Fuel Processing Technology 109 (2013) 156–162

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Fuel Processing Technology

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Upgrading of heavy crude oils: Castilla

Jesús Alirio Carrillo ⁎, Laura Milena Corredor
Ecopetrol S.A, Instituto Colombiano Del Petróleo, A.A. 4185 Bucaramanga, Santander, Colombia

a r t i c l e i n f o a b s t r a c t

Article history: Oil resources similar to WTI and Brent crude oils are dwindling, so heavy and extra-heavy crude oils, and bi-
Received 29 February 2012 tumen must be used to meet the growing demand for fuels. The vast majority of the world's refineries are not
Received in revised form 24 August 2012 suitable for processing these types of feed stock, so upgrading processes are required to make synthetic crude
Accepted 6 September 2012
oils from those resources compatible with the equipment installed. By its viscosity Castilla crude oil is not
Available online 12 October 2012
classified as an extra-heavy crude oil, as even on surface it flows. However, it has 45.6 wt.% of vacuum bot-
Keywords:
toms and high concentrations of Conradson Carbon (CCR of 34 wt.%) and metals (nickel and vanadium
Castilla content of 928 ppm) within it.
Coking This article presents various alternatives for the upgrading of the crude Castilla, using as raw material crude
Visbreaking oil free of lights (199 °C+), reduced crude (370 °C+) and vacuum bottoms. The technologies used in the studied
Deasphalting scheme were visbreaking (VBK), delayed coking (DC), solvent deasphalting (DAF), hydrotreating and distillation.
Upgrading The studies were conducted at pilot plant scale and the analysis of the products was done using standard tech-
Hydrotreating niques such as ASTM. Among the outstanding results we have the operational scheme of the vacuum bottoms
Visbreaking, but this is not a typical Visbreaking process because the coke production was 8.2 wt.%. A furnace
with some characteristics of a DC furnace, and a pair of soakers that function as coking drums should be used
to avoid coke deposition within the internal walls of the coils. This is an innovative technology that sits between
visbreaking and delayed coking.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction the refining margin can be bigger if properly handled with higher
profits per barrel. Besides the production of synthetic crudes from
The world needs energy, and the best source, crude oil, is scarce. It heavy crude oils and bitumen, there is the problem of their transpor-
is increasingly difficult to find light crudes with low-sulfur, and low tation by pipe line because of their high viscosity and high concentra-
acidity. Heavy crude oils, whose reserves exceed 6 trillion barrels tion of contaminants, problems that are avoided by their upgrading,
[1], are quite the opposite, with high concentrations of coke pro- which produces a syncrude with higher API gravity, lower viscosity
moters (CCR and asphaltenes), high concentrations of sulfur, high and less concentration of contaminants like sulfur, nitrogen and
levels of acidity and difficult to transport because they are very vis- acidity [2].
cous or even solid when recovered from the producing wells. In addi- Heavy crude oils can be upgraded through various existing pro-
tion, traditional refineries are not suitable for their processing, thus it cesses [3–5], combining different technologies: fractionation and
is necessary to transform them into synthetic crude oils of a similar thermal (visbreaking — VBK and delayed coking — DC) [6]. The DC is
composition, either light or medium crude oils. mainly applied to remove carbon and sulfur, and HDT technology is
Today, synthetic crudes are part of the basket of crudes offered in applied to stabilize the liquids and to remove sulfur and nitrogen.
the market, and are being processed mainly in North American refin- Solvent deasphalting process (SDP) such Kerr-McGee's ROSE (Residue
eries. Such is the case of synthetic crude oils produced from heavy Oil Supercritical Extraction) and UOP's DEMEX are still two SDA pro-
and extra heavy crudes located in the Orinoco Belt (Venezuela), and cesses of high importance in the world [7,8].
tar sands from the Province of Alberta (Canada). However, there The catalytic cracking process is not applied for the first step of
will be an increased production of heavy and extra heavy crude oils upgrading because of the high concentration of catalyst contaminants
in several regions like the Gulf of Mexico and Northeastern China, as within the feed stock: asphaltenes and resins that increase coke
there is a necessity to replace the declining production of convention- formation, sulfur and metals like Ni and V that are catalyst poisons.
al middle and light oil over the next two decades. Nowadays, heavy Because of that, thermal cracking is the preferred route to the
and extra heavy oils are cheaper than conventional petroleum and upgrading of bitumen and heavy crude oil.
In addition to these well-known technologies, there is noticeable
⁎ Corresponding author. Tel.: +57 6571521.
effort of researchers for reaching more efficient ways of production
E-mail addresses: [email protected] (J.A. Carrillo), and upgrading bitumen and heavy crude oils using different ap-
[email protected] (L.M. Corredor). proaches such as hydrotreating using cheap hydrogen produced

0378-3820/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fuproc.2012.09.059
 J.A. Carrillo, L.M. Corredor / Fuel Processing Technology 109 (2013) 156–162 157

from wind energy [9], applying solar energy for bitumen recovering standard methods (such as ASTM), in the laboratories of
from sand [10], studying the reactivity of the greater sources of ECOPETROL-ICP certified by ISO 9001.
heavy crude oils and bitumen like Athabaska bitumen [11], or looking The operating conditions used in the pilot plants were:
for non conventional ways of bitumen processing [12].
– For delayed coking: load 2000 g, temperature 510 °C, pressure
As a result of the application of these technologies, relatively light
10 psig and time of run 2 h.
crude oils with low yields of vacuum bottoms, and high yields of
– For visbreaking: temperature 480 °C and residence time 60 s.
middle distillates and diesel with low concentration of sulfur and
– For deasphalting the relationship of solvent/feed was 6/1 vol/vol,
nitrogen are obtained. These features allow its use as part of the
the bottom temperature 60 °C and the top temperature 100 °C.
diet of crude in the refinery to improve production of medium fuels
such as diesel and Jet of excellent quality. The studied operational schemes were:
The objective of the present study was to visualize alternatives of
1. Upgrading of Castilla crude oil 199 °C +
producing synthetic crude from Castilla crude, compatible with the
1.1 n-C4 solvent deasphalting of crude 199 °C+ and delayed coking
existing technologies available in the refineries, at the lowest possible
(DC) of its demetallized oil (DMO).
cost and with the best cost/benefit ratio, using well-known technolo-
1.2 n-C4 solvent deasphalting of the crude 199 °C + and DC of the
gies applied for the heavy crude oil upgrading in both Orinoco belt
deasphalted bottoms (DAB).
(Venezuela) and Alberta province (Canada), the greater source of
2. Upgrading of reduced Castilla crude (long residue)
synthetic crude. Castilla crude has the following characteristics:
2.1 n-C4 solvent deasphalting of the reduced crude and DC of the
viscosity 2297.9 cSt at 40 °C, sulfur concentration 2.39 wt.%, atmo-
Deasphalted bottoms.
spheric distillate yield 27.6 wt.%, and concentration of asphaltenes
2.2 Delayed coking of reduced crude.
(insolubles in n-C7) in the crude 14.09 wt.%, and in the vacuum bot-
3. Upgrading of the vacuum bottoms from Castilla crude.
tom 31.08 wt.%.
3.1 Vacuum bottoms DC
3.2 n-C4 solvent deasphalting of the vacuum bottoms; DC of the
DAB, and hydrotreating (HDT) of the coker distillates.
2. Experimental
3.3 Visbreaking (VBK) of the vacuum bottoms
For the upgrading of Castilla crude oil, operational schemes that The cut composition of each sample for each scheme was done by
combine the commercial technologies, using as raw material crude simulated distillation.
oil free of lights (199 °C +), reduced crude, and vacuum bottoms
were studied. These cuts were obtained by Castilla crude ASTM distil- 3. Results and discussion
lation. The distillation yields of the Castilla crude and the properties
of the crude 199 °C + are given in Table 1. For the Castilla crude the 3.1. Upgrading of Castilla crude oil 199 °C +
amount of refined cuts are: atmospheric distillates 27.6 wt.%, and
vacuum distillates 26.8 wt.%, so the amount of vacuum bottoms are 3.1.1. n-C4 solvent deasphalting of crude 199 °C + and DC of its DMO
45.6 wt.%. As a reference the amount of vacuum bottoms in the medi- Table 2 presents the consolidated results of each scheme with
um crude oil is about 20 wt.% and in the light crude oil is about respect to the original crude oil. To obtain the crude cut of 199 °C +
5 wt.%. When there are no facilities for the upgrading of vacuum bot- the amount of naphtha withdrawal was 6 wt.%. In the process of
toms in the refinery, the alternatives are the production of asphalts deasphalting 61.1 wt.% of demetallized oil (DMO) and 32.9 wt.% of
for the pavement of the roads or the production of fuel oils by dilution deasphalted bottoms (DAB) with respect to the whole crude (column
with distillates or by visbreaking of the vacuum bottoms. 2), and 65 wt.% of DMO and 35 wt.% with respect to the crude
On the other hand, the amount of metals (Ni + V) in the Castilla 199 °C + (column 3 in bold) were produced. Within the same column
crude 199 °C + is 500.9 ppm, in the medium crude oil is less than the results of DMO's simulated distillation are given. In column 4 the
50 ppm, in the demetallized oil is less than 35 ppm and in the gas recomposition of the whole crude is given.
oil pool to FCC is less than 10 ppm. Metals are catalyst poisons, so it The quality of the DMO obtained was similar to that of a synthetic
is important to reduce their amount in the feeds to the catalyst crude, with CCR of 4.4 wt.%, however, the metals concentration, Ni =
processes. 16.6 ppm, and V = 69.5 ppm is too high (Table 3). These amounts
The runs were performed at pilot plants designed and built at exceed the allowable limits of metal concentrations within the DMO
ECOPETROL-ICP [13–15]. The analysis were performed according to (35 ppm) that is processed in the traditional hydrotreating–catalytic
cracking scheme. The metals are deposited on the hydrotreating
Table 1 catalyst surface deactivating it and reducing the turnaround of the
Distillation of the Castilla crude and properties of the cut 199 °C+. plant from 1 year or more to just a couple of months. On the other
Distillation Crude 199 °C+ hand, taking into account the SARA analysis, the obtained DMO is a
very good feed to the DC process as its asphaltene concentration is
Atmospheric Properties
Gases Density at 15 °C 1.0058 too low (0.2 wt.%), which means high distillate yields.
Naphthas 6.7 API 9.1 The DC of the DMO produces 10.1 wt.% of gases, 82.4 wt.% of
Jet 3.8 CCR, wt% 17.23 distillates and only 7.5 wt.% of coke (column 5 in bold, Table 2) as it
Diesel 8.0 Sulfur, wt% 2.427 was foreseen by the DMO's low asphaltene concentration, however,
AGO 9.1 Ca, ppm 10.76
the amount of coke related to the CCR is high and is 1.7 times the
Vacuum Ni, ppm 95.64 amount of CCR within the feed stock. In the same column the simu-
LGO 5.6 V, ppm 405.26 lated distillation of the DC distillates is given. The little coke yield is
MGO 12.6 Na, ppm 13.81 the result of coke promoter removal within the deasphalting process.
HGO 8.6 Sum: Ni + V 500.9
Among coke promoters the insolubles in cyclohexane predominate
Vacuum bottoms 45.6 i-nC7, wt% 18.54
i-nC5, wt% 28.82 with a concentration of 10 wt.% [16]. Within the distillates diesel
Viscosity-1, cP 227 at 100 °C and naphtha predominate.
Viscosity-2, cP 94 at 120 °C The distillates of the DMO's delayed coking were processed in
Basic N, wt% 0.112 HDT (column 6), and the consolidated balance with respect to the
Total N, ppm 4446
61.1 wt.% production of DMO is presented in column 8.
158 J.A. Carrillo, L.M. Corredor / Fuel Processing Technology 109 (2013) 156–162

Table 2
Deasphalting of Castilla 199 °C+, and DC of its DMO and its DAB.

Naphtha 6 wt %
6.2 wt% Gases
Demetallised oil
(DMO), 61.1 wt % 50.3 wt %
Consolidated
DC HD
scheme
Castilla Crude Deasphalting
crude 199°C 4.6 wt % Coke
DC of DAB
Bottoms from Deasphalting (DAB), 32.9 wt %
1 2 3 4 5 6 7 8 9 10 11

Deasphalting Deasphalting Delayed Coking of DMO Total DC of DMOHDT DC of FDA Total DC of FDA

Crude DMO Total DC HDT-Distillates Distillates 82.4 % Total HDT/DMO

Atmospheric distillation
Gases 10.1 10.1 6.2 6.2 7.7 2.5
Naphthas 6 6.0 16.2 21 17.3 10.6 16.6 18.0 9.4
Jet 5 3.1 8.7 11 9.1 5.5 5.5 8.0 3.7
Diesel 12 7.3 16.9 15 12.4 7.6 7.6 15.0 9.6
AGO 13 7.9 14.2 13 10.7 6.5 6.5 14.0 10.1

Vacuum distillation
LGO 14 8.6 12.4 13 10.7 6.5 6.5 15.0 10.8
MGO 12 7.3 8.6 12 9.9 6.0 6.0 7.0 8.4
HGO 15 9.2 4.6 12 9.9 6.0 6.0 10.0 10.7
Vacuum bottoms 29 17.7 0.9 3 2.5 1.5 1.5 13.0 19.7
DMO 61.1 65.0
DAB 32.9 35.0 32.9 32.9
DC Distillates 82.4 46.4
Coke 7.5 7.5 4.6 4.6 45.9 15.1
Total 100 100.0 100.0 100.0 61.1 100.0 100.0 100.0

DC — delayed coking; DAB — bottoms from the deasphalter; DMO — demetallized oil.

This is a scheme of high production of gasoline (16.6 wt.%) and 3.1.2. Deasphalting of the crude 199 °C + and DC of the deasphalted
residues (32.9 wt.% of deasphalting bottoms and 4.6 wt.% of coke). bottoms
The high gasoline production is due to the severe thermal process The deasphalted bottoms cannot be processed in the visbreaker due
that the diesel and middle distillates undergo. The quality of the prod- to their high concentration of coke promoters (39.8 wt.% of CCR). Usu-
ucts from this scheme is presented in Table 3. The high sulfur concen- ally the CCR concentration within the feed to the visbreaking process is
tration within the DC distillates is handled in the HDT process. lower than 20 wt.%. Because of that, the alternative process is the DC.
Within column 10 of Table 2 in bold the yields of coke, distillates
and gases are given. The coke yield is 45.9 wt.% which is signifi-
cantly lower than expected. According to the University of Tulsa
[17], the amount of expected coke for feed stocks having 20–27 wt.%
Table 3 of CCR is 1.5 times the amount of CCR, and for this case is
Properties of the products from the crude 199 °C+ deasphalted with n-C4, and of the 1.5 ∗ 39.8 wt.% = 60 wt.%. Considering the type of feed stock, the distil-
DC distillates. late yield is very high (46.4 wt.%); the gas production is 7.7 wt.%
DMO DC of DMO DAB DC of DAB (column 10 in bold). In the same column the simulated distillation
Density at 15 °C 0.9546 0.9113 1.086 0.9300
of the DC distillates is given. The only explanation for the high distil-
API 16.6 23.7 −1.2 20.6 late yield taking in account the high coke promoter's concentration
CCR, wt% 4.4 2.1 39.8 3.5 in the feed stock is that the asphaltenes have high concentrations of
Sulfur 1.9 1.5 3.7 2.3 naphthenic and paraffinic carbons within their micelles.
Heat of combustion − 40.599
In column 11, the composition of the synthetic crude obtained
Ashes, wt% − 0.2
Ca, ppm 17.1 21.0 from the scheme of the deasphalting of crude and DC of the bottoms
Ni, ppm 16.6 243.3 from the Deasphalted is given.
V, ppm 69.5 981.7 In both DC schemes studied, the concentration of sulfur is reduced
Na, ppm 49.2 67 with respect to the value of the raw material (Table 3). The same ap-
Sum: Ni + V 86.14 1225.0
plies to the CCR, which is reduced in the first scheme from 4.4 wt.% to
i-nC7 42.9
i-nC5 50.8 2.1 wt.%, and in the second scheme from 39.8 wt.% to 3.5 wt.%. The
Viscosity-1, cP 28 at 80 °C 4,170,000 at 135 °C CCR reduction is due to the conversion of coke promoters in coke,
Viscosity-2, cP 14 at 100 °C 476,000 at 147 °C which also leads to the reduction of sulfur because of its association
Basic N, wt% 0.07 0.065 0.254 0.118
with coke promoters.
Total N, ppm 1883 1727 3467
SARA analysis, wt%
S 49.3 3.2. Upgrading of reduced Castilla crude
A 40.0
R 10.5 These alternatives preserve the atmospheric distillates quality and
A 0.2
seek to maximize the middle distillates' production (Table 4).
 J.A. Carrillo, L.M. Corredor / Fuel Processing Technology 109 (2013) 156–162 159

Table 4
Alternatives for the upgrading of Castilla reduced crude oil.

DMO, 51 wt%
FCC
Reduced Crude 370 °C+
Deasphalting
DAB, 49 wt%
Delayed Coking
Delayed Coking

1 2 3 4 5 6 7 8 9 10 11 12 13

Scheme DA–DC of DAB Scheme DC of R. Crude

Crude RC DA/RC DMO DMO at 51 wt.% DAB DC of DAB DC of DAB at 49 wt.% DMO + DC of DAB DC of RC HDT Total/crude

Atmospheric distillation
Gases 13.0 6.4 4.6 7.2 7.2 5.2
Naphthas 6.7 8.0 3.9 9.5 15.7 15.2 18.0
Jet 3.8 1 3.4 1.7 5.0 7.5 8.1 9.2
Diesel 8.0 2 1.02 5.3 2.6 10.6 13.6 14.5 17.9
AGO 9.1 3 7 3.57 5.5 2.7 13.6 15.8 16.5 20.5

Vacuum distillation
LGO 5.6 11 18 9.18 5 7.2 3.6 9.2 9.1 9.0 6.6
MGO 12.6 12 18 9.18 4 7.0 3.4 9.2 7.5 6.7 5.4
HGO 8.6 14 21 10.7 7 5.8 2.8 9.8 4.4 3.8 3.2
Vacuum Bottoms 45.6 59 34 17.3 84 2.8 1.4 13.6 1.1 0.8 0.8
DMO 51
DAB 49

DC distillates
Coke 42.0 20.6 14.9 18.2 18.2 13.2
Total 100 100 100 100 51.0 100.0 100.0 49.0 100.2 100.0 100.0 100.0

DAB — bottoms from the deasphalter; RC — reduced crude; DA — deasphalting.

Two operational schemes were considered: to those presented in the schemes of the 199 °C + crude oil upgrading.
The concentrations of Ni and V in the DMO of the reduced crude are
▪ n-C4 solvent deasphalting of the reduced crude and DC of the lower than those presented in the DMO of 199 °C + crude oil (Ni =
deasphalted bottoms. 13.9 vs. 16.6 ppm, V = 45.5 vs. 69.5 ppm; see Tables 3 and 5). This
▪ DC of reduced crude. is due to the atmospheric distillates present in the crude 199 °C +,
which act as a heavy solvent that slightly increase the yields of
3.2.1. n-C4 solvent deasphalting of the reduced crude and DC of the DMO, but reduces their quality by increasing the concentrations of
deasphalted bottoms (DAB)
The objective of this scheme is to reduce technology costs re-
quired to obtain good quality synthetic crude. Taking in count the
CCR concentration in the vacuum bottoms it is appropriate to consid-
er the DC technology for their upgrading. However the DC of the Table 5
Quality of the products obtained from the upgrading of Castilla reduced crude oil.
reduced crude increases significantly the cost of the upgrading tech-
nology. For that reason the deasphalting process was considered as Properties Reduced DMO DAB DC of DC of R.
an upgrading alternative. crude DAB Crude
Deasphalting was applied to the reduced crude which represents Density at 15 °C 1.0367 0.9729 1.0483 0.932 0.9236
72.4 wt.% of the original crude (column 2 of Table 4, LGO+ MGO + API 4.9 13.9 3.4
HGO). In column 3 the reduced crude simulated distillation is given, CCR, wt.% 21.4 4.61 38.97 4.19 2.53
Sulfur, wt.% 3.1 1.952 3.65 2.2 1.98
and within them, the vacuum bottoms correspond to 59 wt.%. Heat of – – 40.549
As a result of the deasphalting 51 wt.% of demetallized oil (DMO) combustion
and 49 wt.% of DAB (column 4) were produced. In column 5 the Ashes, wt.% – – 0.227
DMO's simulated distillation is given. It includes almost all vacuum Ca, ppm 14.7 2.23 10.04
Ni, ppm 123.5 13.87 245.84
gas oils and 58 wt.% of the vacuum bottoms. The extraction related
V, ppm 519.8 45.52 1052.48
to the vacuum bottoms was poor considering the asphaltene concen- Na, ppm 64.4 16.49 40.64
tration within the feed (CCR = 21.4 wt.%). In column 6, the DMO Sum: Ni + V 643.3 59.39 1298.32
production reduced to its yield (51 wt.%) is given. i-nC7 19.2 0.1 40.16
Simulated distillation of DAB indicates that bottoms are mainly com- i-nC5 24.0 0.3 49.58
Viscosity-1, cP 2070 at 100 °C 117 1,090,000
posed of vacuum bottoms (84 wt.%) and vacuum gas oils (column 7 of at 140 °C
Table 4). Viscosity-2, cP 1230 at 120 °C 53 370,000
The DC was applied to DAB (35.5 wt.% of the original crude), and at 148 °C
was performed at 520 °C. The yields are given in column 8. The coke Basic N, wt.% 0.1 0.1 0.2 0.133 0.1
N Total, ppm 5862 2651 9200 5395 5351
production was 42 wt.%, and the gas production 13 wt.%. In column 9
SARA analysis, wt.%
the yields of DC reduced to the production of DAB (49 wt.%) are given. S 19 24.2 –
The coke yield is high but corresponds to the high asphaltene concen- A 46.4 63.7 –
tration within the feed (CCR = 38.97 wt.%, Table 5, column 4). R 15.8 12.1 –
Table 5 shows the product quality of the studied upgrading A 18.8 – –

schemes that start with reduced crude. The change trends are similar DMO — demetallized oil, DAB — bottoms from the deasphalter, DC — delayed coking.
160 J.A. Carrillo, L.M. Corredor / Fuel Processing Technology 109 (2013) 156–162

Table 6
Alternatives for the upgrading of the Castilla crude oil vacuum bottoms.

Scheme 1
Delayed Coking DMO, 27 wt% Delay
HDT
Vacuum Bottoms 510°C+, Scheme 2 Coking
Deasphalting
= 45.6 wt% of the whole crude
DAB, 73 wt%
Scheme 3 Delayed Coking HD
Visbreaking
(VR)

1 2 3 4 5 6 7 8 9 10 11 12 13 14

Delayed coking of vacuum Deasphalting of vacuum bottoms Delayed coking of DAB VR of vacuum
bottoms bottoms

Crude DC HDT of Consolidated DMO HDT of DMO at DAB, DC of HDT of DAB at Consolidated VR Consolidated
distillates DMO 27 wt.% 482 °C DAB distillates 73 wt.% scheme

Atmospheric distillation
Gases 10.0 10.0 4.6 10 10.0 7.3 3.3 0.7 0.3
Naphthas 6.7 11.9 11.1 11.7 9.0 8.6 6.3 9.5 3.2 8.1
Jet 3.8 4.8 5.9 6.5 3.9 4.7 3.5 5.4 2.0 4.7
Diesel 8.0 7.3 8.3 11.8 6.0 6.6 4.8 10.2 4.1 9.9
AGO 9.1 6.5 7.2 12.3 2 0.5 5.4 5.9 4.3 11.3 6.7 12.1

Vacuum distillation
LGO 5.6 6.9 7.4 9.0 3 0.8 5.8 6.3 4.6 8.1 1.0 6.1
MGO 12.6 6.9 6.9 15.7 6.0 8 2.2 1.0 6.1 6.1 4.5 15.6 1.4 13.2
HGO 8.6 7.4 6.7 11.7 34.0 31 8.4 8.0 7.1 6.3 4.6 14.5 11.5 13.9
Vacuum bottoms 45.6 3.1 1.5 0.7 60.0 56 15.1 91.0 3.7 2.4 1.7 7.7 51.4 23.4
DMO 27
DAB 73.0
Coke 35.0 35.0 16.0 43.0 43.0 31.4 14.3 18.0 8.2
Total 100 100 100.0 100.0 27.0 100.0 27.0 73.0 100.0 100.0 73.0 100.0 100.0 100.0

DC — delayed coking, DAB — bottoms from the deasphalter, VR — visbreaking.

metals and CCR. However the sum of metals is too high for hydro- ▪ Visbreaking (VBK) of the vacuum bottoms and HDT of the VBK
treating in order to improve the feed to the FCC process. distillates.
In column 10 (Table 4) the consolidated results for the scheme com-
posed of atmospheric distillates plus the products from the deasphalting All consolidates are presented in reference to the original crude oil
of the reduced crude and DC of the DAB are given. With respect to the and correspond to the synthetic crude oils.
original crude oil, a high yield of gasoline is detected.

3.4.1. Vacuum bottoms DC (Table 6, columns 2–4)

3.3. Delayed coking of reduced crude
In this scheme the upgrader capacity is reduced because only vac-
uum bottoms are processed (45.6 wt.% of the crude oil). The naphtha
Normally delayed coking has excellent feed flexibility and it can
production in the synthetic crude with respect to the original oil near-
process feedstocks with large CCRs, however CCR values above
ly doubled, from 6.7 wt.% to 11.7 (columns 1 and 4). The sum of jet
27 wt.% increase the coke yield significantly and the process becomes
plus diesel increases from 11.8 wt.% to 18.3 wt.%. The gas oil produc-
too expensive. Castilla crude vacuum bottoms significantly overcome
tion increases from 35.9 wt.% to 48.7 wt.%, and the coke production
that value, which suggests that for this technology the reduced crudes
is 16 wt.%. The amount of CCR in the feedstock is 31.2 wt.% which
should be processed instead of their vacuum bottoms.
according to the rule of thumb means 31.2 × 1.5 = 46.8 wt.% of
Castilla reduced crudes correspond to 72.4 wt.% of the total crude
expected coke yield with respect to the vacuum bottoms, however
oil, which implies a significant increase in the processing capacity of
the real coke yield was 35 wt.%. This value is too low and suggests
the DC, but at the same time implies greater conversion, highlighting
the high production of diesel and naphtha. The coke production
is similar to the previous scheme and corresponds to 13.2 wt.%. In
column 11, (Table 4) the yields from the DC of the reduced crude
42.5 y = 1.0833x + 0.2402
are given; in column 12 the hydrotreating of DC distillates is given, R² = 0.9661
37.5
and in column 13 the synthetic crude which includes the atmospheric
Coke yield, wt%

distillates plus the products from the DC of the reduced crude is given. 32.5
In comparison to the previous scheme, this is a scheme of high
atmospheric distillates and lower yields of vacuum distillates. All 27.5
distillates need HDT processing as they are unstable and can't be
22.5
blended with finishing distillated products as jet or kerosene.
17.5
3.4. Upgrading of the vacuum bottoms from Castilla crude
12.5

The alternatives for the upgrading of the vacuum bottoms are: 7.5
4 14 24 34
▪ Delayed coking of the vacuum bottoms and HDT of distillates. CCR in the feed stock, wt%
▪ n-C4 deasphalting of the vacuum bottoms; DC of the DAB, and HDT
of the coker distillates. Fig. 1. Correlation between coke yield and CCR in the feed.
 J.A. Carrillo, L.M. Corredor / Fuel Processing Technology 109 (2013) 156–162 161

Table 8
Technology costs.

Value of the technology Taken value

US$/Bl US$/Bl

Atmospheric distillation 1000

Atmospheric and vacuum distillation 750–2200 2000
Deasphalting 1850–8000 4000
Delayed coking 5800–12,000 8000
Vacuum
Hydrotreating 3000–3500 3000
bottoms Visbreaking 1800–3500 3000
Crude for the process, bl/day 50,000

Furnace Coker drums Distillater

Fig. 2. VBK of the vacuum bottoms with coker drums as soakers.

That value is too high, however it should be considering that the
concentration of CCR within the feedstock is 39.76 wt.%, and that
the coke prediction according to the rule of thumb should be
that for feedstocks having CCR values higher than 25 wt.%, the multi- 39.76 × 1.5 = 59.6 wt.%. That result confirms that for a feedstock
plier for the rule of thumb should be less than 1.5. having a CCR concentration higher than 25 wt.% the multiplier factor
The HDT of the DC distillates increases the production of jet, diesel, for coke forecast should be 1.1 times the concentration of the CCR
GOA, and LGO due to the conversion of some molecules of heavy gas within the feedstock. The HDT of the DMO produces a slight conver-
oil and vacuum bottoms to lights. sion of heavy gas oil (HGO) and vacuum bottoms to middle vacuum
gas oil (MGO), light vacuum gas oil (LGO) and AGO as shown in the
3.4.2. n-C4 solvent deasphalting of the vacuum bottoms (Table 6, comparison between the columns 3 and 4 (Table 6). The HDT of DC
columns 5–8); DC of the DAB, and HDT of the Coker distillates (Table 6, distillates register a similar pattern to that of the HDT of the DMO.
columns 9–12) In general, it was observed that the yield of coke in the DC process
The DMO yields (27 wt.%, in bold) and the simulated distillation is about 1.1 times the amount of CCR in the feed stock as can be seen
of the DMO are given in column 5. The results of the DMO hydro- from Fig. 1. This result is very important for take decisions about the
treating are given in column 6, and in column 7 we have the same scheme that should be chosen for the upgrading of heavy crude oils
results as column 6, but are taken to the sum of 27 wt.% (the yields because the rule of thumb followed for the refineries is 1.5 times
of DMO). the amount of CCR in the feed stocks, and this value is very high.
The yields of the DAB (73 wt.%, in bold), and their simulated distil- The results of the comparison between the schemes of VB DC
lation are given in column 8. The yields of the DC of DAB are given in (Table 6 column 4) and n-C4 solvent deasphalting of the vacuum bot-
column 9; the distillates from the DC are hydro-treated and the yields toms and DC of the DAB, and HDT of the coker distillates(Table 6,
are given in column 10. In column 11 we have the same results as columns 12) show that both schemes arrive at similar yields of distil-
column 10 but are taken to the sum of 73 wt.% (the yield of DAB). lates and coke.
The consolidated scheme is given in column 12.
The low DMO yield means that the vacuum bottoms are composed
mainly of asphaltenes. That corresponds to the concentration of insol- 3.4.3. Visbreaking (VBK) of the vacuum bottoms (Table 6, columns
ubles in n-C7 (28.81 wt.%) within the feedstock. 13–14)
In the DC of the DAB the coke yield with respect to the vacuum In column 13 the yields of the vacuum bottoms visbreaking are
bottoms is 43 wt.%, and with regard to the crude oil is 14.3 wt.%. given, and in column 14 we have the synthetic crude of this scheme.

Table 7
Quality of the products from the upgrading of the vacuum bottoms obtained from the Castilla crude oil.

Properties Vacuum bottoms (VB) DC of Vacuum bottoms DMO DAB DC of DAB VB of vacuum bottoms visbreaking

Density at 15 °C 1.036 0.9182 0.9854 1.0537 0.929 1.081

API 5 12 2.7 -0.6
CCR, wt.% 31.2 4.21 6.88 39.76 5.41 38.5
Sulfur, wt.% 3.48 2.18 2.473 3.8 2.44 3.22
Heat of combustion – – 40.455 40.6
Ashes, wt% – – 0.226
Ca, ppm 4.77 2.1 5.18 14.75
Ni, ppm 185 19.81 232.91 206
V, ppm 735 72.81 1014.83 802
Na, ppm 25 7.68 39.58 44
Sum: Ni + V 920 92.62 1247.74 1008
i-nC7, wt.% 28.81 – 40.98 20.7
i-nC5, wt.% 35.6 – 47.86 36.8
Viscosity-1, cP 1,217,082 at 40 °C 959 at 80 °C 4,400,000 at 140 °C 578,000 at 120 °C
Viscosity-2, cP 233,653 at 50 °C 270 at 100 °C 1,010,000 at 148 °C 279,000 at 135 °C
Basic N, wt.% 0.203 0.129 0.098 0.189 0.143 0.253
Total N, ppm 7625 6973 3410 – 7455 10,105
N.N, mg KOH/g 0.6
SARA analysis, wt.%
S 9.2 24.5 11.6
A 42.3 61.1 44.9
R 19.6 14.4 22.8
A 28.9 – 20.7

VB — vacuum bottoms, DC — delayed coking, DAB — bottoms from deasphalting.

162 J.A. Carrillo, L.M. Corredor / Fuel Processing Technology 109 (2013) 156–162

Table 9 withdrawing of produced coke during the process. The residence

Investment cost of the proposed schemes. time in the coking drums is about 5–7 min. Additionally, this scheme
Economic impact of the studied upgrading alternatives of the MMUS$ maintains the yields of the atmospheric distillates and stabilizes
Castilla crude distillates (HDT) from the visbreaking process.
1 Visbreaking (VR) of the vacuum bottoms and HDT of the 224 Another aspect to highlight for coke yield prediction according to
distillates from VR the rule of thumb is that as the CCR concentration in the feed stocks is
2 Deasphalting of crude 199 °C + and DC of its DMO 250 increasing, the multiplier number of the CCR is reduced: for feed
3 Deasphalting of the crude 199 °C + and DC of the bottoms 250
stocks having a concentration of CCR lower than 5 wt.%, the yield of
obtained in the deasphalting.
4 DC of the vacuum bottoms and HDT of DC distillates 351 coke is 1.7 times the concentration of CCR in the feed stocks. For
5 n-C4 deasphalting of the vacuum bottoms; DC of the DAB, and 374 feed stocks having a concentration of CCR higher than 25 wt.%, the
HDT of the distillates from DC yield of coke is about 1.1 times the amount of CCR in the feed stocks.
6 n-C4 deasphalting of the reduced crude and DC of the 390 Applying the formula:
deasphalted bottoms
7 Delayed coking of reduced crude 448
Coke yield; wt:% ¼ 1:0833  CCR ðwt :%Þ þ 0:2402

With regard to the vacuum bottoms, a high yield of coke (18 wt.%) the coke yield is quite well predicted knowing the CCR concentration
is detected, which is unusual in the VBK technology (the usual values in the feedstock.
are less than 1 wt.% at pilot plant scale). However, with respect to the
crude oil, the coke production is only 8.2 wt.%. In contrast there was a Nomenclature
significant reduction in the vacuum bottoms within the synthetic DAB deasphalted bottoms
crude oil which reduced from 45.6 wt.% to 23.4 wt.%. DMO demetallized oil
The VBK process of a feed stock that produces high levels of coke is DC delayed coking
inconvenient because it means that the plant should be shutting HDT hydrotreating process.
down every day for cleaning. An alternative to improve this effect LGO light vacuum gas oil
is to install two soakers in parallel, which operate in a similar way MGO medium vacuum gas oil
as the coker drums, but with the residence time reduced to 7 min HGO heavy vacuum gas oil
(Fig. 2). This way there will be an upgrading scheme of low conver- AGO atmospheric gas oil
sion, low investment and low coke yield. An additional advantage of VBK visbreaking
this process is the reduction of the crude oil viscosity for its transport R. Crude reduced crude
by pipeline. The distillates from this synthetic crude should be
hydrotreated because they are unstable and have high sulfur
concentrations. References
Table 7 shows the quality of products from the upgrading of [1] J. Plotkin, Exploiting unconventional heavy oils, in: PTQ — Q1, 2007, pp. 65–67.
the Castilla crude oil vacuum bottoms. The CCR is reduced from [2] R. Martínez-Palou, et al., Transportation of heavy and extra-heavy crude oil by
31.2 wt.% in the vacuum bottoms to 4.2 wt.% in the DC distillates pipeline: a review, Journal of Petroleum Science and Engineering 75 (2001)
274–282.
from the vacuum bottoms and to 5.4 wt.% in the distillates from DC
[3] M. Rana, et al., A review of recent advances on process technologies for upgrading
of DAB. The DMO from the vacuum bottoms has a CCR of 6.9 wt.%. of heavy oils and residua, Fuel 86 (2007) 1216–1231.
The scheme of vacuum bottom deasphalting and DC of the DAB [4] Le Page, J., Chatila, S. and Davidson, M. Residue and heavy oil processing. Editions.
Technip, Paris, 1992
shows yields and qualities similar to those given by the vacuum bot-
[5] M. Gray, Upgrading Petroleum Residues and Heavy Oils, Marcel-Dekker, 1994.
toms DC scheme. [6] J. Speight, in: Chapter 5: Thermal Cracking The Refinery of the Future, and
Hydrotreating (HDT), 2011, pp. 147–180.
3.4.4. Cost of technologies for evaluated schemes [7] J. Gearhart, L. Garwin, Resid-extraction process offers flexibility, Oil and Gas Journal
74 (1976) 63–66.
The calculations were performed with the values presented in [8] R. Newcomer, R. Soltau, Heavy oil extraction ups FCC feed at first three-stage
Table 8 [18] and on the basis of 30,000–50,000 barrels/day. grass roots ROSE unit, in Kansas, Oil and Gas Journal 80 (1982) 108–110.
In Table 9 the values of the different technological alternatives for [9] B. Olateju, A. Kumar, Hydrogen production from wind energy in Western Canada
for upgrading bitumen from oil sands, Energy 36 (11) (2011) 6326–6339.
the processing 50 KBPD of crude Castilla are given. The lower cost al- [10] D. Kraemer, et al., Solar assisted method for recovery of bitumen from oil sand,
ternative is the visbreaking of the vacuum bottoms and hydrotreating Applied Energy 86 (9) (2009) 1437–1441.
of the distillates obtained from the VBK, followed by the alternatives [11] P. Danial-Fortain, et al., Reactivity study of Athabasca vacuum residue in
hydroconversion conditions, Catalysis Today 150 (2010) 255–263.
of deasphalting of the crude and DC of the DMO or the DAB. Between [12] Wahyudiono, et al., Non-catalytic liquefaction of bitumen with hydrothermal/
the last two alternatives, the better conversion is obtained in the solvothermal process, Journal of Supercritical Fluids 60 (2011) 127–136.
alternative of deasphalting of the crude 199 °C + and DC of the DAB. [13] J. Carrillo, F. Pantoja, G. Vela, Visbreaking pilot plant, in: Gaceta 444 del 7 de
Mayo, 1997, p. 200.
[14] J. Carrillo, F. Pantoja, G. Vela, Liquid–liquid in continuous extraction pilot plant,
4. Conclusions in: Gaceta 448 del 9 de Julio, 1997, p. 216.
[15] J. Carrillo, H. Picón, L. Garzón, L. Corredor, Delayed coking: Castilla and Jazmín
crude oils, ACS National Meeting, Fuel Chemistry 52 (2007) 2.
Of all alternatives studied, the visbreaking of the vacuum bottoms
[16] J. Carrillo, L. Corredor, M. Valero, Characterization and studies of kinetic and severity
is the most economical and innovative alternative, taking into in the visbreaking of heavy crude oils: Castilla, Rubiales, and Nare-Jazmín, ACS
account that it combines a furnace that operates at the visbreaking National Meeting, Fuel Chemistry 49 (2004) 2.
conditions, but includes design elements of DC furnace to control [17] M. Volk, et al., Fundamentals of delayed coking, Joint Industry Project, University
of Tulsa. Departamento f Chemical Engineering, 2002.
the accumulation of coke in the coils. Furthermore in this arrange- [18] Refining Processes Handbook 2011. Hydrocarbon processing
ment there are coke drums instead of soakers for accumulation and