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