分分布略有误差.     

Study on a multifunctional energy system producing coking heat, methanol and electricity

A multifunctional energy system (MES) capable of consuming coke oven gas (COG) and coal, and simultaneously producing coking heat, methanol and electricity, was subject to an exergy analyses based on Energy Utilization Diagrams (EUDs). In this system a coal-fired coke oven is adopted to produce coke and COG, where non-coking coal is burned to supply thermal energy to the coking process. The COG and coal gas gasified from coal in a gasifier, were mixed to produce syngas for methanol synthesis. Since COG rich in hydrogen and coal gas rich in CO, the mixture of COG and coal gas can easily adjust the mole ratio of CO to H₂ of syngas instead of the conversional reforming and shift processes. The active component of syngas is firstly converted into methanol and then the rest is introduced to a gas turbine for power generation. As a result, the overall efficiency of the MES system is about 62.3%, and its energy savings ratio is about 15% comparing with individual systems. The paper provides a new approach to use coal more efficiently and cleanly.     

Gasification of heavy fuel oils: A thermochemical equilibrium approach

Combustion of heavy fuel oils is a major source of production of particulate emissions and ash, as well as considerable volumes of SO_x and NO_x. Gasification is a technologically advanced and environmentally friendly process of disposing heavy fuel oils by converting them into clean combustible gas products. Thermochemical equilibrium modeling is the basis of an original numerical method implemented in this study to predict the performance of a heavy fuel oil gasifier. The model combines both the chemical and thermodynamic equilibriums of the global gasification reaction in order to predict the final syngas species distribution. Having obtained the composition of the produced syngas, various characteristics of the gasification process can be determined; they include the H₂:CO ratio, process temperature, and heating value of the produced syngas, as well as the cold gas efficiency and carbon conversion efficiency of the process. The influence of the equivalence ratio, oxygen enrichment (the amount of oxygen available in the gasification agent), and pressure on the gasification characteristics is analyzed. The results of simulations are compared with reported experimental measurements through which the numerical model is validated. The detailed investigation performed in the course of this study reveals that the heavy oil gasification is a feasible process that can be utilized to generate a syngas for various industrial applications.     

Dry reforming of coke oven gases over activated carbon to produce syngas for methanol synthesis

The dry reforming of coke oven gases (COG) over an activated carbon used as catalyst has been studied in order to produce a syngas suitable for methanol synthesis. The primary aim of this work was to study the influence of the high amount of hydrogen present in the COG on the process of dry reforming, as well as the influence of other operation conditions, such us temperature and volumetric hourly space velocity (VHSV). It was found that the reverse water gas shift (RWGS) reaction takes place due to the hydrogen present in the COG, and that its influence on the process increases as the temperature decreases. This situation may give rise to the consumption of the hydrogen present in the COG, and the consequent formation of a syngas which is inappropriate for the synthesis of methanol. This reaction can be avoided by working at high temperatures (about 1000 °C) in order to produce a syngas that is suitable for methanol synthesis. It was also found that the RWGS reaction is favoured by an increase in the VHSV. In addition, the active carbon FY5 was proven to be an adequate catalyst for the production of syngas from COG.     

熔融盐粗燃气调质实验研究

在固定床内进行了熔融盐粗燃气成份调质实验,对熔融盐粗燃气调质实验的运行稳定性、反应过程对熔融盐的物性变化的影响、粗合成气成份对调质实验的影响等问题进行了考察.结果分析表明,350～500℃所有实验工况下,熔融盐均能有效的吸收粗燃气中的CO2,得到的合成气中CO2体积分数在2％附近,熔融盐处理技术能有效增加合成气中H2体积分数,降低CO体积分数,连续运行11h后合成气成份仍相对稳定.实验完成后熔融盐中Na2CO3分布呈现中部高两头低的分布规律,Na2CO3和NaOH比例变化时熔融盐熔点变化较小.这些特性都表明熔融盐粗燃气成份调质适合作为气化、热解制备合成气的后续工艺,提升燃气品质.     

Validation and Application of a Kinetic Model for Downdraft Biomass Gasification Simulation

Biomass gasification is widely recognized as an effective method to obtain renewable energy. To accurately predict the syngas and tar compositions is a challenge. A chemical reaction kinetics model based on comprehensive gasification kinetics is proposed to simulate downdraft biomass gasification. The kinetic model is validated by direct comparison to experimental results of two downdraft gasifiers available in the literature and is found to be more accurate than the widely used Gibbs energy‐minimizing model (GEM model). The kinetic model is then applied to investigate the effects of equivalence ratio (ER), gasification temperature, biomass moisture content, and biomass composition on syngas and tar production. Accurate water‐gas shift and CO shift reaction kinetics are found critical to achieve good agreement with experimental results.     

解吸气部分替代天然气制合成气可行性分析

针对解吸气部分替代天然气制取合成氨用合成气的反应过程,建立了数学模型,基于Aspen Plus软件,模拟2种进料情况下的反应,验证解吸气部分替代天然气可行性。分析了主要工艺条件如氧气/原料气体积比、蒸汽用量对气化炉出口气体成分和炉膛温度的影响。对比解吸气部分替代和纯天然气进料的经济性,当天然气价格为1.875元/m3时,2种原料气合成氨的成本相同。但随着天然气价格的上涨,采用解吸气部分替代后将有明显的经济性优势。     

Thermodynamic Equilibrium Calculations for the Reforming of Coke Oven Gas with Gasification Gas

Thermodynamic analyses of the reforming of coke oven gas with gasification gas for syngas were investigated as a function of coke oven gas‐to‐gasification gas ratio (1–3), oxygen‐to‐methane ratio (0–1.56), pressure (25–35 bar) and temperature (700–1100 °C). Thermodynamic equilibrium results indicate that the operating temperature should be approximately 1100 °C and the oxygen‐to‐methane ratio should be approximately 0.39, where about 80 % CH₄ and CO₂ can be converted at 30 bar. Increasing the operating pressure shifts the equilibrium toward the reactants (CH₄ and CO₂); increasing the pressure from 25 to 35 bar decreases the conversion of CO₂ from 73.7 % to 67.8 %. The conversion ratio of CO₂ is less than that in the absence of O₂. For a constant feed gas composition (7 % O₂, 31 % gasification gas, and 62 % coke oven gas), a H₂/CO ratio of about 2 occurs at temperatures of 950 °C and above. Pressure effects on the H₂/CO ratio are negligible for temperatures greater than 750 °C. The steam produced has an effect on the hydrogen selectivity, but its mole fraction decreases with temperature; trace amounts of other secondary products are observed.     

Syngas production through gasification and cleanup for downstream applications — Recent developments

In the present paper various gasification technologies/gasifiers and syngas cleaning options are critically reviewed keeping in view various types of feedstocks and various downstream applications of syngas such as power generation, chemicals and hydrogen production, liquid fuels production and synthetic natural gas (SNG) production. Recent developments on gasification technologies including fixed bed dry bottom (FBDB) gasification, power high temperature Winkler (PHTW) gasification, catalytic steam gasification, transport reactor gasifier as well as syngas cleanup technique including hot gas filter and warm cleaning are discussed. Techno-economic analysis of various gasifiers as well as syngas cleaning processes along with the world scenario of syngas production and its various downstream applications is also discussed.     

IGCC系统燃气轮机变工况对气化岛性能的影响

采用Thermoflex软件建立200MW级IGCC系统模型,简要地对气化岛设计参数进行了分析,并对燃气轮机在100％～40％负荷下的气化岛变工况进行计算,分析比较气化岛主要设备性能参数的变化。结果表明：燃气轮机负荷降低时,在氧碳比不变的条件下,入气化炉的煤浆量和氧气量都减小,空分系统等耗功减少;废锅出口合成气温度、压力降低,废锅吸热功率也同时减少,废锅蒸汽做功能力下降;脱硫系统吸收塔入口合成气温度降低;燃气湿饱和器出口合成气压力降低,导致合成气中H2O的体积分数减小,不利于减少NOx排放。