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TERMINAL OBJECTIVE

Upon completion of this module, the


participant will be able to select the
proper treating chemicals and the
best treating methods, given
corrosion-related operating systems.
ENABLING OBJECTIVE
Define chemical treating terms
and describe treating chemicals.
Describe treatment methods.
Describe bacteria monitoring
techniques in terms of purpose,
methods, and significance of
results.
Operating Problems and Treating
Chemicals
Operating Problem Treating Chemical
Equipment corrosion Corrosion inhibitor,
Oxygen scavenger
Microbiologically-influenced Biocide
Corrosion
Mineral scale deposits Scale inhibitor
Suspended solids Coagulant, flocculant
Water-in-oil emulsion Emulsion breaker
Oil-in-Water emulsion Reverse breaker
coagulant, flocculant
Chemical Treating Terminology
Typical Treating Chemical Composition
1/3 Active
Ingredients
2/3 Solvents
or additives
Treating Chemicals
Additives: a treating chemical usually
contains an active compound and one or
more additives
Solvents: are add to most treating chemicals
to keep them from separating also lower pour
point
Solubility: is chemicals ability to dissolve in
solution
Dispersibility: is chemicals ability to
transported by fluids or gases
Chemical Treating Terminology
Emulsion tendency: a chemicals ability to
disperse one liquid phase into another
liquid phase
Oil Soluble-Water Dispersible Inhibitors :
are normally used in oil wells and gas
condensate wells
Water Soluble Inhibitors : they are soluble
in fresh and brine water
Chemical Treating Terminology
Corrosion Inhibitors
They adsorb on metal surfaces
They combine with corrosion product film
They form precipitates
Work by one or more of the following
mechanisms:
Inhibitor Classifications
Corrosion Inhibitors
Inorganic Organic
Anodic
Cathodic Film Forming
Chromates
Nitrites
Molybdates
Phosphates
Zinc inhibitors
Polyphosphates &
Phosphonates
Amines
Amine salts
Imidazoilnes
Inorganic & Organic
inhibitors
Inorganic inhibitors are used mainly in boilers,
cooling towers, and fractionation units.
Organic inhibitors are used mainly in oil field
systems.
Organic inhibitors are also used to prevent
overhead corrosion in some refinery crude
units
Often used to reduce corrosion in open
(aerated) and closed cooling water systems.
used alone or in combination with other
inhibitors.
Not enough anodic inhibitor lead to severe
localized pitting.
Inorganic Anodic Inhibitors
Inorganic Inhibitors
Electrochemical Corrosion Reactions in
an Open (Aerated) Cooling Water System
Precipitation of Black
Oxide
Hydrolysis and
Oxidation
Hydrolysis of Dissolved
Iron Lowers pH
ACIDIC PIT SOLUTION
WITH LOWER OXYGEN
CONTENT
6
5
3
1
7
2
Precipitation of Red Oxide
Iron Dissolves (ANODE) ANODIC AREA
Reduction of Oxygen
(CATHODE)
CATHODIC AREA
4
Evolution
of Hydrogen
(CATHODE)
MAGNETITE MAGNETITE
Fe
2
o
3
Fe
3
o
4
RED OXIDE
BLACK OXIDE
H
2
O
2
OH
-
Fe
e
-
e
-
e
-
e
-
Fe
+2
H
+
+ FeOH
+
Fe(OH)
2
+ FeOH
+2
Ferric Iron Deposits as a Gamma
Iron Oxide Film
Inorganic Anodic Inhibitors
4 Fe
0
+ 3 O
2
= 2 Fe
2
O
3
Inorganic Inhibitors
Inorganic Anodic Inhibitors
Combined Iron Oxide and chromium oxide
film on a Metal Surface
Inorganic Anodic (Passivating) Inhibitors
Shift in Anode Potential Caused by Anodic Inhibitors
Before anodic inhibitors
After anodic inhibitors
Potential Difference
More
negative
More
positive
Anode
Cathode
Cathode
Anode
Inorganic Inhibitors
Inorganic Anodic Inhibitors
Estimate of Proper Concentration of
Sodium Nitrite
Weight NaNO
2
(in mg/L)
Wt NaCl + Wt Na
2
SO
4
(in mg/L)
= 1
Inorganic Inhibitors
Not as effective as inorganic anodic inhibitors
but safer to use.
Inorganic Cathodic Inhibitors
O
2
+ 4H
+
+ 4e
-
2H
2
O
O
2
+ 2H
2
O + 4e
-
4(OH
-
)
In acidic systems:
In neutral or alkaline systems:
Reduction Reactions
Shift in Cathode Potential Cause by
Cathodic Inhibitors
Inorganic Cathodic Inhibitors
Inorganic Inhibitors
Zinc Inhibitors
Inorganic Cathodic Inhibitors
Zn
+2
+ 2 OH Zn (OH
2
)
Zinc Ion Hydroxide Ion Zinc Hydroxide
Inorganic Cathodic Inhibitors
Polyphosphate Structure
P NaO
O
P
O
O
ONa ONa
ONa
x
x = 0 Orthophosphate
x = 1 Pyrophosphate
x = 2 Tripolyphosphate
x = 12-14 Polyphosphate
Inorganic Inhibitors
Polyphosphates Prevent Reduction Reactions
at Cathodic Areas
Inorganic Cathodic Inhibitors
Polyphosphate
inhibitor
molecules
H
+
O
2
Metal
Fe
2+
O
2
H
+
e e
Polyphosphates reacts with Ca and other divalent
ions in water such colloids are attracted to +ve
cathode
Organic Inhibitors
Electrical potential of metal
Inhibitor molecule chemical
structure
Size and shape of inhibitor
molecule
Complex mixtures of many different
molecular compounds
Affect both cathodic and anodic sites
Their effectiveness depends upon:
Representation of an Organic Inhibitor Molecule
Using an Aliphatic Amine
Organic Inhibitors
H
C
H
Electrons available for bonding to
metal (chemisorption bond)
Polar amine
nitrogen group
N
Hydrocarbon chain
Oil soluble and attract crude oil
molecules to form oily layer
barrier
Chemisorption & Physical
Adsorption
Organic inhibitors molecules attach to metal
surfaces by chemisorption and physical
adsorption
Physical adsorption is weaker than
chemisorption
Physical adsorption does not involve sharing
of electrons
Organic Inhibitors
Organic Inhibitors
Mechanism for Organic Film Forming Inhibitors
Inhibitor molecule
dispersed in process
stream
Metal
Process Stream
H
H C
N
H H H H H H H H H H H H H H H H C C C C C C C C
N N
N
N N N N N N
Chemisorption & physical
adsorption by polar
amine group
Hydrocarbon
Oil molecule
Hydrocarbon
chain R
H
H C
Organic Inhibitors
Molecular Structure of Common
Oil Field Inhibitors
Name
NH
2
R CONH
2
R C
CH
2
N
CH
2
N
R
1
R
N
(CH
2
CH
2
O) y H
(CH
2
CH
2
O) x H
Primary Amine
Amine
Amine
Polyethoxylated Amines
Structure
R
Organic Inhibitors
Laboratory Static Test
Laboratory Wheel Test
Laboratory Electrochemical Test
Field Corrosion Test Coupons
Field Corrosion Probes
Corrosion Inhibitor Testing
Corrosion Inhibitor Testing
Corrosion Rate
Where -
W = weight loss in grams
A = coupon surfaces area ( in
2
)
d = metal density (g/in
3
) = g/cm
3
x 16.387 cm
3
/in
3
t = time (days)
A x d x t
mpy =
= 3.9 mpy
Weight in grams x 365000
0.037 g x 365000
mpy =
3.875 in
2
x 7.85 g / cm
3
x 16.387 cm
3
/ in
3
x 7 days
Laboratory Electrochemical Tests
LPR Test Apparatus for Continuous
Inhibitor Evaluation
Corrosion Inhibitor Testing
Corrosion Coupons
Field Corrosion Test Coupons
0.5 or 1
3
0.0625 or 0.125
Strip coupon Rod coupon Flush-mounted disc
Corrosion Inhibitor Testing
Field Corrosion Test Coupons
Flush-Mounted Corrosion Coupon in an Access Fitting
Disc coupon
holder assembly
Flush disc
Retriever
Service
valve
1 2 3 4 5
Retrieval Procedure
1. Access fitting in service,
externals removed.
2. Service valve installed,
retriever goes in.
3. Retriever is attached to plug.
4. Retriever extended, plug pass
gate, valve closed.
5. Plug removed.
Corrosion Inhibitor Testing
Field Corrosion Test Coupons
Pitting Severity
Where -
Penetration Rate (mpy)
Pitting Severity =
Maximum Pit Rate (mpy)
Time (days)
Maximum Pitting Rate =
Maximum Pit Depth x 365
Corrosion Inhibitor Testing
Field Corrosion Test Coupons
Interpretation of Corrosion Rates and Pitting Rates
Corrosion Inhibitor Testing
Quality Control
of Corrosion
Inhibitors
Comparison of NMR*
Spectra for Two
Samples of a
Corrosion Inhibitor
*NMR = Nuclear Magnetic Resonance
Quality Control
of Corrosion
Inhibitors
FT-IR* Spectra of Two
Samples of a
Corrosion Inhibitor
* FT-IR = Fourier-Transform Infrared
Oxygen Depolarizes the Cathode
Oxygen accepts
electrons
at the cathode.
Electrolyte
Cathode
Cathode
Metal
Fe
2+
H
+
H
+
H
2
H
2
H
2
H
2
H
2
O
2
e
e
Anode
Oxygen Scavengers
O
2
main cause of corrosion in many water systems
As low as 0.05 ppm O
2
can cause corrosion in water
Arabian seawater contains 5-7 ppm O
2
Sources of O
2
in water systems (open vents, thief hatches on
water tanks, suction side of centrifugal pumps, etc)
Gas blankets
Gas stripping
towers
Vacuum deaeration
Oxygen Scavengers
Mechanical techniques:
Reduce O
2
to about 1 ppm
High-temp scavengers are commonly used in
boiler feedwater treatment
For boiler: O
2
recommended conc. 7 ppb
Sulfite are commonly used in oil field systems
In oil field systems: O
2
to be reduced to 50 ppb
High-Temperature Oxygen
Scavengers
Hydrazine
N
2
H
4
+ O
2
2H
2
O + N
2
Hydrazine Oxygen Water Nitrogen
6Fe
2
O
3
+ N
2
H
4
4Fe
3
O
4
+ 2H
2
O + N
2
Iron (III) Hydrazine Magnetite Water Nitrogen
Oxide
Hydrazine will react with iron oxide as follows:
Sulfite and Bisulfite Oxygen
Scavengers
Na
2
SO
3
+ 1/2 O
2
Na
2
SO
4
Sodium Sulfite Oxygen Sodium Sulfate
NH
4
HSO
3
+ 1/2 O
2
NH
4
HSO
4
Ammonium Oxygen Ammonium
Bisulfite Bisulfate (Ammonium Acid
Sulfate)
Are used in most oil field systems
Biocides
Planktonic and Sessile Bacteria
Planktonic
Bacteria
Metal Surface
Sessile
Bacteria
Biofilm
Cause two major operating problems in oil field water systems:
declining water quality
corrosion
Biocide Application
Bacteriostats or bactericides.
Bacteriostats do not kill bacteria.
Bactericides inhibit bacterial growth.
Chemicals that control bacteria growth are classified as:
Performance is based on success in
controlling sessile bacteria.
Planktonic counts are used first to screen
several biocides.
Further testing using sessile counting
techniques.
Biocide Performance
List of Biocides Frequently Used in
Oil Field Operations
Primary Cocoamine RC NH
2
HOOCH
Amine Salts acetate
Diamine Cocodiamine RC N C C C NH
2
HOOCH
Salts acetate
Quarternary Dialkyl-benzyl
Ammonium ammonium chloride
Salts
Aldehydes Glutaraldehyde OCH(CH
2
)
3
CHO
Acrolein CH
2
= CHCHO
Oxidizing Chlorine CI
2
Agents
Chlorine dioxide CIO
2
R
C
R
C
N
H
C
C
6
H
5
CH
2
CI
-
+
H H H H
H H H
Biocides
Biocide Effectiveness
((10,000 - 100) / 10,000) x 100 = 99%
Biocides
A biocide conc. is consider effective if
it kills at least 99% of the bacteria
compared to an treated blank sample.
Scale can inhibit or promote corrosion
Prevent & Remove oil field scale whether or not it protects the metal.
Scale can cause operation problems in addition to corrosion
Scale deposits are mainly caused by supersaturation:
Temp. decrease
Temp. increase
Press. Decrease
Incompatible waters are mixed
Water evaporates
Saturated waters become stagnant
Scale Inhibition
Most Common Oil Field Scales
NAME FORMULA COLOR WHEN PURE
Barium sulfate BaSO
4
White
Calcium carbonate CaCO
3
Colorless to white
Calcium sulfate
Anhydrite CaSO
4
Colorless to white
Gypsum CaSO
4
.2H
2
O Colorless to white
Iron carbonate FeCO
3
Gray
Iron oxide Fe
2
O
3
Redish brown to
black
Iron sulfite FeS Brown to black
Strontium sulfate SrSO
4
Colorless to white
Scale Inhibition
Ca
+2
+ 2HCO
3
-

Ca
+2
+ CO
3
-
2
+ CO
2
+ H
2
O
CaCO
3
+ CO
2
+ H
2
O
Calcium Carbonate Formation
Scaling tendency of CaCO
3
as temp
Scales
Normally produced waters contain Ca
+2
, HCO
3
-
, and CO
2
Colors of Pure Oil Field Scales
NAME FORMULA COLOR WHEN PURE
Barium sulfate BaSO
4
White
Calcium carbonate CaCO
3
Colorless to white
Calcium sulfate
Anhydrite CaSO
4
Colorless to white
Gypsum CaSO
4
.2H
2
O Colorless to white
Iron carbonate FeCO
3
Gray
Iron oxide Fe
2
O
3
Redish brown to
black
Iron sulfite FeS Brown to black
Strontium sulfate SrSO
4
Colorless to white
Identifying Scales
Composition of a Typical Scale Inhibitor
30% Active
Ingredients
70% Water
Scale Inhibitors
Scale Inhibitor
Are water based products.
Reduce rate of scale deposition.
Distort scale micro crystals in solution.
Scale Inhibitors Used Most
Often in Oil Field Operations
NaO
O
P O
ONa
O
P O
ONa
O
P ON
a
ONa
n
R N C C O P N
O
OH
R
1
HOP
O
CH
2
OH
HOP
O
CH
2
OH
N CH
2
CH
2
N
HOP CH
2
OH
HOP
O
CH
2
OH
O
CH2 CH
C=O
C H
+
,Na
+
n
CH
2
CH
C=O
NH
2
x
Inorganic
Polyphosphates
Organic Phosphates
Esters
Organic
Phosphonates
Organic Polymers
CLASS STRUCTURE
overall effectiveness.
Thermal stability
Compatibility with water ands solubility in.
Scale Inhibitors Selection
Most important factors are:
Scale Inhibitors Selection
Inhibitor Type Solubility* Thermal Stability
Phosphate Esters Most soluble Least stable
Phosphonates
Polymers Least soluble Most stable
* Solubility in high-calcium brines.
Organic Scale Inhibitor Properties
Flocculation
process in which
water droplets
gather into groups
Coalescence
process in which
surfactant film
breaks hence water
droplets become
larger
Settling larger
droplets settle to the
bottom
Water
Oil
Flocculation
Coalescence
Settling
The Oil-Water
Separation Process
Emulsion Treatments
Continuous Chemical Injection
Chemical
reservoir
Injection
pump
Pipeline
Batch
Treatments
Batch and
Fall
Application
Method
Casing
Tubing
Gas
Inhibitor
mixture
falls down
tubing wall
Tubing
Displacement
Treating
Method
Displacing
fluid or
nitrogen
Inhibitor
mixture
Oil
Perforations
Champion
Tubing
saver
Connection for
weight bar
Gas
Wire line tie
Nylon brush
Knuckle joint
Nylon brush
Inhibitor
mixture
Corrosion
Inhibitor
Squeeze
Treatment
Casing
Displacing
Fluid
Tubing
Inhibitor
mixture
Parker
Perforations
Inhibitor
Serial Dilution Technique
GAB and SRB Broth Media Bottles
9 ml of
broth media
Nail
GAB 9 ml
dextrose broth
SRB 9 ml
lactate broth
9 ml of
broth media
28 days
incubation
period
5 days
incubation
period
Serial Dilution Technique
Dilution Ratio 1:10 1:100 1:1,000 1:10,000 1:100,000 1:1,000,000
Dilution Level 10
-1
10
-2
10
-3
10
-4
10
-5
10
-6
Syringe
with 1 ml of
water sample
Triplicate Test for Sulfate Reducing
Bacteria
Test 1
Test 2
Test 3
10
0
10
1
10
2
10
3
10
4
10
5
10
6
BACTERIA / ML