Catalytic cracking of endothermic fuels in coated tube reactor

Suspensoid of HZSM-5 or HY zeolites mixed with a self-made ceramic-like binder was coated on the inner wall of a tubular reactor by gas-aided fluid displacement technology. The coated zeolites were characterized by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The coating thickness is 10–20 μm and the particle size of the zeolites is in the range of 1–5 μm. In the coated reactor, cracking of endothermic fuels including n-dodecane and aviation fuel RP-3 was carried out separately under supercritical conditions at 600°C and 625°C to investigate their heat sinks and conversion of catalytic reactions. For the reaction catalyzed by HY (25% mass fraction) coating, the heat sink capacity of n-dodecane are 815.7 and 901.9 kJ/kg higher than that of the bare tube at 600°C and at 625°C, respectively. Conversion of n-dodecane also increases from 42% to 60% at 600°C and from 66% to 80% at 625°C. The coated zeolite can significantly inhibit the carbon deposition during supercritical cracking reactions. __________ Translated from Petrochemical Technology, 2007, 36(4): 328–333 [译自: 石油化工]     

吸热燃料催化裂解研究进展

高超声速飞行是航空航天领域的最新前沿技术,是国家科技发展水平的重要标志。吸热燃料是实现高马赫（>5）超声速飞行器实际应用的核心技术之一,因而具有特殊的意义。本文介绍了吸热燃料的研究历程,重点从吸热燃料及其热沉、吸热燃料催化剂、催化剂的结焦以及催化裂解机理等方面对吸热燃料催化裂解进行介绍和评述。分子筛催化剂是吸热燃料催化裂解最具应用前景的一类催化剂,但同时也面临了吸热燃料原料的选择、分子筛骨架结构的改进和表面性质调变、催化剂结焦等基础研究以及催化剂负载、催化剂真实工况模拟等一系列工程应用研究双重挑战。吸热燃料催化裂解机理和动力学研究目前还很薄弱,未能真正深入到分子尺度把催化剂的微观作用与物质形态的变化有机结合,针对这方面的研究还应该大力加强,以更好地为催化剂的设计提供指导意义。     

乙二醇单甲醚防冰剂对吸热型碳氢燃料的裂解特性研究

探究了乙二醇单甲醚防冰剂对吸热型碳氢燃料裂解的影响,其中乙二醇单甲醚加入的质量百分比分别为0.05%,0.10%,0.15%,0.20%。利用微型气相色谱仪、气相色谱-质谱联用仪、CO2红外分析仪对燃料裂解气相产物、液相产物、结焦量等进行分析。结果表明,乙二醇单甲醚在低温下对燃料的裂解影响并不明显,但在高温(≥650℃)条件下能够促进燃料的裂解,产气率和热沉增大。添加0.15%乙二醇单甲醚时,燃料裂解产生的结焦量最少,与对照组相比,降低了42.44%。     

Catalytic conversion of canola oil to fuels and chemicals over various cracking catalysts

The catalytic conversion of canola oil to fuels and chemicals was studied over HZSM-5, H-mordenite, H-Y, silicalite, aluminum-pillared clay (AL-PILC) and silica-alumina catalysts in a fixed bed micro-reactor. The reactor was operated at atmospheric pressure, a temperature range of 375?500°C and weight hourly space velocity (WHSV) of 1.8 and 3.6 h^?1. An organic liquid product (OLP), light hydrocarbon gases and water were the major products. The objective was to maximize the amount of OLP and its hydrocarbon content as well as optimize the selectivity for gas phase olefinic hydrocarbons. In addition, the performance of each catalyst in terms of minimizing the coke formation was examined. Among the six catalysts, HZSM-5 gave the highest amount of OLP of 63 mass% at 1.8 WHSV and 400°C. The hydrocarbon content of this OLP product was 83.8 mass%. With the exception of silica-alumina and aluminum-pillared clay catalysts, the other catalysts gave high concentrations of aromatic hydrocarbons which ranged between 23.1–95.6 mass% of OLP. The gas products consisted mostly C₃ and C₄ hydrocarbons. Ethylene, propylene and butanes were some of the valuable hydrocarbon gases. The olefin/paraffin ratio of the gas products was highest for AL-PILC catalysts but it never exceeded unity. The results showed that it was possible to significantly alter the yield and selectivity for the different hydrocarbon products by using different catalysts or changing the catalyst functionality such as acidity, pore size and crystallinity. Reaction pathways based on these results are proposed for the conversion of canola oil     

Modelling endothermic reactions in a compound membrane reactor

This paper models the performance of a membrane reactor. The membrane, a composite alumina-based one, is packed with a catalyst and allows low molecular weight gases to diffuse through it at a faster rate than gases with a higher molecular weight. This allows a greater conversion to be achieved in one pass through the reactor. The reaction that is specifically considered in this paper is the dehydrogenation of methyl-cyclohexane to toluene with the production of hydrogen. This latter species is preferentially removed by the membrane. Data for the performance of the membrane have been estimated from previous experiments using single gases and the mechanisms considered are Knudsen and bulk flow. Surface flow is not considered in the model as it is possibly not important as the endothermic reaction is carried out at a high temperature. A standard kinetic model is also incorporated in the calculations. The correlations of maximum effective length of membrane reactors and maximum percentage conversion as functions of the feed velocity and the membrane diameter are demonstrated in this paper. This paper also considers the behaviour of a compound reactor in which the first section is a straightforward ‘plug flow’ reactor where the catalyst is confined in an impermeable tube with the same internal diameter as the membrane. This is followed by a section containing the membrane. The reason for considering this configuration is to avoid unnecessary leakage of methyl-cyclohexane feed in the initial stages of the reaction. This innovation leads to predicted increases in the overall conversion of the process.     

Catalytic cracking reaction of used lubricating oil to liquid fuels catalyzed by sulfated zirconia

The conversion of used lubricating oil to transport fuel by direct cracking is a suitable way to dispose of waste oil. The aim of this research was to study the catalytic cracking of used lubricating oil, and thus change its classification from a waste produce to a liquid fuel as a new alternative for the replacement of petroleum fuels. The experiments were carried out in a 70-cm³ batch microreactor at a temperature of 648-698 K, initial hydrogen pressure of 1-4 MPa, and reaction time of 10-90 min over sulfated zirconia as a catalyst. The conditions that gave the highest conversion of naphtha (~20.60%) were a temperature of 698 K, a hydrogen pressure of 2 MPa, and a reaction time of 60 min, whereas, under the same conditions, kerosene, light gas oil, gas oil, long residues, hydrocarbon gases, and a small amounts of solids were present (~9.04%, 15.61%, 5.00%, 23.30%, 25.58%, and 0.87%, respectively). The liquid product consisted of C₇-C₁₅ of n-paraffins, C₇-C₉ of branched chain paraffin and aromatic compounds such as toluene, ethylbenzene and xylene. The kinetic study reveals that the catalytic cracking of waste lubricating oil follows a second order reaction, and the kinetic model is defined as k(s⁻¹)=2.88×10⁴exp[−(103.68 kJmol⁻¹)/(RT)].     

基于CFD模拟的甲烷裂解太阳能管式反应器结构优化

太阳能裂解甲烷具有产物纯度高且环保的优点。对湍流条件下的甲烷高温裂解太阳能管式反应器进行计算流体力学（CFD）模拟,为提高太阳能甲烷裂解反应器的转化率,通过调节反应器结构对流场进行优化。为了更加准确计算太阳能辐射的加热效应,在湍流反应扩散模型中引入碳颗粒的生成和聚集模型,并采用离散坐标（DO）模型进行辐射模型求解。然后,在太阳能管式反应器中引入射流及挡板进行流场调节,并对挡板高度、射流流速及角度进行优化,达到强化反应过程的目的。优化后的反应器中,甲烷转化率可以提高约8%。以反应转化率和代表强化成本的黏性耗散为指标,筛选出不同离散条件下的Pareto最优解,并用支持向量机回归（SVR）算法对离散的Pareto最优解进行插值,得到操作曲线和与之相对应的最优射流角度及流速。     

A novel reverse flow reactor coupling endothermic and exothermic reactions. Part I: comparison of reactor configurations for irreversible endothermic reactions

A new reactor concept is studied for highly endothermic heterogeneously catalysed gas phase reactions at high temperatures with rapid but reversible catalyst deactivation. The reactor concept aims to achieve an indirect coupling of energy necessary for endothermic reactions and energy released by exothermic reactions, without mixing of the endothermic and exothermic reactants, in closed-loop reverse flow operation. Periodic gas flow reversal incorporates regenerative heat exchange inside the reactor. The reactor concept is studied for the coupling between the non-oxidative propane dehydrogenation and methane combustion over a monolithic catalyst.Two different reactor configurations are considered: the sequential reactor configuration, where the endothermic and exothermic reactants are fed sequentially to the same catalyst bed acting as an energy repository and the simultaneous reactor configuration, where the endothermic and exothermic reactants are fed continuously to two different compartments directly exchanging energy. The dynamic reactor behaviour is studied by detailed simulation for both reactor configurations. Energy constraints, relating the endothermic and exothermic operating conditions, to achieve a cyclic steady state are discussed. Furthermore, it is indicated how the operating conditions should be matched in order to control the maximum temperature. Also, it is shown that for a single first order exothermic reaction the maximum dimensionless temperature in reverse flow reactors depends on a single dimensionless number. Finally, both reactor configurations are compared based on their operating conditions. It is shown that only in the sequential reactor configuration the endothermic inlet concentration can be optimised independently of the gas velocities at high throughput and maximum reaction coupling energy efficiency, by the choice of a proper switching scheme with inherently zero differential creep velocity and using the ratio of the cycle times.In this first part, both the propane dehydrogenation and the methane combustion have been considered as first order irreversible reactions. However, the propane dehydrogenation is an equilibrium reaction and the low exit temperatures resulting from the reverse flow concept entail considerable propane conversion losses. How this ‘back-conversion’ can be counteracted is discussed in part II Chemical Engineering Science, 57, (2002), 855-872.     

Performance studies of various cracking catalysts in the conversion of canola oil to fuels and chemicals in a fluidized-bed reactor

Studies were conducted at atmospheric pressure at temperatures in the range of 400–500°C and fluidizing gas velocities in the range of 0.37–0.58 m/min (at standard temperature and pressure) to evaluate the performance of various cracking catalysts for canola oil conversion in a fluidized-bed reactor. Results show that canola oil conversions were high (in the range of 78–98 wt%) and increased with an increase in both temperature and catalyst acid site density and with a decrease in fluidizing gas velocity. The product distribution mostly consisted of hydrocarbon gases in the C₁–C₅ range, a mixture of aromatic and aliphatic hydrocarbons in the organic liquid product (OLP) and coke. The yields of C₄ hydrocarbons, aromatic hydrocarbons and C₂–C₄ olefins increased with both temperature and catalyst acid site density but decreased with an increase in fluidizing gas velocity. In contrast, the yields of aliphatic and C₅ hydrocarbons followed trends completely opposite to those of C₂–C₄ olefins and aromatic hydrocarbons. A comparison of performance of the catalysts in a fluidized-bed reactor with earlier work in a fixed-bed reactor showed that selectivities for formation of both C₅ and iso-C₄ hydrocarbons in a fluidized-bed reactor were extremely high (maximum of 68.7 and 18 wt% of the gas product) as compared to maximum selectivities of 18 and 16 wt% of the gas product, respectively, in the fixed-bed reactor. Also, selectivity for formation of gas products was higher for runs with the fluidized-bed reactor than for those with the fixed-bed reactor, whereas the selectivity for OLP was higher with the fixed-bed reactor. Furthermore, both temperature and catalyst determined whether the fractions of aromatic hydrocarbons in the OLP were higher in the fluidized-bed or fixed-bed reactor.     

Efficient reactor concepts for coupling of endothermic and exothermic reactions

Multifunctional autothermal reactors are a novel concept in process integration and intensification. They can be implemented as a countercurrent or reverse-flow reactor. A promising field of application is the coupling of endothermic and exothermic reactions. Methane steam reforming coupled with methane combustion is considered as a particular example. Several novel reactor configurations with co- and countercurrent flow in the reaction zone will be discussed by numerical simulation and an example for experimental verification will be presented.     

废塑料裂解制燃料的研究进展

介绍了废塑料裂解制燃料的4种方式:热裂解、催化裂解、热解-催化改质和催化热解-催化改质,分析比较了它们各自的优缺点,认为催化技术是制约该领域发展的关键因素.重点阐述了废塑料裂解催化剂和裂解产物改质催化剂在国内外的一些研究进展,对进一步研究和开发废塑料裂解制燃料催化剂提出了一些建议.     

裂解炉炉管开裂原因分析

对发生失效破裂的炉管进行了宏观形貌分析、断口形貌分析、金相分析、有限元应力分析等 ,得出导致炉管破裂的主要原因是炉管在制造过程中产生缺陷引起的应力集中和特定的腐蚀环境共同作用下产生应力腐蚀断裂。     

Minimum entropy generation for isothermal endothermic/exothermic reactor networks

It was shown in an earlier work by us that entropy generation and energy (hot utility or cold utility) consumption of isothermal, isobaric reactor networks depend only on the network's inlet and outlet stream compositions and flow rates and are not dependent on the reactor network structure, as long as the universe of realizable reactor units and network outlet mixing units are either all endothermic interacting with a single hot reservoir, or all exothermic interacting with a single cold reservoir, respectively. It is shown that when the universe of realizable reactor/mixer units, of isothermal, isobaric, continuous stirred tank reactor networks, consists of both endothermic units interacting with a single hot reservoir and exothermic units interacting with a single cold reservoir, the network's net (hot minus cold) utility consumption depends only on the network's inlet and outlet stream compositions and flow rates (and does not depend on the network's structure). In contrast, the network's entropy generation depends on the network's inlet and outlet stream compositions and flow rates, and the network's hot utility (or cold utility) consumption. The latter, in general, depends on the network structure, thus making entropy generation also, in general, depend on network structure. Thus, the synthesis of isothermal, isobaric reactor networks, with fixed inlet and outlet stream specifications, is equivalent to the synthesis of minimum hot (or cold) utility consuming such networks. The Infinite DimEnsionAl State‐space conceptual framework is used for the problem's mathematical formulation, which is then used to rigorously establish the above equivalence. A case study involving Trambouze kinetics demonstrates the findings. © 2014 American Institute of Chemical Engineers AIChE J, 61: 103–117, 2015     

Catalytic conversion of commingled polymer waste into chemicals and fuels over spent FCC commercial catalyst in a fluidised-bed reactor

A commingled post-consumer polymer (CPW#1) was pyrolysed over spent fluid catalytic cracking (FCC) commercial catalyst (ECat-1) using a laboratory fluidised-bed reactor operating isothermally at ambient pressure. The influence of reaction conditions including catalyst, temperature, ratios of commingled polymer to catalyst feed and flow rates of fluidising gas was examined. The conversion for spent FCC commercial catalyst (82.7 wt%) gave much higher yield than silicate (only 14.2 wt%) and the highest yield (nearly 87 wt%) was obtained for ZSM-5. Greater product selectivity was observed with ECat-1 as a recycled catalyst with about 56 wt% olefins products in the C₃–C₇ range. The selectivity could be further influenced by changes in reaction conditions. Valuable hydrocarbons of olefins and iso-olefins were produced by low temperatures and short contact times used in this study. It is also demonstrated that the use of spent FCC commercial catalyst and under appropriate reaction conditions can have the ability to control both the product yield and product distribution from polymer degradation, potentially leading to a cheaper process with more valuable products.     

不同原料的催化裂化性能研究

在固定流化床装置上进行了长庆原油的常压渣油、减压渣油和脱沥青油的催化裂化反应,并考察了常压渣油掺炼脱沥青油对产物分布的影响。结果表明:常压渣油裂化性能最好,汽油产率和总液收最高;脱沥青油裂化性能次之,柴汽比约为1;减压渣油的裂化性能最差。常压渣油掺炼脱沥青油对汽柴油的产率和柴汽比有较大影响,但对总液收和轻油收率影响不大。     

Modular reactors with electrical resistance heating for hydrocarbon cracking and other endothermic reactions

We propose and demonstrate by calculations novel modular reactor configurations with electrical resistance heating for endothermic reactions such as cracking and steam reforming of hydrocarbons. The basic unit of each module consists of a set of wires, tubes, plates, monolith, or gauze/wire meshes arranged in parallel or series to satisfy the current–voltage constraints. The smaller dimensions such as spacing and diameter are selected to obtain nearly uniform heating temperature within the reaction zone.     

Catalytic cracking in presence of an aromatic addition

Fluidized bed catalytic cracking of vacuum gas oil fractions in the presence of extract from phenol purification of heavy lubricating oil fraction as an aromatic addition was investigated. Results show that, at the optimum concentration of the addition, coke formation on the catalyst decreases by 50 to 70% while the content of olefinic hydrocarbons in gasoline decreases, with a corresponding increase in the content of paraffin/naphthene hydrocarbons. The yield of gasoline increases, while its octane number increases by about two units.     

A novel reverse flow reactor coupling endothermic and exothermic reactions: Part II: Sequential reactor configuration for reversible endothermic reactions

The new reactor concept for highly endothermic reactions at elevated temperatures with possible rapid catalyst deactivation based on the indirect coupling of endothermic and exothermic reactions in reverse flow, developed for irreversible reactions in Part I, has been extended to reversible endothermic reactions for the sequential reactor configuration. In the sequential reactor configuration, the endothermic and exothermic reactants are fed discontinuously and sequentially to the same catalyst bed, which acts as an energy repository delivering energy during the endothermic reaction phase and storing energy during the consecutive exothermic reaction phase. The periodic flow reversals to incorporate recuperative heat exchange result in low temperatures at both reactor ends, while high temperatures prevail in the centre of the reactor. For reversible endothermic reactions, these low exit temperatures can shift the equilibrium back towards the reactants side, causing ‘back-conversion’ at the reactor outlet.The extent of back-conversion is investigated for the propane dehydrogenation/methane combustion reaction system, considering a worst case scenario for the kinetics by assuming that the propylene hydrogenation reaction rate at low temperatures is only limited by mass transfer. It is shown for this reaction system that full equilibrium conversion of the endothermic reactants cannot be combined with recuperative heat exchange, if the reactor is filled entirely with active catalyst. Inactive sections installed at the reactor ends can reduce this back-conversion, but cannot completely prevent it. Furthermore, undesired high temperature peaks can be formed at the transition point between the inactive and active sections, exceeding the maximum allowable temperature (at least for the relatively fast combustion reactions).A new solution is introduced to achieve both full equilibrium conversion and recuperative heat exchange while simultaneously avoiding too high temperatures, even for the worst case scenario of very fast propylene hydrogenation and fuel combustion reaction rates. The proposed solution utilises the movement of the temperature fronts in the sequential reactor configuration and employs less active sections installed at either end of the active catalyst bed and completely inactive sections at the reactor ends, whereas propane combustion is used for energy supply. Finally, it is shown that the plateau temperature can be effectively controlled by simultaneous combustion of propane and methane during the exothermic reaction phase.     

一种甲醇低温裂解反应器设计及反应特性研究

设计了一套集成式甲醇低温裂解反应器,开发了电控反应装置系统,并进行了反应特性实验.实验结果表明,该反应装置系统适宜的甲醇裂解反应温度为310℃,最佳甲醇加料速度为25.50 h-1,甲醇裂解率为84.5%,裂解气中CO和H2含量高,反应装置简单,长期运行稳定性好,适合实际应用.     

用于吸/放热反应耦合的金属基整体式催化反应器性能模拟

利用计算化学工程方法,针对甲烷催化燃烧和甲烷水蒸气重整的模型反应体系,研究了一种结构较复杂的金属基整体式催化反应器用于吸/放热反应耦合时的性能.模拟结果表明,这种金属基整体式催化反应器应用于吸/放热反应耦合具有很大的研发潜力.初步分析了操作参数的影响,重整侧与燃烧侧入口气体速度的比值、气体入口温度以及燃烧部分和重整部分的甲烷体积流量比都是影响反应器性能的重要因素.