SPE-196620-MS

Modelling Dispersed Chemical Droplets Injection in the Gas Stream for EOR
Applications

Juan D. Valencia, Universidad Nacional de Colombia, Exergy - Modeling and Analytics; Juan M. Mejía, Universidad
Nacional de Colombia; Alonso Ocampo, GaStimTechnologies; Alejandro Restrepo, Equion Energía

Copyright 2019, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Reservoir Characterisation and Simulation Conference and Exhibition held in Abu Dhabi, UAE, 17 - 19 September
2019.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
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Abstract
This paper address the numerical simulation of the chemically enhanced gas injection technology (ChEGas-
EOR) at core and reservoir scales. In this technique, a liquid chemical solution, having engineered
properties, is sprayed along with the gas stream. The mist travels through the wellbore and further introduced
in the reservoir. Previous lab tests, pilot studies in light & intermediate oil reservoirs indicate that the
application of CheGas-EOR allows for a reduction in operational costs, increases the chemical penetration
radii and decreases the retention rate in the rock. However, the associated uncertainty is still too high to
develop this process on a productive scale. In this work we use a developed phenomenological model to
build a tool that assist in design and evaluation of Chemical Gas EOR operations aiming to reduce the
uncertainties and optimize oil recovery.
We developed a mathematical model, based on the most important transport and surface phenomena.
Non-equilibrium mass transfer between phases during the interception of the chemical solution droplets
with the liquid phases. Active chemical concentration in miscible liquid phases is much lower than liquid-
based chemical injection opperations. As a consequence, dissolution and adsorption rate of active chemicals
with reservoir rocks are slow. The model is base on the extended black-oil model formulation coupled to
local mass balance equations of active chemicals. Non-equilibrium mass transfer processes are represented
with interception, dissolution and a first order kinetic sorption models.
The model was adjusted and then validated using experimental data from core-.floodint tests. Good
agreement of the simulations results with experimental observations were obtained. The model can predict
the relevant behavior of the disperse chemical injection in the gas phase in porous media. Also, well
injections simulations at reservoir scale using the matched parameters from laboratory, reproduced pilot
field results. Simulation experiments predict that the CheGasEOR process can increased substantially the
oil recovery factor.
For the first time, a model for disperse chemical injection for EOR applications is developed and validated
at core and reservoir scale. The simulation model allows the evaluation of this technology at different scales.
Therefore, it is possible to use it to optimize operating conditions and perform sensitivity analysis for field
applications.
2 SPE-196620-MS

Introduction
The advantages of injecting dispersed chemicals in the gas injection wells have been observed in pilot
studies, initially for condensate mobilization and asphaltene control (Restrepo et al., 2012, 2014), and more
recently for in-situ foams (Ocampo et. al., 2018, 2019; Valencia et al.,2018a;2018b) and chemicals for EOR
applications (Valencia et al., 2018c). An engineered nozzle is placed to atomize the chemicals into the gas
injection line. The droplets travel through the wellbore being dragged by the gas flow and further they are
introduced into the reservoir.
Previous pilot studies and lab tests in light & intermediate oil reservoirs indicate that the application of
ChemGas-EOR allows for: 1. a reduction in operational costs, 2. increases the chemical penetration depth,
and 3. decreases the chemical retention rate in the rock. However, there exists a high level of uncertainty to
deploy the dispersed chemicals technology at a field-scale: experimental information is still limited, since
core-flooding setups are not standard and are expensive; no pilot studies have been reported; and commercial
reservoir simulators do not have incorporated most of the relevant phenomena.
Given a fluids/rock/chemical system, the chemical injection rate may determine the Technical-Economic
success or failure of the operation; when chemical fluids are used for both, well stimulation operations and
enhanced oil recovery processes, complex mass transfer, phase transitions and transport properties alteration
are present. As a result, the main uncertainty factors are the chemical distribution and penetration in the
reservoir, and the impact on oil and gas. Chemicals transport and retention on the reservoir rocks have a
profound role in the field operation effectiveness.
Uncertainty can be reduced by implementing a systematic methodology between experimental-modeling-
field pilots studies to make the process extensible and repeatable. Consequently, logistical and operational
costs can be minimized while maximizing the oil and gas recovery, having such methodology. One key
aspect is the understanding of the governing physics taking place in the dispersed chemical injection
technology, and its impact on oil and gas production.
A rigorous mathematical model, based on the most relevant transport phenomena of the dispersed
chemical technology, is presented in this paper. The main model equations are presented in the next section.
Then, the numerical solution strategy is presented in Section 3 as well as the parameter fitting at lab scale.
Results of a pilot study in a Colombian reservoir are discussed in Section 4. Finally, some conclusions are
highlighted.

Model development
In the dispersed chemical injection technique, the chemical solution is dispersed into droplets using a nozzle.
The generated mist travels through the well, reaching the formations opened for injection. Once the chemical
droplets are transported into the formation, some of these will be transferred to the liquid phase by an
interception mechanism. Consequently, the chemical concentration in the liquids phases increases as a result
of the droplets interception. Depending on the amphiphilic behaviour of the chemicals used for the operation,
they will be partitioned between the water and oil phases. Furthermore, the chemical is adsorbed into the
rock matrix. Because the concentrations are initially low, the interfacial mass transfer is slow and may
proceed under non-equilibrium conditions. Finally, the chemical solution is advected through the porous
rocks and dispersed in the liquid phases.
Gas, oil and water flow through the reservoir is described using the extended black-oil model (Turgay
et al., 2001), as follows:
SPE-196620-MS 3

where ϕ is porosity, S is phase saturation, ρ is fluid density, b is the inverse of the formation factor volume,
u is the phase velocity, q is well production-injection term, Rs is the dissolved gas in the oleic phase and Rv
is the volatilized gas-oil ratio. Subscripts sc indicates standard conditions, g, w and o denote gas, water and
oil respectively. The momentum equation is reduced to the Darcy's law.
On the other hand, the concentration of the ith component of the chemical solution injected into the
reservoir can be modeled using the following set of equations:

where xi,p denotes the solvent-free mass fraction of active component ith, in phase p. is the mas transfer
rate of i component between phase p and other fluid phases and the rock (denoted by subscript r).
th

To define the mathematical model, expressions for mass transfer terms are required. Droplets being
carried by the gas phase collide with the liquid phases. Concentration of active chemicals increases in the
liquid phases as a result of effective collisions. The transfer rate from the chemical solution droplets to the
liquid phases is described using the interception model, presented in Equations (5) and (6).

where Kint is the kinetic interception coefficients, and V is the interstitial velocity.
Once the active chemicals are dissolved in (miscible) liquid phases, their concentration is initially very
low. It is then expected that adsorption rate to be initially very slow. Consequently, the adsorption rate
can be expressed as a linear distribution function between the actual thermodynamic state, and the one at
equilibrium conditions. The model for sorption kinetics is presented in Equation (7)).

where Kads and Neq is the kinetic sorption coefficient and adsorption at equilibrium state of ith component on
the rock. Subscripts r and p represent the rock phase and liquid phases, respectively. Superscript eq denotes
equilibrium conditions. Both, Kads and Neq depend on temperature and surfactant concentration, and their
dependence have to be measured in the lab.
According to the affinity of ith component with liquid phases, it can be partitioned in both phases. The
mass transfer rate will depend on the difference between actual concentration and the one at equilibrium
conditions, as follows:

where Kdis is the kinetic diffusion coefficient from the aqueous phase to the oleic phase.
Some chemicals in porous system can change the phase mobility due to interfacial and wettability
alterations. The quantification of this change has to be done using experimental evaluation of pre and post-
treatment relative permeability curves. The progressive change in phase mobility during the simulation is
modeled by a linear interpolation between these curves. The interpolation model is based on the Coat's
approach (Coats, 1980), where the relative permeability of a phase depends on the saturations and the
chemical concentration. The interpolation reads:
4 SPE-196620-MS

where krp is phase p relative permeability, Ct is chemical block concentration, krp-pre is pre-treatment relative
permeability, krp-post is post-treatment relative permeability, and Ct,eff is effective concentration.

Numerical method and parameter fitting

Space and time discretization is needed to numerically solve the resulting set of conservation equations.
The conservation equations are discretized based on finite volume method (Versteeg & Malalasekera 2007),
using the upstream weighting method for implicit mobilities calculation (Ertekin et al. 2001). Primary
variables are pressure, gas-phase saturation, water-phase saturation and chemical concentration in each
phase. Equations are linearized using Newton method and solved using GMRES with ILU preconditioning
(Saad, 2003), commonly used to solve reservoir simulation equations systems (Qi, 1990). The Newton
method is described by equations to.

where the R(X) term is the vector that contains the residuals of the conservation equation system, X is the
solution vector of system unknowns and J is the Jacobian matrix containing the variation of each residual
function with respect to the change of each variable of the solution vector. The Jacobian matrix is calculated
numerically. The discretized equations system expressed in terms of residuals is presented in equations to.
The discrete modified black oil model is composed by gas, oil and water equations showed in, and. And the
discrete chemical transport equations in each phase are represented by equations,, and.

Model parameters are estimated from core flooding tests. Initially, adsorption and desorption kinetic
coefficients are adjusted using dynamic retention tests. In these tests, a batch of the chemical solution is
injected in the rock core sample. A separator is placed after the core exit and the gas stream is directed to a
chiller where liquids are condensed to measure volume and active chemical concentration. The process is
repeated for different inlet concentrations. We evaluated 4 different inlet concentrations: 5, 10, 50 and 100
ppm. The core properties and test conditions are reported in Table 1.
SPE-196620-MS 5

Table 1—Core properties and operational conditions of core flooding tests

Parameter Value

Sample length [cm] 18.4

Sample diameter [cm] 4.48

Absolute permeability [mD] 33

Porosity 0.089

Pore pressure [psi] 2500

Overburden pressure [psi] 3500

Gas injection flow [cm3/min] 1000

Initial Sw 0.2394

Initial So 0.7606

The results of the dynamic adsorption test at 5 ppm of inlet concentration are presented reported in Figure
1, along with the simulation results.

Figure 1—Chemical retention at 5 ppm and 2000 psi. Symbols: core-flooding measurements; line: simulation results.

Based on results presented in Figure 1, the kinetic adsorption coefficient for 5 ppm is 0.13494 min-1, and
the equilibrium retention is 0.01182 cm3 g-1. Simulation results are in close agreement with experimental
observations, indicating that the model reproduces the physical behaviour. The adsorption kinetic coefficient
and equilibrium adsorption concentration for 10,50 and 100 ppm of inlet concentration are presented in
Table 2.

Table 2—Experimental sorption kinetics

Inlet k - kinetic Nads in Equilibrium

Concentration

(ppm) (min-1) (cm3 g-1)

0 0 0

5 0.01015 0.01182

10 0.013494 0.02350

50 0.038223 0.0354

100 0.040486 0.0471

6 SPE-196620-MS

Once the adsorption coefficients are calibrated, core floodings recovery tests with reservoir fluids are
done. The recovery flooding tests with different chemical concentration are used to adjust the parameters
related to mass transfer between phases and their effect on the oil mobility. Initially, dry hydrocarbon gas
is injected in the core until no additional liquid recovery is registered at the core exit. Then, the chemical
solution is dispersed in the injection line, incrementing its concentration from 1.7 ppm to 50 ppm. Gas is
injected at a rate of 1000 cm3/min at SC, having presaturated the with So = 0.76 and Swi = 0.24. Measured
and simulated pressure drop and recovered volumes are presented in Figures 2 and 3, respectively.

Figure 2—Pressure drop along the core at different inlet chemical

concentrations. Symbols: core-flooding measurements; line: simulation results.

Figure 3—Accumulated liquids recovery at different inlet chemical

concentrations. Symbols: core-flooding measurements; line: simulation results.

Pressure drop (see Figure 2) increases as the gas is injected in the core. The injected gradually displaces
liquids, having a maximum vale after a few injected pore volumes and reaching a plateau where no additional
liquids were recovered. However, the simulated pressure drop during this period is higher than the measured
one, because the model assumes that the core is homogeneous in the transverse direction. The recovered
volumes are very similar between experimental measurements and simulation results, as presented in Figure
3. Pressure drop increases when the chemical solution is dispersed at a concentration of 1.7 ppm, but no
SPE-196620-MS 7

incremental liquids are recovered at the core exit. The chemical solution, then, is being retained in the
porous system during this stage. The model also predicts that the chemical is retained in the core, but a
few volume of liquids, including the chemical solution, are being produced. By increasing the chemical
concentration, pressure drop decays and more liquids are being recovered at the core exit. The simulation
results are in good agreement with experimental observations. The maximum difference between measured
and simulated pressure drop is 1.4 psi. The chemical injection improves the recovery factor from 70% (base
line) to 89% (at an inlet concentration of 50 ppm).

Field scale results

The adjusted parameters are upscaled to reservoir conditions to simulate the dispersed chemical process.
Here, we simulated a sector model from a volatile oil reservoir located in the Colombian foothills, Llanos
Basin. A simulation grid with 37960 blocks was used to simulate the recovery process at reservoir scale.
Permeability changes between 1 and 100 mDa and porosity between 1 – 6.7%. The mesh and permeability
distribution of an intermediate layer are shown in Figure 4; production and injection wells are represented
by the vertical dashed lines.

Figure 4—Simulation grid with porosity and permeability distributions. Vertical lines denote location of wells 1 and 2.

To initialize the simulation model, an initial pressure of 4500 psi is set at 12000 ft. Connate water
saturation is 0.22 and an average oil saturation of 0.78. The interwell distance is about 11000 ft. The Well 1
is programmed to produce with an increasing bottom hole pressure from 3000 psi at the beginning, to 3500
psi at day 1110, then the well is producing at constant pressure @ 3500 psi. The Well 2 is programmed to
start injection with 45 MMSCFD from day 1110. The dispersed chemical injection begins at day 1423 in
well 2 with an injection concentration of 10 ppm. Figure 5 shows the arrival of an inert chemical in well 1.
8 SPE-196620-MS

Figure 5—Chemical arrival in the production well -Straight line (The dashed line indicates the injection time)

Results presented in Figure 5 indicate that the time of flight of a gaseous tracer is 110 days between the
injector and the producer wells. Oil and gas production are presented respectively in Figures 6 and 7.

Figure 6—Oil production in well 1. Symbols: field measurements;

continuous line: Ch Gas EOR predictions; Dashed line: base line.
SPE-196620-MS 9

Figure 7—Gas production in well 1. Symbols: field measurements;

continuous line: Ch Gas EOR predictions; Dashed line: base line

Figures 6-7 show that the model is able to capture the gas injection and dispersed chemical injection
stages. The simulation results are in good agreement with field measurements. Oil and gas production results
presented in Figures 6 and 7, show a reduction of the gas production when the chemical is dispersed in the
injection well, but the oil flow is increased in approx. 45 Bbl/d. Although the active chemical dispersed
in the gas stream can reach deeper penetration radius than liquid – based injections, it does not reach the
producer after one year. The gas saturation distribution is presented in Figure 8, and Figure 9 shows the
distribution of active chemical concentration in the gas phase in the reservoir (day 1770).

Figure 8—Gas saturation distribution in the reservoir (day 1770)

10 SPE-196620-MS

Figure 9—Active chemical concentration distribution in the reservoir (day 1770). Units in mass fraction.

Conclusions
A mathematical model of the dispersed chemical method was developed in this work. The model accounts
for non-equilibrium adsorption of active chemicals on the rock surface, as well as dynamic interception of
chemical droplets with liquid phases.
The mathematical model was calibrated using dynamic retention and recovery core-flooding tests using
reservoir rocks and fluids.
The model reproduced the behavior of the dynamic adsorption of active chemicals on the rock surface.
In addition, the model reproduces very well the liquids production in the recovery tests. Some deviations
were noted between the measured and the simulated pressure drop. At field scale, the simulation results
showed a good agreement with field measurements. As a result, the good performance of the model suggests
that the hypothesis of mass transfer processes away from the equilibrium state, occurs during the dispersed
chemical injection method.

Acknowledgments
The authors acknowledge COLCIENCIAS and ANH for the support provided in contract
#FP44842-273-2017, to Equion Energia and Universidad Nacional de Colombia for logistical and financial
support

Nomenclature
A Transverse area
B Volumetric factor inverse
J Diffusion flux, Jacobian matrix
K Kinetic mass transfer term
Mass transfer
N Adsorbed mass fraction
Q Flow
S Phase saturation
T Time
SPE-196620-MS 11

U Darcy velocity
V Block volume
w Mass fraction
X Component concentration
P Phase density
Φ Porosity
Φ Potential

Subscripts
0 Reference condition
g Gas phase
j Flow direction
k K component
m Matrix
o Oil
p Phase
r Rock
i Chemical copmponent
Sc Standard conditions
w Water phase

Superscripts
0 Reference
Ads Adsorption
Des Desorption
Eq Equilibria
Np Phase number
V Iteration number

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