pubs.acs.

org/EF Article

Desulfurization of Fluid Catalytic Cracking Naphtha by Extractive

Distillation: A Universal Simulation Method Established Using the
Universal Quasi-Chemical Functional Group Activity Coefficient
Model
Yuhao Zhang, Feng Chen, Liang Zhao,* Jinsen Gao, Chunming Xu, Qingfei Meng, and Xiangqi Liu
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ABSTRACT: The extractive distillation process is gradually being used

for the desulfurization of fluid catalytic cracking (FCC) naphtha because
of its excellent octane number protection performance during
desulfurization. The key to this process is the separation of sulfides.
However, the composition of FCC naphtha is complicated and easily
changes, which seriously affect the separation performance. The
operating conditions need to be adjusted frequently with the change in
the different properties of feedstocks, which cost time, manpower, and
investment. In this study, we introduce a simulation method using the
universal quasi-chemical functional group activity coefficient (UNIFAC)
model to predict the process of desulfurization. In the simulation, the
group binary parameters for the UNIFAC model seriously affect the
reliability of the method. Therefore, the lacking parameters of the solvent
and sulfides were first regressively calculated by the experimental results
of the binary vapor−liquid equilibrium (VLE). All the values of (D−J) by the Herington integral method were under 10, which
means that the parameters obtained in this work were well correlated to those of the VLE experiments. Based on this, the prediction
simulation method was established and the maximum error of the compositions of the products between simulation and real-oil
experiment was only 0.5 wt %. According to the simulation, 98% of sulfides could be extracted under the optimal conditions (113 °C
at the extraction column, 178 °C at the solvent recycle column, etc.). The rule of the extraction of sulfides was thiophene sulfur >
mercaptan sulfur > thioether sulfur, which is consistent with the VLE study results. The sulfur content of the raffinate oil was
decreased to 9.3 mg/kg. It well met the latest gasoline standard and is appropriate for the prediction of the desulfurization of FCC
naphtha by the extractive distillation process.

1. INTRODUCTION could be used for blended components or transformed into

The desulfurization of fluid catalytic cracking (FCC) naphtha
is an everlasting problem that is always a hot topic in the
upgrading of the new process.1−4 The latest standard for
gasoline limits the sulfur content under 10 mg/kg.5 Gasoline
products lose about 2−3 units of octane number (ON)
because several high-ON olefins in FCC naphtha are saturated
to low-ON paraffin by the hydrodesulfurization (HDS) process
(the main desulfurization process used worldwide). In
addition, the saturation of olefins during HDS consumes a
large amount of hydrogen, which is contrary to the principle of
efficient resource utilization.6 On the basis of molecular
refining, controlling the saturation of olefins in the HDS
process can be used for the separation of olefins from FCC
naphtha, rather than improving the catalysts and HDS process.
Therefore, the desulfurization of the extractive distillation
process has been developed because it separates the olefins and
enriches the sulfides at the same time.7−9 The separated olefins
other high-ON components. The enriched sulfide fraction,
called as sulfur-rich oil, can be sent to the HDS unit directly for
deep desulfurization and can lose a small amount of ON
because the high-ON olefins are separated from the sulfur-rich
oil.10,11 The alkanol amines, morpholines, ester solvents, and
ionic liquids were used in the extractive distillation process,
which showed unique properties.12−17 However, the sulfolane
(SUL) solvent is still widely used because of its excellent bulk
properties, such as high selectivity, appropriate solubility, high
boiling point, high thermostability, and so on18−24 Although
Received: January 18, 2021
Revised: March 14, 2021
Published: March 22, 2021

© 2021 American Chemical Society https://doi.org/10.1021/acs.energyfuels.1c00195

6322 Energy Fuels 2021, 35, 6322−6331
Energy & Fuels
selecting the appropriate solvent is important for the extractive
distillation process, the composition of FCC naphtha seriously
affects the separation performance. For example, in our
previous study, we found that the SUL solvent was easier to
combine with thiophene than with 1-hexene.25 This is because
thiophene is an aromatic compound that can induce dipole
interactions and then selectively combine with the solvent.26
Moreover, the combination of SUL and thiophene was tighter
than that of SUL and benzene. This is because the initial dipole
moment of thiophene is 0.786D, which is greater than that of
benzene (0D). The initial dipole moment also affects the
combination of the component and solvent.27 Last but not
least, thiophene is more likely to combine with the SUL
solvent than 3-methylthiophene. This is because the ring
structure of thiophene is “clean,” whereas that of 3-
methylthiophene contains a methyl chain. The space steric of
thiophene is smaller than that of 3-methylthiophene. In
summary, the different components to be separated can
significantly affect the separation performance due to their
different structures. Moreover, the content of each component
can also affect the separation performance.
The composition of FCC naphtha is complicated, which
consists of paraffin, olefin, naphthenic hydrocarbon, aromatic
compounds, and sulfide.28−30 Moreover, the content of each
kind of component is always changing due to the different
properties of the materials and operating conditions of the
FCC equipment. The operating conditions for the separation
of FCC naphtha should be modified frequently to produce the
certified product, which consumes time, manpower, and
investment. It is indeed to establish a convenient and reliable
simulation method to swiftly offer the optimal industrial
operating conditions for the refinery. However, using the
vapor−liquid equilibrium (VLE) experiment to study the
relationship between sulfides and SUL could be time-
consuming, considering the wide variety of sulfides present
in FCC naphtha.31 Many predictive calculation methods have
been developed to improve the efficiency of research, such as
the Wilson,32 NRTL,33 and UNIQUAC models.34 Moreover,
the greater the number of binary parameters, the higher the
reliability of the predicted result.35,36 The binary parameters
between components and solvents should be calculated as
much as possible, which requires huge VLE experiment data.
In recent years, the universal quasi-chemical functional
group activity coefficient (UNIFAC) predictive model has
been used to predict the VLE process because only a limited
number of VLE experimental data are needed for the system
with a complex composition.37−39 For the SUL solvent
separation process, Habaki et al.40 established a simulation
method using the UNIFAC model to predict the separation
performance of aromatic compounds from reformate gasoline
by the SUL solvent. The distribution coefficient mi of the
calculation was well correlated with the experimental results.
Wang et al.41 used the UNIFAC model to study the VLE of
SUL and aromatic compounds. The group binary parameters
were successfully established, and the maximum and average
absolute deviations of each component between the simulation
and experiment were 0.0237 and 0.0137, respectively. Li et
al.42 used the UNIFAC model to predict the extractive
distillation of benzene and cyclohexane using the SUL solvent
entraining an ionic liquid. The method established using the
UNIFAC model could well describe the solvent separation
performance and screened the optimal entrainer for the
process.
pubs.acs.org/EF Article
Although the VLE between component molecules was
simplified to the interaction between groups by the UNIFAC
model, the lack of group binary parameters of a new field, such
as the separation of FCC naphtha, affects the reliability of
prediction. To improve the accuracy of the simulation results,
the unknown group binary parameters should be calculated.
The NIST and Aspen Plus databases lack the group binary
parameters between the SUL solvent and the sulfides for the
simulation of the desulfurization by the extractive distillation
process, which significantly reduces the reliability of the
simulation method by the UNIFAC model. This is the major
reason why this model is not used in the simulation of this
process.
Based on these findings, the SUL solvent was used in
desulfurization by means of extractive distillation. Moreover,
the typical sulfides of FCC naphtha such as thiophene,
mercaptan, and thioether were used in this study. The VLEs of
SUL + thiophene, SUL + mercaptan, and SUL + thioether
were determined. According to these VLEs, the group binary
parameters of SUL and sulfides were calculated, and the
simulation method established using the UNIFAC model was
evaluated with a continuous extractive distillation experiment.
2. EXPERIMENTAL SECTION
2.1. Materials. 2.1.1. Chemical Materials. SUL was selected as
the solvent. Thiophene, dimethyl sulfide, and ethanethiol were
selected as sulfides. Benzene and toluene were used as aromatics. The
materials were purchased from Aladdin Reagent. The chemical
structures and physical properties of materials are listed in Table 1.
Table 1. Chemical Structures and Physical Properties of
Materials in the Vapor and Liquid Phase Studied
2.1.2. Heavy-Fraction FCC Naphtha. The Huabei refinery heavy-
fraction FCC naphtha was used to evaluate the reliability of the
simulation method in this study. Its composition of paraffin (P), olefin
(O), naphthenic hydrocarbon (N), and aromatics (A) is shown in
Table 2.
2.2. Apparatus and Procedures. 2.2.1. Binary VLE Experiment.
Binary VLE measurements were performed in a Rose equilibrium still
(Figure 1) and conducted under atmospheric pressure. A
thermocouple measured the temperature of the vapor and liquid
phases. For the partial condensation, the temperature of condensate
water was controlled under 2 °C to achieve sufficient reflux. To
ensure that the apparatus was airtight, a U-type manometer filled with
water was attached to the outlet. During the experiment, the binary
mixture was carefully and slowly heated to place the liquid and vapor
phases into circulation. When the temperature of the mixture reached
the expected equilibrium temperature or tended to stable, the heating
power was continued to increase. If the temperature is still constant,
the temperature may be the equilibrium temperature. The heating
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Table 2. Composition of Heavy-Fraction FCC Naphtha 2.2.3. Analysis and Calculation Method. The composition of the
(>100 °C)a product was determined using the Agilent 7890B GC station (Agilent
Technologies Corporation, USA). The chromatographic column was
cnum n−P, wt % i−P, wt % O, wt % N, wt % A, wt % total, wt % 50 m × 0.2 mm × 0.2 μm, and the detector used was the flame
6 0.0 0.0 0.6 0.0 0.0 0.6 ionization detector. For the testing, 0.2 μL of the sample was injected
7 0.4 0.1 4.8 0.6 0.7 6.6 into the port. Then, the liquid sample was quickly vaporized to gas at
250 °C. During the detection process, the initial temperature was kept
8 1.2 3.9 11.6 7.2 0.3 24.1
at 35 °C for 10 min. Then, the temperature of the detector was
9 0.4 5.3 13.3 11.7 4.1 34.8 increased to 130 °C at a rate of 2 °C/min until the temperature
10 0.1 5.2 7.8 4.8 4.4 22.3 reached 280 °C and maintained for 10 min. The composition of
11 0.4 5.8 1.9 0.3 1.2 9.6 vapor- and liquid-phase samples was analyzed using PONA software,
12 0.0 1.9 0.0 0.0 0.0 2.0 which was purchased from the Sinopec Research Institute of
total 2.5 22.2 40.0 24.6 10.7 100.0 Petroleum Processing. Each sample was measured three times to
a
The sulfur content is 456 mg/kg. ensure accuracy.
2.2.4. Process Simulation. In this study, the process simulation was
carried out using Aspen Plus v8.8. The UNIFAC-Original model was
used to predict the process of extractive distillation of FCC naphtha
to separate its sulfides. The binary interaction parameters of critical
components, such as thiophene sulfur−SUL, mercaptan sulfur−SUL,
and thioether sulfur−SUL, were established in this study. The process
simulation could be realized and the accuracy could be improved only
through this way. Huabei FCC naphtha was used as the composition
of the feedstock for the simulation (Table 10). Seven sulfides that
contained all three kinds of sulfides in FCC naphtha were studied in
the process simulation, and the total sulfur content was 456 mg/kg.
To simulate the feedstock close to the actual FCC naphtha, typically,
C6−C7 hydrocarbons were chosen for calculation.
The initial operating conditions for this simulation are shown in
Table 3, which were based on an industrial situation.

3. RESULTS AND DISCUSSION

Figure 1. Diagram of a modified Rose equilibrium still. (1) Heating
rod, (2) sample connection of the liquid phase, (3) thermocouple, (4)
sample connection of the vapor phase, (5) condensate water, (6)
attachment of a U-type manometer to ensure that the Rose apparatus
was airtight, and (7) condenser pipe.
power is maintained and if the temperature could hold for more than
30 min, it can be considered as two-phase equilibrium. In this study,
we first tested the binary VLE of benzene and toluene using this
apparatus. The experimental data were compared with the literature
data to confirm the accuracy of the experiment. Then, we controlled
the content of SUL and sulfide in the binary mixture, starting with
pure sulfide, increasing the concentration of SUL, and finally pure
SUL. Each group of experiments contained 11−14 experimental data,
and each experiment sample was collected three times.
2.2.2. Continuous Extractive Distillation Experiment. The
extractive distillation column (EDC) and solvent recycle column
(SRC) were designed by the simulation results; the flowchart of
continuous extractive distillation is shown in Figure 2. The theoretical
stage number of the EDC and SRC was 30. The operating conditions
were set by the optimized simulation results, which are shown in
Figure 5. The solvent and FCC naphtha were sent from the top and
middle of the extraction column, respectively. The solvent and FCC
naphtha were in countercurrent contact in the extraction column.
Then, the rich solvent extract oil was sent to the middle of the SRC
using the pump for the separation of sulfur-rich oil and the solvent.
The reflux ratio of extraction and SRC could be controlled to
determine the flow rate of the raffinate oil and sulfur-rich oil. The
recycled solvent was sent back to the extraction column after solvent−
water separation using the solvent tank.
6324
3.1. Verification Experiment for the Rose Equilibrium
Still. To test the accuracy and stability of the VLE data
obtained, the known VLE data for benzene (1) and toluene
(2) were determined using this apparatus. This group of VLE
experiments was started with pure benzene at 101.325 kPa, and
then, the toluene content was gradually increased until the
system was all toluene.
The VLE data are shown in Table 4, where x represents the
mass fraction of components in the liquid phase and y
represents the mass fraction of components in the vapor phase.
T is the temperature of equilibrium. As can be seen, the
equilibrium temperature increased with the increase in toluene
content in the binary system because the boiling point of
toluene is higher than that of benzene.
Figure 3 shows the T−x−y phase diagram of benzene (light
component) in benzene (1) and toluene (2) binary mixture.
The solid triangle and circle represent the content of benzene
in the vapor and liquid phases from this experiment,
respectively. The hollow triangle and circle represent the
content of benzene in the vapor and liquid phases from the
literature,43 respectively. Figure 3 shows that the experimental
data corresponded closely to the data reported in the literature,
which indicated that the high accuracy and stability were due
to the Rose equilibrium still. Therefore, this apparatus could be
adapted to measure the VLE data of the FCC naphtha system
effectively.
3.2. Binary VLE Experiments of Sulfides and SUL.
Currently, the most widely used solvent for extractive
distillation to separate sulfides of FCC naphtha is SUL.
Therefore, we used SUL as a solvent to study its VLE
relationship with sulfides of FCC naphtha. The VLE
experiments were performed for three different binary
sulfide−SUL systems at 101.325 kPa. After a careful study of
the composition of the FCC naphtha, the thiophene,
ethanethiol, and dimethyl sulfides comprised the most content
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Figure 2. Flowchart of continuous extractive distillation.

Table 3. Operating Conditions of Simulation of FCC Table 4. VLE Data in the Mass Fraction for the Binary
Naphtha Extractive Distillation System Benzene (1) and Toluene (2) at 101.325 kPa
feed and columns items data feed volume ratio
(benzene:toluene) Ta , K x1 x2 y1 y2
FCC naphtha total flow rate, kg/h 1000−1500
temperature, °C 30 prue benzene 353.15 1 0 1 0
pressure (absolute), kPa 500−1000 9:1 355.45 0.8822 0.1178 0.9555 0.0445
total flow rate, kg/h 3000−4500 8:2 357.15 0.7925 0.2075 0.9123 0.0877
SUL temperature, °C 50−60 7:3 359.75 0.6815 0.3185 0.8112 0.1888
pressure (absolute), kPa 400−800 6:4 362.55 0.5695 0.4305 0.7682 0.2318
EDC number of stages 15−40 5:5 364.25 0.5044 0.4956 0.7169 0.2831
pressure (absolute), kPa 500−1000 4:6 368.45 0.3752 0.6248 0.5866 0.4134
number of stages 15−40 3:7 372.55 0.2558 0.7442 0.4421 0.5579
SRC condenser total 2:8 376.65 0.1475 0.8525 0.2920 0.708
reflux ratio 0.5−2 1:9 380.65 0.0673 0.9327 0.1322 0.8678
pressure (absolute), kPa 10−60 pure toluene 383.75 0 1 0 1
a
T is the equilibrium temperature.
and typical sulfides in thioether, mercaptan, and thiophenic
sulfide sulfides, which were chosen for the binary VLE significantly increased with the addition of SUL because the
experiments. When the compositions were fully circulated boiling point of SUL (285 °C) is much higher than that of
and became identical both in the vapor and liquid phases, the thiophene (84 °C). The ratio of the final group of binary
temperature of the system was regarded as the equilibrium mixtures was 1:9, of which the equilibrium temperature was
temperature. The content of components in the vapor and 478.15 K.
liquid phases was only related to the equilibrium temperature Normally, components with relatively low boiling points are
under constant-pressure conditions. selected as the key components for the research when
The content of thiophenic sulfur in FCC naphtha is not less analyzing binary VLE results. Therefore, the T−x−y phase
than 85% of total sulfur, which is the most important sulfide. diagram of thiophene was drawn in this present study, which is
Therefore, it is necessary to study the VLE relationship shown in Figure 4.
between such sulfides and SUL when using the extractive As can be seen in Figure 4, the dash line (vapor phase)
distillation process to separate sulfides of FCC naphtha. Table represented the change in saturated steam composition with
SI2 shows the results of binary VLE for thiophene (1) and temperature. The region above this line was a vapor-phase
SUL (2), wherein thiophene is the most basic and typical zone. Conversely, the full line (liquid phase) indicated the
sulfide in thiophenic sulfurs. The equilibrium temperature was relationship between the boiling point and the composition of
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Figure 3. T−x−y phase diagram for benzene (1) and toluene (2) in
experiments and the literature. Blue triangle up solid, liquid-phase
data of the experiment; red circle solid, vapor-phase data of the
experiment; triangle up open, liquid-phase data of the literature; and
circle open, vapor-phase data of the literature.
Figure 4. Experiment and calculation of the VLE phase diagram for
sulfide(1) and SUL(2). Dark blue box solid, content of thiophene
(experiment); box, content of thiophene (calculation); yellow star
solid, content of ethanethiol (experiment); star open, content of
ethanethiol (calculation); green tilted square solid, content of
dimethyl sulfide (experiment); and tilted square open, content of
dimethyl sulfide (calculation).
the liquid phase. The region above this line was the liquid-
phase zone. The area surrounded by the vapor- and liquid-
phase line was a two-phase zone, in which the point of the
system was divided into two conjugated vapor−liquid phases.
T1* and T2* represent the boiling point of pure thiophene and
SUL, respectively. The solid and hollow symbols represent the
composition of the experimental and calculation results,
respectively.
At first, we attempted to add SUL to thiophene with equal
proportions, which could be seen from the distribution of
liquid-phase data points and in Table SI1 as well. However,
when the content of thiophene in the binary system was lower
than 40 v % (thiophene/SUL = 4:6), the distribution of vapor-
phase data points was sparser than that of high thiophene
content. The equilibrium temperature changed obviously when
the thiophene content was lower than 40 v % in the thiophene
and SUL binary VLE experiment, which is to say that the
interaction between thiophene and SUL was tighter with low
thiophene content. Moreover, the content of thiophene in the
vapor phase decreased remarkably to less than 0.98 wt % when
the content of thiophene in a binary system was less than 40 v
%. This also indicated that the effect of SUL on thiophene was
increased when the content of thiophene was below 40 v %.
pubs.acs.org/EF Article
This is because the structure of thiophene is similar to that of
SUL, thereby facilitating the combination, which has been
carefully studied in our previous research.25,27
Then, the mercaptan sulfur was studied. Although the
content of mercaptan sulfur was much lower than that of
thiophenic sulfur in FCC naphtha and mainly concentrated in
light fractions, the influence on the sulfur content in vehicle
gasoline cannot be ignored. In this section, we selected
ethanethiol, which is a typical mercaptan sulfur in FCC
naphtha, to study its VLE relationship with SUL. The result is
shown in Table SI2. The amount of SUL added each time
could be controlled, whereas the amount of the VLE sample
taken from each group was difficult to fix. Therefore, in the
following experiments, we only increased the content of SUL
group by group and no longer fixed the change in the ratio for
each group. The equilibrium temperature was changed from
310.45 to 558.15 K. After the penultimate group, the
equilibrium temperature changed inconspicuously, so we
used pure SUL VLE data as the final group. The equilibrium
temperature of the last set of binary mixtures (SUL content =
80 v %) was 471.15 K, which was lower than that of the group
of thiophene and SUL.
Ethanethiol was selected as the key component to create the
T−x−y VLE phase diagram. The content of ethanethiol in the
vapor phase was not less than 0.9980 wt % when the content of
SUL in the binary mixture was less than 70 v %. Thereafter, the
content of ethanethiol decreased obviously in the vapor phase.
The interaction between ethanethiol and SUL was tighter than
that of thiophene and SUL when the content of SUL was high.
This may be because the S atom of ethanethiol was attached to
the end position of the molecule. The steric hindrance was
relatively low compared with that of the S atom of thiophene.
At low concentrations, the chance of approaching SUL is
greater than with thiophene.
The content and distribution of thioether sulfur in FCC
naphtha are similar to those of mercaptan sulfur. In this
section, dimethyl sulfide was studied because of its
representative structure and large content in thioether sulfur.
The VLE results of dimethyl sulfide and SUL are shown in
Table SI3. The equilibrium temperature increased with the
addition of SUL. The last equilibrium temperature of the
binary mixture we made was 410.15 K, which was the lowest in
the three kinds of sulfides. It was difficult for the binary
mixtures to reach a VLE state when the content of SUL was
higher than 65 v %.
The distribution of dimethyl sulfide in the vapor phase was
different from that of the other two kinds of sulfide that the
content in the vapor phase is hard to find and obviously
changed with the change in concentration of binary mixtures.
This is because the S atom of dimethyl sulfide was linked in the
middle of the molecule. Although the presence of the S atom
allows dimethyl sulfide to get close to SUL, the decrease in the
bilaterally symmetric branch hinders its combination with
SUL.
3.3. Thermodynamic Consistency Test. Verifying the
accuracy of the experimental data is an important part of the
phase equilibrium experiment. The semi-empirical method of
the thermodynamic consistency test for VLE data proposed by
Herington was employed to evaluate the results of the
experiments. The VLE data suit the thermodynamic
consistency if (D−J) < 10.44 D and J are defined as follows
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Table 5. Parameters for the Extended Antoine Equation

materials C1 C2 C3 C4 C5 C6 C7
thiophene 93.1930 −7001.5000 0 0 −10.7380 8.23 × 10−6 2
ethanethiol 65.5510 −5027.4000 0 0 −6.6853 6.32 × 10−6 2
dimethyl sulfide 84.3900 −5740.6000 0 0 −9.6454 1.01 × 10−5 2
SUL 150.6600 −13283.0000 0 0 −19.4290 1.34 × 10−2 1

(S + ) − (S − ) VLE data mentioned above. Normally, the component

D = 100 × molecules should be divided into some groups in a certain
(S + ) + (S − ) (1)
way at first, which are shown in Table 7.
where S+ and S− represent the area coming from the diagram
of ln(γ1/γ2) ≈ x1. Table 7. UNIFAC Groups for Thiophene, Ethanethiol,
Dimethyl Sulfide, and SUL
(Tmax ) − (Tmin)
J = 150 × molecular group type group code group number
Tmin (2)
thiophene ACS 3750 1
where Tmax and Tmin are the maximum and minimum CH3 1015 1
temperature of equilibrium, respectively. ethanethiol CH2SH 2400 1
As can be seen from the abovementioned equations, the dimethyl sulfide CH3 1015 1
calculation of the activity coefficient of each component under CH3S 3650 1
the experimental conditions was the focus of this section. The SUL (CH2)4Su2 3250 1
saturated vapor pressure in different equilibrium temperatures CH2 1010 2
could be calculated first by the extended antoine equation,
which is expressed as follows With these groups and VLE experimental data, we used VB
C 2i programming to calculate the binary interaction parameters
ln pi* = C1i + + C4iT + C5i ln T + C6iT C7i between three kinds of sulfides and SUL using the UNIFAC-
T + C 3i (3)
Original equation,45 which is expressed as follows
i a y
Ψnm = expjjj− nm zzz
where Pi* (bar) is the saturated vapor pressure in the
k T {
temperature T (K). The values of C1−C7 are listed in Table 5.
Then, the saturated vapor pressure could be calculated using (5)
the abovementioned parameters. With these parameters, the anm is the binary interaction parameter that we need to
activity coefficients of each component could be calculated calculate using the VLE experimental data, where n and m
using the following equation represent different group types.
Pyi During the calculation, some factors such as the volume
γi = parameter (Rk) and surface area parameter (Qk) were
Pi*xi (4) indispensable, which are shown in Table 8.
Therefore, the values of γi and ln(γ1/γ2) are also presented
in Table SI4, and Figures SI1−SI3 show the curve of ln(γ1/γ2) Table 8. Volume Parameter (Rk) and Surface Area
≈ x1 of the three groups of experiments. Parameter (Qk) of the UNIFAC-Original Model
Finally, the factors of the Herrington semi-empirical method main-group type sub-group type Rk Qk
(D and J) were calculated, and the results are listed in Table 6. C4H4S C4H4S 2.8569 2.1400
CH3 CH3 0.9011 0.8480
Table 6. Results of the Consistent Thermodynamic Test CH2S CH3S 1.6130 1.3680
binary system D J D−J CH3SH CH2SH 1.6510 1.3680
(CH2)4SO2 (CH2)4Su2 2.6869 2.1200
thiophene (1)-SUL (2) 1.78 49.04 −47.26
CH2 0.6744 0.5400
ethanethiol (1)-SUL (2) 35.17 38.06 −2.89
dimethyl sulfide (1)-SUL (2) 25.90 26.86 −0.96

The value of D−J in the three binary systems was lower than
Therefore, the binary interaction parameters for C4H4S−
10, which means that all VLE data were reliable regarding the
(CH2)4SO2, CH3S−(CH2)4SO2, and CH3SH−(CH2)4SO2
standard of the Herington semi-empirical method.
were calculated (Table 9).
3.4. Correlation of the VLE Data with the UNIFAC
Method. The VLE relationship between sulfides and SUL is
the basis of extractive distillation to separate sulfides of FCC Table 9. Calculation Results of Group Interaction
naphtha. In this study, we selected the UNIFAC method to Parameters (anm and amn) for the UNIFAC-Original Model
predict the process of extractive distillation of FCC naphtha to
binary system (n−m) anm amn
separate sulfides. The binary interaction parameters of
thiophene sulfur−SUL, mercaptan sulfur−SUL, and thioether CH3−(CH2)2Su2 −23.4922 −1.3190
sulfur−SUL were still lacking after checking the NIST and C4H4S−(CH2)4Su2 −23.4922 −1.3190
Aspen Plus database. Therefore, in this study, the parameters CH3S−(CH2)4Su2 53.0419 55.4901
of sulfides and SUL of FCC naphtha were established using the CH3SH−(CH2)4Su2 −5.2344 −20.8452

6327 https://doi.org/10.1021/acs.energyfuels.1c00195
Energy Fuels 2021, 35, 6322−6331
Energy & Fuels pubs.acs.org/EF Article

3.5. Simulation of Extractive Distillation to Separate Table 10. Composition of Simulation Feedstock
Sulfides in FCC Naphtha. The UNIFAC-Original model
components molecular formula contents, wt %
with parameters added could be used to simulate the
separation of sulfides of FCC naphtha by extractive distillation, n-hexane C6H14-1 1.8
which could quickly predict the separation effect of extractive 2-methylpentane C6H14-2 9.8
distillation on sulfides in FCC naphtha and evaluate the 1-hexene C6H12-3 13.7
feasibility of the separation scheme. The most popular software Benzene C6H6 1.3
for process simulation is Aspen Plus, which is suitable for the n-heptane C7H16-1 1.5
combination of laboratory research data and industrial 2-methylhexane C7H16-2 3.7
applications. 1-heptene C7H14-7 7.1
However, the accuracy of the binary interaction parameters Cycloheptane C7H14-1 5.3
that we calculated and applicability to Aspen Plus software toluene C7H8 6.1
need to be verified first. The binary interaction parameters of 1-methyl-2-ethylbenzene C9H12 1.5
thiophene and SUL that were calculated were inputted into the 1,2,4-trimethylbenzene C9H12 6.2
software. The contents of thiophene and SUL in the vapor and 1,3,5-trimethylbenzene C9H12 2.5
n-octane C8H18-1 0.7
liquid phases were simulated with a computer using the
2,6-dimethylheptane C9H20 4.0
UNIFAC-Original model. The comparison of the T−x−y
3-methylnonane C10H22 1.1
phase diagram is shown in Figure 4. Thiophene was selected as
4-methylnonane C10H22 1.0
the key component for comparison.
5-methylnonane C10H22 0.4
As can be seen in Figure 4, the simulated data were in
2-methylheptane C8H18-2 4.5
satisfactory agreement with the experimental data. The
1-octene C8H16-16 6.0
simulation points were well close to the experimental data.
2-methylnonane C10H22 2.4
Therefore, an FCC naphtha extractive distillation process was
Cyclooctane C8H16-D6 3.0
simulated with Aspen Plus using the UNIFAC-Original model
7-methyl-1-octene C11H24 5.3
with added binary interaction parameters. Then, the binary
Ethylbenzene C8H10-4 10.6
interaction parameters between paraffin−SUL, olefin−SUL,
Tetrahydrothiophene C4H8S 4.2 × 10−3
and aromatic−SUL from the Aspen Plus v8.8 database could
Thiophene C4H4S 2.2 × 10−2
be used. The initial operating conditions are shown in Table 3,
2-ethylthiophene C6H8S-D1 6.7 × 10−3
and the composition of the feedstock for the simulation is
2,5-dimethylthiophene C6H8S-D2 3.4 × 10−3
shown in Table 10.
n-hexyl mercaptan C6H14S 3.2 × 10−3
The flowchart of the extractive distillation process is shown
di-n-propyl-sulfide C6H14S-D1 4.3 × 10−3
in Figure 5. The plate number of the EDC and SRC was 30.
2-n-propylthiophene C7H10S 1.8 × 10−3
SUL was chosen as the solvent, which was sent to the 8th plate
of the EDC. At the same time, the heavy fraction of FCC
naphtha was fed to the 25th plate, and raffinate oil was naphtha extractive distillation process using these conditions is
collected from the top of the column. D1 was called as raffinate shown in Table 12. The solvent was barely residual in the
oil, which was an ultra-low sulfur fraction. The rich-solvent raffinate oil and sulfur-rich oil.
fraction (W1) flowed to the middle of the SRC. The mixed Importantly, 98.0% of sulfides in FCC naphtha were
liquid was separated to recycle the solvent (W2) and sulfur- separated into the sulfur-rich fraction. In addition, the
rich oil (D2). After adjusting the initial operating conditions, aromatics were also concentrated into the sulfur-rich fraction,
the optimal operating conditions of the EDC and SRC are whereas alkanes such as olefin were separated into the raffinate
shown in Figure 5. As can be seen, the top temperature of the oil. In this way, the hydrogen consumption in the
EDC column was 113 °C, which indicates that components desulfurization process, the difficulty of the HDS process,
with a high boiling point could be separated from the top and the loss of the octane number could all be significantly
column. In the condenser, the extract oil was sent to the SRC reduced.
column at 82 °C. This temperature ensures the fluidity of the For more details, Table 13 shows the results of the content
extract oil with both heavy fractions of FCC naphtha and the of seven sulfides in raffinate and feedstock. As can be seen, the
SUL solvent. The bottom temperature of the SRC was separation rate of each kind of sulfides was ordered as
controlled at 178 °C, which was lower than the boiling point of thiophene sulfur > mercaptan sulfur > thioether sulfur, which
the SUL solvent (about 213 °C at 0.3 kPa). Therefore, the was consistent with the VLE study results.
SUL solvent and heavy fraction of FCC naphtha could be well
separated. On this basis, about 48.7% of FCC naphtha was 4. CONCLUSIONS
separated to the raffinate oil, whereas the rest of the FCC In this work, a series of VLE experiments for binary mixtures
naphtha fraction was extracted to the sulfur-rich oil. including the SUL solvent with thiophenic sulfur, mercaptan
The simulation result was compared with the continuous sulfur, and thioether sulfur (thiophene, ethanethiol, and
extractive distillation experiment data, wherein the exper- dimethyl sulfide, respectively) was conducted at 101.325 kPa
imental operating conditions were set by the optimal in a Rose equilibrium still.
simulation results. As can be seen in Table 11, the maximum According to the VLE experimental results, the strength of
error of the component content between the simulation and the interaction of SUL with each sulfide was ordered as
experiment was only 0.5 wt % (C10 of i-paraffin). This follows: thiophene−SUL > ethanethiol−SUL > dimethyl
indicates that the simulation method we established using the sulfide−SUL. Thiophene and ethanethiol showed significant
UNIFAC model could well describe the separation process of interactions with SUL when the concentrations of thiophene
FCC naphtha. On this basis, the simulation result of the FCC and ethanethiol were below 40 and 30 wt % of the binary
6328 https://doi.org/10.1021/acs.energyfuels.1c00195
Energy Fuels 2021, 35, 6322−6331
Energy & Fuels pubs.acs.org/EF Article

Figure 5. Simulation flowchart of the extractive distillation process for FCC naphtha.

Table 11. Composition of Raffinate Oil in Experiment and Simulationa

nP, wt % iP, wt % O, wt % N, wt % A, wt %
cnum EXP. SIM. EXP. SIM. EXP. SIM. EXP. SIM. EXP. SIM.
6 1.0 1.1 14.4 14.2 29.6 29.6 3.8 3.6 0.0 0.0
7 1.4 1.5 5.2 5.7 6.0 6.1 3.2 2.8 6.1 5.7
8 1.1 1.3 2.2 2.3 3.0 3.3 2.7 2.5 2.1 2.4
9 0.6 0.8 1.2 1.3 2.7 2.8 1.6 1.8 1.5 1.4
10 0.5 0.6 0.7 0.8 1.3 1.2 1.7 1.4 0.5 0.7
11 0.7 0.5 2.4 2.7 0.3 0.4 1.6 1.2 1.0 0.7
total 5.3 5.8 26.1 27.0 42.9 43.4 14.6 13.3 11.2 10.9
a
EXP means the experiment data; SIM means the simulation data.

Table 12. Product Composition of the EDC and SRC

column n−P, wt % i−P, wt % O, wt % N, wt % A, wt % sulfur content mg/kg SUL wt %
EDC D1 5.8 27.0 43.4 13.3 10.9 9.2 0.0
W1 0.2 0.1 6.1 13.0 80.5 448.9 100.0
SRC D1 0.2 0.1 6.1 13.0 80.5 594.2
W1 >99.9

Table 13. Distribution of Sulfur Content in Raffinate and could be decreased from 456.0 to 9.3 mg/kg. The highest
Feedstock separation rate of thiophenic sulfur was 99.4% (thiophene).
The separation rate of mercaptan sulfur was 93.1%, whereas
feedstock, raffinate, separation
sulfides mg/kg mg/kg rate, % that of thioether sulfur was 91.7%. Moreover, the optimal
operating conditions were used for the continuous extractive
Tetrahydrothiophene 42.0 0.8 98.1
distillation experiment. The maximum error of the product
Thiophene 220.0 1.4 99.4
composition was only 0.5 wt %, indicating that the simulation
2-ethylthiophene 67.0 0.9 98.7
method that we built could well describe the FCC naphtha
2,5-dimethylthiophene 34.0 0.4 98.8
extractive distillation process and is convenient for optimizing
2-n-propylthiophene 18.0 0.2 98.9
industrial operating conditions. On this basis, a process
n-hexyl mercaptan 32.0 1.9 94.1
simulation method was established. It could quickly predict
di-n-propyl-sulfide 43.0 3.7 91.4
the effect of FCC gasoline extractive distillation on the
total, mg/kg 456.0 9.3
separation of sulfides and swiftly offer optimized operating
conditions for the industrial application.

■
mixture, respectively. Based on the binary VLE data, the group
binary interaction parameters of C4H4S−(CH2)4Su2, CH3S− ASSOCIATED CONTENT
(CH2)4Su2, and CH3SH−(CH2)4Su2 were calculated using the
UNIFAC-Original model. By applying these parameters and
*
sı Supporting Information
The Supporting Information is available free of charge at
the UNIFAC-Original model provided by Aspen Plus, the
https://pubs.acs.org/doi/10.1021/acs.energyfuels.1c00195.
calculation of the VLE data was well correlated with the
experimental results. Then, the simulation model of the FCC Binary VLE data of thiophene−SUL, ethanethiol−SUL,
naphtha extractive distillation process was established. The and dimethyl sulfide−SUL and thermodynamic con-
operating conditions were optimized that the number of sistency test of these three groups of experimental data
theoretical plates of the EDC and SRC was 30 and the highest (PDF)
temperature of the EDC and SRC was 113 and 178 °C, Simulation method of the FCC naphtha extractive
respectively. In this way, the sulfur content of FCC naphtha distillation process, group binary parameters of SUL and
6329 https://doi.org/10.1021/acs.energyfuels.1c00195
Energy Fuels 2021, 35, 6322−6331
Energy & Fuels
sulfides for the UNIFAC model, sulfides of FCC
naphtha separated into six groups, and sulfur content
of raffinate oil (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Liang Zhao − State Key Laboratory of Heavy Oil Processing,
China University of Petroleum, Beijing 102249, China;
orcid.org/0000-0003-3585-6020; Phone: 86-10-
89739078; Email: liangzhao@cup.edu.cn; Fax: 86-10-
69724721
Authors
Yuhao Zhang − State Key Laboratory of Heavy Oil Processing,
China University of Petroleum, Beijing 102249, China
Feng Chen − State Key Laboratory of Heavy Oil Processing,
China University of Petroleum, Beijing 102249, China
Jinsen Gao − State Key Laboratory of Heavy Oil Processing,
China University of Petroleum, Beijing 102249, China
Chunming Xu − State Key Laboratory of Heavy Oil
Processing, China University of Petroleum, Beijing 102249,
China
Qingfei Meng − Hebei Jingzhi Technology Company, Limited,
Cangzhou, Hebei 061000, People’s Republic of China
Xiangqi Liu − Hebei Jingzhi Technology Company, Limited,
Cangzhou, Hebei 061000, People’s Republic of China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.energyfuels.1c00195
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors acknowledge the support from the National
Natural Science Foundation of China (21838011, 21822810,
and 22021004), National Key Research and Development
Program (2018YFC1902603), reaction of olefin catalytic
pyrolysis-fundamental meso-science of transfer process and a
new generation industrial application (92034302), National
key Research and Development Program Nanotechnology
Specific Project (2020YFA0210900), National Postdoctoral
Program for Innovative Talent (BX20200383), and Science
Foundation of China University of Petroleum, Beijing
(462020xkbh002).
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