Optimization of Fe2O3-, Co2O3-, NiO-

and/or PdO-Functionalized CeO2

Nanoparticles for Heavy Oil Upgrading
Through Catalytic Steam Gasification
Oscar E. Medina
Camilo A. Franco
Farid B. Cortés

Grupo de Investigación en Fenómenos de Superficie - Michael Polanyi, Departamento de

Procesos y Energía, Facultad de Minas, Universidad Nacional de Colombia, Sede Medellín.
Schedule
-Introduction
-Methodology
-Results
-Conclusions
-Bibliography
Introduction
Introduction
Unconventional Crude Oil Reserves: 80%
• Heavy Oil (HO)  15%
• Extra Heavy Oil (EHO)  65% [1]

Daily Production of Crude Oil in Colombia:

• 52% Heavy Oil.

In 10 years it will represent 90% of the

national crude production.
Introduction
Decrease of
conventional Increase in the
crude reserves production of heavy
and increase in (HO) and extra heavy
energy demand oil (EHO).
.

Issues in
production, Main cause: Solution: Improvement in
transportation Heavy fraction - Decomposition of crude oil quality
and refining Asphaltenes the heavy fraction [2]
.
 Introduction
Requirement of a large amount of
Solvents expensive solvents

in-situ treatments Low stability and compatibility

[3]. Chemical Recovery mixtures and formation damage

Emulsions
High surface area [3]
formation, channeling
Gases injection and
Production life ofinwells
abrupt changes canof
the pH
the medium
be extended[4]
 Catalytic Activity
Alternative Nanotechnology
 Highly Dispersible
solution
treatment  Low size
 Adsorption capacity
 Complementary to EOR
Diagram 1. Heavy and extra heavy oils extraction methods process

6
Introduction
Selectivity towards the
NANOMATERIALS adsorption / catalytic
decomposition of heavy
Enhancement using hydrocarbons[5]
supported oxide
nanoparticles
EOR process
No blocking and trapping
(Air/steam Injection)
risk

Paladium, Cobalt, Iron or Low cost.

Nickel supported over
soportados CeO2
nanoparticles
Introduction Gas-Support
CeO2 [4] Addition of Metals Interaction +
Catalytic Effect

Gas Production
Catalyst
𝐶𝑂 + 𝜎 → 𝐶𝑂𝑎𝑑𝑠
Storage, absorption and Water Gas Shift 𝐶𝑂𝑎𝑑𝑠 + 2𝐶𝑒𝑂2 → 𝐶𝑂2 + 𝐶𝑒2 𝑂3 + 𝜎
release of oxygen. 𝐶𝑒2 𝑂3 + 𝐻2 O → 2𝐶𝑒𝑂2 + 𝐻2

𝐶𝑂 + 𝜎 → 𝐶𝑂𝑎𝑑𝑠
𝐻2 𝑂 + 𝐶𝑂 = 𝐶𝑂2 + 𝐻2
𝐶𝑂𝑎𝑑𝑠 + S−𝑂𝐻 → S−𝐻𝐶𝑂𝑂 + 𝜎
𝑆 + 𝐻2 O → S-𝐻2 O
S−𝐻𝐶𝑂𝑂 + S−𝐻2 O → 𝐶𝑒𝑂2 + 𝐻2 + 𝑆 +
 Stabilization of free radicals.. S−𝑂𝐻
 Avoid aggregation of
disaggregated asphaltenes.
8
Introduction
Injection Production
Well Well.

Figure 1. Trajectory between injection well and production well

°API
Viscosity
Metals
9 Heteroatoms
 Methodology
Optimization:
Better Bimetallic system, Activation energy
Nanoparticles Nanoparticles Better bimetallic
evaluate its load of and reaction
Functionalization evaluation system-Better
asphaltenes kinetics.
concentration
Nanoparticles Adsorption isotherms 0.02g/m2
Isothermal
Characterization 0.05g/m2 SCMD
Conversion
Thermogravimetric 0.2g/m2
SBET analysis
Profiles of
gaseous
Isothermal Conversion
DLS products

Coke Yield

10
 Solvent
(n-heptane)
Methodology
Asphaltenes
Extraction

Volume ratio
40/1 Sonicated 2h at 25°C
Heptane/Crudo Oil

Asphaltenes 80

Centrifuged at 4500rpm for Stirred at 300rpm for 20 h

20 min
Methodology
CeM# = CeNi1

Nanoparticle
Pd(NO3) 22H2O Optimization Ce: Support
M: Metal
FeCl36 H2O
#: Impregnation dosage

NiCl26 H2O
Formation of Metal Oxide
120°C por 4 h
450°C por 6 h.

CeNi1Pd1 CeFe1Pd1

CeO2
Metallic charge 1%
CeCo1Pd1

Calcination temperature
450°C
12
Methodology
Evaluation of
Adsorptive Capacity

8
8
8
0 0 0

100ppm 500ppm 1500ppm

Solvent
(toluene) Centrifuged at 4500rpm for 45 min

Initial concentration of Asphatenes

UV-Vis Spectrophotometer
(Co) (mg/L)
𝑉
𝑁𝑎𝑑𝑠 = 𝐶𝑂 − 𝐶𝑒
𝐴
Methodology Asphaltenes

Thermogravimetric
Analysis
(TGA) Atmosphere
Nanoparticle -Nitrogen+H2O (g)
-Air

Ramp 25-600°C

Isotherms: 240°C
 Methodology Simplex-Centroid Mixture Design (SCMD)
Ce: 100% of Ceria
Nanoparticles
𝑛

෍ 𝑥𝑖 = 𝑥1 + 𝑥2 + 𝑥3 +. . . +𝑥𝑛 = 1, 𝑥𝑖 ≥ 1
𝑖=1
0,98 ≤ 𝐶𝑒 ≤ 1,00
CePd1: 1%Pd and 98% Ce CeNi1: 1%Ni and 99% Ce 0,00 ≤ 𝑁𝑖 ≤ 0,02
0,00 ≤ Pd ≤ 0,02

𝑥𝑖 − 𝐿𝑖
𝑥 ′𝑖 =
CeNi0.66Pd0.66: 0.66%Ni, 1−𝐿
0.66%Pd and 98.66% Ce
CePd2: 2%Pd and 98% Ce CeNi2: 2%Ni and 98% Ce

CeNi1Pd1: 1%Ni, 1%Pd and

98% Ce
N ads  1 x1´  2 x2 ´ 3 x3´ 12 x1´x2 ´ 13 x1´x3´  23 x2 ´x3´
𝑇𝑑𝑒𝑠𝑐
Methodology
SLE Model (Solid Liquid Equilibrium).
Activation Energy and Reaction Kinetic Rate

𝑑𝛼 𝐸𝛼 𝑔 𝛼 𝐸𝛼 H  
= 𝐾𝛼 exp − 𝑓 𝛼 ln 𝑡𝑎,𝑖 = ln + CE  exp  
𝑑𝑡 𝑅𝑇 𝐾𝛼 𝑅𝑇𝑖 1  K  qm 
𝐾 1  1  4 K    q q 
𝐻𝑑𝛼 =    m 
𝛼 =(𝑚𝑜 − 𝑚𝑡 )/( 𝑚𝑜 − 𝑚𝑓 )
𝑑𝑡 𝑡𝑎,𝑖 2K  qm  q 

• K (g/g): indicates the association grade of

• 𝑬𝜶 : Effective activation energy for a constant degree of
conversion (kJ/mol)
• R: Ideal gas constant (J/mol K)
• T: Reaction temperature (K)
• 𝒇 𝜶 is the reaction mechanism function
asphaltenes molecules over material surface
• H (mg/g): an indicator of the adsorption affinity
of asphaltenes onto solid surface. A lower value
indicates a higher affinity.
• Nads(mg/m2): the maximum adsorption capacity
of asphaltenes (g/g).
Results
 Results
• Crude oil characterization. Table 1. SARA analysis and API severity for the EHO evaluated.

3500000
Property EHO
3000000
2500000 °API 6.4
Viscosity (cP)

EHO-25°C
2000000
EHO-35°C Saturated (%) 13.02
1500000
1000000 Aromatics (%) 16.93
500000 SARA
0 Resins(%) 49.86
0 20 40 60 80 100
Shale Rate Asphaltenes (%) 20.19
Figure 2. Rheological behavior measured for the EHO at 25°C and
35°C.
Table 2. CHONS-elemental analysis of asphaltenes n-C7 of the crude oil evaluated.
Fraction C H O N S H/C
Asphaltenes 81,70 7,80 3,57 0,33 6,60 1,15
 Results Sample
SBET ± 0.01
m2/g
• Nanoparticle characterization CeO2 67,0184
CeNi1 66,2364
1800

D50 CeNi2 66,7952

Normalized distribution

1600

1400
21,6nm CePd1 65,6445
1200

1000 CePd2 63,5435

800

600
CeNi0.66Pd0.66 63,5915
400
CeNi1Pd1 63,8507
200

0 CeNi0.89Pd1.1 64,4669
0 5 10 15 20 25 30 35 40

Hydrodynamic diameter (nm) CeFe1Pd1 64,1074

Figure 3. Normalized numerical distribution for the size of CeO2 CeCo1Pd1 63,9114
Table 3. Surface area (SBET) of nanoparticles evaluated.
nanoparticles based on DLS measurements.
 Results
• Evaluation of the adsorptive capacity. CeNi0.89Pd1.1
Ce1Ni1Pd
2 2 Ce2Pd
Ce CeNi0.66Pd0.66
CeFe1Pd1 CeNi2
CeCo1Pd1 Ce1Pd
CeNi1Pd1 Ce1Ni
Ce100
SLE SLE

q (mg/m2)
q (mg/m2)

1 1

0 0
0 200 400 600 800 0 200 400C (mg/L) 600 800
E
CE (mg/L)

Figure 4 Asphaltene adsorption isotherms n-C7 in (a) main systems and (b) SCMD nanoparticles at 25°C. The symbols are
experimental data, and the solid lines are of the SLE model.
Results
• Evaluation of the adsorptive capacity. Table 4. Parameters of the SLE model for the adsorption of
asphaltenes on nanoparticles evaluated at 25°C.
Sample H K N max %RSM
Ce 0.1012 0.207 0.1274 0.02
With the addition of
CePd1 0.0719 0.285 0.1566 0.03
metals on the surface of
the nanoparticles, an CeNi1 0.0734 0.0330 0.1489 0.04
increase in the CePd2 0.0625 0.390 0.1819 0.01
adsorptive capacity is CeNi2 0.0670 0.0397 0.1558 0.01
observed. The CeNi0.66Pd0.66 0.0661 0.0522 0.1605 0.02
nanoparticle CeNi1Pd1 0.0602 0.0391 0.2207 0.01
CeNi0.89Pd1.1 being the CeFe1Pd1 0.0658 0.0398 0.1701 0.02
one that most absorbs CeCo1Pd1 0,0634 0,0577 0.1905 0,01
asphaltenes on its Ce Ni0.89Pd1.1 0,0284 0,0404 0.2493 0,01
surface.
 Results
• Catalytic Activity / Mass loss.
0.025 2.50
CeNi1Pd1
CeCo1Pd1
0.02 CeFe1Pd1 2.00
Ce With the addition of metals on the
Deriv. Weight (%/°C)

Asphaltenes
0.015 1.50
surface of the nanoparticles, an
increase in the catalytic activity is
0.01 1.00 observed, with the CeNi1Pd1 system
the one that most decreases the
0.005 0.50 decomposition temperature of the
asphaltenes.
0 0.00
0 100 200 300 400 500 600 700
Temperature (°C)

Figure 5. Mass loss rate as a function of temperature for gasification with

asphaltene vapor n-c7 in the absence and presence of Ce nanoparticles, CeNi1Pd1,
CeCo1Pd1 and CeFe1Pd1. Nitrogen flow rate = 100 ml / min, flow rate of , H2O(g) =
6.30 ml / min, heating rate = 20°C / min.
 Results
• Isothermal conversion • Coke Yield
1.00
100
0.90 CeNi1Pd1
0.80 CeCo1Pd1
80
0.70 CeFe1Pd1
α (fraction)

Ce
0.60

Coke yield
Asphaltenes 60
0.50
0.40
40
0.30
0.20
20
0.10
0.00 0
0 50 100 150 200
Asphaltenes Ce CeFe1Pd1 CeCo1Pd1 CeNi1Pd1
Time (min)
Figure 6. Isothermal conversion for the thermal oxidation of Figure 7. Coke yield for the decomposition of n-C7 asphaltenes
asphaltenes at 360°C without nanoparticles and at 240°C in the under steam gasification in the absence and presence of Ce
presence of Ce nanoparticles, CeNi1Pd1, CeCo1Pd1 and nanoparticles, CeNi1Pd1, CeCo1Pd1, CeFe1Pd1. Nitrogen flow rate
CeFe1Pd1. Nitrogen flow rate =100 ml/min, , H2O(g) flow rate = 100 ml / min, flow rate of , H2O(g) = 6.30 ml / min, heating rate =
20 ° C / min.
=6.30 ml/min..
 Results
• Gases Profiles Produced.
1 1
Nox Nox 1
0.9 0.9 Nox
CO2 CO2 0.9
0.8 0.8 CO2
LHC LHC 0.8
LHC

Normalized Area
Normalized Area

0.7

Normalized Area
CH4 0.7 CO 0.7 CO
0.6 CO 0.6 CH4 0.6 CH4
0.5 0.5 0.5
0.4 0.4
0.4
0.3 0.3
0.3
0.2
0.2
0.2 0.1
0.1
0.1 0
0 0 50 100 150 200 250 300 350
0 100 200 300 0
Tiempo (min)
0 50 100 150 200 250 300 350
Time (min) Time (min)
1 1
Nox 0.9 Nox
0.9
CO2 CO2
0.8 LHC
Normalized Area 0.8
LHC
Figure 8. Gaseous product evolution profiles during
Normalized Area

0.7
0.7 CO CO steam gasification under isothermal conditions at
0.6 CH4 0.6 CH4
0.5 0.5 240°C of n-C7 asphaltenes in the presence and absence
0.4 0.4 of the selected catalysts (a) Virgin asphaltenes, (b) Ce,
0.3 0.3 (c) CeNi1Pd1, (d) CeFe1Pd1, (e) CeCo1Pd1; Nitrogen
0.2 0.2
0.1 0.1
flow rate = 100 ml/min, , H2O(g) flow rate = 6.30 ml/min.
0 0
0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350
Tiempo (min) Time (min)
Results
• Effect of Asphaltene Loading on Asphaltene Decomposition

0.045
1.0 CeNi1Pd1-0.2mg/m2
0.04
0.9 CeNi1Pd1-0.05mg/m2
0.8 0.035
CeNi1Pd1-0.02mg/m2

Deriv. Weight (%/°C)

0.7 0.03
α (fraction)

0.6 0.025
0.5 0.02
0.4
CeNi1Pd1-0.02mg/m2 0.015
0.3
CeNi1Pd1-0.2mg/m2 0.01
0.2
0.1 CeNi1Pd1-0.05mg/m2 0.005
0.0 0
0 50 100 0 100 200 300 400 500 600 700 800
Temperature (°C)
Time (min)
Figure 9. Isothermal conversion at 240°C for asphaltenes in the Figure 10. Graph of mass loss rate as a function of temperature with
presence of CeNi1Pd1 nanoparticles with an asphaltene load of an asphaltene load of 0.2, 0.05 and 0.02 mg/m2. Nitrogen flow rate
0.2, 0.05, 0.02 mg / m2; Nitrogen flow rate = 100 mL/min, , = 100ml/min, flow rate of , H2O(g)= 6.30 ml/min, heating rate =
H2O(g) flow rate = 6.30 mL/min. 20°C/min.
Results
• Maximization of asphaltene conversion through a SCMD
Contornos de la Superficie de Respuesta Estimada

Ce=1,0 1.00 CeNi0.89Pd1.1

Tiempo 0.90 CeNi1Pd1
0,0068 CePd2
0,0072 0.80 CeNi0.66Pd0.66
Series7
0,0076 0.70 CePd1

α (fraction)
0,008 0.60 CeNi1
0,0084 Ce
0.50 Asphaltenes
0,0088
Pd=0,0 Ni=0,0 0,0092 0.40
0,0096 0.30
0,01 0.20
0,0104
0.10
0,0108
0.00
0 50 100 150 200
Time (min)
Figure 11. Isothermal conversion for thermal oxidation of asphaltenes at 360°C
Ni=0,02 Ce=0,98 Pd=0,02 without nanoparticles and at 240°C in the presence of SCMD nanoparticles.
Nitrogen flow rate = 100mL/min, H2O(g) flow rate = 6.30 mL/min.

Table 5. Calculated parameters of the Special Cubic Model for the n-C7 asphaltenes conversion time in the
presence of SCMD nanoparticles.
 Results
• Activation Energy and Kinetics of the catalytic thermo-oxidation of Asphaltenes
1.0 1.0 1.0
Asf-360°C Ce 250
0.8 Asf-370°C 0.8 Ce 240
0.8
α (fraction)

α (fraction)
Asf-380°C

α (fraction)
Ce 230
0.6 0.6 0.6 CeNi1Pd1 250
0.4 0.4 CeNi1Pd1 240
0.4 CeNi1Pd1 230
0.2 0.2 0.2
0.0 0.0 0.0
0 100 200 300 400 500 0 50 100 150 200 250 0 20 40 60 80 100
Time (min) Time (min) Time (min)
1.0
0.8
α (fraction)

0.6 CeNi0.89Pd1.1 250

Figure 12. Isothermal conversion times at different
CeNi0.89Pd1.1 240 temperatures for virgin asphaltenes (360, 370 and 380 ° C),
0.4 CeNi0.89Pd1.1 230
and asphaltenes adsorbed onto (a) Ce, (b) CeNi1Pd and (d)
0.2 CeNi0.89Pd1 (200, 210 and 220 ° C).
0.0
0 20 40 60 80 100
Time (min)
 Results
• Activation Energy and Kinetics of the catalytic thermo-oxidation of Asphaltenes
6 Tabla 6. Energía de activación cinética y estimada para la gasificación isotérmica
de asfaltenos con nanopartículas Ce, CeNi1Pd1 y CeNi0.89Pd1.1
5.5
𝒅𝜶 𝟏
𝐊𝐢𝐧𝐞𝐭𝐢𝐜 𝐫𝐚𝐭𝐞, at 50%
Sample Temperature ° C 𝑬𝒂 𝑲𝑱 𝒅𝒕 𝒎𝒊𝒏
5 conversion
360 0,012
4.5
Asphaltenes 370 211,5183 0,018
ln (t)

380 0,032
4 230 0,013
Asphaltenes Ce 240 44,0430 0,021
3.5 Ce 250 0,379
CeNi1Pd1 230 0,0187
3 CeNi1Pd1 240 29,5901 0,0401
CeNi0.89Pd1.1
250 0,1002
2.5 230 0,029
1.2 1.4 1.6 1.8 2 2.2
CeNi0.89Pd1.1 240 25,3564 0,084
1000/T(𝐾^(−1)) 250 0,179

Figure 13. Isothermal model of thermal gasification of

asphaltenes in the presence and absence of nanoparticles
Conclusions
• In the adsorption process, the functionalized Ceria nanoparticles reduce the degree of self-
asphaltene association and increase the adsorption affinity as confirmed by the values of the
K and H parameters of the SLE model.
• The synergic effect between the Nickel and Palladium metals showed a better performance in
terms of the catalytic and adsorptive activity on the asphaltenes compared to Cobalt-
Palladium and Iron-Palladium.
• The process of gasification of asphaltenes was enhanced by the presence of improved
nanoparticles, decreasing the decomposition temperature of the asphaltenes and increasing
the maximum conversion in a shorter time possible
• The design of simplex mixtures with centroid was successfully carried out yielding an optimal
concentration that improved the catalytic activity of the nanoparticle.
Acknowledges
The authors acknowledge COLCIENCIAS, ANH and Universidad Nacional de
Colombia for their support, which was provided by Agreement 272-2017.
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Journal of the American Chemical Society, vol. 60, pp. 309-319, 1938
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combustion. J Can Pet Technol. 1999;38(13):1–8.
[5] Mousavi-Dehghani S, Riazi M, Vafaie-Sefti M, et al. An analysis of methods for determination of onsets of
asphaltene phase separations. J Pet Sci Eng. 2004;42(2):145–56. [6] Mullins OC. The asphaltenes. Annu Rev Anal
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