Hydrocracking Kinetics of a Heavy Crude Oil on a Liquid Catalyst

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HYDROCRACKING KINETICS OF A HEAVY CRUDE OIL ON A LIQUID CATALYST Felipe de Jesus Ortega García, José Antonio Muñoz-Arroyo, Patricia Flores Sanchez, Elizabeth Mar Juárez, and Jose Manuel Dominguez Esquivel Energy Fuels, Just Accepted Manuscript • Publication Date (Web): 12 Jun 2017 Downloaded from http://pubs.acs.org on June 13, 2017

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HYDROCRACKING KINETICS OF A HEAVY CRUDE OIL ON A LIQUID CATALYST F.J. Ortega Garcia*, J. A Muñoz Arroyo, P. Flores Sánchez, E. Mar Juárez, J. M. Dominguez Esquivel Instituto Mexicano del Petróleo, Ave. Eje Central Lázaro Cárdenas Norte 152, Col. San Bartolo Atepehuacan, 07730, México, D. F. *Corresponding author, email: [email protected]; phone +52 55 91758538

Abstract Heavy crude oil hydrocracking was carried out in a continuous reactor using a liquid acid catalyst. Experiments were conducted at 100 kg/cm2 pressure, low to moderated reaction temperature (350 and 370 °C) and a hydrogen/hydrocarbon ratio of 10 m3/barrel during 180 hr. Reaction temperature was below typical industrial hydrocracking reactors in order to avoid coke or sediments formation. Experimental results demonstrated that heavy oil was importantly upgraded, hydrocracked oil resulted much less viscous, lighter and with a higher content of valuable distillates than the original heavy crude oil. Kinetics of the process based on a 5 lumps reaction scheme was determined using a modified Marquard-Levenberg optimization technique. The experimental and calculated yield comparison for each of the lumps are in close agreement.

Keywords Heavy crude oil, upgrading, hydrocracking, kinetics, lumps, core reservoir

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Introduction Global energy demand continues to increase at a rapid pace; however, clean energy sources have not been sufficiently developed to replace fossil fuels, which means that at least in the short and medium term, they will continue to be the main source of energy in the world. As conventional oil reserves are depleting, it is necessary to develop technologies to extract and to process heavy oil, of which there are vast reserves in the world [1-2]. Heavy petroleum is characterized by its high viscosity, specific gravity and low content of valuable distillates (naphtha and diesel), as well as a high content of high boiling hydrocarbons such as asphaltenes and resins which also usually contain large amounts of undesirable elements such as sulfur, nitrogen, oxygen and heavy metals (iron, nickel and vanadium) [3]. Heavy oil is not easy to exploit nor to refine, its huge viscosity imposes severe technical and economic constraints, both for its exploitation and its transport to the refining centers it is necessary to use additives, heating or dilution systems, which increase costs and decrease profitability; Also, heavy oil cannot be processed in conventional refineries and should be mixed with lighter oils in proportions that depend on the specific configuration of each refinery. Heavy oil refining demands more severe operating conditions, increases the consumption of catalysts and chemicals, increases corrosion and the amount of contaminants to the treatment and environmental protection systems; all this is also reflected in a lower profitability. Nowadays, there are commercial catalytic hydrocracking processes designed to refine heavy oils, these processes use solid catalysts whose main disadvantage is the rapid deactivation, this implies among other things less profitability due to the high consumption of catalyst as well as problems of supply of fresh catalysts and the disposal of spent catalysts [4]. As an alternative in this work, the results of the hydrocracking of a heavy oil


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using a liquid catalyst are presented, whereby the problems mentioned above would decrease substantially.

Experimental Crude oil characterization Heavy crude oil was obtained directly from the reservoir (Aguacates field, México), whose physical and chemical properties are reported in Table 1.

Catalyst preparation The liquid catalyst used for the experimental evaluation was prepared with 50 ml of demineralized water at 60 °C which were placed in a continuously stirred flask. 1 g of sulfuric acid (H2SO4, from Fermont) was added, thereafter 5 g of ammonium heptamolybdate (NH4 6Mo7O24 4H2O from J T Baker) were incorporated until they were completely dissolved and finally 10 g of nickel sulfate (NiSO4 6H2O, from Sigma-Aldrich) were added and dissolved until a clear emerald green solution was obtained. The solution was aged for 24 hours at room temperature to check for stability. Properties of the catalyst are as follows: Specific gravity @ 15.6 °C/15.6°C 1.198; Viscosity @ 25 °C 1.88 cSt; pH < 1; Nickel, 5.3 wt %; Molybdenum, 4.5 wt %.

Hydrocracking Heavy crude oil was hydrocracked according to the following procedure: 1250 g of heavy oil and 25 g of liquid catalyst were poured into a 1500 cm3 continuous stirred tank reactor (CSTR); the reactor was closed and pressurized with nitrogen up to 120 kg/cm2 to check for hermiticity. Nitrogen was vented and the reactor was pressurized again to 100 kg/cm2 with


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hydrogen. Reactor was heated to 90 °C to melt the oil; at this point the agitator was started and set at 50 RPM. Temperature was then increased at a rate of 100 °C/h to reach the desired reaction temperature, and then the mixture was allowed to react for 180 h. Hydrogen was continuously fed to the reactor at rate of 100 cm3/h and gas product was allowed to leave the reactor to control reactor pressure, it was cooled, separated from entrained liquid in a cold separator, measured and vented to a gas burner. Liquid samples from the reactor and gases from the separator were taken and analyzed every 24 hours to follow reaction progress. Reaction temperature was 350 °C and 370 °C. Catalyst was decanted from the liquid reaction product and analyzed. Physical and chemical properties of the feed and hydrocracked product were determined according to the ASTM methods. API gravity was measured according ASTM-D-287 method; kinematic viscosity was determined by ASTM-D-445. SARA (saturates, aromatics, resins and asphaltenes) analysis were determined by ASTM-D-4124 method. Sulfur content was measured by ASTM-D-4294 method and distillation curves were obtained by ASTM-D-2887 method. To develop and feed the kinetic model a 5 pseudo components reaction network was considered, these pseudo components or hydrocarbon fractions are defined as follows: gases, constituted by C1-C4 hydrocarbons, H2S and NH3; naphtha, constituted by hydrocarbons boiling from C5 up to 221 °C; light gasoil, which is the fraction boiling from 221 to 343 °C; heavy gasoil (GOP), boiling from 343 to 540 °C, and residue, which are hydrocarbons boiling above 540 °C. Yields from each hydrocarbon fraction were calculated from simulated distillation and mass balance. Kinetic modelling. The accurate analytical or numerical modelling of hydrocracking process plays an important role in order to correctly interpret experimental measurements that lead to a


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better understanding and design of industrial scale processes. Most published reaction models are based on a complex approach involving a set of reactions and kinetic rate equations, we adopted the same approach [5-8]. Based on experimental results the hydrocracking reaction system can be described by the scheme depicted in figure 1: Residue is hydrocracked into heavy gasoil, light gasoil, naphtha and gases; heavy gasoil is converted into light gasoil, naphtha and gases; light gasoil is transformed into naphtha and gases; and naphtha is transformed into gases. According with this reaction network and considering pseudo-first order for the reaction rate equations, reaction kinetics can be expressed as follows: =

0 0 0 0 0 0 0 0 = 0 0 0

(1)

K1= -(k1+k2+k3+k4) K2= - (k5+k6+k7) K3=-(k8+k9) (2)

The hydrocarbon fractions mass balance in a CSTR reactor can be expressed as: ἰ =

!(#$% (3) !&

Where % is the reaction rate, V is the crude oil volume in the reactor and the crude oil density, $% the mass fraction of each of the hydrocarbons pseudo-component and & the

time. The mass balances for all hydrocarbon pseudo-component constitute an ordinary differential equation system (ODE) with 10 unknown kinetic coefficients. The kinetic parameters can be determined through the minimization of the following multiresponses objective function:


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1

1

)*+, = - - . /9 0_

/0

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8

-3$4/ − $ 6%0 7 3$%0 − $ 6%0 7 49

(4)

+ :

→

Where . /0 is the inverse error of covariance matrix, elements, n represents the number of experiments, and $ 6/ .is the model value of the l-th response for the h-th experiment defined

as: $ 6 = ? *@4 , + , + C4 (5) This minimization can be achieved through the modified Newton-Gauss technique leading to an iterative cycle. 8

+ :

)*+ , = -3E% − ?(@4 , +7 → (6) %9

These methods are based upon a linearization of the model equation with respect to the parameters by a Taylor series development around an initial guess b0 for +, neglecting all partial derivatives of second and higher order. The resulting set of observation equations is linear in the ∆bj as follows [9]. +++ + ?*@4 , + , = ?(@4 , G

!?(@% , +++ ) I !6H

+ 9JK :

∆G0 (7)

With models that are nonlinear in the parameters, the derivatives in last equation do not lead to the settings x the independent variables, but to ∆GNO = (PQR PQ )S PQR Q (8)

Where


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PQ = UPQVW X = Y

and

!?(@% , +) I !6H

+ 9JZ :

[ (9)

N = $ − ?(@, GN ) (10)

This value will not lead in one step to the minimum. The value ∆GNO is then added to GN and so on, until convergence is achieved. The kinetic parameters estimation was performed using the experimental results at the temperature range, as well as the mass balance for each lump expressed by the NavierStokes equation for a CSTR reactor. The minimization of the objective function was done by a combination of the Runge-Kutta 4th order integration and the Marquard –Levenberg optimization models [10].

Results Crude oil properties, shown in table 1, indicate that this is a heavy crude oil having a specific gravity of 12 API and a viscosity @ 98 °C of 14600 cSt. Distillation data revel that it contains more than 70 wt % of heavy hydrocarbons (37.3 wt % heavy gasoil and 34.3 wt % residue), and less than 30 wt % of valuable distillates (10.6 wt % naphtha and 17.8 wt % light gasoil). About 70 wt % of the residue hydrocarbons are asphaltenes. Sulfur and nitrogen content are very high, 5.3 and 0.36 wt % respectively. This is a heavy crude oil which hardly can be processed in a conventional refinery and even mixed with a lighter oil it will increase the refining costs, since it will require more severe operating conditions, will consume more catalysts and chemicals and will increase corrosion velocities and pollutants emissions.


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Figures 1 and 2 show the evolution of the reaction system as reaction time goes on, in both cases evolution is similar, suggesting that reactions occurring at 350 °C also occur at 370 °C and vice versa. Residue and heavy gasoil concentrations decrease whereas light gasoil, naphtha and gases concentrations increase, concentrations of all hydrocarbon fractions change regularly and no important perturbations are observed. Thus, it can be assumed that in both cases the system is subjected to the same phenomena and may be represented by the same set of equations. As it could be expected, heavy hydrocarbons are transformed into lighter ones by hydrocracking, residue hydrocarbons were transformed at the highest rate, followed by heavy gasoil hydrocarbons; yields of light gasoil and naphtha increases as reaction time goes on, indicating than they are produced at higher rate than they are hydrocracked; gases are produced by hydrocracking of all hydrocarbon fractions, however the low gases yield that those reactions occur at a low rate. At 350 °C and at the end of run, residue was converted by 58 wt % and heavy gasoil by 13 wt %. Light gasoil, naphtha and gases yield increased by 7, 12 and 3 wt % in absolute terms, which means that residue and heavy gasoil were converted into light gasoil by 33 %, into naphtha by 55 % and into gases by 13 %. At 370 °C all hydrocracking rates increased significantly, residue and heavy gasoil conversions were 88 and 79 wt % respectively. Light gasoil yield increased during the first 50 hr, then decreased slightly, indicating that its hydrocracking velocity was higher than its production velocity. Naphtha yield increased to 52 wt % at the end of run, confirming that its selectivity was the highest. At this temperature, heavy hydrocarbons were converted into naphtha by 70 wt %, into light gasoil by 17 wt % and only 13 wt % into gases.


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It is remarkable that no coke nor sediments formation was observed, it is because of the relatively low reaction temperature, which is not enough to promote thermal cracking reactions that produce free radicals which may condense or polymerize to yield coke, nor alpha carbon-carbon scissions that produces methane and ethane and reduces the hydrogen/carbon ratio of heavy hydrocarbons, nor hydrogen transfer reactions from naphthenic rings in resins and asphaltenes that produces poly fuzzed aromatic rings which are associated with sediments or solid hydrocarbons insoluble in toluene. After experiments catalyst was decanted from the hydrocracked product, its properties were different from the fresh catalyst (Specific gravity @ 15.6 °C/15.6°C 1.10, Viscosity @ 25 °C 1.6 cSt, pH < 4, Nickel, wt % 4.2, Molybdenum, wt % 3.1, indicating that some of the acid and some of the metals remained in the reaction product. Tables 2 and 3 show the comparison between experimental and predicted yields according with the reaction scheme model proposed. Except for gases yield, which deviate up to 30 % between predicted and experimental yields, the yields of the other hydrocarbon fractions show a close agreement between experimental and predicted values, a deviation of no more than 3 % for each one of the fractions. This indicates that the reaction scheme model represents well the experimental reaction system. In table 4 the calculated kinetic parameters are summarized. As indicated by experimental data residue is the fraction which shows the highest rate of conversion, followed by heavy gasoil, the sum of the rate constants at which reside converts is higher than the sum of the rate constants at which heavy gasoil is transformed; at 350 °C reaction temperature the global residue rate constant was 0.00661 h-1, higher than the global rate constant of heavy gasoil, which was 0.00581 h-1; at 370 °C reaction temperature, rate constants were 0.00745 and 0.00641 h-1 respectively. Residue rate constants indicate that it is transformed into


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light gasoil at a higher velocity than it is transformed into naphtha or heavy gasoil and much higher that it is transformed into gases. Likewise, heavy gasoil transforms faster into naphtha and light gasoil than into gases. This suggests that carbon-carbon bonds breakage occurs preferentially at the inner bonds of the heavy hydrocarbons (catalytic cracking by beta scission) rather than at the external carbons (thermal cracking by alpha scission), this is consistent with the low experimental reaction temperature. Light gasoil yield is the only fraction that shows an atypical trend at 370 °C reaction temperature, first its yield increases, as reaction time goes on it reaches a maximum and then decreases. Light gasoil is produced by hydrocracking of residue and heavy gasoil, when concentrations of these fractions are the highest, light gasoil production is higher than its consumption, as a result its yield increases. As reaction time goes on, concentration of residue and heavy gasoil decrease and light gasoil production also decreases until a point were consumption rate is higher, it transforms into naphtha and gases, from this point light gasoil yield decreases. Naphtha is the most produced fraction, reaction rates indicate that it is mainly produced by heavy gasoil hydrocracking , followed by light gasoil and residue hydrocracking; when concentration of those fractions decrease its production rate also decreases, but its yield never decreases since its consumption rate (hydrocracking towards gases) is always lower than its production rate. Activation energies indicate that the lowest reaction barrier is that of the transformation of heavy gasoil into light gasoil, only 8.5 kJ/mol, followed by the transformation of heavy and light gasoils into naphtha (19 kJ/mol). The highest activation energy correspond to hydrocracking of residue into gases (58.4 kJ/mol), this can be explained by the low reaction temperatures or because residue contains


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few low chain (C1-C4) branches. This barrier is lower as the molecular structure of the hydrocracked fraction is smaller, 39 kJ/mol for heavy gasoil, 27 for light gasoil and 17.5 for naphtha. Cracking probability at the extremes of the molecule increases as the molecule chain is smaller. Activation energy of residue hydrocracking towards naphtha also shows a very high value (50.4 kJ/mol), suggesting that residue hydrocarbons have very few C5-C11 branches attached to the main structure. Finally, properties of hydrocracked product shown in table 5, clearly indicate that heavy crude oil was successfully hydrocracked into a lighter oil that can be processed in a conventional refinery at a lower cost and producing higher yields of valuable distillates. The kinetics of hydrocracking of heavy oil fractions have been studied by many researchers, each using particular charges and conditions. The reaction schemes proposed in some cases are simple: one or two reactions occurring simultaneously; in others more complex models have been used in which multiple reactions occur, some simultaneously and others in series. For instance, Aboul proposes a scheme of three simultaneous reactions, in which heavy gas oil is transformed into light gas oil, naphtha and gases; Callejas, proposes a very simple scheme, in which the atmospheric residue is simultaneously transformed into light oil and gases; the other researchers use a reaction scheme similar to that used in this work [5,11-15]. In Table 6, the kinetic parameters reported by these authors are presented, the values have been recalculated at a reaction temperature of 350 ° C using the Arrhenius equation. In all cases the proposed models are able to reproduce the particular experimental data satisfactorily. The magnitude of the rate constants reported in this work is in all cases in the range of values reported by other authors and in most cases they are lower indicating a lower


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activity of our catalyst. For example, in our case the constant rate of the transformation of residue into heavy gasoil is 2.45 E-4 h-1, 30 times lower than that reported by Sanchez, Galarraga or Hassan. In some cases, however, the rate constant is higher than that found by the other authors, as is the case of transformation of residue into light gasoil, 6.10 E-3 h-1. It is important to point out that the activation energies found in this work are in all cases smaller than those reported by the other authors, this can be explained by the fact that being our catalyst liquid, diffusional effects are smaller compared with those of supported catalysts; it is clear that in order to improve our catalyst performance it is necessary to improve the activity of the catalytic species.

Conclusions The experimental results have shown an important heavy crude oil conversion level on the liquid catalyst that modify the physical and chemical properties (API gravity and viscosity) as well as the hydrocarbons fractions distribution. Therefore an important increment of the valuable liquid light fractions such as Naphtha and Light gasoil were obtained. The experimental work has allowed to obtain enough information to determine the kinetic parameters for the 5 lumps reaction scheme. The estimated kinetic parameters (Arrhenius parameters) indicate that the hydrocracking is completely carried out on catalytic instead of thermal region. Comparison of kinetic parameters obtained against reported values by some authors indicate that our liquid catalyst is less active than supported catalysts they used, however, activation energies were lower, suggesting that diffusional effects were lower with the liquid catalyst.


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References [1] International Energy Outlook 2016, Report Number: DOE/EIA-0484(2016), May 11, 2016 [2] F. J. Hein. Nat. Resour. Res., 15 (2) (2006), 67–84 [3] A. Shah, R.P. Fishwick, J.Wood, G.A. Leeke, S.P. Rigby, M. Greaves. Energy Environ. Sci. 3 (2010), 700–714 [4] Gray MR. Upgrading petroleum residues and heavy oils. In: Marcel Dekker, editor. New York, 1994. [5] Hassan H., Abedi J, Fuel, 2010,89, 2822-2828. [6] Speight, J. G., The Chemistry and Technology of Petroleum, Fourth Edition, 1996. [7] Pereira Almao P., 19th World Petroleum Congress, Spain, Forum 04: Unconventional Petroleum Resources. (2008). [8] Le Thlez, P. A. and Lemonnler P. A., SPE Reservoir Engineering, 1990. 285-292. [9] Froment G. F., Bischoff K. B., Wilde J., Chemical Reactor Analysis and Design, 3rd. ed.;2011 [10] Press, W. H., Teukolsky S. A., Flannery B P, Numerical Recipes in FORTRAN 77, The Art of Scientific Computing Second Edition, 1997 [11] Sanchez S., Rodríguez M., Ancheyta J., Ind. Eng. Chem. Res. 2005, 44, 9409-9413 [12] Galarraga C., Scott C, Loria H, Pereira P., Ind. Eng. Chem. Res. 2012, 51, 140–146 [13] Orozco C. Master of Science Thesis, University of Calgary, 2016 [14] M.A. Callejas, M.T. Martı´nez, Ind. Eng. Chem. Res. 38 (1999) 3285–3289. [15] K. Aboul-Gheit, Erdoel Erdgas Kohle 105 (1989) 319–320.

Acknowledgments


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Fondo Sectorial CONACYT-SENER-HIDROCARBUROS D5/CH2011-02 and Instituto Mexicano del Petróleo, project Y.61006

Figures Caption Figure 1. Hydrocracking reaction network Figure 2. Experimental yield of hydrocracking @ 350 °C reaction temperature Figure 3. Experimental yield of hydrocracking @ 370 °C reaction temperature Tables Caption Table 1 Crude oil characterization Table 2 Experimental yields of heavy oil hydrocracking at 350 °C reaction temperature Table 3 Experimental yields of heavy oil hydrocracking at 370 °C reaction temperature Table 4 Kinetic parameters Table 5 Hydrocracked oil properties Table 6 Kinetic parameters comparison


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Figure 1

Figure 2


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Figure 3


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Table 1

Physical & chemical properties wt. % 0 10 20 30 40 50 60 70 80 90 100

ASTMD-2887 °C 36 234.1 322.3 395.1 457.8 510.6 547.5 587.8 632 681.2 742.9

Asphaltenes Saturated Resins Aromatics Total S Total N Carbon H H2O Specific gravity Viscosity @ 98 °C Ni+V

wt. % wt. % wt. % wt. % % wt. ppm wt. % wt. % wt. % API cSt ppm

23.3 26.16 28.28 21.27 5.25 3532 83.7 10.64 0.29 12 14600 370

Table 2

Residue, wt % Heavy gasoil, wt % Light gasoil, wt % Time, h Exp Calculated Exp Calculated Exp Calculated 0 34.30 34.30 37.30 37.30 17.80 17.80 12 31.13 31.12 35.66 35.65 19.43 19.42 36 28.47 27.95 34.74 34.22 20.39 20.05 60 26.10 25.58 34.45 33.89 21.26 20.79 84 23.93 23.44 34.09 33.51 22.08 21.52 108 22.22 21.75 33.93 33.34 22.74 22.09 132 20.36 19.92 33.42 32.82 23.86 23.10 156 18.43 18.03 33.25 32.64 24.82 23.94 180 16.53 16.14 32.35 31.73 25.08 24.08

Table 3


Naphtha, wt % Exp Calculated 10.60 10.60 13.33 13.34 15.90 16.27 17.61 17.99 19.29 19.67 20.45 20.82 21.54 21.92 22.52 22.89 22.99 23.37

Gases, wt % Exp Calculated 0.00 0.00 0.45 0.47 0.49 1.51 0.57 1.74 0.61 1.86 0.65 1.99 0.81 2.24 0.97 2.50 3.04 4.68

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Residue, wt % Exp Calculated 34.30 34.30 24.26 24.09 17.30 17.01 12.59 12.37 9.93 9.76 8.02 7.89 6.13 6.04 4.13 4.07

Time, h 0 12 36 60 84 108 132 156

Heavy gasoil, wt % Exp Calculated 37.30 37.30 32.69 32.50 25.95 25.60 20.52 20.23 17.65 17.41 14.33 14.14 10.99 10.85 7.77 7.68

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Light gasoil, wt % Exp Calculated 17.80 17.80 26.01 25.72 29.03 28.07 29.76 28.64 29.27 28.15 28.87 27.78 28.57 27.51 28.32 27.29

Naphtha, wt % Exp Calculated 10.60 10.60 13.33 15.53 15.90 25.11 33.16 33.26 38.23 38.25 42.91 42.86 47.48 47.36 52.01 51.84

Table 4

-1

K0 [h ]

1 2 3 4

0.05 0.2 4.3 0.82

5 6 7

0.0089 0.14 0.082

8 9

0.084 2.9

10

0.099

Kinetic parameters EA (KJ/mol) Residue 27.65 18.08 50.42 58.42 Heavy gasoil 8.65 18.63 39.16 Light gasoil 19 27.2 Naphtha 17.58

k* [h-1] 350 °C

370 °C

2.45E-04 6.10E-03 2.55E-04 1.04E-05

2.89E-04 6.80E-03 3.45E-04 1.47E-05

1.68E-03 3.84E-03 2.94E-04

1.76E-03 4.29E-03 3.51E-04

2.14E-03 1.52E-02

2.40E-03 1.79E-02

3.3241E-03 3.6943E-03


Gases, wt % Exp Calculated 0.00 0.00 1.66 2.16 2.81 4.19 3.97 5.49 4.92 6.43 5.87 7.33 6.82 8.23 7.78 9.14

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Table 5

Asphaltenes Saturated Resins Aromatics Total S Total N Carbon H H2O Specific gravity Viscosity @ 98 °C Ni+V

Physical & chemical properties Heavy crude oil Hydrocracked oil 350 °C 370 °C 23.3 16.1 8.3 26.16 30.6 35.8 28.28 19.3 17.6 21.27 34 38.3 5.25 3.2 2.7 3532 2811 2340 83.7 84.8 84.6 10.64 11.72 12.3 0.29 12 17.1 26.8 14600 480 212 370 290 223

wt. % wt. % wt. % wt. % % wt. ppm wt. % wt. % wt. % API cSt ppm

Table 6

This work

Orozco

Sanchez

Galarraga

Hassan

Aboul

Callejas

Heavy crude oil

Heavy crude oil

Heavy crude oil

Bitumen

Bitumen

Vaccum gasoil

Heavy crude oil

Liquid acid NiMo

Ultradispersed NiMoCo

CSTR -1

K0 [h ]

EA (KJ/mol)

Liquid NiMoCo

PFR -1

k* [h ]

-1

K 0 [h ]

EA (KJ/mol)


PFR -1

k* [h ]

-1

K 0 [h ]

EA (KJ/mol)


CSTR -1

k* [h ]

-1

K 0 [h ]

EA (KJ/mol)

HY zeolite NiMo

CSTR -1

-1

CSTR

PFR -1

k* [h ]

K0 [h ]

EA (KJ/mol)

k* [h ]

-1

K 0 [h ]

EA (KJ/mol)

k* [h-1]

EA (KJ/mol)

Residue 5.1-E02

27.65

2.45E-04

5.64E+01

48.56

4.78E-03

2.0 E -01

18.08

6.10E-03

5.93E+27

382.16

5.37E-05

4.3 E +00

50.42

2.55E-04

1.90E+30

404.7

2.22E-04

8.2 E -01

58.42

1.04E-05

1.51E+03

790.24

8.9 E -03

8.65

1.68E-03

1.19E+12

175.53

1.4 E -01

18.63

3.84E-03

8.2 E -02

39.16

4.27E-05

203

6.94E-03

1.72E+58

720.41

6.78E-03

5.84E+09

142

6.60E-03

189.7

185

1.55E-03

5.81E+94

1158.26

4.44E-03

3.80E+22

302

1.73E-03

269.3

159

1.95E-03

5.67E+92

1137.34

2.46E-03

2.39E+17

236

4.18E-03

3.57E-04

7.28E+14 5.04E+12 4.19E+10 5.40E+07

114

1.49E-02

1.22E+103 Heavy gasoil

1268.78

5.05E-04

1.62E+17

321

6.76E-05

2.28E-03

2.85E+11

165

4.17E-03

2.65E+52

657.2

2.09E-03

3.50E+22

304

2.01E-03

6.97E+116

1435.4

3.09E-04

19

2.14E-03

2.9 E +00

27.2

1.52E-02

1.48E+01

58.4

1.88E-04

5.02E+81

1013

5.81E-04

17.58

3.32E-03


2.87E-01

2.38E-02

8

5.55E-04

2.60E+06

100.57

4.06E-02

113

4.38E-04

3.05E+04

78.17

2.61E-02

8.89E+06

113

3.02E-03

3.13E+03

82

4.42E-04

5.90E+01

28

2.71E-03

Naphtha 9.9 E -02

73.31

1.45E+06 Light gasoil

8.4 E -02

294.8 1.41E+05

Hydrocracking Kinetics of a Heavy Crude Oil on a Liquid Catalyst

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