微生物电解池制氢技术的研究进展

综述了微生物电解池(Microbial electrolysis cell,MEC)产氢与其他方式产氢的不同,阐述了其基本原理,分析了制氢的影响因素,包括反应器的类型、底物的不同、电极材料以及阴极催化剂等,并展望了微生物电解池以难降解的工业废水为底物产氢的应用前景.     

燃料电池用的乙醇制氢

美国米尼苏达大学 (UniversityofMinnesota ,UM)科学家开发成功具有商业潜力的反应器 ,该反应器能用乙醇制备供燃料电池用的氢。这将是首次以可再生资源而不是以碳氢化合物或甲醇为原料制备氢。最近在《科学》杂志上发表报告的研究人员说 ,此技术可能是生产供小型便携式电器的燃料电池用的氢的成本最低 ,因在便携式电器的燃料电池中液体燃料的储存是主要的。乙醇与水在 1个汽车用燃料喷嘴中混合后在铑 -二氧化铈催化剂上氧化生成氢和二氧化碳。该大学化学工程和材料科学教授LannyD .Schmidt说 ,用乙醇和水制氢的反应是令人感兴趣的 ;在现…     

甲醇氧化重整制氢过程(Ⅰ)反应条件对制氢过程的影响

通过对甲醇氧化重整 (POX)自热体系物料衡算、能量衡算 ,以及床层反应行为的研究 ,优化了POX过程操作条件 ,获得了理论产氢能量效率 η,分析了氢源与质子交换膜燃料电池 (PEMFC)衔接中的关键环节———合适的原料配比、反应压力、蒸发器和换热器中换热效率 ,以及适应PEMFC变载或电动汽车变速、爬坡的有效手段等     

天然气制氢反应器的研究进展

氢是一种理想的能源,高纯氢的制备是近年研究的一个重点,反应器的结构是制氢的关键。本文综述了固定床、流化床、膜反应器、等离子体反应器、太阳能反应器和微通道反应器在甲烷制氢研究中的应用,分析了各种反应器在制氢过程的特点以及不足之处,指出了制氢反应器的发展方向。     

利用厌氧折流反应系统进行有机废水发酵制氢

以厌氧折流形式的发酵生物制氢反应器进行了连续流有机废水发酵产氢试验研究。反应器由有机玻璃制成,三格室,单格有效容积9.16L。以好氧生物处理系统剩余污泥为种泥,在容积负荷为8.89kg COD·(m~3·d)~(-1),水力停留时间为13.5 h,温度(35±1)℃等条件下,系统启动运行25 d后达到稳定运行状态。系统稳定运行时,总产气量和产氢量分别稳定在59.0 L·d~(-1)和32.0 L·d~(-1)左右。其中,第一格室、第二格室和第三格室的平均产气量及其氢含量分别为14 L·d~(-1)、25 L·d~(-1)、20 L·d~(-1)和50％、60％、50％。系统污泥的比产氢速率为76.64 L·(kg VSS·d)~(-1)。与同类生物制氢反应器相比,厌氧折流发酵生物制氢反应器具有结构简单、运行稳定、操作灵活、容积利用率高、生物持有量高以及运行费用较低等优点,在发酵生物制氢技术领域有很好的开发前景。     

考虑多对耦合源阱的氢网络优化方法及其应用

在氢网络中,氢源氢阱通常连接于同一个耗氢反应器,为耦合源阱;反应器操作参数的改变影响该耦合源阱参数。在同一个氢网络中可能存在多对耦合源阱,考虑多对耦合源阱的氢网络优化能够进一步为炼厂降低氢耗,提高经济效益。通过分析氢网络的公用工程与多对耦合源阱的关系,推导确定了公用工程迁量与反应器耗氢以及耦合源阱之间的方程。据此建立了耗氢反应器参数和氢网络图像集成优化方法。案例研究表明,该方法简单、容易理解,能够直观给出公用工程迁量与反应器进口温度之间的关系。     

变压吸附制氢装置的改造

分析了变压吸附氢装置氢收率低的主要原因，即原料气中氩、氮组分脱除难和部分程控阀内漏。通过在原有装置上增加抽真空系统并在DCS上增设控制程序，提高了氢收率，经济效益显著。     

浅析碳三加氢反应器中丙烯损失的原因及优化对策

通过分析碳三加氢反应器运行中存在的问题,重新调整了操作变量,优化了进料条件,减少了丙烯在碳三加氢反应器中的损失.     

CSTR和ACR丁酸型发酵制氢系统的运行特性比较

为寻求更好的连续流发酵生物制氢反应器模式,以稀释糖蜜为底物,控制反应系统为丁酸型发酵,比较研究了搅拌槽式反应器（CSTR）和厌氧接触式反应器（ACR）的启动运行特性。结果表明,以经曝气培养的下水道污泥为接种物,在接种量4.8 g MLVSS·L^-1、进水COD 5000 mg·L^-1、HRT 12 h、温度（35±1）℃和pH 5.5～6.0等相同条件下,CSTR系统可以更快地达到稳定的丁酸型发酵状态,而ACR系统因其有效的生物持有能力而在产氢性能方面更具优势。在稳定运行状态下,ACR系统的底物酸化率、产氢速率和污泥的比产氢速率分别为44%、9 L·d^-1和0.15 L·(g MLVSS·d)^-1,分别是CSTR系统的1.62、2.05和1.15倍。     

选择性氧化脱除富氢氢源中CO的研究进展

介绍了将富氢氢源中CO脱除到质子交换膜燃料电池PtRu电极可以承受的CO浓度范围(<1×10-4)最经济和最可行的方法,综述了选择性氧化脱除富氢氢源中CO在催化剂、动力学和反应器优化设计等方面的研究进展,评述了Pt催化剂、Au和Ag催化剂及Cu金属催化剂。     

耦合传质的羰基化固定床反应器传热模拟分析

固定床反应器中进行强放热反应时, 反应器的热点温度对操作参数变化敏感,容易引起飞温,导致转化率下降,影响催化剂寿命。为强化羰基化固定床反应器内热质传递与化学反应的协同性,建立考虑颗粒内扩散影响的羰基化固定床反应器拟均相一维传热模型,考察操作参数对床层热点温度、反应转化率、床层温升的影响。不仅体现传热传质和反应的协同作用,而且影响关系明晰、求解方便。为保证反应转化率,本实验条件下确定催化剂颗粒直径小于等于1.5 mm。反应器入口温度/冷却剂油温既要满足床层热稳定性需求,又要使反应转化率和床层温升都在合理范围内。模拟结果表明在床层入口温度升高的同时,可通过降低冷却剂油温获得良好的反应转化率和较小的床层温升。在此基础上,考察入口环氧乙烷浓度对反应转化率和床层温升的影响。本研究可为固定床反应器满足转化率要求、床层合理温升而选择催化剂颗粒直径、床层入口温度、冷却剂油温和床层入口浓度等操作参数提供计算依据。     

乙烯氧乙酰化固定床反应器的模拟与催化剂分布优化

采用拟均相一维和二维模型对乙烯氧乙酰化工业固定床反应器进行了数学模拟,结果表明:反应器进口气温即为热点温度,可以进一步提高催化剂活性和生产能力.当催化剂活性达到现活性的3倍时,传统的反应器将出现热失控(飞温).采用分段填装高活性催化剂的优化分布,可以大大降低反应器的热敏感性,提高反应转化率和选择性.例如,用两段填装催化剂平均活性(?)=2的反应器代替一段填装催化剂的反应器时,热点温度降低了13.9℃,乙烯转化率和乙烯转化为醋酸乙烯的选择性分别提高了1.46%和1.41%.     

Recuperative coupling of exothermic and endothermic reactions

Coupling energy intensive endothermic reaction systems with suitable exothermic reactions improves the thermal efficiency of processes and reduces the size of the reactors. One type of reactor suitable for such a type of coupling is the heat exchanger reactor. In this work, a one-dimensional pseudo-homogeneous plug flow model is used to analyze and compare the performance of co-current and counter-current heat exchanger reactors. A parametric analysis is carried out to address the vital issues, such as the exit conversion of the endothermic reaction, the temperature peak (hot spot) of the exothermic reaction and the reactor volumetric productivity. The measures to reduce the hot spot by different catalyst profiling techniques are also addressed. Some features of the dynamic behavior exhibited by these reactors, which are important from design, operational and control point of view, are presented.     

浆态床中二氧化碳加氢合成甲醇

研究了浆态床中自行开发的LP201甲醇合成催化剂上二氧化碳加氢合成甲醇的过程。探讨了不同操作条件，如温度、压力、气体空速、原料气配比等对反应的影响；考察了该催化剂在浆态床二氧化碳加氢合成甲醇过程中的稳定性。实验结果表明，浆态床二氧化碳加氢合成甲醇过程中主要产物为甲醇、CO和水；随温度的增加，CO2的转化率和甲醇产率呈现上升的趋势，但甲醇的选择性明显下降；压力的升高有利于CO2的转化率、甲醇产率以及甲醇的选择性提高；原料气空速的提高会增大甲醇产率，但同时降低CO2的转化率以及甲醇的选择性；CO2的转化率、甲醇收率以及甲醇的选择性在氢碳摩尔比4～5获得极大值。LP201催化剂的寿命考察结果表明，该催化剂具有较好的催化活性和稳定性。     

低温液相甲醇合成鼓泡浆态反应器数学模拟

建立了经由甲酸甲酯的低温液相甲醇合成鼓泡浆态反应器的数学模型 ,模拟了实验室鼓泡浆态反应器的行为 ,并利用模型考察了工艺参数如表观气速、催化剂浓度对反应的影响 ,对改进和提高低温液相浆态床反应器甲醇合成提供了信息 ,以便对开发低温甲醇合成工艺提供参考和指导     

Hydrogen generation in a Pd membrane fuel processor: Productivity effects during methanol steam reforming

Performance analyses are carried out for the palladium membrane fuel processor for catalytic generation of high purity hydrogen. The reactor model includes detailed particle-scale multi-component diffusion, multiple reversible reactions, flow, and membrane transport. Using methanol steam reforming on Cu/ZnO/Al₂O₃ catalyst as the test reaction, a systematic examination of the effects of operating and reactor design parameters on key performance metrics is presented. Single particle simulations reveal a complex interplay between nonisobaric transport and the reversible reactions (methanol reforming and decomposition, and water-gas shift), which impact overall reactor performance. An analysis of characteristic times helps to identify four different productivity controlling regimes: (i) permeation control, encountered with thick membranes and/or insufficient membrane area; (ii) catalyst pore diffusion control encountered with diffusion of reacting species in larger particles; (iii) reaction control, encountered when intrinsic catalytic rates are too low because of inadequate activity or catalyst loading; and (iv) feed control, encountered when the limiting reactant feed rate is inadequate. The simulations reveal that a maximum in the hydrogen productivity occurs at an intermediate space velocity, while the hydrogen utilization is a decreasing function of space velocity, implying a trade-off between productivity and hydrogen utilization. The locus of productivity maxima itself exhibits a maximum at an intermediate membrane surface to volume ratio, the specific value of which is dependent on the particle size, membrane thickness and reaction conditions. At moderate temperature and total pressure (, 10 bar), particles smaller than 2 mm diameter, Pd membranes with thickness less than , and membrane surface to volume ratio exceeding are needed to achieve viable productivity . A comparison between the packed-bed membrane reactor and conventional packed-bed reactor indicates a modest improvement in the conversion and productivity due to in situ hydrogen removal.     

基于Fluent的微通道天然气废气重整的数值模拟

利用Fluent软件对微通道反应器中天然气废气重整进行数值模拟。利用甲烷来代替天然气进行模拟。多通道反应器由具有平行通道的堇青石块组成,每个平行通道用Rh/Al_2O_3催化剂洗涂。由于堇青石的低热导率,通道之间的热传递被忽略。研究了进料温度,燃料组成和天然气中存在的丙烷对温度和产物分布的影响。通过模拟结果可得出:开始温度沿着通道良好地分布,并且没有形成明显的热点;增加进料温度有利于甲烷转化和氢气生产,但会导致温度分布不均;提高进料中蒸汽的量有助于增加氢气形成,但轻微地减弱了甲烷转化;提高入口处的O_2/C比值可导致甲烷转化率和温度成比例地增加。     

Co‐current and Countercurrent Configurations for a Membrane Dual Type Methanol Reactor

A dynamic model for a membrane dual‐type methanol reactor was developed in the presence of catalyst deactivation. This reactor is a shell and tube type where the first reactor is cooled with cooling water and the second one with feed synthesis gas. In this reactor system, the wall of the tubes in the gas‐cooled reactor is covered with a palladium‐silver membrane which is only permeable to hydrogen. Hydrogen can penetrate from the feed synthesis gas side into the reaction side due to the hydrogen partial pressure driving force. Hydrogen permeation through the membrane shifts the reaction towards the product side according to the thermodynamic equilibrium. Moreover, the performance of the reactor was investigated when the reaction gas side and feed gas side streams are continuously either co‐current or countercurrent. Comparison between co‐current and countercurrent mode in terms of temperature, activity, methanol production rate as well as permeation rate of hydrogen through the membrane shows that the reactor in co‐current configuration operates with lower conversion and also lower permeation rate of hydrogen but with longer catalyst life than does the reactor in countercurrent configuration.     

Membrane pilot reactor applied to selective oxidation reactions

The partial oxidation of butane to maleic anhydride was studied in a conventional fixed bed as well as a novel reactor configuration consisting of a porous metallic membrane immersed in a gas–solid fluid bed. The diameter of both reactors was at a commercial scale greater than 30 mm. A range of gas flow rates, temperatures and butane concentrations were tested. Maleic anhydride yield was generally higher in the membrane reactor due to higher butane conversion. Maleic productivity in the fixed bed equalled that observed in the membrane reactor when the gas–solid fluid bed was maintained at a higher temperature of as much as 30 °C. The butane feed rate to the membrane reactor was limited by hot spots. These hot spots were unanticipated and underscore the importance of increasing heat transfer in order to commercialize this technology.