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Chemical Engineering and Processing 49 (2010) 9196

Contents lists available at ScienceDirect

Chemical Engineering and Processing:


Process Intensication
journal homepage: www.elsevier.com/locate/cep

Process analysis of the extract unit of vacuum residue through mixed


C4 solvent for deasphalting
Fahai Cao , Dan Jiang, Wudong Li, Pingan Du, Guizhong Yang, Weiyong Ying
School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

a r t i c l e

i n f o

Article history:
Received 11 August 2009
Received in revised form
17 November 2009
Accepted 25 November 2009
Available online 1 December 2009
Keywords:
Mixed C4 solvent
Solvent deasphalting (SDA)
Deasphalted oil (DAO)
Simulation

a b s t r a c t
By employing the EXTRACT module in Aspen Plus Software with the aid of selected PSRK equation from
our previous work [W. Li, P. Du, F. Cao, W. Ying, D. Fang, Simulation and optimization of the extract
segment of solvent deasphalting plant, Computers and Applied Chemistry, 26 (2009) 455460] [18],
this work simulated a solvent deasphalting (SDA) process with mixed C4 solvent and the feedstock of
vacuum residue (VR) obtained from a mixed crude oil (Zhongyuan oil:Tahe oil:Changqing oil:Oman crude
oil:Zaro crude oil = 35:5:2:40:18, wt/wt). The feed of VR was lumped as parafnic, primitive and aromatic
components according to their calculated KUOP values. The relative errors not more than 3.94% illustrated
the simulated results are comparable with the industrial data for both feedstock (VR and mixed C4 solvent)
and products (deasphalted oilDAO and deoiled asphaltDOA). The DAO yield was predicted to reduce
to 47.2% from 58.0% with increasing temperature of mixed C4 solvent from 100 to 120 C under operating
model-I, but increased from 51.6% to 56.1% with solventVR ratio up to 6.5 from 4.5. In addition, a heavier
mixed C4 solvent would facilitate remarkable improvement of DAO yield but deteriorate its quality.
2009 Elsevier B.V. All rights reserved.

1. Introduction
As the crude oil reserves suffer from depletion and available
petroleum feedstock is becoming progressively heavier, and the
demand for light oil is on the rise, it is imperative to upgrade
petroleum residues and convert them into light products. With
the aid of excellent afnity of light hydrocarbon solvent (such as
propane, butane or their mixtures) to parafnic component, the
solvent deasphalting (SDA) process is an effective extraction process intensied by solvent addition which produces light oils of
high quality from vacuum residues (VRs). Thus, SDA is becoming
a dominating technology in the renery plants [14] that avoids
decomposition of hydrocarbons of high molecular weight due to its
lower operation temperature. Now, Kerr-McGees ROSE (Residue
Oil Supercritical Extraction) and UOPs DEMEX are still two SDA
processes of high importance in the world [5,6].
During the SDA process, extraction is a key unit where the
kind of solvent used determines both the quality and the yield of
deasphalted oil (DAO) product. Therefore, a fundamental understanding to the liquidliquid (solventVR) extraction behavior
in the extraction unit is of high interest and consequently, will
advance the industrial application of SDA technology. During the
research, simulation is a simple methodology to observe the extract
results that costs lower than experimental work. Prausnitz et al.

Corresponding author. Tel.: +86 21 6425 2874; fax: +86 21 6425 1002.
E-mail address: fhcao@ecust.edu.cn (F. Cao).
0255-2701/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2009.11.013

[79] developed a continuous distribution function to characterize the composition of heavy hydrocarbon in the ash distillation
and solvent recovery processes for a continuous system, that is,
a perturbed-hard-chain equation of state (PHCT) was used to
describe the phase equilibrium behavior in supercritical propane
system for the separation of continuous oil mixtures. Alessi et al.
[10] lumped VR into four groups (i.e. parafn, aromatic, resin and
asphaltene), then dened each group as a pseudo-components of
average molecular weight. Thus, pseudo-binary equilibrium data
between pseudo-components and solvents could be experimentally determined. Aparcio et al. [11] proposed a KUOP methodology
to re-characterize the unit feedstock of VR, the assay mixture of
which was separated into parafnic, primitive and aromatic components. However, attention to probe the phase behavior was still
less compared with intensive experimental investigations on the
extraction column in SDA process [1216]. It might be attributed
to the lack of precise thermodynamic information of a specic VR
and the lack of suitable state equation to describe the information
concerning liquidliquid extraction.
Zhao et al. [17] concluded that RedlichKwongSoave (RKS) and
PengRobinson (PR) were good for the simulation of sub-critical
extraction in SDA process. However, our previous work [18] turned
out PSRK was much more effective to reect the industrial data with
the feed of VR obtained from a mixed crude oil (Zhongyuan oil:Tahe
oil:Changqing oil:Oman crude oil:Zaro crude oil = 35:5:2:40:18,
wt/wt). To make a further understanding of extraction behavior
in the simulation process, the present work employed lumping
methodology to divide the VR into several dummy components

92

F. Cao et al. / Chemical Engineering and Processing 49 (2010) 9196

Fig. 1. Schematic process for SDA.

according to KUOP values, and continued to investigate the effects


of operation variables and components of mixed C4 solvent on the
quality and the yield of DAO product. The simulation work was performed with the aid of powerful Aspen Plus software [19] and the
results were shown in detail as follows.

As one of the two popular industrial SDA units, UOPs DEMEX


process is an energy-saving one with high yield of DAO and high
solvent recovery. It mainly consists of two parts: sub-critical solvent extraction and supercritical solvent recovery. Fig. 1 shows the
schematic owchart where VR and mixed C4 are employed to be
raw materials and solvent, respectively. The products, DAO and
DOA (deoiled asphalt), can be used as raw materials of FCC and
for asphalt production, respectively.
In the SDA process, both the quality and the yield of DAO mainly
depend on selection of extraction technology or optimization of the
process parameters (such as the extraction temperature, the ratio of
solvent to VR). So, the operation exibility analysis and parameter
optimization of the extraction process play a crucial role in the process. The present work aimed at the DEMEX technology and made
a simulation performance with the help of the extract module of
Aspen Plus Column of ve theoretical plates number. There are two
feed streams of FEED for VR and SOLVENT for the solvent into the
tower from the upper and lower parts of the column, respectively.
The extract phase and the rafnate phase are withdrawn from the
top and bottom of the column, respectively.
Fig. 2 shows the block diagram of calculation program for the
pseudo-components of VR. In the procedure, the specic gravities,
Sp.Gr. (60/60), were calculated according to Eq. (1), and the liquid composition rates of the parafnic component were predicted
according to Eq. (2).
KUOP =

1.8 T (K)

(1)

Sp.Gr.(60/60)

Vol.FRparafnic = 0.8 Vol.FRassay


Sp.Gr. (60/60)aromatic Sp.Gr. (60/60)assay
Sp.Gr. (60/60)aromatic Sp.Gr. (60/60)parafnic

3. Results and discussion


3.1. Approach to lumping VR

2. Extract module and optimization of the


pseudo-components of VR


3

EXTRACT tower; (d) solventVR ratio; (e) DAO density and (f) DOA
density.


(2)

The KUOP values were iterated by a trial and error method


with considering the following variables: (a) DAO yield; (b)
top temperature of EXTRACT tower; (c) bottom temperature of

3.1.1. VR and solvents


The feedstock is the VR obtained from a mixture of several kinds
of crude oils (Zhongyuan oil:Tahe oil:Changqing oil:Oman crude
oil:Zaro crude oil = 35:5:2:40:18, wt/wt). Table 1 summarizes the
characteristics of VR (wherein the distillation data was obtained
by true-boiling-point analysis), and Table 2 presents the solvent
composition of three kinds of operating models (model-I, -II and
-III).
3.1.2. Characteristic curve of the VR
According to the above-mentioned optimizing program (Fig. 2),
the characteristic curve of this kind of VR under operating model-I is
plot in Fig. 3. This curve indicates that the feedstock can be grouped
as parafnic, primitive and aromatic components with KUOP values of around 13, 12 and 11, respectively. (Note that the calculated
KUOP values here will become the base of the following simulations
of Sections 3.23.4.) Consequently, the ow rate and the specic
gravities (Sp.Gr.) of each pseudo-component can be calculated with
feedstock of VR under operating model-I, with results summarized
in Table 3.
3.1.3. Verication of lumping methodology
In order to make sure whether the employed lumping method
is effective to group the present VR or not, simulation results
under operating model-I are listed to compare with the industrial data, as shown in Table 4. This comparison demonstrates that
the relative errors of main parameters (including temperature,
density and mass ow rate) are less than 3.94% for both feedstock (VR and mixed C4 solvent) and products (DAO and DOA),
which validates the effectiveness and suitability of the present
simulation method to the industrial data. What deserves to be
mentioned the most is that, the simulated ratio of solvent to VR
(v/v) and the DAO yield are (289,498/581.6)/(91,324/1016.3) = 5.54
and (49,358/91,324) 100% = 54.0%, respectively, very close to
the industrial values of (289,498/576.0)/(91,324/977.8) = 5.38 and
(49,315/91,324) 100% = 54.0%. More details about the simulation
results will be present in the following section.

F. Cao et al. / Chemical Engineering and Processing 49 (2010) 9196

93

Fig. 2. The block diagram of calculation program for the pseudo-components of VR.

Table 1
Characteristics of VR under operating model-I.

Density/kg m3
Viscosity/mm2 s1
Conradson carbon residue/%
Solidifying point/ C
Parafnic/wt%
Aromatic/wt%
Colloid and asphalt/wt%

977.80
1234.38 (100 C)
17.72
>40
26.47
47.37
25.96

Distillation/wt.%

Temperature/ C

Initial boiling point


5
10
50
60
70
80

401.8
512.0
535.8
640.2
669.4
703.0
749.8

3.2. Effect of solvent component

Table 2
Components of mixed C4 solvent of three operating models.
Content/vol.%

II

III

Propane
Propylene
iso-Butane
n-Butane
1-Butene
Isobutene
Trans-2-butene
Cis-2-butene
C5+

1.57
0.56
6.22
87.21
0.42
0.44
0.95
0.74
1.89

11.59
0.56
0
85.30
0.42
0.44
0.95
0.74
0

0
0.56
1.69
85.30
0.42
0.44
0.95
0.74
9.90

A further understanding about the effects of solvent components on SDA process would benet a better choice of solvent
employed in the industrial process for a renery from the economic perspective. Usually, the heavier the molecular weight of
the solvent is, the higher the DAO yield is, but the worse the quality becomes. DEMEX technology requires n-butane no less than
85.3 vol.% and C5+ not more than 9.9 vol.% within the mixed C4
solvent. This section will focus on the effects of the contents of
propane, iso-butane and C5+ in mixed C4 solvent on the SDA process, with comparable results in detail under different operating
models shown in Table 5.

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F. Cao et al. / Chemical Engineering and Processing 49 (2010) 9196

Table 3
Calculated results for each pseudo-composition under operating model-I.
NBP/ C

Parafnic

Primitive

397
408
425
449
481
509
533
555
573
607
634
674
725

Aromatic

Vol.FRparafnic/m h

Sp.Gr/60:60

Vol.FRprimitive/m h

Sp.Gr./60:60

Vol.FRaromatic/m3 h1

Sp.Gr./60:60

0.7824E3
0.2819E2
0.2692E2
0.4898E2
0.4346E2
0.4026E2
0.3736E2
0.5989E2
0.7617E1
0.3223E1
0.3228E1
0.4119E1

0.8189
0.8227
0.8282
0.8369
0.8478
0.8575
0.8649
0.8720
0.8763
0.8865
0.8934
0.9043

0.6234E3
0.2303E2
0.2172E2
0.4003E2
0.3644E2
0.3376E2
0.3176E2
0.5159E2
0.6745E1
0.2741E1
0.2820E1
0.3701E1

0.9060
0.9117
0.9168
0.9272
0.9407
0.9514
0.9602
0.9689
0.9750
0.9838
0.9929
1.0064

0.1088E2
0.4091E2
0.3824E2
0.7111E2
0.6587E2
0.6103E2
0.5791E2
0.9488E2
0.1262E+0
0.4999E1
0.5233E1
0.6984E1
0.2619E+0

0.9686
0.9730
0.9792
0.9894
1.0020
1.0134
1.0218
1.0301
1.0347
1.0465
1.0542
1.0666
1.1236

Table 5
Simulated results under operating model-I, -II and -III.
Operating
model

Mixed C4 solvent VR

Extract

Rafnate DAO

DOA

Stream phase
Liquid

Liquid Liquid

Liquid

Liquid Liquid

Temperature ( C)
I
108.0
II
108.0
III
108.0

110.0
110.0
110.0

110.4
110.4
110.3

107.8
107.7
107.8

221.0
221.0
221.0

276.0
276.0
276.0

Pressure (MPa) 5.0

4.6

3.9

3.9

1.5

1.5

Total ow rate (kg/h)


I
289,498
II
285,892
III
292,428

91,324 334,492 46,330


91,324 325,181 52,035
91,324 342,371 41,381

49,358 41,964
44,456 46,866
53,632 37,691

Yield (%)
I
II
III

54.0
48.7
58.7

46.0
51.3
41.3
1092.6
1085.9
1099.2

Fig. 3. VR characteristic curve under operating model-I.

The mixed C4 solvent under operating model-I (with average


molecular weight of 57.94) is heavier than that under operating
model-II (with average molecular weight of 56.14), and that under
operating model-III (with average molecular weight of 59.18) is
much heavier. At a solventVR ratio of 5.54 (v/v), operating modelI produced a DAO yield of 54.0%, operating model-II yielded 48.7%
and model-III reached 58.7%. Hence, it can be regarded that a heavier mixed C4 solvent is employed, the higher the DAO yield is
obtained. Through comparing the simulated results of different
Table 4
A comparison results between simulation and industrial data under operating
model-I.
Feedstock

Products

Density (kg/m3 , 20 C)
I
581.6
II
574.3
III
587.5

1016.3 617.5
1016.3 607.3
1016.3 625.8

1009.1
997.9
1020.1

959.4
952.0
965.2

Average molecular weight


I
57.94
II
56.14
III
59.18

618.59 66.84
618.59 64.08
618.59 68.90

329.98
314.58
344.86

597.87 644.83
600.54 636.72
596.27 653.31

Parafnic (kg/h)
I
0
II
0
III
0

16,705 16,705
16,705 16,705
16,705 16,705

0
0
0

16,704 0
16,704 0
16,704 0

Primitive components (kg/h)


I
0
II
0
III
0

16,234 15,293
16,234 14,254
16,234 15,943

941
1980
291

15,292 941
14,253 1980
15,942 291

31,998 17,091
31,998 13,335
31,998 20,578

14,907
18,662
11,420

17,090 14,907
13,335 18,662
20,577 11,419

26,116
26,223
25,980

271
164
407

26,116
26,223
25,980

0.32
0.25
0.53

0.00
0.00
0.00

Stream name

Mixed C4 solvent

VR

DAO

DOA

Stream phase

Liquid

Liquid

Liquid

Liquid

Temperature ( C)
Industrial data
Simulated data
Relative error (%)

110.0
108.0
1.82

110.0
110.0
0.00

221.0
221.0
0.00

276.0
276.0
0.00

Pressure (MPa)

5.0

4.6

1.5

1.5

Aromatic components (kg/h)


I
0
II
0
III
0

Total ow rate (kg/h)


Industrial data
Simulated data
Relative error (%)

289,498
289,498
0.00

91,324
91,324
0.00

49,315
49,358
0.09

42,009
41,964
0.11

Asphalt and impurities (kg/h)


I
0
II
0
III
0

26,388 271
26,388 164
26,388 407

Density (kg/m3 , 20 C)
Industrial data
Simulated data
Relative error (%)

576.0
581.6
0.97

977.8
1016.3
3.94

935.0
959.4
2.61

1063.2
1092.6
2.76

Solvent (kg/h)
I
II
III

0
0
0

289,498
285,892
292,428

285,132 4366
280,723 5169
288,738 3690

F. Cao et al. / Chemical Engineering and Processing 49 (2010) 9196

95

Table 6
Distribution in assay pseudo-components of three operating models.
Operating model

Mass fraction in DAO

Mass fraction in DOA

II

III

II

III

Parafnic
Primitive
Aromatics
Impurities

1
0.9420
0.5341
0.0103

1
0.8780
0.4167
0.0062

1
0.9820
0.6431
0.0154

4.58E10
0.0580
0.4659
0.9897

1.97E09
0.1220
0.5833
0.9938

8.42E11
0.0180
0.3569
0.9846

operating models (I, II and III), it can conclude that there is almost
no signicant difference in the distributions of parafnic components and asphalt in both DAO and DOA products under the three
operating models, and almost all parafnic components are present
in DAO product while most impurities in DOA product.
To clearly observe the mass distribution of each assay pseudocomponent in DAO and DOA under the three operating models,
Table 6 presents more details. As expected, the parafnic and most
primitive components are extracted in the solvent-rich phase of
DAO while the majority of impurities components remains in the
asphaltic residue of DOA. The mass fraction of each new component in DAO product increases as the solvent becomes heavier (III
is heavier than I and much heavier than II), which implies lower
quality was produced with heavier solvent used. Therefore, it can
be concluded that higher yield of DAO would be companied with
lower quality.
Fig. 5. The effect of the ratio of solvent to VR on the yield of DAO.

3.3. Effect of temperature


Fig. 4(a) shows the effects of both VR and solvent temperatures
on the yield of DAO. It is remarkable that VR temperature exhibits
a weaker effect on the yield than solvent temperature. As the temperature of C4 solvent increases from 100 to 120 C (at a constant
VR temperature of 110 C), the DAO yield decreases signicantly
to 47.2% from 57.9%. While for VR, increment of 20 C at starting
of 100 C only reduces 0.9% of DAO yield. Fig. 4(b) illustrates that
DAO yield decreases linearly and signicantly as the top temperature of extraction unit increases, while the bottom temperature
wields a much weaker inuence on the yield. It is well known that
low temperature facilitates improving the capacity of mixed C4 solvent dissolving VR and, thus DAO yield is enhanced at 100 C in
comparison with 120 C.
3.4. Effect of solventVR ratio
Fig. 5 displays the effect of the ratio of solvent to VR (v/v) on the
yield of DAO. DAO yield increases obviously from 51.6% to 56.1%
with the increasing solventVR ratio from 4.5 to 6.5. This result
implies much solvent is benecial to high yield of product, while
surplus solvent would produce a high rate of solvent circulation,
thereby resulting in both enlarging equipment sizes and costing
much more during solvent recovery process. Generally, DAO yield
can be enhanced by improving the properties of used-solvent or
optimizing the operation conditions.
4. Conclusion

Fig. 4. The effect of temperature on the yield of DAO. (a) Feed temperature and (b)
extract temperature.

With the aid of the EXTRACT module in Aspen Plus software and
the selected PSRK equation suggested in our previous research, a
simulation of SDA process was performed here aiming to VR from
the detailed mixed crude oil. The present work rstly calculated
the characteristic curve of the VR and lumped it as parafnic, prim-

96

F. Cao et al. / Chemical Engineering and Processing 49 (2010) 9196

itive and aromatic with calculated KUOP values of around 13, 12 and
11, respectively, then made an optimization for parameters under
operating model-I with relative error less than 3.94% to the industrial data. The results showed that, increase of the temperature of C4
solvent from 100 to 120 C (at constant VR temperature of 110 C)
would decrease DAO yield signicantly to 47.2% from 57.9%, while
increasing solventVR ratio from 4.5 to 6.5 would enhanced DAO
yield from 51.6% to 56.1%. High extract temperature is unfavorable
to the yield of DAO product. In addition, this work also simulated
the extract process operated under three kinds of operating models
with mixed C4 solvent (where model-III was heavier than modelI and much heavier than model-II), at a solventVR ratio of 5.54,
model-III, -I and -II produced DAO yield of 58.7%, 54.0% and 48.7%,
respectively.
In conclusion, this work contributes to the research of deasphalting process intensied by C4 solvent addition and the results
showed the present simulation methodology is effective to simulate the industrial operating process and consequently can make
predictable and valuable results for SDA process, which costs lower
than experimental research.
Acknowledgement
We would like to appreciate the nancial support from the
project (Grant No. 108050) of SINOPEC, China. The authors thank
the senior engineer, Mr. Mannian REN in Luoyang Petrochemical
Complex of SINOPEC, China, for his valuable technical assistance.
Appendix A. Nomenclature
DAO
deasphalted oil
DOA
deoiled asphalt
KUOP
Watson characterization factor
NBP
normal boiling point ( C)
SDA
solvent deasphalting
Sp.Gr. (60/60) specic gravities
Vol.FR volume fraction
VR
vacuum residue
Subscripts
Aromatic aromatic component
Assay
assay component
Parafnic parafnic component
Primitive primitive component

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