Sandstone Acidizing

Hydrofluoric (HF) acid

Marten Buijse - IMPACT Team
 Damage Causes and Acid Types

• Fines/Clay Migration HF acid

• Clay Swelling HF acid
• Inorganic/Organic Scales HCl acid / solvent
• Mud loss
– Bentonite HF acid
– Barite EDTA (or HF acid)
– CaCO3 HCl acid
• Bacteria, Wettability, No acid
Water Block, Emulsions brine w/ surfactants
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 Common Acid Blends and Volumes

Volume
HF Blend gal/ft (m3/m)
12% HCl - 3% HF 100 (1.2)
13.5% HCl - 1.5% HF 150 (1.8)
9% HCl - 1% HF 200 (2.4)
Retarded HF 200 (2.4)

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 HF Acid Flow Diagram

Wellbore Area Damaged?

Don’t use HF
Don’t use HF
Yes No
Yes No

Carbonate Concentration > 20%?

Is damage HF acid soluble? Don’t use HF
Don’t use HF
Yes No
No Yes

Damage removed, will production be economical? Can treatment be controlled to treat all interval of Interest?
Use HF
Don’t use HF

Yes Yes No
No

Pump at reasonable matrix injection rate? Necessary to treat the whole interval to make well economical?

Don’t use HF Use HF

Yes No

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 Past and Present
Traditionally...
Little focus on candidate selection or damage ident.
• Standard Mud Acid of 12/3% HCl to HF was used
• Low success rate (20-40%)

Recent Changes...
Focus is on mineralogy and problem prevention
• Acid blends are tailored to formation conditions
• Use a systematic approach to a complex process
• Large increase in success rates

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 Fundamental HF Research

Started in mid-80’s.

Results of returned fluid analysis could

not be understood with classical theory.

Goal: Understand HF-Rock Chemistry

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 HF Chemistry - Classical Theory

H+ H+ H+
AlF 2+
HF
SiF5-
K+
SiF5 - H+
SiF5- H+ HF
HF
AlF2+ K+
H+

Feldspar - KAlSi3O8 Clay - Al2Si2O5(OH)3

HF dissolves Clays and Feldspars

DAMAGE REMOVAL
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 HF Spending
12 % 10 %

3% 0.1 %
HCl / HF
HCl / HF
+ Al - F
0” _______________ 12” + Si - F

HF Spent Damage Dissolved HCl NOT Spent

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 1985 - Returned Fluids Analysis

Expected Analysis
• Almost no HCl • All HCl consumed
consumption
• Lots of Silicon • NO Silicon
• Some Aluminum
• Lots of Aluminum
• Lots of Sodium
• Little Sodium
and/or Potassium and/or Potassium
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 Primary HF Spending
12 % 10 %

3% 0.1 %
HCl / HF
HCl / HF
+ Al - F
0” _______________ 12” + Si - F

HF Spent Damage Dissolved HCl NOT Spent

Marten Buijse - IMPACT Team

 HF Acid Dissolving Power
How far out does live HF acid go?

1 m3 of 15% HCl 220 kg of carbonate

1 m3 of 1.5% HF 10 kg of clay/ feldspar
0.7 m3/m 1.5% HF 7 kg of clays per meter
14 shots/m (4 shots/ft) 0.5 kg clay per perf.
if clay + feldspar content is 25%, we clean 2 kg of
rock per perforation...about the size of a fist.

Marten Buijse - IMPACT Team

 Secondary HF Spending
10 %
4%
0.1 %
0.1 %
HCl / HF
HCl / HF
+ Al - F High Al - F
+ Si - F No Silicon
6” _______________ 24”

! Silicon and Na/K Fluosilicate Precipitation !

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 Secondary Reaction - Prevent
Precipitation

• Keep HCl to HF ratio high (6:1, or better still

9:1) so that not all HCl is consumed after first
spending.

• Adjust HF concentration accordingly in the

presence of Na or K feldspars.

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 HF Incompatible with K-Spar
2

13.5% HCl - 1.5% HF

200 F
Concentration (M )

1 K - Released
K - Tolerance

0
0 20 40 60 80 100
% Secondary Reaction
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 HF Compatible with K-Spar
2

9% HCl - 1% HF
200 F
Concentration (M )

1 K - Released
K - Tolerance

0
0 20 40 60 80 100
% Secondary Reaction
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 Optimum HCl/HF Ratios for
K-Feldspars

Temp F HF Blend
T > 250 13.5% HCl - 1.5% HF
250 > T > 200 9% HCl - 1% HF
200 > T > 175 7% HCl - 0.75% HF
175 > T > 125 6% HCl - 0.5% HF
125 > T > 100 6% HCl - 0.4% HF
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 Tertiary HF Spending
4%
0.1 % No HCl
HCl / HF No HF
High Al - F Very High
Al - F
24” ______________ 6 ft

! Aluminum Precipitation and Scaling !

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 Tertiary Reaction - Prevent
Aluminum Scaling

• If carbonate content is
2-5%, use higher
HCl/HF ratio to prevent
complete spending

• If CC is above 5%, use

ALCHEK to ensure pH
doesn’t rise above 2.5.

Marten Buijse - IMPACT Team

 New HCl/HF Systems
 Prevent Na- and K- Fluosilicate precipitation
 Prevent Aluminum Scaling

13.5/1.5% HCl/HF High HCl/HF ratio (prevent precip.)

Retarded HF For deep damage (fines migration)
9:1 HCl/HF Low HF, for high feldspar formations
Organic/HF For higher temps
12/3 HCl/HF ‘Mud acid’ for silica scale removal
HCl only Whenever carbonate content > 20%

Marten Buijse - IMPACT Team

 Role of Mineralogy in
Sandstone Acidizing

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 Formation Mineralogy Affects...

• Compatibility with HF Acids

• Preflush Type and Volumes
• Clay Swelling
• Clay Instabilities (in HCl)
• Fines Migration

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 Acid Preflush - Remove
Carbonates from Near Wellbore

• Remove carbonate material from

within 2 ft of wellbore. HF acid will
react with any calcium source to form
an insoluble CaF2 precipitate.

• Aluminum-Silicate can occur when

spent HF contacts carbonate.

Marten Buijse - IMPACT Team

 HCl (15%) Volume for Removing
Carbonates

300
10%
5%
Volume (gal/ft)

200
3%
2%
100
1%

0
0 1 2 3 4 5 6
R (ft)

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 Clay Swelling
Clay swelling occurs when weak brine or fresh water comes in
contact with smectite, illite, or mixed layer clay.
Ion exchanging clays transform some brines from ‘safe’ to
unsafe.

Ion Exchange Rating (kg equ/100 kg)

Kaolinite 3-15
Illite 10-40
Mixed layer 20-80
Smectite 20-80
Mica 100-150
Zeolites 100-250

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 Mixing and Ion Exchange
1.00
Concentration (M)

0.75

Na
0.50 K
Cl
NO3
0.25

0.00
0 200 400 600 800 1000
Volume (ml)
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 Compatible Brines
(1 Molar in Cl)

5% NH4Cl
7% KCl
5% CaCl2
6% NaCl
(seawater is 2-3% NaCl, and < 4% total salts)

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 Clay Instability in Acid
All Clays have a temperature at which they become
unstable in HCl. Unstable clays decompose quickly and
consume all available HCl.

Mineral Max. Temp. in HCl (deg F)

Zeolites 75
Chlorite ((Mg,Fe,Al)12(Si,Al)8O20(OH)16) 150
Illite (K1-1.5Al4Si7-6.5Al1-1.5O20(OH)4) 190
Mixed Layer 200
Smectite ((Mg,Fe,Al)4(Si,Al)8O20(OH)4.nH2O) 200
Kaolinite (Al4Si4O10(OH)8) 250
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 Clay Instability Ratings (CIR)
100

75

e
im

e
e

e
tit
rit
a lc

te

nit
ec
50

lo
I lli

oli
An
C IR

Sm
Ch

Ka
25
Feldspar

0
50 100 150 200 250 300 350
Temperature F

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 Organic Acid in Sandstones

• Compatible with Clays at High Temperature

• Easily Inhibited
• Low Ionic Strength
• Does NOT Prevent Swelling
• Does NOT Dissolve Iron Scales
• Slow to Dissolve Carbonates

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 High Temperature
(HPHT) Wells

• Excessive Corrosion with HCl based systems

(corrosion inhibition expensive!)
• Fast acid-rock reaction prevents deep
penetration
• Risk of unconsolidation and sand production
• Clays instable in HCl above 100 deg C

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 High Temperature
(HPHT) Wells

Use Organic Acids (Acetic, Formic, Citric, etc.)

Organic/HF mixture in STIM2001: Volcanic Acid

• Corrosion inhibition up to 200 deg C

• Weak acids: retarded reaction compared to HCl
• No clay instability problems

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 Horizontal Wells
Main issue is acid placement
• Use CT or Diversion to properly place fluids
• Use STIM2001 to analyse fluid coverage

HF treatments in Horizontal Sandstones NOT

often done
• Gelled acids may damage permeability
• Economically unattractive due to high volumes

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 Sandstone Matrix Acidizing
Typical Treatment Procedures

• Mud Clean-out (whole mud lost)

• Wellbore Cleanout (pickle tubing)
• Non-acid preflush (NH4Cl) 50-100 gal/ft
• Acid Preflush (HCl) 50-100 gal/ft
• Damage Removal System (HF) 50-200 gal/ft
• Overflush (NH4Cl) 25-100 gal/ft
• Nitrogen (optional)

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 Design Process Step 1 - Candidate Selection

A good sandstone acidizing candidate is one that:

 Is damaged, and the damage is soluble in HF acid

 Has carbonate content < 10%
 Has the chance for highest incremental PI
 Has high potential for success (mineralogy,
temperature, known damage mechanism, etc.)

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 Candidate Selection in STIM2001
 Calculate damage skin Sdam
 Calculate production increase when Sdam=0
 Rank wells
Stotal =
Sdam - Skin due to near-wellbore damage (+)
+ Spart - Skin due to partial perforation (+)
+ Sdev - Skin caused by deviation (-)
+ Sturb - Skin due to turbulence (gas, +)
+ Sgravel - Skin caused by gravel packs (+)
+ Sperf - Skin due to perforation effectiveness (+/-)
+ Sstim - Skin caused by stimulation (-)
+S
Marten Buijse - IMPACTfiss- Skin caused by natural or induced fissures (-)
Team
 Design Process Step 2 - Acid Selection based on
Damage, Mineralogy and BHT
(mainflush)
13.5/1.5% HCl/HF High HCl/HF ratio (prevent precip.)

Retarded HF For deep damage (fines migration)

9:1 HCl/HF Low HF, for high feldspar formations

Organic/HF For higher temps

12/3 HCl/HF ‘Mud acid’ for silica scale removal

HCl only Whenever carbonate content > 20%

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 Acid Additives
• Corrosion Inhibitor - ALWAYS !
• Non-emulsifier surfactant
• Penetrating agent (low surface tension
surfactants)
• Iron sequestering agent
• Mutual Solvent (EGMBE)
• Friction reducer (polymer)

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 Use of Nitrogen

• Large expansion at low pressures helps for

rapid turnaround of depleted reservoirs
• N2 foams are excellent for diversion in higher
perm reservoirs and gravel packed wells
• Reduces volume of fluids placed in water
sensitive reservoirs
• High viscosity helps to carry away insoluble
materials

Marten Buijse - IMPACT Team

 Design Process Step 3
Well and Formation Conditioning
(preflush)

 Remove iron and organic deposits from

tubulars
 Remove damage which is not soluble in acid
 Select appropriate brine type (5% NH4Cl)
 Remove carbonates (HCl or acetic)

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 Design Process Step 4 - Determine
Appropriate Volumes and Rates

 Acid Pre-Flush (Remove carbonates within 2

ft, and leave 1 ft spacing between formation
brine and HF)
 HF Mainflush (100 to 150 gpf is common)
 Overflush (Protect 2 ft around wellbore)
 Rate is generally maximum possible below
frac pressure. May be limited by tubulars and
pumping equipment.

Marten Buijse - IMPACT Team

 Acid Preflush and Overflush Volumes
Fluid Invasion
8

6
5

4
3

2
1

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
Penetration Into Formation (ft)
Formation Brine Preflush (50.0 gal/ft) HF Stage (100.0 gal/ft)
Overflush (50.0 gal/ft) Wellbore
Halliburton Energy Services, Inc. STIM2001 Version 1.5.0
Shell International Exploration and Production 15-Oct-01 12:42

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 Design Process Step 5
Choose a Diversion Technique

The purpose of diversion is to help remove damage over a

maximum amount of zone during the acid treatment.

Method Application
Ball sealers Cased and perf’d vertical wellbores
Degr. Particulates Lower temps and perms
Foams Higher perms and injectivity contrasts
Gel Slugs Lower temps and perms
Gelled acid More for carbonate reservoirs
Coiled Tubing Long horizontal intervals, OH, GPs
MPMR Should always be considered

Marten Buijse - IMPACT Team