Development of retarder acid system for oil field
reservoir
Nitish Kumar Choudhary, Parth Sharma
University of Petroleum and Energy Studies
Abstract
In this paper we will build up an acid retarder
system in sandstone and additionally in
limestone reservoir. We will utilize mud acid
(12%HCl and 3% HF) for sandstone supply and
15% HCl arrangement in Limestone reservoir.
We will utilize Xanthum polymer as a retarder,
the polymer ought to be blended in a less extent
with the acid solutions. The retarding agent has a
purpose to increase the reaction time with the
formations. The expanded reaction time between
polymeric acid solutions and the formations
significantly increases the length of the fractures
and too increment the penetration depth in the
formations.
We will utilize the polymeric mud acidic
solution and check its viscosity, compatibility
and solubility in the sandstone reservoir and now
we take after a similar technique for limestone
reservoir. For limestone reservoir we will utilize
polymeric 15% HCl acidic solution to check
viscosity, compatibility and solubility.
To start with we will check the viscosity of the
polymeric based mud acid solution, if the
viscosity of the solution remains relatively
consistent with time at the room temperature. It
demonstrates that our polymer isn't debasing
with the time. Than we will check the viscosity
of the polymeric based 15% HCl arrangement.
After that point we will check the compatibility
of the polymeric based solution with the added
substances/additives utilized as a part of Matrix
acidizing (Acetic acid, citrus acid, Acid
corrosion inhibitor and surfactant). It ought not
form any precipitate with these added substances
demonstrates that polymeric based arrangements
is perfect with these added substances.
Then, we will check the solubility of the
sandstone and limestone in polymeric based
acidic solution. Take fine powder of sandstone
and break down in both plain HCl solution and
Polymeric based mud acid solution. Also, now
take fine powder of limestone test and
disintegrate in both plain HCl solution and in
polymeric based 15% HCl solution.
The dissolvability of the both samples
(sandstone and limestone) in polymeric based
acidic solution ought to be not as much as the
solvency in plain HCl solution with the time
demonstrates that Xanthum polymer increment
the reaction time or we can state it act as a
retarder.
INTRODUCTION
Matrix stimulation is a technique that has been
utilized broadly since the 1930s to enhance
production from oil and gas wells and to
enhance injection into injection wells. Matrix
astimulation is proficient by injecting a fluid
(e.g., acid or solvent) to dissolve and/or disperse
materials that impair well production in
sandstones or to make new, unimpaired flow
channels between the wellbore and a carbonate
formation.
In Matrix Stimulation, fluids are infused below
the fracturing pressure of the formation
(McLeod, 1984). It is assessed that matrix
treatments constitute 75% to 80% of all
stimulation treatments (matrix and fracturing)
around the world; however the aggregate
expenditure for matrix treatments is just 20% to
25% of the aggregate for all stimulation
treatments. In any case, in light of the fact that
the payout time for matrix treatments is
normally days as opposed to a long time
(months) as it is for conventional fracturing
treatments. Numerous operators around the
globe have demonstrated that a normal of 40%
to 50% of their wells have significant damage,
yet routinely just 1% to 2% of their wells are
treated every year. Considerable production
upgrades can be accomplished with matrix
stimulation, if treatments are designed
 Development of retarder acid system for oil field
reservoir
Nitish Kumar Choudhary, Parth Sharma
University of Petroleum and Energy Studies
appropriately. A success rate greater than 90% is
reasonable.
Acidization is a method of injecting acids and
chemicals in the reservoir to reduce damage near
the well bore for enhancing
productivity/injectivity. Inorganic, organic and
blend of these acids alongside surfactants are
used as in variety of well stimulation treatments.
The two basic types of acidizing are
characterized through injection rate and
pressures. Injection rates below fracture pressure
are named matrix acidizing while those above
fracture pressure are named as fracture
acidizing.
Matrix acidizing is primarily applied to remove
near well bore damage caused by
drilling/completion/work over fluids or injection
fluids and by precipitation of scale deposits from
produced or injected water. The objective of
matrix acidizing is to achieve radial acid
penetration in to the formation for removal of
effects of permeability decrease near well bore.
The goal of an acid treatment is to react with the
formation rock and/or pore plugging materials to
form suitable salts that can be produced to the
surface, or displaced into the pore system some
distance away from the well bore - hence giving
broadened or more open flow channels.
Basic acids utilized as a part of different blends
are Hydrochloric Acid, Hydrochloric +
Hydrofluoric Acid, Formic Acid and to lesser
degree Fluoboric Acid and Sulfonic Acid.
Typically, 15 % HCl acid for carbonate
reservoirs and 12 % HCl and 3 % HF corrosive
for sandstone reservoirs is used in wells.
Acid Fracturing can enhance the productivity or
injectivity of the reservoir significantly relying
upon the length of the etched fractures into the
formation. In this regard the objective of the
petroleum engineer is to increase the penetration
depth and the propagation of the fractures by
slowing and controlling the reaction between the
acid solution and the formation. Therefore,
special endeavors are required in order to
achieve deep penetration depth into the
formation before the acid spends. For more
penetration and expanded fractures we require
more reaction time, so we require some
retarding agent which is given by Xanthum
polymer based acid solution.
Meanwhile acid additives are utilized to
overcome the damages created by acidization.
Acid may discharge fines, make precipitants,
form emulsions, create sludge and corrode steel.
Additives are available to rectify these and
number of other problems. Each acid additive
use serves a particular need. However, where
several acid additives are used they should be
painstakingly checked under recreated treatment
conditions to ensure that one additive does not
react with another. Some of the generally used
additives are:-
Corrosion Inhibitor
Corrosion inhibitors are used to prevent metallic
corrosion from occurring and work through
formation of a defensive/protective layer on the
metallic surface. Factors that represent acid
attack on steel will be; steel type and hardness,
temperature, acid compose, acid concentration
and acid contact time.
Surfactant
Surfactants are used to change surface and
interfacial tensions, prevent emulsions, and
water-wet rock and fines near the well bore. The
use of surfactants in acid assists in faster flow-
back of spent acid after acid treatment thereby
improving the chances of early well activation.
Non-Emulsifier
The non-emulsifier contains water-soluble
polymer that is temperature sensitive that helps
to lower surface tension and prevent damage.
Anti-Sludge Agent
 Development of retarder acid system for oil field
reservoir
Nitish Kumar Choudhary, Parth Sharma
University of Petroleum and Energy Studies
“Sludge” is a precipitate resulting from
reaction of high strength acid with crude. The
sludge formation can hamper cleaning of the
well and flow performance
Iron Controller
In order to prevent precipitation of iron, iron
controllers are used in the acid that control iron
precipitation either through chelating (iron
chemically bound) or sequestering (iron held in
solution).
Mutual Solvent
The mutual solvent is used to reduce
water saturation near the well bore, maintain
water wet formation, water wet
insolubleformation fines and help reduce the
absorption of surfactants and inhibitors on the
formation
Diverting Agent
The diverting agent plays a major role in
selective acidization of a particular layer. The
diverting agent blocks the permeable layer and
allows the acid to enter the intended zone and
get stimulated.
Clay Stabilizer
Certain clay compounds can be treated
with acid but result in undesirable reactions
during acidization like swelling and creation of
water blocks that hamper the stimulation job
efficiency. Clay stabilizers are used to keep the
clays and fines in suspension.
Fluid Loss Control Agents
Helps in extending fractures in fracture
acidizing by reducing acid leak off into the
formation.
EXPERIMENTAL PROCEDURES
We will perform three trials of the prepared
polymeric based acidic solution.
 In the first place we will check viscosity
of the polymeric based acidic solution.
 Second we will check the solubility of
the sandstone in polymeric mud
acidbased solution and solubility of
Limestone in 15% HCl based polymeric
solution.
(We cannot take mud acid solution to test
limestone sample as it form precipitate CaF2
(calcium bifluoride) which will further damage
the formation.)
 Third we will check the
compatibility of acid additives in
polymeric based acidic solution.
 Viscosity
We will prepare two solutions to check viscosity
First solution:-
First we have to prepare 200ml solution of
mud acid having composition of 12% HCl and
3% HF, for that we will take 9.428 grams of
ammonium bifluroide (NH4HF2) in 200 ml of
15% HCl solution in a plastic beaker. We cannot
place HF acid solution in glass beaker as it is
highly reactive towards glass. Then we take 3%
of Xanthum polymer and place the mud acid
solution on magnetic stirrer and now add
Xanthum polymer very slowly to mud acid
solution otherwise it will not mix properly and
lumps will form. Stir it properly for 2 hours. We
have now prepared our first solution
Second solution:-
We will take 200 ml solution of 15% HCl
in a glass beaker. Then we will take 3% of
Xanthum polymer, now place the 15% HCl
solution on magnetic stirrer and slowly add
Xanthum polymer. After stirring for 2 hours take
out the solution.
Now we will check the viscosity of our
 Development of retarder acid system for oil field
reservoir
Nitish Kumar Choudhary, Parth Sharma
University of Petroleum and Energy Studies
prepared solution at different intervals at room Viscosity of second solution
temperature.

Viscosity of first solution (measured in Time Viscosity(at

Fannviscometer) 511sec-1or 30 rpm)

We will take the readings just after stirring 0 minutes 9 cp

TIME Viscosity(at 511 sec-1 30 minutes 9 cp

or 30 rpm)
0 minutes 10 cp 60 minutes 9 cp

30 minutes 10 cp
90 minutes 9.5 cp
60 minutes 10.5 cp
90 minutes 10.5 cp 120 minutes 9.5 cp
Table 2
120 minutes 10.5 cp
150 minutes 11 cp
Table 1
Viscosity(at 511 sec-1 or
30 rpm)
Viscosity(at 511 sec-1 9.6

or 30 rpm) 9.5
9.6
9.4
9.5
9.3
9.4 Viscosity(at
511 sec-1 or
9.2
30 rpm)
9.3
Viscosity(at
9.1
511 sec-1 or
9.2 30 rpm)
9
9.1
8.9
9 0 50 100 150

Graph 2
8.9
0 50 100 150

Graph 1
 Development of retarder acid system for oil field
reservoir
Nitish Kumar Choudhary, Parth Sharma
University of Petroleum and Energy Studies
 Solubility
1. Check solubility for Sandstone Sample
Take core sample of sandstone, grind it and
make fine powder. Take 5 grams of sandstone
sample.Now we will take one 100 ml sample of
plain HCl and other 100 ml solution of
polymeric mud acid based solution.
Now we will dissolve sandstone sample in both
HCl solution and polymeric solution and warm
it for 30 minutes at 60 degree Celsius.
1.1 Check solubility of sandstone sample after
1 hour using vacuum pump
Solubility in plain HCl solution
Now pour the solution in vacuum pump and
filter it out and dry the sample in oven for 10
minutes.
Weight of filter paper= 0.79 grams
Weight of sample taken= 5 grams
Weight of dried sample= 4.929 grams
Sample dissolved = (weight of sample
taken+weight of filter paper-weight of dried
sample)
Sample dissolved= (5+ 0.79-4.929)
=0.861 grams
Solubility= (weight of sample dissolved/
weight of sample taken)*100
Solubility= (0.861/5)*100
=17.22%
1.2 Check solubility of sandstone sample after
1 hour using vacuum pump
Solubility in polymeric mud acid solution
Now pour the solution in vacuum pump and
filter it out and dry the sample in oven for 10
minutes.
Weight of filter paper=0.825 grams
Weight of sample taken= 5 grams
Weight of dried sample= 5.2 grams
Sample dissolved = (weight of sample taken+
weight of filter paper-weight of dried
sample)
Sample dissolved= (5+ 0.825-5.2)
=0.625gms
Solubility= (weight of sample dissolved/
weight of sample taken)*100
Solubility= (0.625/5)*100
= 12.5%
Check solubility After 3 hours
1.3 Check solubility of sandstone sample after
3 hour using vacuum pump
Solubility in 100 ml plain HClsolution
Now pour the solution in vacuumpump and filter
it out and dry the sample in oven for 10 minutes.
Weight of filter paper=0.79 grams
Weight of sample taken= 5 grams
Weight of dried sample= 4.2 grams
Sample dissolved =(weight of sample taken+
weight of filter paper-weight of dried
sample)
Sample dissolved= (5+ 0.79-4.2)
=1.59 grams
Solubility= (weight of sample dissolved/
weight of sample taken)*100
Solubility= (1.59/5)*100
= 31.8%
1.4 Check solubility of sandstone sample after
3 hour using vacuum pump
Solubility in polymeric mud acid solution
Now pour the solution in vacuumpump and filter
it out and dry the sample in oven for 10 minutes.
Weight of filter paper=0.825 grams
Weight of sample taken= 5 grams
Weight of dried sample= 4.6 grams
Sample dissolved = (weight of sample taken+
weight of filter paper-weight of dried
sample)
Sample dissolved= (5+ 0.825-4.6)
=1.225 grams
 Development of retarder acid system for oil field
reservoir
Nitish Kumar Choudhary, Parth Sharma
University of Petroleum and Energy Studies
Solubility= (weight of sample dissolved/ weight of filter paper-weight of dried
weight of sample taken)*100 sample)
Solubility= (1.225/5)*100 Sample dissolved= (5+ 0.825-5.05)
= 24.5% =0.775 grams

2. Check solubility for Limestone sample Solubility=(weight of sample dissolved/

Take core sample of limestone, grind it and weight of sample taken)*100
make fine powder. =(0.775/5)*100= 15.5%
Take 5 grams of sandstone sample.
Now we will take one 100 ml sample of plain Check solubility After 3 hours
HCl and other 100 ml solution polymeric 15%
HCl based solution. 2.3 Solubility in 100 ml plain HCl solution
Now we will dissolve sandstone sample in both Now pour the solution in vacuum pump and
HCl solution and polymeric solution and warm filter it out and dry the sample in oven for 10
it for 30 minutes at 60 degree Celsius. mins.
Weight of filter paper=0.79 grams
Check solubility after 1 hour Weight of sample taken= 5 grams
Weight of dried sample= 4.4 grams
2.1 Solubility in 100 ml plain HClsolution
Now pour the solution in vacuum pump and
Sample dissolved = (weight of sample taken+
filter it out and dry the sample in oven for 10
weight of filter paper- weight of dried sample)
minutes.
Sample dissolved= (5+ 0.79-4.1)
Weight of filter paper=0.79 grams
=1.69 grams
Weight of sample taken= 5 grams
Weight of dried sample= 4.4 grams
Solubility=(weight of sample dissolved/
weight of sample taken)*100
Sample dissolved = (weight of sample taken+
Solubility=(1.69/5)*100
weight of filter paper-weight of dried
= 33.8%
sample)
Sample dissolved= (5+ 0.79-4.8)
2.42Solubility in polymeric 15% HCl based
=0.99 grams
solution
Solubility=(weight of sample dissolved/
Now pour the solution in vacuum pump and
weight of sample taken)*100
filter it out and dry the sample in oven for 10
Solubility=(0.99/5)*100
minutes.
= 19.8%
Weight of filter paper=0.825 grams
Weight of sample taken= 5 grams
2.2Solubility in polymeric 15%HCl based
Weight of dried sample= 5.05grams
solution
Sample dissolved = (weight of sample taken+
weight of filter paper-weight of dried sample)
Now pour the solution in vacuum pump and
Sample dissolved= (5+ 0.825-4.55)
filter it out and dry the sample in oven for 10
=1.275grams
minutes.
Weight of filter paper=0.825 grams
Weight of sample taken= 5 grams
Solubility=(weight of sample dissolved/
Weight of dried sample= 5.grams
weight of sample taken)*100
Solubility=(1.275/5)*100
Sample dissolved =(weight of sample taken+
= 25.5%
 Development of retarder acid system for oil field
reservoir
Nitish Kumar Choudhary, Parth Sharma
University of Petroleum and Energy Studies
in the ratio of 1%, acid corrosion inhibitor in
COMPATIBILITY ratio of 1%, citric acid in a ratio of 2%and acetic
acid in a ratio of 2% turn by turn with the
"Additives" can be used to help the penetration solution and heat it and check whether it is
of the liquid or to perform other essential tasks. forming any precipitation or not.
To empower the reactive fluid to be pumped
from the surface through the tubing and into the
formation, corrosion inhibitors for the most part Chemical additives Precipitation
will be required to shield the metal from attack formation
by the fluid itself. Surfactants, solvents, iron
control agents, non-emulsifiers and a few
different sorts of agents likewise might be
available. Normally we have seen that these Surfactant No
additives are compatible with the normal acidic
solution we are using as a part of Acidization
process.
Now we will check whether the chemical Acid corrosion inhibitor Yes
additives, for example, surfactant, citric acid,
acid corrosion inhibitor and acetic acid are
compatible (they should not form any
precipitate) with the polymeric acid based Citric acid No
solution.
No
For Polymeric mud acid based solution Acetic acid
First we take 10 ml of polymeric mud acid based Table 4
solution in a test tube and add surfactant in the
ratio of 1%, acid corrosion inhibitor in ratio of Results and discussions
1%, citric acid in a ratio of 2%and acetic acid in
a ratio of 2% turn by turn with the solution and Viscosity Measurements
heat it and check whether it is forming any
precipitation or not. From both the tables we can easily see that the
viscosity remains constant with the lapse of
time. If the viscosity gets lower with the time
Chemical additives Precipitation then it means that our polymer is getting
formation degraded and we cannot use it in wellbore.

Solubility Measurements
Surfactant No
After analyzing all the results for solubility of
Acid corrosion inhibitor Yes sandstone sample we have concluded that the
solubility of the sandstone sample in polymeric
mud acid based solution is less than the
Citric acid No solubility of sandstone sample in plain HCl
solution with increase in time. Thus we can say
No our Xanthum polymer act as a retarding agent in
Acetic acid acidic solution and increases the reaction time.
Table 3
For Polymeric 15% HCl based solution Compatibility Measurements
First we take 10 ml of polymeric 15 % HCl From both the tables, we can easily see that
based solution in a test tube and add surfactant polymeric based solution is not compatible or
 Development of retarder acid system for oil field
reservoir
Nitish Kumar Choudhary, Parth Sharma
University of Petroleum and Energy Studies
forming precipitate with Acid corrosion
inhibitor. Later we have checked at higher
temperatures (approx. 80 degree Celsius), that
no precipitation takes place with acid corrosion
inhibitor.
Conclusions and Recommendations
Our ultimate aim of this research is to develop
an acid retarder system in oil reservoirs. For
this purpose we have selected the polymer
(xanthan) mixed with acidic solution to act as a
retarding agent to increase reaction time.
Increased reaction time helped in creating
large penetration depth in the formation.
1. The viscosity of the polymer-acid
solution is remaining almost constant
at the same room temperature.
2. We can vary the ratio of our polymer
in Xanthan in acidic solution to get
desired Viscosity according to the
requirement of the formation.
3. Solubility of core samples in
polymeric based acidic solution is less
than the solubility in plain HCl
solution. Thus we have established a
retarding system in oil reservoir.
4. We have also noticed that the
solubility of limestone in polymeric
acid based solution compared to
sandstone sample.
5. Surfactant, acetic acid, citric acid is
compatible with polymeric solution at
room temperature whereas Acid
corrosion inhibitor is compatible at
higher Temperatures.
Acknowledgments
The authors would like to express their
appreciation and thanks to the Well stimulation
Department of ONGC Ahmadabad who
allowed us to perform our Experiments at their
laboratory and University of petroleum and
Energy studies for their support and
cooperation.
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reservoir
Nitish Kumar Choudhary, Parth Sharma
University of Petroleum and Energy Studies
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