Acidizing

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Acidizing Additives

3
)
2000 (
.

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Injectivity test

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Acidizing

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Acidizing Methods

Fracturing

Acidizing

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Washing

Acid

Matrix
Acid

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)Mud
Cake
(

) (Perforations
.

)(Emulsion

)(Water Block

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Washing

Acid

Skin components

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A: Completion geometry
Partial completionPartial penetrationSlantOff center wellB: Damage
Invasion of fluids and solidsCrushed zone in perforationC: Mechanical
Filter cakeGravel packD: Production
Non-Darcy effectClay swellingWater or gas coningE:Others
Cross flow, Heterogeneity,Hydraulic fracturing-

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.

Fracture .

)(Radial Penetration

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Acidizing

Matrix

(Frac Pressure) .
.

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Acid Fracturing

Characteristics Acids Used

HCI

9 HCI - HF

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. H COOH

.
Sulfamic Acid Chloroacetic

Hybrid Acid Mixture

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Characteristics Acids Used

Types of acids
(NIDC)

DOWELL

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HCL 28 %
HCL 15 %
HCL 5 %
Emulsified acid (50:50)
Emulsified acid (70:30)

HCL 28 %
HCL 15 %
Leak off control acid(LCA)
Self diverting acid(SDA)
Super emulsified acid (70:30)

Chemical retarded acid

DAD acid for asphaltene wells

Mud acid (12:3)

Intensified acid

Mud acid (12:3)

Intensified acid
Clay acid

2 HCI
CaCOO3.2 CaCl 2 Co 2 H 2 O
r
H = K (C ) H

Factors Affecting Acid Reactions

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Pressure

Acid Concentration

Acid Type
.

Temperature

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Area To Volume Ratio

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Porosity
)(Fissures
Compressibility

.

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Rock Charactristics

) (Productivity Index PI
.

)
(....

) (

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Sclocelion of
Acidizing Method

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Formation Damage

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)(Acid Fracture

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Physical Properties of HCL acid

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Conc. %

32

28

20

15

10

7.5

Specific
Gravity

1.16

1.14

1.1

1.075

1.05

1.04

Density, PCF 72.38

71.14

68.64

67.08

65.52

64.9

4.265

3.67

2.54

1.84

1.2

1.0

Limestone
Solubility,
lb/gal
(approx)

Acid Dilution Formula

Volume strong acid =

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Vol. Weak acid % weak acid Sp. Gr. of weak acid

_________________________________
% strong acid Sp. Gr. of weak acid

Acid Dilution Formula

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Example:
How many gallons of 32% HCL are required to
prepare 5000 gallons 15% HCL.
Solution:
Vol. of strong acid =
5000 1.075 0.15 0.32 1.16 = 2172


Acidizing Measurements

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100.09 =0.833
2 60.05


Acidizing Measurements

PA
PS

: W
A

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First Rules
.

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) (.

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Corrosion Inhibitor
Surfactant
Mutual Solvent
Anti Sludge
Emulsion Breaker/Prevent
Suspending Agent
Multi-Functional Agent
Clean up additive
Iron control agent
Acid Retarder
Cor. Inh. Intensifier
Emulsifier

www.petroman.ir

Diverting agent
Fluid Loss Control Agent
Friction Reducer
Clay Stablizer
Scale Inhibitor

9
9
9
9
9
9
9 --

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. ,

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Corrosion
inhibitor

Triphenols , nitrogen heterocyclics)

(rosin amine , acetylenic alcohols

1.
Advantages of Inorganic
Corrosion Inhibitors

1. 17%

Disadvantages of
Inorganic Corrosion
Inhibitors

2. H2S
.
3.
.

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2.

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Pitting
1. inhibitor
2. inhibitor

1.

Inhibitor

2.
3.
4.

inhibitor

5.

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Pitting

3.

Pitting
Corrosion
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solvent

%25

water block
fluid recovery

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%20

Diverting agent
.

:
.
) (
.

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Additives

Acid

) (Corrosion Inhibitors

.
). (Surfactants

Complexing
. Agents

) (
) . (Agents Gelling

)
( Diverting Agents

(Retarding Agents) .

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Types of divertors

Unibeads
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Benzoic acid

Non buoyant ball sealers (5/8 & 7/8 )

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 Design of Matrix Acidization Treatment

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) (Frac . Gradient

0.33 0.5

10000
1.2 .

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Design of Matrix Acidization

Treatment

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5000

4500

S=0

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P re s s u re (p s ig )

4000

3500

System performance

3000

S=5

2500

S=12.5

2000

1500
0

1000

2000

3000

Performace analysis of well S-27

4000

5000

6000

Flow rate(bbl/day)

7000

8000

9000

10000

 2-1

.

)(

HCL

HF

. .

)(

) 2-1.1 (
)2-1.1.1 (HCL
HCL .
HCL detergency

)(wetting

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) ( additive

HCL .

HCL .
. HCL HCL
.

. HCL
. HCL
. HCL PH

HCL . %3 %28 .
.

%15 .

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 %15 HCL ) (
.
HCL :

Carbonate acidizing - Fracture and Matrix

Sandstone acidizing - Matrix only

Perflush HF-HCL

Post flush HF-HCL

%15 %20

) (mureatic acid .
%38.1 .
HCL .
) ( .

.
. 1

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 ) (1
.
.
.
.
.
.

2-1.1.2 HF

HF HCL
.
HF :

HCL :HF

Sand stone matrix acidizing

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HCL

%1.5 %6

. 217 HCL:HF 12:3

) ( )
( .
HF ) ( . HF
. HF HCL .

):HCL ( HCL HF.
HCL .

2-1.1.3
.
. ;
.

2-1.2
HCL
. HCL

HF .

.
.
.

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 .

.

2-1.2.1 CH 3COOH

.
HF HCL .

.
.
.

damage

) ( dissolving power %15 HCL HF

1 .
HCL HF.
HCL

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%7.5 %10

Carbonate acidizing

%99
( 16 0 C ) 600 F . (9 0 C )480 F .
.
.
.
.

2-1.2.2
2 0 F

) (- 17 0 C . . .
.113
1.127 .
.
.

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 2-1.2.3 ) ( C6 H 8O7
tubing , casing
. HCL
. PH 2
.
.

) (Ferrotrol 300
HCL . )
( X-14 .
HCL ) (SA-system
.

HCL . 50 1000
2000 ) (ppm ) (SA-Z 50
2000 ppm . 2

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 PH .
HCL PH 2 .
.
:
-1

-2

X-14

-3

X-14

-4

HCL

PH 2
.
2-1.2.4 )(HCOOH
.
HCL . . HCL
.
%8 %10 .
.

HCL

Hot wells

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. HCL
. HCL .
HCL . %25
.
HCL .

2-2
2-2.1
2-2.1.1
) ( H + .

H + + Cl -

HCl + H2O

Hydrochloric Acid.

H+ + F

HF + H2O

Hydrofluoric Acid.

H + + H3C-COO

H3C-COOH + H2O

Acetic Acid.

H + + HCOO

HCOOH + H2O

Formic Acid.

H + + H2N-SO3

H2N-SO2OH + H2O

Sulfamic Acid.

HOH+ H 2 O

Water.

H + + OH -

2-2.1.2

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 . OH -
:
Sodium Hydroxide.

NaOH + H2O

OH - + Na+

Potassium Hydroxide.

KOH + H2O

OH - + K+

Calcium Hydroxide.

Ca(OH)2 + H2O

2 OH - +

Ammonia Gas.

NH3 + H2O

Ca2

OH - + NH4 +

2-2.1.3
. .
:

Sodium Chloride.

HCl + NaOH

Calcium Chloride.

2HCl + CaCO3

CaCl2 + CO2 + H2O

Silicon Tetrafluoride.

4HF + SiO2

SiF4 + 2H2O

Barium Sulphate.

H2SO4 + Ba(OH)2

Magnesium Formate.

2HCOOH + Mg(OH)2

NaCl + H2O

BaSO4 + 2H2O
Mg(HCOO)2 + 2H2O

HCL 2-2.1.1.1
Hydrochloric + Calcium
Acid

2HCl + CaCO3

Carbonate

Calcium +
Chloride

Carbon + Water
Dioxide

CaCl2 + CO2 + H2O

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Hydrochloric +
Acid

Dolomite

Chloride

Calcium +
Chloride

Magnesium + Carbon + Water

Dioxide

4HCl + CaMg(CO3)2

CaCl2 + MgCl2 + 2CO2 + 2H2O

Hydrochloric + Sand

No appreciable reaction.

Acid

HCl + SiO2

No appreciable reaction

HF 2-2.1.1.2
Hydrofluoric + Calcium
Acid

Carbonate

HF + CaCO3

Hydrofluoric + Sand

Calcium + Carbon + Water

Bifluoride Dioxide

CaF2 + CO2 + H2O

Fluosilicic + Water

Acid Acid
6HF + SiO2

H2SiF6 + 2H2O

Fluosilicic + Sodium

Sodium + Hydrogen

Na2SiF6 + H2

Acid Fluosilicate

H2SiF6 + 2Na

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Fluosilicic + Fluoaluminic + Water

Acid

Acid

Clay

4H2SiF6 + 2H3AlF + 2H2O

Hydrofluoric + Bentonite
Acid

36HF + Al2(Si4O10)(OH)2

2-2.1.1.3

Calcium + Carbon + Water

dioxide

Acetate

Acetic + Calcium
Carbonate

Ca(CH3CO2)2 + CO2 + H2O

Acid

2HCH3CO2 + CaCO3

2-2.1.1.4

Calcium + Carbon + Water

Formate dioxide

Ca(HCO2)2 + CO2 + H2O

Formic + Calcium
Carbonate

Acid

2HCCO2H + CaCO3

2-3
.
.
. .

Nac 2 H 3 o 2

HC 2 H 3O 2

. .

www.petroman.ir

(aq) H 3O + (aq) + C 2 H 3O2 - (l) H 2 O (aq) + HC 2 H 3O 2

Nac 2 H 3 o 2

Na +

C 2 H 3O2 -
.

) (
. .
)
( . .
.

PH )
( . .
.
)+ H 2 O (l) C 2 H 3O2 - (aq) + H 3O + (aq

)HC 2 H 3O 2 (aq

very large
Concentration

Large
Concentration

tiny
Concentration

H 3O +

large
Concentration

H 3O +

PH.

.
OH - H 3O +

H 3O +

OH - H 3O +

H 3O +

PH .

.
:

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 .1
.2 PH .
.3
H 3O +

OH - .

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H 3O +


.

:
) ( ) ( ) (
) ( ) ( ) ( ) ( ) ( ) ( ... -

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 (
.

.
.
.
2 90
. .

10 30 .
. 2 90
.

.

.
10 .
:1 .
:2 550
.
:3 3 4
- .
(

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 .
) ( 15 . ) (
) Regular Mud Acid + %12 (%3 .
HF HCl . HF
HCl % 20 .
-1 15
40 150 % 15
. 150
. ) (
HCl 15% .
-2 %15
150 % 15
150 150
. .
HCl 15%
.
(
.
.
.
.
.
-1

. ) (
.
.

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%15 .
.
( ) / (SEM )(EDAX
) (SEM
80000 . EDAX
.
) (...
) 30000(
.
EDAX .
SEM/EDAX :
: : ) (...
.
.
.
:
.
:
. .
- :

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.
.
EDAX .
(
) (fracturing
.

. :
.
-1:
.
.

.
FANN 35 .
-2 ) (
.
.
. -
. 10000 .
.
-3 ) (

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.
-4 ) (
) (breaker
.
.
FANN 35 .
15 RPM 100 %10
.
-5 ) (
.
- .
) %2 ( )
( 1000 .
.
(
.

.
-1
) 25 50 75 50 75 (25
.
%90 10 %100 30 .

.
-2

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.
.
.
(

. .
.
.
(
.
. )
(... .
pH .
( /
.

. .

. .
.
.
.
(

.
.

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 ) (
.
. .


.
(

) (
.

.
(
) (Corrosion Inhibitor .
-1
5617
. )(
.
.
. 10000 500

-2
220 .

.

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.
.


.

.

...
.



.

.


) (
OMV ... .


) (
) ( .


.
" ) (
) ( .

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.


... .
) (Bull head
) (Coil tubing .

.
" .

.
"
.
. "
.

) 10 15(
.
.
) (
. )
20 28( .
"

.
.

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.

. " :
.

.

.

. " "
.
.

.
.

.

.
.
HF HCl
HF .
. HF
HCl-HF .
Diverting System
.
" .
) ( . ) (diverter
.

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.
.
.
.

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. :
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.
16 .
.

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-2

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:( ( (
. 30 65
.
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-3
.
. .

www.petroman.ir


.
.

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-3
.
.
.
.
" :
.

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 .
. c70 .

. .

.


.

.


.
.


.



.
- HP HT Corrosion cell
- Portable PH Meter
- Waters Bath
- Oil Bath
- Spectrophotometer

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- Colorimeter
- Drging oven
- Hamilton Beach Mixture
- weight Balance


.
.


) (Injectivity Test .

) (
0
(

) 264 (268



.




.
"
.

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 (RETENTION TIME 0

15
28
) (Retard
.
.
) 272 (278

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( )(HF
.
(

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) (SiF2-6 AlF-3 AlF-3
AlF-4 AlF+2 AlF+2AlF-5

.

)(

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 (1 SGMA
) (shell ) self Generating Mud
SGMA (Acid
7/5
) (Spacer head . )(NH4CL
3 SGMA .
>NH4F+H2O+Organic Ester(Methy Formate )-
HF+Formic Acid +Ammonium Formate
(2 SHF
) (Halliburton 100
5 ) 50(Preflush )
3 12( 20
) 2 (NH4F 8 PH 7 8 25
15 ) (Afterflush
.
) (Preflush :
(1 ) (Spacer
(2
(3
(4 ) (Mutual Solvent
) (Afterflush :
(1 /
(2 /

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 (3 ) (Surfactants

(4
) (HF
) (HBF4 . NH4FHF
:
NH4FHF+HCL<->2HF+NH4Cl
H3BO3+4HF<->HBF4+3H2O
) (HF ) (Retarder
BF-4 .
-2 )(Carbonate Layers
.

) (Fracture Worm Holing .

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 "
.
.
."
) (Preflush ) (Main Acid )(Afterflush
. 15
) (
.
.
) (Diverting
) (Surfactants
) (Antisludge .
15 2000 F
.
." 100 C
. .
) (Spent Acid ) (Retarder .
) (Retard ."
15 .
.
. 15 2500F 6000

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 . " 10
. " 10

" .
) (Main acid 15 28
. .
" ) (Afterflush
."
50 350 3 5
.

( .
(
( Worm Holing .
( ) (SKIN

Worm Holing .
:
(1
4HCL+CaMg(Co3)2<->CaCl2+MgCl2+2H2O+2Co2

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2HCL+MGCO3<->MgCL2+H2O+CO2
(2
2HCl+CaCo3(CaLCite)<->CaCl2
15 220 ) %90 (
.
(3
2HCL+FeCo3(Siderite)<->FeCL2+H2O+CO2
: 3/2


.
:
(1 ) (S/v
) (Matrisacidizing.
(2 : .
(3 :
.
(4 :
23 .
(5 :
.
(6 :
.

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 (7 :
) (acid fracture
) (S.V .
)(acidizingmethods
-1 )(matrisasiding


) (Radianpenetration

.

.
(3 )(acidfractureng

www.petroman.ir


.
(3 )(acid washing
" ) (Mudcake
.
) (Perforations "
) (Spot
, )(circulation
. )(emulsion
)(water block
.
.


. :
(1
( )(HCI
. "
) ( .
5 37 15
.

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.
( )(HCI-HF

Mud Acid . "

. ) (HCI
.
Mud Acid AIF3
CaF2 .

(2

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 ) (1200 C
.
.
( )(CH3COOH
.
" 15
.
" 42 .

" . :

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 ) (HAC
-1
-2

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 -3

)(Fe(OH3
-4 900C
.
-5 900 C
-6
.
-7 .

-1 ) .(
-2
) (HCI .
-3 .
( )(HCOOH
"
.
. KD
86 .
( )(C6H8O7
"
.

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 (3
( )(Chloracetic Acid
( )(Sulfamic Acid
) (HSO3NH2

.
.
)(HSO3NH2
(3 .
(3 .

(1 .
(2 1800
. 160
.

HSO3NH2--------> H2SO4->CaSo4

(4 )(Hybrid or Mixed Acids

"

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:
(
(
.
(


.


1000 4/2
700 ) (Clay .
(3 )(Retarder Acids
( )(Gelled Acied
.

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 . ) (Acid Fracturing
. :
(1 ) .(Minor Retardation
(2
(3 ( (
(4
) (Flocculate .
(5 .
( )(Oil Wetting Surfactants

.

.
( )(Emulsified Acid

10 30
.

.
.
.
:

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 (
15 1 ) (SLA-48 1/2
) (Ci-27 .
( 70 15 30
1 ) (E-30 1 )(Ci-27
. 4000
2800 15 1200 40 )E-
(30 40 ) (Ci-27 .

1000
.

(1

. :

2HCL+CaCo3->CaCl2+H2O+Co2
.
) (

.

www.petroman.ir


.
.
.

.
(2

.
Rh= -k(y*c)/.2 hcl
: Rh
:Y )
(
:C
: (y*c) Hcl
:K

.

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 (3
75
7*106
150
.

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: KHA

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kha

.
:

HCL

47/36

10

CH2CL-COOH

94/5

H-COOH

46/03

2 104

CH3-COOH

60/05

1/8 105

CH3CH3-COOH

74/08

1/3 105

10

1/5

(5




.
" ) (

www.petroman.ir



) (
.

.

(6 )(S/V

.

.

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www.petroman.ir

 (7

.

.

.

.


.

) (Spot ) (Perforations
.

."

.
.

.

www.petroman.ir

 ) (Productivity Index .
) .
(.

) ( . ) (Matrix Acidizing
) (Fracture Acidizing (Acid
) Washing .

.
(1 ) (Formation Damage
.
.
(2
. )
(.
(3
.

.

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 ."
5 .
.
.
.
.
( .
( .
( .
:
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( )(Sludge
( .
.
:
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(3
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.
2CH3COOH+CaCo3-> (CH3COO)2Ca+CO2+H2O


.

220/19
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.

.


.

.
.

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 .

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.
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.

1947 .

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.

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.

(1
.
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(4
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.

.
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.

.

) (gelatin pad )
(

1
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.
.

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 (1
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.
.
.
. . .

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 .
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