Well Stimulation and Sand Production

Management (PGE 489 )

Acid Types and Reactions with

Different Rocks
By
Dr. Mohammed A. Khamis
09-02-2016
 What is Acidizing?

 Unsteady, non-isothermal, 3-D flow in porous media with

chemical reactions

 Heterogeneous and homogeneous reactions

 Continuous variation in the porosity and permeability of the
porous medium due to dissolution of the rock matrix and
precipitation of the reaction products
 Factors Affecting Acid Formula

 Damage type and location

 Rock mineralogy
 Analysis of formation water
 Bottom hole temperature
 Well completion
 Well type
 OWC Line
 Factors Affecting Acid Formula

 Oil type (wax, asphaltenes)

 H2S content
 Reservoir pressure
 Permeability profile
 Water saturation
 Acids Types

 Mineral acids
 Simple organic acids
 Mineral/organic acids
 Powder or solid acids
 Chelating agents
 In-situ generated acids
 Acids Types

 Mineral acids
 Hydrochloric acid (HCl)

 Sulfuric acid (H2SO4)

 Phosphoric acid (H3PO4)

 Nitric acid (HNO3)

 Acids Types

 Hydrochloric acid (HCl)

 Cost effective

 Available at 31 and 37 wt%

 Ca, Mg chlorides are soluble

 Fast reaction with calcite

 Slower reaction with dolomite

 Corrosive at high temp

 Acids Types

 Hydrochloric acid (HCl)

 Measure acid using titration

 Colorless, slightly yellow/green

 No impurities:
• Iron

• Sulfate

• Phosphate

• Fluoride
 Acids Types

 Simple organic acids

 More expensive

 Mainly acetic and formic acids

 Be careful with their salts

 Less corrosive

 With or without HCl

 Reversible reactions

 Requires especial corrosion inhibitors

 Acids Types

 Simple organic acids

 Contains COOH

 Acetic acid ( CH3COOH)

 Formic acid (HCOOH)

 Maximum concentration for acetic is 13 wt%

 Maximum concentration for formic is 9 wt%

 Mixture of HCl/organic acids

 Mixture of formic/acetic
 Matrix Acidizing

 Matrix acidizing design strongly depends on

information about reservoir properties and formation
damage.
 Acidizing process is complicated, and no model can
describe the process precisely.
 In many cases stimulation results deviate from what is
expected from design.
 Matrix Acidizing

 Matrix acidizing is a well stimulation technique in which an

acid solution is injected into the formation in order to dissolve
some of the minerals present, and hence, recover or increase
permeability in the near-wellbore vicinity.
 Matrix Acidizing of Carbonate Reservoirs
 Matrix Acidizing of Sandstone Reservoirs
 Matrix Acidizing

 The most common acids used in are hydrochloric acid (HCl),

used to dissolve carbonate minerals, and mixture of hydrochloric
and hydrofluoric acids (HCl/HF), for attacking silicate minerals
such as clays and feldspars in Sandstone reservoir.

 Matrix acidizing is a near-wellbore treatment, with all of the acid

reacting within about a foot of the wellbore in Sandstone
formation, and within a few to perhaps 10 ft of wellbore in
Carbonate.
Matrix Acidizing
 Matrix Acidizing

“The lack of a method to determine the

depth of damage penetration by existing
methods of well test analysis continues
to make the acidizing of oil wells an
inexact science”
J. L. Gidley (1970)
 Matrix Acidizing

Q: What can we do to prevent “bad” acid

treatments?

A: Monitor actual skin change during the injection.

• Evaluate acid systems
• Quantify damage removal
• Evaluate diversion process
• IMPROVE design for subsequent treatments
 Field Examples

Example: Successful case Pressure and injection rate record

2500 4
3.5
2000 bottomhole pressure

injection rate (bpm)

3
2.5
pwi (psi)

1500
2
1000 1.5
1
500 injection rate
0.5
0 0
10 15 20 25 33 39 47 53

injection time (min)

 Field Examples

Example: Successful case Skin Evolution of Acidizing

140

120

100
skin factor

80

60

40

20
HCl HF/HCl
0
10 20 30 40 50 60
injection time (min)
 Field Study Examples

Example-1:
 Reservoir properties
 reservoir pressure 8000 psi
 permeability 100 md
 initial skin factor 35
 payzone thickness 138 ft
 well depth 11447 ft
 Treatment data
No. stages V (gal)
 preflush 1 4957
 main 1 9949
 diversion n/a
 spacer 2 5006
 Field Study Examples

Example-1:
35
NH 4Cl HCl HF/HCl
30

25
skin factor

20
15

10

0
0 10 20 30 40 50 60 70 80 90 100
time (min)
 Field Study Examples

Example-1:

 Skin factor reduced from 35 to near zero

 Production was doubled and drawdown was

reduced from 1200 psi to 500 psi by the treatment

 HCl did not remove the damage - common in

sandstone formation with low carbonate
 Field Study Examples

Example-2:
 Reservoir properties
 reservoir pressure 1700 psi
 permeability 150 md
 initial skin factor 8
 payzone thickness 54 ft
 well depth 3600 ft
 Treatment data
No. stages V (gal)
 preflush 2 2095
 main 2 4199
 diversion 1 407
 spacer 3 4000
 Field Study Examples

Example-2:

160
HCl HF N Diverter N HCl HF
140
120
100
skin factor

80
60
viscous skin
40 apparent skin
N: NH4Cl spacer
20 HF: HF/HCl mud acid
Diverter: HEC w/sand
0
0:28 0:57 1:26 1:55 2:24 2:52
time (min)
 Field Study Examples

Example-2:

 The well did not respond as expected to the first

acid injection

 Sudden increasing of skin factor when diverter

reached the perfs showed positive diversion effect

 Two components of diversion effect on skin: filter

cake build-up and viscous effect
 Field Study Examples

Example-3:
 Reservoir properties
reservoir pressure 3100 psi
permeability 150 md
initial skin factor 45
payzone thickness 132 ft
well depth 7460 ft
 Treatment data
No. stages V (gal)
preflush 2 3444
main 2 7732
diversion 1 210
spacer 3 2289
 Field Study Examples

Example-3:
70
N HCl HF N D N HCl HF
60
50
N: NH4 Cl spacer
skin factor

HF: HF/HCl mud acid

40 D: HEC w/sand diverter

30
20
10
0
6:11 6:25 6:40 6:54 7:09 7:23 7:37
time
 Field Study Examples

Example-3:

 Very successful stimulation in the first acid stage

 The second diversion stage could be eliminated since the

second acid stage did not reduce skin factor any further
 Fluid Chemistry
• An acid is a compound that when dissolved in (or hydrolysed by) water, it releases
hydrogen ions (H+) as the cation. Examples of commonly used acids are as follows:

• A salts is a compound formed by the reaction of an acid with a base.

 Reaction Kinetics
• Dissolving power expresses the amount of minerals that can be consumed
by given amount of acid on a mass or volume basis.

 mineralMWmineral  m MWm
  Ca
 acid MWacid  a MWa

• For reaction between 100% HCl and CaCO3:

 mineralMWmineral 1100 .1 Ibm CaCO3
   1.37
 acid MWacid 136.5 Ibm HCl
 Reaction Kinetics
• Volumetric Dissolving power (X) is defined as the volume of mineral dissolved by a
given volume of acid, and related to gravimetric dissolving power by:

 acid solution a
X  
 mineral m

• For reaction between 15% HCl and CaCO3 with acid specific gravity of 1.07 and
CaCO3 density of 169 Ibm/ft3, the volumetric dissolving power is:

 Ibm CaCO3  (1.07)(62.4) Ibm 15% HCl ft 3 CaCO3 

X  (0.15)(1.37)  


 Ibm 15% HCl 
3
ft 15% HCl 169 Ibm CaCO3 
ft 3 CaCO3
X  0.082 3
ft 15% HCl
 Reaction Kinetics

Dissolving Power of Various Acids

X
Formulation Acid 100
5% 10% 15% 30%
Limestone HCl 1.37 0.026 0.053 0.082 0.175
CaCO3 HCOOH 1.09 0.020 0.041 0.062 0.129
=2.71 g/cm3
CH3COOH 0.83 0.016 0.047 0.047 0.096
Dolomite HCl 1.27 0.023 0.031 0.071 0.152
MgCa(CO3)2 HCOOH 1.00 0.018 0.036 0.054 0.112
=2.87 g/cm3
CH3COOH 0.77 0.014 0.027 0.041 0.083
 Matrix Acidizing - Example

In sand stone acidizing treatment, a preflush of HCl is usually injected

ahead of the HF/HCl mixture to dissolve the carbonate minerals and
establish a low-pH environment. A sandstone with a porosity of 0.20
containing 10% (volume) calcite (CaCO3) is to be acidized. If the HCl
preflush is to remove all carbonate to a distance of 1 ft from the wellbore
before HF/HCl stage enters the formation, what is the minimum preflush
volume is required in gallons of acid solution per foot of formation
thinness? The wellbore radius is 0.328 ft.
 Matrix Acidizing - Solution

The required minimum acid volume to dissolve all calcite is:

Vacid=Vpore+Vto dissolve CaCO3+VreplaceCaCO3
The volume of acid needed to react with calcite (Vm/X)
Vm   (rHCl
2
 rw2 )(1   ) xCaCO3
Vm   (1.328 2  0.328 2 )(1  0.20)(0.1)  0.42 ft 3 / ft CaCO3
Vm 0.42
  5.01 ft 3 HCl / ft
X 0.082
The volume of pore space within 1 ft of wellbore is:
V p   (rHCl
2
 rw2 )
V p   (1.328 2  0.328 2 )(0.1)  0.52 ft 3 / ft

VHCl 
Vm
 V p  Vm 
5.01  0.52  0.42  ft 3 7.48 gal
 44.5 gal / ft
3
X ft ft
 Wormhole Modeling

• Acids were used to create wormholes to connect the formation to the

wellbore

• Propagation of wormholes through the damaged zone yields negative skin

• Only a small fraction of the matrix must be dissolved
 Wormhole Modeling

• A few large channels called wormholes form

• Structure of wormholes depends on many factors including:
• Flow geometry
• Injection rate
• Reaction kinetics
• Mass transfer rates
 Wormhole Modeling

• Much larger than pores, hence insignificant pressure drop through

them
• If the wormholes propagate through the damaged zone,

S = -ln(rwh/rw)

• Ex: 1.7 foot long wormholes propagating from a 6 inch radius well
yield Skin of -1.22
• Wormhole structure depends on rock type, acid type, injection rate,
temperature, …
 Wormhole Modeling

• Objective of acid stimulation was to create sufficiently long

wormholes to give a post-treatment negative skin factor of –2 to –3.

• Injection rate may be limited by coiled tubing size

• Low injection rate resulted in compact dissolution of the formation
face with no significant wormhole penetration

• The analysis can show that the skin factor did not change significantly
throughout the entire treatment
 Wormhole Modeling

• Acid selection based on:

 reservoir depth (shallow or deep)

 reservoir fracture gradient

 reservoir permeability

 Heterogeneity
 Optimum Wormhole Condition

Dissolution Patterns in Carbonate Acidizing

a. 0.1 cc/min, face dissolution

b. 0.2 cc/min, conical
c. 1 cc/min, dominant
d. 4.1 cc/min, ramified
Optimum Wormhole Condition
 Optimum Wormhole Characterization

Dissolving Power:
Gravimetric ()

CaCO3 +2HCl CaCl2+CO2 +H2O

100%  100.1 * 1/(36.5 *2) = 1.37 lbmole CaCO3/lbmole HCl

 Optimum Wormhole Characterization

Volumetric dissolving Power ()

 acid
X  ft3 CaCO3/ft3 HClc
CaCO 3

Vacid  VCaCO3 / X


VCaCO3   racid
2

 rw2 1   xCaCO3 ft3 CaCO3/ft
 Optimum Wormhole Characterization

Acid Capacity Number (Nac):is the ratio of the amount of mineral

dissolved by the acid occupying a unit volume of the rock pore
space to the amount of mineral present in the unit volume of the
rock

  %  acid X
N ac, acid  
1    rock 1   
 Optimum Wormhole Characterization

Damköhler Number (NDa): the ratio of reaction rate to convection rate

d w Lw
N Da 
q
dw = wormhole radius, cm
Lw = wormhole length, cm
k = overall dissolution rate constant, cm/s
q = injection rate, cm3/s
Optimum Wormhole Characterization

Mahmoud and Nasr-El-Din, 2010, SPE 133497

 Optimum Wormhole Characterization

The optimum Damköhler number was found to be 0.29, we can

design the treatment based on that number

In the case of irreversible reactions (mass transfer):

1/ 3
1.86 D 2/3
 4q 
  e

 L 

dw  w 
 Optimum Wormhole Characterization

Using these equations, the optimum flux can be estimated:

130 Lw De
uopt  2
d core

uopt= optimum flux, cm/s

Lw = wormhole length, cm
De = diffusion coefficient, cm2/s
dcore = core diameter, cm
 Optimum Wormhole Characterization

From the previous equation the optimum injection rate can be

determined:

Qopt  47.1d 2
u
core opt

Qopt = optimum injection rate, cm3/min

dcore = core diameter, cm
uopt = optimum flux, cm/s
 Optimum Wormhole Characterization

To scale up the optimum injection rate to the field conditions the

following equation can be used:

rwell h f
Qwell  Qcore
rcore Lcore

Qwell = optimum injection rate in the field,

Qcore = optimum injection rate in the coreflood,
rwell = well radius,
hf = reservoir thickness,
rcore = core radius,
Lcore = core length
 Wormhole Penetration Radius

Different models can be used to predict for the wormhole radius:

1/ 3 0.63
 bNacV  2 / 3  q  
rwh   De    Daccord et al., 1989
 h h 

rwh = wormhole penetration radius

b = constant = 1.5 x 10-5 in SI,
Nac = acid capacity number,
V = q * t,
De = diffusion coefficient,
h = formation thickness,
 = formation porosity,
 Wormhole Penetration Radius

To determine the volume of the acid per foot thickness of the formation
the following formula can be used:

1/ 3
q
D  2/3
e
1.6
rwh
V
  h
h bNac
 Wormhole Penetration Radius

Volumetric Model (Hill 1993):

 Assumes acid dissolves a constant fraction of rock volume
penetrated
 Wormhole velocity is constant
 Assume fixed number of PV required to create a wormhole to a
given distance

V
rwh  r 
2

hPVbt
w

V
h

  rwh
2

 rw2 PVbt
 Wormhole Penetration Radius

Example:
Determine V/h (gal/ft) using different models for the following acid treatment:

 15 wt% HCl, 𝜌𝑎𝑐𝑖𝑑 = 1.072 g/cc

 Well radius = 6 in.
 Wormhole penetration = 3 ft
 Injection rate = 0.1 bpm/ft
 Diffusion coefficient = 10-9 m2/s
 Optimum flux = 0.18 cm/min
 Pore volume to breakthrough = 1.3 PV
 Wormhole Penetration Radius

Solution:

  %  acid
N ac, acid   0.02
1    rock
1/ 3
2/3 q 
De   1.6
rwh
V
 h  17.2 gal / ft Daccord
h bNac

V
h
  rwh
2
 
 rw2 PVbt  76.6 gal / ft Volumetric
 Wormholing Rate

Buijse Model:

Vwh  Weff v 2/3

i 
1  e W v 
2
b i

q qopt
vi  vi opt 
2rh 2rh

vi1/ opt
3
4
weff  wb 
PVbt opt v i2 opt
 Wormholing Rate

Huang et al.(1989)

 Ctip  q
vwh  vi ,tip   N Ac vi ,tip 
 C0  2hrwh

Mahmoud and Nasr-El-Din (2011)

4Q N ac
vwh 
d cored wh
 Wormholing Rate

Wormholing rate can be used to determine the volume of the fluid

required to create wormholes

vi
PVbt  Buijse 2005
vwh

d wh
PVbt  Mahmoud and Nasr-El-Din, 2011
d core N ac

Then the PVbt can be used to determine the acid volume required for
the treatment by the volumetric model
 Optimum Injection Rate

Optimum injection rate in acid treatment is the rate at which the

dominant wormhole will be formed with the minimum acid volume
 Optimum Injection Rate

Optimum injection rate cannot be used in certain situations

2hk g fr Dr  pr  •Steady State Flow

Qmax  •Open Hole
 re 
  ln  S  •Vertical Well
 rw 
Qmax = maximum possible injection rate
h = reservoir thickness
k = reservoir permeability
gfr = fracture gradient
Dr = reservoir depth
pr = reservoir pressure
 = fluid viscosity
re = reservoir drainage radius
rw = wellbore radius
S = damage skin
 Optimum Injection Rate

The maximum injection rate can be determined according to

the reservoir and completion type
 Steady state, pseudo steady state, or transient flow

 Open hole, perforate, or slotted liner

 Vertical, inclined, or horizontal well

 Optimum Injection Rate

Scenario 1: Qopt < Qmax, current stimulation fluid is safe to be used

without the fear to frac the formation

This is good in
deep reservoirs,
but take care of
the tubular
corrosion
 Optimum Injection Rate

Scenario 2: Qopt > Qmax, current stimulation fluid is not safe, we have to
look for alternatives

This situation is
common in
shallow reservoirs
where the fracture
pressure is low