M-I Production Chemicals
(A Business Unit of M-I SWACO)
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
M-I Swaco Organisation
M-I Swaco 60:40 JV company
of Smith & Schlumberger
Global market leaders in
Drilling, Completion Fluids
& Waste Management
World Class Technology,
Support & Logistics
delivering value to customer
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
Production Chemicals provides Cradle to Grave portfolio
Engineering & Technical Support
Leadership
World Class experienced and trained
engineers
Proprietary software packages to
optimise drilling, production and
environmental performance
Research centres, technical support
operations strategically located
worldwide
Leader in developing drilling fluids,
production chemicals and waste
management technologies that
deliver value-added performance
with environmental acceptability
Technology Focus
Commitment to R&D
- Significant reinvestment of revenues
in R&D programs
Strong focus on joint customer
research efforts
- Develop practical, fit-for-market
technologies
- Shorten development cycles
Schlumberger offers M-I worlds
most comprehensive reservoir
expertise
- Opportunity to generate
technologies that complement fluid
and production chemicals
disciplines
World Class Infrastructure, Distribution &
Logistics
Integrated procurement,
manufacturing, inventory
management and transportation
system
Blending and storage facilities in
close proximity to customers
Comprehensive network of
centralised warehouses and dock
facilities
Exclusive deepwater port
participation
Global Service Organisation
M-I Production Chemicals
Corporate Capabilities
Health Safety and Environment
Health and Safety is our first
priority
Operating to ISO 9001/2000 and
ISO 14001 standards
In-house ecotoxicology laboratory
operating to GLP. Capable of
performing all OSPARCOM
approved tests
R & D focus on more
environmentally friendly
chemistry
Environmental management
capability
Comprehensive Product Offering
Corrosion Inhibitors
Scale Inhibitors / Dissolvers
Bactericides
Demulsifiers
Wax Inhibitors
Water Treating Chemicals
Antifoams
Hydrate Inhibitors
Hydrogen Sulphide Scavengers
Drag Reducers/Flow Improvers
Cleaning Compounds
Commodities
Research & Technology
30% of technical professionals are
lab-based
Main laboratories in Bergen,
Aberdeen, Dubai and Perth
Long-term, client focused projects
oriented toward novel chemistries
Emphasis on more
environmentally friendly
chemistry
- In-house ecotoxicology laboratory
Scale Dissolvers
MIPC Scale Dissolver Product Line
Mineral Scale Dissolution
Carbonate scale
CAL-Acid
Barium/Strontium Sulphate scale
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
sulphides, waxes, asphaltenes,
etc..
Once deposited, crystal growth
can lead to the development of
severe scaling problems
Mineral scale deposition cuts oil
production by plugging
payzones and blocking tubing
and topsides.
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
Acid soluble scales
SrSO4
SrSO
4
CaSO4
CaSO
4
Acid insoluble scales
Scale Removal
Acid soluble scales
Scale removed through reaction to generate new chemical
species
CaCl2 + CO2 + H2O
CaCO3 + 2HCl
Acid insoluble scales
Much harder scale type to remove. Requires chelation chemistry
BaEDTA + ASO4
BaSO4 + AEDTA
(A - alkali metal)
Calcium Carbonate Dissolution
Carbonate Scale Dissolving
Most common scale type found in oilfield production systems..
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
Carbonate Scale Deposition Factors
pH
Increasing alkalinity leads to carbonate scale deposition
Pressure
Pressure drops lead to CaCO3 deposition, hence deposits at valve
locations
Temperature
CaCO3 solubility decreases with increasing temperature
Carbonate Scale Removal
Traditionally performed with Hydrochloric acid
- Very reactive quick dissolution time
- Cheap
- Readily available
BUT
- Very corrosive
- Hazardous
- Secondary scaling can occur
- Possibility of formation damage
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
Carbonate Dissolvers Compared
Dissolution of Calcium Carbonate
at 60 deg C, static, 260g/ltr CaCO3
100
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
This can lead to formation damage
MIPC CAL-Acid has an inherent sequestering capacity
Scaling ions released by acid treatment are sequestered and held
in solution
No expensive additives are necessary!!
Corrosivity of MIPC CAL-Acid
Mineral acids very corrosive potential for tubular damage
Central to low corrosivity of CAL-Acid is corrosion inhibitor
package
- Stable to 100oC
Corrosivity against L80 & 13Cr steel presented
Corrosivity of MIPC CAL-Acid
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
Barium Sulphate Dissolution
Sulphate Scale Dissolution
Sulphate scales of barium,
strontium and calcium
present a complex
dissolution problem
Characteristics
- 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
Barite - naturally occurring BaSO4
Barium Sulphate Scale Removal
Low solubility yields a difficult dissolution problem
Acid insoluble, thus we must employ a different chemical
approach....CHELATION
Chelating agents complex with metal ions to return water
soluble species - increasing solubility
- e.g. EDTA - Ethylene Diamine Tetra-acetic Acid
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
Sulphate scale dissolver
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)
Favours chelation of ferric rather than ferrous ions
Catalysis
- Enables dissolution process to proceed more efficiently
BaSOL and BaSOL 2000
Latest advance in the field of barium sulphate dissolution
Delivers optimum pH conditions for scale dissolution
Non-corrosive
Non-hazardous for handling
Affords rapid dissolution rates
High loading capacity - 120g/ltr possible
Relative Dissolution Rate
Relative dissolution rate of BaSOL and EDTA
Barium sulphate, 85 deg C, 4% w/v
BaSOL
EDTA
100
Scale remaining (%)
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
Progress in Barium Sulphate Dissolution
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
Sequestering capacity in g/ltr @ 6 hrs @ 90oC
Calcium Sulphate Dissolution
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
Dissolution of Anhydrite scale
80
147 deg
95 deg
60
60 deg
40
20
Time (hours)
0
0
% Scale Remaining
100
Sulphate Scale Dissolvers - Summary
BaSOL 2000
Gypsol
Rapid dissolution rates
Outperforms EDTA
High load capacity
Non corrosive
Non corrosive
Safe to handle
Best Barium/Strontium
sulphate de-scaling solution
Designed specifically for the
removal of calcium sulphate
BaSOL Scale Dissolver
CASE HISTORY
Case History BaSOL Sulphate Dissolver
North Sea well with severe
decline in production
- Sulphate scale across perfs
Tail pipe scale preventing
access to perforating guns
Scale analysis
- 72% BaSO4
- 25% SrSO4
- 3% CaCO3
BaSOL Case History Treatment
Summary
Bullhead application used
Spearhead with KCl brine with demulsifiers
Spot dissolver & allow to reach formation temperature
Series of displacement & soak sequences
- Maximise dissolution
Total of 5 dissolver sequences carried out
- First two across perforations
- Last three in tailpipe
- PI noted after each flowback
BaSOL Case History - Results
Production increased from 350 m3/day to 1975 m3/day
- 464% increase over 5 treatments
Total mass of 500 kg sulphate scale removed
- 233.2 kg BaSO4
- 266.4 kg SrSO4
53 kg sulphate scale removed from perforations/near well bore
- Represents greatest detrimental affect on production
Success meant that well did not need re-perforation
- Represents added value benefit
BaSOL Case History - Results
Dissolver
sequence
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
BaSOL Case History Production Profile
BaSOL Case History Scale Removal
Profile
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
M-I Production Chemicals has the chemical resources
to remove any commonly encountered field scale
MIPC Expertise
Innovative range
COMPREHENSIVE SCALE CONTROL PACKAGE
MIPC Scale Dissolver Product Line
Mineral Scale Dissolution
Carbonate scale
CAL-Acid
Barium/Strontium Sulphate scale
BaSOL
Calcium Sulphate
Gypsol
Iron Sulphide
Pyrisol
Iron deposits/rust
R-Sol
