IFFCO
Presented By:
Sanjay Katheria
GET- Chemical
Ammonia II: CO2 Removal Section
12/8/2011
Outline of the Presentation
Introduction
CO2 Removal Processes
CO2 removal section: Ammonia II
o GV Solution
o Absorber
o First Regenerator
o Second Regenerator
Source and References
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Introduction
Carbon dioxide is a gas at standard temperature and pressure and exists
in Earth's atmosphere in this state. CO2 is a trace gas comprising 0.039% of
the atmosphere.
Carbon dioxide is a greenhouse gas as it transmits visible light but
absorbs strongly in the infrared and near-infrared.
General properties:
Colorless
At low concentrations, the gas is odorless. At higher concentrations it has
a sharp, acidic odor.
CO2 is an acidic oxide and toxic in higher concentrations: 1% (10,000
ppm) will make some people feel drowsy. Concentrations of 7% to 10%
cause dizziness, headache, visual and hearing dysfunction, and
unconsciousness within a few minutes to an hour.
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The triple point of carbon dioxide is about 518 kPa at 56.6 C.
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Industrial production
Industrial carbon dioxide is produced mainly from six processes:
Directly from natural carbon dioxide springs, where it is produced
by the action of acidified water on limestone or dolomite.
As a by-product of hydrogen production plants, where methane is
converted to CO2.
From combustion of fossil fuels and wood.
As a by-product of fermentation of sugar in the brewing of beer,
whisky and other alcoholic beverages.
From thermal decomposition of limestone, CaCO3, in the
manufacture of lime, CaO.
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CO2 Removal Process
To purify the synthesis gas and complete the requirement of CO 2 in Urea
Production, CO2 is removed from synthesis gas.
Methods used in CO2 Removal
Amine Gas Treating
Hot Potassium Carbonate Solution Treatment
There are many different amines used in gas treating:
Monoethanolamine (MEA)
Diethanolamine (DEA)
Methyldiethanolamine (MDEA)
Diisopropylamine (DIPA)
Aminoethoxyethanol (diglycolamine) (DGA)
The most commonly used amines in industrial plants are the alkanolamines
MEA, DEA, and MDEA
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Contd..
Amines particularly MEA have greater affinity towards CO2 which
results in low exit concentration (from Absorber) of CO2 at relatively
low pressure.
Duel Solvent Methods: Mixture of TEA and MEA
HOCH2CH2NH2 + CO2
HOCH2CH2NHCOO- + H2O
HOCH2CH2NHCOO- + H+
HCO3- + HOCH2CH2NH2
MDEA used with some activator.
MEA Process highly corrosive while MDEA Process requires high
residence time.
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Carbonate Solution Process
Amine Gas Treating Process have high regenerative cost.
Hot Potassium Carbonate Solution: Intermediate affinity for CO2
compared to Water and Amines(MEA).
K2CO3 + CO2 + H2O
2KHCO3
Primary and secondary Organic amines, Monoethanol amine
(MEA) and Diethanolamine (DEA) are currently employed alone and
or in combination with hot potassium carbonate solution to catalyse
the CO2 removal Process
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CO2 Removal Section: Ammonia II
Giammarco-Vetrocoke (GV) is a privately-owned company,
located in Venice, Italy.
CO2 removal system of Ammonia II Plant has a conventional
design based on the GV dual activator process. The process
comprises of single stage absorption and two stage
regeneration.
Carbon dioxide is removed by absorption in hot aqueous
potassium carbonate solution containing approximately 30
wt% potash (K2CO3) partly converted into bicarbonate
(KHCO3).
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GV Solution
Dual Activators
Glycine NH2CH2COOH
Diethnolamine NH(CH2CH2OH)
Corrosion Inhibition
V2O5
Composition of fresh solution:
K2CO3/KHCO3
Glycine
DEA
V2O5
27 % w/w
1.2 % w/w
1.0 % w/w
0.4 % w/w
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Chemistry of GV Process
General Reaction
K2CO3 + CO2 + H2O
2KHCO3 + heat
CO2 + H2O
HCO3- + H+ (slow)
CO32- + H2O
HCO3- + OH----------------------------------------------CO32- + CO2 + H2O
2HCO3-
Role of Activator
H2NCH2COO- + CO2
- OOCNHCH COO2
+ H+ (fast)
Glycine Carbamate
-OOCNHCH COO- + H O
H2NCH2COO- + HCO32
2
-----------------------------------------------------------------CO2 + H2O
HCO3- + H+
Hydrolysis of Glycine Carbamate is catalysed by DEA.
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Corrosion Inhibition
Acidic nature of solution because of CO2, Carbonic Acid and
Carbamates.
Addition of Vanadium as Corrosion Inhibitor, Static and Dynamic
Passivation (0.5 % V2O5)
Iron content of the solution representation equilibrium (iron
content more than 200-300ppm considered excessively high).
V+5 Protecting Layer( 5-10 % of total vanadium content).
V+5 equilibrium with V+4
V5+ + Fe2+
V4+ + Fe3+
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Chemistry of GV Process
Operating Parameters
Temperature
- Hot aqueous solution to increase the rate of reaction.
- Keep the bicarbonate in the dissolved form.
- Boiling point temperature for Regenerators.
Pressure
- High pressure in absorber increase the solubility of process
gas in GV solution
Fractional Conversion (Fc )
K2CO3 + CO2 + H2O
Fc =
2KHCO3
%KHCO3
%K2HCO3 + %KHCO3
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CO2 Rich Solution
CO2 Rich Solution
Lean
Solution
Process
Gas Outlet
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CO2 at
P = 0.14 Kg/cm2 g
CO2 at
P = 1.1 Kg/cm2 g
Semilean
Solution
Semilean Solution
Steam
Inlet
Process
Gas Inlet
CO2 Rich
Solution
Lean Solution
1st Regenerator
2nd Regenerator
Absorber
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Process Gas cooled to 104 oC before
Process
Gas Outlet
Lean
Solution
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Absorber
entering into absorber.
Process Gas
Inlet
Outlet
Temperature(oC)
110
71
Pressure(kg/cm2g)
27.9
27.4
Flow Rate(NM3/hr)
312141
203148
% N2
20.75
25.23
% H2
60.74
73.78
% CO
0.12
0.15
% CO2
17.74
0.05
1
4
Process
Gas Inlet
CO2 Rich
Solution
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2 Stage Process:
- 1st Contact with Semilean Solution
- 2nd Contact with Lean Solution
Semilean
Solution
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Absorber
2 Stage Counter Current Absorption Process:
- 1st Contact with Semilean Solution
- 2nd Contact with Lean Solution
Semi Lean Solution Contact: Lower two beds(3rd & 4th Bed of
Absorber)
About 85% of the total solution
Temperature: 107 oC
Most of the CO2 removed in lower 2 beds(~4000 ppm CO2 left)
Lean solution
Rest 15% of the solution
Temperature: 60oC
CO2 in Process Gas leaving Absorber ~ 500ppm
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Absorber Packing
IMTP Packing: Low Pressure drop with high metallic strength w.r.t.
weight.
Volume of the Packing(m3)
Bed
Type
5th Bed(lower)
IMTP 70
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4th Bed
CMR3 & IMTP 50
105
3rd Bed
IMTP 50 & IMTP 40
105
2nd Bed
IMTP 40
48.5
1st Bed (top)
MELLPACK 250
48.5
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First Regenerator
First stage of regeneration process.
Operating Pressure 1.1 kg/cm2g
44% of rich solution extracted from
top tray and send to top of
Vetrocoke
2nd Regenerator.
Process Gas In
Reboiler
CO2 at
P = 1.1 Kg/cm2 g
To 2nd
Regenerator
CO2 Rich Solution
Process Gas out
Semilean Solution
Steam In
Lean Solution
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First Regenerator
41% of the semilean solution is taken from lower part of 2nd Bed,
expanded and send to 2nd Regenerator take-off tray.
Remaining strongly regenerated solution expanded and transfer to
bottom of 2nd Regenerator.
Heat Input:
From process gas cooling in two Vetrocoke Reboiler and one LP
Steam Boiler.
LP Steam from ejector.
Operating Condition:
Temperature(oC) (top)
109
Pressure(kg/cm2g) (top/bottom)
1.1/1.3
LP Steam added(kg/hr)
17000
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2nd stage of stripping at
reduced pressure of 0.14
kg/cm2g.
CO2 at
P = 0.14 Kg/cm2 g
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Second Regenerator
From 1st
Regenerator Top
Semilean Solution from
upper side of take-off tray.
From 2nd Regenerator
second bed bottom
Lean Solution from
bottom of 2nd Regenerator.
Form 1st Regenerator
Bottom
Semilean Solution
P = 0.24 Kg/cm2 g
Take-off
Tray
Lean Solution
P = 0.24 Kg/cm2 g
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Regenerators Packing
Mellapack Packing
Regenerator
Volume of the Packing(m3)
Type of Packing
1st Regenerator(HP)
64.0+223.0
IMTP 40 + IMTP 50
2nd Regenerator(LP)
164.0
IMTP 50
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12/8/2011
Thank You
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