Article

pubs.acs.org/IECR

Modeling Coil and Soaker Reactors for Visbreaking

Rodolfo A. Aguilar and Jorge Ancheyta*
Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas Norte 152, Col. San Bartolo Atepehuacan C.P. 07730, México D.F.
*
S Supporting Information

ABSTRACT: A reactor model to simulate the visbreaking process is developed. The model includes two types of visbreaking
reactors: coil and soaker. For the vaporization in the reactor to be taken into account, the vapor−liquid equilibrium (VLE) is first
determined, and then the reactor model is solved only with the liquid phase because thermal cracking reactions occurring during
visbreaking take place in this phase. The variation of liquid and vapor flow rates are also taken into consideration. A reaction
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scheme based on nine pseudocomponents and kinetic expressions reported in the literature were used. It was found that VLE
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affects the prediction of reactor conversion depending on the feedstock and the operating conditions. The residue conversion
decreases when VLE is considered, which is due to vaporization diminishing the reactor space available for performing the
reactions. The model predicts greater mass fractions of gas and naphtha than the experimental values. This is because the model
assumes that they are produced by all pseudocomponents heavier than them. It is anticipated that the proposed model can be
used in complex refinery planning studies with more reliability than the empirical models available to date.

1. INTRODUCTION formation, enhancing the unit run, and lowering operating

The decreasing supply of light crude oils is a matter of serious
concern for the petroleum industry because the distillation of
heavy crude oils leaves behind a significant amount of vacuum
residue. This vacuum residue needs to be converted into light
distillates to increase the profitability of the entire refinery. To
this end, there are various commercial processes based mainly
on hydrogen addition and carbon rejection routes.1 Visbreaking
(VB), a carbon rejection-based technology, is a mild liquid-
phase thermal cracking process that reduces the viscosity and
pour point of the residue so that, with little or no addition of
light distillates, it can meet the fuel oil quality.
There are two ways to perform the VB reactions: a coil
reactor and a coil-soaker reactor system. The coil visbreaker is a
furnace operated at high temperature and low residence time. It
is also termed a high-temperature, short-residence-time
(HTST) process. The visbreaker feed from the preheater
enters the furnace at 300−330 °C and undergoes thermal
cracking in the coil in the temperature range of 460−480 °C for
a duration of 2−5 min. Steam (∼1 wt %) is injected along with
the feed to generate the turbulence, control the liquid-phase
residence time, and prevent coking along the tube walls.2 The
cracking reactions (C-C cracking) occur in the liquid phase and
are slightly endothermic (192 kcal/kg of product boiling below
204 °C).3
In the coil-soaker operation, the feed first passes through a
coil reactor at relatively lower temperature and residence time
(∼450 °C, 2−3 min). Then, it enters the soaker reactor−an
adiabatic hollow drum−where it is held for a longer amount of
time (15−25 min). The reduction in the coil temperature and
simultaneous increase in the residence time in the soaker give
similar conversions as in the case of the coil type, it is described
as the low-temperature, high-residence-time (LTHT) route.
Some advantages of the coil-soaker process over the coil
process are that the soaker drum allows the heater to operate at
a lower outlet temperature by providing the residence time
required to achieve the desired reaction, decreasing the coke
cost;2 the selectivity to the cracking of the feed in the coil-
soaker mode, due to their relatively lower temperature, allows
only for the cracking of higher molecules and already-cracked
molecules remain unaffected.
Modeling of coil and soaker visbreaking, which can be
broadly classified as gas−liquid systems,2 has been the subject
of various research studies. Mosby et al.,4 using petroleum
fractions (seven lumps) as pseudocomponents, modeled VB
reactor as a CSTR (continuous stirred tank reactor).
Castellanos et al.5 used 51 pseudocomponents to characterize
the feed and modeled the reactor as a two-phase plug-flow
reactor (PFR). Carbonell and Guirardello6 combined the zero-
order turbulence model with the Mosby scheme. Mittal et al.7
modeled the coil VB as a PFR coupled with CSTR soaker in
series but only considering the reaction of vacuum residue to
gas and gasoline. Kulkarni8 used a similar approximation with
more reactions and scale factors in the kinetics coefficients to
adjust pilot plant data. Reza and Sepehr9 modeled a VB
industrial reactor assuming the coil as a PFR and the soaker as a
CSTR. Filho and Sugaya3 modeled the visbreaking reactors
(coil and soaker) considering the VLE (vapor−liquid
equilibrium) using the Peng−Robinson equation of state, but
the kinetic parameters were not reported.
The conversion depends on operation conditions (residence
time, temperature, etc.). Keeping constant the other conditions,
the longer the residence time, the greater the conversion.
Changing the liquid composition results in the conversion also
changing. At the conditions of a visbreaking reactor (temper-
ature of 450−480 °C, pressure of ∼2.5 MPa) and considering
the formation of light products, the VLE in the system makes
the gas phase increase through the reactor and, as a
Received: June 1, 2015
Revised: December 11, 2015
Accepted: December 15, 2015
Published: December 15, 2015

© 2015 American Chemical Society 912 DOI: 10.1021/acs.iecr.5b01985

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Industrial & Engineering Chemistry Research Article

consequence, the amount of liquid decreases, reducing the

residence time and thus affecting the conversion of the reactor.
The pressure in the coil has a significant influence over the
gas formation. At constant pressure, the temperature varies
through the reactor, and the formation of gas is due to the
variation of VLE by temperature and composition originated by
the reaction. If pressure drop through the coil reactor is
considered, it also affects the VLE, increasing the vaporization
of components. If the pressure drop is high, the vaporization
could be excessive.
For modeling the visbreaking reactor including VLE, it is
necessary to account for an adequate characterization of the
feed. For modeling complex mixtures, two main methods have
been used: the lumping approach and detailed molecular
modeling.10 The lumping can be discrete or continuous. In the
discrete lumping approach, the mixture is divided in discrete
pseudocomponents (lumps) based on physical properties. The
continuous approach is based on the description of multi-
compound mixtures using a continuous distribution function.
No matter what approach is used for lumping the feed to a
visbreaking reactor, the conventional cubic EoS is a common
model for hydrocarbon−water systems.10−16 The temperature-
dependent kij of the conventional EoS can be determined using
experimental data17 or estimated with prediction methods, such
as PPR7818 or PR2SK.19
In the petroleum industry, it is a common practice to Figure 1. (a) Reaction scheme for visbreaking of 5 pseudocompo-
perform refinery planning and evaluation of several feedstock. nents,9 including S1, gas; S2, naphtha; S3, light gas oil; S4, heavy gas oil;
To do this, it is necessary to account for reliable models of and S5, residue. (b) Proposed reaction scheme for S1, gas; S2, naphtha;
different processes. The objective of this work is to develop a S3, light gas oil; S4, heavy gas oil; and S5−S9, residues.
visbreaking reactor model to simulate a coil or a coil-soaker
reactor. The model takes into consideration the VLE, the
changes of liquid and gas flow rates during the reaction, and where N is the number of pseudocomponents.
uses kinetic parameters that can be determined from feed Taking into consideration these literature reports and aiming
properties. The proposed model is based on those developed to develop an easy-to-solve model, the residue was divided into
by Kulkarni8 and Joshi et al.2 5 lumps with the following products:
S1: gas
2. MODEL DESCRIPTION S2: naphtha
This section deals with the description of the model that S3: light gas oil
includes the reaction scheme based on 9 pseudocomponents, S4: heavy gas oil
the kinetic model, the calculation of kinetic parameters, and the S5−S9: residues
reactor model (mass balance, energy balance, and VLE). The proposed reaction scheme is then illustrated in Figure
2.1. Reaction Scheme. The reaction scheme of Reza et al.9 1b.
with 5 pseudocomponents (S5: residue, S4: heavy gas oil, S3: 2.2. Kinetic Model. All of the reactions are considered to
light gas oil, S2: naphtha, S1: gas) is shown in Figure 1a, which follow first-order kinetics such that the reaction rate expressions
has been reported in the literature for modeling of visbreaking are
reactors. rij = kijCSi
This model considers the residue as only one pseudocompo- (2)
nent (S5) that can produce all of the other lumps (S1, S2, S3, where i indicates the reactant and j the product of the reaction.
and S4). When solving the mass balance equations, it results in The global rate of reaction for the pseudocomponent i is
higher conversion of residue as compared with experimental i−2 N i−2 N
values. ri = −∑ rij +
Some authors have modeled VLE in the petroleum reservoir
∑ rji = −CSi ∑ kij + ∑ kjiCSj
j=1 j=i+2 j=1 j=i+2 (3)
and have found that some information of the composition is
lost when a few pseudocomponents are used to represent the The first term on the right-hand side of eq 3 represents the
liquid phase.20−22 Joshi et al.2 suggested that the use of narrow reaction rate of the pseudocomponent as reactant, and the
boiling range residue can improve the prediction of conversion second term is the rate of reaction of the pseudocomponent as
when modeling the visbreaking reactor. Castellanos et al.5 product.
proposed to divide the residue feed into 51 pseudocomponents 2.3. Kinetic Parameters. The correlations proposed by
and that the Si reactant produces Sj products through i − 2 Castellanos et al.5 to calculate kinetic parameters from feed
parallel reactions having the products lower molecular weights properties were used.
according to the reaction scheme The temperature dependence of the rate constants is
represented by the Arrhenius equation. Aij and Bij parameters
Si → Sj i = 3, ..., N ; j = 1, ..., N − 2 (1) of the Arrhenius equation are defined in terms of products and
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reactant molecular weights of the reaction i → j, according to where τ = V/ν0 is the space time in h.
the equations Substituting the reaction rate expression (eq 3) in eq 9 gives
Aij = (a0 + a1MWi + a 2 MWi2) ⎡ i−2 N ⎤
CSi0 ⎢
− αCSi = τ CSi(∑ kij) − ∑ kjiCSj⎥⎥
⎡ 2⎤ ⎢⎣
1 ⎛ a4 MWj − MWi ⎞ ⎥ ⎦
exp⎢ − ⎜
j=1 j=i+2 (10)
⎟
⎢⎣ 2 ⎝ a3a4 ⎠ ⎥⎦ (4) Dividing Eq. 10 by the total mass concentration, the mass
fraction is obtained
Bij = b0 + b1MWi + b2 MWj (5)
⎡ i−2 N ⎤
The values of the ai and bi parameters are reported in Table fSi0 − αfSi = τ ⎢fSi (∑ kij) − ∑ kjifSj ⎥
1. ⎢⎣ ⎥⎦
j=1 j=i+2 (11)

Table 1. Values of Parameters for Aij and Bij of the Solving for the pseudocomponent mass fraction I at the
Visbreaking Reactions 5 reactor exit
N
a0 1.5072 × 1012 b0 42894 fSi0 + τ(∑ j = i + 2 kjifSj )
a1 1.9 × 108 b1 −4.5 fSi = i−2
a2 2.0561 × 106 b2 3 α + τ(∑ j = 1 kij) (12)
a3 146.95
a4 11.349 b. Energy Balance. The coil reactor is a nonisothermal−
nonadiabatic reactor. The energy balance for a CSTR with
2.4. Reactor Model. Two modes of operation are found in multiple reactions is
commercial visbreaking: coil reactor and coil-soaker reactor. N
For simulating the coil visbreaking reactor, the cell model Q= ∑ ΔHRirV
i + FT CpΔT
proposed by Deans and Lapidus23,24 and McGuire and i=1 (13)
Lapidus25 are used. In this method, the coil reactor is visualized
as a set of interconnected cells in series. Each cell is an element The soaker reactor is considered to be an adiabatic reactor.
of volume of the coil reactor where the mixing is complete, The mass balance is represented by eq 12, and the energy
obtaining uniform properties. Each cell is represented by a balance is
CSTR. With this procedure, the mass and energy conservation N
expressions of the PFR are transformed into a series of 0= ∑ ΔHRirV
i + FT CpΔT
algebraic equations as CSTRs. The soaker drum reactor is an i=1 (14)
adiabatic reactor that can be considered as a CSTR. In
c. Vapor Liquid Equilibrium. Vapor−liquid equilibrium is
summary, both the coil and soaker reactors are modeled as
modeled as an isothermal flash knowing P, T, and feedstock
CSTR: the coil reactor as a series of CSTR and one CSTR for
composition.26
the soaker drum.
The computational procedure is iterative and consists first of
a. Mass Balance. The mass balance in a CSTR for
using the Rachford and Rice equation to calculate the liquid
pseudocomponent i is
composition assuming a vaporized fraction.
v0CSi0 − vCSi = −Vri (6)
N N ⎡ zj ⎤
where CSi0 and CSi are the concentrations of the reactant i in ∑ xj = ∑ ⎢ ⎥
kg/m3 at the inlet and outlet of the CSTR, respectively, ν0 and j=1
⎢ 1 + f (Kj − 1) ⎥⎦
j=1 ⎣ (15)
ν are the volumetric flow rates at the inlet and outlet of the
CSTR, in m3/h, respectively, V is the volume of the CSTR in and the vapor composition is calculated by
m3, and ri is the rate of reaction of the pseudocomponent i in yj = Kjxj (16)
kg/m3h.
During visbreaking reactions, gas is produced, which causes Initial K-values are obtained by using the Wilson equation,
changes to the mass flow of liquid. Thus, the liquid volume for such that
the visbreaking reactions to proceed is altered. To account for
this variation, a liquid volume fraction resulting after the Pci ⎡ ⎛ T ⎞⎤
Ki = exp⎢5.371 + (1 + ωi)⎜1 − ci ⎟⎥
reaction needs to be calculated. The volumetric flow rate at the P ⎣ ⎝ T ⎠⎦ (17)
reactor outlet is estimated with the liquid mass flow rate at the
reactor outlet and the densities (obtained from the VLE This is done until the sum of x’s and y’s is 1.
calculations). The liquid volume fraction is calculated as Once the x’s and y’s are determined, the K-values are
recalculated with the Peng−Robinson equation.27
v at outlet of CSTR The K-value is a function of liquid and vapor fugacity
α=
v0 (7) coefficients, such that
The difference (1 − α) is the gas volume fraction. ΦLj
Using this parameter, the mass balance gives Kj =
ΦGj (18)
v0CSi0 − αv0CSi = −Vri (8)
The fugacity coefficients are computed using the equation of
CSi0 − αCSi = −τri (9) state of Peng−Robinson.
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For consideration of the vaporization in the reactor

modeling, the VLE is first determined, and then the reactor
model is solved only with the liquid phase. The vapor−liquid
product from the reactor is mixed with the vapor stream from
the VLE prior to entering the following VLE, and so forth, as
illustrated in Figure 2.

Figure 3. Modeling approaches for the different cases of study

Figure 2. Strategy for modeling of the visbreaking reactor.

The VLE and reactor model calculations were performed in

Excel spreadsheets. A program developed as a macro in Excel
Visual Basic was used to link the calculations of VLE with the
reactor model. The macro solves the VLE and determines the
temperature in the reactor using the Solver tool of Excel. This
tool uses the nonlineal optimization code GRG2, which is a
general reduced gradient method.28

3. RESULTS AND DISCUSSION

First, it is worth mentioning that experimental and commercial
information of visbreaking mass fractions in the available
literature is scarce, and the few data that have been provided
surely need rectification due to errors during the collection of
results from plant operation, measuring, and analysis. Despite
this, the reports are of high value and will be used here for
testing the performance of the developed model.
3.1. Case Studies. In this section, a description of the basis
considered to make the simulations is described. Four cases
were studied, including
(Case 1) An industrial plant without soaker drum (coil
visbreaking). The feedstock is a 6.55°API vacuum residue
obtained by mixing two vacuum residua. The coil reactor
consists of three sections. The inlet temperatures to each
915
Figure 4. Temperature and mass fraction profiles without VLE (case
1a). (A) Temperature profile. (B) S5−S9 mass fraction profiles. C) S1−
S4 mass fraction profiles.
section are 343, 368, and 420 °C. The exit temperature of the
reactor is 446 °C.
(Case 2) An industrial plant with two furnaces (coils) in
parallel and an adiabatic soaker (coil-soaker visbreaking).9 The
feedstock is a 9.16° API blend of vacuum residue and vacuum
gas oil. This coil operates with 9.5 min of residence time and
the soaker with 36.4 min. The coil temperatures are 326.5 °C at
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Figure 5. Temperature and mass fraction profiles with VLE at constant
pressure (case 1b). (A) Temperature profile. (B) S5−S9 mass fraction
profiles. (C) S1−S4 mass fraction profiles.
the inlet and 439 °C at the outlet. In the simulation, one
furnace is taken to account, and the soaker is simulated with
twice the flow of the furnace.
(Case3) A pilot plant consisting of a furnace coil with six
independent sections followed by a soaker.29 The feedstock is a
7.24° API vacuum residue from Bombay High crude. The inlet
temperature to the coil is 185 °C, and the outlet temperatures
of each section are 290, 365, 410, 415, 420, and 430 °C. The
residence time in the coil is 1.6 min and in the soaker is 20 min.
(Case 4) An industrial plant with three parallel furnaces and
soakers.30 The feedstock is a 10.44° API vacuum residue. The
inlet coil temperature is 320 °C, and the outlet temperature is
436 °C. The residence times are 2.5 min in the coil and 31 min
in the soaker.
3.2. Calculations of Properties. As mentioned earlier, the
model needs the molecular weight of the feed pseudocompo-
nents and of the products of the reaction. The molecular
weights were calculated using the correlation of Kesler and
Lee.31
When the distillation curves were available, they were fitted
with the Kumaraswamy probability distribution function,32
which according to Sanchez et al.33 is suitable for fitting
distillation data, so that values of fractions for each 1 vol % can
be generated. The API gravity of each fraction is calculated
assuming constant KUOP.34 With the API gravity, the specific
gravity is computed, and then the weight of each fraction is
determined. This weight and the molecular weight of each
fraction permit calculation of the corresponding number of
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Figure 6. Temperature, pressure, and mass fraction profiles with VLE
and pressure drop (case 1c). (A) Temperature and pressure profiles.
(B) S5−S9 mass fraction profiles. (C) S1−S4 mass fraction profiles.
moles and mole fractions. With these data for each 1 vol %, the
molecular weights of all pseudocomponents that constitute the
feed and product are obtained.
When only the specific gravity (or API gravity) and the
temperature range of the cuts are reported, the molecular
weight was calculated using the Kesler and Lee31 correlation
with arithmetic average of temperature and specific gravity.
For case 1, the feed is a mixture of two residues. Data of
distillation curves and specific gravity of both residues and the
specific gravity of the blend are available. The properties of the
mixture were calculated by mixing the pseudocomponents of
both residues.
The distillation curves of naphtha (S2) and light gas oil (S3)
fractions are available. The distillation curve of the heavy gas oil
(S4) fraction was obtained from the distillation curve of
visbroken residue (S5−S9) for a cut temperature of 538 °C.
For case 2, the distillation curve of the feed is the only one
reported. The temperature range and specific gravity of the cuts
are also reported. The molecular weights of S4 and visbroken
residue were obtained with the distillation curve. The molecular
weights of S2 and S3 were calculated with the specific gravity
and the mean value of the cut temperature reported.
Case 3 reports the cut temperatures of the products and
overall information of the Bombay High crude-derived residue
feed.29 For calculating the residue distillation curve, that of the
Bombay High crude was obtained from the literature,35 and
with the pseudocomponents characterization method, the
distillation curves and the molecular weights for each cut
were determined.
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Figure 7. Temperature and mass fraction profiles without VLE (case
2a). (A) Temperature profile. (B) S5−S9 mass fraction profiles. (C)
S1−S4 mass fraction profiles.
Case 4 reports the distillation curves of the feed, S2, S3, and
the visbroken residue fractions.23 For determination of the
molecular weight of S4, the visbroken residue distillation curve
was used.
For the dimensions, operating conditions of the visbreaking
reactors, and the properties of feed and products, refer to Table
S1 in the Supporting Information. The TBP cuts of the
products for case 1 are given as data; for case 2, the cuts S2 and
S3 are also given as data, and S4 and S5 were defined as in case
1; for case 3, all the data are reported; and in case 4, the TBP
curves of each cut are given as data. Table S2 gives the
distillation curves of feed and products.
Table S3 shows the calculated heat capacities and the
molecular weights of the lumps involved in the reaction
scheme. The heat of reaction for the products boiling below
204 °C was assumed to be 800 kJ/kg.3
3.3. Simulations. Once the data for performing the
simulations were either collected from reports in the literature
or calculated with proper correlations from the available
information or, in the worst of the cases, assumed from similar
reported cases, the following situations were simulated: (a)
without considering VLE at constant pressure, (b) accounting
for VLE at constant pressure, and (c) with VLE with pressure
drop.
For all of the cases and situations, the coil temperatures are
available such that the simulations were developed by
modifying the duty of each section until the outlet temperatures
were reached. Reactor pressure drop is calculated using the
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Figure 8. Temperature and mass fraction profiles with VLE at constant
pressure (case 2b). (A) Temperature profile. (B) S5−S9 mass fraction
profiles. (C) S1−S4 mass fraction profiles.
homogeneous model for two phases of flow as reported by
Cooper et al.36
Finally, for each case, the corresponding model of the
reactors system was developed as shown in Figure 3. As was
mentioned above, each section in a furnace is considered as a
plug-flow reactor, and it is simulated with a series of 10 CSTRs,
whereas the soaker reactor is calculated as a single CSTR. The
number of CSTRs in series was determined after developing
simulations for case 1 without VLE using 5, 10, 15, 20, and 50
reactors in series. The maximum difference in the results
considering more than 10 CSTRs in series with respect to that
with 10 reactors was 0.22 wt % in the S2 pseudocomponent.
This difference is not significant and, hence, using 10 CSTRs in
series is reliable.
3.4. Results and Discussions. For each case (1−4), three
figures are reported, one corresponding to situation (a),
another for situation (b) and the last one for situation (c).
Each figure has three other subfigures: (A) for the temperature
and pressure profiles (pressure profile is reported when
pressure drop is considered), (B) for the mass fraction profile
of residue and its pseudocomponents (S5−S9), and (C) for the
mass fraction profile of pseudocomponents S1−S4. When
available, data of experimental mass fractions are included as
symbols.
3.4.1. Case 1. Figures 4−6 show the results of the
simulations for situations 1a−c, respectively.
Figures 4A, 5A, and 6A show the temperature profiles
through the reactor. As was mentioned earlier, the inlet
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Figure 9. Temperature, pressure, and mass fraction profiles with VLE
and pressure drop (case 2c). (A) Temperature and pressure profiles.
(B) S5−S9 mass fraction profiles. (C) S1−S4 mass fraction profiles.
temperature of the coil was available and used to fit the energy
balance as to obtain the outlet temperatures, such that the
temperature profiles are identical. The same behavior occurs for
the other cases. When only the liquid phase is considered
(situation 1a), the mass fraction residue pseudocomponents
(S5−S9) diminish through the coil as the temperature is
increased (Figure 4B) with a more pronounced fall of S7, S8,
and S9. This is due to that fact that pseudocomponents S8 and
S9 are reactants and are not produced in the reaction scheme.
Pseudocomponent S7 is a primary product produced only from
S9; however, its rate of appearance is slower than its rate of
disappearance, which is why it shows a decreasing profile. The
same behavior is observed for all of the pseudocomponents that
constitute the residue fraction (S5−S9) for all of the cases. The
lighter the pseudocomponent (e.g., S5, S6), the smaller the drop
in its mass fraction. In other words, heavy pseudocomponents
of the residue tend to decrease more of their mass fraction as
compared with light pseudocomponents. The mass fraction of
S1−S3 increases through the reactor, whereas for S4, it is
maintained approximately constant between values from 4.51
to 4.66% (Figure 4C). In the case of S4, its rate of appearance is
almost equal to its rate of disappearance, causing a flat profile.
When VLE in the reactor is taken into account at constant
pressure (situation 1b), the trends are the same as in situation
1a without VLE, but the reduction of mass fraction of S5 to S9
pseudocomponents is lower, as can be seen in Figure 5B. The
total mass residue conversion is lower in situation 1b (13.0%)
than in situation 1a (21.4%).
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Figure 10. Temperature and mass fraction profiles without VLE (case
3a). (A) Temperature profile. (B) S5−S9 mass fraction profiles. (C)
S1−S4 mass fraction profiles.
Because of the lower residue conversion predicted, the
increases of mass fraction of S1, S2, and S3 are smaller: 6.56
versus 10.93% for S1; 4.79 versus 7.83% for S2, and 2.51 versus
3.47% for S3 for situations 1b and 1a, respectively. The mass
fraction of S4 is practically constant (decrease from 4.64 to
4.51%) due to the same reasons given before.
When the pressure drop is considered in the simulation with
VLE (situation 1c), the trends of the mass fractions of
pseudocomponents are the same as in the previous cases but
with even lower mass residue conversion (11.6%), as can be
seen in Figure 6B. Consequently, the production of S1−S4 is
also lower (Figure 6C): 5.7 versus 6.56% for S1, 4.15 versus
4.79% for S2, and 2.28 versus 2.51% for S3 for situations 1c and
1b, respectively. The mass fraction of S4 remains the same as in
the previous cases.
3.4.2. Case 2. Figures 7−9 show the simulation results for
coil and soaker of this case (situations 2a−c, respectively).
If VLE is not considered in the simulation (situation 2a), the
trends of the pseudocomponents behavior in the coil reactor is
the same as in case 1 but with less conversion because
temperature and residence time are lower (Figure 7B and C).
The variation of the mass fractions of the S3−S9 pseudocom-
ponents in the coil is less than 2.0%. The increase of the mass
fractions of pseudocomponents S1 and S2 is greater than 2.5%.
In the soaker is where most of the reactions are carried out,
whereas in the coil, the mass fraction of the residue decreases
∼7% and in the soaker it diminishes ∼15%. In all of the
pseudocomponents, the trend is similar. Only S4 varies in lesser
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Figure 11. Temperature and mass fraction profiles with VLE at
constant pressure (case 3b). (A) Temperature profile. (B) S5−S9 mass
fraction profiles. (C) S1−S4 mass fraction profiles.
quantity (1.06 wt %), verifying the fact that its rate of
appearance is practically the same as its rate of disappearance.
In the case of the simulation considering VLE and constant
pressure (situation 2b, Figure 8B and C), the variation of the
mass fractions in the coil is lower than in situation 2a. As the
residence time in the coil is short, the conversion in this reactor
is also low. Thus, the vaporization produced by increasing the
temperature is not too large, and the variation of the volume of
liquid in the reactor is not too high, thus causing the difference
in volume of the coil to not be as significant as in case 1.
However, in the soaker a more significant difference is
observed. Although the temperature is lower, the residence
time is longer, and a higher conversion is obtained. This
conversion affects the VLE because there are more light
pseudocomponents that vaporize and decrease the volume for
reaction in the liquid phase. In situation 2c (simulations
considering VLE and pressure drop), the change in the mass
fractions in the coil with respect to situation 1b is not
significant. In the coil, the pressure drop does not cause a great
effect on the vaporization because there are not many light
pseudocomponents. In the soaker, there is not a significant
variation in the conversion.
3.4.3. Case 3. The results of the coil and soaker simulations
for situations 3a−c are shown in Figures 10−12. When the VLE
is not considered in the simulation (situation 3a), the change in
the mass fractions of the pseudocomponents in the coil is lesser
than 0.28 wt %, as can be seen in Figure 10B and C. On the
other hand, in the soaker, the mass fractions change 3.75 wt %
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Article
Figure 12. Temperature, pressure, and mass fraction profiles with VLE
and pressure drop (case 3c). (A) Temperature and pressure profiles.
(B) S5−S9 mass fraction profiles. (C) S1−S4 mass fraction profiles.
in all of the pseudocomponents except for S4, which varies only
by 0.15 wt %.
In situation 3b (simulation considering VLE and constant
pressure), panels B and C in Figure 11 show that the mass
fraction variation of all of the pseudocomponents in the coil is
lower than 0.26 wt %. In the soaker, the maximum increase in
the mass fraction is 3.35 wt %.
If the pressure drop is considered (situation 3c, Figure 12B
and C), the mass fraction varies 0.25 wt % in the coil. In the
soaker, this mass fraction increases 3.28 wt %.
3.4.4. Case 4. Figures 13−15 show the simulation results of
case 4. In Figure 13B, it can be appreciated that the mass
fractions of the residue pseudocomponents (S5−S9) and the
mass fraction of the total residue are low when the reactor is
simulated without VLE in the coil. Most of the conversion of
the residue is obtained in the soaker, i.e., the mass fractions of
the total residue decreases ∼15%. It can be observed in Figure
13C that the mass fraction of product pseudocomponents S1−
S3 increases only in the soaker reactor. The mass fraction of the
S4 pseudocomponent remains almost unchanged, as in the
previous cases.
The mass fractions of the pseudocomponents for the
simulation of visbreaking considering VLE at constant pressure
are presented in Figure 14B and C. The trend of the behavior is
the same as in situation 4a, but the conversion of the residue
and the increase of the mass fraction of S1−S3 pseudocompo-
nents are lower.
It can be seen in Figure 15B and C that including the
pressure drop with the VLE does not have an effect on the rate
DOI: 10.1021/acs.iecr.5b01985
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Industrial & Engineering Chemistry Research
Figure 13. Temperature and mass fraction profiles without VLE (case
4a). (A) Temperature profile. (B) S5−S9 mass fraction profiles. (C)
S1−S4 mass fraction profiles.
of visbreaking reactions, and the mass fraction of all of the
pseudocomponents is the same as in situation 4b.
3.4.5. Comparison with Experimental Data. Table 2
summarizes the predicted mass fractions of S1−S4 and residue
(S5−S9) and their comparison with experimental data for the 3
situations (a−c).
It can be observed that situation 1c exhibits superior
performance relative to situations 1a and 1b for the prediction
of residue mass fraction seeing as though it is in general closer
to the experimental value. However, the prediction of mass
fractions of S1−S3 is poor. Mass fractions of S1 and S2 predicted
for situation 1c tend to approach the experimental value more
than situations 1a and 1b, whereas the mass fraction of S3 tends
to move away.
Comparing the mass conversion of situation 1a (21.4%) with
those of situations 1b (13%) and 1c (11.2%), it can be deduced
that, in this case, the inclusion of VLE does have a significant
effect on the residue conversion to lighter pseudocomponents.
The light pseudocomponents and some of the heavy
pseudocomponents are vaporized through the reactor, and
the produced vapor diminishes the space in the reactor where
the liquid phase reaction is conducted.
The difference between situations 1b and 1c shows that the
effect of pressure drop on the residue conversion is not
significant. The pressure drop diminishes the conversion 1.8%.
This is because, when the pressure decreases, the vaporized
fraction increases, and there is less space in the reactor for the
liquid.
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Article
Figure 14. Temperature and mass fraction profiles with VLE at
constant pressure (case 4b). (A) Temperature profile. (B) S5−S9 mass
fraction profiles. (C) S1−S4 mass fraction profiles.
From the results of the simulations of case 2 (situations 2a−
c), it can be seen in the reactor simulations that the effect of
taking into account the pressure drop is not significant. For the
residue product, the simulations results are 77 wt % without
VLE; 82.98 wt % considering VLE and constant pressure, and
83.81 wt % in the simulation with VLE and a pressure drop
relative to 93.0 wt % for the industrial plant. For S1−S3, the
mass fractions of the simulations are greater than the
experimental value (for S1, the simulations values ranged
between 7.95 and 11.3 wt %, whereas the experimental value
was 1.85 wt %; for S2, the experimental value was 4.75 wt %,
and the simulations were 6.55−8.74 wt %; and for S3, the
simulations gave 2.15−2.96 wt %, compared with the 0.4 wt %
experimental value).
As expected, the vaporization at constant pressure is lower
than at variable pressure in case 2. The VLE effect on the
results is not as important as in case 1 because the residence
time in the coil is shorter.
With respect to case 3, the values of the simulation results for
the different effects are similar. For the residue product, the
simulation without VLE produces 84.50 wt %; considering VLE
at constant pressure, 83.63 and 83.81 wt % is obtained taking
into account the pressure drop. For S3 and S4, the mass
fractions of the simulation are lower than the experimental ones
(the simulation values of S3 were between 1.08 and 1.31 wt %
compared with 6.69 wt % experimental value, and 7.04−7.05 wt
% in the simulations versus 8.94 wt % of the experimental value
for S4). The simulations for S1 and S2 overestimate the
experimental values (between 3.73 and 5.60 wt % versus 1.43
DOI: 10.1021/acs.iecr.5b01985
Ind. Eng. Chem. Res. 2016, 55, 912−924
Industrial & Engineering Chemistry Research Article

Table 3. Vaporization Fraction and Pressure Drop at the Exit

of the Coil and Soaker
case 1 case 2 case 3 case 4
constant P
coil 0.557 0.226 0.062 0.062
soaker 0.293 0.065 0.108
variable P
ΔP, kg/cm2 9.14 2.81 2.46 2.67
coil 0.573 0.159 0.070 0.086
soaker 0.213 0.072 0.135

Figure 16. Comparison of simulations for case 2C with variation of

Figure 15. Temperature, pressure, and mass fraction profiles with VLE
and pressure drop (case 4c). (A) Temperature and pressure profiles.
(B) S5−S9 mass fraction profiles. (C) S1−S4 mass fraction profiles.
wt % experimental value for S1 and 3.30−3.77 wt % compared
with 1.75 wt % for the experimental value for S2).
volume (empty bar) and without variation of volume (filled bar).
For case 4, it can be observed that the effect of the pressure
considering VLE is not important. For the residue product, the
simulation without VLE produces 81.58 wt %; considering VLE
at constant pressure, 82.64 and 83.04 wt % is obtained taking
into account the pressure drop. For S2 and S1, the mass
fractions of the simulation are greater than the experimental

Table 2. Comparison of Experimental and Predicted Mass Fractions and Conversion for the Different Case Studies
residue
conversion mass fraction S4 S3 S2 S1
case 1
exp 7.8 91.32a 5.58 1.54 1.56
(a) without VLE 21.4 77.78a 3.47 7.82 10.93
(b) VLE const. P 13 86.14a 2.51 4.79 6.56
(c) VLE var. P 11.2 88.10a 2.25 4.07 5.58
case 2
exp 7 93.00a 0.40 4.75 1.85
(a) without VLE 23 77.00a 2.96 8.74 11.30
(b) VLE const. P 16.83 82.98a 2.26 6.62 7.95
(c) VLE var. P 17.1 83.81a 2.14 6.55 8.29
case 3
exp 18.81 81.19 8.94 6.69 1.75 1.43
(a) without VLE 15.50 84.50 7.05 1.19 3.53 3.73
(b) VLE const. P 16.37 83.63 7.04 1.08 3.30 5.60
(c) VLE var. P 16.19 83.81 7.04 1.31 3.77 4.07
case 4
exp 10.00 90.00a 5.20 2.20 2.60
(a) without VLE 18.42 81.58a 2.55 7.36 8.51
(b) VLE const. P 17.36 82.64a 2.37 7.04 7.95
(c) VLE var. P 16.96 83.04a 2.31 6.12 7.65

a
S4−S9 pseudocomponents.

921 DOI: 10.1021/acs.iecr.5b01985

Ind. Eng. Chem. Res. 2016, 55, 912−924
Industrial & Engineering Chemistry Research
ones (6.87−7.36 wt % for simulations, compared with 2.2 wt %
experimental value for S2, and 7.75−8.51 wt % in the
simulations versus 2.6 wt % of the experimental value for S1).
The case of S3 is the opposite, being higher than the
experimental value (5.2 wt %). The simulation values decrease
when both effects are considered (approximately 2.34−2.55 wt
%).
Finally, from Table 2, the mass fraction of the residue
obtained by simulation is always lower than the experimental
one. Only for case 1c are all case 3 values comparable to the
experimental values with variation in mass fraction less than 4%.
In cases 2 and 4, the residue mass fractions are significantly
lower than those reported experimentally. In case 2, the
calculated mass fractions are between 16 and 9.19% lower than
the experimental value. In case 4, the calculated mass fractions
are found to be between 6.96 and 8.42% lower than the
experimental value.
The simulation for products S1 and S2 overpredicts the
experimental values in all of the cases. The values of
pseudocomponent S3 do not follow a trend. In cases 1, 3,
and 4, the experimental value is underpredicted, and for case 2,
it is overpredicted.
When VLE is considered, the residue mass fraction is greater,
which means that the residue conversion diminishes because
when the light components are vaporized, the reactor space
decreases, letting less volume for the liquid reactions to occur
(cases 1a and 1b). If pressure drop is considered, the
vaporization increases when the pressure decreases, and the
residue conversion is lower (cases 1b and 1c).
The high estimates of mass fractions of S1−S3 are due to the
reaction pathway used for developing the kinetic parameters
reported in Castellanos et al.5 The reaction scheme used for
parameter estimation involves the cracking and addition
reactions. In this work, those reactions are not considered.
The values of mass fraction of residue in simulations in the
first two cases without considering VLE are significantly lower
than those in which VLE is taken into account. In cases 3 and 4,
the effect is minor.
When constant pressure is considered in the simulations, or
there is pressure drop, the differences in the mass fractions are
not relevant. The maximum difference is 1.27% for case 1.
From the experimental data, considering the products S1, S2,
and S3 in cases 1, 3, and 4, S3 is the product with the greatest
mass fraction; S1 and S2 have similar values. In case 2, the order
of mass fractions is S2 > S1 > S3.
The vaporization at the exit of the coil and the soaker in each
case is presented in Table 3. As can be seen, the vaporization of
cases 3 and 4 is almost negligible, and the mass fractions of the
residua are close. In cases 1 and 2, the difference between
considering VLE and not results in a greater residue mass
fraction due to the vaporization. This is because the space of
the reactor to perform the reaction decreases as the quantity of
vapor increases.
Case 1 reports the highest temperature at the coil inlet and
outlet. The pilot plant of case 3 has the lower temperature at
the entrance. The temperatures in cases 2 and 4 are similar
(326 and 300 °C at the entrance of the coil, respectively).
In addition to the temperature effect, the residence time is
also important. Case 4 exhibits the longest residence time in the
soaker reactor, where the reaction is mainly performed. The
pilot plant is the case that has the shorter residence time.
Therefore, the residue conversion is the least of the four cases.
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Article
3.4.6. On the Effect of Variation of Liquid and Gas Flow
Rates. As has been stated before, including the change of
volume of the reacting system indeed modifies the flow rates of
liquid and gas during the reaction. For this to be verified, the
reactor model was solved by considering or not considering the
change of volume. The results for case 2C are shown in Figure
16 as an example. It is clearly seen that the inclusion of volume
in the reactor model strongly affects the predictions. Not
considering this change causes the residue mass fraction at the
outlet of the reactor to be approximateyl 6 wt % lower than
taking into account the change of volume.
■
CONCLUSIONS
The following conclusions were reached: A reaction scheme
with 9 pseudocomponents using kinetic expressions reported in
the literature is proposed. The vapor−liquid equilibrium affects
the reactor conversion prediction only at high temperatures and
space-time. The volume of liquid in the reactor decreases when
considering VLE. Pressure drop does not have great effect over
the residue conversion. The inclusion of the change of volume
in the reactor model strongly affects the residue conversion and
product yields. For similar situations, the reaction extent in the
soaker is greater than that in the coil. The temperature in the
soaker is lower than that in the coil, but the residence time is
much larger. The effect of residence time is greater than the
effect of temperature.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.iecr.5b01985.
Simulation data for the different cases, distillation curves
of feed and products, and heat capacity and molecular
weight of lumps (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: jancheyt@imp.
Notes
The authors declare no competing financial interest.
■
NOMENCLATURE
Aij = Arrhenius parameter defined in eq 4
ai = constants of the Arrhenius parameter Aij (i = 0−4)
Bij = Arrhenius parameter defined in eq 5
bi = constants of the Arrhenius parameter Bij (i = 0−2)
CSi = final molar concentration of pseudocomponent i
CSi0 = initial molar concentration of pseudocomponent i
Cp = heat capacity (kJ/kg-°C)
FT = liquid mass flow
f Si = mass fraction of pseudocomponent Si (i = 1−5)
f Si0 = initial mass fraction of pseudocomponent Si
f = vaporized fraction
Kj = equilibrium constant of pseudocomponent j
ΔHRi = reaction enthalpy (kJ/kg)
kij = rate constant for the reaction i → j (i,j = 1−5)
MWi = molecular weight of pseudocomponent “i”
N = number of pseudocomponents
P = pressure of the system
Pci = critical pressure of pseudocomponent I
Q = heat transfer rate from CSTR
ri = rate of reaction i (kg/h-m3)
DOI: 10.1021/acs.iecr.5b01985
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Industrial & Engineering Chemistry Research
rij = rate reaction of pseudocomponent i to produce
pseudocomponent j
Si = pseudocomponent i (i = 1−9)
S1 = gas
S2 = naphtha
S3 = light gas oil
S4 = heavy gas oil
S5−S9 = vacuum residue pseudocomponents
T = reaction temperature (°C)
ΔT = temperature difference between inlet and outlet of the
CSTR
Tci = critical temperature of pseudocomponent I
V = reactor volume
xj = molar fraction of liquid phase in VLE
yj = molar fraction of gas phase in VLE
zj = feed molar fraction composition
Greek Letters
α = relation between volumetric flow rate at inlet and outlet,
eq 7
ν0 = volumetric flow rate at the inlet of the CSTR (m3/h)
ν = volumetric flow rate at the outlet of the CSTR (m3/h)
ρ = density of reaction mixture (kg/m3)
τ = residence time (h)
ΦLj = fugacity coefficient of pseudocomponent i in liquid
phase
ΦGj = fugacity coefficient of pseudocomponent i in gas phase
ωi = acentric factor of pseudocomponent i
■
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