催化裂化生产清洁燃料

介绍了当前轻质油品脱硫的一些方法,包括传统的加氧脱硫和吸附脱硫等工艺过程。21 世纪的炼油企业将围绕炼油厂清洁化生产和生产更加清洁的燃料方向发展,重点发展各种汽油加氢技术并开发非加氢技术、发展轻烯烃改质以及催化汽油降烯烃技术。     

Thermal and catalytic degradation of waste high-density polyethylene (HDPE) using spent FCC catalyst

Thermal and catalytic degradation using spent fluid catalytic cracking (FCC) catalyst of waste high-density polyethylene (HDPE) at 430 °C into fuel oil were carried out with a stirred semi-batch operation. The product yield and the recovery amount, molecular weight distribution and paraffin, olefin, naphthene and aromatic (PONA) distribution of liquid product by catalytic degradation using spent FCC catalyst were compared with those by thermal degradation. The catalytic degradation had lower degradation temperature, faster liquid product rate and more olefin products as well as shorter molecular weight distributions of gasoline range in the liquid product than thermal degradation. These results confirmed that the catalytic degradation using spent FCC catalyst could be a better alternative method to solve a major environmental problem of waste plastics. This paper is dedicated to Dr. Youn Yong Lee on the occasion of his retirement from Korea Institute of Science and Technology.     

流化催化裂化(FCC)催化剂跑损机制及故障树分析

炼油厂中流化催化裂化（FCC）装置催化剂跑损的故障原因分析多数来自现场工程师,在故障机理方面少有报道。为了解决这一问题,本文利用故障树分析方法（FTA）,研究FCC装置催化剂跑损机制。采用催化剂跑损为顶事件,结合跑损途径和跑损机理,确定FCC装置故障、操作工艺异常和催化剂颗粒物性3个因素作为中间事件,并通过逐层向下深入分析,确定诸如翼阀磨损等21个因素作为底事件,建立催化剂跑损故障树模型。根据FCC装置故障树风险分析,得到任何一个底事件出现都有可能导致顶事件发生,且对FCC装置催化剂跑损的贡献度相同。研究结果表明：利用FTA方法可以更深层次了解装置跑剂原因,对考察FCC装置催化剂跑损机理具有指导意义,并提出了相应的故障判定流程和跑剂预防措施。     

Modeling,simulation and structural analysis of a fluid catalytic cracking (FCC) process

Fluid catalytic cracking (FCC) is an important chemical process that is widely used to produce valuable petrochemical products by cracking heavier components. However, many difficulties exist in modeling the FCC process due to its complexity. In this study, a dynamic process model of a FCC process is suggested and its structural observability is analyzed. In the process modeling, yield function for the kinetic model of the riser reactor was applied to explain the product distribution. Hydrodynamics, mass balance and energy balance equations of the riser reactor and the regenerator were used to complete the modeling. The process model was tested in steady-state simulation and dynamic simulation, which gives dynamic responses to the change of process variables. The result was compared with the measured data from operating plaint. In the structural analysis, the system was analyzed using the process model and the process design to identify the structural observability of the system. The reactor and regenerator unit in the system were divided into six nodes based on their functions and modeling relationship equations were built based on nodes and edges of the directed graph of the system. Output-set assignment algorithm was demonstrated on the occurrence matrix to find observable nodes and variables. Optimal locations for minimal addition of measurements could be found by completing the whole output-set assignment algorithm of the system. The result of this study can help predict the state more accurately and improve observability of a complex chemical process with minimal cost.     

Separation and recovery of vanadium from leached solution of spent residuehydrodesulfurization (RHDS) catalyst using solvent extraction

Leached solution, generated by oxalic acid washing of spent residue hydrodesulfurization (RHDS) catalyst, was used for separation and recovery of vanadium. First of all, solvent extraction, using mixture of 20% (v/v) Alamine-336 and 5% (v/v) tri-butyl phosphate (TBP) as a phase modifier, was conducted to extract molybdenum completely at pH 0.50. Then molybdenum-free solution was used for vanadium extraction at pH 1.25 with 20% Alamine-336 and 5% TBP. Stripping of vanadium from loaded organic solution was performed with 1.5 M H₂SO₄ at O/A phase ratio of 5:1 where more than 99% of vanadium was stripped in two stages. The stripped vanadium solution was further processed by precipitating with ammonium hydroxide to recover ammonium-meta-vanadate which was calcined to obtain vanadium pentoxide. Finally a conceptual process was established for recovery of high purity vanadium pentoxide from oxalic acid leached solution of spent residue hydrodesulfurization (RHDS) catalyst.     

A novel method for enhancing on-stream stability of fluid catalytic cracking (FCC) gasoline hydro-upgrading catalyst: Post-treatment of HZSM-5 zeolite by combined steaming and citric acid leaching

This article describes a novel modification method consisting of steaming and subsequent citric acid leaching to finely tune acidity and pore structure of HZSM-5 zeolite and thereby to enhance the on-stream stability of the zeolite derived fluid catalytic cracking (FCC) gasoline hydro-upgrading catalyst. A series of dealuminated HZSM-5 zeolites and their derived catalysts were prepared and characterized by X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), ²⁷Al MAS NMR, nitrogen adsorption, temperature programmed desorption of ammonium (NH₃-TPD) and infrared (IR) spectroscopy of chemisorbed pyridine. The results showed that the citric acid leaching could preferentially remove the extra-framework Al (EFAl) species formed by steaming treatment and thus reopen the EFAl-blocked pore channels of the steamed zeolite. The steaming treatment at a suitable temperature and subsequent citric acid leaching not only decreased the strength of acid sites to a desirable degree but also increased the ratio of medium and strong Lewis acidity to medium and strong Brönsted acidity, both of which conferred the resulting catalyst with superior selectivity to aromatics, good hydroisomerization activity and gasoline research octane number (RON) preservability, as well as enhanced on-stream stability. The results fully demonstrated that the treatments by steaming and followed citric acid leaching can serve as an important method for adjusting the physicochemical properties of HZSM-5 zeolite.     

催化汽油过氧乙酸氧化及溶剂萃取脱硫

以钨酸钠为氧化催化剂,开展过氧乙酸氧化及溶剂萃取催化汽油脱硫实验研究。研究结果表明,随着氧化溶液中钨酸钠质量分数的升高,脱硫率先升高后趋于不变,汽油收率略降。溶剂萃取对催化汽油脱硫也有贡献,3种溶剂脱硫率为聚乙二醇-400＞三甘醇＞二甘醇,而汽油收率的顺序相反,聚乙二醇-400是汽油脱硫的较好萃取溶剂。随着氧化温度升高或氧化溶液用量增大,脱硫率增大,汽油收率减少。随着氧化时间延长,脱硫率先增大后降低,而汽油收率降低。较佳的氧化温度为70 ℃,氧化时间10 min。萃取时间和萃取温度对脱硫率影响不大,适当降低萃取温度有利于提高汽油收率。     

A new generic approach for the modeling of fluid catalytic cracking (FCC) riser reactor

A new kinetic model for the fluid catalytic cracking (FCC) riser is developed. An elementary reaction scheme, for the FCC, based on cracking of a large number of lumps in the form of narrow boiling pseudocomponents is proposed. The kinetic parameters are estimated using a semi-empirical approach based on normal probability distribution. The correlation proposed for the kinetic parameters’ estimation contains four parameters that depend on the feed characteristics, catalyst activity, and coke forming tendency of the feed. This approach eliminates the need of determining a large number of rate constants required for conventional lumped models. The model seems to be more versatile than existing models and opens up a new dimension for making generic models suitable for the analysis and control studies of FCC units. The model also incorporates catalyst deactivation and two-phase flow in the riser reactor. Predictions of the model compare well with the yield pattern of industrial scale plant data reported in literature.     

A comparative study of liquid product on non-catalytic and catalytic degradation of waste plastics using spent FCC catalyst

Non-catalytic and catalytic degradation of waste plastics (high-density polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP) and polystyrene (PS)) using spent fluid catalytic cracking (FCC) catalyst into liquid product were comparatively studied with a stirred semi-batch reactor at 400 ‡C, under nitrogen stream. Liquid product characteristics were described by cumulative distribution as a function of lapse time of reaction, paraffin, olefin, naphthene and aromatic (PONA) composition, and also carbon number distribution on plastic type of reactant. For degradation of waste PE with relatively high degradation temperature, the effect of adding spent FCC catalyst greatly appeared on cumulative distribution of liquid product with a reaction lapse time, whereas those for waste PP and PS with low degradation temperature showed a similar trend in both non-catalytic and catalytic degradation at 400 ‡C. In PONA and carbon number distribution of liquid product, the characteristics of waste PS that was mainly degraded by end chain scission mechanism were not much altered in presence of spent FCC catalyst. However, waste polyolefinic polymer that was degraded by a random chain scission mechanism significantly differed on PONA and carbon number distribution of liquid product with or without spent FCC catalyst. The addition of spent FCC catalyst in degradation of polyolefinic polymer, which economically has a benefit in utilization of waste catalyst, significantly improved the light olefin product by its high cracking ability and also the aromatic product by cyclization of olefin as shape selectivity in micropore of catalyst.     

Optimization of a solvent extraction route for the recovery of Mo from petroleum refinery spent catalyst using Cyphos IL 102

In this study, trihexyl(tetradecyl)phosphonium bromide (Cyphos IL 102) diluted in toluene has been explored for the first time as an organic phase for the extraction, separation, and recovery of Mo(VI) from hydrochloric acid medium. The study focuses on the recovery of metals from spent catalyst, a hazardous solid waste. The metal recovered in the form of metal oxide has further applications in various fields. The widespread use of solvent extraction for metal recovery can be assigned to its economic feasibility and the built-in concentration step thereby providing an appropriate commercial technology for the beneficiation of low-grade sources of metals and recovery of substances from complex matrices. The influence of fundamental extraction variables on Mo(VI) extraction and loading and recycling capacity of the extractant has also been evaluated. Binary separations of Mo(VI) from other associated metal ions have been achieved with high separation factors. Optimized conditions have been employed for the extraction and recovery of Mo(VI) from petroleum refinery spent catalyst leach liquor containing Mo-1141.18 ppm, Al-2158.42 ppm, Ni-270.39 ppm, and Co-61.82 ppm. Quantitative and selective extraction (98.4%) of Mo from spent petroleum refinery catalyst was achieved in two stages at A:O = 3:2 using 2.0 × 10^?2 mol/L Cyphos IL 102. Almost 99% Mo was stripped with 1.0 mol/L (NH₄)₂CO₃ in two stages at O:A = 1:1. MoO₃, obtained from the stripped solution by thermal decomposition was characterized by XRD, FESEM, and EDX techniques. Economical and environmental aspect of present work is supported by high loading capacity and reusability of extractant.     

Optimization of solvent crystallization process in obtaining high purity anthracene and carbazole from crude anthracene

Solvent crystallization is the main method used for preparing anthracene and carbazole from the crude anthracene. The key to the optimization of this method is improving the solubility selectivity of the solvent by means of solvent modulating and process optimization. In this study, the solubility of anthracene, phenanthrene, and carbazole in xylene, dimethylformamide (DMF), DMF with amine/amide, isopropanolamine, and chlorobenzene is examined and the solid‐liquid ternary anthracene–carbazole–DMF/(DMF+19.96% isopropanolamine) system phase diagram is determined and applied in the solvent crystallization process. The results showed that the solubility selectivity of xylene increases with increased temperature. Also, selectivity increases with an increase of the amount of isopropanolamine in the mixture of DMF and isopropanolamine, while decreases with increased temperature. Through multiple washings of crude anthracene with xylene, DMF+19.96% isopropanolamine, and chlorobenzene, it was possible to obtain anthracene and carbazole of purity higher than 98 wt %. © 2013 American Institute of Chemical Engineers AIChE J, 60: 275–281, 2014     

Phase equilibrium studying for the supercritical fluid extraction process using carbon dioxide solvent with 1.35 mole ratio of octane to ethanol mixture

Supercritical fluid extraction is a clean environmental chemical engineering process that has been given an interest to many researchers worldwide. The assessment of the feasibility of the extraction process utilizing a near critical solvent would be speeded up if it is possible to predict solubility data. Solubility data were measured for carbon dioxide with a mole ratio 1.35 of octane to ethanol using a phase equilibrium loading re-circulating high-pressure type apparatus at pressures up to 100 bar and at temperature 75 °C. The experimental data were then compared with calculated theoretical data which is calculated form the regular solution equations. A thermodynamic procedure is employed to each phase by applying activity coefficient expressions related to interaction parameters which are dependent on the pressure.     

前置烧焦式催化裂化装置稳态模拟:再生器取热器负荷对过程的影响

应用本文作者课题组开发的前置烧焦式催化裂化装置过程模拟平台,对某工业装置进行现场条件下的稳态模拟,并完成全装置模型的校正及验证。在此基础上,模拟分析了再生器取热器负荷对该装置操作产生的影响。模拟结果显示,改变再生器取热器的负荷,能够有效调节两器热量平衡,在确保工艺范围不超限的前提下提高装置剂油比,原料油转化率提高,装置产品分布得到有效调节,但是使得密相床再生器密相区床层温度降低,从而影响再生器的再生效果,不利于提升管进口再生催化剂初始活性的提高。     

Preparation of high purity methylal by extractive distillation using N,N-dimethylformamide (DMF) as solvent

通过溶剂选择原理粗选出萃取精馏制备甲缩醛产品的溶剂,既而通过Chemcad软件模拟和汽液平衡实验确定合适的溶剂及溶剂比。结果表明,N,N-二甲基甲酰胺（DMF）能够消除甲缩醛-甲醇共沸物系的共沸点;采用UNIQUAC模型对常压下甲缩醛-甲醇物系和加入溶剂N,N-二甲基甲酰胺的汽液平衡进行模拟,模拟结果和实验数据吻合较好。用间歇萃取精馏实验对甲缩醛粗品进行了分离,在实验条件下,可以从塔顶得到质量浓度为99.9%的高纯度甲缩醛产品。     

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%).     

Preparation of poly(L-lactic acid) membrane from solvent mixture via immersion precipitation

Poly (L-lactic acid) (PLLA) membranes were fabricated through immersion precipitation method. 1, 4-dioxane (DX), N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethyl-acetamide (DMAc), and DX/NMP, DX/DMF and DX/DMAc were used as solvents severally. With a focus on the PLLA/DX/NMP/H₂O system, the effect of solvent mixture on PLLA membrane was investigated by altering the ratio of DX/NMP. Various membrane morphologies were obtained, which were further correlated by mean of solubility parameter and viscosity of casting solution. It was found that the membrane cast with DX/NMP (1/1) exhibited ideal structure and better performance compared with membranes cast with same concentration of PLLA.     

Hydroprocessing of straight run diesel mixed with light cycle oil from fluid catalytic cracking,using sulfide NiMo catalyst on zeolite-containing supports

It is proposed that the sulfide NiMo system supported on alumina-SAPO-31 composite (NiMo/Al₂O₃-SAP catalyst) be used to obtain high-quality diesel fuel from a mixture of straight run diesel (SRGO) and light cycle oil (LCO) produced by fluid catalytic cracking (FCC). It is shown that the use of this catalyst ensures the synthesis of diesel fuel of higher quality upon hydroprocessing a feedstock with 30 wt % LCO, compared to the traditional sulfide NiMo/Al₂O₃ or CoMo/Al₂O₃ catalysts. It is found that the content of aliphatic hydrocarbons is raised in the products of hydrotreatment, compared to the initial feedstock. This confirms the ability of NiMo/Al₂O₃-SAP catalyst to facilitate the reaction of ring opening. Using the proposed catalyst should improve the quality of diesel fuels obtained via the hydroprocessing of LCO-containing feedstock.