Statistical analysis of the performance of a bi-functional catalyst under operating conditions of LPDME process

Liquid phase direct synthesis of dimethyl ether (LPDME™) under various operating conditions (temperature, H₂/CO molar ratio of feed) was conducted in a mechanically agitated slurry reactor system. Each run was monitored for 60 h time on stream (TOS) in order to confirm the high activity and long-term stability of a bi-functional catalytic system (CuO–ZnO–Al₂O₃/H-MFI-90). Statistical experimental design was applied for determining the optimum operating conditions under which the catalytic system shows the highest performance. A significant improvement in the performance of the bi-functional catalyst was observed when the temperature and H₂/CO molar ratio of feed were increased from 200 to 240 °C and 1 to 2, respectively at a constant pressure of 35 bar and GHSV equal to 1100 mLn/(g-cat h). CO conversion was increased from 9.1 mol% at T = 200 °C and H₂/CO = 1 to 79.6 mol% at T = 240 °C and H₂/CO = 2 and the yield and selectivity of DME also increased from 7.11% to 47.05% and 41.57% to 59.96%, (molar basis) respectively. No significant deactivation has been observed during 60 h TOS at different operating conditions. Furthermore, from the main effect plots and response table results, it was concluded that the most effective factor on activity and stability of bi-functional catalytic system is temperature.     

浆态床合成气合成二甲醚的工艺研究

考察了反应温度、反应压力、进料空速对浆态床合成二甲醚反应过程的影响,结果表明,在245～300℃范围内,随着反应温度的升高,一氧化碳转化率、二甲醚选择性和时空收率逐渐增加,在265℃时达到最大值后开始下降;在3.0～5.0MPa范围内,随压力的升高,一氧化碳转化率、二甲醚选择性和时空收率逐渐增加;在700～2500h-1范围内,一氧化碳转化率、二甲醚选择性随空速的增加而逐渐减小,空速以1200h-1为宜。     

三相床中合成气一步法制二甲醚

在反应温度 2 30～ 2 70℃、压力 2～ 5MPa下 ,以医药用石蜡油为惰性液相介质 ,使用C30 2铜基催化剂和CM - 3- 1改性分子筛组成的复合催化剂 ,在三相搅拌釜中研究了合成气 (CO、CO2 、H2 )一步法合成二甲醚的反应。结果表明随着温度的升高 ,碳的转化率增加 ,二甲醚的选择性提高 ,甲醇的选择性降低 ;随着压力的增加 ,碳的转化率升高 ,二甲醚的选择性提高 ,甲醇的选择性降低     

Liquid-phase preparation of catalysts used in slurry reactors to synthesize dimethyl ether from syngas: Effect of heat-treatment atmosphere

A CuZnAl slurry catalyst was prepared directly from a solution of metal salts by an entirely liquid-phase method. The influence of heat-treatment atmospheres with different proportions of CO₂ on the single-step synthesis of dimethyl ether (DME) from syngas was investigated and the catalysts were characterized by powder X-ray diffraction (XRD), H₂ temperature-programmed reduction (H₂-TPR), temperature-programmed desorption of ammonia (NH₃-TPD), X-ray photoelectron spectrometry (XPS) and thermogravimetry-mass spectrometry (TG-MS). Results showed that the introduction of CO₂ into the heat-treatment atmosphere made it easier to reduce the catalyst. It also adjusted the Cu⁰/Cu⁺ ratio on the catalyst surface, the CO₂ reacting with the metallic carbide there to form CO, which then reduced part of the Cu₂O to Cu. Moreover, it was concluded that the final phase structure of the catalyst and the Cu/Zn ratio on its surface depended mainly on its composition and the reaction environment and less so on the heat-treatment atmosphere. In the DME synthesis reaction, it was found that the introduction of CO₂ into the heat-treatment atmosphere restrained the water–gas shift reaction and raised the DME selectivity. An optimal amount of CO₂ in the heat-treatment atmosphere favored the increase of the DME space–time yield. The catalysts performed best when the heat-treatment atmosphere contained 50% CO₂.     

Deactivation and regeneration of hybrid catalysts in the single-step synthesis of dimethyl ether from syngas and CO2

Synthesis of dimethyl ether (DME) has been studied in a single reaction step, from H₂ + CO and H₂ + CO₂, in a fixed bed reactor on CuO-ZnO-Al₂O₃/γ-Al₂O₃ and CuO-ZnO-Al₂O₃/NaHZSM-5 hybrid catalysts. It has been proven that water content in the reaction medium (which is higher when CO₂ is fed) contributes to efficiently decreasing deactivation by coke in both catalysts and, consequently, when water is in the feed deactivation is insignificant for 30 h reaction. Nevertheless, water also decreases the activity of γ-Al₂O₃ acid function, due to its high adsorption capacity on the acid sites. Due to its importance in the viability of the industrial process, a study has been carried on the regeneration of both catalysts by coke combustion under controlled conditions (in order to avoid CuO sintering). For this study, the catalysts have been used under severe deactivation conditions. It has been proven that γ-Al₂O₃ does not have a suitable hydrothermal stability and that CuO-ZnO-Al₂O₃/NaHZSM-5 catalyst has an excellent performance and is suitable for using it in uninterrupted reaction–regeneration cycles.     

Effect of H2O on Cu-based catalyst in one-step slurry phase dimethyl ether synthesis

One-step dimethyl ether (DME) synthesis in slurry phase was catalyzed by a hybrid catalyst composed of a Cu-based methanol synthesis catalyst and a γ-Al₂O₃ methanol dehydration catalyst under reaction conditions of 260 °C and 5.0 MPa. It was found that instability of the Cu-based catalyst led to rapid deactivation of the hybrid catalyst. The stability of the Cu-based catalyst under DME synthesis conditions was compared with that under methanol synthesis conditions. The results indicated that harmfulness of water, which formed in DME synthesis, caused the Cu-based catalyst to deactivate at a high rate. Surface physical analysis, elemental analysis, XRD and XPS were used to characterize the surface physical properties, components, crystal structures and surface morphologies of the Cu-based catalysts. It was found that Cu⁰ was the active component for methanol synthesis and Cu₂O might have less activity for the reaction. Compared with methanol synthesis process, crystallite size of Cu became bigger in DME synthesis process, but carbon deposition was less severe. It was also found that there was distinct metal loss of Zn and Al caused by hydrothermal leaching, impairing the stability of the catalyst. In slurry phase DME synthesis, a part of Cu transformed into Cu₂(OH)₂CO₃, causing a decrease in the number of active sites of the Cu-based catalyst. And some ZnO converted to Zn₅(OH)₆(CO₃)₂, which caused the synergistic effect between Cu and ZnO to become weaker. Crystallite size growth of Cu, carbon deposition, metal loss of Zn and Al, formation of Cu₂(OH)₂CO₃ and Zn₅(OH)₆(CO₃)₂ were important reasons for rapid deactivation of the Cu-based catalyst.     

Intrinsic kinetics of Fischer–Tropsch reactions over an industrial Co–Ru/γ-Al2O3 catalyst in slurry phase reactor

The rate of Fischer–Tropsch synthesis over an industrial well-characterized Co–Ru/γ-Al₂O₃ catalyst was studied in a laboratory well mixed, continuous flow, slurry reactor under the conditions relevant to industrial operations as follows: temperature of 200–240 °C, pressure of 20–35 bar, H₂/CO feed ratio of 1.0–2.5, gas hourly space velocity of 500–1500 N cm³ g_cat^− 1 h^− 1 and conversions of 10–84% of carbon monoxide and 13–89% of hydrogen. The ranges of partial pressures of CO and H₂ have been chosen as 5–15 and 10–25 bar respectively. Five kinetic models are considered: one empirical power law model and four variations of the Langmuir–Hinshelwood–Hougen–Watson representation. All models considered incorporate a strong inhibition due to CO adsorption. The data of this study are fitted fairly well by a simple LHHW form − R_H2 + CO = ap_H2^0.988p_CO^0.508 / (1 + bp_CO^0.508)² in comparison to fits of the same data by several other representative LHHW rate forms proposed in other works. The apparent activation energy was 94–103 kJ/mol. Kinetic parameters are determined using the genetic algorithm approach (GA), followed by the Levenberg–Marquardt (LM) method to make refined optimization, and are validated by means of statistical analysis. Also, the performance of the catalyst for Fischer–Tropsch synthesis and the hydrocarbon product distributions were investigated under different reaction conditions.     

乙烯在银催化剂上氧化本征动力学的研究

采用固定床恒温积分反应器，对YS-6型银催化剂进行乙烯氧化本征动力学研究。选择与工业应用接近的条件进行动力学实验，根据建立的动力学模型。用动力学试验数据采用双响应Marquardt法，以转化率，选择性为目标函数进行待定参数估值。确定待定参数，得到本征动力学方程，根据数学统计检验，文中所建立的模型残差分布合理。参数回归显著，能够反映YS-6型催化剂的反应特性。     

Intrinsic kinetics of one-step dimethyl ether synthesis from hydrogen-rich synthesis gas over bi-functional catalyst

The reaction kinetics of the dimethyl ether synthesis from hydrogen-rich synthesis gas over bi-functional catalyst was investigated using an isothermal integral reactor at 220–260°C temperature, 3–7 MPa pressure, and 1,000–2,500 mL/g·h space velocity. The H₂/CO ratio of the synthetic gas was chosen between 3 : 1 and 6 : 1. The bi-functional catalyst was prepared by physically mixing commercial CuO/ZnO/Al₂O₃ and γ-alumina, which act as methanol synthesis catalyst and dehydration catalyst, respectively. The three reactions, including methanol synthesis from CO and CO₂ as well as methanol dehydration, were chosen as independent reactions. The Langmuir-Hinshelwood kinetic models for dimethyl ether synthesis were adopted. Kinetics parameters were obtained using the Levenberg-Marquardt mathematical method. The model was reliable according to statistical and residual error analyses. The effects of different process conditions on the reactor performance were also investigated.     

Simulation of DME synthesis from coal syngas by kinetics model

DME (Dimethyl Ether) has emerged as a clean alternative fuel for diesel. There are largely two methods for DME synthesis. A direct method of DME synthesis has been recently developed that has a more compact process than the indirect method. However, the direct method of DME synthesis has not yet been optimized at the face of its performance: yield and production rate of DME. In this study it is developed a simulation model through a kinetics model of the ASPEN plus simulator, performed to detect operating characteristics of DME direct synthesis. An overall DME synthesis process is referenced by experimental data of 3 ton/day (TPD) coal gasification pilot plant located at IAE in Korea. Supplying condition of DME synthesis model is equivalently set to 80 N/m³ of syngas which is derived from a coal gasification plant. In the simulation it is assumed that the overall DME synthesis process proceeds with steadystate, vapor-solid reaction with DME catalyst. The physical properties of reactants are governed by Soave-Redlich-Kwong (SRK) EOS in this model. A reaction model of DME synthesis is considered that is applied with the LHHW (Langmuir-Hinshelwood Hougen Watson) equation as an adsorption-desorption model on the surface of the DME catalyst. After adjusting the kinetics of the DME synthesis reaction among reactants with experimental data, the kinetics of the governing reactions inner DME reactor are modified and coupled with the entire DME synthesis reaction. For validating simulation results of the DME synthesis model, the obtained simulation results are compared with experimental results: conversion ratio, DME yield and DME production rate. Then, a sensitivity analysis is performed by effects of operating variables such as pressure, temperature of the reactor, void fraction of catalyst and H₂/CO ratio of supplied syngas with modified model. According to simulation results, optimum operating conditions of DME reactor are obtained in the range of 265–275 °C and 60 kg/cm². And DME production rate has a maximum value in the range of 1–1.5 of H₂/CO ratio in the syngas composition.     

合成气直接合成二甲醚的工艺研究

本文考察了二氧化碳浓度、空速、温度在合成气直接合成二甲醚过程中对双功能催化剂的影响，结果表明，合成比2．85，在CO2浓度4．2％－7．15％范围内，随着CO2浓度增加，CO的转化率和DME的选择性逐渐下降，在进气空速1300－3200h^-1范围内，CO的转化率和DME的选择性随空速的增加而减小，但在1500h^-1左右CO的转化率和DME的选择性较高；在反应温度265－300℃范围内，CO的转化率和DME的选择性随浊度的升高而增加，但在285－300℃之间两者变化不大，最佳条件：CO2浓度5．2％，空速1500h^-1,温度285℃。     

合成气一步法5000t/a二甲醚管式反应器设计

应用实验所得动力学数据,建立管式固定床反应器的一维数学模型。通过计算典型工况下5000t/a二甲醚反应器,得到了反应器的工艺与设备设计参数。     

复合固体酸催化剂在合成气制二甲醚中的应用研究

对镁碱沸石(FER)进行Zn、Mn金属改性,对γ-Al2O3进行S2O2-3、Ni2+改性,将改性后的FER和γ-Al2O3复合用于合成气直接制二甲醚催化剂中,作为甲醇脱水催化剂组分,制备出了Cu-Zn-Al/ASN/FZM双功能催化剂.在连续固定床高压反应器中,研究了改性条件、复合比及反应温度对催化剂性能的影响.在2...     

一步法合成二甲醚反应器的研究进展

综述了合成气一步法合成二甲醚反应器的发展近况,着重介绍了固定床、浆态床及组合床的研究进展,并根据国内外的研究对几种反应器进行了工艺比较。     

合成气直接制二甲醚技术及催化剂的研究进展

本文在合成气直接制二甲醚的热力学分析的基础上,阐述了一步法合成二甲醚由于多个化学反应同时进行所产生的协同效应,提高了合成气的转化率,而较两步法合成具有更多的优势。综述了合成气直接制二甲醚技术和催化剂制备的进展情况,介绍了所取得的最新研究成果及动态。     

二甲醚一步法合成技术研究进展

综述了从合成气直接制取二甲醚的催化剂、固定床工艺和浆态床工艺的研究状况 ,对比了 5种催化剂的组成和性能 ,介绍了日本钢管公司 (NKK)和美国空气产品化学品公司开发的浆态床工艺进展情况     

BX 型中温变换催化剂上CO 变换反应本征动力学研究

采用常压等温直流积分反应器, 研究了在BX 型中温变换催化剂上CO 变换反应的本征动力学。应用正交实验设计方法, 模拟生产条件进行测试, 用非线性最小二乘法优化参数估值, 获得本征动力学模型, 并经F 检验、相关指数检验及运用此数学模型进行某工厂变换炉催化剂用量的计算, 证明了实验数据及数学模型的准确性。     

Performance characteristics of fluidized bed syngas methanation over Ni-Mg/Al2O3 catalyst

The performance characteristics of isothermal fluidized bed syngas methanation for substitute natural gas are investigated over a self-made Ni–Mg/Al2O3 catalyst. Via atmospheric methanation in a laboratory fluidized bed reactor it was clarified that the CO conversion varied in 5% when changing the space velocity in 40–120 L·g?1·h?1 but the conversion increased obviously by raising the superficial gas velocity from 4 to 12.4 cm·s?1. The temperature at 823 K is suitable for syngas methanation while obvious deposition of uneasy-oxidizing Cγoccurs on the catalyst at temperatures around 873 K. From a kinetic aspect, the lowest reaction temperature is suggested to be 750 K when the space velocity is 60 L·g?1·h?1. Raising the H2/CO ratio of the syngas increased proportionally the CO conversion and CH4 selectivity, showing that at enough high H2/CO ratios the active sites on the catalyst are sufficient for CO adsorption and in turn the reaction with H2 for forming CH4. Introducing CO2 into the syngas feed suppresses the water gas shift and Boudouard reactions and thus increased H2 consumption. The ratio of CO2/CO in syngas should be better below 0.52 because varying the ratio from 0.52 to 0.92 resulted in negligible increases in the H2 conversion and CH4 selectivity but decreased the CH4 yield. Introducing steam into the feed gas affected little the CO conversion but decreased the selectivity to CH4. The tested Ni–Mg/Al2O3 catalyst manifested good stability in structure and activity even in syngas containing water vapor.     

The interaction effects of dehydration function on catalytic performance and properties of hybrid catalysts upon LPDME process

Three bi-functional catalysts have been prepared by physical mixing of a commercial methanol synthesis catalyst (CuO–ZnO–Al₂O₃) with three different methanol dehydration catalysts including: H-MFI90, γ-Al₂O₃ and H-Mordenite in order to investigate the role of interaction effects of dehydration component on characteristic properties and performance of these admixed catalysts. The bi-functional catalysts have been characterized by XRD, N₂ adsorption, H₂-TPR, NH₃-TPD and XRF techniques and tested in a mixed slurry bed reactor at the same operating conditions (T = 240 °C, P = 50 bar, H₂/CO = 2, SV = 1100 ml g-cat^− 1 h^− 1) for 60 h time on stream. Among the examined bi-functional catalysts, the physical mixture of KMT + HMFI-90, which had lower reducing peak temperature (T = 200 °C), higher S_Cu (39.1 m² g-cat^− 1) and Cu Dispersion (11.6%), showed higher X_CO (84 mol%), yield of DME (Y_DME = 55.5 mol%), DME selectivity (Select_DME = 66.7 mol%) and also good stability over 60 h time on stream as compared to the other catalysts. This could be assigned, from NH₃-TPD results, to more middle strength acidic sites of H-MFI90 zeolite (SiO₂/Al₂O₃ = 90, total acid site density = 476 µmol/g-cat) which inhibits detrimental interactions with methanol synthesis catalyst and deep dehydration of methanol.     

Effect of pressure on direct synthesis of DME from syngas over metal-pillared ilerites and metal/metal-pillared ilerites

The effect of pressure on the direct synthesis of dimethyl ether (DME) from syngas over metal (Cu, Zn) pillared ilerites and metal (Cu, Zn) impregnated metal-pillared ilerites was explored. The prepared catalysts were characterized by XRD, BET, ICP-AES, SEM and FT-IR. The direct DME synthesis reaction was carried out in a differential fixed bed reactor with the prepared catalysts at various pressures (10, 20, 30 bar), 250°C and H₂/CO ratio of 2. The Cu/Zn-pillared ilerite catalyst showed the highest catalytic activity among the prepared catalysts at 20 bar, in which CO conversion was about 62% and DME selectivity was about 89%. CO conversion increased with pressure, and DME selectivity increased with pressure in the range of 10–20 bar, and above the pressure slightly decreased with pressure. The optimum pressure for this reaction was 20 bar.