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Scale Dissolution
Scale Dissolution
Scale Dissolution
OBJECTIVE
To demonstrate how the M-I PC Scale
Dissolver Range can assist in restoring well
productivity impaired by scale deposition
Agenda
M-I Swaco Organisation
Calcium Carbonate dissolvers
Sulphate dissolvers
Case history well stimulation
Integrated
Integrated
Fluids
Fluids
Engineering
Engineering
Drilling
DrillingFluids
Fluids
Completion
Completion
Fluids
Fluids
Drilling
DrillingWaste
Waste
Management
Management
Federal
Federal
Wholesale
Wholesale&&
Industrial
Industrial
PRODUCTION
PRODUCTION
CHEMICALS
CHEMICALS
Technology Focus
Commitment to R&D
- Significant reinvestment of revenues
in R&D programs
Corporate Capabilities
Scale Dissolvers
CAL-Acid
BaSOL
Calcium Sulphate
Gypsol
Iron Sulphide
Pyrisol
Iron deposits/rust
R-Sol
What is Scale?
An adherent mineral deposit
precipitated from solution
Commonly found in
conjunction with other fouling
deposits
- e.g. iron hydroxides and
Causes of Scale
The causes of scale and fouling deposits are many, varied and
complex
Oilfield waters contain a large number of potential scaling
species
These include soluble ions such as calcium, magnesium, barium,
etc which precipitate when they encounter changes in water
conditions
- e.g. temperature, pH, concentration effects and incompatibilities
In addition, corrosion by-products, process contaminants and
incompatible chemical treatments lead to fouling and scaling
Types of Scale
Scalingspecies
species
Scaling
CaCO3
CaCO
3
BaSO4
BaSO
4
FeCO3
FeCO
3
FeS
FeS
FeO/OH
FeO/OH
SrSO4
SrSO
4
CaSO4
CaSO
4
Scale Removal
Acid soluble scales
Scale removed through reaction to generate new chemical
species
CaCl2 + CO2 + H2O
CaCO3 + 2HCl
BaSO4 + AEDTA
(A - alkali metal)
Calcium Carbonate
Formed by the combination of the calcium ion with either
carbonate or bicarbonate in water
Ca2+ + CO3
Ca2+ + 2(HCO3)
CaCO3
CaCO3 + CO2 + H2O
MIPC CAL-Acid
Developed as a viable alternative to HCl
Low corrosivity
Sequesters scaling ions
Loading capacity comparable to HCl
Slower to react, but
- Allows better reaction control in contacting critical scale
- Penetrates deeper into affected reservoir areas
MIPC CAL-Acid
Affords rapid, yet controlled reaction
Loading capacity 260 g/ltr (neat product)
Typically applied as 50% solution
- Maximises performance vs. concentration effects
Inherent sequestering capacity ensures prevention of secondary
scaling
EDTA
% Scale dissolved
90
CAL-acid
15% HCl
80
70
60
50
40
30
20
10
0
3
Time (Hours)
Secondary Scaling
Mineral acids liberate calcium and iron which can re-precipitate
during the treatment
MIPC CAL-Acid
Advantages
Low corrosivity
Sequesters scaling ions
Load capacity similar to HCl
Better reaction control in
contacting critical scale
Penetrates deeper into
affected reservoir areas
Disadvantages
Longer contact time
- Insoluble in acid
- Very low solubility in water
- Forms hard, consolidated
scales
- Usually found as mixed
scale deposit
Barium Sulphate
Least soluble scale found in
oilfield systems
- 2.3 mg/l at 25oC
Many formation waters
contain high barium
concentrations
Not usually a problem until
seawater breakthrough
- High SO4 levels
Chelation Process
Divalent metal ions can form stable complexes with chelating
agents
Even with low solubility, barium ions solvate in water
BaSO4 Ba+ + SO42 Addition of a chelating agent (L) gives
Ba2+ + L BaL
Effectively removing barium ions from solution
BaSO4 + L BaL + SO42 Driving solvation of more barium ions and thus scale
Dissolver Formulation
Sulphate scale still has a low solubility even in the presence of
some chelating agents
To deliver effective dissolver chemistry we need to consider...
Chelation
Conversion
Catalysis
Dissolver Formulation
Chelation
- Must have high metal affinity log K1
- Operate at optimum pH
Conversion
- Conversion agents assist in metal ion chelation eg
Fe (II)
Fe (III)
Catalysis
- Enables dissolution process to proceed more efficiently
BaSOL
EDTA
100
90
80
70
60
50
40
30
20
10
0
0
0.5
1.5
2.5
Time (hours)
12
Temperature Effects
Wettability
Dissolution of barium sulphate scale as a function of wettability
80 deg C, static conditions
100
% Scale remaining
90
80
Water w et
70
Crude w et
60
Asphaltene w et
50
40
30
20
10
0
0
6
Time (hours)
10
Analar BaSO4
Field scale
Comments
Converter + acid
High
low
Multi-stage
EDTA
20
12
Very slow
DTPA
30
30
Slow
BaSOL
40
80
Fast
BaSOL 2000
120
120
Best so far
Calcium Sulphate
Formed in a similar way to
Barium and Strontium
Sulphates
Often found as a co-deposit
with Barium & Strontium
Removal assured with
chelation chemistry
Gypsum - naturally occurring CaSO4
MIPC Gypsol
Gypsol dissolves calcium sulphate at ~2.8 times the speed of
BaSOL
Designed specifically for Calcium sulphate scale
Outperforms EDTA - traditional calcium sulphate dissolver
Non- corrosive
Supplied as a pH 7-8 solution, thus low handling hazard
Comparative Dissolution
Temperature Effects
80
147 deg
95 deg
60
60 deg
40
20
Time (hours)
0
0
% Scale Remaining
100
Gypsol
Outperforms EDTA
Non corrosive
Non corrosive
Safe to handle
Best Barium/Strontium
sulphate de-scaling solution
CASE HISTORY
Kg BaSO4
removed
Kg SrSO4
removed
Production
rate (m3/day)
Dissolver
target zone
350
20
19.5
1390
Perfs
4.5
9.1
1560
Perfs
100.9
110.9
1755
Tail Pipe
93.2
82.9
1800
Tail Pipe
14.6
44.0
1975
Well Bore
Summary
Summary
The MIPC range of Scale Dissolvers represent leading edge
technology in the market place
- CAL-Acid for carbonate scales
- BaSOL 2000 for barium & strontium sulphates
- Gypsol for calcium sulphate
Field experience in removal of barium & strontium sulphate
scales from tubulars and formations
- Significant increase in productivity
Personnel in China with experience in scale dissolver and scale
inhibitor squeeze treatments
Innovative range
CAL-Acid
BaSOL
Calcium Sulphate
Gypsol
Iron Sulphide
Pyrisol
Iron deposits/rust
R-Sol