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Home , Catalytic reforming, Cracking (chemistry), Fluid catalytic cracking

International Journal of Research and Review www.ijrrjournal.com E-ISSN: 2349-9788; P-ISSN: 2454-2237

Review Paper

Review of Catalytic Processes Design and Modeling: Fluid Catalytic Unit and Unit

Mbinzi Kita Deddy Ngwanzaa*, Diakanua B. Nkazi b, Hugues S. Ngwanzac, Hembe E. Mukayad

aSchool of Chemical and Metallurgical Engineering, University of the Witwatersrand, Johannesburg, 2000, South Africa. bSchool of Chemical and Metallurgical Engineering, University of the Witwatersrand, Johannesburg, 2000, South Africa. cDépartement de Chimie et Métallurgie Appliquée, Institut Supérieur des Techniques Appliquées, Lubumbashi, République Démocratique du Congo. dSchool of Chemical and Metallurgical Engineering, University of the Witwatersrand, Johannesburg, 2000, South Africa.

*Corresponding Author: Mbinzi Kita Deddy Ngwanza

ABSTRACT

Catalytic processes are involved in different sectors that influence human life, world economy and environment. Different daily used products depend on catalytic processes: fuel, energy, plastics, cosmetics, pharmaceuticals products, etc. Considering the wide spread application of catalytic processes, and knowing that transport and environment are priority for some researches; this paper is focus on production of fuel (especially ), that needs two important catalytic processes unit: and catalytic reforming. Studies and development of design and modeling of fluid catalytic cracking and catalytic reforming were reviewed in this paper. At last, some paths were lighted in aim to pursue a design and modeling study further. Keywords: Catalytic process, Fluid catalytic cracking (FCC), Catalytic reforming (CR), design, modeling, Gasoline.

INTRODUCTION in different product distribution. That is why It has been many centuries since the we have operation such as decomposition catalyst technology was used in wide some and reforming of others. sectors. Firstly used in 1875 in production Gas and oil is one of the sector need the of , catalyst usage have been most such properties held by catalyst. In developed in several fields such in fact, in refining and production of nitric acid (1903), industries, presence of catalyst is a very synthesis (1908-1914), catalytic cracking important in reforming process for process (1935-1940) that change the energy producing high gasoline, aromatic evolution, catalytic process feedstock and in (Hu, (reforming in 1950) and hydrotreating Su and Chu, 2002). And the process of (1960)(Guwahati, 2014). catalytic cracking is used to convert higher- With the propriety of not altered molecular-weight to lighter. reversible of equilibrium of reactions, and to As ensure by Sadeghbeigi (2012), accelerate both forward and reverse amongst conversion processes cracking is reactions, the presence of catalyst can result the key unit used in modern refinery. The

International Journal of Research & Review (www.ijrrjournal.com) 136 Vol.5; Issue: 11; November 2018 Mbinzi Kita Deddy Ngwanza et.al. Review of Catalytic Processes Design and Modeling: Fluid Catalytic Cracking Unit and Catalytic Reforming Unit primitive way used to crack petroleum crude 1. PROCESS oil was the thermal cracking was, but  FCCU process because increasing of gasoline production Through FCC unit process, crude oil and the need of higher octane number, it has is mixed with a specific catalyst and then been replaced by catalytic cracking (Hug, enters a fluidized bed reactor. About 45% of 1998). More valuable products are obtained all gasoline contained in crude oil is during fluid catalytic cracking of crude oil extracted from FCC and ancillary units. such as gasoline, olefin compounds having a The catalyst used is catalyst (Han, Riggs and Chung, 2000; Barbosa, which behaves like a liquid when it is Lopes, Rosa, Mori and Martignoni, 2013). properly aerated by gas (air) (Sadeghbeigi, Another process that is important for 2012). During feed residence time in the conversion of low-octane into high- reactor, reactions take place on the surface octane without any change of of zeolite and long molecules are cracked numbers in the , is the catalytic into lighter molecules. During cracking of reforming; it has high yield of aromatics long molecules, carbon and other non- production in petroleum-refining and cracked organics components (hydrocarbon) petrochemical industries (Liang, Guo and get deposit over the catalyst causing its Pan, 2005; Taskar, 1996). A couple of deactivation. To remove that from surface conversion reactions (, of catalyst, a stripping is done and produces dehydrocyclization, ) occur in spent catalyst which is taken to regenerator. the process and there is also by-products In the generator the carbon is burned with such as hydrogen and lighter hydrocarbons. air and the regenerated catalyst is then re- A good reforming feed must have high circulated back into reactor beforehand naphtene and aromatic hydrocarbon content. mixing with fresh feed (Stephanopoulos, To reach this paper goal 1984). investigation have been made on different Reactor and regenerator therefore constitute methodologies used by researchers to design the central nerve of FCCU. Beside reactor both unit FCC and CR. That includes the and regenerator there is the riser. Through investigation on the data that must be the riser a preheated feed enter and react provided to assist designer. Knowing that with regenerated catalyst. The feed is then simulation has been developed and vaporized and cracking as soon as the vapor improved during the last decade in refining contacts the catalyst. The process is industry, survey of modeling method was represented in the figure below. done on some studies.

Figure 1. Fluid catalytic cracking process (Farshi, Shayeigh, Burogerdi and Dehgan, 2011) International Journal of Research & Review (www.ijrrjournal.com) 137 Vol.5; Issue: 11; November 2018 Mbinzi Kita Deddy Ngwanza et.al. Review of Catalytic Processes Design and Modeling: Fluid Catalytic Cracking Unit and Catalytic Reforming Unit

 CRU process CRU is fed with Naphtha that passed through adequate hydrotreatment. During reforming, the fee pass over a slow moving bimetallic catalyst bed in a series of adiabatic reactors in presence of hydrogen under low pressure and high temperature conditions. The catalyst is continuously circulated and regenerated in a Regenerator. The product obtained is then stabilized and routed for blending in specific vessel. Some quantity of hydrogen rich gases produced in reformer is recycled to reformer and the rest is sent the naphtha hydrotreatment section or any unit that need hydrogen.

Figure 2. Catalytic reforming process (Raseev, 2003)

2. DESIGN OF CATALYTIC UNIT . Measured variables: riser temperature, Design projects have as goals to regenerator, temperature, reactor meet specific requirement and feasibility of pressure, reactor pressure, wet gas a process by considering sustainability, , regenerator pressure, economy and environment impact of the reactor stripper, total air flow through system build. This study has considered the regenerator, etc. only the technical part which is . Manipulated variables: total feed rate, determination of operating parameters. In preheat temperature, catalyst circulation the next sections, an accent will be put on rates, air flow rate, stack gas variables that are base of each unit design. flow rate, stack gas flow rate, etc. . Disturbance: Variations in feed coking  Fluid Catalytic Cracking Unit characteristics, feed temperature Different studies previously changes, fluctuations in reactor, published (Arbel, Huang, Rinnard, Shinnar pressure, etc. and Sarp, 1995; Grosdidier, Mason, Among those variables, the major operating Aitolhti, Heinnen and Vahamaki, 1993; variables influencing production of FCC Hovd and Skogested, 1993, Monge and there are cracking temperature, catalyst/oil Georgakis, 1987) have suggested several ratio, space velocity, catalyst type and variables that influence FCC process. The activity. To these we can add the quality of following list is giving some of them: the feed. Some of the previous terms are International Journal of Research & Review (www.ijrrjournal.com) 138 Vol.5; Issue: 11; November 2018 Mbinzi Kita Deddy Ngwanza et.al. Review of Catalytic Processes Design and Modeling: Fluid Catalytic Cracking Unit and Catalytic Reforming Unit defined (Rao, 1990; Gary and Handwerk, To obtain RON (Research Octane 2001; Delhi, 2013): Number), there are two types of reactions . Activity: It is the ability to crack a gas that take place during reforming: Desirable oil o lower boiling fractions. reaction (dehydrogenation, . Catalyst/oil ratio: dehydrocyclization, isomerization) which lb catalyst C = gives to higher octane number and to higher O lb feed purity and adverse . Conversion: (hydrocracking, coking, , hydroalkylation,…) reaction which 100 ∗ (volume of feed volume of cycle stock) volumedecreases of feed octane number and the purity of hydrogen (Delhi, 2013). . Cycle stock: Portion of catalytic-cracker The quality and yield of reforming effluent not converted to naphtha and products are affected by following lighter products variables: reaction temperature, space . Efficiency: conversion velocity, reaction pressure, ratio H /HC and . Recycle ratio: 2 feed stock quality (Litle, 1985; Raseev volume recycle volume of fresh feed 2003; Mohan, 2011). The temperature is the most important operating parameter of . Selectivity: It is the ratio of yield of reforming process because by simply raising desirable products to the yield of or lowering reactor inlet temperature, undesirable products ( and gas) operators can raise or lower the ON. The . Space velocity: It may be defined on higher is pressure, the higher is rates of either LHSV (volume) or a WHSV hydrocracking reducing reformate yield. (weight) basis. Lower H2/HC ratio reduces energy costs for −1 LHSV [hr ] compressing and circulating hydrogen and Liquid Hour Space Velocity in volume feed = favours naphtene and Volume ctalyst dehydrocyclisation reactions (1.7 times −1 WHSV [hr ] from C8 to C4, 3.6 times from C4 to C2) Weight Hour Space Velocity in lb feed = (Delhi, 2013). H2/HC ration is given by the lb ctalyst equation below: Catalyst design consists in calculation of hydrogen: Hydrocarbon Ratio weight and deactivation, and catalysts Mples of H in Recycle Gas = 2 parameter and specifications as follows: Moles of Hydrocarbons . Mass of the catalyst at any given time is In order to calculate the catalyst volume or given as follows: weight in each reactor, space velocity is 푚푐푎푡 = 휌퐶푎푡 푉푐푎푡 needed and can be obtained using space Where:푉퐶푎푡 = 푡푐 푄푐푎푡 velocity: 휌퐶푎푡 : Density of the catalyst . Liquid hourly Space −1 푉퐶푎푡 : Volume of the catalyst Velocity: LHSV (hr ) = 푡 : Residence time Volume of Reactor Charge 퐶 Hour 푄푐푎푡 : Flow rate of catalyst Volume of Catalyst . Catalyst deactivation: . Weight Hourly Space Velocity: 퐸 WHSV (hr−1) = 훼 = 훼 푒푅푇 Weight 표 of Reactor Charge Where: Hour Weight of Catalyst 훼표 : Catalyst deactivation coefficient at the Volume of each reactor can be obtained entering temperature using relation propose by Fuente (2015), 훼: Catalyst deactivation coefficient at the where 휀 is an industrial bed void fraction of exit temperature 0.5 as stated by Korsten and Hoffman  Catalytic Reforming Unit (1996):

International Journal of Research & Review (www.ijrrjournal.com) 139 Vol.5; Issue: 11; November 2018 Mbinzi Kita Deddy Ngwanza et.al. Review of Catalytic Processes Design and Modeling: Fluid Catalytic Cracking Unit and Catalytic Reforming Unit

V (m 3) V (m3) = catalyst process design/operating conditions. FCCU reactor 1−ε and CRU are both process that depend on

certain variables which can help to model 3. MODELING OF CATALYTIC UNIT according to the need. As defined by Eykhoff (1974), a Fluid Catalytic Cracking Unit model is a representation of an essential Many modeling work has been published, aspects of an existing system (or designed) each different because of researcher focus. which represents knowledge of that system Some of the researches are represented in in usable form. It has objective to improve the table below: understanding of process and to optimize

Table 1. Summary of some model of FCCU Author(s) Title Outcome Sample of equation used Pahwa and CFD Modeling of FCC The riser is considered as the most Rate equation: 푛 Gupta Riser Reactor import part of FCC process from a 푅푖,푟 = 푘푟 퐶푖 (2016) modeling point of view. Simulation (31) uses Eulerian-Eulerian approach, gas Where, 푘푟 is rate constant for rth cracking reaction, 퐶푖 and solid energy equations and four is concentration of ith species (kmol/m3). lump kinetic schemes. Fadhil Modeling and The riser is considered as a plug flow Concentration profile for gasoline lump: 2012 simulation of FCC reactor incorporating the four lumps dy Aεg∅ρg 2 = [K Y 2 − K + K y ] risers model for kinetics of cracking dz m 1 1 1 1 2 reactions. Catalyst deactivation g

function is calculated based on linear With Kj: Constants of cracking reactions Relationship between the catalyst coke content and its retention activity. Faray and Simulation of Fluid Simplification of the complicated The model used in the present work may be written in Tsai Catalytic Cracking process variables and development of the following form: (1987) operation a computer model to simulate the x C n = F (WSHV)n−1exp⁡(−ERT ) operation of an FCC at different 1 − x O RX conditions, were both objectives of With: this study. The model provides a good n = 0.65 (decay exponent by the model of base for troubleshooting and Wallaston). debottlenecking and may be useful in E: activation energy E, independent of temperature and optimal control of the FCC. catalyst hold-up. F: function coefficient and may be computed from known design conditions. Ahsan Prediction of gasoline Granular Eulerian multiphase model Chemical for gasoline lump: (2013) yield in a fluid catalytic with species transport are dy 1 = −(K +K )Y 2∅ = −K y 2∅ cracking (FCC) riser implemented and predicted in this dt 1 3 1 0 1 using k-epsilon study. The breaking of heavy With Kj: Constants of cracking reactions turbulence and 4-lump hydrocarbon in the presence of kinetic models: A catalyst is demonstrated. An approach computational fluid proposed in this study shows good Dynamics (CFD) agreement with the experimental and approach numerical data. de Modeling of regenerator In this study a model of FCC was The equation below describes the mass balance of the Almeida units in fluid catalytic developed, based on fluidized bed elements present in the coke, typically considered (2016) cracking process reactor, using gPROMS as modeling carbon and hydrogen: language. It has showed the necessity 퐹푐,푖푛 푌푘,푖푛

of combustion of hydrogen in the 푀푊푐푘 퐿푑 regenerator modeling and catalyst 퐹푐,표푢푡 푌푘,표푢푡 flow-rate and air flow-rate as = ΨL zd ΦL zd ρprclk zd ARdzd 푀푊푐푘 0 manipulated variables for regenerator 퐿푑 control. − ΨH zd ΦH zd ρp rchk zd ARdzd 0 퐿푓 − Φ (zf)ρp rck (zf)Ardzf 0

 Catalytic Reforming Unit amongst some researchers who want to find Catalytic reforming process has been collective information on catalytic topic of many investigations. Improvement reforming process due to fact that the of the process is reached either by studying number of articles published is so much the effectiveness of catalysts, or studying (Rahimpour, Jafari and Iranshashi, 2013). kinetics and deactivation, or designing more From 1949 many studies mainly based efficient reactors. There is confusion

International Journal of Research & Review (www.ijrrjournal.com) 140 Vol.5; Issue: 11; November 2018 Mbinzi Kita Deddy Ngwanza et.al. Review of Catalytic Processes Design and Modeling: Fluid Catalytic Cracking Unit and Catalytic Reforming Unit research on three important axes of good production, and should be coupled (Rahimpour, et al., 2013): with reduction catalyst deactivation. Such . For better operational conditions and target may be reached by modifying either higher yield, study of reactor the metal function or the acid function of the configuration and operating mode; catalyst. Addition of a secondary or ternary . For better selectivity, stability and metal component to can modify performance, study on invention and/or metal function (Rahimpour, et al., 2013). investigation of new catalysts; Addition of components to the acid . For better kinetic and less deactivation, function, such as chloride, changes the study of catalytic reforming nature. strength and amount of support acid sites. Studies on catalysts have shown that Kinetic modeling of catalytic catalysts used for catalysts reforming need reforming is a complex problem because of to a bifunctional which consists of a metal all the consideration that has to be taken: (mainly platimium) and an acid function. complexity of the feed (mixture of These functions promote reactions in the hydrocarbon) and multiplicity of reactions process such as , occurring (Marin and Froment, 1982; dehydrogenation, isomerization and Marin, Froment, Lerou and De Backer, cyclization (Benitez and Pieck, 2010; 1983). Benitez, Mazzieri, Especel, Epron, Vera, Thereby, came up ‘‘lumped’’ Marecot, 2007). Adequate balance is then models, in which the large number of needed in order to reach optimum chemical components are classified to production of the process. To be able to smaller set of kinetic lumps. Some steps of optimize such process improvement of the evolution of lumped models throughout stability and selectivity of catalyst is the key the time are retraced in the table below:

Table 2. Some steps of evolution in number of lumped components and number of reactions considered in catalytic naphtha reforming kinetic References Number of reactions Number of lumped component Smith (1959) 4 3 Jenkins and Stephens (1980) 78 31 Saxen, Das, Goyal and Kapoor (1994) 40 22 Padmavathi and Chaudhuri (1997) 48 26 Hu, Su and Chu (2004) 17 17 Weifeng, Hongye, Yongyou and Jian (2006) 17 18 Hongjun, Mingliang, Huixin and Hongbo (2010) 52 27 Wang , L; Zhang Q, Q; Liang, C; (2012) 86 38

Studies on reactor configuration and them can be categorized according to the operational mode have suggested different shape of the reactor and the entrance flow process and reactors. For a process point of pattern of the feedstock as follow view, categorization of catalytic reforming (Rahimpour, et al., 2013): units is done according to the catalyst . Axial-flow tubular reactor; regeneration procedure. This categorization . Radial-flow tubular reactor; proposes three main groups of process . Axial-flow spherical reactor; (Rahimpour, et al., 2013; Bell, 2001): . Radial-flow spherical reactor. . Semi-regenerative catalytic reformer (SRR): the most used around the 4. SUGGESTIONS worldwide; Due to the perpetual need of . Cyclic catalytic reformer; gasoline in the world and environmental Continuo us catalyst regeneration reformer issue that comes with, FCC and CR have to (CCR). be improved. Although myriad of papers Researchers have proposed various reactor have been published on both topics, configurations, each one having different researcher still need investigate on the advantages and disadvantages and all of nature and heat production of reactions

International Journal of Research & Review (www.ijrrjournal.com) 141 Vol.5; Issue: 11; November 2018 Mbinzi Kita Deddy Ngwanza et.al. Review of Catalytic Processes Design and Modeling: Fluid Catalytic Cracking Unit and Catalytic Reforming Unit occurring during processes. That obviously computational fluid. Journal pf King Saud influences yield and production of main University - Engineering Sciences, 27(2013), pp. product. For further studies design and 130-136.  Arbel, A., Huang, Z. P., Rinnard, I. H. & Sarpe, modeling of catalytic process more tests and A. V., 1995. Dynamic and control of fluidized many comparisons are required to asses any catalytic crackers. Modeling of current reactor sized or model developed. Models generation of FCC's. Ind. Eng. Chem., Volume are built with different assumptions that can 34(4), pp. 1228-1243. be parameters to optimize. Further  Barbosa, A. C. et al., 2013. Three dimensional simulation of catalytic cracking reactions in an researches can also be focused on catalyst as industrial scale riser using a 11-lump kinetic. it does not give of volume yield optimal yet. s.l., In AIDIC Conference Series, 11, 31-40. Finally, as crude oil has different  Bell, L., 2001. Worldwide refining. Oil GAs J, p. components, to validate a model required a 46. study of applicability with different  Benitez, V. B. et al., 2007. Preparation of composition of feed. trimetallic Pt–Re–Ge/Al2O3 and Pt–Ir– Ge/Al2O3 naphtha reforming catalysts by surface redox reaction. Appl. catal., pp. 319:210- 5. CONCLUSION 7. For production of gasoline with high  Benitez, V. M. & Pieck, C. L., 2010. Influence octane number, cracking and reforming of of indium content on the properties of Pt– petroleum cut are very important. Element Re/Al2O3 naphtha reforming catalysts. Catal Lett, Volume 136, pp. 45-51. that make possible such production is  de Almeida, M. A. F., 2016. Modeling of actually catalyst. Catalysts play a role key regenerator units in fluid catalytic cracking in favorite process of gas and oil industry. process. Lisboa: Tecnico Lisboa. Among parameters that are used to  Delhi, I., 2013. design FCC, variables that involve catalyst http://petrofed.winwinhosting.net/upload/16- 19March11/Day2/3_V%20Srikanth.pdf.. are the main elements that influence the [Online] design. It is then imperative to keep Available at: • investigating on catalyst as well for design http://petrofed.winwinhosting.net/upload/16- as for modeling. Literature review has 19March11/Day2/3_V%20Srikanth.pdf. shown that fluidized bed reactor is the [Accessed 13 September 2018]. suitable reactor for conversion of gas oils  Eykhoff, P., 1974. System identification: Parameter and state estimation. London: Wiley- into gasoline. Design with optimization of Interscience. configuration of this reactor is then very  Fadhil, W., 2012. Modeling and simulation of important. Design of FCC involves design FCC risers. Iraq: Departement of Chemical of one facility unit (fractionner) as well. As Enginering, University of Technology. FCC, design of CR unit involves design of  Faray, I. & Tsai, K.-Y., 1987. Simulation of Fluid Catalytic Cracking operation.. Department facilities such as furnace, catalyst and of . reactors design.  Farshi, A., Shaiyegh, F., Burogerdi, S. H. & This paper had the objective of Dehgan, A., 2011. FCC process role in investigating the established papers on propylene demands. Petroleum science and catalytic process, especially FCC and CR. technology, Volume FCC process role in Afterward the obtained results shows that propylene demands, pp. pp. 875-885.  Fuente, J. R., 2015. Equipment Sizing and impressive number of studies in both field Costing. In: o. c. ware, ed. Chemical Process have been published and some of them were Design. Cantabria: s.n., pp. pp. 2-30. presented all along this paper. To rule off  Gary, J. H. & Handwerk, G. E., 2001. • James this paper some suggestions were given for H. Gary and Glenn E.Petroleum Refining: further researches. Technology and Economics (4th ed.). ISBN 0- 8247-0482-7 ed. s.l.:CRC Press. 6. REFERENCES  Grosdidier, P., Mason, A., Heinonen, P. &  Ahsan, M., 2015. Prediction of gasoline yield in Vanhamaki, V., 1993. FCC Unit Reactor- a fluid catalytic cracking (FCC) riser using k- Regenerator Control. Comp. and Chem. Eng, epsilon turbulence and 4-lump kinetic models: A Volume 17(2), pp. 165-179.

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How to cite this article: Ngwanza MKD, Nkazi DB, Ngwanza HS et.al. Review of catalytic processes design and modeling: fluid catalytic cracking unit and catalytic reforming unit. International Journal of Research and Review. 2018; 5(11):136-143.

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International Journal of Research & Review (www.ijrrjournal.com) 143 Vol.5; Issue: 11; November 2018