Mejoramiento de aceite pesado In-Situ por

inyeccion de Nano-Catalizadores Ultra-

dispersos en YNF

Carlos R. Orozco C.

Monterrey, Nuevo Lon a 11 de junio de 2016

OBJECTIVE
 To demonstrate at laboratory scale, the feasibility of catalytic
upgrading of heavy oils in naturally fractured reservoirs, to
produce enhanced oil recovery and upgraded crude oil, using
heavy oil, rock, and conditions adequate to Mexican reservoirs.

To demonstrate at laboratory scale, the reactivity and

upgrading of heavy oils using ultra-dispersed nano-catalyst and
hydrogen, obtaining a kinetic model for further process
simulations.
INTRODUCTION
 Introduction

Oil production history

Third oil producer in America (2.5 mbd).

Declining production with stabilization in recent

years.

70% of total production comes from NFR.

54% of total production corresponds to heavy oil.

Low recovery factor.

Oil reserves

Heavy oil reserves: 32, 000 million barrels (56%)

Proven: 6,000 mb (18%) Enhance oil recovery

Probable: 10,200 mb
Reclassification
Posible:15,800 mb

U.S. Energy Information Administration, 2014 PEMEX, 2014

 Enhance Oil Recovery (EOR) Processes

Chemical Gas Thermal Others

Polymer flooding VAPEX Steam flooding MEOR

Surfactant N2 CSS SMART water
Alkali CO2 ISC (low salinity)
A-S-P FCM SAGD
MCM THAI
CAPRI

Most experience of EOR processes are in sandstone formations.

For NFR application, just a few pilot tests and laboratory experience.

Temperature, depth, pressure, and logistics limit applicability.

Manrique, E., Thomas, C., Ravikiran, R., Lantz, M., Romero, J., & Alvarado, V. (2010). EOR: Current status and oportunities. Society of Petroleum Engineers, SPE
130113
METHOD
 Proposed EOR method
Nano-Catalytic In Situ Upgrading (n-CISU)

Takes surface refinery concepts to the reservoir:

Reservoir acts as a reactor.
High temperature.
High pressure.
Long residence time.
Injection fluids:
Vacuum residue mixed with UD n-catalyst.
Hydrogen.
Surface facilities:
Vacuum distillation unit.
UDC preparation unit.
Hydrogen generation unit.
Injection method:
Not restricted
8
Pereira Almao, P., Chen, Z., Maini, B., & Scott Algara, C. (2013). Canada Patent No. CA 2810022.
 Proposed EOR process
Key factors
Thermal energy: Reduction of viscosity. VR + N-Catalyst
Hydrogen
Increase of oil mobility Upgraded oil
from matrix
Thermal cracking and fractures
H2 addition: Use catalysts and hydrogen injection
Hydroprocessing reactions
Oil Upgrading (API, viscosity, MCR)
Reservoir formation:
Catalyst deposition in porous media or
fractures
Heat transfer
Wettability alterations
Rock expansion
Oil drainage from the matrix
Spontaneous imbibition
Objective:
Increase RF
Increase proved reserves
Increase production rate
N-catalyst + H2+VR
 Research Scheme

H2S elimination UDC

Reactivity Test Analytical
Desalting Integration

API and density

ISC Lab Skid RTU-2
Viscosity
Pilot plant unit
 5 Lumps model
k1
Lump BPT (C) Component
k7
k5 k6 Gases C 1 C4
k2 Naphtha IBP 216 C5 C12
k8 k9 Distillates 216 343 C13 C20
k3
k10 VGO 343 550 C21 C44
k4 Residue >550+ C45+

10 Reaction constants

Sanchez, Rodriguez and Ancheyta 2005

 Reactivity Test Unit - 2

Sampling Sampling
Section: Feed Pump Reaction Stability
(liquid) (gases)

Stab To exhaust
Tank
1
1
MB
BPV
Tank
1
To exhaust
BPV
2 Multi Position
2 Valve

Gas Flow Meter

MB
Feed Tank
3 2
tank BPV
To
exhaust
GC
3

Stab To
Tank BPV exhaust
MB
Tank
3

N2
 RTU-2

Residence time: 24 120 hrs. Stabilization period prior condition (3PV)

Temperature: 320C 360C. Two MB samples.
Pressure: 1,450 psi. Gas rate and GC measurements.
RESULTS
 Crude Oil Upgrading
Simulated Distillation
Increase of light components (low BP) and decrease of the heaviest

Parameter Unit Feed Min Max

API 10 11 19
Viscosity cP 75,000 87 13,400
Conversion % 0 7.8 46
MCR % 18 11 14
Sulfur ppm 37,000 24,000 35,000
 Crude Oil Upgrading
Residue conversion
VR

VGO

Distillates
Naphtha
Gases

VR

Gases
Gases Residue converted to VGO
Distillates
VGO Naphtha Naphta
Naphtha Gases
Distillates
Distillates
 Crude Oil Upgrading
Approximation model

6 reactions model: Activation energies and Pre-exponential factors:

E
k 320 C 340 C 360 C Ln A0 R2
kJ/mol
1 0.003376 0.003174 0.006343 4.0 48.56 0.659
2 1.22E-06 1.9E-05 0.000163 63.9 382.16 0.997
3 4.47E-06 6.13E-05 0.000798 69.7 404.65 0.999
4 0.000167 0.000276 0.00046 7.3 79.02 0.999
5 0.000421 0.001284 0.003995 27.8 175.52 0.999
8 0.000107 0.000156 0.000226 2.7 58.38 0.999

Activation Energy Ea:

60 kJ/mol
 Crude Oil Upgrading
Approximation model

Model prediction:
320 C 340 C 360 C
 Vacuum Residue Upgrading
Simulated Distillation
Increase of light components (low BP) and decrease of the heaviest

Parameter Unit Feed Min Max

API -0.4 4 13
Viscosity cP 570,000 56 20,000
Conversion % 0 14 51
MCR % 30 15 22
Sulfur ppm 45,000 27,000 38,800
 Vacuum Residue Upgrading
Residue conversion

VR

VGO
Naphtha
Distillates
Gases

Gases

Naphtha
Residue converted to VGO
Distillates Distillates
Naphta
Gases
 Vacuum Residue Upgrading
Approximation model

6 reactions model: Activation energies and Pre-exponential factors:

EA
k 320 C 340 C 360 C Ln A0 R2
kJ/mol
1 0.00099 0.00237 0.00509 19.1 128.1 1.00
2 0.00020 0.00055 0.00144 22.7 153.8 1.00
3 0.00002 0.00013 0.00074 45.3 276.5 1.00
4 0.00006 0.00012 0.00041 20.0 147.1 0.95
5 0.00044 0.00105 0.00241 19.0 131.8 1.00
8 0.00061 0.00107 0.00183 9.9 85.8 1.00

Activation Energy Ea:

139 kJ/mol

Loria, 2011
Da Silva, 2014
 Vacuum Residue Upgrading
Approximation model
Model prediction:
320 C 340 C 360 C
DISCUSSION
 Vacuum Residue Upgrading
Correlation
Viscosity Viscosity

Vacuum residue
Crude oil

API API

P-value P-value
 Vacuum Residue Upgrading
Comparison
Arrhenius plot:
Ea Ao
Fluid
kJ/mol
Bitumen (At) 160.2 4.70E+11
Pitch (At) 153.5 1.97E+10
VR (Ag) 2 139.2 2.31E+09
VR (Ag) 1 131.7 5.14E+08
CO (Tk) 125.6 2.18E+08
CO (Ag) 1 86.9 9.81E+04
CO (Ag) 2 60.4 6.50E+02
VR (At) 44.8 2.75E+01

Mexican crude oil comparison:

CONCLUSION
 The crude oil tested was upgraded, from 7 % to 40 %. For the residue, the conversion ranged from 13
% to 50 %.

Hydrotreating was observed in the reduction of the sulfur content, lowering of micro-carbon (MCR)
percentage and metal elimination (V, Fe).

The catalyst added to the crude oil and vacuum residue in concentrations of 780 ppm and 670 ppm
respectively, are sufficient to provoke the hydroprocessing reactions. With particle sizes of catalyst
incorporated range between of 178 nm and 172 nm.

Activation energies calculated for hydroprocessing of the crude oil and residue are in the catalytic
range. For the crude oil: 89 kJ/mol, and for the vacuum residue 131 kJ/mol.

A kinetic model was established with good agreement to the experimental data for both fluids.