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ISSN: 1091-6466 print/1532-2459 online DOI: 10.1081/LFT-200038172
A Four Lump Kinetic Model for the Simulation of the Hydrocracking Process
G. Valavarasu, M. Bhaskar, and B. Sairam
Research and Development Centre, Chennai Petroleum Corporation Limited, Manali, Chennai, India
K. S. Balaraman
Centre for High Technology, New Delhi, India
Chemical Engineering Department, A. C. College of Technology, Anna University, Chennai, India
Abstract: Hydrocracking is a very important secondary reﬁning process used to convert low value vacuum gas oils into high value fuels. The chemistry of the hydrocracking process is very complex due to the involvement of high molecular weight complex hydrocarbons in the reactions. Process modeling and simulation of the hydrocracking unit is very challenging due to the complexities of chemistry and the process. In the present work, a mathematical model is described to analyze the performance of the hydrocracking process in terms of product yields. A four lump discrete lumping approach is employed with a hydrocracking reaction scheme involving six reactions. The kinetic constants for the reactions were estimated by minimizing the error between the experimental and predicted yields of kinetic lumps. Experimental data reported by Ali et al. (2002) were used to validate the proposed model. The model predictions were found to agree well with the experimental data. The proposed model can be used to simulate the performance of commercial hydrocrackers using kinetic parameters estimated from pilot plant experiments. Keywords: hydrocracking, discrete lumping, simulation, kinetics
Received 4 March 2004; accepted 8 July 2004. Address correspondence to G. Valavarasu, Research and Development Centre, Chennai Petroleum Corporation Limited, Manali, Chennai 600 068, India. E-mail: email@example.com 1323
Generally. . and the hydrogenation components include noble metals like Pt. aromatics. it becomes essential to develop process models to simulate the performance of hydrocrackers. A typical process ﬂow diagram of the hydrocracking unit is given in Figure 1. including various reactions. etc.1324 G. such as hydrogenation-dehydrogenation. paring reaction and ring saturation. like studying the effect of operating parameters such as reactor temperature. etc. Valavarasu et al. isomerization. the cracking components include silica/ alumina or zeolite. Hydrocracking employs a dual function catalyst with both cracking and hydrogenation components. The versatility and ﬂexibility of the process makes it economically attractive to process different types of feedstocks to yield various product slates. These models can be used to predict the individual product yields and product qualities and for sensitivity analysis. W. hydrogen transfer. Co. Hydrocracking units produce very clean middle distillate products with minimum impurities. or diesel. Process ﬂow diagram of once-through hydrocracking process. INTRODUCTION The environmental regulations to improve the quality of petroleum fuels led to the development of hydrocracking as a major reﬁning process. and non-noble metals like Ni. Because hydrocracking is becoming a prominent reﬁning process of choice in modern petroleum reﬁneries. and dealkylation.. Pd. The hydrocracking of petroleum fractions involves complex chemistry. pressure. Modeling and simulation of hydrocracking units is a difﬁcult task due to the complex hydrocracking reaction kinetics. gasoline. Mo. ring opening. disproportionation. Hydrocracking units can take up feedstocks ranging from naphtha to heavy residues and produce products like LPG. space Figure 1. jet fuel. C−C bond scission. such as sulfur. etc.
and continuous lumping. Strangeland and Kittrell (1972) developed different hydrocracker models based on the discrete lumping approach. Some researchers viewed hydrocracking chemistry of petroleum fractions with respect to the hydrocracking of a set of model compounds or pseudo compounds. which used analogy of cracking with comminution of particles to develop a correlative method for predicting the entire TBP curve of the product for a speciﬁed set of operating conditions. Because the hydrocracking process involves various reactions and components. the discrete lumping approach was developed initially to describe the hydrocracking chemistry and kinetics. researchers have studied the hydrocracking process with different modeling approaches. structure-oriented lumping. design of new units. They developed models based on some form of lumping of the compound types present in the feedstock and products (e. This is a simplistic model with a minimum number of parameters. and selection of suitable hydrocracking catalysts. The accuracy of discrete lumping models lies in the number of kinetic lumps chosen to analyze the reactions.) and devised various series and parallel reactions for the hydrocracking reaction scheme. Several approaches. one that considers hydrocracking analogous to axial dispersion. the various individual reactions involved have been lumped and viewed as an overall hydrocracking reaction. To simplify the hydrocracking process and to develop simple models. In all the discrete lumping models.. They used TBP of the reaction mixture as a characterization parameter and reformulated the mass balance equations in terms of rate constant as a continuous variable. Lakshminarasimhan et al. etc. naphtha. The models can also be used for process optimization and control. (1996) developed a mathematical model to represent the hydrocracking process based on continuous lumping approach. They used a novel distribution function to determine the fractional yield distribution of species and formulated integrodifferential equations to obtain yields of various fractions as a function of reactor residence time. on product yields and qualities.. This model requires complex mathematical procedures to solve the resulting integrodifferential equations.Four Lump Kinetic Model for the Hydrocracking Process 1325 velocity. jet fuel. etc. Various experimental yield distribution data on hydrocracking of several model compounds have been generated and used as guiding factors for analyzing the chemistry of hydrocracking (Sullivan et al. 1964). which results in the distribution of a particular lump of a heavier petroleum fraction into lighter lumps. have been developed over the past few decades. lumps of LPG. it is not possible to keep track of all the possible reactions and reaction mechanisms occurring simultaneously in the reactor. like sophisticated model compounds. diesel. Strangeland (1974) suggested a better and simpler approach for modeling hydrocracking kinetics. Based on the product distribution patterns generated.. . Krishna and Saxena (1989) suggested a different approach.g.
Gas (0–32◦ C) Naphtha (32–150◦ C) Middle Distillates (150–343◦ C) VGO Feed (343◦ C+) The kerosene and diesel fractions were lumped together as middle distillates. can be written as follows: dCF = −(k1 + k2 + k3 )CF dt dCMD = k1 CF − k4 CMD − k5 CMD dt dCN = k2 CF + k4 CMD − k6 CN dt dCG = k3 CF + k5 CMD + k6 CN dt (1) (2) (3) (4) . a four lump mathematical model was formulated with six signiﬁcant reactions among them. Valavarasu et al. In the present work. 2. The proposed reaction scheme for the hydrocracker model is represented as follows: This reaction scheme was developed based on the available information on the chemistry and kinetics of the hydrocracking process. 4. and naphtha. These four lumps are considered to undergo six reactions to yield different product yield patterns. any given lump reacts to give all the products boiling below it. middle distillates. 3. for the case of plug ﬂow.1326 G. The proposed model takes the following kinetic lumps into consideration: 1. The structure of the mathematical description of the hydrocracking process in accordance with the preceding reaction scheme. MODEL FORMULATION In the present work. This reaction scheme takes into account the reactions of the feedstock.
0236 0.0333 0.1 wt% of VGO (343◦ C+) and 8. and 5. was minimized using a standard optimization procedure.4285 × 104 /RT ) 1.0 h−1 are presented in Table 2 and Figure 2.9366 × 104 /RT ) 4. Ali et al. The data generated for the effect of operating temperature on the product yields at a constant space velocity of 1.Four Lump Kinetic Model for the Hydrocracking Process 1327 There are four differential equations to describe the conversion of each of the kinetic lumps with six kinetic constants. Solving these equations with the initial product distribution as boundary conditions will yield the product distribution at various reaction times.9559 × 104 /RT ) 4. The estimated kinetic constants are presented in Table 1. (2002) have generated extensive data on the hydrocracking of heavy vacuum gas oil using amorphous silica-alumina and zeolites as catalyst supports.9 wt% of middle distillates (150–343◦ C). The kinetic constants for the model were estimated by minimizing the error between experimental data and predicted values of product yields. The error function deﬁned to estimate these parameters. (2002) has 91. Kinetic parameters for the proposed hydrocracking reactions Kinetic parameter (h−1 ) k1 k2 k3 k4 k5 k6 Kinetic expression 1.1627 × 104 /RT ) k at 410◦ C 0.4232 × 1012 Exp(−4.6665 × 1012 Exp(−3. The hydrocracking reactions are considered to be isothermal. It is assumed that a particular lump yields all the products boiling below it.5902 × 104 /RT ) 85. The vacuum gas oil (VGO) feedstock used in the work of Ali et al. MODEL ANALYSIS In recent years.2094 × 1013 Exp(−4.1577 0. (Y exp −Y pred)2 . The model equations were solved to generate data on the effect of reaction time (inverse of liquid hourly space velocity) and temperature on product yields. 395◦ C.3508 × 1014 Exp(−4. The experimental data reported by Ali et al.1715 Exp(−1. Table 1.7755 × 104 /RT ) 1. and 410◦ C) are shown in Figures 3.0160 . 4. The effect of reaction time on the product yields for various temperatures (380◦ C.4462 0. The axial dispersion and mass transfer effects are neglected in the present work. (2002) for the USY-ASA/NiMo catalyst at three different temperatures was used to validate the proposed model in the present work.0193 0. Then the model differential equations were solved to obtain product yield distributions at various residence times in the reactor using the estimated kinetic parameters.6868 × 1017 Exp(−5. The ﬂow inside the reactor is assumed to follow plug ﬂow pattern.
93 36.20 19. The yield of middle distillates increased with increasing temperature from 350–430◦ C and then dropped above the temperature of 430◦ C. Effect of Temperature Product Yields The effect of temperature on the yields of various products was studied at a constant LHSV of 1. Effect of temperature on product yields.00 3.21 0. Valavarasu et al. This is due to the increased Figure 2. it is observed that the conversion of feed into naphtha and gas is more temperature sensitive compared to the conversion into middle distillates. Table 2.68 1.84 43. The yield of the VGO feedstock was found to reduce as the temperature increased from 350–450◦ C.24 1.50 83.55 48.89 Middle distillates 11. .99 5.89 72.0 h−1 Product yield (wt%) Temperature (◦ C) 350 370 390 410 430 450 Feed 88.51 43.20 14.59 1. The conversion of middle distillates into naphtha and gas is also more temperature sensitive.0 h−1 using the model.06 0.27 26.06 10.48 From the kinetic parameters. Effect of temperature on product yields at a constant LHSV of 1.98 Gas 0.89 22.66 11.73 50.65 Naphtha 0.1328 G.
Four Lump Kinetic Model for the Hydrocracking Process 1329 Figure 3. . Effect of reaction time at 380◦ C on product yields. i. The predictions of the model were consistent with the general chemistry of hydrocracking reactions. at higher reaction severities. The increase in the yield of naphtha and gas was lower at lower temperatures. Figure 4. rate of secondary cracking reactions of middle distillate fractions above this temperature. indicating high temperature sensitivity of these reactions..e. The yield of naphtha and gas increased sharply with increasing temperature. At higher temperatures the yields of these products was very high. Effect of reaction time at 395◦ C on product yields.
5 67. 395◦ C. such as middle distillates.0 78. the yield of VGO decreased. increased gradually.3 Pred. experimental data is presented in Figure 6.97 1. 1.0 18. Effect of reaction time at 410◦ C on product yields.9 19.3 410 1. while the yield of middle distillates increased sharply initially and then showed a steady value at higher reaction times. (2002) Temperature (◦ C) LHSV (h−1 ) Reaction time (h) Product yields (wt%) Gas Naphtha Middle distillates Feed 380 0. and gas.6 53.4 34. Experimental vs. The proposed Table 3. 0. 0.9 5.5 410 1.6 . At 410◦ C.2 37. predicted yields for the data of Ali et al.9 10.8 10.0417 Exp. 1. The yields of naphtha and gas were found to increase steadily with residence time. This also follows the general trend of hydrocracking reactions. and 410◦ C. naphtha.8 52. Similar trends were observed for 380◦ C and 395◦ C.3 48.0309 Exp. The yield of VGO feedstock decreased with increasing residence time.5 79. Figure 5.4 1.9009 Exp.9 35.3 35. The parity data of the model predictions vs. 0.1 26.2 12.8 69.96 1.9524 Exp.8 10.1330 G.4 2. Valavarasu et al.1 Pred.6 Pred.9 4. 0.1 395 0.7 24. 2. 1.6 51. Effect of Reaction Time on Product Yields The effect of reaction time on the product yield pattern was predicted based on the model output at three different temperatures of 380◦ C. The model predictions were compared with the experimental data used in the present work and shown in Table 3.7 Pred. while the yields of other products.11 0.05 0.
The yield of middle distillates initially increased with residence time and then decreased due to secondary cracking mechanisms. The yield of VGO feed decreased continuously as the reaction time increased. The model was validated with the data of Ali et al. The model can be used for predicting the performance of commercial hydrocrackers. provided kinetic parameters are estimated from pilot plant experiments. The effect of temperature on product yields was studied using the model and found to represent the hydrocracking process.Four Lump Kinetic Model for the Hydrocracking Process 1331 Figure 6. . model was found to represent experimental data satisfactorily with the speciﬁc catalyst and feed system in the range of operating conditions studied. Parity plot for the data of Ali et al. The model can also be used for any catalyst and feed system. while the yields of naphtha and gas increased. The model predictions followed the general trend of the hydrocracking process. ACKNOWLEDGMENT The authors thank the management of Chennai Petroleum Corporation Limited for allowing us to publish this paper. (2002). provided kinetic parameters are determined from pilot plant experiments. CONCLUSIONS A model for the hydrocracking process was developed based on a discrete lumping approach. (2002) and found to ﬁt well with the experimental data in the range of operating conditions studied.
Proc.1332 G. Sullivan. Chem. C. h−1 First order reaction rate constants for the proposed reactions. at time t. A. Jet fuel selectivity in hydrocracking. Tatsumi. Continuous lumping model for simulation of hydrocracking. R. K. CN . Valavarasu et al. Egan. Dev.. 13(1):72. Hydrocracking of alkyl benzenes and polycyclic aromatic hydrocarbons on acidic catalysts. Eng. h REFERENCES Ali. C. . F. NOMENCLATURE F MD N G CF . B. and Kittrell.. Catalysis 3:183–195.. naphtha. Sci. (1964). Kinetic model for prediction of hydrocracker yields. Des. and Langlois. (2002). J. Ind. gas. R. (1972). (1974). Development of heavy oil hydrocracking catalysts using amorphous silica-alumina and zeolites as catalyst supports. Proc. A. and Masuda. M. and Saxena. J. R. Dev. 44:703. B. Applied Catalysis A: General 233:77–90. T. Chem.. (1989). S. J. and Ramachandran. P. h−1 Reaction time. Eng. A. Use of axial dispersion model for kinetic description of hydrocracking. Chem.. Lakshminarasimhan. Verma. E. AIChE Journal 42(9):2645–2653. Krishna. 11(1):15–20. Eng. middle distillates. E. Strangeland. (1996). Des. wt% Liquid hourly space velocity. R. k3 . P. Evidence for cyclization of the side chains. CMD .. Strangeland. k6 t Feedstock VGO Middle distillates Naphtha Gas Concentrations of feedstock. T.. G. respectively. k 5 . k4 . CG LHSV k1 .. Ind. k2 . E.