57

* To whom correspondence may be addressed

CT&F - Ciencia, Tecnologa y Futuro - Vol. 4 Num. 2 Dec. 2010
MODIFIED DESIGN FOR VACUUM
RESIDUE PROCESSING
Sandro-Faruc Gonzlez
1*
, Jess Carrillo
1
, Manuel Nez
1
, Luis-Javier Hoyos
1*
and Sonia-A. Giraldo
2
1
Ecopetrol S. A. Instituto Colombiano del Petrleo (ICP), A.A. 4185 Bucaramanga, Santander, Colombia
2
Universidad Industrial de Santander (UIS), Bucaramanga, Santander, Colombia
e-mail: [email protected] [email protected]
(Received, Feb. 16, 2010; Accepted, Nov. 30, 2010)
ABSTRACT
T
he world petroleum industry shows a decreasing in the oil reserves, specially the light kind. For this
reason is very important to implement process schemes that give the possibility to improve the re-
cuperation of valuable products of heavy oil. In this case the residue processing in each one of the
petroleum refining stages earns great importance with the purpose of maximizing the quantity of fuel by barrel
of feedstock processed. Therefore, it has been proposed the modification of the currently vacuum residues
process scheme in the Ecopetrols Barrancabermeja refinery (DEMEX-Visbreaker-Hydroprocessing). That modi-
fication consists in the incorporation of an additional Visbreaker stage, previous at DEMEX extraction stage.
This investigation was developed with plant pilot tests combined with statistical models that predict the yield
and the quality of the products obtained in the industrial plants. These models were developed by the Instituto
Colombiano del Petrleo (ICP).
The modified scheme Visbreaker I-DEMEX- Visbreaker II- Hydroprocessing, gives the possibility to increase
the yield of middle distillates. Besides decrease the quantity of demetalized oil produced in DEMEX stage.
This reduction is very favorable since environmental point of view, because it allows have a percentage of
free capacity in the Hydroprocessing unit in order to removed sulfur of valuable products like Diesel and in
this way to respect the environment law to this kind of fuel.
Keywords: visbreaking, Demex, hydrotreating, vacuum residues, light gas oil.
58 CT&F - Ciencia, Tecnologa y Futuro - Vol. 4 Num. 2 Dec. 2010
RESUMEN
E
l panorama mundial de la industria del petrleo muestra una preocupante escasez de las reservas
de crudo, en especial de las del tipo liviano. Por esta razn se hace imperante la necesidad de
implementar esquemas de procesamiento que permitan aumentar la recuperacin de productos
valiosos de los crudos pesados. Ante esta situacin el procesamiento de los fondos de las diferentes etapas
de la refinacin del petrleo cobra gran importancia con el fin de maximizar la cantidad de los combustibles
recuperados por barril de crudo procesado. En este sentido se plantea la modificacin del esquema actual
de procesamiento de fondos de vaco de la refinera de Ecopetrol en Barrancabermeja (Desasfaltado con
solvente (DEMEX)- Viscorreduccin- Hidrotratamiento); dicha modificacin consiste en la incorporacin de
una etapa de viscorreduccin adicional, previa al proceso de Extraccin DEMEX.
La investigacin se realiz mediante pruebas a nivel piloto combinadas con modelos estadsticos que predi-
cen el rendimiento y la calidad de los productos obtenidos en las plantas industriales. Estos modelos fueron
desarrollados por el instituto Colombiano del Petrleo (ICP).
El esquema de procesamiento modificado Viscorreduccin I-DEMEX- Viscorreduccin II- Hidrotratamiento,
brinda la posibilidad de incrementar el rendimiento de destilados medios, y a su vez permite disminuir la
cantidad de aceite desmetalizado producido en el proceso DEMEX. Esto ltimo es muy favorable desde el
punto de vista medioambiental, pues permite tener un porcentaje de capacidad libre en la etapa de hidro-
tratamiento, la cual puede ser aprovechada para desulfurizar productos valiosos tales como el combustible
Diesel, y de esta manera cumplir la legislacin ambiental para este tipo de productos.
Palabras clave: viscorreduccin, Demex, hidrotratamiento, fondos de vaco, destilados medios.
59
MODIFIED DESIGN FOR VACUUM RESIDUE PROCESSING
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1. INTRODUCTION
Currently, faced with the scarcity of light crudes,
the oil refning industry is concerned with increasing
the yield of its products, granting an important role to
the residue treatment processes as a means to achiev-
ing this goal.
The vacuum residue processing design, (Figure 1),
solvent deasphalting (SDA) - Visbreaker (VBK) hy-
drotreatment (HDT) that is currently being used in the
Barrancabermeja refnery, it is not very effective in
respect to middle distillate yield and in addition has an
association to high fuel oil production. These weak points
can be attributed to the fact that the potential of chemical
conversion that visbreaker offers is applied to a feedstock
actually quite poor in valuable distillates. The feed to
the visbreaker process has been previously subject to a
solvent deasphalting process which has had demetallized
oil (DMO) removed, and which has a high potential to
be chemically transformed using thermal treatment.
Due to operational limitations, it is not possible to
transform the entire virgin vacuum residue by means
of thermal cracking since the visbreaker plant capacity
is smaller than the quantity of Vacuum Residue (VR)
produced. Therefore the Visbroken Vacuum Residue
(VBVR) should be mixed with virgin vacuum residue
to be fed to the DEMEX process.
Figure 1 Current Residue Processing Design
Figure 2 Modified Processing Design
Vacuum residue, although a residue fow, offers the
possibility of still having valuable products extracted
from it. The incorporation of a chemical transforma-
tion stage via thermal conversion, prior to the SDA
process (Figure 2), offers the possibility of a larger
yield of valuable products within the vacuum residue
processing design. The above-mentioned is possible,
since in the thermal conversion processes there are
a series of large-molecule breakdown reactions,
hydrogen redistribution, and also condensation and
polymerization reactions.
2. METHODOLOGY
The study of the potential of a refning design im-
plies being able to draft at least the mass balance of the
proposed design with the qualities of its products, and
to carry out its respective economic evaluation. Since
establishing this mass balance can imply a great quan-
tity of pilot plant runs and their respective analytical
work. For this paper we made the decision of acceler-
ating the production of results using a combination of
simulations and pilot plant runs.
Base Feedstock for the Study
To make a same-base comparison for both the cur-
rent design and the design proposed in this work, the
feedstock of the two designs should be the same.
The preliminary evaluation of the experimental de-
sign shows that to develop the entire simulation work
of the two visbreakers, the solvent deasphalting units,
and the hydrotreatment of the deasphalted oil, based
on pilot plant data would take too long. Since in the
Cartagena refnery the vacuum residue are sent to a
reaction chamber type visbreakers unit, this feedstock
was used as basis for the study. Samples were taken of
VISBREAKER
STAGE II
VISBREAKER
STAGE I
DEASPHALTED WITH
SOLVENT (DEMEX)
HYDROTREATMENT
DMO
SLURRY
DEMEX
RESIDUE
DMOH
DIESEL
NAPHTA
GASES
NAPHTA
GASOIL
COKE
GASES
NAPHTA
GASOIL
COKE
VISBREAKER I
RESIDUE
VISBREAKER II
RESIDUE
VACUUM
RESIDUE
VACUUM
RESIDUE
VISBREAKER
DEASPHALTED WITH
SOLVENT (DEMEX)
HYDROTREATMENT
DMO
DEMEX
RESIDUE
DMOH
DIESEL
NAPHTA
GASES
NAPHTA
GASOIL
COKE
VISBREAKER
RESIDUE
VACUUM
RESIDUE
SANDRO-FARUC GONZLEZ et al.
60 CT&F - Ciencia, Tecnologa y Futuro - Vol. 4 Num. 2 Dec. 2010
both the feedstock, and the products of this visbreaker
industrial unit that were used for the remaining simula-
tion runs of the proposed design.
Simulation of the Current Vacuum Residue Proces-
sing Design of the Barrancabermeja Refnery
Since the characteristics of the vacuum residue
of the Cartagena refnery are slightly different from
those of the residue of the Barrancabermeja refnery,
the semi rigorous models that are based on frst order
kinetics and that were previously developed by the
ICP were used to simulate the processing of vacuum
residue. These models are used as a tool with which
to carry out operational follow up to the plants. This
simulation was used as basis in this study. These deas-
phalting unit models with propane-butane mixtures,
hydrotreatment of demetallized oil, and visbreaker
of asphaltene were drafted based on pilot plant runs
of different types of feedstock and different operating
conditions, which were validated with the industrial
unit data of this refnery. Therefore, these are models
that combine statistical correlations and pseudo-
homogeneous kinetic models; they additionally use
the feedstock properties and the main operating con-
ditions of these units to predict the yield and quality
of their products.
Simulation of the Processing Design Proposed for
Vacuum Residue of the Barrancabermeja Refnery
This part of the study was developed in the pilot
plants of the ICP.
Visbreaker of Vacuum Residue
Samples were taken from the feedstock and the
products of the visbreaker industrial unit of the Carta-
gena refnery; we verifed that the mass balance of the
performance run in which the samples were taken did
not surpass 2%m. Visbroken residue of the Cartagena
refnery were used as feedstock for the pilot plants of
solvent deasphalting.
Visbroken Residue Solvent Deasphalting (SDA)
A mixture of visbroken vacuum residue from the
visbreaking unit in the Cartagena refnery (46%) and
vacuum residue from the same refnery (54%) were
loaded to the deasphalting unit.
These runs were carried out in the ICP deasphalting
pilot plant at typical operating conditions to represent
the industrial unit.
The typical operating conditions of the SDA process
are:
Rectifcation temperature: 125 - 130C
Solvent / feedstock relationship: 6,5 and 8,5
Rectifcation pressure: 500 psi
Visbreaker of Asphaltenes Obtained from Visbro-
ken Residue
The tests were carried out in the ICP visbreaker
pilot plant.
In the initial tests it was not possible to pump the
visbroken deasphalted residue due to its high viscosity;
therefore the visbroken deasphalted residue was mixed
with diluents samples from the Barrancabermeja refn-
ery. This mixture was made based on the proportions of
diluents available in the refnery. The mixture that was
loaded in the pilot plant had the following composition:
Residue: 82,7%
Slurry: 15,4%
Light Cycle Oil (LCO): 1,9%
A series of runs were performed with this mixture
within the typical operating conditions of the pilot
plant, since with these previously established condi-
tions we satisfactorily reproduce the results obtained
at an industrial level.
These conditions were:
Visbreaker type runs in oven coil
Residence times: 1,2 - 1,4 - 1,6 min
Reaction temperatures: 473 - 477 - 481C
Hydrotreatment of the Demetallized Oil Obtained
by Extraction of Visbroken Residue
These tests were carried out in hydrotreatment unit
700 of the ICP at the typical operating conditions of
the pilot plant, but taking into account the effect of the
reaction temperature.
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MODIFIED DESIGN FOR VACUUM RESIDUE PROCESSING
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3. ANALYSIS AND DISCUSSION OF RESULTS
Yield and Quality of the Products of the Current De-
sign of the Barrancabermeja Refnery
Figure 3 shows a diagram of blocks and fows of the
current residue processing design of the Barrancaber-
meja refnery that were calculated with the simulation
model developed by the ICP.
Table 1 presents the main features of the fows of
this processing design.
As can be seen in Table 1, in the solvent deasphalt-
ing stage, the reduction of the metals and sulfur content
that is present in DMO, and the increase in Conradson
Carbon content in asphaltene stand out. As for the
visbreaker stage, the aspect that is worthwhile men-
tioning is the reduction in residue viscosity in respect
to the feedstock at this stage (residue of the solvent
deasphalting stage DMXR) and its high sulfur content.
The topics previously mentioned are evidence that the
model predicts well the feedstock behavior in each of
the studied processes.
The typical operating conditions were:
Spatial velocity "LHSV" = 1, Flow 90 ml/h
Operating pressure: 1300 psi
Temperature: 330 - 350 - 370 C
Hydrogen/hydrocarbon ratio= 624
Catalysts: Ni-Mo / Al
2
O
3
bed of three commercial
catalysts of various size.
Evaluation of the Economic Potential of the Modifed
Processing Design
A preliminary study was carried out to compare the
proposed and the current designs in economic terms.
Based on the data of the visbreaker industrial plant
of the Cartagena refnery and those of the pilot plant,
we drafted the mass balances of both the current and
proposed designs.
The unit production prices and operating costs were
obtained from the tool used by Ecopetrol to plan their
refneries, which is based on linear programming. The
price scenario of March, 2008 was used for this analysis.
Table 1 Characterization of the main flows of the current processing design
FEEDSTOCK SOLVENT DEASPHALTING
HYDRO
TREATMENT
VISBREAKER
VACUUM
RESIDUE
DEMEX RESIDUE
(DMXR)
DMO DMOH
VISBREAKER
RESIDUE
VBK NAPHTA
Yield, %V N.A. 54 46 97 96,2 1,88
Density, %m 1,02 1,075 0,956 0,94 1,048
API Gravity 7,6 0,13 16,51 19 3,5
Sulfur, %m 1,8 2,2 1,34 0,443 2,5 0,8
Nitrogen, %m 0,2 0,12 0,003
Ni ppm 140 237 13,1 1,6
V ppm 240 413,9 12,6 1,05
Conradson
Carbon l %m
19,6 30,9 4,8 2,44
Aromatic
Content, %m
44,7 16,5
n-C7 Insolubles,
%m
10,8 22 29
V50 Viscosity 42 53,4 35 50,4
SANDRO-FARUC GONZLEZ et al.
62 CT&F - Ciencia, Tecnologa y Futuro - Vol. 4 Num. 2 Dec. 2010
Vacuum Residue Modifed Processing Design
Visbreaker Stage I (VBK I)
In this project-level pilot runs were not carried out
in this frst stage due to operating limitations, since it
implied a work of several months in the pilot plant due
to the amount of product necessary for the research;
in addition, in the Cartagena refinery the vacuum
residue are submitted to this process. This situation
was favorable to the interests of the project, since we
counted on samples of visbroken vacuum residue. This
consideration was validated through the simulation
model of the visbreaker unit of the Barrancabermeja
refnery, developed by Ecopetrol-ICP. In said validation,
a satisfactory reproduction of the yield and quality of
the products was obtained.
This extrapolation was carried out considering
as subject of comparison the sum of the yield of the
naphtha and kerosene fraction, considering them as a
single fow, and the sulfur content of these fows was
predicted using the model. After feeding the model with
the physical and chemical characteristics of the residue
(VBK I stage feed) the following aspects stand out:
The naphtha and kerosene yield difference between
the one provided by the model and the operating
datum of the industrial plant was of 6,57% in vol-
ume (5,4% of the model in comparison to the actual
5,78%).
The sulfur content of the naphtha resulting from
the model was of 0,9% mass and the datum of the
naphtha characterization was of 0,912% mass with
a difference of 1,31%.
Figure 4 and Table 2 show the characterization of
the feed fow and the respective products and yield of
the Cartagena visbreaker.
30845
VISBREAKER
DEASPHALTED WITH
SOLVENT (DEMEX)
HYDROTREATMENT
DMO
20608
DILUENT
6653
DEMEX RESIDUE
24192
DMOH
21190
DIESEL 577
NAPHTA 185
NAPHTA 580
LPG 46
GASES 52
COKE 494
VISBREAKER
RESIDUE 29670
VACUUM
RESIDUE
44800
Figure 3 Volumetric yield of the current processing design
Figure 4 Simulated Distillation of VBK I Residue
0 20 40 60 80
750
700
650
600
550
500
450
400
350
% Recovered Weight
T
e
m
p
e
r
a
t
u
r
e

(

C
)
As can be seen in the Table 2, the vacuum residue
have a high content of aromatic compounds; therefore,
based on the studies of Raseev (2003) on the impact of
feedstock characteristics on thermal cracking processes,
we can predicted that due to the high percentage of
aromatic type species in the feedstock during the ther-
mal conversion, high fraction yields are obtained; both
light and heavy; and also a lesser conversion toward
middle distillates and gas oils (Di Carlo & Janis, 1992;
Raseev, (2003).
After the visbreaker process there is a recovery of
7,2% of middle distillates, 25,8% of diesel oils, in ad-
dition to a conversion of gasses of 4,56%.
The increase in the production of valuable distil-
lates, in the modifed processing design, according to
Salazar and Meyers (1986), is attributed to the action of
the thermal cracking on the feedstock. In this cracking,
the breakdown of some aliphatic type chains that are
bound to the complex aromatic structures present in the
feedstock, allows the attainment of a larger conversion
percentage. This result concurs with the data reported
by Salazar and Meyers (1986), in which he shows that a
signifcant yield of diesel oils is obtained in the vacuum
visbreaker process.
The visbroken vacuum residue, when compared to
the feedstock, show an increase in the content of Con-
radson Carbon and of the nickel and vanadium content.
Fainberg, Podorozhasky, Hetsroni, Brauch, & Kalchouck
(1996) found that these pollutants are strongly bound to
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MODIFIED DESIGN FOR VACUUM RESIDUE PROCESSING
CT&F - Ciencia, Tecnologa y Futuro - Vol. 4 Num. 2 Dec. 2010
Table 2 Feedstock and Product Characteristics of VBK I Stage

VACUUM
RESIDUE
NAPHTA KEROSENE
ATMOSPHERIC
GAS OIL
1
LIGHT GAS
OIL
2
HEAVY
GAS OIL
3
VBK
RESIDUE
YIELD - 3,84 1,94 10,61 1,06 13,59 68,1
Density 15C, g/
ml
1,02 0,7416 0,8076 0,8845 0,8685 0,9356 1,05
API Gravity, API 7,6 59,2 43,6 28,4 31,3 19,7 3,1
Viscosity 79C, cP 367 23 400 - - - - 742 000
Viscosity 100C, cP 279 3580 - - - - 216 000
Viscosity 121C, cP 248 886 - - - - 10 600
Sulfur, %m 1,8 0,912 0,913 1,258 1,373 22,715 1,97
CCR., %m 19,6 - - <0,10 <0,10 0,19 30,6
Iron, ppm 23 - 66,331 6,22 6,22 365,765 19,265
Vanadium, ppm 240 - <7,20 <7,20 <7,20 - 340,24
Nickel, ppm 140 - 1,066 17,274 17,274 1,47 171,761
Saturates, %m 12,5 - - - - - 15
Aromatics, %m 44,7 - - - - - 40,1
Resins, %m 32,3 - - - - - 23,6
Asphaltenes, %m 10,5 - - - - - 12
Basic Nitrogen,%m 0,2 - - - - - 0,292
Insolubles in
nc5,%m
16,7 - - - - - 26,21
Insolubles in
nc7,%m
10,8 - - - - - 26,84
Initial Ebullition
Point, C
217 169 207 206 270 380
Final Ebullition
Point, C
716 256 396 387 520 716
complex aromatic structures and in face of the diffculty
of being removed by the action of the thermal rupture,
said compounds concentrate on the residue product.
Solvent Deasphalting of the Visbroken vacuum
Residue
Table 3 presents the yield and quality of the demet-
allized oil and of the asphaltenes obtained in this
processing stage.
The yield in demetallized oil which is obtained from
visbroken vacuum residue is of 40,9%, while with
vacuum residue the yield is of 46,2%. These results
are explained by the fact that when comparing the vis-
broken vacuum residue with the vacuum residue, the
former present smaller content of resins; this concurs
with the research by Ditman and Van Hook (1981) and
Celestino and Hernandez (1982), who stated that in
the deasphalting process, the solvent extracts mainly
the fraction of resins present in the feedstock, which
concentrate on the DMO.
Although the sulfur content of the visbroken residue
is larger than that of the vacuum residue, the sulfur
content of the demetallized oil obtained from the vis-
broken residue is similar to that of the demetallized oil
obtained from vacuum residue. This could be attributed
to the fact that in the visbreaker stage, the sulfur atoms
of easier removal were extracted; and in the visbroken
vacuum residue the remaining sulfur atoms were mostly
SANDRO-FARUC GONZLEZ et al.
64 CT&F - Ciencia, Tecnologa y Futuro - Vol. 4 Num. 2 Dec. 2010
bound to complex polyaromatic structures. Therefore,
based on the work of Bonilla and Meyers (1986), one
could claim that in the deasphalting process the solvent
did not extract this sulfur compounds because they are
bound to complex aromatic structures; which implies
the attainment of a DMO similar to the DMO that re-
sults from the current processing design.
When comparing the physical and chemical proper-
ties of the DMO obtained from the modifed processing
design (DMO-MPD) with the properties of the DMO
from the current design (DMO-CD) in addition to the
improvement obtained in the reduction of ni + v, we
obtain a value of Conradson Carbon that is 6% above
DMO-CD. This phenomenon is attributed to the fact
that the MPD DMO is a fow coming from residue that
has been subjected to thermal cracking and in this pro-
cess reaches an asphaltene concentration. This implies
an increase of the property in question. This conclusion
is based on the fact that these results concur with those
presented by Bonilla and Meyers (1986), who compare
the deasphalting process of two feedstocks; Conradson
Carbon is amongst these.
The largest nitrogen content present in the DMO of
the proposed design is a property that affects the activity
of this fow in the subsequent hydrotreatment process
since it implies additional hydrogen consumption for
its processing.
The metal content in the MPD DMO is only 8%
lower than the one in the CD DMO. This property, ac-
cording to what Valeri, Dusfresne, & Jacquier (1997)
claim, has a positive impact on later processes that
imply the use of catalysts, since it decreases their de-
activation due to metal poisoning
DMXR Visbreaker Produced from Deasphalting
of Visbroken Residue (VBK II Stage)
Determination of Maximum Allowable Severity
The most important control variable of the vis-
breaker process is visbroken residue stability, since
unstable visbroken residue generate sediments and
therefore storage and transport problems. This stability
is measured through the merit test. Therefore a series
of preliminary experiments were performed in order
CURRENT DESIGN PROPOSED DESIGN
VACUUM
RESIDUE
DMO ASPHALTENES
VACUUM
RESIDUE
DMO DMX RESIDUE
Yield, %m - 46,2 53,8 - 40,9 59,1
Density, g/ml 1,02 0,956 1,075 1,05 0,96 1,09
Sulfur, %m 1,8 1,34 2,2 1,97 1,3 2,01
Nickel, ppm 140 13,1 237 340 10 213
Vanadium, ppm 240 12,6 414 171 14 451
CCR, %m 19,6 4,8 30,9 30,6 5,8 36,6
V50 42 - 53,4 47 - -
n-C7 Insolubles, %m 10,8 - 19,4 26,8 - 33,1
Basic Nitrogen, %m 0,2 0,12 - 0,292 0,129 -
N Total, ppm - 3200 - - 4058 -
Bromine Number - - - 8,04
Mono-Aromatics, %m - 4,6 - - 4,3 -
Bi-Aromatics, %m - 3,3 - - 3,1 -
Tri-Aromatics, %m - 3,6 - - 4,3 -
Tetra-Aromatics - 5 - - 3,7 -
Table 3 Yield and Quality of the Products of the SDA Stage
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to determine the maximum allowable severity in the
visbreaker process. Table 4 summarizes the yield and
merit test of the visbroken residue of these tests.
The visbreaker operating conditions of run 6 are the
ones that produce the lowest yield in visbroken residue
and coke in addition to the highest yield of naphtha;
this run was carried out with the following processing
conditions:
Reaction temperature = 477C
Residence time = 1,6 minutes
Merit test = 7,5 (at the stability limit)
At the VBK II stage we only took into account as in-
teresting analysis of characterization the viscosity of the
visbroken residue and the simulated distillation of naphtha
and visbroken residue. These are shown in Figures 5 and 6.
The V50 viscosity of the residue obtained in the
second visbreaker stage was of 52,8. This value when
compared with the 50,4 of the visbroken residue obtained
through the current design implies a larger percentage of
diluents used for the preparation of the fuel oil.
Another aspect to highlight in this process is the
recovery of approximately 1,3% naphtha; which is
equivalent at an industrial level to an additional recov-
ery of 700 bbl/day.
Hydrotreatment Stage
In this stage three runs were performed at different
temperatures (330, 350, and 370C) and with the other
operating variables fxed.
Table 4 Summary of the Balances of the runs of VBK II stage
Run 1 2 3 4 5 6 7 8 9
Reaction T, C 473 473 473 477 477 477 481 481 481
Time, min 1,2 1,4 1,6 1,2 1,4 1,6 1,2 1,4 1,6
Merit test 6,5 7 7,5 7 7 7,5 6,5 7 7,5
Naphta, % 0,73 0,86 1,29 1,02 1,02 1,36 0,89 1,00 1,32
Residue, %m 97,2 96,3 95,0 97,1 96,4 96.5 96,7 96,2 96,4
Gasses, %m 0,53 0,59 0,89 0,56 0,75 0,91 0,70 0,71 0,85
Coke, %m 1,53 2,21 2,82 1,34 1,87 1,24 1,75 2,08 1,44
Figure 5 Simulated Distillation of VBK II Naphtha
Figure 6 Simulated Distillation of VBK II Residue
0 20 40 60 80 100 120
600
500
400
300
400
100
0
% Recovered Weight
T
e
m
p
e
r
a
t
u
r
e

(

C
)
0 20 40 60 80
800
700
600
500
400
300
200
% Recovered Weight
T
e
m
p
e
r
a
t
u
r
e

(

C
)
After having concluded the operating stage, we
proceeded to the characterization of the Hydrogenated
Demetallized Oil DMOH and the gasses obtained in
each of the tests. The characterization results corre-
sponding to these products are presented in Tables 5
and 6, and in addition in Figure 7.
The test performed at 370 C presented the largest
sulfur removal; since it was possible to remove ap-
proximately 82% of the pollutant in question; achieving
a fnal product with 2350 ppm of sulfur.
SANDRO-FARUC GONZLEZ et al.
66 CT&F - Ciencia, Tecnologa y Futuro - Vol. 4 Num. 2 Dec. 2010
Table 5 DMOH Characteristics
0 20 40 60 80 100
700
600
500
400
300
200
% Recovered Weight
T
e
m
p
e
r
a
t
u
r
e

(

C
)

330C
350C
Figure 7 Simulated DMOH Distillation
Analysis
DMOH
C-330C
DMOH
C-350C
DMOH
C-370C
Sulfur, %mass 0,635 0,422 0,235
Density, g/ml 0,9467 0,9409 0,9345
Basic nitrogen,
% mass
0,129 0,121 0,098
CCR, % mass 3,41 2,97 2,28
Total nitrogen,
ppm
3450 3317 3050
Bromine number,
g Br
2
/100g
4,51 4,42 4,25
Sodium, ppm 19,82 8,556 8,25
Nickel, ppm 1,661 1,225 0,369
Vanadium, ppm 1,388 1,161 >0,005
Nickel +
Vanadium, ppm
3,049 2,386 >0,374
After comparison of the results contained in
Tables 3 and 6 we highlight the behavior of the
basic nitrogen content, since it is notable that in the
DMOH processed at 330C there was no decrease of
this element in respect to the content present in the
DMO; however, at temperatures of 350 and 370C
we did achieve a reduction of basic nitrogen; based
on the studies of Sumbogo, Yang, Choi, Korai, &
Mochida (2003) this can be attributed to the fact that
at lower temperatures there is removal of nitrogen in
species with basic nitrogen and simultaneously with
the fact that some compounds of non-basic nitrogen
are hydrogenated to compounds of basic nitrogen,
before eliminating the nitrogen molecule from the
compound.
The DMOH obtained in the run at 370C presents
a decrease in the sum of nickel and vanadium present
in the sample since according to the results this reduc-
tion was of approximately of 98,5%. This indicates that
Table 6 HDT Gas Chromatography
Compounds C 330C % m C 350C %m C 370C %m
Hydrogen 91,339 91,160 87,701
Hexanes + - 0,396 1,191
CO
2
0,352 0,033 0,900
Propane 0,215 0,416 1,172
i-Butane 0,173 0,324 0,248
n-Butane 0,396 0,845 0,624
H
2
S 6,660 5,635 5,526
i-Pentane 0,062 0,134 0,171
N Pentane 0,043 0,109 0,176
Ethylene 0,078 - -
Ethane 0,321 0,355 1,024
Methane 0,228 0,495 1,267
CO 0,134 0,097 -
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MODIFIED DESIGN FOR VACUUM RESIDUE PROCESSING
CT&F - Ciencia, Tecnologa y Futuro - Vol. 4 Num. 2 Dec. 2010
these metals have been deposited as metal sulfdes on
the surface of the catalyst, poisoning the active sites
and obstructing the catalytic pores, leading to the ir-
reversible deactivation of the catalyst.
Additionally, it is worthwhile to highlight that de-
spite it being a feedstock where more compounds of
the olefnic type are present than there are in a typical
feedstock, no fow problems occurred during the opera-
tion. Proof of this was the behavior of the catalyst in
respect to sulfur removal, since the percentage of the
removed pollutant is within the range that is usually
obtained with products of lesser olefn content.
In respect to the bromine number, it is remarkable
that in the three hydrotreatment tests its value in the
products decreased 45% on average in respect to the
value of the feedstock. The latter is proof of the reduc-
tion of the quantity of olefn present in the products after
the hydrotreatment process. According to Cabrera and
Meyers (1986) this phenomenon is due to the rupture
of the double bonds in unsaturated compounds, due to
hydrogenation reactions.
According to what was observed in the gas chroma-
tography (Table 6) increasing the operating tempera-
ture implies an increase in the quantities of methane,
ethane, propane, n-pentane, and hexanes in the sample.
On the other hand, the analysis shows that an increase
in the operating temperature causes a decrease of the
quantities of H
2
S, CO, and ethylene. In the particular
case of H
2
S reduction, the results obtained are far from
the expected results, since due to the increase of the
operating temperature, the quantity of sulfur removed
from the liquid product is increased, and this removed
sulfur should be transformed to H
2
S in the gaseous
fow of the process. This could be attributed to the
fact that before the directly proportional relationship
of the solubility with temperature, the compound in
question presents separation problems after the reac-
tion, since it is solubilized in greater proportion within
the liquid sample.
Global Yields of the Modifed Design of Visbreaker
I- Solvent Deasphalting - Visbreaker II Hydro-
treatment
Figure 8 presents the experimental volumetric yield
of the modifed processing design.
Figure 8 Experimental Volumetric Yields of the Modified Processing Design
After comparing the volumetric yields of the prod-
ucts in each of the processing designs shown in Figures
3 and 8, the main aspects of the modifed processing
design that outperform the current design are evident.
The distillate yield (naphtha, kerosene, and diesel)
passes from 3,1%, in the current residue processing
design, to 5,3% in the modifed processing design.
The quantity of recovered distillates with the cur-
rent design is of 0,5 KBPD; small quantity, if we
considered that with the modifed processing design
the recovery of these products reaches 0,6 KBPD
and that additionally, 6,45 KBPD of gas oils is
recovered in the visbreaker stage.
The fuel oil production is reduced by 11%, since
its main feedstock material, the visbroken tar, de-
creases by that same percentage.
In the modifed processing design, the feedstock
to the hydrotreatment stage decreases, since DMO
production drops by 27%. This situation is favor-
able since it provides the option of using the surplus
capacity to hydrogenate other types of products.
Table 7 presents the volumetric balance, in barrels, of
both the current and proposed residue processing designs.
Economic Outlook of the Modifed Processing Design
In this preliminary study we took into account the
operating costs of the process units, the estimated cost
of the feedstock materials, and the products of each of
the stages of the design.
Table 8 presents the cash fow, in dollars, of the two
refning designs.
27540
36550
VISBREAKER II
VISBREAKER I
DEASPHALTED WITH
SOLVENT (DEMEX)
HYDROTREATMENT
DMO
14950
DILUENT
5940
DEMEX RESIDUE
21600
DMOH
14790
DIESEL 4277
NAPHTA 137
NAPHTA 375
GASES 248
COKE 342
NAPHTA 960
GASOIL 6450
GASES 200
KEROSENE 485
VBK II
RESIDUE
26580
VACUUM
RESIDUE
19800
VACUUM
RESIDUE
25000
VACUUM
RESIDUE
44800
VBK I
RESIDUE
16750
SANDRO-FARUC GONZLEZ et al.
68 CT&F - Ciencia, Tecnologa y Futuro - Vol. 4 Num. 2 Dec. 2010
Table 7 Comparison of the Volumetric Balance of CD and MPD
CURRENT DESIGN CD [KBPD] PROPOSED DESIGN MPD [KBPD]
FEEDSTOCK PRODUCTS FEEDSTOCK PRODUCTS
Vacuum Residue 44 800 44 800
Slurry 18 599,6 17 950
LCO 11 405,7 12 040
Gas 52,4 447,9
Naptha 765,4 1471,8
Diesel 577 426,9
Kero - 485
GLP 46,267 -
Gas Oil - 6450
Coke 493,5 341,5
Fuel Oil 53 025,1 50 627
DMOH 20 189,7 14 790,5
TOTAL 74 805 75 149 74 790 75 041
Table 8 Comparison of the Economic Balance of CD and MPD
CURRENT DESIGN [USD] PROPOSED DESIGN [USD]
FEEDSTOCK PRODUCTS FEEDSTOCK PRODUCTS
Vacuum Residue 2 926 336,00 2 926 336,00
Slurry 1 262 909,52 1 218 822,82
LCO 1 078 975,62 1 138 986,48
Gas 31,72 270,96
Naphta 87 740,21 168 726,41
Diesel 60 529,82 44 786,22
Kero 0,00 48 131,40
GLP 3,90 0,00
Gas Oil 612 750,00
Coke 0,00 0,00
Fuel Oil 2 900 473,55 2 769 318,34
DMOH 2 027 041,62 1 484 965,31
TOTAL 5 268 221,14 5 075 820,83 5 284 145,31 5 128 948,64
Operation 85 185,18 89 424,74
Delta - 277 585,50 - 244 621,40
Margin/bbl (us$/bbl) - 6,20 - 5,46
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CT&F - Ciencia, Tecnologa y Futuro - Vol. 4 Num. 2 Dec. 2010
Although the economic balance is negative for both
cases, as a main conclusion we point out that while by
the current residue processing design we obtain a proft
of 6,2 USD/feedstock barrel, the proposed design
reaches values of 5,46 USD/feedstock barrel. This
improvement in the refning margin allows a saving of
approximately 10 000 000 USD per year.
4. CONCLUSIONS
One of the main advantages of the addition of a
visbreaker stage, to the vacuum residue process-
ing design of the Barrancabermeja refnery is the
increase that appears in the percentage of recovery
of valuable products originating in vacuum residue.
The percentage in question varies from 3,1% to a
value of 5,3%.
The increase in the yield of valuable products ob-
tained in the modifed processing design is attributed
to the modifying action of the thermal cracking on
the chemical structure of the vacuum residue.
In the modifed processing design, the amount of
the feedstock to the hydrotreatment stage decreases,
since DMO production drops by 27%. This situation
is favorable since it provides the opportunity to use
the surplus capacity to hydrogenate other types of
products, such as diesel, and in this way comply with
the goals imposed by environmental legislation.
The mixture of virgin and visbroken vacuum residue
improves the quality of the DMO obtained during
the SDA stage, due to the decrease of the nickel +
vanadium content. This reduction of pollutants has
a signifcant effect on the hydrotreatment process
since it extends the service life of the catalyst.
Although the economic balance is negative for both
the current processing design and the modifed de-
sign, the latter has an advantage from an economic
point of view since the proft margin per vacuum
residue barrel processed in the proposed design is
$0,74 under the proft margin reached with the cur-
rent vacuum residue processing design.
ACKNOWLEDGMENTS
The autor thanks to the Instituto Colombiano del
Petrleo (ICP), and to Germn Garzn and Luis Maren-
co (RIP) for their valuable guidance and friendship.
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