SPE-191545-MS

The Role of Chemicals Loss in Sandstone Formation in ASP Flooding

Enhanced Oil Recovery

Huiying Zhong, Tingbao Yang, Hongjun Yin, and Chunquan Fu, Northeast Petroleum University; Jun Lu, The
University of Tulsa

Copyright 2018, Society of Petroleum Engineers

This paper was prepared for presentation at the 2018 SPE Annual Technical Conference and Exhibition held in Dallas, Texas, 24-26 September 2018.

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
Chemical combination flooding technique especially alkali/surfactant/polymer (ASP) flooding has proven
to be an indispensable way to enhance oil recovery (EOR). The progress of this flooding technique in Daqing
Oilfield (China) shows that it is promising to keep production from falling and help oil companies make
profit in a low-oil-price era. However, the ASP chemicals chromatographic separation and loss in sandstone
formation are still the weaknesses in the promotion of ASP flooding.
Laboratory investigations for characterizing the behavior and distinction of chemicals loss in sandstone
reservoir with strong base (NaOH) and weak base (Na2CO3) ASP flooding were recently carried out.
The experiments were designed to pointedly study the chromatographic separation, and consumption loss
behaviors of alkali and surfactant in sandstone reservoirs with ASP flooding. Furthermore, the incremental
oil recovery factor in heterogeneous sandstone reservoirs with strong base (NaOH) and weak base (Na2CO3)
ASP flooding process was evaluated and compared. The loss rates of chemicals and the permeability
damage degree in various experiments were determined respectively, the consumption loss mechanism and
influencing factors were discussed, and the formulation composition and slug combination patterns were
also optimized. Then, the role of ASP chemicals loss in sandstone formation during ASP combination
flooding EOR process was worked out.
The results indicated that the chemicals loss behaviors could be weakened and the chemicals
chromatographic separation phenomenon could be alleviated in weak base (Na2CO3) ASP flooding, and
the average loss rate of alkali and surfactant could drop 9.61% and 15.67% respectively in heterogeneous
sandstone reservoirs comparing to strong base (NaOH) ASP flooding. The profitable EOR effect could also
be obtained with weak base (Na2CO3) ASP flooding, and the enhanced oil recovery could still reach 20% or
more. Moreover, an approximately 15% reduction in permeability damage rate could be realized in the weak
base (Na2CO3) ASP flooding instead of strong base (NaOH) system, and the reservoir flow assurance issues
related to chemicals loss behaviors could be addressed. The optimal design of ASP formulation and slug
combination pattern could technically and economically achieve high oil recovery in sandstone reservoirs
with weak base (Na2CO3) ASP flooding.
2 SPE-191545-MS

The results are beneficial to well understand the chemical combination flooding mechanism and can
contribute to the existing knowledge in the chemicals super additive effects during EOR process, and
it is also significant to further improve the oil displacement efficiency and reduce the injection cost in
heterogeneous sandstone reservoirs with weak base (Na2CO3) ASP flooding process.

Introduction
It is generally known that crude oil plays a vital role in providing the energy supply to the world among
the various sources of energy (Lu et al., 2014; Du et al., 2018; Liu et al., 2015). Typically, only about
40% of crude oil can be recovered from the reservoir after primary and secondary recovery techniques
(Wang et al., 2000; Zhong et al., 2018; Rui et al., 2012). This leaves a considerable amount of remaining
oil in the formation. The remaining oil left after waterflooding process is either from water swept area or
zone bypassed by the water displacement. There is a high interfacial tension (IFT) between the bypassed
remaining oil and the water. Against this background, one promising method of recovering this capillary
trapped oil is to employ ASP flooding process. As the most efficient chemical combination flooding EOR
technique, a combination of chemicals (alkali, surfactant and polymer) is used to improve sweep efficiency
and recover capillary trapped oil, and capillary-number theory is potentially the most important mechanism
of this technique (Sharma et al., 2015; Shen et al., 2009). Polymer increases the viscosity of the injected
water in order to provide stable displacement for crude oil and significantly enlarge the sweep area of the
reservoirs. Surfactant can reduce the IFT between the crude oil and displacing fluid. And alkali can decrease
surfactant adsorption on the rock by increasing the pH value of the displacing fluid, and can also produce
in-situ soaps if the crude oil demonstrates a high total acid number. This synergy mechanism results in
significant amounts of the trapped oil to be mobilized and recovered (Hosseini-Nasab et al., 2016; Wang
et al., 2013; Zhong et al., 2017a; Zhu et al., 2018).
ASP flooding technique has been widely used in sandstone reservoirs and carbonate reservoirs (Liu et al.,
2014; Panthi et al., 2016; Guo et al., 2017). It seems that ASP flooding has little market prospect under the
hovering background of low oil price, however, the progress of this flooding technique in Daqing Oilfield
shows that ASP flooding is a promising technique to keep oil production from falling and help oil companies
make profit. Since 2014, ASP flooding process entered commercial-scale application in Daqing Oilfield,
ASP flooding production has increased with a velocity of 7 million barrels (bbl) every year (Wang et al.,
2017). The oil production of ASP flooding approached to 30 million bbl in 2017, which accounted for about
35.6% and 12.0% of the chemical flooding production and total production of the oilfield, respectively. As
for a huge sandstone reservoir, the type I reservoirs, type II reservoirs, and type III reservoirs are classified
based on the sedimentary characteristics and development status in Daqing Oilfield (Zhong et al., 2017b). It
is to be observed that the type II reservoirs, which have a medium permeability, a strong heterogeneity, thin
oil layers and poor connectivity, have become the indispensable subject for implementing ASP flooding
processes for EOR. Furthermore, employing polymer flooding or ASP flooding technique in heterogeneous
type II reservoirs has proven to be a necessity for stable production levels of a mature onshore field (Olajire,
2014; Mandal, 2015; Guo et al., 2016; Zhong et al., 2017b). However, there are still some intractable issues
in the industrialized-application of ASP flooding technique, including ASP chemicals chromatographic
separation in reservoirs, scaling deposition in formation and production facilities, and the injection cost
management related to ASP chemicals consumption in formation.
Similar as performing flow assurance studies in wellbores and pipelines during production, evaluation of
formation damage and understanding of formation protection, which are involved in reservoir engineering,
are also part of flow assurance issues in oil & gas industry. Chromatographic separation and chemicals loss
behaviors corresponding to such reservoir flow assurance are considered unfavorable for ASP flooding,
the undesirable oil displacement effect and potential permeability damage could be caused (Li et al., 2009;
Tang et al., 2014). The physical and chemical effects between chemicals and formation mineral as well as
SPE-191545-MS 3

formation fluid are one of the main concerns of ASP flooding. Adsorption and retention of the chemicals
are essential performances of the issues. Both laboratory studies and pilot tests indicated that breakthrough
of the polymer occurred before the alkali followed by the surfactant in ASP flooding process (Guo et al.,
2016; Li et al., 2009). The amount of adsorption for surfactant is the largest, followed by the amount for
alkali and polymer, and there is a potential competition of adsorption sites between surfactant and polymer.
In ASP system, except the most important function for alkali is to reduce IFT, alkali not only can reduce
the adsorption of polymer but also can reduce surfactant adsorption by increasing the negative charge
density on reservoir rock surface and make it preferentially turn to water-wet (Olajire, 2014). French and
Burchfield (1990) proposed that surfactant retention originated from adsorption behavior can be reduced by
49% when the formulation pH was increased from 6.3 to 10.2. Nevertheless, high surfactant adsorption and
high alkaline consumption could also be caused due to the existence of clays in sandstones (Sheng, 2014).
Although some sacrificial agents could reduce the adsorption of surfactants in formation, there was still no
attractive effect on chromatographic separation (Li et al., 2009). The reason why there exist such complex
and non-negligible adsorption and retention of the chemicals in ASP flooding EOR is due to the molecular
weight of the chemicals, molecular structure, and the volume difference after hydration. To achieve a much
lower cost and some other benefits is the central purpose for addressing the issues in industrial application of
ASP flooding technique. Although the loss pattern of chemicals and the effect on formation damage in type
II reservoirs with strong base (NaOH) ASP flooding process have been reported by our group (Wang et al.,
2016), the difference of chemical loss between strong-alkali ASP flooding and weak-alkali ASP flooding
has not been concerned and quantified previously, and the role of chemical loss on threatening sandstone
formation flow assurance and improving oil recovery was not well understood. Laboratory investigations
for characterizing the behavior and distinction of chemicals consumption loss in sandstone reservoir with
strong base (NaOH) and weak base (Na2CO3) ASP flooding were recently conducted. The experiments
were designed to pointedly study the chromatographic separation, and consumption loss behaviors of
alkali and surfactant in type II reservoirs with ASP flooding. Furthermore, the incremental oil recovery
factor in heterogeneous type II reservoirs with strong base (NaOH) and weak base (Na2CO3) ASP flooding
was assessed and compared. The loss rates of chemicals and the permeability damage degree in various
experiments were determined respectively, the loss mechanism and influencing factors were discussed,
and the formulation composition and the slug combination patterns were also optimized based on a series
of routine measurements, pore structure identification, and coreflood experiments. Then, the role of ASP
chemicals loss in sandstone formation during ASP flooding EOR process was worked out. This study can
be beneficial for providing further insight into how ASP chemicals behave and, in particular, the importance
of chemicals synergism in oil displacement process.

Experiments
The loss of chemicals originated from adsorption and retention would have significant impact on the
recovery efficiency and cost-effectiveness of ASP flooding. It is dominated by multiple factors including
reservoir permeability, rock minerals, fluid properties, chemicals composition and reservoir temperature
(Zendehboudi et al., 2013; Wang et al., 2016). Revealing the behavior and distinction of chemicals loss by
experiments shows great importance for improving ASP flooding technique and further understanding.

Experimental Mechanism
Being one of the main transport characteristics in porous media, the behavior of chemicals loss in formation
is typically caused by chemical reaction, ion exchange, adsorption and entrapment in ASP flooding EOR.
Furthermore, the surface of rock matrix can selectively adsorb ASP chemicals if the reservoir is regarded as
a large chromatographic column. That's because ASP chemicals have different molecular dimensions and
exhibit hydrophilic-hydrophobic properties in the displacement process. Hence, the breakthrough time and
4 SPE-191545-MS

adsorption capacity of ASP chemicals in porous media would show inevitable differences, and will result in
the associated chromatographic separation phenomenon of chemicals loss (Mannhardt and Novosad, 1991).
Although it has been confirmed that except the unique loss characteristics of surfactant in formation, the
adsorption of both polymer and alkali obeys the Langmuir adsorption isotherm (Volokitin et al., 2014; Li et
al., 2009), however, the chemicals loss behavior, especially the distinction of chemicals loss during strong
base (NaOH) and weak base (Na2CO3) ASP flooding needs to be characterized and identified by breaking
through conventional static adsorption experiments.
In dynamic chemical combination displacement experiments, the normalized concentration can be
defined as (Li et al., 2009):

(1)

where Cn is the normalized concentration, dimensionless; C is the chemical agent concentration in the
produced liquid of flooding process, mg/mL; and Co is the initial chemical agent concentration in displacing
phase, mg/mL.
Characteristic relation between the normalized concentration and the injection pore volume (PV) in
displacement process can be established and shown in Figure 1.

Figure 1—Schematic diagram of chemicals loss behavior in displacement process

As a result, the normalized volume can be expressed as Equation (2)), and the chemicals loss behavior
can be revealed quantitatively. The normalized volume demonstrates the loss situation of chemicals in
reservoirs. As shown in Figure 1, the consumption loss decreases (e. g., S1) when the area inside the typical
characteristic curve increases, and it increases (e. g., S2) when the area inside the typical characteristic curve
decreases.

(2)

where S is the normalized volume, dimensionless; is the cumulative injection PV; Cn(IPV) represents
that injection PV is on the function of Cn; and IPV is the injection PV.
Thus, the calculation formula for the consumption loss rate of ASP chemicals in flooding process could
be written as follows:

(3)
SPE-191545-MS 5

where Ci is the chemical concentration in the produced liquid of a certain flooding process, mg/mL; Vi is the
volume of produced liquid in the flooding process, mL; Co is the initial chemical concentration in displacing
phase, mg/mL; Vo is the cumulative injection volume of chemicals in the flooding process, mL; and LR is
the chemical loss rate, %.
After considering the existing consensus that the breakthrough for polymers is the earliest, the amount
of adsorption for polymers is the least, and the adsorption and retention of alkali and surfactant are more
complicated, it is indicated the adsorption and retention behavior of alkali and surfactant need to be
evaluated. Therefore, the loss behaviors of alkali and surfactant are mainly emphasized in this experimental
work, and the chemicals involved in above Equations represent alkali or surfactant.
If the mercury intrusion data of cores before and after displacement experiments are available, the
permeability reduction ratio of the formation, which is related to chemicals loss behavior and reservoir flow
assurance, can be estimated using the following well-known equations (Murray et al., 1999; Zhou et al.,
2017; Wang et al., 2016):

(4)

where η is permeability reduction ratio, %; is average throat radius before ASP slugs injection, μm; is
average throat radius after ASP slugs injection, μm.

Experimental Material and Procedure

Experimental materials
ASP system. Both strong base ASP system and weak base ASP system were used in experiments. The
polymer used in these system was partially hydrolyzed polyacrylamide (HPAM). It has a property of salinity-
tolerance, a relative molecular weight of 2.5×107 Da and a hydrolysis degree of about 25%. The used
strong base was sodium hydroxide (NaOH), and the weak base was sodium carbonate (Na2CO3). The
surfactant of alkylbenzene sulfonate (ABS) and petroleum sulfonate (DPS) were used together with strong
base (NaOH) and weak base (Na2CO3), respectively. Both ASP systems were created by mixing the required
stock solutions of HPAM, NaOH or Na2CO3, and ABS or DPS with water in stirring conditions. The detailed
formulations of various ASP systems are shown in Table 1.

Table 1—Experimental matrix

Formulation compositions of ASP system

ASP dominating slug formulation ASP dominating slug property

Chemical Formulation
Number IFT, ×10−3 mN/m Viscosity, mPa.s
composition Alkali, wt.% Surfactant, wt.% Polymer, mg/L

SF-1 1.2 0.3 2000 1.88 63.5

SF-2 alkali: NaOH 1.2 0.5 2000 1.95 62.2

surfactant: ABS
SF-3 polymer: HPAM 1.5 0.5 2000 2.67 59.5

SF-4 1.2 0.1 1800 7.33 49.4

WF-1 1.2 0.3 2000 3.12 61.7

WF-2 alkali: Na2CO3 1.2 0.5 2000 3.05 59.8

surfactant: DPS
WF-3 polymer: HPAM 1.5 0.5 2000 5.30 57.6

WF-4 1.2 0.1 1800 8.74 46.5

6 SPE-191545-MS

Slug combination patterns of ASP flooding

Number ASP dominating slug

SS-1 same slug pattern: 0.5 PV strong-alkali ASP system with formulation of number SF-1

SS-2 succession pattern: 0.50 PV of NaOH (1.2 wt.%)+ 0.50 PV of polymer (2000mg/L)+ 0.50 PV of ABS (0.3 wt.%)

SS-3 succession pattern: 0.50 PV of polymer (2000mg/L)+0.50 PV of ABS (0.3 wt.%)+0.50 PV of NaOH (1.2 wt.%)

WS-1 same slug pattern: 0.5 PV weak-alkali ASP system with formulation of number WF-1

WS-2 succession pattern: 0.50 PV of Na2CO3 (1.2 wt.%)+ 0.50 PV of polymer (2000mg/L)+ 0.50 PV of DPS (0.3 wt.%)

WS-3 succession pattern: 0.50 PV of polymer (2000mg/L)+0.50 PV of DPS (0.3 wt.%)+0.50 PV of Na2CO3 (1.2 wt.%)

Cores preparation. The natural rock particles with various grain diameters were collected by crushing and
screening the sandstone particles in type II reservoirs of Daqing Oilfield, and the experimental cores with
permeability variation factor of 0.30, 0.72 and 0.90 were made be means of epoxy resin bond technology.
Three thin layers with constant-thickness and positive rhythm characteristic were designed to simulate
heterogeneity in the cores. Mudstone particles were obtained and used as the interlayer when the simulation
of inter-layer heterogeneity was required in the cores. The size of cores was 30×4.5×4.5 cm. All the effective
permeability were about 0.4 μm2, and all the average porosities were distributed in the range of 22.0~24.0%.
Oil and brines. The crude oil was sampled from central processing station of Daqing Oilfield, which has
a total acid number of 0.08 mg (KOH)/g. The experimental oil was compounded by the actual crudes and
aviation kerosene in a certain volume ratio, and its viscosity was about 10 mPa.s at 45°C. The used brines
consist of synthetic formation water, clean water, and the actual produced water. The synthetic formation
water belongs to NaHCO3 category and has a salinity of 6.778 g/L. The clean water was employed as the
solvent of polyerm stock solutions, and the total concentration of divalent cation (e. g., Mg2+, Ca2+) in clean
water was about 0.03 g/L. The oilfield produced water, containing a salinity of 5.19 g/L after advanced
treatment in surface facilities, was employed to dilute the stock solutions and conduct the displacement.

Experimental procedure
Viscosity and IFT measurements. Viscosity of the ASP systems were measured by means of stress
controlled rheometer with the practical shear rate of 7.34 s−1 at 45°C. The equilibrium interfacial tension
is invariably is chosen as the evaluation parameter in most fields when the ASP flooding is considered.
Thus, equilibrium interfacial tension between various ASP systems mentioned in Table 1 and crude oil were
tested at 45°C using spinning drop method, and the IFT values in 2 hours were recorded as the effective
IFT of the ASP systems.
Chemicals loss tests of various ASP formulations. As shown in Table 1, the strong-alkali ASP system and
weak-alkali ASP system with different formulation compositions were used in the tests, and employed as
ASP dominating slug respectively. The cores with short of mudstone interlayers, which have a permeability
variation factor of 0.72, were used in the tests. After water flooding process was performed and water
fraction of the produced liquid reached over 98%, the 0.10 PV polymer pre-slug of 2000 mg/L concentration
was injected firstly, and then the amount of 0.50 PV ASP dominating slug with the designed formulation
composition was injected, followed by injecting the amount of 0.10 PV polymer post-slug of 1500 mg/
L concentration. Afterwards the post-waterflooding was performed until there was no oil produced in the
effluent of the cores. The displacement velocities of all slugs were 0.28 mL/min in experiments, same as
the flow rate in actual porous media. The produced liquids were all gathered and analyzed to identify the
content of alkali and surfactant at different injection PV following ASP dominating slug injection. Both the
acid-base titration method and two-phase titration method were employed in concentration measurement of
SPE-191545-MS 7

alkali and surfactant (Wang et al., 2016). Then, chemicals loss behavior and the incremental oil recovery
in the flooding process can be determined. Change the formulation of ASP dominating slug and repeat the
procedures as mentioned above, and the distinction of chemicals loss during strong-alkali and weak-alkali
ASP flooding can be characterized and identified.
Chemicals loss tests of different slug combination patterns. As shown in Table 2, three types of the
combination patterns of ASP dominating slug were designed in the flooding process. The pre-slug, post-
slug and the basic procedures are all exactly the same as above. Similarly, the produced liquids from
various patterns were completely gathered and analyzed to identify the concentration of alkali and surfactant
at the corresponding accumulated injection pore volume after 0.10 PV polymer pre-slug injection. The
chemicals loss behavior and the incremental oil recovery under the different slug combination patterns can
be determined. The cores with short of mudstone interlayers were similarly used in the tests, and they have
a permeability variation factor of 0.72.

Table 2—Experimental results of permeability damage related to chemicals loss behavior

Average throat Average pore Average throat Average pore- Permeability

radius (μm) radius (μm) radius (μm) throat ratio reduction ratio (%)

blank-SF 168.542 8.937 20.756 —

SF-1 165.301 8.605 21.914 14.05

SF-3 162.025 8.504 22.237 18.02

blank-WF 170.014 9.036 21.602 —

WF-1 164.657 8.933 21.031 4.48

WF-3 165.280 8.859 21.856 7.60

Chemicals loss tests in different heterogeneous cores. As mentioned above, three types of experimental
cores with permeability variation factor of 0.30, 0.72 and 0.90 were used to creat heterogeneity intensity in
the tests. Moreover, the inter-layer heterogeneity and intra-layer heterogeneity were simulated by replacing
and removing mudstone interlayers in the cores. The ASP dominating slug used in the experiments
were formulation compositions of number SF-1 and number WF-1. The pre-slug, post-slug and the basic
procedures are all exactly the same as above. The produced liquids in different heterogeneous cores were
completely gathered and analyzed to identify the concentration of alkali and surfactant at the corresponding
accumulated injection pore volume after 0.10 PV polymer pre-slug injection. Then, the chemicals loss
behavior and the incremental oil recovery in the different heterogeneous cores were determined.
All of the displacement experiments above were performed at a temperature of 45°C, which is just the
same as reservoir temperature. Furthermore, the characteristic parameters of pores and throats in cores were
measured before and after the above ASP system displacement experiments using constant rate mercury
intrusion method (Shikhov and Arns, 2015; Cai et al., 2010). And the microscopic pore-structure was also
revealed by scanning electron microscope method (Chen et al., 2017). The permeability reduction ratios of
the formation, which are related to chemicals loss behavior and reservoir flow assurance in the strong-alkali
and weak-alkali ASP flooding process, were estimated and evaluated.

Results and Discussion

Characterization of the Chemicals Loss Behavior
Consumption loss of alkali and surfactant under various ASP formulations. As reported, the type and
concentration of alkali are essential conditions for achieving optimal phase behavior in surfactant soap
system (Gregersen et al. 2013). Both strong base (NaOH) and weak base (Na2CO3) have been applied in
8 SPE-191545-MS

ASP flooding processes because of the low divalent salt content in Daqing Oilfield. The basic concentration
for general application of alkali is 1.2 wt.%, and the basic formulation of ASP system is 1.2 wt% alkali, 0.3
wt% surfactant and 2000 mg/L HPAM. As can be seen in Table 1, although the mobility control of ASP
system could be weakened with the decrease of polymer concentration, the properties of ASP dominating
slug showed that, for both the strong-alkali ASP dominating slug formulations and the weak-alkali ASP
dominating slug formulations, the IFT can reach 10−3 mN/m order of magnitude. It indicated that the
approach, which is to enhance oil recovery by increasing capillary number and overcome the trapping
by capillary forces, can be expanded. And ASP formulation can be screened considering petrophysical
features, EOR potentiality and cost management. Nevertheless, understanding the physical and chemical
effect between various ASP system and reservoir rock is principal for the further evolution of low damage
formulation of ASP system.
As shown in Figure 2, when a total cumulative injection volume for about 4.0~4.5 PV of the displacement
phase was injected, which including the ASP dominating slug, the polymer post-slug and the post-
waterflooding slug, the chromatographic separation phenomenon was obviously presented, and the alkalis
were produced before the surfactants. This is in agreement with the existing understanding that the
breakthrough of the polymer occurred before the alkali, and followed by the surfactant in ASP flooding
process (Guo et al., 2016; Li et al., 2009). The maximum normalized concentration of the surfactant was
about 1/5 of the alkali in the displacement process of various ASP system, and the normalized volume of
the surfactant was much smaller than the normalized volume of the alkali. The results revealed that the
consumption loss of the surfactant is greater than that of alkali. Moreover, the consumption loss behaviors
of surfactant and alkali were intensified when the concentration of polymer decreased in ASP dominating
slug formulation, and the consumption loss behaviors of surfactant and alkali were weakened when the
concentration of surfactant and alkali increased in the ASP formulation. This can be attributed to the
differences in the formation characteristics of double molecule adsorption layer at the solid-liquid interface
when the ASP slug was injected into the porous media. The extraction of chemicals was delayed when the
adsorption and retention was high in porous media. The diffusion efficiency of ASP system increased due
to the decrease of the polymer viscosity, and the potential role of carrying and adsorption displacement
was hindered in a certain degree. The change of rock surface properties was promoted and the competition
of adsorption sites between surfactant and alkali was strengthened when the concentration of surfactant or
alkali increased in the ASP system. However, the chromatographic separation phenomenon was alleviated
in weak base (Na2CO3) ASP flooding using the same chemical concentration. Breakthrough of the alkali
occurred at 0.20PV for strong base (NaOH) ASP flooding experiments but was delayed until 0.30 PV for
weak base (Na2CO3) ASP flooding experiments. Furthermore, both of the normalized volume and maximum
normalized concentration of alkali and surfactant increased in weak base (Na2CO3) ASP flooding process.
It revealed that the consumption loss behaviors of ASP chemicals were weakened in weak base (Na2CO3)
ASP flooding. In the four ASP formulation compositions, the average loss rates of alkali and surfactant
decreased from 72.30% and 89.70% for strong base (NaOH) ASP flooding to 64.91% and 75.83% for
weak base (Na2CO3) ASP flooding, respectively. The chemicals loss rates for formulation compositions
of number SF-4 and number WF-4 were the greatest, and the ultimate loss rates of alkali and surfactant
in sandstone formation reached 76.68%, 95.07% and 67.41%, 82.60%, respectively. The results indicated
that the weak base (Na2CO3) ASP system, which meets the requirements of favorable mobility control and
high interface activity, can alleviate the chromatographic separation of ASP chemicals and decrease the
consumption loss of ASP chemicals during the displacement process. In addition, adjusting each chemical
concentration properly with the consideration of economical cost management can be also a potential
approach for reducing chemicals loss in ASP flooding process.
SPE-191545-MS 9

Figure 2—Consumption loss of chemicals under various ASP dominating slug formulation

Consumption loss of alkali and surfactant under different slug combination patterns. As can be seen
in Figure 3, there was a significant difference between the normalized volume and maximum normalized
concentration of surfactant and alkali under different slug combination patterns, and the consumption loss
behavior in sandstone formation was still in the order of surfactant and alkali. However, the consumption loss
was reduced in weak base (Na2CO3) ASP flooding using the same slug combination pattern, and a lower loss
rate of chemicals was presented both in succession patterns of strong base (NaOH) and weak base (Na2CO3)
ASP dominating slug. The loss rate of alkali decreased from 77.16%, 74.97% and 64.81% for the strong
base (NaOH) ASP slug combination patterns of SS-1, SS-2 and SS-3 to 64.39%, 67.24% and 57.58% for the
weak base (Na2CO3) ASP slug combination patterns of WS-1, WS-2 and WS-3, respectively. The loss rate of
surfactant decreased from 91.05%, 85.08% and 83.85% for the strong base (NaOH) ASP slug combination
patterns of SS-1, SS-2 and SS-3 to 72.77%, 66.81% and 68.09% for the weak base (Na2CO3) ASP slug
combination patterns of WS-1, WS-2 and WS-3, respectively. The result revealed that the adsorption and
retention of surfactant is lower in the presence of Na2CO3 than in the presence of NaOH at the equal injection
volume, and this difference can be attributed to the fact that divalent ion in Na2CO3 in contrast to the
monovalent ion in NaOH. It is agreement with the statement proposed by Liu et al. (2008) that the weak
base (Na2CO3) ASP flooding process can substantially decrease the adsorption of anionic surfactants on
carbonate surfaces. Furthermore, when the succession patterns of weak base (Na2CO3) ASP dominating
slug were employed and the polymer took the second position, the decrease of DPS consumption loss was
further highlighted, and the loss rate was 5.96% lower than that of the same slug pattern with equal injection
volume. And when the succession patterns of weak base (Na2CO3) ASP dominating slug were employed and
the polymer took the first position, the consumption loss of DPS and Na2CO3 are all decreased and the loss
rates were 4.68% and 6.81% lower than that of the same slug pattern, respectively. It can be concluded that
the available carrying and displacement effect of viscous HPAM can effectively suppress the adsorption,
ion-exchange and chemical reactions of surfactant and alkali in formation environment. Thus, the loss of
surfactant and alkali in the succession slug pattern are normally lower than that in the same slug pattern.
This is also in agreement with a greater loss rate of surfactant and alkali indicated in ASP dominating slug
formulation with low-polymer concentration flooding experiments above.
10 SPE-191545-MS

Figure 3—Consumption loss of chemicals under different slug combination patterns

Consumption loss of alkali and surfactant in different heterogeneous cores. The chemicals loss tests
indicated that the chromatographic separation of chemicals intensified with the increase of the permeability
variation factor. In other words, the chromatographic separation of ASP chemicals was also related to the
heterogeneity of sandstone formation. As shown in Figure 4, although the consumption loss behavior of ASP
chemicals was weakened in weak base (Na2CO3) ASP flooding process, the same as strong base (NaOH)
ASP flooding, both the normalized volume of Na2CO3 and DPS decreased with the increase of permeability
variation factor of cores. Eventually, the average consumption loss rates of Na2CO3 and DPS increased from
58.78% and 64.95% for permeability variation coefficient of 0.30 to 67.34% and 75.51% for permeability
variation coefficient of 0.90, respectively. This mainly resulted from the noticeable contribution of the low-
permeability layers to the adsorption and trapping behavior. The permeability ratio rises with the increase
of permeability variation factor. That is to say, the permeability of the low-permeability layer will be lower
when the designed effective permeability of the cores is the same. These features of smaller pore-throat
dimensions and higher pore internal surface areas are responsible for the adsorption and retention of ASP
chemicals as well as the potential reservoir flow assurance issues when the ASP slugs are injected in porous
media. Moreover, the consumption loss behaviors of surfactant and alkali will be intensified when mudstone
interlayers exist in the experimental cores. If the weak base (Na2CO3) ASP flooding was performed in the
strongest heterogeneous cores with a permeability variation factor of 0.90, the loss rates of Na2CO3 and DPS
were close to 70% and 75% when mudstone interlayers exist, respectively. And the loss rates decreased by
65% and 70% when mudstone interlayers lack, respectively. It indicated that the adsorption sites decreased
with the emergence of the "crossflow" in the heterogeneous cores without mudstone interlayers.
SPE-191545-MS 11

Figure 4—Consumption loss of chemicals in different heterogeneous cores

Evaluation on the Incremental Oil Recovery

EOR in the strong base ASP flooding. The admirable EOR effect was presented in the strong base
(NaOH) ASP flooding process with various formulations, as demonstrated in Figure 5, the incremental oil
recovery reached 20% (OOIP) over water flooding and was distributed in 22~26% under four kinds of
ASP formulation composition. The results proved there was a slight decrease in sweep improvement when
the low polymer-concentration formulation was employed. It indicated that the favorable mobility control
was important in ASP flooding EOR, and the residual oil can be further recovered under the combined
mechanism with high interfacial activity. In addition, as discussed above, the consumption loss of ABS in
porous media was restrained with the increase of NaOH concentration, and the role of synergistic mechanism
in EOR was facilitated, so the reasonable increases of the concentration of NaOH and ABS considering
cost-effectiveness are profitable to improve oil recovery in the strong base (NaOH) ASP flooding process.

Figure 5—Effect of ASP dominating slug formulation on the incremental oil recovery
12 SPE-191545-MS

The effect of slug combination patterns on EOR indicated that the synergistic effects of alkali, surfactant
and polymer are vital to reduce residual oil saturation, as shown in Figure 6, when the successive patterns
were employed and the polymer took the first position, the incremental oil recovery was 4.06% lower than
the same slug pattern with the equal injection volume of ASP chemicals. And when the successive patterns
were employed and the polymer took the second position, the incremental oil recovery was 4.25% lower
than the same slug pattern. This finding is in agreement with other references (Krumrine and Falcone, 1987;
Wang et al., 2016). Although the favorable EOR can be achieved in the strong base (NaOH) ASP flooding
process, the incremental oil recovery deteriorates as the heterogeneity of sandstone formation strengthen.
As shown in Figure 7, the average incremental oil recovery of the experimental cores decreased from
26.23% for permeability variation coefficient of 0.30 to 23.10% for permeability variation coefficient of
0.90, respectively. A further decrease can be found when the heterogeneous cores without interlayers were
employed. This is in agreement with the conclusion discussed above that the adsorption sites were reduced
and the loss of chemicals was decreased because of the impact of the "crossflow". This contributes to a
sharpened insights into the ASP flooding mechanism in heterogeneous sandstone reservoirs.

Figure 6—Effect of slug combination patterns on the incremental oil recovery

Figure 7—Effect of heterogeneity on the incremental oil recovery

EOR in the weak base ASP flooding. As mentioned above, all of the weak base (Na2CO3) ASP systems
with various ASP formulations, which were employed in this experiments, meet the requirements of ultralow
IFT and the favorable mobility control. As demonstrated in Figure 5, the incremental oil recovery can also
reach more than 20% (OOIP) with the ASP dominating slug formulation of number WF-1, number WF-2,
number WF-3 and number WF-4, and the value of 24.19% was achieved with the basic formulation of
SPE-191545-MS 13

number WF-1, which was close to the incremental oil recovery for strong base (NaOH) ASP flooding. This
revealed that the incremental recoveries of strong base (NaOH) ASP flooding and weak base (Na2CO3) ASP
flooding were nearly the same. There was only a slight increase in EOR improvement shown because of the
wider surfactant range and the stronger emulsification ability of strong base (NaOH) ASP system. Similarly,
the reasonable increase of the concentrations of alkali and surfactant is profitable to improve oil recovery
in the weak base (Na2CO3) ASP flooding process.
As shown in Figure 6, an extra 5% of the incremental oil recovery was obtained in the same slug pattern
compared with the successive pattern of the weak base (Na2CO3) ASP dominating slug. It also revealed
that the favorable chemicals transportation can be realized by maximizing the synergistic effects of ASP
system. That is to say, the use of polymer (HPAM) and alkali (Na2CO3) with low-concentration surfactant
(DPS) in the same slug pattern is more cost-effective to EOR than either used alone or in successive pattern.
Additionally, the results indicated that the weak base (Na2CO3) ASP flooding effectiveness for EOR was
improved with the decrease of heterogeneity of the sandstone formation. As shown in Figure 7, the average
EOR of experimental cores increased from 21.67% for permeability variation factor of 0.90 to 25.00% for
permeability variation factor of 0.30. A further improvement was also shown when heterogeneous cores
with mudstone interlayers were employed.
Furthermore, although the desired EOR can be achieved in weak base (Na2CO3) ASP flooding process,
the results indicated that the response of the strong base (NaOH) ASP flooding was sooner than the weak
base (Na2CO3) ASP flooding, and the injection pressure gradient in the strong base (NaOH) ASP flooding
was higher than that in the weak base (Na2CO3) ASP flooding. This can be concluded that there was a faster
physical and chemical reaction of strong base (NaOH) with crude oil and the rock minerals. Moreover,
the difference of emulsification performance between strong-alkali and weak-alkali ASP system can not
be ignored, and the potential permeability damage should be further concerned. This finding is also in
good agreement with the recent knowledge that weak base (Na2CO3) ASP flooding is both technically and
economically better than strong base (NaOH) ASP flooding under the field conditions in the Daqing Oilfield
(Guo et al., 2016).

The Role of Chemicals Loss Behavior to Reservoir Flow Assurance

Potential permeability damage in the strong base ASP flooding. Except the challenge of produced liquid
treatment due to high emulsified level, one of the main drawbacks remained in strong base (NaOH) ASP
flooding process is the potential scaling and formation damage (Wang et al., 2013; Guo et al., 2017). The
microscopic pore-structure of cores before and after the strong base (NaOH) ASP dominating slug injection
was observed with SEM, as shown in Figure 8, the smoothness of rock grain surface decreased after the
basic formulation of ASP system was injected in the same slug pattern. It can be identified that the carbonate
scales and silicate scales were produced together, the erosion of the feldspar minerals occurred, and there
were quartz and kaolinite around the eroded residual structure after the strong base (NaOH) ASP dominating
slug injection. This revealed that the consumption loss of NaOH dominated the physical and chemical
effect between displacing phase and reservoir rock, and the potential threat to reservoir flow assurance was
motivated. The migration and precipitation of rock-mineral particles resulted from the erosion effect of
alkali can form bridge-plug at the pore-throat, and the increase in pore-throat radius ratio would be caused.
14 SPE-191545-MS

Figure 8—Electronic imaging of pore throat characteristics for the slices of cores (strong-alkali ASP flooding)

As can be seen in Table 2, the permeability reduction ratio estimated by the petrophysical parameters
of pores and throats in cores was around 20%, and there is a positive correlation relationship between
permeability reduction ratio and ASP chemicals loss rates. It seems that there is a remarkable deviation in
the aspect of formation damage degree comparing with the case reported by Fang et al. (2016) that the extent
of permeability damage induced by scaling is up to 40% or more. This can be attributed to the constraints
of rock-mineral and model-scale in the experiments.
Potential permeability damage in the weak base ASP flooding. As shown in Figure 9, the smoothness
decrease of rock grain surface was almost indistinguishable after the weak base (Na2CO3) ASP dominating
slug injection. Although few rock-mineral particles that precipitated by erosion can be observed in the core
pores after the weak base (Na2CO3) ASP dominating slug injection, an approximately 15% reduction in
permeability damage ratio could be realized in the weak base (Na2CO3) ASP flooding instead of strong base
(NaOH) system. As shown in Table 2, the potential reservoir flow assurance issues related to chemicals
loss behaviors were addressed with the weak base (Na2CO3) ASP system. This is responsible for the lower
injection pressure and more stable injection-production capacity in the weak base (Na2CO3) ASP flooding.
Eventually, the desired EOR could be guaranteed. This indicated that the weak base (Na2CO3) ASP system
with lower PH value realized a lower formation damage comparing with the strong base (NaOH) ASP
system. The result is in agreement with the previous findings proposed by Kazempour et al. (2012). This
finding also provided a powerful and convincing explanation for the reason why weak base (Na2CO3) ASP
flooding has been a developing trend and some of the latest ASP flooding tests outside Daqing in China
are all operated based on weak base (Na2CO3).

Figure 9—Electronic imaging of pore throat characteristics for the slices of cores (weak-alkali ASP flooding)
SPE-191545-MS 15

Conclusions
1. The recent progress in fields further demonstrates that ASP flooding is a promising EOR technology to
keep production from falling and help oil companies make profit. The experimental results supported
that the desirable EOR of more than 20% could be achieved in weak base (Na2CO3) ASP flooding
instead of strong base (NaOH) system. The injection-production capacity can be further improved by
maximizing the synergistic effects of ASP system.
2. Although the physical and chemical effects between ASP chemicals and formation minerals as well
as formation fluid are complex and inevitable in ASP flooding process, the chemicals loss behaviors
could be weakened and the chemicals chromatographic separation phenomenon could be alleviated
in weak base (Na2CO3) ASP flooding, and the average loss rate of alkali and surfactant could drop
9.61% and 15.67% respectively in heterogeneous type II reservoirs comparing to strong base (NaOH)
ASP flooding. The optimal design of ASP formulation and slug combination pattern is essential for
achieving high oil recovery in sandstone reservoirs both technically and economically.
3. The reservoir flow assurance issues related to chemicals loss behaviors are noticeable in the ASP
flooding EOR process. The migration and precipitation of rock-mineral particles result from the
erosion effect of alkali will form bridge-plug at the pore-throat, and the formation damage will be
induced. However, an approximately 15% reduction in permeability damage ratio could be realized
in the weak base (Na2CO3) ASP flooding instead of strong base (NaOH) system.

Acknowledgements
This work presented in this paper was financially supported by the National Natural Science Funds for
Young Scholars of China (Grant no. 51604079) and the Natural Science Foundation of Heilongjiang
Province (Grant no. E2017012). The Natural Science Foundation of Heilongjiang Province (Grant no.
E2016015) and the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang
Province (Grant no. UNPYSCT-2016126) are also gratefully acknowledged.

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