Fe_2O_3氧载体四氢呋喃部分氧化制合成气的热力学分析

采用Gibbs自由能最小化法对Fe_2O_3氧载体四氢呋喃(C_4H_8O)部分氧化制合成气反应进行热化学平衡计算,考察了反应物摩尔比n(Fe_2O_3):n(C_4H_8O)、温度和压力等因素对Fe_2O_3氧载体C_4H_8O部分氧化制合成气反应产物的影响,结果表明:随反应物摩尔比增大,合成气摩尔分数及氢碳比(H_2/CO)先增大后减小,在反应物摩尔比为1时,合成气摩尔分数及氢碳比最大;随温度升高,合成气摩尔分数及氢碳比明显增大,800—1 200℃时,合成气摩尔分数较高,氢碳摩尔比在1附近,有利于合成气的制备;随压力增加,合成气摩尔分数及氢碳比减小,低压有利于合成气的制备。在反应物摩尔比为1,800—1 200℃、常压条件下,合成气摩尔分数 95%、氢碳比 0. 94。     

KCl气溶胶对整体式镍基催化剂重整性能的影响

采用分步浸渍法制备了以堇青石为载体的Ni-MgO/γ-Al2O3整体式催化剂,在800℃时,以300 mL/min N2作为载气,将KCl沉积在催化剂上,考察碱金属盐气溶胶对Ni-MgO/γ-Al2O3整体式催化剂重整净化生物质燃气性能的影响,并利用ICP. BET. XRD和SEM等测试手段对沉积前后的催化剂性能进行表征.结果表明,KCl沉积后的催化剂比表面积降低,催化剂的活性受到影响,CH4转化率降低,H2/CO也略有降低.750℃时,在模拟生物质燃气中添加KCl气溶胶,经过17 h,CH4的转化率由88.56%降至32%,重整后H2体积分数由35.09%降至26.74%,CO体积分数由33.19%降至29.78%;而未添加KCl时,经过60 h,CH4转化率始终保持在90%左右,重整后各气体组分基本无明显变化.     

双流化床生物质气化动力学建模与分析

为进一步研究双流化床生物质气化器中合成气含量分布,将气化器鼓泡床层分为气泡相和乳化相,依据动力学反应分别进行各相质量和热量衡算,计算结果与实验值吻合较好. 随气化温度升高,CO含量增加,而H2和CO2含量降低;蒸汽与生物质质量比(S/B)增加促进水蒸汽变换和重整反应,消耗CO和CH4,生成H2和CO2,当S/B从0变化到1.2时,CO/H2变化44%,说明S/B增加主要促进了水蒸汽变换反应. 气化温度870℃及S/B=0.75条件下,当气化器高度为0~0.5 m时,H2O含量急剧下降,H2含量急剧上升,CO与CO2含量逐渐上升,当该高度大于0.5 m后,气化反应基本完成.     

NiO-MgO固溶体蜂窝催化剂部分氧化重整净化生物质气特性

采用分步浸渍法制备了NiO-MgO固溶体蜂窝催化剂,以60 h连续重整实验,考察了不同临氧条件下MCM催化剂催化生物质气重整净化的性能。利用TG-DSC对催化剂的表面积炭进行了分析,采用GC、GC-MS等手段对生物质气组成及焦油转化产物进行了分析。结果表明：加入O₂后进行临氧重整,可改善出口合成气的品质,H₂/CO摩尔比较干重整时提高了10%左右。但当O₂/fuel摩尔比超过0.127时,H₂/CO摩尔比有所下降。O₂的加入可明显提高催化剂的催化活性和稳定性,随着O₂ 含量的增加出口合成气中的CH₄含量降低,临氧重整条件下焦油的转化率较无氧条件时提高了5%,转化率达到99%以上。热重分析表明,O₂ 含量的增加会减少催化剂表面积炭量。实验中添加从气化现场提取的生物质焦油,经检测焦油大部分转化为H₂、CO及痕量轻质组分,且对干重整中难于转化的含氧有机化合物等转化更为彻底。     

熔融盐处理技术对粗燃气成分影响实验研究

为考察熔融盐对粗合成气成份的影响,在固定床内进行了熔融盐粗燃气成份调整实验。在350~500℃温度范围内,考察了温度、流速、挡板开孔直径、气泡停留时间等操作条件对粗燃气成份的影响。研究结果表明,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,改善合成气品质。温度、流速、气泡停留时间对H2和CO的体积分数影响明显。熔融盐粗燃气成份调整适合作为气化、热解制备合成气的后续工艺,提升燃气品质。     

工艺条件对Ni/A12 O3和Ni/CeO2-A12O3催化剂在甲烷自热重整制氢反应中催化性能的影响

采用共沉淀法制备γ-A12O3载体和不同Ce添加量的CeO2-A12O3载体,然后用浸渍法制备Ni负载质量分数10%的Ni/γ-A12O3和Ni/CeO2-A12O3催化剂.在固定床微反装置中考察了反应温度、原料气配比和CH4空速等工艺条件对Ni/γ-A12O3和Ni/Ce30A170Oδ催化剂在甲烷自热重整制氢反应中催化性能的影响.结果表明,添加Ce的催化剂催化性能有较大提高,在Ni/Ce30A170O3催化剂上,反应温度750 ℃时,CH4转化率94.3%,与Ni/A12O3催化剂相比,提高20%.Ni/γ-A12O3和Ni/CeO2-A12O3催化剂的CH4转化率均随反应温度的升高而增大.原料气中n(O2):n(CH4)和n(H2O):n(CH4)的增加均能提高各催化剂的CH4转化率.但n(O2):n(CH4)和n(H2O):n(CH4)的变化对各催化剂的催化性能的影响不同.随着n(O2):n(CH4)的增大,产物中n(H2):n(CO)降低,n(CO2):n(CO CO2)升高;而n(H2O):n(CH4)增大时,产物n(H2):n(CO)和n(CO2):n(CO CO2)均升高.随着CH4空速的增加,Ni/A12O3催化剂上CH4转化率、n(H2):n(CO)和n(CO2):n(CO CO2)均较大程度下降;而在Ni/Ce30A170Oδ催化剂上,随着CH4空速的增加,CH4转化率、n(H2):n(CO)和n(CO2):n(CO CO2)变化不大.     

城市生活垃圾气化粗燃气与甲烷气流床高温重整制合成气模拟计算

对垃圾气化粗燃气(FG)与填埋气中分离出来的甲烷共重整过程进行了模拟分析。考察了温度、H_2O与O_2添加量、甲烷与气化粗合成气混合比例等对气化气和甲烷共重整制合成气特性的影响。结果表明,在气流床操作温度范围内(1 100℃),反应温度的升高有助于提高甲烷转化率;合成气组分随H_2O∶O_2∶CH_4变化明显,所有工况下水蒸汽的加入都会显著降低反应系统的理论温度、CH_4转化率以及合成气中CO的含量。综合考虑CH_4转化率、冷煤气效率,将O_2/CH_4及H_2O/CH_4分别控制在0.65~0.8、0~0.3是比较合理的操作区间。     

Shell煤气化制合成气与甲烷重整二氧化碳耦合研究

为了优化化工合成过程,节约资源,减排温室气体CO2,采用Aspen Plus软件,基于Gibbs自由能最小原理,对Shell煤气化制合成气与CH4、CO2耦合过程进行模拟。分析了CH4、CO2、O2三者之间的比例对于重整合成气的影响。结果表明:当CO2/CH4体积比为1.02时,O2/CH4体积比为0.1时,得到氢碳比为0.829。通过灵敏度分析了O2量和压力对反应的影响,O2量的增加,反应温度升高,有利于耦合反应的进行;压力的增加,不利于耦合反应,但是加压可以提高生产强度,因此一般都选用加压条件下进行。     

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.     

热等离子体催化耦合重整CH_4和CO_2制合成气

常压下,利用实验室制备的Ni-Ce/Al2O3催化剂,进行了热等离子单独重整与热等离子体催化耦合重整CH4和CO2制合成气的实验研究。实验中,催化剂被放置在等离子体反应区,催化剂床层由高温等离子射流气体加热。固定原料气配比V(CO2)/V(CH4)=1、等离子体工作载气流量0.8 m3/h及放电功率3.5 kW不变,考察了原料气总流量对原料转化率、产物选择性、化学能效和催化剂积碳速率的影响;并探讨了助剂Ce在重整反应中的作用。结果表明:随原料气总流量的增加,CH4和CO2转化率降低,H2和CO选择性无明显变化,C2H2选择性和催化剂积碳速率增加。热等离子催化耦合重整比热等离子单独重整具有较高的原料转化率、H2和CO选择性、化学能效值和较低的C2H2选择性。     

催化部分氧化甲烷制合成气的平衡热力学研究

The catalytic partial oxidation of methane to syngas (CO H2) has been simulated thermodynamically with the advanced process simulator PRO/Ⅱ. The influences of temperature,pressure,CH4/O2 ratio and steam addition in feed gas on the conversion of CH4 selectively to syngas and heat duty required were investigated, and their effects on carbon formation were also discussed. The simulation results were in good agreement with the literature data taken from a spouted bed reactor.     

甲烷空气催化部分氧化制含氮合成气的研究

采用常规的浸渍法制备了镍基催化剂和经过镧改性的镍基催化剂,研究了甲烷催化部分氧化制备含氮合成气的催化功能,结果说明,镍含量在8％时催化活性达到最好,同时加入镧进行改性后催化剂的活性和选择性有所提高;该催化剂对甲烷空气催化部分氧化制合成气在常压下具有较高的转化率,随压力升高,转化率明显下降,并且积极严重,通过向体系加入H2O和CO2可以提高加压条件下甲烷的转化率并抑制催化剂积碳,还可以获得H2／CO接近2的合成气,满足合成液体燃料的要求。     

Kinetic and CFD Modeling of Exhaust Gas Reforming of Natural Gas in a Catalytic Fixed-Bed Reactor for Spark Ignition Engines

Fuel reforming is an attractive method for performance enhancement of internal combustion engines fueled by natural gas, since the syngas can be generated inline from the reforming process. In this study, 1D and 2D steady-state modeling of exhaust gas reforming of natural gas in a catalytic fixed-bed reactor were conducted under different conditions. With increasing engine speed, methane conversion and hydrogen production increased. Similarly, increasing the fraction of recirculated exhaust gas resulted in higher consumption of methane and generation of H₂ and CO. Steam addition enhanced methane conversion. However, when the amount of steam exceeded that of methane, less hydrogen was produced. Increasing the wall temperature increased the methane conversion and reduced the H₂/CO ratio.     

Kinetic contribution of CO2/O2 additive in methane conversion activated by non-equilibrium plasmas

A temperature-controlled and pressure-controlled coaxial dielectric barrier discharge(DBD) reactor was developed to decouple the thermal and kinetic effects of radio frequency(RF) discharge on methane conversion,and further to compare the kinetic behaviors of the mechanistically similar reactions of methane conversion with O_2 and CO_2 additives. A kinetic mechanism for RF plasma assisted methane conversion was assembled. The formation of products in the RF plasma reactor was measured with Gas Chromatography(GC–TCD) and the data were used to validate the kinetic model. The experimental and computational results showed the different kinetic roles of carbon dioxide and oxygen additives in methane conversion, due to the different dissociation and ionization energy of the two additive gases, as well as the thus produced electron energy distribution function(EEDF). Fuel oxidation by plasma generated O, O(~1 D), O_2(a~1Δg), O_2(b~1Σ_g~+) and O+in partial oxidation of methane was observed essential for methane consumption, which resulted in an increase in methane conversion rate,compared to pure methane pyrolysis and dry reforming of methane with CO_2 additive. It was also found that dry reforming of methane with CO_2 was by far the easier to produce the syngas as well as C_2 hydrocarbon species,due to the weak oxidation ability of CO_2 and also the significant deposition of the electron energy on CH_4 dissociation in a dry reforming discharge mixture. This kinetic study produced comparative data to demonstrate the contribution of CO_2/O_2 additive in non-equilibrium plasma assisted methane conversion.     

褐煤热解-气化-制油系统的CO2减排策略

褐煤热解-气化-制油系统是现代煤化工发展的一个重要研究内容。来自系统多个单元产生的CH₄和CO₂如果发生重整反应,将重整得到H₂/CO比值较高的合成气添加到制油流程中,可实现更多的C被固定到产品中而减少CO₂的直接排放量。对CH₄-CO₂和CH₄-H₂O两种重整反应方式、来自煤热解和费托合成两股甲烷气和典型的干粉气化和水煤浆气化两种流程进行了组合研究。分析结果显示,来自热解和费托合成的甲烷重整后不足以提供调节合成气H₂/CO比例所需的氢气,水煤气变换反应对于褐煤制油系统来说是必需的。从C转化成油的角度来看,采用干粉气化和CH₄-H₂O重整的方案是较好的选择。     

气化参数对气流床粉煤气化影响实验研究

为评价和优化中国高、低灰熔点煤气化运行参数对气流床气化特性的影响,在1600℃的一维常压沉降式气流床气化实验系统上,着重研究了中国典型高、低灰熔点煤在1200～1600℃温度范围内、O／C摩尔比在0．9～1.2范围内的干煤粉气化特性。结果表明：随着温度的升高,产气中CO、H2含量逐渐增多,CO2、CH4含量逐渐减少,碳转化率有很大提高;随着O／C的增加,CO、H2含量不断减少,CO2逐渐增加;煤的灰熔融性也是影响煤气组分一个重要因素,当气化反应温度接近煤灰熔点温度时,煤气组分（CO＋H2＋CH4）达到一个最大值。     

Carbon dioxide reforming of methane with a free energy minimization approach

Carbon dioxide reforming of methane to syngas is one of the primary technologies of the new poly-generation energy system on the basis of gasification gas and coke oven gas. A free energy minimization is applied to study the influence of operating parameters (temperature, pressure and methane-to-carbon dioxide ratio) on methane conversion, products distribution, and energy coupling between methane oxidation and carbon dioxide reforming methane. The results show that the methane conversion increases with temperature and decreases with pressure. When the methane-to-carbon dioxide ratio increases, the methane conversion drops but the H₂/CO ratio increases. By the introduction of oxygen, an energy balance in the process of the carbon dioxide reforming methane and oxidation can be realized, and the CO/H₂ ratio can be adjusted as well without water-gas shift reaction for Fischer-Tropsch or methanol synthesis. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

甲烷及水蒸气对生物质催化气化合成气和焦油的影响

以松木木屑为生物质原料，在两段式反应器上进行甲烷、水蒸气对生物质催化气化影响的实验研究，考察了甲烷与生物质之比α、水碳比S/C对气体产率、碳转化率、焦油产率、焦油组分和露点温度影响的变化规律。结果表明：α从0增加到0.4，合成气中H₂的产率增加了57.4%，甲烷的加入有利于生成富含氢气的合成气；α为0.2时碳转化率最高，为86.9%，焦油产率下降了30.5%，第二、五类焦油的产率达到最低，可见适量CH₄的添加能促进焦油的转化，特别是大分子焦油和酚类的反应。随着S/C的提高，H₂产率升高，CO产率降低；S/C从1增加到1.5，各类焦油的含量均有所降低，当S/C进一步增加到2时，第二、五类焦油含量却有所上升，说明水蒸气可以促进焦油向气体分子转化的反应，但过量的水蒸气抑制酚类和大分子焦油的分解。总之，甲烷和水蒸气的适量添加均可以提高合成气中H₂的含量，降低焦油产率，提高合成气的品质，有利于气化产物的进一步利用。     

Thermodynamic analysis of carbon dioxide reforming of methane in view of solid carbon formation

A thermodynamic equilibrium analysis on the multi-reaction system for carbon dioxide reforming of methane in view of carbon formation was performed with Aspen plus based on direct minimization of Gibbs free energy method. The effects of CO₂/CH₄ ratio (0.5-3), reaction temperature (573-1473 K) and pressure (1-25 atm) on equilibrium conversions, product compositions and solid carbon were studied. Numerical analysis revealed that the optimal working conditions for syngas production in Fischer-Tropsch synthesis were at temperatures higher than 1173 K for CO₂/CH₄ ratio being 1 at which about 4 mol of syngas (H₂/CO = 1) could be produced from 2 mol of reactants with negligible amount of carbon formation. Although temperatures above 973 K had suppressed the carbon formation, the moles of water formed increased especially at higher CO₂/CH₄ ratios (being 2 and 3). The increment could be attributed to RWGS reaction attested by the enhanced number of CO moles, declined H₂ moles and gradual increment of CO₂ conversion. The simulated reactant conversions and product distribution were compared with experimental results in the literatures to study the differences between the real behavior and thermodynamic equilibrium profile of CO₂ reforming of methane. The potential of producing decent yields of ethylene, ethane, methanol and dimethyl ether seemed to depend on active and selective catalysts. Higher pressures suppressed the effect of temperature on reactant conversion, augmented carbon deposition and decreased CO and H₂ production due to methane decomposition and CO disproportionation reactions. Analysis of oxidative CO₂ reforming of methane with equal amount of CH₄ and CO₂ revealed reactant conversions and syngas yields above 90% corresponded to the optimal operating temperature and feed ratio of 1073 K and CO₂:CH₄:O₂ = 1:1:0.1, respectively. The H₂/CO ratio was maintained at unity while water formation was minimized and solid carbon eliminated.     

煤/钙基载氧体化学链燃烧操作参数分析

化学链燃烧作为一种新颖的燃烧技术,在化石燃料燃烧释放能量的同时能够有效分离CO2。今以CO2为气化剂气化煤炭,基于Aspen Plus流程模拟软件,研究了煤/钙基载氧体化学链燃烧过程。结果表明,以CO2为煤气化剂,各反应器含水分少,可减少热损失。CaSO4载氧体具有载氧能力大以及反应活性良好等优点。气化炉中CO+H2含量随二氧化碳煤比增大逐渐增加后下降;随温度升高其含量先增加,后趋于平稳。燃料反应器中CO2+H2O含量随载氧体煤比增大,呈现先增大后减小的趋势;随温度升高其含量逐渐下降。空气反应器中CaSO4含量随空载比增大先增加后趋于平稳,随温度升高其含量趋于平稳后下降。气化炉中硫化物和氮化物含量随温度升高而下降,而燃料反应器和空气反应器中硫化物含量随温度升高增加趋势明显,氮化物含量变化不明显。最后确定了关键反应器操作参数:气化炉的二氧化碳煤比为1.8;燃料反应器的载氧体煤比为4.5;空气反应器的空载比为10.5和三反应器的操作温度分别为950、1000和1100℃。