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Inorganic Scale Management

in Oil Field
By:

Alok Dwivedi
AEE(P)
Corrosion & Scale Management Deparatment-IOGPT

Objective
Concept of Scale in oil field
Identifying the scale
Causes of Scale Deposition
Commonly Encountered form of
Scale
Mechanism of scale deposition
Chemistry of CaCO3 Scale
Chemistry of SrSO4 Scale
Various Scale Removal
Techniques

Inorganic & Organic


Deposits
Before the well is drilled & Completed, the fluids
in the formation are in equilibrium.
As soon as flow starts, equilibrium gets disturbed.
Solid precipitation starts.
Inorganic deposits are SCALE
Organic deposits are
Waxes (Saturated Hydrocarbons)
Asphaltenes (Unsaturated & Cyclic
hydrocarbons)
Gas Hydrates etc.

Information Analysis
Plugged Wells
Deposit
Organic Deposit

Non Plugged Wells

Prediction:
PVT
Asphaltenes Solubility
Inorganic DepositCharacterization

Paraffins

Scale

Asphaltenes

Sand

% Asphaltene
(Each 2 Months)
% Asphaltene
Reduction

SCALE
Scale is a deposit that plugs or fouls
equipments & systems.
Inorganic mineral constituents of water
that precipitate to form hard, adhere
deposits.
Scale begins to form when the state of
any natural fluid is perturbed in such a
way that solubility limit for one or more
5

SCALE
Scale formation is a dynamic process
and changes in magnitude during the
life cycle of a field as the composition of
produced water changes.

Produced water changes and life-cycle


trends may differ well to wells because
of differences in production zone and
stratigraphic heterogeneities.
6

Problems due to
Scale
Restricts Flow
Reduce Production
Reduce Injectivity
Catastrophic Failure
Can Be Radioactive
7

Types of Waters
Formation Water: Water present in hydrocarbonproducing formation or related rock layers and is found
in the pore spaces of rock.
Produced Water: Formation or condensed waters, or
both, in various combinations and salinities that are
received topside with the oil and gas being produced.

Injection Water: Supplied from surface sources and


used to maintain formation pressure

Water Chemistry
Produced/Formation water is analyzed to
determine the concentration of following species
(In General)
Major Ions:
SO42-, OH-

Na+ , Ca+2, Mg+2, Ba+2, Sr+2, Cl-, HCO3-,

Minor Ions: Li+, Fe2+, Zn2+, Pb2+, SiO44-, Br-, F-

s:

Dissolved
Gases:
O2,Dependent
CO2, H2S, CH
4, C2H6 etc..
igrams
per Litre:
Temp.
Unit
m: Temp. Independent Unit = 1 mg of solute in 1000 g of sol
ppm=(mg/L)/(Sp.Gr)

Concept of Solubility
Product
The equilibrium constants for saturated solution and solid
formation (precipitate) are called solubility product, Ksp. For
unsaturated and supersaturated solutions, the system is not at
equilibrium, and ion products, Qsp, which have the same expression
as Ksp is used.
Equilibrium Expression for Ksp and Qsp

AgCl(s) = Ag+(aq) + Cl-(aq)


[Ag+] [Cl-]
CaCO3(s) = Ca2+(aq) + CO32-(aq)
[Ca2+] [CO3-]
Li2CO3(s) = 2 Li+(aq) + CO32-(aq)
[CO3-]

[Li+]2

Diagnosing Scale
Scale formation can be predicted from water
chemistry and system physical conditions.

Diagnosing Scale

Diagnosing scale in Surface Equipments

Diagnosing Scale

nosing scale in Down hole tubing or Production fo


Down hole tubing
or Production
formation
Suspended
scale
particles in
water

Scale In
tubing

Well
stimulat
ions not
effectiv
e

Predictio
n from
water
chemist
ry

Evidence
of
Producti
on
Decline

Well or
field
history

Diagnosing Scale

nosing scale in Down hole tubing or Production fo

Types Of Scales
Types of Inorganic Scales:
Water Soluble
Deposits

Acid Soluble
Deposits

Acid Insoluble
Deposits

Salt

Calcium
Carbonate

Calcium Sulfate

Calcium
Chloride

Dolomite

Barium Sulfate

Chemical
Deposits

Iron Sulfide

Strontium
Sulfate

Iron Oxide
Iron Carbonate

15

Scale
Identification
Start
Organ
ic

Yes

Floats
in
Water

No

Solubl
e in
H2O

Yes

FeS
(Probably)

No
Soluble
in
Na4ED
TA

Yes

No

Solubl
e in
hot
HCl

No

Soluble
in HCl

Yes

NaCl
(Probably)

Yes
Yes

Odor of
rotten
egg

No

Iron Oxide

SrSO4
CaSO4
BaSO4

Magneti
c
Magnetite
(Fe3O4)

Yes

CaCO3
FeCO3
MgCO3

Cause of Scale
Deposition
Scales are formed by change in water chemistry
causing super saturation
Causes for Scale
Deposition

Change in
pH,
Temperat
ure
Pressure
etc.

Mixing
Incompati
ble
Waters

Water
Evaporati
on
Flashing

Poor or
No
Inhibitor
Treatmen
t
17

Scale Mechanism

Scale Mechanism

Chemistry of
Scale Formation

Reactions involved
Effect of CO2
CO2 + H2O
H2CO3
H2CO3
H+ + HCO3HCO3H+ + CO3- -

Ca+2 + CO3- - = CaCO3 ---------------------------(1)


Ca+2 + 2HCO3- = CaCO3 + CO2 + H2O
------- (2)
20

Chemistry of
Scale Formation
The Equilibrium will shift to
right if:

An increase in temperature
Decrease in pressure
Loss of dissolved CO2
An increase in pH

Parameters Affecting
Carbonate Scaling

CO2 partial pressure


Operating temperature
Operating pressure
pH
Calcium & Bicarbonate
concentration
Total Dissolved solids
22

Parameters Affecting
Carbonate Scaling
Contd

Effect of CO2

pH
of
water
increases
with
decrease in CO2 concentration
Decrease in CO2 partial pressure
gas over water results in CaCO3
precipitation.
Partial
Pressure
=
Pressure*Mole Fraction

Total
23

Parameters Affecting
Carbonate Scaling
Contd
of Operating Temperature

lity of CaCO3 decreases with increase in tempera

Parameters Affecting
Carbonate Scaling
Contd

Effect of Operating Pressure


Solubility of CaCO3 decreases with
decrease in pressure
Solution pH increases with decrease
in pressure
Calcite is very sensitive to pressure
changes

25

Parameters Affecting
Carbonate Scaling
Contd
Effect of pH

recipitation of CaCO3 increases with increase i

Parameters Affecting
Carbonate Scaling
Contd

Effect of Ca+2 & HCO32concentration


Formation of solid CaCO3 from
aqueous phase increases with
increase
in
Ca
and
HCO3
concentration.

Effect of TDS
Solubility of CaCO3 increases
27
with increase in salt content.

In Summary
CaCO3 precipitation increases as

the operating temperature,


pH,
Ca++
and
HCO3concentration increase
the Pressure (partial pressure
of CO2) & TDS decrease
ecipitation of CaCO3 occurs in the Reserv
ine remains saturated at reservoir condi
28

SrSO4
Occurs as Mineral
Celestine or Celestite
Poorly soluble in water
( 1 part in 8,800 part of water)

Why SrSO4 Scale


Forms??
Mixing of Incompatible water
Ion Species

Formation
Water

Sea Water

Sodium

31,275

10,890

Potassium

654

460

Magnesium

379

1368

Barium

269

Strontium

771

Sulfate

2960

Chloride

60,412

19,766

Calcium

5038

428

Software/Empirical
Tech. to predict Scaling
Link

Scale Management
Change/Optimize Process Parameters
Prevent deposition by using scaleinhibitors etc
Allow scale to form, but periodically
remove it.
Use pretreatments that remove
dissolved & suspended solids.

Combating Scale

Combating Calcium Carbonate Scales

Combating Scale
Combating Sulphate Scales.

Scale Inhibitors
Inorganic Polyphosphates
Organic phosphate esters
Organic phosphonates
Organic polymers
phosphonates,
polyacrylic acids (PAA)
phosphinopolycarboxylic acids (PCA) and
polyvinylsulphonic acids (PVS).

How do Antiscalants
Work

Three Predominant Mechanims


Threshold Inhibition
Dispersion
Crystal Modification

How do Antiscalants
Work

Antiscalants
Mechanisms

Popular Scale
Inhibitors

DP, AMP, PBTC = Phosphonate


HEDP= 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid

Scale Inhibitors
An ideal Scale Inhibitor should have
following properties
Effective scale control at low inhibitor
concentration
Compatibility with sea water &
formation water
High thermal stability
Low toxicity & high biodegradability
Low Cost

Scale Removal
Sequestration using Co-ordinate complex

SrSO4 = Sr+2 + SO4-2


Sr+2 + L = SrL
L=chelating agent

Co-ordination
Complex
A co-ordinate complex is the product of Lewis
acid-base reaction in which neutral molecules
or anions (Ligands) bonds to a central metal
atom by coordinate covalent bonds.
Ligands are Lewis base.
Metal atoms/ions are Lewis acids.
Coordination complexes are distinct chemical
species: Their properties and behaviour are
different from the metal atom/ion and Ligands
from which they are composed.
Typical examples: [Ag(NH3)2]+ , [Zn(CN)4]2etc.

EDTA

EDTA , Ethylenediaminetetraacetic acid.


A Polyamino carboxylic acid
Colorless, water-soluble solid
Hexadentate ligand
Chelating agent
Used to sequester metal ions, Ca++, Fe++

DTPA
DTPA , Diethylene triamine pentaacetic acid.
A Polyamino carboxylic acid
8-active metal-complexing sites, octadentate
ligand
Chelating agent
Used to sequester metal ions, Ba++, Sr++
Oxallic acid can be added as a synergists

Srskill

Srskill
Effect of Oxallic Acid additive

Srskill
IOGPT developed & Patented Recepie,
Srkill is an effective and fast way to
remove SrSO4 scales.
DTPA+KOH+Oxallic acid at a pH>12
Implemented in many wells of MH
Asset.
Increased liquid production
Minimize tubing intervention
Minimize the production loss
Increased safety

Any Questions???

hbti03.alok@gmail.com

Thank You