Vous êtes sur la page 1sur 23

Corrosion and corrosion control

in oil and gas industry


Dipartimento di Chimica, Materiali e Ingegneria Chimica
Giulio Natta

Politecnico di Milano

Oilfield
Corrosion
Inhibitors

Environment modification

SOLUTION COMPOSITION
Modification of chemical composition
Oxygen removal
pH control

FOULING
FOULING
biocide (chlorination)
chlorination)
Mechanical polishing

CORROSION INHIBITOR

1
3

Chemical Treatments

Injection into pipelines includes


Corrosion inhibitors - hydrotest and operation
Biocides/bactericide - hydrotest and operation
Scale control chemicals - operation
MEG/hydrate control chemicals - operation
Detergents - demulsifiers, antifoam and anti-sludge
agents
pH control - caustic into condensate
Oxygen scavengers - hydrotest fluids

BIOCIDES

1. Organic/ non oxidisers


2. Demonstrated effectiveness versus SRB/ aerobes
3. Able to penetrate deposits to access sessile bacteria
4. Compatible with system/ other chemicals/
downstream refinery processes
5. Low environmental impact
6. Customer awareness of toxicity hazards + handling
requirements
Bioc. 01

2
5

TYPES OF BIOCIDES: oxidizing

CHLORINE
ADVANTAGES
IT IS ECONOMICAL
IT HAS BROAD SPECTRUM ACTIVITY
MONITORING DOSAGES AND RESIDUAL IS
SIMPLE
DISADVANTAGES
OPERATOR HAZARD CONCERNS
INEFFECTIVENESS AGAINST BIOFILM BACTERIA
Bioc. 02

CHLORINATION
source: chlorine gas, sodium hypochlorite,
electrochlorinators
treatment required to
1 satisfy chlorine demand
2 mussel control at water intake
3 free chlorine residual 0.5 - 1.0 ppm to reduce total
bacteria to <10 colonies/ml
chlorine is highly corrosive and a strong oxidiser
corrosion resistant materials needed
chlorine key to
optimum fine filter performance
chemical oxygen scavenging reaction

3
7

CHLORINATION

Over-treatment reacts with oxygen scavenger = poor


economics
Under-treatment = passage of infection into anaerobic
area, downstream of deaerator(s)
Chlorine effective versus planktonics, but not sessiles
Chlorine is not persistent

Chlorination should be continuous otherwise


microbiological problems will occur downstream

Bioc. 04

CHLORINATION CHEMISTRY

Cl2 + H2O H+ + Cl- + HOCl


HOCl + H2O H3O+ + OCl-

pH % HOCl % OCl-
7 70 30
7.5 50 50
8 30 70

OCl- / HOCl EFFECTIVE SPECIES


HOCl MOST EFFECTIVE
Bioc. 05

4
9

TYPES OF BIOCIDES: non oxidizing

FORMALDEHYDE
Advantages
It is economical

Disadvantages
High dosages are required
Reacts with ammonia, hydrogen sulfide and
oxygen scavengers

Bioc. 06

10

TYPES OF BIOCIDES: non oxidizing

GLUTARALDEHYDE
It is widely used in the petroleum industry. It is
sometimes used in a blend with other biocides and
surfactants to increase its effectiveness
Advantages
broad-spectrum activity
relatively insensitive to sulphide
it is compatible with many other chemicals
it tolerates salts and hardness

Bioc. 07

5
11

TYPES OF BIOCIDES: non oxidizing

Isothiazolone SULFUR COMPOUNDS


compatible with brines
good anti-sessile bacteria activity
it is degradable
cannot be used in sour system
it is expensive
carbamates
effective against SRB and spore formers
effective in alkaline pH
high concentration are required
react with metal ions
metronidazole
it is effective only against anaerobic organisms
it has been used in squeeze applications
Bioc. 08

12

TYPES OF BIOCIDES: non oxidizing

QUATERNARY PHOSPHONIUM SALTS


are new to the oilfield biocide market
they have been reported to travel through the
formation with injection water
good stability
low toxicity
unaffected by sulfides

Bioc. 09

6
13

TYPES OF BIOCIDES: non oxidizing

AMINES AND DIAMINES


Advantages
broad-spectrum activity
effective in sulfide bearing waters
they are surface active

Disadvantages
react with other chemicals
less effective in waters with high levels of
suspended solids
Bioc. 10

14

TYPES OF BIOCIDES: non oxidizing

QUATERNARY AMINE COMPOUNDS


Advantages
broad-spectrum activity
good surfactancy
good persistency
low reactivity with other chemicals

Disadvantages
inactivated in brines
they are foaming
they are slow acting Bioc. 11

7
15

Oxygen removal

Stripping (steam, inert gas )

Oxygen scavanger
Sulphite SO3-- + O2 => SO4--
cold environment (normal temperature)

Idrazina N2H4 + O2 => 2H2O + N2


hot environment (T > 140 C)
ctz 70 90 C

16

Oil Field Corrosion Inhibitors

GENERAL DEFINITION

INHIBITOR
A SUBSTANCE THAT DECREASES THE RATE
OF A CHEMICAL REACTION

CORROSION INHIBITOR (C.I.)


A SUBSTANCE THAT, ADDED TO A
CORROSIVE ENVIRONMENT, DECREASES
THE CORROSION RATE OF THE MATERIAL

0012

8
17

CLASSIFICATION OF INHIBITORS

ORGANIC OR INORGANIC
ANODIC, CATHODIC OR MIXED
OXIDISING OR NON-OXIDISING
SAFE OR DANGEROUS
ADSORPTION AND FILM-FORMING
BARRIER LAYER FORMERS
SCAVENGERS
NEUTRALISERS
MISCELLANEOUS
0015

18

COMMERCIAL C.I.

A COMMERCIAL C.I. IS A FORMULATION, SOLD BY A


SUPPLIER, WHICH TYPICALLY INCLUDES:
ACTIVE PRINCIPLE (THE TRUE INHIBITOR)
SOLVENT (PUMPABILITY & PARTITIONING)
SURFACE ACTIVE COMPONENTS (DEMULSIFIERS,
DISPERSANTS, ...)

0013

9
19

INHIBITOR CLASSIFICATION BY
SOLUBILITY

WATER SOLUBLE
OIL (HYDROCARBON) SOLUBLE
OIL & WATER INSOLUBLE (GUNKERS)
WATER DISPERSIBLE
OIL DISPERSIBLE
(PRODUCTS WITH DUAL SOLUBILITY IN A
LIMITED CONCENTRATION RANGE ARE UNDER
DEVELOPMENT FOR DOWNHOLE INJECTION)

0023

20

OIL SOLUBLE INHIBITORS

LONG CHAIN PRIMARY AMINES


IMIDAZOLINES
FATTY ACIDS
PHOSPHATE ESTERS

GENERALLY MORE EFFECTIVE AT HIGH


TEMPERATURES AND HIGH VELOCITIES

0024

10
21

WATER SOLUBLE INHIBITORS

QUATERNARY AMINES
AMINE SALTS
IMIDAZOLINE SALTS

- More effective in stratified flow conditions


- May lose solubility in very concentrated brines (high tds,
total dissolved solids)
- Insoluble or less soluble salts are formed (salt out problem)
- Supplier must know the problem and take necessary action
at production stage, i.e. maintaining an excess of active
principle in the formulation
0025

22

COMPOSITION OF A COMMERCIAL
INHIBITOR
25 - 30 %
ACTIVE
65 - 75 % PRINCIPLE
SOLVENTS 80% MAX

0 - 10 %
SURFACTANTS

Product cost 48.5


ELEMENTS OF Service 24.3
THE COST R&D 3.7
Profits 17.4
Others 6.1
TOTAL 100.0

11
23

Typical Inhibitor Molecules


Oil field corrosion inhibitors usually have a long hydrocarbon chain C18

Aliphatic (straight chain) fatty acid derivatives


Mono amines
Diamines
more efficient in oil systems than mono amines
Amides
Poly ethoxylated compounds made with differing oil and water
solubilities
Solubility increases with amount of ethylene oxide (CH2 CH2O)
Diamines
Amides
Acetic, Oleic, Dimeric, Naphthenic or Phosphate salts
Amphoteric compounds
Imidazolines and derivatives
Quarternary salts

24

Inhibitors for Use in Oil and Gas Systems

Primary Amine R NH2

Amide R CONH2

N CH2
Imidazoline R C
N CH2
R1
(CH2 CH2O)y H
Polyethoxylated
R N
Amines
(CH2 CH2O)x H

12
25

Oil Field Corrosion Inhibitors

Primary Amine R CH 2 NH 2

O
Amide R1 CH2 C NH R2

N
Imidazoline N
R CH2
CH2 CH2 NH2

Quaternary CH3
CH2 R
N
Ammonium Ion CH3

Polyethoxylated O CH2 CH2 OH


n
Amines R N
O CH2 CH2 OH
n

26

Inhibitor Adsorption

Hydrocarbon chain Electrons available for


bonding to metal
Inhibitor molecule dispersed
Polar amine in process stream
Hydrocarbon
nitrogen group

Oil molecule

Hydrocarbon
chain R

Chemisorption &
physical adsorption
by polar amine group

Metal

13
27

Adsorption inhibitors

Reduce the kinetics of either anodic or


cathodic reaction, or both.

Effects on exchange current densities or


Tafel slopes

28

Mechanism of inhibition

Cagg >> Cmin


minimum threshold content,
content, Vcor
everywhere,
everywhere, and in relation
to service life Vo
Cinib > Cmin
Efficiency
e% = 100
100(Vo-Vinib)/Vo Vinib
Addition techniques Cmin Concinib
(continuos,
continuos, batch,
batch, )

14
29

Mechanism of inhibition

Safe inhibitors Dangerous inhibitors


Vc Vc
or or

Vo Vo

Vinib Vinib

Cmin Concinib Cmin Concinib

30

Mechanism of inhibition

Cathodic Inhibitors E Acid Environment

Anodic Inhibitors
Ecor
Mixed inhibitors Ecor

icor icor Log(i)

15
31

Mechanism of inhibition

Cathodic Inhibitors E Neutral-alkaline


environment
Anodic Inhibitors
Ecor
Mixed inhibitors Ecor

icor icor Log(i)


Salts of Na, Ca, K =
deposits

32

Mechanism of inhibition

Cathodic Inhibitors E Passivanting


Ecor Inhibitor
Anodic Inhibitors

Mixed inhibitors Ecor

icor icor Log(i)


Phosphates

16
33

Mechanism of inhibition

Passivanting
Cathodic Inhibitors E Oxydant
Ecor
Inhibitor
Anodic Inhibitors

Mixed inhibitors Ecor

icor icor Log(i)


Nitrites and Cromates

34

Mechanism of inhibition

Cathodic Inhibitors E

Anodic Inhibitors
Ecor
Mixed inhibitors

icor icor Log(i)

17
35

Iinhibition efficiency

Related to the metallic material


(compatibility with other metals)

Environmental conditions
(T, pH, P)

36

Adsorption
1

0.9 coverage
Coverage - corrosion rate

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1 corrosion rate


0
0 10 20 30 40 50 60
Concentration

18
37

Inhibitor Products

Multicomponent mixtures

Often effective in wide range of conditions

Less complex formulations may be more


restricted

38

What is Required of an Inhibitor?

Predict uninhibited rate

Define required inhibited rate

-> required efficiency?

19
39

Required Efficiency

If too high select CRAs?

Large CAPEX consequences

40

What Performance is Possible?

Often assumed that 85 95 % efficiency is


possible, but no higher

Is this true?

Is an assumed efficiency the best way?

20
41

Actual vs Predicted Rate

42

Corrosion Risk Category (BP)


Risk Maximum Max. Proposed
Category Required Expected Category
Availability Uninihb. Comment Name
Corr. Rate
(mm/yr)

1 0% 0.4 Benign fluids, corrosion inhibitor use not Benign


anticipated. Predicted metal loss may be
accommodated by corrosion allowance.
2 50% 0.7 Corrosion inhibitor probably required but with Low
expected corrosion rates there will be time to
review the need for inhibition based on inspection
data.
3 90% 3 Corrosion inhibition required for majority of field Medium
life but inhibitor facilities need not be available
from day one.
4 95% 6 High reliance on inhibition for operational lifetime. High
Inhibitor facilities must be available from day one
to ensure success.
5 >95% >6 Carbon steel and inhibition is unlikely to provide Unacceptable
integrity for full field life. Select corrosion resistant
materials or plan for repairs and replacements.

21
43

Inhibition Risks (Shell)

Condition green
Standard inhibitor packages Predicted rates < 10 mm/yr Must ensure properties such as
correctly selected should Temperature < 60 C solubility, dispersibility and
perform satisfactorily based on Velocities between 1 & 5 m/s compatibility are satisfactory,
lab and field experience dosage 10 50 ppm based on
water phase

Condition yellow
State of the art packages, Predicted rates 10 50 mm/yr Inhibitor dosage 20 100 ppm if
laboratory tests have Temperature 60 120 C oil present,
demonstrated feasibility but only Velocities between 5 15 m/s 50 200 ppm in absence of
a few field confirmations to date oil/condensate,
(usually < 100C) Only specialist organisations have
test equipment

Condition red
Leading edge or frontier Predicted rates > 50 mm/yr Inhibitor dosage > 200 ppm.
products. Feasibility Temperature >120 C??? Require adequate inhibitor
demonstrated in some fields Velocities < 15 m/s (may be injection & careful monitoring.
(downhole, flow lines and upto increased to 20 m/s in Thermal stability crucial,
30 km pipelines) absence of sand production) performance falls at > 140/150 C
Limited availability of test facilities

44

Inhibitor Efficiency and Availability

Target acceptable corrosion rate to give


required system life

Inhibitor availability must also be taken into


account

22
45

Availability Approach

Assume a certain corrosion rate when


inhibitor added (e.g. 0.1 or 0.05 mm/y)

Assume uninhibited rate when inhibitor not


added

Emphasises that inhibitor downtime is


critical

46

C Steel + Inhibitors vs CRA

CRA
High Capital Expenditure (CAPEX)
Low Operating Expenditure (OPEX)

Cost of CRA increase with pipeline length

Cost of inhibition does not

23