Study of cracking FCC naphtha in a secondary riser of the FCC unit for maximum propylene production

To satisfy the increasing propylene demand, reprocessing FCC naphtha in a secondary riser of the FCC unit was investigated. To this aim, a full range FCC naphtha was cracked over a mixture of two kinds of commercial equilibrium FCC catalysts, which contained 95 t.% Y zeolite-based catalyst and 5 wt.% ZSM-5 zeolite-based additive. The effects of operating parameters such as reaction temperature (temperature of the riser outlet), catalyst-to-oil ratio and residence time on FCC naphtha cracking were studied in a continuous pilot plant. This work demonstrates that FCC naphtha requires high operating severities to crack, and approximately 12–19 wt.% FCC naphtha can be transformed into propylene. The conversion and yield of propylene showed a rapid increase with increasing reaction temperature, and the increase of catalyst-to-oil ratio also enhanced FCC naphtha cracking, even at high reaction temperature. However, at high catalyst-to-oil reactions, hydrogen-transfer reactions constrain further increases in light olefin yields. At these high operating severities, shortening residence time is an appropriate way to obtain high yields of propylene combined with (i) lower yields of dry gas and (ii) a lower apparent hydrogen-transfer coefficient.     

Integration of the Total Petrochemicals-UOP olefins conversion process into a naphtha steam cracker facility

Integration of the Total Petrochemicals-UOP olefins conversion process (OCP) into a conventional naphtha steam cracker allows maximizing the propylene to ethylene yield ratio while converting olefinic feedstocks such as Raf 2, Raw C4s, HT Raw C4s and light FCC gasoline.

Comparisons are made between the product yields obtained from these olefinic streams through conventional steam cracking, and the combined yields when the olefinic feedstocks are first converted on an OCP process and the C4+ product further processed on a steam cracker furnace

OCP as a feed-pretreatment for steam cracking of olefinic feedstocks allows shifting the P/E ratio in the global product slate to values well outside the normal ranges observed on SR naphtha. In an existing steam cracker that is furnace limited, the concept may permit to increase the propylene yield dramatically. The highest potential is observed when the plant has no other option than to recycle crack the Raw C4s.     

灵活多效催化裂化工艺及其工业应用

灵活多效催化裂化技术采用并联双提升管反应器及相应的工艺条件,选择性地控制裂化、氢转移等反应,实现了降低汽油烯烃和硫含量、增产丙烯的目的。工业应用结果表明,该工艺可使汽油烯烃体积分数降低至16%以下,硫质量分数降低22%~24%,研究法和马达法辛烷值分别提高1~2个单位,催化裂化装置的丙烯产率提高2~3个百分点。     

催化裂化汽油的二次反应

从降烯烃、降硫和增产丙烯的现实需要出发,分析了FCC汽油二次反应中的理想和非理想反应.用小型提升管催化裂化实验装置考察了FCC粗汽油在REUSY、ZRP和MO-REY沸石催化剂上二次反应的产品分布和改质汽油组成;探讨了操作强度对二次反应转化率和选择性的影响.结果表明：在Y型或ZRP沸石催化剂作用下,FCC汽油二次反应不仅产生更轻的干气和富含丙烯的液化气,也产生更重的柴油和焦炭.二次反应得到的改质汽油与原料汽油相比,其烯烃含量和硫含量降低,芳烃含量和辛烷值明显提高.二次反应的转化深度和选择性取决于原料汽油的烯烃含量、催化剂沸石类型和操作强度.     

Data analysis, modeling and control performance enhancement of an industrial fluid catalytic cracking unit

Considerable fluctuations were observed in the riser temperature of one of the fluid catalytic cracking (FCC) unit of a Southeast Asian refinery. This undesired occurrence has an adverse effect on the performance of the process unit. In the present study, several statistical tools are developed and then used, for the first time, for analyzing routine operating data in order to characterize the dynamics of the riser temperature and other critical variables that may be affecting the riser temperature. Subsequently, a first-principles-based dynamic model of the FCC unit is implemented to closely simulate the FCC unit under investigation. The model is validated by predicting the measured operating data of the FCC unit. This facilitated an in-depth study of the FCC unit, leading to the identification of several strategies for improving the control loop performance of the riser temperature.     

INTEGRATING ALBEMARLE RESOLVE DESULFURIZATION TECHNOLOGY WITH NOVEL PETRO-CANADA PROCESS CONCEPTS IN COMMERCIAL FCCU OPERATIONS

The gasoline and distillate sulfur regulations promulgated throughout the world to reduce tail-pipe emissions are now strongly impacting refinery operations and investments. FCC gasoline is recognized as the principal contributor of sulfur to the gasoline pool and has become the focus for meeting the new specifications. The difficulty in removing sterically hindered sulfur species in the fluid catalytic cracking unit (FCCU) cycle oil drives up the hydrogen and investment costs for treating the distillates. Although installation of pre- and post-treatment facilities is planned by many refiners, other non-capital approaches such as undercutting are being evaluated to meet interim and future sulfur levels. Even when expensive treatment facilities are installed, operating costs can be lowered and the flexibility of the facility increased with improvements in the ability to remove sulfur in the FCCU. In this article, we detail Petro-Canada's experience in integrating Albemarle's RESOLVE sulfur reduction technology with a combination of innovative process ideas. These concepts include heavy naphtha recycle, coprocessing of hydrogen donor feeds, and recycle of light cycle oil (LCO) to a specially designed stripper reactor. Special attention is paid to the interaction of deep FCC feed hydrodesulfurization with the FCC performance. The results demonstrate that very low FCC gasoline sulfur levels can be achieved without significant capital investment through novel approaches to recycle, creative integration of cat feed hydrotreating unit (CFHTU)-FCCU designs and operations, and application of state-of-the-art sulfur reduction additive technology. An added benefit of the RESOLVE 950 sulfur reduction technology is the substantial elimination of sulfur oxides in the FCC flue gas. This has been observed in Petro-Canada operations and numerous other RESOLVE 950 applications around the world.     

INTEGRATING ALBEMARLE RESOLVE DESULFURIZATION TECHNOLOGY WITH NOVEL PETRO-CANADA PROCESS CONCEPTS IN COMMERCIAL FCCU OPERATIONS

The gasoline and distillate sulfur regulations promulgated throughout the world to reduce tail-pipe emissions are now strongly impacting refinery operations and investments. FCC gasoline is recognized as the principal contributor of sulfur to the gasoline pool and has become the focus for meeting the new specifications. The difficulty in removing sterically hindered sulfur species in the fluid catalytic cracking unit (FCCU) cycle oil drives up the hydrogen and investment costs for treating the distillates. Although installation of pre- and post-treatment facilities is planned by many refiners, other non-capital approaches such as undercutting are being evaluated to meet interim and future sulfur levels. Even when expensive treatment facilities are installed, operating costs can be lowered and the flexibility of the facility increased with improvements in the ability to remove sulfur in the FCCU. In this article, we detail Petro-Canada's experience in integrating Albemarle's RESOLVE sulfur reduction technology with a combination of innovative process ideas. These concepts include heavy naphtha recycle, coprocessing of hydrogen donor feeds, and recycle of light cycle oil (LCO) to a specially designed stripper reactor. Special attention is paid to the interaction of deep FCC feed hydrodesulfurization with the FCC performance. The results demonstrate that very low FCC gasoline sulfur levels can be achieved without significant capital investment through novel approaches to recycle, creative integration of cat feed hydrotreating unit (CFHTU)-FCCU designs and operations, and application of state-of-the-art sulfur reduction additive technology. An added benefit of the RESOLVE 950 sulfur reduction technology is the substantial elimination of sulfur oxides in the FCC flue gas. This has been observed in Petro-Canada operations and numerous other RESOLVE 950 applications around the world.     

催化汽油改质降烯烃多产丙烯反应规律的研究

在小型固定流化床实验装置上,以燕山石化催化汽油为原料,对催化汽油改质过程进行了实验研究,并对反应过程气体产品和液体产品的组成进行了详细分析,考察了反应温度、重时空速、剂油比以及催化剂的活性对改质过程产物分布的影响,发现在催化汽油改质过程中,各操作条件对改质过程产物分布均有不同程度的影响,通过选择合适的操作条件,在保证低烯烃含量的同时,实现多产丙烯是可行的,在适宜的条件下,汽油烯烃体积分数可降到11.8%,同时,液化气中丙烯质量分数达到了44.4%.     

影响FCC再生立管输送催化剂影响因素的分析

再生立管是FCC装置再生器和提升管反应器之间再生催化剂循环的输送管,其操作复杂性在于立管内催化剂的流态受多种因素影响。本文中在1.0Mt/a FCC装置上,通过测量立管改造前后不同操作条件时的轴向压力分布,考察再生立管输送催化剂的影响因素。生产运行结果表明,影响立管操作的主要因素包括催化剂密度和平均粒径、立管几何结构、滑阀安装位置、松动风性质和流量等;选用低密度催化剂和高黏度流化介质可以减小气泡尺寸,维持反应温度稳定;松动风流量应根据立管推动力、滑阀压降和反应温度及时调整,避免填充流。另外,立管结构和滑阀的安装位置对立管推动力影响较大,分析结果可供立管设计和装置改造参考。     

Enhancing the Production of Light Olefins by Catalytic Cracking of FCC Naphtha over Mesoporous ZSM-5 Catalyst

The enhanced production of light olefins from the catalytic cracking of FCC naphtha was investigated over a mesoporous ZSM-5 (Meso-Z) catalyst. The effects of acidity and pore structure on conversion, yields and selectivity to light olefins were studied in microactivity test (MAT) unit at 600 °C and different catalyst-to-naphtha (C/N) ratios. The catalytic performance of Meso-Z catalyst was compared with three conventional ZSM-5 catalysts having different SiO₂/Al₂O₃ (Si/Al) ratios of 22 (Z-22), 27 (Z-27) and 150 (Z-150). The yields of propylene (16 wt%) and ethylene (10 wt%) were significantly higher for Meso-Z compared with the conventional ZSM-5 catalysts. Almost 90% of the olefins in the FCC naphtha feed were converted to lighter olefins, mostly propylene. The aromatics fraction in cracked naphtha almost doubled in all catalysts indicating some level of aromatization activity. The enhanced production of light olefins for Meso-Z is attributed to its small crystals that suppressed secondary and hydrogen transfer reactions and to its mesopores that offered easier transport and access to active sites.     

Effect of feed atomization on FCC performance: simulation of entire unit

Entire fluid catalytic cracking (FCC) unit, comprising of a riser and a regenerator, is simulated by integrating FCC riser model presented in our earlier work (Chem. Eng. Sci. 56 (2001) 4489) with an FCC regenerator model. The effect of feed atomization (quantified by average drop size generated by the feed nozzle) on the performance of the unit is evaluated.     

Steady state multiplicity in an UOP FCC unit with high-efficiency regenerator

The possibility of existence of multiple steady states in fluid catalytic cracking (FCC) units has a major impact in the supervision of these systems. The origins of these behaviours are usually due to the exothermicity of the catalyst regeneration reactions and to the strong interactions between the reactor and the regenerator system.Prior work has focused on modelling and control problems of different operating FCC units. However, none of these studies have considered a high-efficiency regenerator. This paper presents an analysis of the existence of output and input multiple steady states in an UOP FCC unit with a high-efficiency regenerator.The influence of unit disturbances and model uncertainties, such as coke composition and cracking enthalpy, in the output multiplicity, was studied and the results show that the high-efficiency regenerator exhibits at least three multiple output steady states and a maximum of five output steady states, in the operating range considered. Moreover, the state multiplicity analysis revealed that input multiplicity can be present in this FCC unit, depending on the choice of the control structure, and that operating the unit in full combustion mode can prevent instabilities due to input and output multiplicities. Therefore, these results can be used to guide the design of the most appropriate control structures in industrial applications. For the FCC unit with high-efficiency regenerator the most appropriate control structure corresponds to the control of the riser reactor temperature and the oxygen level in the flue gas, with the catalyst circulation rate and the combustion air flow rate, respectively.     

混合蜡油加氢处理改善催化裂解产品质量

原油劣质化后,要生产符合环保要求的清洁燃料,一种经济合理和行之有效的途径就是采用催化裂解原料加氢预处理技术,通过改善催化裂解原料,来降低燃料硫含量,提高催化裂解产品的质量。     

提升管与气-固环流床层耦合反应器的流体力学特性及流动模型

针对催化汽油辅助反应器改质降烯烃技术,在一套提升管与气-固环流床层耦合反应器大型冷模实验装置上,研究了上部环流床层的流体力学特性。结果表明,在环流床层与提升管耦合操作的情况下,床层内颗粒环流存在两种推动力,分别为静压差推动力和颗粒喷射推动力;环隙与导流筒之间的整体平均固含率差随导流筒表观气速增加而增加,随颗粒外循环强度增加而降低;颗粒环流速度随导流筒表观气速和颗粒外循环强度增加而增加。通过对环流床层进行动量衡算,建立了提升管与环流床层耦合流动的数学模型,模型平均相对误差在15.95％以内。     

Olefins and BTX-production by thermal cracking of hydrotreated vacuum gas oil and related fractions

Aramco vacuum gas oil was catalytically hydrotreated to conversions of 20, 40 and 60%, and subsequently fractionated into naphtha, kerosene, gas oil, and hydrotreated vacuum gas oil. These fractions were thermally cracked to test their potential as feedstock for olefins and BTX production. The olefin yields from the hydrotreated vacuum gas oil obtained from hydrotreating with 40 and 60% conversion favorably compare with those of straight-run naphthas. Cracking in conventional naphtha/atmospheric gas oil units becomes possible. The naphtha, kerosene and gas oil fractions are preferably added to standard refinery streams.     

提升管-流化床耦合反应器颗粒约束返混区的流动特性及约束作用分析

针对催化汽油辅助反应器改质降烯烃工艺,在一套提升管-流化床耦合反应器大型冷态实验装置上,系统研究了提升管出口段的颗粒流动特性,通过定义约束指数R_i（R_i为颗粒约束返混区实际截面平均固含率与理论截面平均固含率之比）定量反映提升管出口分布器及流化床层的约束作用。结果表明,与常规提升管相比,耦合反应器提升管出口存在一个颗粒约束返混区,其长度主要受表观气速、颗粒循环强度及上部流化床内颗粒静床高度影响;由于出口设置了倒锥形分布器,使得颗粒约束返混区靠近提升管出口区域在表观气速较低和颗粒循环强度较大时,局部固含率最大值出现在量纲 1半径Φ＝0.7处;颗粒约束返混区的约束指数在靠近出口的过程中逐渐增大,气固流动受到分布器及上部流化床层的约束作用亦逐渐增强。     

催化裂化装置回炼加氢石脑油对产品的影响

加氢石脑油作为催化裂化装置急冷油进入提升管进行回炼,对回炼加氢石脑油期间产品分布和产品性质有较为明显的影响。干气、液化气和柴油收率明显下降,汽油收率明显升高,汽油辛烷值和芳烃含量也呈下降趋势,稳定汽油有效烯烃含量明显降低,对醚化反应操作有较大的影响。通过分析催化裂化装置回炼加氢石脑油对产品分布和产品性质的影响,为未来生产调整提供数据参考。     

Downer reactor: From fundamental study to industrial application

Downer reactor, in which gas and solids move downward co-currently, has unique features such as the plug-flow reactor performance and relatively uniform flow structure compared to other gas-solids fluidized bed reactors, e.g., bubbling bed, turbulent bed and riser. Downer is therefore acknowledged as a novel multiphase flow reactor with great potential in high-severity operated processes, such as the high temperature, ultra-short contact time reactions with the intermediates as the desired products. Typical process developments in industry have directed to (1) the new-generation refinery process for cracking of heavier feedstock to gasoline and light olefins (e.g., propylene) as by-products; and (2) coal pyrolysis in hydrogen plasma which opens up a direct means for producing acetylene, i.e., a new route to synthesize chemicals from a clean coal utilization process. This paper is to give a comprehensive review on the development of fundamental researches on downer reactors as well as the particular industrial demonstrations for the fluid catalytic cracking (FCC) of heavy oils and coal pyrolysis in thermal plasma.     

Laboratory evaluation of the impact of the addition of resid in FCC

The conversion and product distributions from a mixture of 10% atmospheric tower bottom resid and a DO hydrocarbon cut similar to LCO that represented commercial feedstocks were assessed over two equilibrium commercial FCC catalysts in a laboratory CREC Riser Simulator reactor. The reaction temperature was 550 °C, the catalyst to oil ratio was 5.8 and the reaction times were up to 25 s. The conversion of the mixture as compared to the DO base feed was higher in the case of the most active, conventional catalyst, and remained very similar on the resid catalyst. Since the yields of the main hydrocarbon groups dry gas, LPG, gasoline and coke followed very similar trends when the two pure feedstocks were converted, the corresponding yields from the mixture also obeyed that behaviour, and were the consequence of the conversion reached. The impact of the different catalyst formulations was observed in, for example, the selectively different yields obtained from the conversion of the resid, and in the composition of the gasoline. Independently of the catalyst, the gasoline was more olefinic and less aromatic when the resid was present. It was shown that in order to evaluate properly a given combination of feeds, catalysts and conditions, they must be considered together.     

催化裂化多产丙烯

丙烯作为重要的基本有机化工原料, 其市场需求快速增长, 除蒸汽裂解工艺外, 流化催化裂化(FCC)是丙烯生产的另一重要来源。本文主要综述了国内外开发并应用的一系列催化裂化多产丙烯的工艺技术, 着重介绍了各生产工艺技术的特点、产品分布及其工业应用情况, 并从催化剂、操作条件和反应器三个方面对催化裂化多产丙烯的影响因素进行了分析。FCC多产丙烯工艺与常规FCC工艺相比较表明, 丙烯收率均有较明显的提高, 并指出通过FCC工艺技术改造增产丙烯已是重要技术路线。