Using hybrid neural networks in scaling up an FCC model from a pilot plant to an industrial unit

The scaling up of a pilot plant fluid catalytic cracking (FCC) model to an industrial unit with use of artificial neural networks is presented in this paper. FCC is one of the most important oil refinery processes. Due to its complexity the modeling of the FCC poses great challenge. The pilot plant model is capable of predicting the weight percent of conversion and coke yield of an FCC unit. This work is focused in determining the optimum hybrid approach, in order to improve the accuracy of the pilot plant model. Industrial data from a Greek petroleum refinery were used to develop and validate the models. The hybrid models developed are compared with the pilot plant model and a pure neural network model. The results show that the hybrid approach is able to increase the accuracy of prediction especially with data that is out of the model range. Furthermore, the hybrid models are easier to interpret and analyze.     

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.     

LHO-1和CDC型重油裂解降烯烃催化剂的性能评价

利用XTL-5型提升管中试装置,对LHO-1和CDC型重油裂解降烯烃催化剂的裂化性能进行了评价。结果表明, 与参比催化剂相比,LHO-1和CDC型重油裂解降烯烃催化剂具有较强的重油转化、降烯烃和芳构化能力。     

Catalytic conversion of vegetable oils in a continuous FCC pilot plant

In this paper the influence of admixtures of rapeseed, soybean and palm oil into VGO on FCC performance has been studied. The oils were mixed in steps of 20 wt.% and tested in a fully continuous operated FCC pilot plant. The experiments show that the product distribution changes slightly. Higher ratios of vegetable oils hardly affect the gasoline yields but cause a decrease in cracking gas. Oxygen contained in the vegetable oils is converted predominantly to water. It has been demonstrated that the obtained gasoline is oxygen free and shows improved properties for RON and MON. The cracking gas contains high amounts of propene and ethene, which can be used as base materials for the production of synthetic materials from renewable sources.     

Integrated FCC riser—regenerator dynamics studied in a fluid catalytic cracking pilot plant

In this paper a dynamic simulator of the fluid catalytic cracking (FCC) pilot plant, operating in the Chemical Process Engineering Research Institute (CPERI, Thessaloniki, Greece), is presented. The operation of the pilot plant permits the execution of case studies for monitoring of the dynamic responses of the unit, by imposing substantial step changes in a number of the manipulated variables. The comparison between the dynamic behavior of the unit and that predicted by the simulator arise useful conclusions on both the similarities of the pilot plant to commercial units, along with the ability of the simulator to depict the main dynamic characteristics of the integrated system. The simulator predicts the feed conversion, coke yield and heat of catalytic reactions in the FCC riser on the basis of semi-empirical models developed in CPERI and simulates the regenerator according to the two-phase theory of fluidization, with a dilute phase model taking account of postcombustion reactions. The riser and regenerator temperature, the stripper and regenerator pressure drop and the composition of the regenerator flue gas are measured on line and are used for verification of the ability of the simulator to predict the dynamic transients between steady states in both open- and closed-loop unit operation. All the available process variables such as the reaction conversion, the coke yield, the carbon on regenerated catalyst and the catalyst circulation rate are used for the validation of the steady-state performance of the simulator. The comparison between the dynamic responses of the model and those of the pilot plant to step changes in the feed rate and preheat temperature reveals the ability of the simulator to accurately depict the complex pilot process dynamics in both open- and closed-loop operation. The dynamic simulator can serve as the basis for the development of a model-based control structure for the pilot plant, alongside its use as a tool for off-line process optimization studies.     

催化裂化金属钝化剂的研究

催化裂化过程中沉积在催化剂上的重金属会导致催化剂严重失活,文中叙述了重金属污染危害及减少污染的几种方法。在研究有害金属对催化裂化催化剂污染机理的基础上,分析了钝化剂的作用、钝化机理以及在优化催化剂的使用环境,改善产品分布等方面所起到的积极作用。阐述了重油催化裂化金属钝化剂(钝钒剂、钝镍剂)今后的发展方向。     

FCC催化剂失活与再生

论述了近年来国内外对FCC催化剂失活,特别是中毒和积炭失活的研究现状。重点论述了FCC平衡剂再生利用的发展,并对其前景进行了展望。     

Study of direct and indirect naphtha recycling to a resid FCC unit for maximum propylene production

To satisfy the increasing propylene demand, direct and indirect naphtha recycling schemes around an existing resid fluid catalytic cracking (FCC) unit were investigated. To this aim, light cracked naphtha (LCN), heavy cracked naphtha (HCN) and a PolyNaphtha (PN) oligomerisation product were cracked under a wide range of operating conditions over a commercial Y zeolite based equilibrium catalyst. Experimental data were acquired in three different units: a fixed bed bench scale unit, a fixed fluidised bed unit and an adiabatic circulating fluidised bed pilot plant. It was shown that FCC naphthas require high operating severities to crack, and that even then their conversion remains relatively moderate. Hence, direct recycling to the main riser does not seem a viable pathway to increase propylene product. Feeding FCC naphthas to a second reaction zone operating at high severity allows to increase the propylene yield in a significant manner. Increasing conversion, however, not only leads to higher LPG and propylene yields, but also results in very high dry gas yields. An alternative scheme was proposed, in which the olefinic C₄ and C₅ fractions are converted into a naphtha fraction through oligomerisation in a dedicated unit before being recracked in the secondary riser. As the highly olefinic oligomerised effluent mainly consist of dimerised and trimerised butenes and pentenes, this feed is more easily cracked and high conversions can be achieved. This indirect interconversion of butenes and pentenes into propylene therefore effectively allows to convert these butenes and pentenes into propylene, resulting in a significant increase in propylene yield. Each of the three main naphtha recycle options (directly to the main riser, directly to a secondary riser or indirectly via a light olefin oligomerisation unit) have been analysed and compared to a base case. In the evaluation of each of these schemes, all heat balance effects, both on the riser and the regenerator side, have been accounted for. The proposed process scheme with an indirect recycle via an oligomerisation unit enhances the already inherent flexibility of the FCC unit. The naphtha recycle can be turned on or off, the second reaction zone can be used to crack naphtha or to crack resid feed to maximise throughput, while the effluent of the oligomerisation unit can be recycled to the FCC unit for propylene production or hydrogenated and sent to gasoline and kerosene pool.     

我国FCC催化剂的发展近况

阐述了国内近几年FCC催化剂在重油催化裂化、汽油降烯烃、脱硫及多产低碳烯烃方面的进展.提高抗重金属污染能力、用中孔沸石代替 ZSM-5小孔沸石及大幅度提高催化剂基质的活性仍是今后研发 FCC催化剂的热点.     

Comparative Study of Flow Structure in Circulating Fluidized Bed Risers with FCC and Sand Particles

The combined influences of particle properties and nozzle gas distributor design on the axial and radial flow structure in two 100 mm i.d., 15.1 m and 10.5 m long risers with FCC and sand particles were investigated by measuring the axial pressure gradient profiles, and the axial and radial profiles of solids concentration. The results show that the nozzle gas distributor design has significant effects on the axial and radial flow structure for the FCC and sand particles. At lower superficial gas velocity of less than 8.0 m/s, the upward gas‐solid flow of the sand particles decelerates in various degrees with the disappearing of the nozzle gas distributor effect. The upward gas‐solid flow of the FCC particles, however, occurs without noticeable deceleration within the range of this study. In the acceleration section, the radial distributions of the local solids concentration of the FCC particles are more uniform than those of sand particles under the same operating conditions; while in the fully developed zone, the sand particles have a more uniform radial distribution than the FCC particles. The gas‐solid flow is first developed in the center region, and then extends towards the wall. The overall flow development in the riser mainly depends on the local gas‐solid flow in the wall region.     

Study of the accessibility effect on the irreversible deactivation of FCC catalysts from contaminant feed metals

Two commercial FCC catalysts were investigated to explore the effect of their different accessibility on the catalyst activity, selectivity and deactivation due to deleterious feed metals (V and Ni). Feed metal Fe was not included in the present study. E-Cats (equilibrium samples from a commercial FCC unit) of both FCC catalysts and the corresponding laboratory-deactivated samples (applying the cyclic deactivation (CD) and the cyclic propylene steaming (CPS) methods) were thoroughly studied. Extensive characterization (XRD, N₂ physisorption, measurement of Akzo Accessibility Index (AAI), SEM-EDS analysis) of all samples was realized to investigate variations in their crucial properties due to metal deposition. Comparison of E-Cats, CD and CPS samples revealed a very different nickel deposition profile over the CPS samples. In all cases, V was homogenously distributed throughout the particle, as expected due to its mobility. Ni–Al mixed phases, observed on the E-Cat samples, were probably formed during ageing and are expected to be inactive. The absence of such phases on the laboratory-deactivated samples can be attributed both to the inability of the two deactivation methods to simulate metal ageing during commercial utilization of the FCC catalyst and the absence of Fe incorporation during laboratory deactivation. All catalytic samples (E-Cats and artificially deactivated FCC catalysts) were evaluated in the laboratory using two bench-scale Microactivity Test (MAT) units of different reactor configuration: fixed-bed (SCT-MAT unit) and fluid-bed (AUTOMAT unit). Similar ranking of the catalysts is achieved when using both units. However, AUTOMAT unit seems to provide a clearer diversification of catalysts with different accessibility. Both laboratory deactivation methods seem to be rather inefficient in simulating the real deactivation, since they are always exaggerating metal effects.     

钒对催化裂化催化剂活性的影响

随着石油加工技术的拓展，二次加工原料使用越来越广泛，但同时带来了重金属对催化裂化催化剂中毒问题。镍对催化裂化催化剂的中毒作用已被国内认识，但钒对催化裂化催化剂的中毒影响尚未引起人们重视。     

催化裂化汽油加氢精制催化剂的研究进展

介绍了催化裂化汽油加氢精制催化剂的种类和研究进展.从活性组分和载体方面分析了不同催化剂的优缺点,并对目前工业FCC汽油加氢精制工艺和催化剂进行了概述.同时对FCC汽油加氢精制催化剂的发展方向进行了展望.     

From waste to best: excellent desulfurization performance of spent FCC catalyst

Fluidized catalytic cracking (FCC) is an important link in heavy oil processing. Industrial FCC catalyst which mainly consists of molecular sieves, substrates and adhesives is used in large quantities every year. Spent FCC catalyst is one kind of hazardous solid waste that is hard to handle. In this paper, we used a spent FCC catalyst as a desulfurization adsorbent, and show that it displays advanced desulfurization property. Furthermore, regeneration experiment showed that calcination was an effective method to remove the sulfides adsorbed in spent FCC catalyst, after four cycles it still owned a high sulfur adsorption ability. The results of metal impregnation indicated that the high ability to remove sulfur in LPG was due to those metals deposited on WC. The sulfur removal further increased by calcination of the spent catalyst since carbon deposition on the catalyst surface which blocked the active sites was minimized by calcination, thus leading an increase in the number of active sites available.     

高岭土型FCC催化剂的特性研究

采用TG-TPD、IR等表征手段和MAT活性测定法研究了以高岭土原位晶化的特殊工艺所制备的各种高岭土型FCC催化剂的特性。结果表明,各种高岭土型催化剂具有酸强度、酸类型和孔分布合理的特点,其结构稳定,并具有优异的抗重金属性能。     

FCC催化剂现状及其发展方向

阐述了国内外FCC催化剂发展现状和未来的发展方向。指出未来FCC催化剂的开发将向抗金属污染能力更强、焦炭选择性更好、基体活性更高和更多使用中孔沸石方向发展。     

新一代全白土型FCC 催化剂LB-2的研究与开发

本文研究了新一代全白土型LB-2 催化剂的制备与性能, 并对已实现工业化生产的LB-2 工业品使用性能进行了评价。使用结果表明, 其性能优于同类工业用催化剂, 催化剂活性高、焦炭选择性好、汽油辛烷值高, 有很强的抗重金属污染性能, 是一种优良的重质油FCC催化剂。     

Pilot synthesis and commercial application in FCC catalyst of MCM-41 zeolite

MCM-41 zeolite in the grade of 600 kg was successfully synthesized and the MCM-41 added FCC catalyst was firstly prepared. The results indicate that the pilot samples of mesoporous Al-MCM-41 bear the typically uniform mesopore structure and considerable acidity and hydrothermal stability. The MCM-41 added FCC catalyst is positively capable to crack heavy oil feedstock, in which the yields of the diesel and lighter oil increased 1.85 and 3.47%, respectively and coke yield decreased 0.29%. Commercial application in FCCU indicate that optimization of nanopores of MCM-41 added faujasite zeolite might result in an industrial process to design novel FCC catalysts.     

废FCC催化剂在LPG吸附脱硫中的资源化利用

金属污染是导致流化催化裂化（FCC）催化剂失活的重要因素,充分利用沉积的重金属是废FCC催化剂资源化的关键。本文将废FCC催化剂引入到轻质油品吸附脱硫领域,以脱除液化石油气（LPG）中的二甲基二硫醚作为考核目标,验证了废FCC催化剂作为脱硫剂的可行性。除去废FCC催化剂表面积炭后,其脱硫性能得到明显改善,在常温、质量空速为4.0h^-1的条件下,LPG中硫化物质量分数从382mg/m³脱除至40mg/m³。镧、铁、镍、钒、钙、锑6种金属在新鲜催化剂和焙烧后废催化剂上的总质量分数从10.2%升高至46.6%,6种金属按照对应含量分别固载在新鲜催化剂上,脱硫效果较未改性新鲜催化剂均有明显提升。验证实验表明,导致FCC催化剂失活的金属具有较高脱硫活性,废FCC催化剂作为轻质油品脱硫剂具备工业前景。     

FCC废催化剂中金属分布规律及赋存状态研究进展

FCC催化剂是当前用量最大的炼油催化剂,FCC废催化剂的综合处理和资源化利用必然会取代现有的填埋处理方式。综述近年来国内外关于FCC废催化剂中污染金属的分布规律及存在形态方面的研究进展。对于FCC废催化剂的处理和利用,明确污染金属分布状态和物质存在形式将有利于处理方案的选择与制定。在各种污染金属元素中,Ni是FCC废催化剂中最为关键的一种污染金属,对于Ni是以何种化合物形式存在,仍有待进一步的研究。