甲醇水蒸气重整制氢固定床反应器的数学模拟

建立二维拟均相固定床反应器数学模型用于描述Cu₅₀Zn₃₀Ce₁₀Al₁₀催化剂颗粒的甲醇水蒸气重整制氢反应过程，该模型由流体相的质量、热量和动量传递方程组成，耦合催化剂颗粒内部的扩散-反应模型。通过将模型预测值与实验数据进行比较，验证反应器数学模型的准确性。在此基础上，分析关键组分CO₂和CO的效率因子随床层轴向的变化规律以及催化剂床层的轴径向温度分布。结果表明：催化剂床层的轴径向温差较大，导致CO₂效率因子变化较大，而CO由于浓度低，反应速率慢，其效率因子变化不明显。     

催化剂颗粒形状对甲烷水蒸气重整反应的影响及工业反应器模拟

甲烷水蒸气重整工艺是现阶段最主要的工业制氢技术,催化剂颗粒形状和反应器操作条件是影响重整反应器性能和产物组成的重要因素。首先从颗粒尺度研究催化剂形状对甲烷水蒸气重整反应的影响,在不同的反应温度和压力下,计算并比较了球形、柱形和环形催化剂的效率因子,其大小顺序为:柱形 < 球形 < 环形。其次,将反应器床层的质量、热量和动量传递与环形催化剂颗粒的扩散-反应方程相结合,建立了用于描述甲烷水蒸气重整工业反应器的一维轴向数学模型。计算并分析了反应器进口温度和压力对反应器床层的温度和压力分布、催化剂效率因子以及甲烷转化率和各组分浓度分布的影响,确定了适宜的工业反应器进口温度和压力,分别为773 K和3 MPa。     

流化床在甲烷临氧CO2重整反应中的作用研究

在流化床反应器中进行甲烷临氧CO₂重整制合成气反应。通过计算分析了催化剂颗粒在床层内的流化特性。对比实验表明,流化床反应器在催化剂活性、稳定性、自热过程以及催化剂积炭等方面均体现出比固定床反应器的优越性。在流化床反应器中进行的甲烷自热重整反应,甲烷的转化率接近热力学平衡值,床层温度梯度小于10 ℃, 反应20 h后,催化剂表面无积炭。     

CH4-CO2重整反应过程中炭催化剂失重特性

在反应温度950～1 200℃,升温速度20℃/min的实验条件下,用热重分析仪对炭催化剂作用下CO2气化和CH4-CO2重整过程中炭催化剂失重进行了研究.结果表明,在炭催化剂-CO2气化过程中,随着CO2流量的增加和反应温度的提高,炭催化剂的失重率明显增加,CO2流量和反应温度是造成炭催化剂失重的重要原因.在炭催化CH4-CO2重整过程中,随着CO2/CH4比值的增加炭催化剂质量先增加后减少,表明炭催化剂的失重率可以通过CO2/CH4来调节;而随反应温度升高,炭催化剂质量变化表现为低温(<1 100℃)单阶段和高温(>1100℃)双阶段两种类型.即在反应温度低于1 100℃时,炭催化剂失重反应主要由化学反应过程控制,CH4裂解碳沉积和CO2的气化消碳很快达到平衡,炭催化剂失重宏观上表现为维持恒定的单一阶段;当反应温度高于1 100℃后,炭催化剂的失重表现为双阶段,开始的第一阶段,主要受化学反应过程控制.炭催化剂急剧失重,然后逐步过渡到扩散过程控制的第二阶段,失重率逐渐趋于平缓;炭催化CH4-CO2重整过程中,反应温度和CO2/CH4比是导致炭催化剂失重的主要因素.     

合成氨变换系统生产组织及技术改造的原则商榷

变换工段是合成氨生产系统中的一个生产单元，它的主要作用是把半水煤气中的CO转化为CO2，并辅以部分的有机硫转化反应。CO变换反应过程是一个典型的气固相催化反应过程，在生产过程中，催化剂床层阻力会随之上升，催化剂的活性也会随之减弱。控制并保护好催化活性，抑制床层阻力的上升是变换系统生产组织和所需技术改造的总体原则，如果离开这一原则而片面地去追求能耗或短时间的高产均不是一个适宜的做法。     

甲醇水蒸气重整工艺的优化

甲醇在常温常压下为液态且具有极高的载氢密度，因而是一种较为理想的载氢介质。甲醇重整反应器的设计对于甲醇在线重整制氢燃料电池系统的设计具有重要意义。对于甲醇重整反应器，反应温度较高时重整气中CO浓度高，不利于后续的CO深度脱除；而反应温度较低时，甲醇转化率与液相空速低，会导致催化剂利用率低并且反应器体积较大。基于以上问题，本工作提出了一种由第一段300℃下等温重整和第二段300℃～220℃下绝热重整组成的两段变温重整工艺。基于Aspen Plus对该工艺进行了模拟研究，证明该工艺在理论上可以实现。然后通过固定床反应器进行实验研究，结果表明在甲醇完全转化的条件下，本变温工艺的甲醇液相空速为4.08h^-1，重整气中CO浓度为0.56%，重整制氢效率为108.98mL/(min·mL催化剂)。而220℃下等温重整工艺的液相空速为1.5h^-1，重整气中CO浓度为0.40%，重整制氢效率为44.89mL/(min·mL催化剂)。变温工艺可以在较大的液相空速下获得更高的重整制氢效率，降低催化剂用量，使重整器结构更加紧凑。同时，与300℃下等温重整工艺相比，...     

泡沫碳化硅基整体催化剂用于强化甲烷绝热转化制合成气

为实现强化耦合甲烷部分氧化和水蒸汽重整的绝热转化反应,采用了整体泡沫碳化硅为载体制备镍基整体催化剂,进行了整体结构催化剂床层优化设计,在由6块整体催化剂组成的4.8 cm床层高度的固定床反应器上进行了催化剂小试样品的性能评价,并完成了中试验证。通过采用多层催化剂床层结构设计,避免了整体催化剂反应物流旁路,同时还实现氧二次分散。首次开展进料规模为200 t/a天然气绝热转化中试实验验证了天然气绝热转化技术的安全性,为该技术进一步发展放大奠定基础。     

XNC-98催化剂甲醇合成本征动力学

在等温积分反应器中研究了XNC-98催化剂上甲醇合成反应本征动力学.实验压力为4~8MPa,空速7000~13000h-1,反应温度200~260℃.实验采用粒度为0.154~0.198mm的细颗粒催化剂.选取以各组分逸度表示的CO、CO2加氢合成甲醇的Langmuir-Hinshelwood本征动力学模型.采用正交实验设计,实验测定了25组数据,用全局通用算法结合马夸特算法确定动力学模型参数.残差分析和统计检验表明,动力学模型是适宜的.随温度升高,反应器出口甲醇浓度、CO和CO2转化率先增加后降低,在4~8MPa下,230~245℃为较佳反应温度范围:随着反应压力的提高,反应器出口甲醇浓度、CO和CO2转化率都有显著增加,提高反应压力能够有效提高反应器的生产能力.     

中低温换热式焦炉气合成天然气新工艺

焦炉气经净化、加热之后,采用不循环一次性通过或少量循环、不补加蒸汽的2种不同试验工况,直接进入中低温换热式反应器进行甲烷化反应,合成的天然气减压后送煤气管网,催化剂床层温度通过汽包压力控制。2种不同工况经72 h考核,CO转化率达100%,CO2转化率达～99%。     

基于催化剂活性分布的甲醇重整制氢研究

为了探索填充床内催化活性分布对甲醇重整制氢的影响,文中采用铜基催化剂设计了3种不同活性布置的催化剂床层,并在管式反应器内开展了实验研究,考察了3种不同活性分布的床层上空速和温度对甲醇转化率及产氢速率的影响。通过甲醇蒸汽重整实验表明,3种床层上甲醇转化率及产氢速率随着反应温度和空速的变化规律相同。但床层Ⅰ的催化剂布置形式,改善了局部热效应,提高了催化剂的利用效率。结果显示:床层Ⅰ的催化剂布置形式优于其他2种催化剂布置形式;相同催化剂用量下,床层Ⅰ中的甲醇转化率比床层Ⅱ的甲醇转化率提高9.91%;最佳的活性布置方式是,催化剂用量由反应器入口到出口梯级增加。且在甲醇裂解实验中,床层Ⅰ中的H2体积分数高于床层Ⅱ中的。     

A dual catalyst bed for the autothermal partial oxidation of methane to synthesis gas

Dual bed catalysts were found to produce high yields (>85%) of hydrogen from methane and air in a millisecond contact time reactor. The dual bed catalyst consisted of a 5 mm platinum combustion catalyst followed by a 5 mm nickel steam reforming catalyst. The platinum catalyst was used to totally oxidize approximately one-quarter of the methane feed to carbon dioxide and water. In the nickel catalyst, the carbon dioxide and water reformed the remaining methane to hydrogen and carbon monoxide. This process is favored at high flow rates, because the heat generated in the platinum catalyst is convected to the nickel catalyst at a higher rate. The heat delivered to the nickel catalyst favors the endothermic reforming reactions that generate the hydrogen and carbon monoxide.     

CO催化偶联制草酸二乙酯催化剂的宏观反应动力学

采用固定床积分反应器,研究了自制的负载型钯系催化剂上CO气相催化偶联主、副反应的宏观动力学模型.所采用的催化剂是经过模式1000 h连续运转、性能稳定的φ1.5 mm×（3～5）mm圆柱状催化剂.在适宜的反应条件下测定了动力学实验数据,并采用一维拟均相模型建立了微分方程组.使用了幂函数宏观动力学模型,采用Runge-Kutta法解微分方程组,并用单纯形法确定动力学模型参数,同时进行了残差分析和统计检验.结果表明,所得的动力学模型与实验数据吻合良好,可以为草酸二乙酯合成反应器设计和放大提供依据.     

Steam Reforming of Methanol in a Compact Copper Microchannel Foam Reactor

Hydrogen production via steam reforming of methanol over a rare earth‐promoted Cu‐based catalyst washcoated on a microchannel foam reactor (MFR) was investigated. A low reforming temperature of 242 °C at a weight hourly space velocity for the methanol/catalyst of 10 h^–1 was observed in the MFR, which is lower than the 270 °C reforming temperature observed in a traditional packed‐bed reactor (PBR). According to a measurement of the reforming temperature distribution, the MFR made of Cu foam in this study exhibits extraordinary heat conductivity. The heat rate supplied from the external heating source can be transferred instantly to the reaction sites of the washcoated catalyst layer through a three‐dimensional framework of Cu microchannels. As a result, the cold spots normally encountered in a PBR are minimized effectively so that a high conversion of steam reforming of methanol is obtained. Moreover, the use of a high performance compact MFR with a volume of 4 mL as a portable hydrogen source is suggested. A hydrogen production rate of 280 mL min^–1 with a CO fraction of 1.5% was obtained, which can yield a practical power output of 25 W using a commercial proton exchange membrane fuel cell with an operational efficiency of 50%.     

流化床甲烷化基础与应用最新进展

由于CO甲烷化的快速表面反应、强放热特性,相比固定床,采用小颗粒催化剂的流化床甲烷化技术在反应活性和催化剂稳定性方面具有明显的技术优势。从高耐磨催化剂、流化床反应器及其创新、短流程两段甲烷化技术构建及其验证等方面总结了流化床甲烷化技术开发的最新进展。优化催化剂前体制备方法、调变催化剂组成可获得具有较高骨架强度和均匀性的催化剂一次微粒,进而通过优化的喷雾造粒工艺和填充黏结剂,制备出具有可调变粒度分布、高强度和高球形度的流化床用粉末催化剂,但其黏结剂的添加明显影响催化剂的低温活性。通过改性如Al₂O₃和FCC催化剂的球形颗粒,进而负载活性组分,开发了制备高活性、磨损指数小于1.5的流化床甲烷化Ni基催化剂的另一种技术方法。实验室研究证实了流化床甲烷化反应速率极快,在分布板上数毫米处即可实现可能的最高转化率,且在转化率和催化剂稳定性方面明显优于固定床,不仅由于流态化催化剂床层温度均匀,而且催化剂在床层内不停循环,加快了颗粒表面的更新。增大空速和表观气速,流化床的催化剂床层膨胀,反应气体与催化剂颗粒表面间的有效接触面积增加,使得流化床甲烷化对空速和表观气速的可调范围大。操作在更高气速条件的输送床甲烷化避免了操作气速的上限限制,可大幅降低反应器尺寸,有效提高单位截面的原料气负荷能力。输送床甲烷化可采用高热导率的催化剂颗粒传递反应热,相对于气体移热效率高、能力大。流化床甲烷化已在生物废弃物利用和焦炉煤气甲烷化方面开展了侧线示范,形成了相对多段绝热固定床工艺更简单的短流程两段甲烷化新工艺。     

Computational fluid dynamics modeling of hydrogen production in an autothermal reactor: Effect of different thermal conditions

A numerical model was developed and validated to simulate and improve the reforming efficiency of methane to syngas (CO+H₂) in an autothermal reactor. This work was undertaken in a 0.8 cm diameter and 30 cm length quartz tubular reactor. The exhaust gas from combustion at the bottom of reactor was passed over a Ru/γ-Al₂O₃ catalyst bed. The Eddy Dissipation Concept (EDC) model for turbulence-chemistry interaction in combination with a modified standard k-? model for turbulence and a reaction mechanism with 23 species and 39 elementary reactions were considered in the combustion model. The pre-exponential factors and activation energy values for the catalyst (Ru) were obtained by using the experimental results. The percentage of difference between the predicted and measured mole fractions of the major species in the exhaust gas from combustion and catalyst bed zones was less than 5.02% and 7.73%, respectively. In addition, the results showed that the reforming efficiency, based on hydrogen yield, was increased with increase in catalyst bed’s thermal conductivity. Moreover, an enhancement of 4.34% in the reforming efficiency was obtained with increase in the catalyst bed wall heat flux from 0.5 to 2.0 kW/m².     

Fischer–Tropsch synthesis on ceramic monolith-structured catalysts

This paper reports recent research results about the impact of different catalyst bed configurations on Fischer–Tropsch (FT) synthesis product distributions. A powdered CoRe/γ-alumina catalyst with a particle size ranging from 60 to 100 mesh was prepared and tested in a packed bed reactor. The same catalyst was ball milled and coated on a ceramic monolith support structure of channel size about 1 mm. The monolith catalyst module was tested in two different ways, as a whole piece and as well-defined channels. Steady-state reaction conversion was measured at various temperatures under a constant H₂/CO feed ratio of 2 and a reactor pressure of 25 bar. Detailed product analysis was performed. Significant formation of wax was evident with the packed particle bed and with the monolith catalyst that was improperly packed. By contrast, wax formation was not detected in the liquid product by confining the reactions inside the monolith channel. This study presents an important finding about the structured catalyst/reactor system, in that the product distribution highly depends on how the structured reactor is set up. Even if a catalyst is tested under identical reaction conditions (T, P, H₂/CO ratio), hydrodynamics (or flow conditions) inside a structured channel may have a significant impact on the product distribution.     

流化床甲醇合成催化剂的制备及其性能

采用碳酸钠共沉淀法制备了5种不同组成的铜基甲醇合成催化剂,并对其进行了活性评价和形貌及抗磨损性能表征. 结果表明,氧化锆可使催化剂的耐磨损强度显著提高,磨损指数(AJI)可达0.056;催化剂的活性和稳定性较好,CO转化率约40%,260℃高温下长达50 h基本不失活. 氧化铝与铜锌发生复合使催化剂的活性显著下降,CO转化率仅有10%,对催化剂的强度提高作用不明显,AJI值达0.103. 组成为铜锌锆的催化剂较适用于流化床中甲醇的合成.     

生物质催化气化实验研究

在常压流化床上进行了生物质在水蒸气条件下的实验研究。实验装置主体由常压流化床反应器和固定床催化裂解反应器组合而成。生物质原料为木屑,焦油裂解催化剂分别选用煅烧白云石和镍基重整催化剂。实验结果表明,H2/CO(H/C)的摩尔比随着气化温度、水蒸气质量/生物质质量（S/B）的升高迅速增加,但催化裂解温度变化对H/C的影响较小。另外,在催化裂解反应器中使用催化剂种类不同,H/C也不同。本文采用两段催化裂解,一段催化剂采用煅烧白云石,二段采用镍基催化剂,焦油裂解率达到96.70％。采用两段催化裂解,不但可以提高焦油的裂解率,增加了H2和CO收率,净化生物质裂解气,而且可以防止镍基重整催化剂失活,延长其使用寿命。     

One-dimensional heterogeneous model of a Fischer-Tropsch synthesis reactor with a fixed catalyst bed in the isothermal granules approximation

A one-dimensional heterogeneous model has been developed for a cat6alytic fixed-bed Fischer-Tropsch (FT) synthesis reactor in the isothermal granules approximation. The FT process has been simulated for a laboratory-scale reactor. The effects of the linear gas velocity and of the inner diameter of the reactor on the thermal stability of the process are considered. The size of the reactor is limited by the possibility of a “thermal explosion” occurring in the frontal layer of the catalyst. Raising the linear gas velocity enhances heat transfer, thereby reducing the overheating of the catalyst bed. The synthesis of solid hydrocarbons can be conducted in reactors no larger than 18 mm in diameter. According to calculations, the maximum temperature drop in a 3-, 4-, and 6-m-long reactor is 4.7, 4.2, and 3.6°C, respectively. The corresponding CO conversion is 35.0, 34.4, and 33.9%, respectively. For producing liquid hydrocarbons in a high-performance reactor, it is necessary to decrease its inner diameter to 12 mm. In this case, the maximum temperature drop at a reactor length of 3, 4, and 6 m is 9.6, 8.7, and 7.6°C, and the CO conversion is 78.0, 77.4, and 76.7%, respectively. The mathematical model devised here provides means to estimate the necessary design parameters of the reactor and the appropriate FT synthesis conditions for producing liquid or solid hydrocarbons.     

A301氨合成催化剂活性的单管反应器测试

引　言在实验室研究中 ,通常是在消除了内外扩散效应的情况下测定催化剂的活性的 ,因此所获得的动力学方程属本征动力学 ,所得到的催化剂的活性 ,也是基本消除了内外扩散效应时的活性 ,与工业使用条件有较大的差别 .为了考核Ａ30 1催化剂应用于等压合成氨的可能性 ,仅有实验室条件下的催化活性数据是不够的 ,还必须提供在工业使用条件相同或近似的条件下测定催化剂的活性 .为此本课题分两部分试验来达到这个目的 .一是在实验室内进行原粒度催化剂的单管试验 ;二是在大型合成氨装置建立旁路试验 .后者将在另文报道 .在合成氨生产中 ,空间速度…