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Anodic Protec,on Systems Corrosion Protec,on for Sulfuric Acid Tanks

Hugo Chagas hugo.chagas@clark-‐koch.com Date: 11/11/13

SUMARY

Direct and Indirect Costs of Corrosion Worldwide •  Study conducted by US federal highway administra,on showed the

following figurers: –  Direct and indirect corrosion costs nowadays

•  US$ 1.8 trillion WORLDWDE •  276 Billion US dollars (For US) •  Represen,ng 3-‐4% of the Gross Domes,c Product

•  According to the Hoar Report 25% of the annual cost of corrosion could be saved! –  Which Means: US$ 450 billions worldwide!!!!

The Challenge is to iden,fy and apply the op,mal Corrosion Control Method for each specific case.

It is clear that Corrosion must be avoided and well controlled.

Virmani, Paul, Corrosions Costs and Preven,ve Strategies in the US 2002

SUMARY

An Op&on to Minimize and control Corrosion in Sulfuric Acid Storage Tanks.

Reducing Risks, Capital investments, and maintenance costs.

ANODIC PROTECTION SYSTEMS

Topics

•  Sulfuric Acid Corrosion •  Principles of Anodic Protec,on – Main Concepts •  Equipment for Anodic Protec,on •  Design Opera,on and Maintenance of Anodic

Protec,on Systems •  Sulfuric Acid Storage Equipment’s Protec,on •  Economical Advantages of Anodic Protec,on

Systems for Sulfuric Acid Storage Tanks

Sulfuric Acid Corrosion

What governs Carbon Steel corrosion rates in sulfuric Acid: •  Temperature; •  Acid concentra,on •  Ferrous Sulfate Diffusion Velocity

Boundary-‐Work – Equipment, Material and Condi,ons •  Carbon Steel Storage Tanks •  Under ambient Condi,ons •  Mainly with 80 – 100% acid concentra,on

Understanding how these Physical Proper,es impacts on Corrosion Rates will help to understand how Anodic Protec,on works


Temperature & Concentra,on – At which condi,on Corrosion Rate increases?

Extracted from: NACE SP0294-‐2006 Design, Fabrica:on, and Inspec:on of Storage Tank Systems for Concentrated Fresh and Process Sulfuric Acid and Oleum at Ambient Temperature Originally: Mars G. Fontana and Norbert D. Greene, Corrosion Engineering (New York, NY: McGraw-‐Hill, 1986), p. 319 If no other proper,es vary, Carbon Steel Corrosion will increase with temperature increase.


Diffusion Velocity During the Corrosion Reac,on a sol film of FESO4 is formed on the surface and works as a physical barrier for the diffusion of the reactants (H+; SO42-‐)

FESO4 Film is a protec,on and can be really effec,ve for Storage Tanks since the types of Erosion-‐Corrosion Effects are not related to the main func,on of the equipment and thus can be avoided.

Mechanism

FESO4 Film Disintegra:on

Diffusion Barrier

Corrosion Reac:on H2SO4 + Fe à FESO4 + H2

Sol Film of FeSO4 is formed on the metal surface.

Natural FESO4 Diffusion

FESO4 Diffusion

Erosion Corrosion Effect

Inlet Nozzles

Hydrogen Grooving

Splashing acid

Principles of Anodic Protec,on – Main Concepts

How does Anodic Protec,on Works? Ø  Anodic Protec,on is a Method to achieve an electrochemical barrier between the

corrosive electrolyte and metal base by forming an oxides thin layer. Ø  Passivity is aoributed to the forma,on of a protec,ve Layer, at the metal-‐

electrolyte interface. This “Passive” Layer Prevents the contact between the metal and the electrolyte reducing corrosion rate at a minimum value.

Ø  Metal Tendency to be passivated can be measure and this measures provides an representa,on of the electrochemical corrosion characteris,cs. Measurements can be represented by a Anodic polariza,on curve

Zones Comments

Passive Passive Film Acts as a Barrier No Corrosion Reac,on Thus Very Small Current Density

Ac,ve Corrosion Occurrence Current Density is constantly increasing with the Poten,al increasing Passive Film Forma,on

Poten,

al Increasin

g


•  Connected to the (–) pole of power supply •  Can be one or mul,ple depending on design/tank size

•  (+) dc connected to the tank sidewall

• Provides direct current for the System

• Responsible for the system control. • Receives FEEDBACK from the Poten,al Sensing and responds with direct current actual value

• Responsible by sensing the Poten,al between the solu,on and the tank sidewall


How Anodic Protec,on Works

Cathode Coupon Ref.

Electrode

Equipment for Anodic Protec,on

Cathodes

Ø  Cathode shall be stable and resist aoack by impressed cathodic current

Ø  Cathode should have a h igh conduc,vity that does not contribute to the overall circuit resistance.

Ø  The Cathode Area determines the contact resistance between Cathode and Anode solu,on. So cathode area should be as high as is economically and physically to keep power requirements low.

Ø  Usually for Sulfuric Acid Storages Cathodes Material is HASTELOY C

SPARK PREVENTION Ø  In order to avoid spark in cases of

minimum level switch failure a silicon rope is used to make sure that there are solu,on to conduct electrical current between the cathode and the tank wall.


Reference Electrodes

Ø  Poten,al of the Tank wall must be measure and controlled Ø  Reference Electrode gives a comparison of tank wall poten,al. Ø  It senses the solu,on poten,al with an minimum error. Ø  For Acid Tanks most common material used is Pla,num/Pla,num (Inert Metal).


Coupons Ø  Coupons are used for v isual

verifica,on of the Anodic Protec,on Effec,veness.

Ø  While one metal sample (same material of the tank) is connected to the tank sidewall, and the other one not.

Ø  Result it is possible to compare the corrosion rate between them.


Posi,ve Tank Connec,on

Ø  Detail of the Posi,ve side connected to the tank sidewall.


Rec,fer Panel

Rec,fier Panel

Power Distribu,on

Transformers

Control

TPCC

Buffer Driver

Monitoring

Alarms

Remote Monitoring

LCD Displays

Panel Condi,oning

Inner Temperature

Control

Shield and Earth grounding


Rec,fer Panel

Poten,al Controller Ø  It is proven that precision of the

control poten,al in field instruments need not to be as high as that of laboratory poten,ostat. Sa,sfactory Control were achieved if the poten,al were maintained within + 5mV.

Ø  This Permits the use of on-‐off controls

Ø  The other possibility is Propor,onal Control

Ø  In the past most of the applica,ons in USA and CANADA used ON-‐OFF Control. Propor,onal would be used only for cri,cal nature in which the poten,als would instantly shil to corrosive value when the current was off.

Power Supply Ø  Usually transforming AC Current on

DC as demanded.

Design Opera,on and Maintenance of APS

Experiments in the Laboratory

Result: Anodic Polariza,on

Behavior Curve

Par,cular Aoen,on to simulate process

condi,ons

Establish Electrochemical

Parameter Size Power Supply Ref. Electrode and

Cathode Selec,on

Size and number of Cathodes

Electronic Hardware Selec,on

Power Supply Criteria

Simplified Process Trough Design


Usual Electrochemical Parameters (Theory)

Solu:on Concentra:on %

Temperature oC

Passivate mA/cm²

Maintain mA/cm²

Oleum -‐ 25 2.64 0,00380

Sulfuric Acid 93-‐98 25 2.64 0,0398

Sulfuric Acid 78 25 3.08 0,0550

General Comments Ø  Generally design phase takes up to 180 days. Ø  Documenta,on received by the Client is similar to a common Electrical

Panel and cable rou,ng; Ø  IT is possible to remotely monitor some parameters of the AP System

such as direct current supply, ref electrodes, AC power supply.

Common Values Found in industry Ø  For a Tank of aprox. 7000 m³ with Sulfuric Acid at aprox. 94-‐96% and T=

25oC (for this case ) Ø  Current to Passivate à aprox. 350A Ø  Current to Maintain à aprox. 0,6 A

REF: Riggs, OL; Locke, CE; Anodic Protec,on


Installa,on and Startup

Ø  There are some criteria's to posi,on the Cathode and Electrode in the Tank.

Ø  If more than one Cathode is used; they should be installed evenly in the radius orienta,on

Ø  There is no cri,cal issues related to the distance between the cathode and the tank wall, but generally they should be at the middle of the distance between the center and the wall of the tank

Ø  Cathode should reach 1 feet above the booom of the tank Ø  Reference Electrode should be spaced radially as far from the cathodes

as possible. Ø  Reference Electrode should be at 18” from the booom of the tank

Opera,on and Maintenance Ø  Does not require excessive amount of

aoen,on from opera,ng personnel Ø  Keep a record of current demand as func,on

of ,me and opera,ng condi,ons Ø  Limits are setup and when achieved alarm is

ac,vated and unit turned off.

Protec,on of Sulfuric Acid Storage Tanks

Reduc,on of Iron Content Verifica,on

Loca:on Iron Cont. (ppm) BEFORE

Iron Cont (ppm) AVer

Discharge 145 35

Feed 31 26

Iron Pickup 114 9

Effec,veness of Anodic Protec,on Tanks REF: Riggs, OL; Locke, CE; Anodic Protec,on

0,00

0,01

0,01

0,02

0,02

0,03

0,03

0 5 10 15 20 25 30

Conc. %

DAYS 0C 25C NO Protec,on

Rate of accumula,on of iron in Sulfuric Acid REF: Riggs, OL; Locke, CE; Anodic Protec,on

Table – Average Iron Content before and aler Anodic Protec,on of Storage Tanks, 100% Sulfuric Acid

Minimum 40 ppm Aler a week

Ø  Data Shows that Anodic Protec,on can reduce the Iron content from 1273 ppm to less than 40 ppm.

Ø  At lower temperature effec,veness is even beoer


Reduc,on of Corrosion Rate Verifica,on

39

29

17.5

5.5

1.0

1.6

10.5

11.1

10

9.9

2.6

2.6

2.2

2.2

MPY Unprotected

MPY Protected

48 FT Side

Wall

Data Taken using Corrosion Coupons in a 10,000 ton 93% Sulfuric acid tank REF: D Fyfe, Chem Eng Proc, 73, 65 (1977)

Dist. of the Coupon From Tank BoXom

(V)

Corrosion Rates (mpy) Unprotected

Corrosion Rates (mpy)

Protected

0 35.3 3.6 1 34.1 3.4 2 31.2 3.1 3 2.0 3.2 4 29.9 3.5 5 22.1 5.8 6 4.3 5.4 7 6.3 5.3 8 3.8 4.1 9 2.2 1.4 10 0.8 0.9 11 0.8 0.8

Table: Results of test on Anodically Protected and Un protected Coupons exposed 50 Days in 100% Sulfuric Acid Storage Tank. REF: A. O. Fisher and J. F. Brady, Corrosion, 19, 37 (1963)

Economical Advantages of Anodic Protec,on Systems for Sulfuric Acid Storage Tanks

Anodic Protec,on as an Op,on

Ø  Reduc,on of Product Contamina,on Ø  Increase of Tank Life Cycle Ø  Reduc,on of Corrosion allowance

Ø  Reduc,on of plates thickness, which impacts on materials and fabrica,on costs

Ø  Low Maintenance Costs Ø  Minimum interven,on during opera,on;

Pictures – PERU DOE RUN/ Southern Copper Peru/ Corrosion Service

•  Tanks -‐ Cathodes

•  Rec,fier Panel


•  Tanks – Reference Electrodes


References •  Riggs, OL; Locke, CE; Anodic Protec,on – Theory and Pac,ces in the Preven,on of Corrosion. •  O,L,Riggs, JR. M. Hutchson and NL Conger, Corrosion 16(2), 1960 •  YAM Kolotyrkim et al •  D Fyfe, Chem ENG PROG, 73, 65, 1977 •  A. O. Fisher and J. F. Brady, Corrosion, 19, 37 (1973)

Contato: Hugo Chagas hugo.chagas@clark-‐koch.com

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