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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
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
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.
Coke Yield
10
Solvent
(n-heptane)
Methodology
Asphaltenes
Extraction
Volume ratio
40/1 Sonicated 2h at 25°C
Heptane/Crudo Oil
Asphaltenes 80
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
Solvent
(toluene) Centrifuged at 4500rpm for 45 min
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
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
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
1600
1400
21,6nm CePd1 65,6445
1200
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
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)
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
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
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)
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