Thermodynamic analysis of reaction pathways and equilibrium yields for catalytic pyrolysis of naphtha

The chain length and hydrocarbon type significantly affect the production of light olefins during the catalytic pyrolysis of naphtha. Herein, for a better catalyst design and operation parameters optimization, the reaction pathways and equilibrium yields for the catalytic pyrolysis of C_5–8 n/iso/cyclo-paraffins were analyzed thermodynamically. The results revealed that the thermodynamically favorable reaction pathways for n/iso-paraffins and cyclo-paraffins were the protolytic and hydrogen transfer cracking pathways, respectively. However, the formation of light paraffin severely limits the maximum selectivity toward light olefins. The dehydrogenation cracking pathway of n/iso-paraffins and the protolytic cracking pathway of cyclo-paraffins demonstrated significantly improved selectivity for light olefins. The results are thus useful as a direction for future catalyst improvements, facilitating superior reaction pathways to enhance light olefins. In addition, the equilibrium yield of light olefins increased with increasing the chain length, and the introduction of cyclo-paraffin inhibits the formation of light olefins. High temperatures and low pressures favor the formation of ethylene, and moderate temperatures and low pressures favor the formation of propylene. n-Hexane and cyclohexane mixtures gave maximum ethylene and propylene yield of approximately 49.90% and 55.77%, respectively. This work provides theoretical guidance for the development of superior catalysts and the selection of proper operation parameters for the catalytic pyrolysis of C_5–8 n/iso/cyclo-paraffins from a thermodynamic point of view.     

碳五烷烃裂解制低碳烯烃反应性能的分析

考察了碳五烷烃的热裂解和催化裂解反应性能,发现正戊烷和异戊烷的裂解反应产物存在差异;进一步分析了正戊烷和异戊烷的裂解反应机理,以及裂解生成低碳烯烃和甲烷的区别。结果表明,在热裂解条件下,正戊烷的（乙烯+丙烯）选择性高于异戊烷,异戊烷的丁烯和甲烷选择性高于正戊烷;650℃时,正戊烷和异戊烷的热裂解产品中（乙烯+丙烯）、丁烯、甲烷的选择性分别为37.48%、7.23%、6.75%和19.57%、25.16%、9.36%。而在催化裂解条件下,异戊烷的（乙烯+丙烯）、丁烯、甲烷选择性均高于正戊烷;650℃时,正戊烷和异戊烷的催化裂解产品中（乙烯+丙烯）、丁烯、甲烷的选择性分别为37.16%、9.11%、7.80%和47.70%、14.45%、13.79%。此外,发现在高温裂解条件下异构烷烃比正构烷烃容易裂解生成丁烯和甲烷。     

Dehydrogenative cracking of n-butane using double-stage reaction

Dehydrogenation-cracking double-stage (tandem) reaction of n-butane was studied using a Pt-Sn type dehydrogenation catalyst and a cracking catalyst (rare earth-loaded HZSM-5). n-Butane was firstly dehydrogenated to n-butene (1- and 2-butene) over the Pt-Sn catalyst loaded at the upper part of the reactor. Then n-butene was successively converted to ethylene and propylene over the cracking catalyst loaded at the lower part of the reactor. The yield of light olefins (ethylene+propylene) was 58% at 650 °C. The key to obtaining ethylene and propylene in high yield was to determine how the bimolecular reactions of olefins to aromatic and heavier products can be inhibited. It was proved that the loaded rare earths played an important role in inhibiting the bimolecular reactions.     

A molecular kinetic model for heavy gas oil catalytic pyrolysis to light olefins

Petroleum catalytic pyrolysis to light olefin technology has received wide-ranging research interest in the refining industry. This work built a molecular kinetic model for the catalytic pyrolysis of a heavy gas oil from bitumen synthetic crude oil (SCO) to light olefins. A feedstock compositional model was constructed containing 1311 molecules using bulk properties information. A variety of reaction rules was summarized and digitized, and from which, a reaction network involving 2631 substances and 6793 reactions was generated via a reaction network autogeneration algorithm. The reaction network for the catalytic pyrolysis was transformed into reaction rate equations. Systematical pilot-scale catalytic pyrolysis experiments were carried out, which were used to regress the molecular kinetic model parameters. The tuned model is able to predict the product yield and molecular distribution. Moreover, a range of sensitivity analysis was performed, revealing the dependence of light olefins yields on the reaction conditions.     

轻烃催化裂解制低碳烯烃反应规律与原料特征化

利用小型固定床实验装置对比研究了轻烃模型化合物的催化裂解性能,从优到劣的顺序依次是正构烯烃、正构烷烃、环烷烃、异构烷烃、芳香烃。正构烷烃、异构烷烃与环烷烃催化裂解的总低碳烯烃收率有较大差别,但是总低碳烯烃选择性却均在56.57%左右。研究了直馏石脑油的催化裂解性能,发现乙丙烯收率和总低碳烯烃收率随反应温度的升高及重时空速的降低而逐渐增大;在反应温度680℃、重时空速4.32 h^-1和水油稀释比0.35的条件下,乙丙烯收率35.87%（质量）,总低碳烯烃收率为41.94%（质量）。针对轻烃催化裂解提出了原料特征化参数KF,它是原料H/C原子比、相对密度与分子量的函数,能较好地表征轻烃原料的催化裂解性能。     

新型银基低共熔溶剂制备及其在1-己烯/正己烷分离中的应用

相同碳数的正构烯烃与正构烷烃因其结构相似,使其相对挥发度较小、分离难度较大。低共熔溶剂（DES）作为一种可设计的绿色分离介质被广泛应用于该类混合物的分离中,此外过渡金属与烯烃双键之间的化学络合作用是促进正构烯烃/烷烃分离的一个重要方法。鉴于此,开发了新型银基低共熔溶剂（Ag-DES）,并将其应用于1-己烯/正己烷的分离,系统探究了原料中烯烃浓度、银离子与烯烃摩尔比、分离温度等对1-己烯分离性能的影响,结果显示Ag-DES具有良好的1-己烯/正己烷分离选择性,选择性在3.5~18之间,并具有出色的循环稳定性。进一步通过FT-Raman表征和量化计算揭示了Ag-DES与烯烃之间的化学络合作用和较强氢键作用是实现其与烷烃分离的本质原因,表明应用Ag-DES的反应萃取分离强化方法可实现从F-T合成油中绿色高效分离C₆α-烯烃。     

Effects of large pore zeolite additions in the catalytic pyrolysis catalyst on the light olefins production

To increase the light olefins selectivity of catalytic pyrolysis catalyst for heavy oil processing, the effects of large pore zeolite additions on the selectivity to light olefins (ethylene and propylene) were studied in a micro-activity test (MAT) unit at 625 °C by using Daqing heavy oil and n-decene/n-decane as feedstocks. Rare earth containing ultra-stable Y, Hβ and four types of alkali-treated Hβ with different pore size distributions were employed as the large pore zeolite components. The yields of C₂–C₃ light olefins showed a volcano trend with the increasing amount of large pore zeolite additions. They reached up to 24.5 and 26.7 wt%, respectively, when an optimum combination of zeolites ZSM-5 and RE-USY or ZSM-5 and alkali-treated Hβ was used. Moreover, increasing the pore size of large pore zeolites also led to the increases in the yields of light olefins, the maximum total yields of ethylene and propylene reached up to 26.7 wt% when the total pore volume of the zeolite Hβ added was 0.452 cm³ g⁻¹.     

重油催化裂解制低碳烯烃工艺条件研究

采用固定流化床催化裂化试验装置,以中国石油兰州石化公司3.0 Mt·a-1重油催化裂化装置所用原料油为原料,考察反应温度和剂油质量比对重油催化裂解制低碳烯烃性能的影响,在确定的适宜操作条件下研究中国石油兰州石化公司重催装置原料在不同催化剂上的催化裂解制低碳烯烃的反应性能。结果表明,较适宜的操作条件为:反应温度590℃,剂油质量比为7,与降烯烃催化剂和重油裂解催化剂相比,多产丙烯催化剂的低碳烯烃产率可达25.53%,更适合作为重油催化裂解制低碳烯烃时使用。     

Highly effective oxidative cracking of n-butane in light olefins on a novel cobalt catalyst

A Co-N on alumina catalyst yielded high performance in the oxidative cracking of n-butane to ethylene and propylene. A total of 47.7 wt.% yield of olefins including 31% of ethylene and 13% of propylene were obtained at 82% of n-butane conversion at 600 °C. Catalyst characterization by SEM, X-ray photoelectron spectroscopy (XPS), XRD and TPR studies suggested that a cobalt oxynitride phase was formed. This resulted in lowering the oxygen binding energy leading to enrichment in mobile, low energy, oxygen species that significantly accelerates the formation of lower olefins.     

Production of clean transportation fuels and lower olefins from Fischer-Tropsch Synthesis waxes under fluid catalytic cracking conditions: The potential of highly paraffinic feedstocks for FCC

The potential of Fischer-Tropsch Synthesis (FTS) waxes as a feedstock for fluid catalytic cracking (FCC) has been evaluated with a once-through microriser reactor operating under realistic conditions. The highly paraffinic feedstock has a high reactivity and can be converted under industrial conditions to a high extent (>90 wt%). The product distribution can be optimised by the process parameters and catalyst formulation. A high gasoline fraction (70 wt%) with a very low aromatics concentration can be obtained. As a result of the formation of i-paraffins, n-olefins and i-olefins the gasoline is expected to possess an acceptable octane number. The reaction scheme derived predicts that the degree of branching in the paraffinic diesel-range product is lower than that of the gasoline-range product and that a relatively good diesel is expected. Due to the absence of sulfur and nitrogen in the feed extremely clean transportation fuels are obtained. The addition of ZSM-5 to an equilibrium catalyst allows the production of significant amounts of light olefins, in particular propene (16 wt%) and butenes (15 wt%).     

IR studies on the activation of C–H hydrocarbon bonds on oxidation catalysts

The total oxidation of propane and its oxy-dehydrogenation to propene have been studied on spinel-type catalysts Mn₃O₄, Co₃O₄ and MgCr₂O₄ in a flow reactor and in an IR cell. Analogous studies have been performed on the oxy-dehydrogenation of n-butenes to 1,3-butadiene over MgFe₂O₄. Information on the reaction mechanism have been reached. The activation of the hydrocarbons is thought to occur by abstraction of a hydrogen from the weakest C–H bond, with a simultaneous reduction of a surface site and with the formation of a surface alkoxy-group.     

Destruction of trichloroethylene (TCE) and trichloromethane (TCM) in the presence of selected VOCs over Pt-Pd-based catalyst

Catalytic oxidation of trichloroethylene (TCE) and trichloromethane (TCM) oxidized alone and in two-component mixtures with selected volatile organic compounds (VOCs) such as toluene, n-hexane, ethanol or acetone was investigated over a Pt-Pd-based catalyst on a monolithic, metallic, γ-Al₂O₃-washcoated support. TCE and TCM were more difficult to oxidize than VOCs and temperatures of their 50% conversion (T_50%) amouted to 420 and 330 °C, respectively. All the VOCs added were found to enhance the conversion of the two chlorinated compounds, drecreasing T_50% by 20 °C, at the most, for TCM in the presence of toluene and by 50 °C for TCE in the presence of acetone. Both the chlorinated compounds lowered the conversion of the VOCs added (except that of toluene), and this lowering was particularly distinct with n-heptane; they also raised the concentration of acetaldehyde formed during the oxidation of oxyderivative compounds.     

不同溶剂萃取小球藻油脂结构及组分差异

随着化石能源枯竭, 微藻生物柴油日益成为研究热点, 但对藻油的高效、高选择性萃取仍存在技术瓶颈。该文选择不同沸点、极性和油水分配系数的有机溶剂萃取微藻藻油, 并通过FTIR及GC-MS对微藻生物质结构及藻油组分差异进行明晰。结果表明:乙腈和正庚烷对藻油的提取率最高, 分别为22.10%和18.71%, 且与温度正相关, 但是溶剂的极性和油水分离系数对其萃取率无显著影响, 主要取决于所萃取产物的组分及结构;对微藻生物质结构及藻油组分研究表明不同溶剂对烃类、醇类、酯类等不同物质的萃取有较强的选择性;二氯甲烷和丙酮对烃类的萃取率高, 为72.74%和69.50%, 正庚烷对酯类的萃取率较高, 为80.46%, 乙腈对胺类的萃取率较高, 为58.52%, 乙酸乙酯对醇类的萃取率较高, 为24.65%。     

CO2-烃类液相混合物比定容热容的实验与模型研究

近年来,二氧化碳(CO₂)提高原油采收率(CO₂-EOR)技术得到了广泛的研究。充分了解CO₂-烃类混合物的热容性质是该项目能够成功实施的基础,但是目前对此性质的研究非常有限。基于绝热量热法,搭建了一个绝热量热计,测量了温度为317.15~353.15 K,压力高达29.49 MPa时,CO₂-碳氢化合物(正己烷、正辛烷、十一烷、环己烷、乙苯)二元液相混合物的比定容热容(C_v )数据,共获得335个数据点。此外,采用预测模型(结合热力学关系的PR状态方程)和经验模型计算C_v,计算平均绝对相对偏差(AARD)分别为0.81%~3.66%和小于2.56%。经验模型的形式简单,但PR模型有较强的预测能力。实验测得的C_v 数据以及建立的两种计算模型对CO₂-EOR项目的实施至关重要。     

混合碳四选择加氢制1-丁烯工艺设计

根据裂解混合碳四选择加氢制丁烯工艺和催化剂评价研究结果,提出一种提高1-丁烯收率的加氢工艺流程设计方案。该工艺流程采用烃类蒸汽裂解装置所产混合碳四做原料,经过两段加氢反应器进行选择加氢,将混合碳四中的炔烃和1,3-丁二烯加氢生成富含1-丁烯的碳四物流。流程模拟计算结果表明,加氢后,1,3-丁二烯含量小于10×10^-6,1-丁烯选择性大于55%。     

Conversion of naphthenes to a high value steamcracker feedstock using H-ZSM-5 based catalysts in the second step of the ARINO-process

Future regulations for the limitation of sulfur and aromatics in fuels driven by the European Auto Oil Program (AOP II) stimulate the need for an alternative utilization of the resulting surplus of pyrolysis gasoline (pygas). The conversion of heavy pyrolysis gasoline into valuable steam cracker feedstock with a maximum yield of C₂–C₄ n-alkanes is achieved via the ARINO^® two-step process, jointly developed by Linde, VEBA Oil and Süd-Chemie. The first step involves a hydrogenation of aromatics to naphthenes followed by the subsequent ring opening and cracking in the second step.

Süd-Chemie developed a new commercial cracking catalyst for the second step of the ARINO^® process with the aim to maximize the yield of C₂–C₄ n-alkanes at low formation of methane and aromatics. The ring opening and cracking reaction of naphthenes was studied in a bench scale tubular reactor over extruded H-ZSM-5 based zeolite catalysts.

In a series of screening tests using a commercial, hydrogenated and desulphurized heavy pyrolysis gasoline, the influence of the preparation parameters such as zeolite acidity, palladium content as well as the type of binder were investigated. Furthermore, the influence of the process conditions space velocity and temperature was studied.

High yields of C₂–C₄ n-alkanes at low formation of undesired methane and aromatics were achieved over an alumina bound zeolite with medium Brønsted acidity loaded with palladium.

The reduction of the space velocity resulted in an increase in the C₂–C₄ n-alkane yield and lower formation of aromatics, but a simultaneous increase in the methane make. Raising the temperature from 280 to 370 °C significantly increased the catalyst activity.     

Experimental investigation and modeling of steam cracking of Fischer–Tropsch naphtha for light olefins

The characteristics of product distribution and the kinetic model for predicting the yields of the major products from steam cracking of Fischer–Tropsch (F–T) naphtha have been investigated in a pilot plant under various conditions. An analysis of the experimental data suggests that the naphtha produced via the low-temperature slurry-phase F–T process is an excellent feedstock for the production of light olefins, especially ethylene. For steam cracking of two F–T naphthas studied, ethylene is the primary product varying from 36.89 to 41.83 wt%, and the total yield of valuable light olefins (C₂H₄, C₃H₆ and 1,3-C₄H₆) is not less than 60.34 wt% under the conditions estimated. The experimental product distributions could be satisfactorily predicted by use of a detailed molecular reaction scheme which consists of a first-order primary reaction and 37 secondary reactions.     

Catalytic purification of waste gases containing VOC mixtures with Ce/Zr solid solutions

This study has been undertaken to investigate the efficiency of ceria, zirconia, and Ce_xZr_1−xO₂ mixed oxides as catalysts for the vapour-phase destruction in air of single model VOCs (n-hexane, 1,2-dichloroethane and trichloroethylene) and non-chlorinated VOC/chlorinated VOC binary mixtures. Considering all catalyst compositions examined for the individual destruction of these compounds, activity for complete oxidation decreased in the following order: n-hexane < 1,2-dichloroethane < trichloroethylene. The compositions with the best performance for chlorinated VOCs abatement (Ce_0.5Zr_0.5O₂ and Ce_0.15Zr_0.85O₂) were different than that with the best performance for n-hexane oxidation (CeO₂). Concerning chlorinated VOCs conversion, it was observed that notable improvements in catalyst activity of CeO₂ could be achieved through structural doping with Zr ions. Mixed oxides exhibited promoted redox and acid properties, which resulted catalytically relevant for the oxidation of 1,2-dichloroethane and trichloroethylene. In contrast, the combustion of n-hexane was essentially controlled by surface oxygen species, which were more abundant on CeO₂. Attainment of high n-hexane conversions with CeO₂ was also attributed in part to the hydrophobicity of the support and the reduced interaction with carbon dioxide.

Significant ‘mixture effects’ on both activity and selectivity were noticed when a given chlorinated feed was decomposed in the presence of n-hexane. On one hand, each VOC decreased the reactivity of the other relative to that of the pure compound resulting in higher operating temperatures to achieve adequate destruction. Competitive adsorption played an important role in the reciprocal inhibition effects detected with all catalysts. On the other hand, the selectivity to HCl was noticeably enhanced when n-hexane was co-fed, probably due to the increased presence of water generated as an oxidation product.     

Experimental data and modeling for excess enthalpies of 2-Pentanol with n-alkanes(C7–C9) at T =(293.15, 298.15 and 303.15) K

Excess molar enthalpies, H~E, for the binary mixtures of 2-pentanol with n-alkanes(n-heptane, n-octane, and nnonane) have been determined at three different temperatures T =(293.15, 298.15 and 303.15) K and normal atmospheric pressure over the entire composition range using a Calvet microcalorimeter. All mixtures show endothermic mixing with the maximum values of the excess enthalpies occurring in the n-alkane-rich region. The H~Edata are smoothed using Redlich–Kister equation. The applicability of the Treszczanowicz–Benson, ERAS,Renon–Prausnitz and Chen–Bagley models to correlate H~Eof studied mixtures is tested, and the agreement between experimental and theoretical results is satisfactory. Each model includes a self-association equilibrium constant that represents hydrogen bonding and an adjustable parameter that reflects physical interactions.     

减压柴油管式炉裂解制烯烃

中国某些产地的原油具有低硫、高石蜡烃和低芳烃含量的特性。用这类原油炼制所得的减压柴油馏分具有同样特征,因而预测将有良好的裂解性能。为此进行了工艺研究。 在处理量约为2公斤/时,温度和压力分布可以模拟的裂解装置中,进行了中国减压柴油动力学研究和裂解产品分布规律试验。根据模试结果;综合中试和部分工业数据,提出了减压柴油裂解反应速度常数方程的有关参数值,以及原料特性和工艺参数对裂解产品收率关联图及数学关联式。 在处理量为100公斤/时的中试裂解装置中进行产品分布试验和工艺过程有关技术研究,着重考察了炉管对流段、辐射段的运转情况、高压急冷锅炉的操作特性。 研究结果表明,在760℃中等裂解深度时,汽油比为0.75—1,停留时间0.4—0.5秒,烃分压0.8公斤/厘米~2,主要产品收率为:乙烯22.5—23%,丙烯16—17.5%,丁二烯4.7—5.2%,重质燃料油10—12%。该油品与国外中东轻柴油裂解所得产物收率相仿,是工业管式炉的一种好原料。