Matrix Acidizing

Formation Damage

Kellyville Training Center

WPS
Types of Formation Damage
Drilling
1. Well Construction
Cementing
Operations Completion/Workover
Perforations
2. Fines & Clays

3. Scale Deposits Mixed

4. Organic Deposits Deposits

2 KTC-WPS Formation Damage

 5. Emulsion
6. Wettability
change
7. Water block
8. Bacteria Production
9. Well Production Injection
Stimulation
Operations

3 KTC-WPS Formation Damage

1. Well Construction Operations
 Drilling / Cementing /
Completion

Filtrate
& solids
invasion

5 KTC-WPS Formation Damage

Drilling

 Filter cake ~ 0.001md Filter cake Formation

 impaired formation K

 How to bypass in OH?

• Filter cake removal maybe a

necessity!
RDF (STARDRILL) Filter Cake
Formation Damage
 1. Drilling Mud Solids 3. Oil Based Muds
• Poor Mud Cake • High Solids Oil
• Overbalance • Cationic Emulsifiers
• Invasion/Relative
• Particle Size vs. Pore
Permeability
Size/Fissures Filtration
– 3”
2. Drilling Mud Filtrate
• Formation Sensitivity
(pH, salinity, scale)
• High Penetration
Capillarity
• Fines Dispersion
• Additive Residues
• Cooling
7 KTC-WPS Formation Damage
 Cementing
 Washes & spacers
• Destroy mud cake
• Dispersants
• Filtrate invasion inches
 Cement slurries
• High pH
• Precipitation CaCO3
• Free H2O water block
 Squeeze
• Formation breakdown
8 KTC-WPS Formation Damage
 Completion/Workover Fluids
 Suspended Solids  Fluids
• Polymer Residue • oxidized crude
• refined diesel
 Fluid Loss Control
• Formation Sensitivity  Excess pipe dope
• Clays
• Wettability
• Scales

9 KTC-WPS Formation Damage

 Perforations

 Debris
Radial Distance (mm)

 Compacted

Zone

 Fluid solids

 Balance

10 KTC-WPS Formation Damage  Rock softness

  Off-centered perf’s
• defective cleanup
• shorter penetration
 Plugged perforations evidence
• Screens
• Productivity profiles
• Injectivity profiles
• Pulsed neutron logs

 Spot clean fluid

11 KTC-WPS Formation Damage

 2. Fines
Migration &
Clay Swelling

12 KTC-WPS Formation Damage

 2. Fines Migration & Clay Swelling
 Clays, mica, Secondary
Cement Quartz
feldspar (Carbonate
weakly Quartz)
*Feldspar
bonded to Clays
(Pore lining
s

pore walls i.e., illite)

Clays *Chert
(Pore filling Remaining
i.e.,
 Salinity Kaolinite)
Pore Space
*Mica
changes and
shear by
moving pore
water

 Salinity shock
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Sedimentary Rock
Classification Clastic Rock -
Formed From Debris (weathering and erosion) of Older Rock
Rock Type Particular Diameter

Conglomerate Pebbles - 2 to 64 mm
Sandstone Sand - 0.06 to 2 mm
Siltstone Silt - 0.003 to 0.06 mm
Shale Clay - Less than 0.003 mm

Nonclastic - Mostly of Chemical or Biochemical Origin

Rock Type Composition

Limestone Calcite - CaCO3

Dolomite Dolomite - CaMg(CO3)2
Salt Halite - NaCI
Gypsum Gypsum - CaSO4.2H2O
Chert Silica - SiO2
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Coal Chiefly Carbon
 Migrating Clays: Kaolinite

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SEM photo

Quartz

Kaolinite
 Swelling Clays: Smectite

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 Chlorite

15000
x
magnifi
cation

18 KTC-WPS Formation Damage

19 KTC-WPS Formation Damage
  Problems
• Plugging
• Clay swelling
 Causes
• High production rates
can entrain particles
and cause bridging
• Replacement of
formation water
 Indicators
• Production decline
increases with
increasing choke size
• Produced water may
be turbid
• Surface samples
» Clays and silica fines
are insoluble in HCl
• Pump-in test

21 KTC-WPS Formation Damage

 Location

22 KTC-WPS Formation Damage

 3. Inorganic Scales
Water-soluble
chemicals that
precipitate out of
solution in
response to
1. supersaturation
or
2. commingling of
incompatible
fluids
3. Evaporation
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Scales
Acid Soluble Scale
Both calcium and bicarbonate in the formation
Calcite (CaCO3)
brine
Corrosion products and bicarbonate in the
Siderite (FeCO3)
formation brine
Corrosion products and sulfate reducing
Pyrite (FeS, FeS2)
bacteria
Corrosion products and oxygen rich injected
Iron Oxide (Fe2O3, Fe3O4)
water
Acid Insoluble Scale*
Barium in formation water and sulfate in
Barite (BaSO4)
injected seawater
Strontium in formation water and sulfate
Celestite (SrSO4)
commonly in injected seawater
Anhydrite (> 110 C) Calcium in formation water and sulfate
Gypsum (< 110 C), CaSO4 commonly in injected water
Mixed Barium/ strontium Barium and strontium in formation water and
sulfate ((Ba, Sr) SO4) sulfate in injected sea water

* Requires specially formulated solvents

24 KTC-WPS Formation Damage
 Supersaturation Dissolution
Mineral matter
dissolves in water

Transportation
Produced water carries
minerals through formation
wellbore and tubing

Deposition
Changes in water causes
supersaturation and precipitation.
Scale adheres and grows

25 KTC-WPS Formation Damage

 Incompatible waters

Supersaturation Ion pairs Clusters / Nuclei

Ba2+ SO4 Ba2+ SO42

2

Transient Stability
Ba2+ SO42

Imperfect Crystallites
Further growth at sites of
crystal imperfections

26 KTC-WPS Formation Damage

  Causes:  Indicators
• P, T change • Restricted production
• Outgassing • Water flow
• Choke obstruction
• pH change
• CT/wireline trips
 Most common • Water analysis
scales: CaCO3,
CaSO4, BaSO4

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 Common Ions in Formation Brines

Cations Anions
Na+ Cl-
K+ HCO3-
Ca+ CO32-
Mg2+ SO42-
Barium2+
Strontium2+
Fe2+, Fe3+
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 Solubility of Various Minerals

Scale Solubility mg/liter

Sodium Chloride 318,300.0
Calcium Sulfate 2,080.0
Calcium Carbonate 53.0
Barium Sulfate 2.3

(in Distilled Water)

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 Scale Deposits

inorganic scales:
mixing, T, P

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Case: Iron
 Sources of Dissolved Iron

 Contaminated acid
 Equipment corrosion
 Iron scales
 Formation minerals

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 Iron Scales
 Types
• Iron Carbonate
• Iron Sulfide.- only 2 out of 7 forms are HCl-
soluble
• Iron Oxide

 Precipitation mechanism
• Aeration (oxidation)
• pH, pressure or temperature change
• Corrosion products
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 Contaminated Acid

 Acid delivered by service companies

generally contains < 180 ppm
 Fe levels in contaminated acid can
exceed 3000ppm
 Contamination occurs when acid is
transferred to dirty storage tanks

37 KTC-WPS Formation Damage

 Millscale
Important Source of Fe in a New Well

Millscale Fe3O4
Pipe 10,000 Ft, 2 7/8 in, 6.5 lb/ft
Scale 0.073 lb/ft
15% HCl 69 gal/1000 ft to clean scale
2+
Fe 29,000 ppm
3+
Fe 57,000 ppm

Hall et al, SPE

17157
38 KTC-WPS Formation Damage
 Acid Corrosion of Iron

 Acid corrosion of iron only produces Fe2+

 O2 dissolved in the acid will be < 8 ppm
 Oxidation of Fe 2+ will yield only about 55
ppm Fe 3+
 Corrosion Inhibitors effectively control this
source of iron

39 KTC-WPS Formation Damage

 Typical Formation Minerals (Fe)
MINERAL FORMULA OXIDATION
STATE OF
IRON
Hematite Fe2O3 3+
Magnetite FeO.Fe2O3 3+, 2+
Pyrite FeS 2+
Siderite FeCO3 2+
Chlorite 2+
Mixed-layer 2+
Hall et al, SPE
clays
17157
40 KTC-WPS Formation Damage
 Recovered Acid
 Most recovered spent acid is greenish
• not a problem as this is the color of the
soluble Fe2+ species
 If recovered spent acid is reddish,
indicative of downhole problem
 Greenish samples will turn red & or
precipitates will form upon standing
due to oxidation at surface
 Black?
41 KTC-WPS Formation Damage
 Iron Precipitation

 Fe+3 precipitates as Fe(OH)3 at pH » 2

 Fe+2 precipitates as Fe(OH)2 at pH » 7

 What is the pH of the recovered acid?

42 KTC-WPS Formation Damage

 Solubility of Fe(OH)3
Fe+3, ppm
+3
pH Fe , ppm 3000
0.5 2.66E+03
1.0 8.40E+01
2000
1.5 2.66E+00
2.0 8.40E-02
2.5 2.66E-03 1000
3.0 8.40E-05
7.2 2.11E-17
0
8.0 8.40E-20 0.5 1 1.5 2 2.5 3 7.2 8

43 KTC-WPS Formation Damage

 Effect of H2S on Iron Precipitation
 Ferrous Sulfide
Fe++ + H2S FeS + 2H+
• When pH » 2

 Sulfur
H2S + 2Fe+3 S + 2Fe+2 + 2H+

• Sequestering Agents Do Not Prevent Sulfur

Precipitation

44 KTC-WPS Formation Damage

 Reactions on Acidizing Sour Wells
2HCl + CaCO3 = CaCl2 + CO2 + H2O (1)

2HCl + FeS = FeCl2 + H2S (2)

Fe2O3 + 6HCl = 2FeCl3 + 3 H2O (3)

2HCl + Fe = FeCl2 + H2 (4)

2Fe3+ + S2- = S + 2Fe2+ (5)

Fe3+ + 3OH- = Fe(OH)3, pH > ~ 1.5 (6)

Fe2+ + 2OH- = Fe(OH)2, pH > ~ 5 (7)

Fe2+ + S2- = FeS (precipitates at pH 1.9) (8)

45 KTC-WPS Formation Damage

 FeS Removal Guidelines
 100 gal/1000 ft of tubing
• If small diameter tubing (1.315-in. or less) or CT is used, 50
gal/1000 ft

 Tubeclean pump rate should be 2 bbl/min

• If small diameter tubing (1.315-in. or less) or CT is used, 0.5
bbl/min

 Tubeclean should be reversed out

 Tubeclean should not be pumped through ports/bypass in a

packer assembly: plugging may result

 Add L62 to ensure FeS does not reprecipitate

46 KTC-WPS Formation Damage
4. Organic Deposits

47 KTC-WPS Formation Damage

 Paraffins
 Linear or branched-chain saturated
aliphatic hydrocarbons C20H42 to
C60H122

 Heavy HC phases, insoluble in oil at

producing conditions

 Cloud point, pour point

48 KTC-WPS Formation Damage
 Paraffin Deposition
 Precipitated
paraffins are
attracted to crystal
growth sites (and
other paraffins)

 Paraffin crystals
can deposit onto
surfaces
• Diffusion
49 KTC-WPS Formation Damage
• Collisions
 Paraffin Related Production Loss

 Temperature
 Amount of gas in
solution
 Presence of water,
sand and other
organic compounds
 Action of resins and
asphaltenes
 Surface roughness

50 KTC-WPS Formation Damage

 Asphaltene Deposits

• Hard coal-
like
deposits

• Sludges
and rigid
film
emulsions
51 KTC-WPS Formation Damage
 Factors Governing Asphaltene
Deposition

 Solubility and
deposition
 Iron contamination
 pH effects
 Pressure
 Injection of cold
fluids or hot oiling
acid

52 KTC-WPS Formation Damage

 Sludge

53 KTC-WPS Formation Damage

 Characteristics of Organic
Deposits
Paraffins Asphaltenes
• Precipitate upon • Destabilized by drastic
cooling and pressure temperature changes,
reduction low pH or high pH
• Waxy, may be tacky or fluids and Ferric ions.
brittle. • Black sticky-to-hard
• Burn with a clean solid or slushy mass.
flame • Burn with a black,
• Soluble in aromatic sooty flame.
solvents (Xylene, • Soluble in aromatic
Toluene). solvents (Xylene,
Toluene).
54 KTC-WPS Formation Damage
 Asphalt Tars
 Aggregate of condensed polycycllic
aromatic ring
 Molecular weight, SG = 1.2
 Black, sticky to hard solid
 Colloidally dispersed in crude oils
 Burns with black sooty flame
Asphaltene
Micelle

55 KTC-WPS Formation Damage

 Mixed Deposits
 Fines/scale particles becoming oil wet and
acting as a nucleation site for organic
deposits
• organic compounds
• either scales, silts or clays

 Strip organic phase with an organic solvent

and dissolve inorganic material
• xylene followed by HCl
• DAD
56 KTC-WPS Formation Damage
 5. Emulsion

 Stabilized by fines and

surfactants

 Treatment: Mutual
Solvents, Clean
Sweep, demulsifiers
(surfactants)

57 KTC-WPS Formation Damage

 6. Wettability
water wet oil wet

58 KTC-WPS Formation Damage

 7. Water Block 1 1

Water Wet
 Sw increase
Oil Wet

 Favored by pore- K
ro

lining clay K
ro K
rw
K
rw

minerals (Illite)
 Treatment:
reduction of
interfacial tension
• surfactants 0

• alcohol 0 Swc 1-S

or
1

• mutual solvent S
w

59 KTC-WPS Formation Damage

 8. Bacteria
 Water injection, disposal wells
 Growing colonies
 Slime corrosion/plugging
 SRB
• H2S corrosion spots
• corrosive waters lead to sulfide cracking
 Iron bacteria
• ferric hydroxide gelatinous sheath
• 1 ppm
60 KTC-WPS Formation Damage
9. Well Production Operations
 Pressure and Rate

p > pb
p < pb

62 KTC-WPS Formation Damage

 Production

 Fines Migration/Bridging
High
 Precipitations Scale, Paraffins…
Drawdown

 Turbulence

 Increased Effective Stress

 In Situ Distillation/Wettability Changes

63 KTC-WPS Formation Damage

 % of Original Permeability

64 KTC-WPS
0
20
40
60
80
100

High Drawdown
( p/l = 50 )

Low Drawdown

Berea Sandstone
( p/l = 2-5-10-20-50 )

Formation Damage
High Drawdown
Effect of Drawdown on PI

( p/l = 40 )
Oil Well Cores

Low Drawdown
( p/l = 2-5-10-20-40 )
(Miocene, Pliocene)
 Injection

“dirty” incompatible
water water

65 KTC-WPS Formation Damage

 Injection Operations
 Water Injectors
• Suspended Solids/Scales/Clays
 Alkaline/Steam Flood
• Mineral Dissolution/Precipitation
• (scales, zeolites, silica…)
 CO2 Flood
• Sludge/Scale Formation
• Carbonates Dissolution
 Polymer Flood
• Gel Residues
• Fines Transport/Bridging

66 KTC-WPS Formation Damage

 Stimulation
 No wellbore cleanup
 Wellbore cleanup  Deconsolidation
invasion  Secondary
 Poor iron control precipitation
 Surfactants  Clay dispersion
• wettability changes
• sludges
• emulsions
 Additive breakdown
• T limit
• overexposure time
67 KTC-WPS Formation Damage
 Areas of Damage

Tubing Gravel Pack Perforations Formation

Scales
Organic deposits
Silicates, Aluminosilicates
Emulsion
Water block
Wettability change

69 KTC-WPS Formation Damage