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。     

丙烷脱氢制丙烯技术研究

介绍了几种丙烷脱氢制丙烯技术：催化脱氢、氧化脱氢、膜反应器脱氢。综述了丙烷催化脱氢制丙烯催化剂的研究现状，虽然丙烷催化脱氢生产丙烯虽已实现了工业化，但其催化剂的性能需进一步提高；综述了丙烷氧化脱氢制丙烯反应催化剂的研究现状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。     

丙烷脱氢制丙烯技术研究

介绍了催化脱氢、氧化脱氢、膜反应器脱氢等几种丙烷脱氢制丙烯技术,综述了丙烷催化脱氢制丙烯催化剂的研究现状,虽然丙烷催化脱氢生产丙烯已实现了工业化,但其催化剂的性能需进一步提高;对丙烷氧化脱氢制丙烯反应催化剂的研究现状及膜反应器在丙烷脱氢反应上所具有的优越性进行了描述,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。     

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.     

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.     

丙烯生产技术进展

综述了传统炼油石化行业乙烯蒸汽裂解、轻烃催化裂解、重油增产丙烯的主要技术及其应用情况。对于近年来快速发展的丙烷脱氢制丙烯和非石油路线制烯烃技术,煤基甲醇制丙烯技术特点和生产现状做了详细介绍,并简要分析其发展趋势。     

Advanced Catalytic Dehydrogenation Technologies for Production of Olefins

Catalytic dehydrogenation is a critical and growing technology for the production of olefins, especially for propylene production. This paper will give an overview of advances in the catalysis science and technology for production of olefins by catalytic dehydrogenation, including the concomitant removal of H₂ by selective oxidation. For light paraffin dehydrogenation, UOP has licensed the Oleflex? process widely for production of polymer-grade propylene as well as isobutylene with over 12 million metric tons of capacity announced. Today there are nine UOP C₃ Oleflex? units in operation accounting for 55?% of the installed world-wide propylene production capacity from propane dehydrogenation technology. The heart of the process is a noble metal multi-metallic catalyst and the continuous catalyst regeneration (CCR) process. The coupling of catalytic dehydrogenation with selective oxidation of hydrogen allows one to design a process, which greatly improves equilibrium conversions while maintaining very high selectivity to olefin. The Lummus/UOP SMART? SM process (Styrene Monomer Advanced Reheat Technology) allows 30?C70?% capacity expansion, achieves a higher per-pass ethylbenzene conversion, and provides the most cost-effective revamp for higher capacity. Styrene Monomer Advanced Reheat Technology (SMART?) uses an oxidation catalyst and novel reactor internals to allow oxidative reheating between dehydrogenation stages. In the case of selective oxidation catalysts containing dispersed metal active sites, the role of diffusion and pore architecture is as important as the active metal sites.     

Analysis of Membrane Reactors for Integrated Coupling of Oxidative and Thermal Dehydrogenation of Propane

This study presents strategies capable to intensify the thermal dehydrogenation of propane (TDH) using integrated reactor concepts. An inert packed bed membrane reactor for distributed dosing of oxygen to realize the oxidative dehydrogenation (ODH) was studied and compared to a reactor with catalytically active membrane. The latter concept allows to combine TDH and ODH in one apparatus to overcome the chemical equilibrium by in situ conversion of the by‐product H₂ using O₂ or in a reverse water‐gas shift reaction by CO₂. If CO₂ is used as active sweep gas the reactor offered better performance regarding yield and selectivity. Strategies for further thermal integration are discussed.     

Oxidative dehydrogenation of ethane and propane over Mn-based catalysts

The catalytic performances of Mn-based catalysts have been investigated for the oxidative dehydrogenation of both ethane (ODE) and propane (ODP). The results show that a LiCl/MnO_x/PC (Portland cement) catalyst has an excellent catalytic performance for oxidative dehydrogenation of both ethane and propane to ethylene and propylene, more than 60% alkanes conversion and more than 80% olefins selectivity could be achieved at 650°C. In addition, the results indicate that Mn-based catalysts belong to p-type semiconductors, the electrical conductivity of which is the main factor in influencing the olefins selectivity. Lithium, chlorine and PC in the LiCl/MnO_x/PC catalyst are all necessary components to keep the excellent catalytic performance at a low temperature. 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.     

The effects of bimetallic interactions for CO2-assisted oxidative dehydrogenation and dry reforming of propane

The catalytic reduction of CO₂ by propane may occur via dry reforming to produce syngas (CO + H₂) or oxidative dehydrogenation to yield propylene. Utilizing propane and CO₂ as coreactants presents several advantages over conventional methane dry reforming or direct propane dehydrogenation, including lower operating temperatures and less coke formation. Thus, it is of great interest to identify catalytic systems that can either effectively break the C C bond to generate syngas or selectively break C H bonds to produce propylene. In this study, several precious and nonprecious bimetallic catalysts supported on reducible CeO₂ were investigated using flow reactor studies at 823 K to identify selective catalysts for CO₂-assisted reforming and dehydrogenation of propane.     

Economic feasibility of silica and palladium composite membranes for industrial dehydrogenation reactions

This article addresses the economic feasibility of silica and palladium composite membranes for gaseous dehydrogenation reaction schemes. Unlike other methodologies addressed so far, this work presents the economic assessment of dehydrogenation reaction schemes using a conceptual design based simulation methodology for the comparative economic assessment of membrane reactors with conventional reactors. The suggested methodology is applied to two industrially prominent reaction schemes namely styrene (from ethylbenzene) and propylene (from propane) production using silica and palladium composite membrane reactors. Various sub-cases studied in this work include the influence of membrane area per reaction zone volume, reaction zone temperature, reaction and permeation zone pressure, membrane thickness and sweep gas flow rate on process economics. Based on this work, the propylene production scheme is evaluated to provide 60–70% excess profits using membrane reactors when compared with the conventional reactor based technology. However, the gross profit profiles for both conventional reactor and membrane reactor configurations have been found to be similar for styrene production case. For all cases, the cost contribution of membranes and other auxiliary equipment is estimated not to exceed 20% of the total costs. In addition, similar economic performance has been observed for both silica and palladium membranes. Based on these studies, it has been concluded that the industrial applicability of membrane reactors is economically suitable for those dehydrogenation reactions that enable significant conversion enhancement with respect to the conventional reactor technologies.     

Kinetic study of propane dehydrogenation and side reactions over Pt–Sn/Al2O3 catalyst

The kinetics of reactions involved in dehydrogenation of propane to propylene over Pt–Sn/Al₂O₃ catalyst was studied. The simultaneous deactivation of individual dehydrogenation, hydrogenolysis and cracking sites was also studied. A model was developed to obtain the transient conversion of propane, product selectivity and catalytic site activity. The dehydrogenation reaction was considered as the main reaction governing propane and hydrogen concentrations along the reactor. Catalytic test runs were performed in a fixed-bed quartz reactor. The kinetic expressions developed for the main and side reactions were verified by integral and a combination of integral–differential analysis of reactor data, respectively, and the kinetic parameters were obtained. The deactivation of the active sites for the three reactions was found to follow a first-order independent decay law. The rate constants of deactivation were found to decrease in the order of dehydrogenation, hydrogenolysis and cracking. Noncatalytic thermal cracking was found to be comparable to the catalytic route resulting in a very low apparent deactivation rate constant for cracking reaction.     

多孔膜反应器中丙烷催化脱氢制丙烯的模拟研究

针对丙烷高效脱氢制丙烯的多孔膜反应器构建了无量纲数学模型并进行了模拟研究,考察了催化剂活性、透氢膜性能、操作条件对多孔膜反应器中丙烷脱氢的转化率、丙烯收率、氢气收率和纯度的影响。结果表明,移走产物氢气可以有效提升膜反应器的性能,其性能的提升程度由不同温压条件下催化剂和透氢膜性能共同决定。高活性催化剂是丙烷高效转化的基础,催化剂活性越高,膜反应器内的产氢速率越快;其次,膜的选择性和渗透通量越高,氢气的移除效率越高,可在最大程度上打破热力学平衡的限制,使反应向生成丙烯的方向移动。当多孔透氢膜的氢气渗透率在10^-7~10^-6 mol·m^-2·s^-1·Pa^-1,H₂/C₃H₈选择性达到100时,其丙烷转化率可以与Pd膜反应器内的转化率相当,但分离的氢气纯度低于Pd膜反应器。与传统的固定床反应器相比,膜反应器由于促进了化学平衡的移动,可以在较低的反应温度下获得相当高的丙烷转化率,且丙烷转化率随着反应压力的增加呈现出一个最大值。该模拟研究可为实际生产过程中膜反应器用于PDH反应的高效强化提供有益的技术指导。     

丙烷脱氢制丙烯经济及技术分析

丙烯是重要的有机化工原料，除用于生产聚丙烯外，还是生产丙烯腈，丁醇、辛醇、环氧丙烷、异丙醇、丙苯、丙烯酸、羧基醇及壬基酚等产品的主要原料，丙烯的齐聚物是提高汽油辛烷值的主要成分，丙烷催化脱氢制丙烯比烃类蒸气裂解能产生更多的丙烯。当用蒸气裂解生产丙烯时，丙烯收率最多只有33％、而用催化脱氢法生产丙烯，总收率可达74％－86％，用唯一原料生产唯一产品，催化脱氢的设备投资比烃类蒸气裂解低33％。并且采用催化脱氢的方法，能有效地得用液化石油气资源使之转变为有用的烯烃。     

Development and Application of Oxygen Permeable Membrane in Selective Oxidation of Light Alkanes

In this paper, oxygen permeable membrane used in membrane reactor for selective oxidation of alkanes will be discussed in detail. The recent developments for the membrane materials will be presented, and the strategy for the selection of the membrane materials will be outlined. The main applications of oxygen permeable membrane in selective oxidation of light alkanes will be summarized, which includes partial oxidation of methane (POM) to syngas and partial oxidation of heptane (POH) to produce H₂, oxidative coupling of methane (OCM) to C₂, oxidative dehydrogenation of ethane (ODE) to ethylene and oxidative dehydrogenation of propane (ODP) to propylene. Achievements for the membrane material developments and selective oxidation of light alkanes in membrane reactor in our group are highlighted.     

Comparison of different catalysts in the membrane-supported dehydrogenation of propane

Dehydrogenation of propane is studied in a high temperature packed bed catalytic membrane reactor with a hydrogen-selective silica membrane. The silica membrane is prepared by a two-step sol–gel process. The removal of hydrogen in the membrane reactor results in higher propane conversion and higher propene yields in comparison to an equivalent fixed-bed reactor. Unfortunately, as a result of the H₂ removal coking is favoured in the membrane reactor. Therefore, the higher propene yields are found only for the first 100–120 min time on stream. However, the lower selectivity of the membrane reactor due to coking is compensated to some extend by a reduced hydrogenolysis. Two commercial dehydrogenation catalysts of different activity were tested in the membrane reactor: Cr₂O₃/Al₂O₃ and Pt–Sn/Al₂O₃. The two catalysts show a different activity, coking, and regeneration behaviour in the membrane-supported propane dehydrogenation.     

丙烯/丙烷分离的ZIF-8膜研究进展

同碳数烯烃/烷烃的分离是目前石油化工行业中最耗能的过程之一,开发新型的、低能耗的丙烯/丙烷分离过程被认为是改变世界的七项化工分离技术之一。气体膜分离技术因其高效、节能和环境友好等优点被认为是一种可取代传统低温精馏分离丙烯/丙烷混合气体的新型技术。金属有机骨架材料ZIF-8的有效孔径介于丙烯和丙烷的分子动力学直径之间,可对丙烯/丙烷实现高效分离,是目前分离丙烯/丙烷性能最好的膜材料。本文系统总结了ZIF-8膜的制备方法及用于丙烯/丙烷高效分离的发展历程;探讨了ZIF-8膜微结构的调控,尤其是膜缺陷的修复及ZIF-8骨架柔性的控制;总结了ZIF-8膜在分离丙烯/丙烷时,过程参数对于分离性能的影响规律;并提出ZIF-8膜规模化制备及潜在工业分离丙烯/丙烷研究中存在的问题和未来发展方向。     

Silica-Based Ziegler–Natta Catalysts: A Patent Review

Silica-based Ziegler–Natta catalysts are important industrially in the manufacture of polyethylene and polypropylene. They are scientifically very interesting because of the complex effects of porous silica on catalyst performance. This patent review explains how silica–based Ziegler–Natta catalysts are related to Phillips chromium–silica catalysts and explores their value for the gas phase and slurry processes for the manufacture of polyolefins. The subcategories dealt with are the following: magnesium–titanium–silica catalysts, which are valuable for high-density polyethylene, for the ethylene copolymers called linear low-density polyethylene;and ethylene–propylene rubber, and for isotactic polypropylene; vanadium–silica catalysts, which are useful in the polymerization and copolymerization of ethylene; and vanadium plus titanium–silica catalysts which often exhibit reactivity synergism. Dual-site and multisite catalysts are also reviewed.     

Pyrolysis of polyolefins in high-boiling solvents

The pyrolysis of polyethylene and polypropylene in vacuum residue and coal-tar pitch solvents was studied in a batch reactor at atmospheric pressure in a temperature range of 380–420°C. Aliphatic hydrocarbons and C₅–C₃₂ normal olefins and isoolefins were the main pyrolysis products of the polyolefins and vacuum residue, which also underwent thermal degradation at these temperatures. The total conversion of a polypropylene-vacuum residue mixture into gaseous and distillate products was nearly additive; upon the pyrolysis of polypropylene in pitch and of polyethylene in vacuum residue and pitch, the yield of distillate products decreased and the paraffin/olefin ratio in these products increased. The observed regularities were explained by hydrogen transfer from the solvents to the intermediate radical products of the thermal decomposition of polymer chains. The reactions of the resulting of olefins with the solvents can also occur to a lesser degree. The greatest deviations from additivity were observed in the pyrolysis of polyethylene in the solvents used.