Corrosion

Corrosion is the deterioration that occurs when a metal reacts with its environment. It is impractical to eliminate corrosion Effective engineering is to control corrosion rather than to prevent corrosion All metals and alloys are susceptible to corrosion
Nitin Raut / BPCL

Consequences of Corrosion
Safety : Sudden failure may cause fire, explosion,
release of toxic products, construction collapse

Health : Pollution due to escaping or corrosion

products.

Shut down Loss of efficiency Loss of valuable product

Nitin Raut / BPCL

CDU overhead Corrosion

Major reason - Presence of acidic species in crude

Acids commonly encountered

. . . . . & Hydrochloric acid Hydrogen sulphide Carbonic acid Organic acids Acids derived from Sulphur Oxides viz. Sulphuric Sulphurous acids

Nitin Raut / BPCL

Corrosion due to HCl

Comes from incomplete desalting
Calcium & Magnesium chlorides not removed get hydrolyzed to form HCl in presence of heat and water especially at temperature higher than 122 deg C HCl , a strong acid lowers the pH of water by several units leading to severe corrosion In the presence of H2S corrosion of iron due to HCl increases substantially Nitin Raut / BPCL

Chemical Reactions of corrosion

Primary Corrosion Fe + 2HCl --------

FeCl2 + H2

Regeneration of HCl FeCl2 + H2S ------- 2 HCl + FeS

Nitin Raut / BPCL

Overhead corrosion due to HCl can be reduced by

Proper salt removal in the desalting operation

Addition of caustic to the crude charge

Injecting Ammonia or neutralizing amines & Filming amines in the overhead system

Nitin Raut / BPCL

Corrosion due to H2S

H2S itself is present in the crude and gets generated due to decomposition of organic sulphur compounds
In presence of H2S corrosion potential due to HCl increases substantially Corrosion potential due to H2S is minimum in the pH range of 5.5 to 6.5

Nitin Raut / BPCL

Mechanism of H2S Corrosion

The reaction representing the corrosion mechanism is : H2S <> (H+) + (HS-) (Fe++) <> FeSH+ The FeSH+ further reacts to form a complex sulphide scale.

The dissociation of H2S is minimum at a pH of 5.0. As pH increases towards neutral region, the bisulphide ion concentration increases.
Nitin Raut / BPCL

 An increase in corrosion rate is the result of faster reduction of bisulphide ion from scale lattice and solution. As the scales lattice is altered, FeS is released, exposing the unreacted Fe. This FeS thus released enters into the water phase.
This phenomena in CDU is referred as Black Water

Nitin Raut / BPCL

Corrosion due to Carbonic acid

Carbon Dioxide is released from crudes with high content of Naphthenic acid. Carbon Dioxide is a weakly acidic gas and becomes corrosive when it dissolves in water to form Carbonic Acid. The primary cause corrosion is the formation of HCO3- which acts as a buffer for H2CO3 corrosion, the source of FeCO3 precipitation(insoluble corrosion product) and product of cathodic protection.
Nitin Raut / BPCL

Mechanism of Carbonic Acid Corrosion

The reactions can be represented as following CO2(g) + H2O == H+ + HCO3Fe + 2HCO3- == FeCO3 + H2O + CO2 The FeCO3 formed is an insoluble corrosion product which forms a film on the carbon steel surface. This helps in inhibiting corrosion. Conditions favoring the formation of the FeCO3 film are elevated temperature, increased pH and lack of turbulence.
Nitin Raut / BPCL

 In areas of high velocity, the corrosion rates are increased as high turbulence prevents the formation of the preventive FeCO3 film. This further exposes fresh surface for further corrosion attack. The corrosion is generally localized in nature.

Nitin Raut / BPCL

Can be reduced by
pH control with caustic soda. Continuous injection of corrosion inhibitors in the overhead system.

Nitin Raut / BPCL

Corrosion due to Organic acids

1

Organic acids - acetic acid, propanic acid, butyric acid etc.

Organic acids change pH in the CDU overhead system Increase demand of neutralizer ------2
Nitin Raut / BPCL

Corrosion due to Naphthenic acids

2

Naphthenic acid attack often occurs in the parts operating over 230 deg C such as heater tubes, transfer lines, column flash zones and pumps. In sour crude units a crude TAN (Total Acid Number) of 1.0 is sufficient to be concerned about Naphthenic acid corrosion, in sweet units TAN of 0.5 may be high enough to cause corrosion Naphthenic acid corrosion results in sharp edged, smooth grooves, gouges or holes with no corrosion scales or deposits
Nitin Raut / BPCL

 Isolated deep pits in partially filmed areas and impingement type attack in film free areas are typical type of Naphthenic Acid Corrosion attack. SS316 or SS 317H has good resistance for Naphthenic acid corrosion with TAN no. greater than 0.5.

Above 288C and low Naphthenic acid content 5 Cr or 12 Cr cladding are recommended. When H2S is evolved an alloy with 9 Cr is preferred.

Nitin Raut / BPCL

Factors affecting Naphthenic Acid Corrosion

Naphthenic acid chemistry Crude oils with TAN no. higher than 0.5 and cuts with TAN no. higher 1.5 are considered corrosive between 230 C and 400 C. Sulphur Compounds A level of 0.2% and above is considered corrosive between 230 C and 455 C Temperature Occurs primarily in the range of 220 C and 400 C. Above 400 C, no corrosion is observed because of decomposition of Naphthenic acids. Velocity High velocity results in higher corrosion rates.
Nitin Raut / BPCL

Mitigation measures to be adopted

Blending to reduce the Naphthenic acid content of the feed by diluting a high TAN crude with a low one. Injection of corrosion inhibitors.

Process control changes to provide adequate corrosion control if there is a possibility to reduce charge rate and temperature. Upgrading the material of construction to higher chrome and/or molybdenum alloy.
Nitin Raut / BPCL

Areas prone to Naphthenic Acid attack

Furnace Tubes and Transfer Lines Accelerated corrosion due to velocity and two-phase flow. Factors affecting this are temperature, velocity and degree of vaporization. High temperature activates even small amount of Naphthenic acid in oil thereby increasing corrosion significantly. Vacuum Column Preferential vaporization and condensation of Naphthenic acids increase TAN of the condensates. Velocity has little effect.
Nitin Raut / BPCL

 Naphthenic acids are most active at their boiling point but the severe corrosion occurs on condensation. Corrosion mechanism is mainly a condensate corrosion and related to content, molecular wt and boiling point of the Naphthenic acid.
Side Cut Piping Factors affecting corrosion are medium fluid velocity, low vaporization and Naphthenic acid and H2S content. Increase in velocity increases the corrosion rate upto the point where the impingement starts and then corrosion is further accelerated.

Nitin Raut / BPCL

CDU overhead Corrosion Control Methods

Blending Proper desalting Caustic Injection Ammonia injection

Neutralizing & Filming amine injection

Water washing
Nitin Raut / BPCL

CDU overhead Corrosion Control Methods

Blending
Most commonly used technique Blending of problem crudes with non-problem crudes Sometimes the flexibility may not exist or blending may not provide enough reduction of the problem

Nitin Raut / BPCL

CDU overhead Corrosion Control Methods

Desalting
Crude oil contains varying degrees of impurities like naturally occurring salts, water, solids etc. The total salt (NaCl, MgCl2 and CaCl2) content in crude varies from 3 to 300 ptb Wash water is employed to wash out these impurities Desalter removes the added water and most of the the inorganic salts

Nitin Raut / BPCL

Desalter operating conditions

Addition of wash water - 3 to 10 % on total crude charge Residence time ~ 2 hrs. Temperature - 120 to 150 deg C Mixing valve delta P - 10 to 20 psi

Nitin Raut / BPCL

Caustic Injection
Addition of small amount of dilute caustic (NaOH) to the desalted crude is often an effective way to reduce the amount of HCl released in the preheater Caustic converts the HCl to thermally stable NaCl, thus reducing the amount of free HCl Disadvantages of caustic Crude preheat train fouling Stress Corrosion cracking Catalyst contamination problems In d/s units Furnace coking problems
Nitin Raut / BPCL

Ammonia injection in overhead system

To control pH of the overhead accumulator water (pH range 5.5 to 6.5)

Disadvantages
Inability to reliably control pH within the water dew point range Its salt, NH4Cl causes fouling and under deposit corrosion

Nitin Raut / BPCL

Neutralizing Amines
Neutralizing amines are nitrogen containing organic compounds which are weak bases
Morpholine, Ethylene diamine (EDA), Monoethanolamine (MEA), Methoxypropylamine (MOPA)

Propietary formulations of amines by vendors

All of the neutralizer salts are water soluble
Nitin Raut / BPCL

Filming Amines
Filming amine provides a barrier between the metal surface and the corrosive aqueous environment by providing micro-molecular film. For effectiveness proper pH control is necessary Effectiveness of the filmer gets diminished as pH of the overhead system drops Typical injection rate is 3 - 5 ppmv during normal operation Typically naphtha dilution is provided
Nitin Raut / BPCL

Water washing
Products of the neutralization reactions, amine chlorides or ammonium chlorides can be highly corrosive and fouling Stripped sour water, water condensate or overhead receiver water recirculation to overhead vapour line Water containing dissolved oxygen should be avoided as it can accelerate corrosion
Nitin Raut / BPCL

Engineering of Water injection system

Too little water can add to the acid making process and too much can cause grooving of overhead line A proper spray nozzle is necessary to prevent impingement corrosion of the pipe d/s of injection point Good distribution system to ensure evenly divide flow among the different banks of the condensers Ideal water injection rate - 5 - 10 % of the overhead stream

Nitin Raut / BPCL

Corrosion Monitoring
Water analyses - Overhead receiver water
Hydrocarbon analyses Corrosion rate measurement

On stream non-destructive examination

Nitin Raut / BPCL

Overhead receiver Water analyses

pH - System pH can change from acceptable pH to aggressively
corrosive pH in matter of minutes so the pH should be measured as frequently as possible

Metals - Fe, Cu, Zn are typically measured but depends on

material of construction

Chlorides - Aqueous corrosion is always related to the

quantity of HCl or chloride salts. Measurement of chlorides confirm when the event of corrosion began and how long it sustained. Regular measurement helps in optimizing caustic addition or blending of crudes which result in minimum corrosivity

Hardness - Hardness detected means leak in cooling water

exchanger. If recycled water wash in use, it means oxygenated water wash I.e. increased corrosion so adjustments in corrosion Nitin Raut / BPCL control programme

Hydrocarbon Analyses
Inhibitor residual - To detect the presence of
inhibitor (Filmer)

Metals - The only tool for naphthanic acid corrosion

measurement is metal analyses of oils. For this historical data is useful as a check on current conditions.

Nitin Raut / BPCL

Corrosion rate Measurement

1

Weight Loss Coupons - Calculated corrosion

rate based on initial surface area and weight. Visual examination Can be replaced on stream Commonly used in overhead systems

ER Probes - Change in x section of measuring

element is measured in terms of change in its electrical resistance On stream measurement can be retracted also Used in tower overhead systems ---------2
Nitin Raut / BPCL

Corrosion rate Measurement

2

Linear Polarization (LPR) Probes Instantaneous corrosion rate based on measurement of corrosion current of the probe element - Works only in conductive medium - Used in cooling water systems, application in overhead receiver water is feasible but limited - On stream measurement - Can be retracted also
Nitin Raut / BPCL

On stream non-destructive examination

Ultrasonic (UT) & Radiography (RT)
NDE normally not used for extensive routine corrosion monitoring because of its cost Often used as inspection tool

Used on exception basis for corrosion monitoring when there is a confirmed or suspected problem which is being watched closely
Nitin Raut / BPCL