SPE-211905-MS

Dynamic Adsorption of Enzyme on Sand Surfaces- An Experimental Study

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Tinuola Udoh and Utibeabasi Benson, Akwa Ibom State University, Akwa Ibom State, Nigeria.

Copyright 2022, Society of Petroleum Engineers DOI 10.2118/211905-MS

This paper was prepared for presentation at the SPE Nigeria Annual International Conference and Exhibition held in Lagos, Nigeria 1 - 3 August 2022.

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
Enzyme can reduce interfacial tension between oil and water thereby mobilising more oil than would
originally be produced but its adsorption on the porous rock surfaces reduces its efficiency. This study
presents experimental investigation of dynamic adsorption of enzyme on sand surfaces. The experiment
was carried out at varied brine salinities and enzyme concentrations on different sand grain sizes. The
concentration depletion method that accounts for the difference in enzyme concentrations in solution before
and after its contact with the sand was used to determine the enzyme adsorption on relevant surfaces.
The effluent sample from the adsorption process was collected after every three minutes until equilibrium
was reached and the final concentration of the enzyme in the effluent solutions was measured and used
to determine its adsorbed concentration on the sand surfaces. The results of this study show that increase
in concentration of enzyme results in increase in its adsorption on sand surfaces. Also, increase in brine
salinity increased enzyme adsorption on the sand surfaces but increase in sand grain size however reduced
its adsorption. The result of this study is relevant in the design of enzyme enhanced oil recovery process.
Keywords: enzyme, dynamic adsorption, grain size, salinity and, enanced oil recovery

Introduction
Enzymes are a specific group of proteins that are synthesized by living cells to work as catalysts for the
many thousands of biochemical reactions [1]. In enhanced oil recovery (EOR) process, enzyme flooding
has gained relevance due to its ability to lower interfacial tension between oil and water thereby mobilizing
more oil to the production wells [2, 3]. The enzyme EOR process has a great potential of maximizing oil
recovery factor of existing reservoir rocks, where a significant volume of the unrecovered oil is targeted
after the conventional method, its adsorption rate may however reduce its efficiency [4, 5, 6]. Adsorption is a
dynamic process that involves an interaction between the adsorbed substance (adsorbate) and the substance
on which adsorption takes place (adsorbent). Adsorption may result from physisorption or chemisorption
process. The difference between them is usually based on their temperature dependence. In physisorption
process, adsorption reduces generally with increase in temperature while chemisorption adsorption process,
adsorption increases with temperature [7].
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From literatures, two methods are generally used to determine the adsorption of different adsorbates
on solid surfaces. These methods are static and dynamic adsorption processes. The static method allows
adsorbate solution to reach equilibrium with crushed solid surfaces over a period. In the case of dynamic
process, the solid grains packed in a column are flooded with adsorbate solution and the effluent
concentration of the adsorbate at different cumulative injected volumes is determined [8]. A few studies have
been conducted on static adsorption of enzyme, but little or no studies on dynamic adsorption of enzyme are
available. For example, Udoh [9] investigated static adsorption of rhamnolipid and greenzyme on carbonate

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and sandstone rock surfaces and observed strong affinity of rhamnolipid for sandstone surfaces while
greenzyme adsorbed more carbonate surfaces. Also, in the study conducted by Udoh and Ekanem [10] on
static adsorption of greenzyme on sand surfaces of different grain sizes at varied temperatures, their results
showed that the adsorption of greenzyme on sand surfaces increases with increase in its concentrations and
decrease in sand particles but reduces with increase in temperature.
Furthermore, salinity of the brine also plays an important role in the adsorption of enzyme. According to
Udoh [9], increase in salinity leads to increase in enzyme adsorption on the porous rock surfaces (carbonate
and sandstone). Also, small grain size rock surfaces exhibit high adsorption efficiency because of their large
surface areas available for adsorption [10]. Hence, the aim of this study is to experimentally investigate the
dynamic adsorption of enzyme on different sand surfaces in different brine salinities relevant to hydrocarbon
reservoirs. The concentration depletion method which involves comparison of concentrations of enzyme
in aqueous solutions before and after their dynamic contacts with sand surfaces was used to determine the
enzyme equilibrium concentration from effluent analyses.

Material and method

Materials and sample preparation
Brine. The brines used in this study were prepared based on the composition of the formation brine of the
reservoir used as case study. The formation brine has salinity of 32g/L with the compositional breakdown
of 98.2% sodium chloride, 0.6% calcium chloride, 0.8% magnesium carbonate, 0.2% potassium chloride
and 0.2% sodium sulphate. The salts were dissolved in distilled water and three brine salinities (10%, 50%
and 100%) were used during this experiment. The 100% salinity is the formation brine, while the 50% and
10% brines are fifty and ninety percent diluted formation brine. The details of the compositional breakdown
of the brines are presented in Table 1.

Table 1—The brine compositional breakdown.

Components 100% Brine (g/L) 50% Brine (g/L) 10% Brine (g/L)

NaCl 31.4240 15.712 3.1424

CaCl2 0.1920 0.0960 0.0192
MgCO3 0.2560 0.1280 0.0256
KCl 0.0320 0.0320 0.0064
Na2SO4 0.0320 0.0320 0.0064

Enzyme. The enzyme used in this study is a commercial enzyme with 100% concentration supplied by the
Biotech Processing Supply, Dallas, Texas. Four different concentrations of the enzyme solutions (1-, 3-, 5-
and 10 wt. %) were prepared with distilled water and saline solutions and used in this study.
Dynamic adsorption. The experimental variables investigated in this study are salinity, grain size and
enzyme concentration variations based on the concentration depletion method [8]. This method involves
comparison of enzyme concentrations in the aqueous solutions before and after their dynamic contacts
SPE-211905-MS 3

with different sand surfaces. The experiment was carried out with different enzyme concentrations, brine
salinities and sand grain sizes. The sand grains used this experiment were gotten from a river in Akwa
Ibom state, Nigeria. Prior to the test, the sand grains were sorted into three sizes (0.424, 0.85 and 1.70 mm)
with the aid of orbital mechanical shaker. 150 g of each grains size was then cleaned with methanol and
distilled water, to remove dirt and impurities from the sand. Thereafter, the sand grains were dried in the
oven at 70 °C for a period of 24 hours. After cooling, the different grain sizes were loaded into the sand-pack
columns that were used for the dynamic adsorption tests. Fixed mass of sand (32.6 g) was measured and

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packed continuously into the sand pack column after a mesh of 0.30 mm size was placed in the column to
prevent grain migration during flooding. The relevant fluids (distilled water and brines) were first injected
through the sand pack to ensure saturation of the porous system. Thereafter, the enzyme solutions were
injected through the system and the effluents from the flooding were collected periodically for analysis.
The conductivity method was used to determine the concentrations of enzyme in all the effluents based on
the measured conductivities of enzyme-aqueous solutions and their relevant concentrations before flooding.
The effluents from each flooding were collected and their conductivity was measured every three minutes
untill an equilibrium concentration (i.e., the point at which the concentration of effluents did not change
with time) was reached. The final concentrations of enzyme were determined from effluents measured
conductivity using Equation 1:
(1)
The dynamic adsorption of the enzyme on sand surfaces was calculated using Equation 2:

(2)

where A0 and A1 are the initial and final conductivity of enzyme solutions before and after flooding,
respectively (μS/cm), q is the enzyme adsorption on sand surface (mg/g), C0 is the primary enzyme
concentration before adsorption (wt.%), V is the total volume of injected enzyme solution until the effluent
concentrations reached equilibrium (mL), C1 is the effluent enzyme concentration (wt.%), V1 is the volume
of every collected effluent sample (mL), m is the mass of the sand in the pack column (g) and n is the total
number of the effluent samples collected until equilibrium was attained. This procedure was repeated for
different enzyme concentrations and brine salinities on the three grain sizes.

Results and discussion

Figure 1 shows the effect of variation in the concentrations of enzyme on its adsorption on different grain
sizes. A general increase in the adsorption of enzyme was observed with increase in its concentration in all
the solution irrespective of the different grain sizes. For instance, increase in enzyme concentrations from
1 wt.% to 10 wt.% on 0.424 mm grain size resulted in increase in adsorption from 0.03 mg/g to 1.61 mg/
g. For 0.85 mm grain size, increase in concentrations from 1 wt.% to 10 wt.% also gave a corresponding
increase in adsorption density from 0.02 mg/g to 1.29 mg/g. Finally, for 1.70 mm grain size, similar trend
was observed with increase in concentrations from 1 wt.% to 10 wt.% that resulted in increase in adsorption
density from 0.01 mg/g to 0.95 mg/g. The observed increased in enzyme adsorption with increase in its
concentrations is related its molecular interactions on the sand surfaces. At low concentration, a spontaneous
adsorption of enzyme occurs, but as the concentration increases, lateral interactions between the adsorbed
and bulk molecules takes place until equilibrium is reached, and the adsorption density plateaus [9]. The
maximum adsorption is attained when the equilibrium is reached, and the adsorption density becomes
relatively constant.
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Figure 1—The effect of varied enzyme concentrations on its adsorption on different grain sizes.

Also, the effect of sand grain size variation on enzyme adsorption can be seen in Figure 1. Generally, the
adsorption of enzyme on the different grain sizes increases with increase in the concentration of enzyme until
all the surfaces were covered and equilibrium condition was attained. This is evidenced by the plateaued
adsorption density that remain constant with increase in enzyme concentration in the aqueous solution.
The highest adsorption density of 1.59 mg/g was however observed with the smallest size grains (0.424
mm), while the lowest adsorption of 0.97 mg/g was observed with the biggest size grains (1.70 mm) and
an intermediate adsorption of 1.27 mg/g was observed with medium size grains (0.85 mm). That is, the
adsorption of enzyme on sand surfaces decreases with increase in grain sizes. This is consistent with the
results of the previous study by Udoh and Ekanem [10] on static adsorption of greenzyme on sand surfaces
in which decrease in adsorption was observed with increase in the sand grain sizes. This was attributable
to availability of more adsorption site on smaller grains than the bigger grains. The observed enzyme
adsorption in this study is however higher than their study due to variance in the quantity of sand grains
available for adsorption. This shows that irrespective of the adsorption method (static or dynamic) used, the
enzyme adsorption reduces with increase in the grain sizes.
The results of the combined effect of grain size and salinity on enzyme adsorption are presented in
Figure 2. Generally, a decrease in adsorption of enzyme was observed with increase in the size of the grains
respective of the brine salinity being used. For the 10% salinity, increase in grain size from 0.424mm to
0.85mm and 1.70mm led to reduction of the adsorption of enzyme from 1.15 mg/g to 1.01 mg/g and 0.96
mg/g, respectively. Also, the use of the 50% salinity brine resulted in reduction of adsorption of enzyme
from 1.31 mg/g to 1.25 mg/g and 1.18 mg/g on grain sizes 0.424 mm, 0.85 mm and 1.70 mm, respectively.
Finally, the use of 100% salinity gave a corresponding decrease in adsorption of enzyme from 2.58 mg/
g to1.52 mg/g and 1.41 mg/g on grain sizes 0.424 mm, 0.85 mm and 1.70 mm, respectively. This further
shows that, the smaller the grain size, the more the adsorption of enzyme on the surfaces due to increased
surface areas. This result is consistent with previous study on static enzyme adsorption on different sand
grains in which higher adsorption was observed on small grain size [10].
SPE-211905-MS 5

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Figure 2—The effect of combined salinity variation and grain size difference on
enzyme adsorption in (a) 10% salinity, (b) 50% salinity and 100% salinity brines.

The brine salinity plays a fundamental role in the adsorption of enzyme. Previous study [9] showed that
increase in brine salinity can lead to increase in adsorption of enzyme on the porous rock surfaces. Figure 3
shows the results of the effect of brine salinity on the adsorption of enzyme on different grain sizes. Increase
in adsorption was observed with increase in salinity and reduction in grain sizes. Figure 3a shows the effect
salinity on the adsorption of enzyme on 0.424 mm grain size. Increase in salinity from 10% to 50% and
100% resulted in a corresponding increase in adsorption of enzyme from 1.15 mg/g to 1.31 mg/g and 1.58
mg/g. Figures 3b and 3c show the effect of salinity on adsorption of enzyme on the 0.85 mm and 1.70
mm grain sizes. It was observed that increase in salinity from 10% to 50% and 100% also increased the
adsorption of enzyme from 1.01 mg/g to 1.25 mg/g and 1.52 mg/g, respectively for 0.85 mm grain size and
from 0.96 mg/g to 1.18 mg/g and 1.41 mg/g, respectively for 1.70 mm grain size. This shows that lower
adsorption of enzyme will be achieved in low salinity brine than high salinity formation brine and emzyme
adsorption decreases with increase in grain size irrespective of the brine salinity.
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Figure 3—The effect of brine salinity on enzyme adsorption on grain size (a) 0.424 mm (b) 0.85 mm and (c) 1.70 mm.

Conclusion
Dynamic adsorption of enzyme on three different grain sizes (0.424 mm, 0.85 mm and 1.70 mm) was
systematically investigated with varied brine salinities and enzyme concentrations. The results show that
increase in the concentrations of enzyme and brine salinity resulted in increase in adsorption of enzyme on
the sand surfaces irrespective of the grain size. The reverse was however the case with the grain sizes, as
increase in grain size resulted in decrease in adsorption of enzyme on the sand surfaces.

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