CATACARB CHEMISTRY

By NOUMAN KHALEEQ BUTT

A PEP SESSION ON

PRODUCTION OF AMMONIA:
Feed Gas Purification Synthesis Gas Production Synthesis Gas Purification Synthesis of Ammonia

REFORMING REACTIONS:
CH4 + H2O CH4 + 2H2O CO + 3H2 CO2 + 4H2O

SHIFT CONVERSION:
CO + H2O CO2 + H2

SYNTHESIS GAS PURIFICATION

REMOVAL OF CO2
Synthesis gas contains appreciable amount of CO2 (15-20%) in it. It is removed at this stage and sent to Urea Production Facilities.

HOW CO2 CAN BE REMOVED? Alkanolamines Potassium Carbonate Ammonia Solutions Ordinary Water

SCHEMATIC VIEW OF CATACARB ABSORPTION SYSTEM

Scrubbed Gas

190 oF, 412 psig

230 oF, 15 psig

wet CO2

187 oF CATACARB REGENERATOR C-2515

EM-2511

Semi-Lean Solution
240 oF MP-2503 CO2 ABSORBER C-2519

Feed Gas 198 oF, 416 psig

270 oF
E-2508

40 psig steam

250 oF

Rich Solution
260 oF

Lean Solution
MP-2504

THE CATACARB
It is a solution of Potassium Carbonate K2CO3 in water. K2CO3 acts as main reagent for removal of CO2 from the system. Many other chemicals are also added in to the CATACARB system for enhancing the absorption process and maintain proper conditions in the system. Catacarb works in TWO ways:
Physical Absorption Chemical Reaction

AS SOLUTION IN WATER
BORIC ACID

DEA

K2CO3

V2O5

ANTI-FOAM, DEFOAMER etc

ROLE OF K2CO3:
To facilitate the presence of additional hydroxyl ion for direct reaction with CO2. The rate of absorption of CO2 in water is accelerated. The faster the rate of absorption, greater will be the absorption required, the less amount will be needed

K2CO3 itself does not reacts with CO2 directly.

Absorption reaction is characterized in two reactions: HCO3- + H+ HCO3-

CO2 + H2O CO2 + OH-

Concentration of hydroxyl ion is proportional to the concentration of the carbonate ion. So K2CO3 facilitates the hydrolysis of water and rate of CO2 absorption is increased. These reactions are favored by high pressure and low temperatures.

DEA:

It promotes CO2 absorption by forming intermediate salts of amine carbamate.

CO2 + R2NH

R2NCOO- + H+

R2NH + HCO3-

H2O

Amine Carbamate

R2NH + HCO3-

DEA degrades with temperature to produce organic salts of complicated nature, degradation is excessive at 275 F.

BORIC ACID (H3BO3):

It acts a buffer (i.e. a chemical which minimizes change in pH of a solution when an acid or base is added to a system.) preventing fluctuation of pH during CO2 absorption. It also acts as a promoter for the absorption reaction. Reaction of carbon dioxide is further catalyzed in the presence of borates.

VANADIUM:
It is not involved in absorption process. It is added as a corrosion inhibitor compound to protect the internals of the catacarb absorber and regenerator. (EXPLAINED LATER)

Vanadium exists in five different forms

V2O2
basic

V2O3
basic

V2O
basic

VANADIUM

amphoteric

V2O4

V2O5
acidic

Vanadium pentaoxide V+5 is the most important from the corrosion inhibition point of view. V2O5 is anhydride of vanadic acid which exists in different forms.

PYRO H4V2O7 pH 9-12 Vanadic adic

Meta HVO3 pH 7-10

Per HVO4

Ortho H3VO4 pH > 12 pH 2-2.7

Prevention of Foaming:
Foaming is caused by the presence of suspended particles and organic compounds. Little foaming is good for gas liquid contact but excessive foaming decreases absorber efficiency. To prevent foaming, antifoam (a chemical added before foaming to prevent foam formation) and Defoamer (a chemical added after foaming to destroy the foam) are added to the system. WBU is an organic antifoam. However, it acts as a good defoamer as well.

Formation of Potassium Formate:

Potassium Formate (KCOOK) is an undesirable by-product. K+ + CO + OHHCOOK

This reaction is very sensitive to temperature. Rate of formation is high above 300oF Its presence reduces the effective potassium carbonate solution strength.

DEA DEGRADATION:
During CO2 absorption, DEA absorbs other compunds which degrade the amine into complex organic compounds. This degradation: Wastes valuable DEA Fouls equipment Produces foaming. Increases strongly with increasing temperature. increases with pressure up to about 600 psig then remains constant.

Catacarb Regeneration:
Regeneration of catacarb is achieved by Stripping (a mass transfer operation where a liquid is contacted with a gas for the purpose of selectively removing a component of the liquid by transferring it to the gas). For this purpose 40 psig steam is injected into the system which has following benefits:
Reduction of CO2 partial pressure by reducing the mole fraction of CO2. Better tray efficiency Some heat is added to the stripper to regenerate the solution.

CORROSION PHENOMENA:
Catacarb solutions are very corrosive to carbon steel; corrosion is primarily due to local formation and ionization of carbonic acid. Corrosion products are mixture of insoluble iron carbonate and iron oxides. Corrosivity of catacarb solutions increases with the concentration of carbon dioxide.

Fundamental chemical reactions taking place during corrosion are:

Fe + 2H2CO3 Fe(HCO3)2 Fe(HCO3)2

Fe(HCO3) 2 + 2H+ FeCO3 + CO2 + H2O FeO + 2CO2 + H2O

The V5+ is very effective inhibitor. The action of inhibitor is to passivate the carbon steel by means of red-ox coupling reaction with the corroding metal. This passive film protects the metal by preventing any further corrosion since corrosion rate in passivation zone is practically zero.

PASSIVATION:
To treat of coat a metal in order to reduce the chemical reactivity of its surface. Different metals have different tendency to form a protective layer (usually by oxidation) of the metal present on the surface.

During corrosion, iron exists in following different forms.

Fe

O2

FeO

O2

Fe3O4

O2

Fe2O3

FeO is unstable and it reacts with CO2 in the solution to form respective carbonates as secondary products of corrosion. Fe3O4 has the ability to form the passive layer and protect carbon steel from further corrosion. Fe2O3 becomes transpassive and hence can not stop corrosion.

ROLE OF V2O5:
By means of Reduction-Oxidation (Red-Ox) reactions, Vanadium Penta oxide, oxidizes FeO to Fe3O4 and during this reaction it is reduced to V2O4. Hence a passive layer of Fe3O4 is formed and any further corrosion is inhibted.

O FeO V2O5 Fe3O4 V2O4 + O

(OXIDATION)

(REDUCTION)

ROLE OF AIR INJECTION:

The predominant role of air injection in the catacarb process is reactivation of the corrosion inhibitor. It oxidizes the inactive V4+ to active V5+ form. The effect of air injection in the passivation of carbon steel is negligible.

KEY PARAMETERS UNDER OBSERVATION DURING OPERATION OF CATACARB SYSTEM

EFFECT OF VARIABLES ON CO2 ABSORPTION:

Increase Circulation Rate Increase pressure Drop Increase Temperature Increase Solution content Increase Solution Strength Increase Feed Gas Rate

Increases Increases Decreases Decreases Increases Decreases