Multiobjective optimization of an industrial styrene monomer manufacturing process

Multi-objective optimization of the operation and design of a styrene manufacturing process has been studied with the elitist non-dominated sorting genetic algorithm (NSGA-II). In the first part, the study focused on bi-objective optimization and comparative analysis of three different styrene reactor designs—the single-bed, the steam-injected and the double-bed reactors. The objectives were to simultaneously maximize styrene flow rate and styrene selectivity. In the second part, on the other hand, a tri-objective optimization study was performed involving the entire manufacturing process consisting of the reactor, heat-exchangers and separation units. Only the double-bed reactor was considered in this study for maximizing the styrene flow rate and selectivity and minimizing the total heat duty required by the manufacturing process. Results are presented and discussed in detail.     

Demonstration of a packed bed membrane reactor for the oxidative dehydrogenation of propane

An experimental demonstration of the oxidative dehydrogenation of propane (ODHP) in a lab-scale packed bed membrane reactor has been performed. Experiments were carried out with both premixed and distributed oxygen feed over a Ga₂O₃/MoO₃ catalyst and compared, and the influence of the gas composition, flow rate and the extent of dilution was investigated. The experimental results were found to compare very well with detailed reactor simulations. The results revealed that, in comparison with conventional reactor concepts for the ODHP (fixed bed with premixed reactants feed), a significantly higher propylene yield can be achieved at higher propane conversions in a packed bed membrane reactor.     

Fixed‐Bed Multi‐Tubular Reactors for Oxidative Dehydrogenation in Ethylene Process

An industrial‐scale reactor for ethylene production was modeled using the oxidative dehydrogenation of ethane (ODHE) in a multi‐tubular reactor system, examining a variety of parameters affecting reactor performance. The model showed that a double‐bed multi‐tubular reactor with intermediate air injection scheme was superior to a single‐bed design, due to the increased ethylene selectivity while operating under lower oxygen partial pressures. The optimized reactor length for 100 % oxygen conversion was theoretically determined for both reactor designs. The use of a distributed oxygen feed with a limited number of injection points indicated a significant improvement on the reactor performance in terms of ethane conversion and ethylene selectivity. This concept also overcame the reactor runaway temperature problem and enabled operations over a wider range of conditions to obtain enhanced ethylene production.     

C3液相选择加氢催化剂宏观动力学研究

在固定床积分反应器上研究了一种C3馏分液相选择加氢催化剂的宏观动力学。在不同的空速、温度、氢炔比条件下测定了反应的转化率和选择性，探讨了C3液相选择加氢的基本规律，并根据试验数据回归出了宏观动力学方程式。     

Effect of catalytic combustion of hydrogen on the dehydration processes in a membrane reactor. III. calculation of the industrial reactor

This paper describes the mathematical simulation of an industrial membrane reactor for propane dehydrogenation in the thermodynamic coupling with hydrogen combustion (oxidation). Due to the effective removal of hydrogen through a membrane and the heat release as a result of an exothermic reaction, the temperature of the reaction stream at the input could be reduced to 500?C. The fact that the process is carried out on an industrial-level membrane reactor makes it possible to reach a propane conversion of 75% with a propylene selectivity of 97%, which exceeds the figures obtained per pass in existing industrial devices at higher temperatures.     

Propane Dehydrogenation over a Commercial Pt-Sn/Al2O3 Catalyst for Isobutane Dehydrogenation: Optimization of Reaction Conditions

The applicability of a commercial Pt-Sn/Al₂O₃ isobutane dehydrogenation catalyst in dehydrogenation of propane was studied. Catalyst performance tests were carried out in a fixed-bed quartz reactor under different operating conditions. Generally, as the factors improving propane conversion decrease the propylene selectivity, the optimal operating condition to maximize propylene yield is expected. The optimal condition was obtained by the experimental design method. The investigated parameters were temperature, hydrogen/hydrocarbon (H₂/HC) ratio and space velocity, being changed in three levels. Constrains such as the susceptibility of the catalyst components to sintering or phase transformation were also taken into account. Activity, selectivity and stability of the catalyst were considered as the measured response factors, while the space-time-yield (STY) was considered as the variable to be optimized due to its commercial interest. A STY of 16 mol·kg^-1·h^-1 was achieved under the optimal conditions of T 620℃, H₂/HC 0.6 and, weight hourly space velocity (WHSV) 2.2 h^-1. Single carbon-carbon bond rupture was found to be the main route for the formation of lower hydrocarbon byproducts.     

Pure Hydrogen and Propylene Coproduction in Catalytic Membrane Reactor-Assisted Propane Dehydrogenation

Propane dehydrogenation on a commercial Pt-Sn/Al₂O₃ catalyst in a Pd-Ag membrane reactor is considered. A mathematical model is developed to evaluate the performance of the catalytic membrane reactor for the process of propane dehydrogenation. Design and operating conditions are systematically evaluated for key performance metrics such as propane conversion, propylene selectivity, hydrogen selectivity, and hydrogen recovery under different operating conditions. The results confirm that the high performance of the membrane reactor is related to the continuous removal of hydrogen from the reaction zone to shift the reaction equilibrium towards the formation of more propylene and hydrogen.     

Kinetic modelling of oxygen dependence in oxidative dehydrogenation of propane

Several Mars—Van Krevelen‐type redox kinetic models were developed for the catalytic oxidative dehydrogenation of propane and examined for their ability to predict high propene yields at low oxygen/propane feed ratios. The intent in this study was to use modelling as a means of extracting further mechanistic insight from experimental data rather than to identify the best model. Thus, a conventional redox model with a consecutive reaction mechanism and a single pathway for the production of carbon oxides predicts higher propene selectivity but only at the expense of low propane conversion. Experimental data indicated, however, that even at the same propane conversion, propene selectivity increased as the oxygen partial pressure was lowered. Models that successfully describe the data had an additional carbon oxide production path involving the reaction of propane with deeply oxidizing surface oxygen species. Kinetic models and experimental data examined do not fully resolve how these deeply oxidizing surface oxygen species are formed. However, they do reflect the accepted view that lattice oxygen selectively produces propene whereas more weakly bound surface adsorbed oxygen reacts to completely oxidize propane.     

Modification and optimization of benzene alkylation process for production of ethylbenzene

In this paper, an industrial ethylbenzene production unit has been simulated and the results are compared against five-day experimental data. According to prevailing unit condition, i.e. recycled ratio of benzene, benzene selectivity, and energy consumption, the unit is not working under its optimum conditions for minimum cost of ethylbenzene production. In the current design, high amount of benzene recycle (6:1) causes to have an additional cost due to fractionation of ethylbenzene from benzene. A new approach is proposed to modify the benzene alkylation process and reduce the unit's energy consumption. In the newly designed scheme, two double-bed alkylation reactors converted into four single-bed reactors. The amount of injected ethylene, alkylation reactors temperature, and recycled stream are regulated as adjustable parameters for the optimization of the process. In the modified process, the reflux ratio reduced to 1.87 and the benzene selectivity increased. The optimized process shows a considerable decrease in the unit's energy consumption in compare to the current process. Also, the mass fraction of ethylbenzene would reach to 99.12% of purity before entering to the transalkylation reactor for further purification. Therefore, if the presented purity is acceptable for the final application, the transalkylation reactor could be eliminated from the new design.     

丙烷脱氢制丙烯研究新进展

介绍了丙烷催化转化制丙烯的研究状况,综述了丙烷催化脱氢制丙烯的铬系催化剂、铂系催化剂及其助剂Sn的研究进展;评述了丙烷氧化脱氢反应机理低温和高选择性的催化剂及膜反应器在丙烷脱氢反应上所具有的优越性,认为研发具有高稳定性和高透氢性能的氢分离膜,将有望能大幅度提高丙烯的收率。     

A high propylene productivity over B2O3/SiO2@honeycomb cordierite catalyst for oxidative dehydrogenation of propane

Boron-based metal-free catalysts for oxidative dehydrogenation of propane (ODHP) have drawn great attention in both academia and industry due to their impressive activity and olefin selectivity. Herein, the SiO₂ and B₂O₃ sequentially coated honeycomb cordierite catalyst is designed by a two-step wash-coat method with different B₂O₃ loadings (0.1%-10%) and calcination temperatures (600, 700, 800 ℃). SiO₂ obtained by TEOS hydrolysis acts as a media layer to bridge the cordierite substrate and boron oxide via abundant Si-OH groups. The welldeveloped straight channels of honeycomb cordierite make it possible to carry out the reactor under high gas hourly space velocity (GHSV) and the thin wash-coated B₂O₃ layer can effectively facilitate the pore diffusion on the catalyst. The prepared B₂O₃/SiO₂@HC monolithic catalyst exhibits good catalytic performance at low boron oxide loading and achieves excellent propylene selectivity (86.0%), olefin selectivity (97.6%, propylene and ethylene) and negligible CO₂ (0.1%) at 16.9% propane conversion under high GHSV of 345,600 ml·(g B₂O₃)^-1·h^-1, leading to a high propylene space time yield of 15.7 g C₃H₆·(g B₂O₃)^-1·h^-1 by suppressing the overoxidation. The obtained results strongly indicate that the boron-based monolithic catalyst can be properly fabricated to warrant the high activity and high throughput with its high gas/surface ratio and straight channels.     

On the reactivity of K2O‐, CaO‐ and P2O5‐doped nickel molybdate catalysts in a periodic‐flow reactor

The propane oxydehydrogenation with monolayer lattice oxygen of undoped and K₂O–, CaO– and P₂O₅–NiMoO₄ was investigated by using a periodic‐flow reactor (PFR). The influence of the nature and the extent of the promoter has been emphasized relative to the doped catalysts with respect to pure NiMoO₄ phases. It was observed that calcium and potassium promoters satisfactorily enhance propylene selectivity, and phosphorus promoter specifically increases the total activity while maintaining the propylene selectivity. Evidence found by thermogravimetric (TG) analyses (oxygen depletion rate) has shown a dependence on lattice oxygen mobility due to the presence of promoters. This dependence has been correlated to the propane conversion while the propylene selectivity was attributed to the acid–base properties. This revised version was published online in July 2006 with corrections to the Cover Date.     

Simulation of Propane Dehydrogenation to Propylene in a Radial‐Flow Reactor over Pt‐Sn/Al2O3 as the Catalyst

Catalytic paraffin dehydrogenation for manufacturing olefins is considered to be one of the most significant production routes in the petrochemical industries. A reactor kinetic model for the dehydrogenation of propane to propylene in a radial‐flow reactor over Pt‐Sn/Al₂O₃ as the catalyst was investigated here. The model showed that the catalyst activity was highly time dependent. In addition, the component concentrations and the temperature varied along the reactor radius owing to the occurring endothermic reaction. Moreover, a similar trend was noticed for the propane conversion as for the propylene selectivity, with both of them decreasing over the time period studied. Furthermore, a reversal of this trend was also revealed when the feed temperature was enhanced or when argon was added into the feed as an inert gas.     

丙烷脱氢固定床反应器的动态模拟与优化

在丙烷脱氢制丙烯反应过程中,由于焦的沉积使催化剂活性不断降低,而且失活速度很快。本文建立了径向绝热固定床反应器丙烷脱氢 失活过程的动态模型,在Pt-Sn催化剂动力学基础上对脱氢过程进行了模拟和分析。得到了不同时刻反应器内的压力、温度、催化剂活性等的分布情况以及转化率、选择性、收率等的变化规律,并在分析反应器入口温度、流量及压力对过程影响的基础上对反应的操作条件进行了优化。     

PtSn负载量对PtSn/Al2O3催化剂上丙烷脱氢性能的影响

由丙烷直接催化脱氢制取丙烯已经成为增产丙烯的重要手段之一。以水热法制备Al_2O_3载体,采用等体积浸渍法制备不同PtSn负载量的PtSn/Al_2O_3催化剂。通过XRD、N2-吸附、拉曼光谱和H2-TPR等对其进行表征,并考察不同PtSn负载量对催化剂催化丙烷脱氢性能的影响。结果表明,在制备的催化剂中,Pt1.5Sn3/Al_2O_3具有最高的催化丙烷脱氢活性和稳定性,丙烷初始转化率高达55.6%,丙烯选择性98.1%。反应330 min后,丙烷转化率仅降约10%,选择性保持不变。     

纤维状BPO4/SiO2催化剂的制备及其丙烷氧化脱氢性能

通过静电纺丝法制备了一种高温焙烧后具有纤维状结构的磷酸硼/二氧化硅（BPO₄/SiO₂）催化剂,并考察了BPO₄负载量和焙烧温度对该催化剂的结构和催化丙烷氧化脱氢性能的影响。研究发现焙烧过程使纤维直径减小。随着BPO₄负载量的增加,丙烷氧化脱氢活性增高。当BPO₄负载量为7%（质量分数）,焙烧温度为600℃时,BPO₄/SiO₂催化剂具有最佳的催化性能;在反应温度为480℃下,丙烷转化率和丙烯产率分别达到17.0%和13.0%,且催化剂稳定性良好。当焙烧温度较低时（550℃）,催化剂中的有机物分子未被除尽,导致烯烃的选择性偏低;当焙烧温度较高时（700℃）,SiO₂结构收缩紧密,抑制了活性相的暴露。由于纤维结构可暴露更多活性位点,该催化剂较相同条件下粉末状BPO₄催化剂有着更高的催化活性。     

Bi4Cu0.2V1.8O11−δ based electrolyte membrane reactor for selective oxidation of propane to acrylic acid

An electrochemical membrane reactor using Bi₄Cu_0.2V_1.8O_11?δ as a solid electrolyte membrane was employed to investigate the selective oxidation of propane to acrylic acid over a MoV_0.3Te_0.17Nb_0.12O catalyst. By applying an external current to the membrane reactor, the ionic oxygen was pumped to the surface of the MoV_0.3Te_0.17Nb_0.12O catalyst, which exhibited higher conversion of propane and selectivity to acrylic acid than that in the fixed-bed reactor. The results indicate that the enhancement of catalytic performance in the membrane reactor is mainly due to the presence of the lattice oxygen, which has been proved to be necessary for the formation of acrylic acid. Thus, the Au/Bi₄Cu_0.2V_1.8O_11?δ/Au/MoVTeNbO membrane reactor achieved a higher conversion of propane (42%) and selectivity to acrylic acid (79.6%) at 380 °C with a 0.6 A current.     

A modeling study of the effect of reactor configuration on the cycle length of heavy oil fixed-bed hydroprocessing

This article analyses how the configuration of an industrial fixed-bed reactor affects the cycle length of a heavy oil hydroprocessing unit. It is well-known that during the hydroprocessing of heavy feeds, catalyst aging is counterbalanced by continuously increasing reaction temperature. In addition, the exothermality of the reaction provokes a huge temperature rise along the reactor, which is why quenching is necessary. Thus, there is an increasing temperature profile that evolves with time until a maximum allowable temperature is reached and then the operation is shut down. For this reason, there is an optimum reactor configuration (i.e. number of quenches and their positions) that must be established when designing new processes in order to maximize unit run length. To evaluate this problem, a reactor performance model with time varying catalyst activity was constructed. Kinetic and catalyst aging data were obtained from bench-scale tests. The model showed to reproduce sufficiently well the experimental data set. The analysis of various reactor designs indicated that for this process the use of single-bed or double-bed reactors is unpractical in terms of cycle length. A more complex configuration consisting of multiple beds of increasing lengths is necessary to delay shut down.     

Performance evaluation of a novel reactor configuration for oxidative dehydrogenation of ethane to ethylene

A one-dimensional non-isothermal steady state model was developed to simulate the performance of three-reactor configurations for the oxidative dehydrogenation of ethane (ODHE) to ethylene. These configurations consist of side feeding reactor (SFR), conventional fixed bed reactor (CFBR) and membrane reactor (MR). The performance of these reactors was compared in the terms of C₂H₆ conversion, C₂H₄ and CO₂ selectivity and temperature profiles. The use of sectional air injections on the wall of SFR with a limited number of injection points showed that the performance of reactor significantly improves and optimum pattern of oxygen consumption is also obtained. Moreover, our SFR with a liquid coolant medium operates in an effectively controlled temperature profile that is comparable with that of the MR, which is cooled by a coolant stream of air. Hence, an enhancement in the level of selectivity is obtained for the SFR configuration. Consequently, the side feeding procedure can decrease the high operating temperature problem and low ethylene selectivity in the ODHE process. According to obtained results, the SFR would be a proper alternative for both the MR and CFBR.     

氯醇法环氧丙烷含氧尾气的回收利用

以CO为还原剂,在复合脱氧催化剂FS的存在下,在列管式固定床反应器内利用一步深度脱氧技术将氯醇法环氧丙烷生产中氯醇化工序放出的含氧尾气（PO尾气）中夹带的体积分数为15％的O2转化为CO2。用模拟PO尾气、真实PO尾气的脱氧小试和工业应用试验考察了反应温度、体积空速、CO与O2的物质量的比、饱和水蒸气、丙烯等因素对催化剂活性的影响,和反应温度、CO与O2的物质量的比对丙烯、丙烷回收率的影响,以及催化剂的稳定性。试验结果表明：O2转化率能达到97％左右,脱氧后尾气中的O2体积分数小于0．5％,对PO尾气进行一步深度脱氧的工业化过程是可行的。根据大量的试验数据提出了工业化初步设计方案。