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Conventional Fire Flood [19, 20], Toe-to-Heel Air Injection The supported catalysts were previously treated with a
(THAI) process [21-23], Aquathermolysis [24,25], and the sulfur compound (250 ml of CS2) mixed with 20 L of diesel.
above mentioned Down-Hole Catalytic processes [26-28]. The The operating conditions during the sulfurization stage were as
main contribution of these processes is to decrease the follows: A pressure of 56 kg.cm-2, space velocity of 3 hr-1, and
viscosity of the heavy crude oil to improve its flow from the reaction times of 4 h at 533 K, and 12 h at 593 K.
reservoir to the producer well. This viscosity reduction can be
carried out by increasing the reservoir temperature (from 353- The organometallic catalysts were dissolved in a hydrogen-
393 at 673 K) or by injecting a hydrogen-donor compounds donor, and it was activated with the heavy crude oil at 543 K.
[29-31]. There are two more points to improve the quality of Some samples were commercially acquired while other
the heavy-crude oil: (1) the hydrocracking, and (2) the catalysts were synthesized in laboratory.
hydrotreating, such as aromatic hydrogenation and the
desulfurization sulfur heteroatoms and porphyrins compounds Experimental Stages
removal. This removal can be fulfilled by injection of a
catalytic solution (organic-metallic compounds of Mo, Fe, Co, Thermal Hydrocracking. An amount of 1200 g of heavy
Ni) with hydrogen-donor, homogenously mixed with the crude oil was charged in a batch reactor and pressurized with
heavy crude oil [32, 33]. Intelligent horizontal wells [24, 35] hydrogen (99.99 %) at 10.8 MPa, and 673 K. Under these
can be used to the diffusion of this catalytic solution in the operating conditions the heavy crude oil was homogenized at
reservoir, and in-situ combustion can be an alternative to 1000 rpm, during 4 h. This experiment was done as a
supply to the catalyst the activation energy necessary in the reference test to compare the obtained results in the upgrading
process. of the heavy crude oil, using both of them supported and
unsupported catalysts.
The present work shows the upgrading of heavy crude oil
Hydrocracking of heavy crude oil with supported
through the application of the thermal and catalytic
catalysts. In this stage the heavy crude oil upgrading was
hydrocracking using both supported and unsupported
accomplished in a batch reactor, using MoCoP/Al2O3
catalysts. Thermal hydrocracking has shown a significant
commercial catalysts or NiMoCoWP/Al2O3 experimental
increase of API gravity of the heavy oil produced, including
catalyst with 1200 g of heavy crude oil were mixed with 120 g
an undesirable high coke formation (25 wt%), and a
of the supported catalysts at the following operating
decreasing content of contaminants. The catalytic
conditions: hydrogen pressure of 10.8 MPa at 623 K and 1000
hydrocracking showed not only a lower increase of the API
rpm, with a residence time of 24 h.
gravity than in the previous experiment, but also a better
product quality because of its decreasing content of coke,
Hydrocracking of heavy crude oil without supported
sulfur, and metal compounds (porphyrins). These
catalysts. The same batch reactor was charged with 1200 g of
improvements are consequences of the perfect balance
crude heavy oil mixed with 500, 700, 1000 wt ppm of (MoO2
between metal and acid functions of the catalysts. Increasing
(acac)2 or Fe(acac)3), and 500-1000 wt ppm of MoO2(acac)2-
metallic load and the acidity in the experimental catalyst
Fe(acac)3 dissolved in a mixture of tetraline-1-butanol at
allowed to decrease the reaction temperature (10 K). API
hydrogen pressure of 10.8 MPa (99.99 % purity), at 673 K,
gravity showed a greater increase comparing with a
1000 rpm, and residence time of 4 h.
commercial catalyst.
A finally experiment was made to compare the upgrading
Using MoO2(acac)2, Fe(III)(acac), Co(acac)2 and Ni(acac)2
of heavy crude oil using commercial supported catalyst versus
(where acac= acetylacetonate) catalysts which are soluble in
unsupported catalysts evaluated at the same operating
hydrogen-donor compounds, Alkylhexanoates presented a
condition. Another 1200 g of heavy crude oil were mixed with
higher increasing in the API gravity than the supported
60 g of commercial catalysts (MoCoP/Al2O3), or 500-1000 wt
catalysts, but a lower sulfur and porphyrins removal.
ppm of unsupported catalysts (Fe(acac)3-Mo-alkylhexanoate)
in the batch reactor with a hydrogen pressure of 10.8 MPa, at
Experimental Test Method 673 K, 1000 rpm, and a residence time of 4 h.
Heavy crude oil was carried out in batch reactor with a Characterization Method. The heavy crude oil physical
capacity of 1800 ml. Table 1 shows physical and chemical and chemical properties were characterized by ASSAY
properties of offshore heavy oil from the Gulf of Mexico. according to the ASTM methods. The MoCoP/Al2O2
In the upgrading heavy crude oil were used two supported commercial and the MoWNiCoP/Al2O3 experimental catalysts
catalysts as follows: (1) MoCoP/Al2O3 commercial catalysts, with high metallic load were characterized by N2
with a specific area of 256 m2.g-1, and an average pore adsorption/desorption isotherms measured at 77 K, using a
diameter of 75 , and (2) MoCoNiWP/Al2O3 experimental Micrometric ASAP 2405 analyzer, and pore size distribution
catalysts with a specific area of 280 m2.g-1, and an average BarrettJoynerHalenda (BJH) model on the adsorption
pore diameter of 78 . The same support was used in both branch.
catalysts, and the impregnation of the active species was The metals content were determined using Perkin-Elmer
carried out by pore volume. Atomic Absorption Spectometer AAnalyst 200.
SPE 107837 3
The acids properties of both commercial and the heptane soluble; kA, first-order reaction rate constant for
experimental catalysts were calculated by Infrared Spectra. In reactant asphaltene thermolysis (min -1); kH first-order reaction
the Infrared study, the samples were finely ground and rate constant for the thermolysis of reactant heptane soluble
dispersed in KBr pellets with a ratio of 1 mg/ 100 mg of KBr. (min -1); m, stoichiometric coefficient; n, stoichiometric
The Thermal treatments of catalyst supported were carried out coefficient; SL, solubility limit (wt%/wt%); TI, toluene-
on self-supported pellets and by adsorption of pyridine using insoluble coke; and finally V, volatiles.
Nicolet Magna 560 equipment.
The coke formation through the aforementioned
mechanism can be avoided by a hydrogenating metal, which
Results and Discussion can transfer the available hydrogen atoms to the free radicals,
The thermal hydrocracking or thermolysis of the heavy preventing condensation and polimeration reaction, and finaly
crude oil without catalyst led an increase of the API gravity coke formation.
from 12.5 to 25.9; a reduction of the kinematics viscosity from Catalytic Hydrocracking. The upgrade reaction of the heavy
18,130 to 35.86 cSt at 298 K, besides sulfur content was crude oil with the MoCoP/Al2O3 catalyst under the operating
reduced in 28.5 wt%. However, in the reaction there was a conditions above mentioned increases the API gravity from
high coke formation (25 wt%). The coke formation affects the 12.5 to 21.2, reducing kinematics viscosity from 18,130 to 117
yield of the distillable fraction mainly in the gasoline and cSt, and reducing besides sulfur content from 5.56 to 1.68
diesel production. wt%.
The coke formation can be explained through the free- As a consequence of the hydrotreating reactions the
radical chain reactions caused by three facts: (1) the absence products composition was modified being reflected in the
or a weak metallic function, (2) the low hydrogen partial reduction of the resins and asphaltene. The resins
pressure, and (3) the high reaction temperature (693 K). concentration was reduced from 35 to 15 wt%, and the
asphaltene concentration was reduced from 26 to 7 wt%. On
Moreover, the chemistry of asphaltene coking has been the other hand, the paraffin and aromatic concentrations were
suggested to involve the thermal cracking of labile bonds to increased from 18 to 40 wt%, and from 22 to 37.5 wt%
form reactive species that react with each other through respectively. The Figure 1 shows the viscosities behaviour at
polymerization and condensation reaction, from lower different temperatures of original heavy crude oil and
molecule weight compounds to form coke. In addition, the hydrocracking product using MoCoP/Al2O3 commercial
highly aromatic compounds and highly polar heteroatom catalyst. The catalyst showed a high activity in the removal of
containing products are separated from surrounding oil sulfur (69.8 %), according to the kind of heavy crude oil used
medium as an insoluble phase and proceed to form coke. and low severities conditions of pressure and temperature in
experimental tests.
The initial reaction in the coke formation from resins and
asphaltene involves the cracking of the aromatic-alkyl to The increase of the API gravity and the strong reduction of
generate volatiles species (paraffins and olefins) and the viscosity helps to increase the distillable products
nonvolatile species (aromatics), changing the ratio between (approximately 18 wt%). The Figure 2 shows a Simulated
asphaltene constituents and carbon residue formation. Distillation (ASTM-D-5307 method) of the heavy crude oil
and the reaction products.
The thermal cracking model confirm that the volatily of
the fragments is the major influence in the carbon residue The behavior of the supported catalysts for upgrading
formation. According to the Wiehe model [36-38], the coke heavy crude oil can be explained by its high specific area,
formation is preceded by a liquid-liquid phase separation of great average pore diameter of the Al2O3 support, high metal
reacted asphaltenes to form a lean in the abstractable-hydrogen content and high dispersion of the catalytic active species [37,
phase according with the follow mechanisms: 38], and an appropriate balance between the metal load and
acidity in the support.
H +
kH
aA* + (1 a )V
The hydrocracking of the heavy crude oil with the
A+
kA
mA* + nH * + (1 m n)V
MoWNiCoP/Al2O3 experimental catalyst was evaluated at the
* + * same previous operating conditions, except that the reaction
Solubility limit: Amax = S L ( H + H )
temperature was reduced in 10 K. The experimental catalysts
showed a higher catalytic activity than the MoCo/Al2O3 at 613
Aex* = A* Amax
*
K. The API gravity was increased from 12.5 to 23.5; the
kinematics viscosity was reduce from 18,130 to 78 cSt at 298
Aex*
(1 y )TI + yH *
K, the sulfur removal was 67.8 %; the asphaltene content
Where a is a stoichiometric coefficient; A+, reactant decreased to 6.0 wt %, the resin content was reduce until 14.5
asphaltenes; A*, asphaltene cores; A*max, maximum asphaltene wt% and the distillable fraction was increased to 20 wt%. The
cores that can be held in solution; A*ex, excess asphaltene cores paraffins and aromatics content were increased until 41 and
beyond that can be held in solution; H+, product, non-volatile 38.5 wt% respectively. Table 1 shows the physical and
4 SPE 107837
chemical properties of the original heavy crude oil, and the catalyst showing as result the presence of coke (25 wt%); this
Figure 3 shows the simulated distillation for both original result indicates higher concentration than the values obtained
heavy crude oil and the obtained product. using the organometallic catalysts.
The higher hydrocracking activity of the experimental As result of the hydrocracking process, coke formation was
catalysts can be explained by an increase in the total acidity of reduced until 14, 12 and 9 wt%; this as consequence of either
the catalyst, a greater metal load, and the impregnation of the due to the probably presence of FeS2 or because of the
Ni and W, which reduces the coke formation during the presence of FeS1.14 [43]. On the other hand, the coke formation
reaction. Table 2 shows the comparative results between both was reducer using MoS2 due to higher hydrogenating
experiments. The Simulated Distillation of the feedstock and properties than employing FeS2 catalyst. The product
the hydroconversion products are shown in the Figure 3. composition for each experiment is showed in the Table 3.
Unsupported catalysts. The heavy crude oil was also
The next goal was to reduce the coke formation without
upgrading using Mo, Fe catalysts derived from (acac) and a
affect the catalytic activity using a combination of Mo-Fe
Mo-Fe mixture. The upgrading of the heavy crude oil with
catalysts derived from acac. In this case, the concentrations of
MoO2(acac)2 was according to metal concentration based on
the Fe (acac)3 were 250, 500 and 750 wt ppm, and the
the heavy crude oil weight (500, 750 and 1000 wt ppm). In
concentration of MoO2(acac)2 was kept constant at 750 wt
order to perform the hydrocracking of the heavy crude oil was
ppm, at the same operating condition used in the previous
necessary to operate the reactor at 673 K and therefore the
experiments. The results obtained are as follows: API gravity
residence time was reduce to 4 h, with a hydrogen pressure of
was increased to 20.5, 21.3, and 23.7, while kinematic
10.8 MPa. The obtained results using the catalysts showed an
viscosity was reduced to 26.8 cSt at 298 K; on the other hand a
increase of the API gravity from 12.5 to 19.0, 20.2 and 23.0
mixture of Mo-Fe at 750-750 wt ppm produced a
for each previously mentioned concentrations; the viscosities
hydrodesulfuration of 49.6 %. This synergetic effect between
were reduced from 18,130 to 68.6, 52.2, and 27.5 cSt at 298 K
the carbon reduction and the sulfur removal is showed in the
respectively. However, with the Fe(acac)3 there was a higher
Table 3.
increase of API gravity than MoO2(acac)2, obtaining 24.4,
24.6 and 26.0, for catalytic concentrations of 250, 500 and The following test shows the results obtained in the
750 ppm wt respectively, and decreasing viscosity values of upgrading of the heavy crude oil using supported catalyst
10.54, 9.87 and 9.19 cSt at 298 K; all these results were (commercial catalysts MoCoP/alumina) versus Mo-
obtained because of the high molecular weight compound alkylhexanoate liquid catalysts. Reactions were carried out at
hydrocracking, forming lighter compounds as gasoline and 668 K and under operating condition before mentioned. The
diesel. Nevertheless, with this kind of catalysts there was objectives to reduce temperature (5 K) during the reaction
higher coke formation than with Mo catalyst. were to decrease the coke formation and the fast deactivation
of the supported catalysts.
On the other hand, coke formation was reduced when the
The API gravity was increased until 24.3 and the viscosity
catalyst concentration was increased. This behavior can be
was reduced to 10.9 cSt at 298 K using Mo-alkylhexanoate
related with a higher amount of the hydrogenating sites.
catalyst in liquid phase. Sulfur content in the product was 3.0
Figure 4 shows the simulated distillation of the heavy crude
wt%, and the coke formation was 0.5 wt%. The chemical
oil and the product obtained with Fe(acac)3 catalysts. The
composition of the product was as follows: Saturates 46.6
Table 3 shows the properties of the hydroconversion product.
wt%, Aromatics 29.1wt %, Polar compounds 14.3 wt% and C5
insoluble 10.0 wt%. Moreover, the Ramsbotton carbon was
Once the liquid phase catalyst (organometallic) is
reduced from 16 to 8.4 wt%. The catalytic mixture presented a
dispersed in the heavy crude oil during the catalyst activation,
hydrogenation reaction higher than in the case of the
a great number of individual nanoparticles metal sulfides such
evaluation before mentioned because of the low product coke
as molybdenum, nickel, cobalt, and iron are formed [9]. These
content. Nevertheless, the sulfur removal was 46 wt%, which
metal particles are highly dispersed into the resins and
was lower than in the experiment evaluated with Mo-Fe
asphaltene through an ionic mechanism. The reactor
derived from acetylacetonate. The distillation fraction was
temperature and hydrogen partial pressure start the
increased from 48 to 79.5 volume %, being the hydrocracking
hydrocracking of weak links [42], and subsequently resin and
reaction mainly oriented to the gasoline and diesel production.
asphaltene molecules are hydrocracked through the acid
properties of the metal sulfur [41] begining mechanisms of The distillation of heavy crude oil and the product obtained
free radicals. The metal sulfurs highly dispersed in heavy were carried out by TBP (ASTM-D-2992, ASTM-D-5236)
crude oil catalyzed, and the hydrogen transfer [42, 43] to the and ASTM-D-1160 methods. Table 4 shows the comparative
olefins (which were formed during the reaction), reduce the results of product for each experiment, while Figure 5 shows
condensation and polymerization reaction, and therefore the TBP distillation of the heavy crude oil and the products
coke formation. obtained using the Mo(hexanoate)-Fe(acac)3 catalytic mixture.
The obtained results in the heavy crude oil hydrocracking, The MoCoP/Al2O3 commercial catalyst was evaluated at
confirm the hydrogen transfer hypothesis in the coke the same operation condition above mentioned. The API
gravity was increase to 21.1, the viscosity was reduced to 48.5
formation reduction. The experiment was performance without
cSt (determined at 298 K), the sulfur content was reduced to
SPE 107837 5
and Heavy Oil Symposium held in Calgary, Alberta, 1- 32. Fixari, B., Peureux, S., Elmouchnino, J., Le Perchec, P.,
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SPE 107837 7
Method Content
API gravity ASTM-D-287 12.5
Water by distillation, Vol. % ASTM-D-4006 0.2
Viscosity, cSt ASTM-D-445
298.0 K 18130
310.8 K 6250
327.4 K 1490
Total Sulfur, wt % ASTM-D-4294 5.56
Total Nitrogen, wt % ASTM-D-4629 0.75
Carbon Rambsbotton, wt% ASTM-D-524 16.0
SARA, wt % ASTM-D-4124
Saturates 18.0
Aromatics 22.0
Resins 34.0
C7 Insoluble 26.0
Metals Content, wt ppm ASTM-D-5863
Fe 24.05
Ni 119.0
V 496.2
10000 H eav y
API gravity 12.5 Cr u d e
Oil
1000
Total S 5.56 wt%
Viscosity, cSt
n-C7 26 wt%
100
800
700
600
V V
500 Diesel Total
V
400 Gasoline
300
IBP 10 20 30 40 50 60 70 80 90 FBP
Wt % (mass)
1100
Heavy Crude Oil
1000 Hydrotreating product
Boiling Point Distribution, K
900
800
700
600
V
Total
500
V
Gasoline
400 V
Diesel
300
IBP 10 20 30 40 50 60 70 80 90 FBP
Wt % (mass)
Figure 3. Simulated distillation of the product obtained with MoWNiCo/Al2O3
Experimental.
10 SPE 107837
1100
Heavy Crude Oil MoO2(acac)2 Fe(acac)3
1000
Boiling Point distribution, K
900
800
700
600 Wt
Total
500 Wt
Wt
Gasoline
Diesel
400 Wt
Wt
300
IBP 10 20 30 40 50 60 70 80 90 FBP
Wt % (mass)
Product Fe(acac)3-Mo(hexanoate)
800
600
500
400
300
IBP 10 20 30 40 50 60 70 80 90 FBP
Volume %
Figure 5. True Boiling Point (TBP) of the heavy crude oil and
Product obtained with Fe(acac)3-Mo(hexanoate