SPE 117366

Hydrochloric Acid Fracturing Combined with Water Shut-Off

L.A.Magadova, M.A.Silin, V.B.Gubanov, V.N.Marinenko, V.R.Magadov (Russian State University of Oil and Gas
named after I.M. Gubkin, N.A.Demianenko (BelNIPIneft, RUE Production Association Belorusneft)
Copyright 2008, Society of Petroleum Engineers
This paper was prepared for presentation at the 2008 SPE Russian Oil & Gas Technical Conference and Exhibition held in Moscow, Russia, 2830 October 2008.
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 of the paper have not
been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum
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Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE
copyright.

Institute of oilfield chemistry under Russian State University of oil and gas named after
I.M. Gubkin in cooperation with BelNIPIneft, RUE Production Association
Belorusneft have developed the technology of formation hydrochloric acid hydraulic
fracturing combined with water shut-off in producing wells, exposing carbonate reservoirs.
It is known that during interaction of hydrochloric acid solutions and oil, containing big
quantity of tars and asphaltenes sludging and formation of emulsions colmataging porous space
of reservoir take place.
In our work we have used the ability of generating such compounds when hydrochloric
acid contacts hydrocarbon gel, composed using gelling complex Khimeco-H based on ferric
salts of organic orthophosphoric ethers and stock (commercial) oil.
Hydrocarbon gels based on ferric salts of organic orthophosphoric ethers are obtained by
dissoluting in hydrocarbon fluids gelling agent (mixture of alkylphosphoric ethers, mainly
diakylphosphoric ethers) and activator based on ferrous compounds. As a result of interaction
between gelling agent and activator we ontain ferric salts of organic orthophosphoric ethers
which in their turn create associated complexes of molecular weight in hydrocarbons.
Associated complexes explain formation of hydrocarbon gel used in hydraulic fracturing.
Below you see the mechanism of hydrocarbon gel formation:
1. Gelling agent +activator = ferric salts of organic orthophosphoric ethers:
O
||
[R1O - P - O]b(OH)a , where: a= 0-2;
|
b= 1-3;
a+b=3;
R2O
where R1, R2 different hydrocarbon radicals, in the capacity of one of them could be
hydrogen;
ferrum atom.
2. Formation of associated complex while dissoluting the salts obtained (figure 1):

SPE 117366

Fig.1 Formation of associated complex while dissoluting the salts of

organic orthophosphoric ethers
As a result of interaction of hydrocarbon gel and hydrochloric acid and generation of
controlled quantity of asphaltene and tar sediments/sludges we form the layer, having selective
shutting-off impact on watersaturated interlayers.
For checking planned result we carried out filtration experiments on high-pressure and
temperature plant HP-CFS in the formation process simulation laboratory of the Institute of
oilfield chemistry under Russian State University of oil and gas named after I.M. Gubkin.
Schematic diagram of experimental plant HP-CFS is shown on figure 2.
Plant HP-CFS makes possible carrying out filtrarion experiments on sand packed tubes
of porous mediums and core samples under temperatures up to 150C and pressure up to 20,0
MPa. If necessary back pressure system, which provides maximum level of pressure 7,0 MPa
can be used. While working with core samples squeezing pressure can reach 50,0 MPa.
Main functional parts of the plant are thermostatically controlled filling formation model
and core holder for experimenting with core samples. Thereby depending on type of study its
possible to use core holder for composite cores 30 sm long (study of hydrodynamic parameters
of porous medium), or core holder for one core sample (study of compositions for acid
treatment, drilling muds, kill fluids).
Supply of operating fluids into porous medium is performed through press tubes with
separating pistons by fluid presses ISCO. From fluid presses ISCO oil is supplied into under
piston volume of press tubes. Thereby its possible to perform separate-simultaneous supply of
oil into each of press tubes, or just in one press tube with planned supply rate.
Filling the press tubes with operating fluids is carried out under vacuum after the
separating piston is in its lowermost position by gas pressure from the tank.
For injection of high-viscosity compositions, polymer or disperse systems into formation
model high pressure vessel is used. From the vessel reagent is supplied under gas pressure
from the tank or under immissible with reagent fluid from the press tube. During filtration
process pressure drops are being controlled by Gould differential manometer. Fluid filtration can
be performed under fixed flow rates up to 600 sm3/h.
Thermostating of filling model and preliminary heating of input line are performed by heat
tape winded around filling model body and input line. Heat tape is fed from the net 200V

SPE 117366

through autotransformer. The rate of temperature rise is provided by voltage control,

maintenance and control of temperature is provided by temperature sensor-controller -1,
connected to thermocouple, located on the model body.
Heating of the core sample inside the core holder to the temperature of the experiment is
provided by liquid thermostat.
During carried out filtration experiments we used hydrocarbon gel based on stock oil
(20 oil = 825 kg/m3), composition 1, also 12% and 24% inhibited hydrochloric acid with
addition of 4% of volume of multifunctional surface-active substance Neftenol (mark NK-FD),
formation water model of calcium chloride type, carbon oil and light gas oil.
Neftenol (mark NK-FD) is multifunctional surface-active substance based on
multicomponent mixture of anion and cation surface-active substances of different chemical
structure with modified polymer additives hydrochloric acid thickening agent, which is used as
an additive to hydrochloric acid while formation acid hydraulic fracturing.
Description of the experiments is given below (figures 3-4).

SPE 117366

Figure 2.

SPE 117366

Figure 2. Schematic diagram of experimental plant HP-CFS

1,2
3
4
5
6
7,8,9
10, 19
11,12
13
14
15
16
17

press tubes with separating pistons for reagent supply

fluid thermostate
formation model
back pressure system
heating element
high pressure press (IS)
vessels with oil for filling presses
gas tanks
core sampler
core holder
rubber collar
core sample
press for generation of squeezing pressure

SPE 117366

Experiment 1
Objective:
Estimation of acid treatment impact on gel cementing properties
Sample:
filling waters aturated model
filling
diameter
cross-section area
viscosity of
formation water under temperature 20
Initial model parameters:
model length
initial water permeability
porous volume
porosity

silica sand fraction

3,09
sm
7,50
sm2
1,301

MPas

62,4
18,11
163
34,8

sm
mkm2
sm3
%

Reagents under study:

1) gelling complex Khimeco-H-based hydrocarbon gel, composed on base of stock oil (20
oil = 825 kg/m3)
Volume of reagents, l/m3:
Gelling agent Khimeco-H 16,0
activator Khimeco-H18,0;
gel viscosity under temperature 20 = 68,83 MP.s under shear rate 656 s-1;
2) Carbon oil, viscosity under temperature 20 = 1,16 MP.s
3) Inhibited 12% hydrochloric acid with 4% of volume of multifunctional surface-active
substance Neftenol (mark NK-FD), viscosity under temperature 20 = 3,6 MP.s;
4) Formation water model, density 20 = 1,096 kg/m3, mineralization- 140 g/l, viscosity under
temperature 20 =1,301 MP.s.
Experimental stages:
1. Filtration through formation water model under room temperature. Determination of initial
permeability.
2. Gel injection under room temperature and different filtration rates.
3. Injection of 0,3 porous volume of 12% solution of iInhibited hydrochloric acid with addition of
4% of Neftenol (mark NK-FD) volume.
4. Injection of formation water under different filtration rates.
5. Conditioning under room temperature for 15 hours with further filtration of formation water
and determination of resistance factor R.
6. Injection in reverse direction of carbon oil to wash the model off asphalt-tarry paraffin
depositions and determination of resistance factor Rres.
7. Model conditioning for 2 days with further filtration of carbon oil and determination of final
resistance factor Rres.

SPE 117366

Experiment 2
Objective:
Estimation of acid treatment impact on gel cementing properties
Sample:
filling water saturated model
filling
diameter
cross-section area
viscosity of
formation water under temperature 20
Initial model parameters:
model length
initial water permeability
porous volume
porosity

silica sand fraction

3,09
sm
7,50
sm2
1,301
63,11
15,73
161,1
34,03

MPas
sm
mkm2
sm3
%

Reagents under study:

1) gelling complex Khimeco-H-based hydrocarbon gel, composed on base of stock oil (20
oil = 825 kg/m3)
Volume of reagents, l/m3:
Gelling agent Khimeco-H 16,0
activator Khimeco-H18,0;
gel viscosity under temperature 20 = 68,83 MP.s under shear rate 656 s-1;
2) Carbon oil, viscosity under temperature 20 = 1,16 MP.s
3) Inhibited 12% hydrochloric acid with 4% of volume of multifunctional surface-active
substance Neftenol (mark NK-FD), viscosity under temperature 20 = 3,6 MP.s;
4) Formation water model, density 20 = 1,096 kg/m3, mineralization- 140 g/l, viscosity under
temperature 20 =1,301 MP.s.
:
1. Filtration through formation water model under room temperature. Determination of initial
permeability.
2. Gel injection under room temperature and different filtration rates.
3. Injection of 0,3 porous volume of 12% solution of iInhibited hydrochloric acid with addition of
4% of Neftenol (mark NK-FD) volume.
4. Injection of formation water under different filtration rates.
5. Conditioning under room temperature 15 hours with further filtration of formation water and
determination of resistance factor R.
6. Injection in reverse direction of carbon oil to wash the model off asphalt-tarry paraffin
depositions and determination of resistance factor Rres.

SPE 117366

Studies showed, that while injecting gel decrease of permeability of porous medium
sample due to high viscosity of gel takes place, but even higher decrease of permeability takes
place during further acid injection due to sludging of asphalt-tarry paraffin depositions, whilst the
highest decrease is reached by using higher concentration of acid. So, while injecting 12% acid
residual resistance factor made up 17,63; and while injecting 24% acid residual resistance
factor made up 93,88. Necessary to mention that during first contact with acid resistance factor
grows much higher. Decrease of permeability due to sludging of asphalt-tarry paraffin
depositions takes place, and in case acid volume increases permeability increases, which is
explained possibly by the impact of surface-active substances in acid formulation while
formation water injection has practically no impact on resistance factor (see experiment 1,
fig.3).
Carbon oil injection in reverse direction with further conditioning significantly decreases
resistance factor to 5,74 and 9,39 for 12% and 24% acid respectively, and during light gasoil
injection-to 2,2 (experiment 2 fig.4).
For purity of experiment filtration studies were carried out using porous medium,
simulating the conditions of terrigenous reservoir for eliminating negative influence of carbonate
reservoir and hydrochloric acid interaction.
The idea of using hydrocarbon gel for hydrochloric acid fracturing with water shutt-off is
in formation of hydrocarbon-dissoluble sludges of asphaltenes and tars during interaction of
hydrocarbon gel and hydrochloric acid in the process of by-turn injection of hydrocarbon gel pill
and part of 12-24% hydrochloric acid, treated with 40 l/m3 of multifunctional surface-active
substance Neftenol K (mark NK-FD). This lets on one hand to create a fracture by formation
hydraulic fracturing and on the other hand selectively shut it off. Though, acid treated with
Neftenol K (mark NK-FD) in contact with pure oil doesnt sludge which is proved by carried
tests, shown in the table 1.
So, we purposefully shut-off big fractures where hydrocarbon gel comes to. Thereby
hydrocarbon sludges are dissoluted while diluting with oil, which shows selective water shut-off.

SPE 117366

Experiment 1
Experiment temperature 20 . Initial water permeability - 18,11 mkm2

FlR=80
3
sm /h
FlR=600
3
sm /h

10

FlR=400
3
sm /h

FlR=200
3
sm /h

FlR=300sm /h

FlR=600
3
sm /h

FlR=600
3
sm /h

FlR=200
3
sm /h

Rres =5,74

Conditioning
2 days

Rres=17,63

0,1

FlR=200
3
sm /h

Rres =1,00

Conditioning
15 hours

Form. water
injection

Permeability,
mkm2

FlR=600sm /h

100

Acid
injection
Form. water
injection

Gel injection

Carbon oil injection in reverse direction

0,01
0

10

15

20

25

30

35

40

Relative cumulative injection volume,Vinjec/Vpor

Fig. 3 Change in permeability of water saturated model after injection
of gel based on gelling complex "Khimeco -" and stock oil, and 12 % inhibited hydrochloric acid with addition
of Neftenol (mark NK -FD, 4% of volume ), formation water and carbon oil

Experiment 2
Experiment temperature 20 . Initial water permeability - 15,73 mkm2
100,0

Permeability, mkm

FlR=600
3
sm /h

FlR=400
3
sm /h

FlR=300 sm /h

FlR=80
3
sm /h

10,0

FlR=200
3
sm /h

FlR=200sm /h

Rres =7,11
FlR=200
3
sm /h

Rres =2,22
Rres =9,39

1,0
Acid
injection

Conditioning
15 hours

0,1

Rres =93,88
Formation water
injection

Carbon oil injection in

reverse direction

Gel injection

Light gasoil injection

0,0
0

10

12

14

16

Relative cumulative injection volume, Vinjec/Vpor

Fig. 4 Change in permeability of water saturated model after injection of gel based on gelling complex
"Khimeco- " and stock oil, and 24% inhibited hydrochloric acid
with addition of Neftenol K (mark NK-FD, 4% of volume ), formation water, carbon oil and light gasoil

10

SPE 117366

Table 1
Results of studies of interaction of acid compositions with stock oil
(20= 825 kg/m3) and formation water

1
1.
2.
3.

Studied fluid

2
Stock oil
20= 825 kg/m3
Stock oil
20= 825 kg/m3
Stock oil
20= 825 kg/m3

4.

Stock oil
20= 825 kg/m3

5.

Stock oil
20= 825 kg/m3
Stock oil
20= 825 kg/m3
Stock oil
20= 825 kg/m3

6.
7.
8.

Stock oil
20= 825 kg/m3

9.

Stock oil
20= 825 kg/m3+
formation water
Stock oil
20= 825 kg/m3+
formation water
Stock oil
20= 825 kg/m3+
formation water
Stock oil
20= 825 kg/m3+
formation water
Stock oil
20= 825 kg/m3 +
formation water
Stock oil
20= 825 kg/m3+
formation water

10.
11.
12.
13.
14.

Acid composition

HCl 24%

50

Sludging of
asphalt-tarry
paraffin
depositions
5
yes

HCl 12%

50

yes

HCl 12%
+Neftenol K
(NK-FD)
HCl 24%
+ Neftenol K
(NK-FD)
HCl 12%

50

no

50

no

90

yes

HCl 24%

90

much

HCl 12%
+ Neftenol K
(NK-FD)
HCl 24%
+ Neftenol K
(NK-FD)
HCl 12%

90

no

90

no

50

no

HCl 24%

50

much

HCl 12%
+ Neftenol K
(NK-FD)
HCl 24%
+ Neftenol K
(NK-FD)
HCl 12%

50

no

50

no

90

no

HCl 24%

90

yes

SPE 117366

1
15.
16.

11

2
Stock oil
20= 825 kg/m3+
formation water
Stock oil
20= 825
kg/m3+formation
water

3
HCl 12%
+ Neftenol K
(NK-FD)
HCl 24%
+ Neftenol K
(NK-FD)

4
90
90

Table 1 (continuation)
5
no
no

In the process of working we have created a technology of mixing hydrocarbon gel based
on gelling complex Khimeco H and stock oil, and surface-active substance-acid solution
composed of inhibited hydrochloric acid solution and Neftenol K (NK-FD) and also technology of
their injection into formation during hydrochloric acid fracturing with water shut-off by the set of
equipment of Production Assiciation Belorusneft.

Application of developed technology of hydrochloric acid fracturing with water shut-off in

greatly watered well of Berezinskoye oil field let increase fluid inflow and, at the same time,
decrease well water cut from 88,4 to 51,8%. The results are given in table 2.

12

[Paper Number]

Table 2
Efficiency of hydrochloric acid fracturing with water shut-off as of 01.06.2008
Working parameters
before hydrochloric
acid fracturing
Well
number, oil
field

Ending
date of
treatm
ent

3,
Berezinskoy
e

56,
Marmovichs
koye

Working parameters
after hydrochloric acid
fracturing

Work efficiency

Qoil,
t/d

Water
cut,
%

Producti
on rate
increase,
t/d

Increme
ntal
productio
n,
t

Note

Qfl,
t/d

Qoil,
t/d

Wate
rcut,
%

31.07.
2007

3,27

0,38

88,4

5,56

2,4

51,8

1,99

601

Effect
contin
ues

07.03.
2008

4,45

3,81

14,3

6,65

6,29

4,9

2,48

196

Effect
contin
ues

Qfl,
t/d

In total we have mixed and injected 30 m3 of hydrocarbon gel based on stock oil with
density 810 kg/m3, effective viscosity of gel under 100 rotations/minute was within 200-300
MPas, and 50 m3 of 18% hydrochloric acid, containing 4% of Neftenol K
(NK-FD) volume.
Injection was performed in stages as follows: pill of hydrocarbon gel-15 m3, pill of
hydrochloric acid-30 m3, again pill of hydrocarbon gel-15 m3, again pill of hydrochloric acid-20
m3; flushing was performed by oil-based water-oil emulsion with density 843 kg/m3 and fresh
water in proportion 1:1 using emulsifying agent Neftenol NZ-1% of volume, effective viscosity of
emulsion under 100 rotations/minute was within 60 80 MPas.
Applying this technology in a well of Marmovichskoye oilfield with lower water cut
(14,3%) the effect of water cut decrease (4,9%) was also reached.