Ni-CeO2-K/γ-Al2O3催化剂上沼气联合重整制合成气

采用超声波辅助等体积浸渍法制备Ni-CeO₂-K/γ-Al₂O₃催化剂用于沼气联合重整反应，采用 BET、XRD、TG/DTG等技术对催化剂性质进行了表征，在微型固定床反应装置中研究了反应温度、体积空速、原料气组成等对沼气联合重整反应特性的影响，并对催化剂的稳定性进行了研究。结果表明，助剂CeO₂的加入，提高了催化剂中Ni的分散度，降低了催化剂还原温度。升高反应温度和减小体积空速，能够提高沼气中CH₄和CO₂的转化率；原料气中加入水蒸气，能够明显提高H₂/CO体积比；加入的O₂容易与H₂、CO发生反应，CH₄转化率稍有提高。在常压、反应温度850℃、体积空速为100000h^-1、摩尔比CH₄∶CO₂∶H₂O∶O₂∶Ar=1∶0.5∶0.5∶0.1∶0.01的优化条件下，沼气中CH₄转化率超过95%，CO₂转化率超过75%，生成合成气H₂/CO体积比约为1.6，反应48h后，催化剂未见积炭，保持稳定的活性。与沼气干重整相比，沼气联合重整不利于沼气中CO₂的转化。     

胜利褐煤水蒸气气化制富氢合成气及其固有矿物质的催化作用

利用微型固定床反应装置,研究了内蒙古胜利褐煤水蒸气气化过程中H₂、CO₂、CO和CH₄生成规律及其固有矿物质的催化效应。原煤(SL-raw)、盐酸洗脱(SL-HCl)、氢氟酸洗脱(SL-HF)及盐酸洗脱液回添煤样(SL-HCl-Re)在水蒸气气化反应过程中,H₂、CO₂和CO生成速率存在明显差异,充分说明胜利褐煤中某些固有的矿物质对其水蒸气气化反应具有显著的催化作用,可大幅度提高其气化反应速率,并使其起始气化温度降低96℃,气化反应主体温度降低150℃以上,同时促进了合成气中H₂生成,抑制了CO的生成,使胜利褐煤水蒸气气化反应过程中一直维持着较高的H₂/CO摩尔比,SL-raw、SL-HCl-Re水蒸气气化所得合成气中H₂/CO摩尔比分别为17.3和4.3,而SL-HCl和SL-HF水蒸气气化所得合成气中H₂/CO摩尔比均只有1.22。SL-HCl和SL-HF水蒸气气化生成H₂、CO₂和CO的规律基本相同,说明起催化作用的物质是可溶解在盐酸洗脱液中的矿物质。经过分析,发现矿物质对胜利褐煤水蒸气气化反应的催化作用主要是通过提高水煤气变换反应(WGSR)速度实现的。最后结合文献报道提出了胜利褐煤水蒸气气化反应过程中矿物质的原位催化机理。     

铁基氧载体化学链CO2重整CH4方法制备合成气

提出一种铁基氧载体（Fe₃O₄/FeO）化学链CO₂重整CH₄方法制备合成气。为评价该系统的性能,采用Aspen Plus软件对其进行过程模拟和热力学分析。以CH₄转化率、CO₂转化率、能源利用效率和产气氢碳比（H₂/CO）为评价指标,得到系统的优化运行条件,并研究各操作参数（包括各反应器的温度和压力、氧载体甲烷比和CO₂甲烷比）对系统性能的影响。结果表明：当系统处于优化工况时,得到CH₄转化率为97.91%、CO₂转化率为32.76%、能源利用效率为93.77%及产气氢碳比为0.93。该系统能有效利用CO₂和CH₄这两种温室气体获得较低氢碳比的合成气,利于二甲醚的高效合成。     

高温煤焦气化反应的Langmuir-Hinshelwood动力学模型

应用基于吸附和脱附原理的Langmuir-Hinshelwood （L-H） 动力学模型来描述煤焦在H₂O和CO₂混合气氛下的气化反应时,存在单独活性位和相同活性位两个相互矛盾的假设。在管式炉实验装置内考察了在不同气化温度和气化剂分压的条件下,内蒙煤焦（NMJ）与H₂O和CO₂的气化反应特性,获得了NMJ-H₂O 和NMJ-CO₂反应的L-H动力学模型,同时考察了H₂、CO对煤焦气化反应的抑制作用,并探究了NMJ在H₂O和CO₂混合气氛下的气化反应机理。研究结果表明：NMJ-H₂O以及NMJ-CO₂反应的活化能分别为214.78 kJ·mol^-1和145.96 kJ·mol^-1。H₂对NMJ-H₂O以及CO对NMJ-CO₂的反应存在明显的抑制作用,且CO的抑制作用随反应温度的降低而愈加明显。基于L-H动力学模型计算得到的反应速率曲线与实验结果十分吻合。对于NMJ在H₂O和CO₂混合气氛下的气化反应,基于相同活性位假设的L-H模型的反应速率预测值与实验结果吻合,更加适用于NMJ在混合气氛下的气化反应机理。     

干馏层气氛对半焦结构及其CO2气化活性影响

固定床煤气化炉中气氛对干馏层生成半焦的活性影响较大。对不同气氛下制得的半焦进行了CO₂气化活性实验，并采用拉曼光谱和氮吸附对半焦进行了表征。结果表明：与N₂气氛下制得的半焦相比，通入其他气体可以提高半焦的CO₂气化活性，单组分中H₂O气氛下制得的半焦的CO₂气化活性最强，双组分中CO₂+H₂和CO+H₂O气氛下制得的半焦的气化活性明显增加，而且双组分气氛下的CO₂气化活性比前者强；半焦比表面积的增加有利于其CO₂气化活性的提高，但半焦化学结构的变化对其CO₂气化活性的提高作用更明显。     

光催化CO2和CH4重整催化剂研究进展

太阳能驱动的CO₂与CH₄转化为合成气是一种非常有前景的生产可再生燃料的技术，然而太阳能驱动的CH₄重整催化剂存在转化效率低、光生电子与空穴复合速率快及催化剂稳定性差等问题。本文简述了光催化CO₂与CH₄重整的可能机理，包括CO₂和CH₄的吸附、光生电子与空穴的迁移及产物的脱附过程。重点介绍了光催化CO₂和CH₄重整过程中贵金属催化剂、非贵金属催化剂及碳氮化合物等催化剂的研究进展，并总结归纳了各类催化剂的优点与不足。最后，本文探讨了光催化转化CO₂与CH₄制合成气研究领域未来可能的发展方向：开发设计高效的光催化剂提高反应效率；通过密度泛函理论计算及高端表征技术探究催化机理。     

带压环境中CO2/H2O/N2气体稀释对合成气层流火焰速度的影响

合成气稀释燃烧是燃气轮机高效低污染燃烧的重要运行方式。本文以CO₂、H₂O和N₂为稀释气体，利用数值模拟方法研究稀释比对不同压力下合成气（CO/H₂/CH₄）层流火焰速度（S_L）的影响规律，并从自由基浓度变化、敏感性数值和生成速率（rate of production，ROP）三个方面解析三种气体的物理和化学作用机理。结果表明，S_L随燃烧压力和稀释比的增大而不断减小，其中CO₂对层流火焰速度的抑制最为显著。稀释气体的物理效应对层流火焰速度的影响远大于化学效应，但CO₂和H₂O的化学效应不能忽略。化学效应则是通过改变H和OH自由基浓度影响S_L，其中CO₂稀释降低H和OH自由基浓度，H₂O稀释则是降低H自由基浓度，从而降低合成气的层流火焰速度。进一步反应动力学分析发现了H/OH浓度变化在低压、加压下的主要化学反应路径，且受H₂O稀释的化学反应速率对压力较CO₂更为敏感。     

生物质快速热解制油试验及流程模拟

使用自主研发的流化床热解反应器对生物质热解制油进行实验研究,通过对不同实验温度450、500、525、550、580、610℃下得到的目标产物进行分析,得到了反应温度对生物油产率的影响规律。实验表明：550℃时,最大液体产率为42.5%（质量）;实验得到的不可冷凝气体的组分以CO、CO₂、CH₄和H₂为主,气相产物产率约为37.7%（质量）。在实验基础上,利用Aspen Plus流程模拟软件,建立了生物质热解制油工艺模拟流程,模拟分析了热解温度对生物油产率的影响,结果表明该模型能准确模拟实际热解过程,具有较好的适用性和可靠性。     

利用TG-FTIR研究造纸黑液碱木质素的热解机理

采用热重-傅里叶红外光谱（TG-FTIR）联用的分析方法对造纸黑液碱木质素的热解失重特性和产物生成特性进行了研究。结果表明：碱木质素热解失重过程可分为3个阶段,其中200~500℃是碱木质素主要的热解挥发阶段,反应符合一级反应动力学模型,利用Coats-Redfern动力学模型计算得出不同升温速率下热解主反应的表观活化能为39.3~43.1 kJ/mol。FTIR的实时分析结果表明：碱木质素热解的气态产物主要有H₂O、CO₂、CO、CH₄、甲醇、酚类和N₂O;产物中的CH₄、甲醇、酚类和N₂O主要在300~500℃区间内释放,随着热解温度的升高,这些气态产物在420℃附近集中释放,且产量达到最大。     

油页岩低温热解过程中轻质气体的析出特性

为研究油页岩低温热解过程中轻质气体的析出特性,在热重-红外-质谱三联机上对国内有代表性的4个地区(FS、HD、MM和NM)油页岩以20℃·min^-1的升温速率进行了热解实验研究,考察了H₂、H₂O、CO、CO₂、CH₄和C_nH_m 6种轻质气体的析出速率和累积产量随温度变化的规律。实验结果表明:油页岩轻质气体析出的温度范围在180～540℃;H₂、CH₄和C_nH_m的析出速率曲线大致相似,呈高斯分布,CO和CO₂的析出速率则是先缓慢增加随后快速增加,达到最大值后又快速下降,直到析出结束,H₂O的析出速率相对比较复杂,油页岩的内水、矿物质的结晶水和热解水在3个阶段析出,析出速率都是先增大,达到最大值而后减小。     

化学链干重整联合制氢热力学分析及实验

提出了一种化学链甲烷干重整联合制氢工艺。该工艺由还原反应器、干重整反应器、蒸汽反应器和空气反应器组成，在实现制氢的同时获得可变H₂/CO比的合成气。借助ASPEN plus软件和小型流化床实验台，在等温条件下，温度900℃，采用Fe₂O₃/Al₂O₃载氧体，对该工艺进行热力学分析和实验验证。结果显示，当铁氧化物被还原至FeO/Fe时，干重整反应器内甲烷转化率可以达到98%，CO产率可以达到94%。干重整反应器中同时发生甲烷干重整和部分氧化反应，载氧体内部晶格氧可以有效降低积炭并提高合成气H₂/CO比。积炭发生于晶格氧消耗殆尽时。积炭进入蒸汽反应器，发生气化反应，降低氢气纯度。     

Reaction and oxygen permeation studies in Sm0.4Ba0.6Fe0.8Co0.2O3 − δ membrane reactor for partial oxidation of methane to syngas

A disk-type Sm_0.4Ba_0.6Co_0.2Fe_0.8O_3 − δ perovskite-type mixed-conducting membrane was applied to a membrane reactor for the partial oxidation of methane to syngas (CO + H₂). The reaction was carried out using Rh (1 wt%)/MgO catalyst by feeding CH₄ diluted with Ar. While CH₄ conversion increased and CO selectivity slightly decreased with increasing temperature, a high level of CH₄ conversion (90%) and a high selectivity to CO (98%) were observed at 1173 K. The oxygen flux was increased under the conditions for the catalytic partial oxidation of CH₄ compared with that measured when Ar was fed to the permeation side. We investigated the reaction pathways in the membrane reactor using different membrane reactor configurations and different kinds of gas. In the membrane reactor without the catalyst, the oxygen flux was not improved even when CH₄ was fed to the permeation side, whereas the oxygen flux was enhanced when CO or H₂ was fed. It is implied that the oxidation of CO and H₂ with the surface oxygen on the permeation side improves the oxygen flux through the membrane, and that CO₂ and H₂O react with CH₄ by reforming reactions to form syngas.     

Oxidation and reforming reactions of CH4 on a stepped Pt(5 5 7) single crystal

The oxidation and reforming kinetics of methane by O₂, CO₂ and H₂O were studied on a stepped Pt(5 5 7) single crystal from 623 to 1050 K under methane rich conditions. The rate of carbon deposition was followed by ex-situ Auger electron spectroscopy under non-oxidative conditions. The apparent activation energy for methane decomposition was significantly lower than the apparent barriers measured for both total oxidation, CO₂ and H₂O reforming. Total oxidation of methane to CO₂ and H₂O followed by combined dry and steam reforming (combined combustion-reforming) led to CO production rates which were higher than direct CO₂ or H₂O reforming rates. The enhanced rates are most likely due to the ability of adsorbed oxygen to prevent carbon nucleation and/or scavenge carbon enabling the reforming reaction to turnover on a larger fraction of sites. Comparable amounts of carbon were found by Auger electron spectroscopy measurements after both direct dry or steam reforming, while combined oxidation-reforming had considerable less carbon. During direct dry or steam reforming, CO₂ and H₂O serve only to scavenge adsorbed atomic carbon, while in the presence of oxygen, carbon is removed by both combustion and reforming routes.     

REACTOR-MEMBRANE PERMEATOR CASCADE FOR ENHANCED PRODUCTION AND RECOVERY OF H2 AND CO2 FROM THE CATALYTIC METHANE-STEAM REFORMING REACTION

The catalytic reforming of methane by steam is an important industrial process that produces H₂, CO and CO₂, thus chemically transforming natural gas, coal gas and light hydrocarbon feedstocks to synthesis gas or hydrogen fuel. Methane-steam reforming may consist of a number of reactions depending on the reforming catalyst, operating conditions and feedstock composition, The typical industrially desirable reactions are the reverse of methanation (CH₄ + H₂O = CO + 3H₂) and the water-gas shift (CO + H₂O = CO₂ + H₂). Both reactions are equilibrium limited and the composition of the mixture that exits the reformer is in accordance with the one calculated thermodynarmically. Removal of reaction products at the reactor exit by means of selective membrane permeation can offer improved CH₄ conversions and CO₂ and H₂ yields, assuming the subsequent utilization of the reject streams by a second methane-steam reformer. We numerically investigated the feasibility of a system of two tubular methane-steam reformers, in series with an intermediate permselective polyimide membrane permeator, as means of improving the overall CH₄ conversion and the H₂, CO₂ yields over conventional methane-steam reforming equilibrium reaction-separation schemes that are currently in industrial practice. The unique feature of the permselective polyimide separator is the simultaneous removal of H₂ and CO₂ versus CH₄ and CO from the reformed streams. The utilized 6FDA-3,3', 5,5'-TMB aromatic polyimide was reportedly characterized [10] and found to exhibit superior permselective properties compared with other polyimides of the same or different dianhydride sequence. Conversion and yield of the designed reactor-membrane permeator reforming system can be maximized by optimizing the permselective properties of the membrane material and the design variables of the reactors and the permeator. Product recovery and purity in the permeate stream need to be compromised to overall enhance methane conversion and product yield. The operating variables that were varied to investigate their effect on the magnitude of conversion and yield included the inlet pressure of the first reformer, the temperature of both reformers, and the permeator dimensionless Pe' number (variation of the first two variables results to a drastic change in the composition of the reformed stream that enters into the permeator). The numerical results show that the new reformer-membrane permeator cascade process can be more effective (it can offer increased CH₄ conversions and H₂, CO₂ yields) than conventional equilibrium methane-steam reforming reaction-separation processes currently in practice.     

La2NiO4 tubular membrane reactor for conversion of methane to syngas

La₂NiO₄ tubular membranes of relative density over 92% were used to separate oxygen from air and facilitate the partial oxidation of methane to H₂ and CO at 900 °C. When methane was fed into a tube of inner surface area 5.11 cm² at a rate of 10.5 ml/min, methane throughput conversion was 89%, CO selectivity 96%, H₂/CO ratio 1.5, and the equivalent oxygen flux was 6.8 ml/min. The surface of the La₂NiO₄ membrane exposed to CH₄ decomposed into La₂O₃ and Ni, while the surface in contact with air remained almost unchanged. It is suggested that the conversion of methane in the membrane reactor involves the reforming of methane by the H₂O and CO₂ catalyzed by nickel.     

Roles of CO2 and H2O as oxidants in the plasma reforming of aliphatic hydrocarbons

Roles of CO₂ and H₂O as oxidants are discussed based on the data on the substrate conversions and the product distributions in the nonthermal plasma reforming of aliphatic hydrocarbons such as methane, propane, and neopentane from 303 K to 433 K. Only small effects of initial concentrations of hydrocarbons and types of oxidants are observed on hydrocarbon conversions, and the initial chemical interaction between hydrocarbons and the oxidants unlikely occurs. CO₂ and H₂O have shown the comparable oxidation powers in the hydrocarbon reforming. Two molar excess of CO₂ or H₂O to methane is required to oxidize methane carbon atoms to CO and CO₂, and larger amounts of CO₂ or H₂O for propane and neopentane. The different natures of CO₂ and H₂O are reflected in the synthesis gas composition as in the ordinary catalytic reforming processes at higher temperatures: higher H₂ yields and higher H₂ to CO ratios on addition of H₂O.     

煤和焦炉气联供制烯烃过程的建模模拟与分析

由于煤富碳少氢,煤制烯烃过程生产1 t产品将排放约5.8 t CO₂.与此同时,中国焦炭工业每年产生约7×10¹⁰ m³的副产物焦炉气,这些富氢的焦炉气大多被燃烧或直接排放进入大气,对环境造成严重影响的同时还浪费了巨大的经济价值.本文对焦炉气辅助煤制烯烃的新过程进行了建模模拟与系统分析.焦炉气与煤元素互补,焦炉气中的H₂可用来调节合成气的氢碳比;CH₄可通过甲烷水蒸气重整和甲烷干重整两个过程,提高合成气的氢碳比的同时降低煤制烯烃过程排放的CO₂,提高碳元素利用率,实现节能减排.这个新的联供过程的能效比煤制烯烃过程提高了约10个百分点,而CO₂排放量则减少了约95%.     

Tri-reforming of methane: a novel concept for catalytic production of industrially useful synthesis gas with desired H2/CO ratios

A novel process concept called tri-reforming of methane has been proposed in our laboratory using CO₂ in the flue gases from fossil fuel-based power plants without CO₂ separation [C. Song, Chemical Innovation 31 (2001) 21–26]. The proposed tri-reforming process is a synergetic combination of CO₂ reforming, steam reforming, and partial oxidation of methane in a single reactor for effective production of industrially useful synthesis gas (syngas). Both experimental testing and computational analysis show that tri-reforming can not only produce synthesis gas (CO + H₂) with desired H₂/CO ratios (1.5–2.0), but also could eliminate carbon formation which is usually a serious problem in the CO₂ reforming of methane. These two advantages have been demonstrated by tri-reforming of CH₄ in a fixed-bed flow reactor at 850 °C with supported nickel catalysts. Over 95% CH₄ conversion and about 80% CO₂ conversion can be achieved in tri-reforming over Ni catalysts supported on an oxide substrate. The type and nature of catalysts have a significant impact on CO₂ conversion in the presence of H₂O and O₂ in tri-reforming in the temperature range of 700–850 °C. Among all the catalysts tested for tri-reforming, their ability to enhance the conversion of CO₂ follows the order of Ni/MgO > Ni/MgO/CeZrO > Ni/CeO₂ ≈ Ni/ZrO₂ ≈ Ni/Al₂O₃ > Ni/CeZrO. The higher CO₂ conversion over Ni/MgO and Ni/MgO/CeZrO in tri-reforming may be related to the interaction of CO₂ with MgO and more interface between Ni and MgO resulting from the formation of NiO/MgO solid solution. Results of catalytic performance tests over Ni/MgO/CeZrO catalysts at 850 °C and 1 atm with different feed compositions confirm the predicted equilibrium conversions based on the thermodynamic analysis for tri-reforming of methane. Kinetics of tri-reforming were also examined. The reaction orders with respect to partial pressures of CO₂ and H₂O are different over Ni/MgO, Ni/MgO/CeZrO, and Ni/Al₂O₃ catalysts for tri-reforming.