Md Shahinoor Islam

1
 Main objective of purification is to remove residual CO and
CO2. Three different methods have been developed:

1. Copper Liquor Scrubbing:

 Early plants used scrubbing solution contains cupric and
cuprous ammoniacal salts of acids such as formic, acetic
or carbonic plus an excess of ammonia. These salts forms
complexes with the CO and hold it loosely.

 Reactions:
Cu(NH3)2A + CO + NH4OH ↔ Cu(NH3)3A.CO + H2O
2NH4OH + CO2 ↔ (NH4)2 CO3 + H2 O

 More expensive than methanation.

 High operating cost and difficult to control.

2
2.Methanation: - Simple, low cost, relatively trouble
free

3.Cryogenic Scrubbing (N2 wash)

 - Most complete purification than any other methods
 - Not only C’oxides removes but also reduce CH4 and
Ar content to low level.
 - No purging is required
 - Used mainly in conjunction with partial oxidation
for synthesis gas production
- In steam reforming process, its use is limited due to
high cost of air separation plant.

4. Shift reaction + Methanation

3
The water-gas shift reaction is favorable for producing carbon dioxide
which is used as a raw material for urea production.

 By means of the CO shift conversion an important portion of

the CO content in the cracked gas is used for additional
hydrogen generation, which is following the chemical
reaction

CO + H2O <=> H2 + CO2

 This process is exothermic and is limited by the chemical

equilibrium.

4
Three different versions of CO shift conversion:

 High temperature (HT) CO shift conversion at about 300 to 450 °C

down to approx. 2.5 % CO on dry basis at the reactor outlet

 Medium temperature (MT) CO shift conversion or so-called

isothermal shift conversion at about 220 to 270 °C down to approx.
0.5 % CO on dry basis at the reactor outlet.

 Low temperature (LT) CO shift conversion at about 180 to 250 °C

down to approx. 0.2 % CO on dry basis at the reactor outlet

5
6
 For every process a special catalyst will be used in a fixed
bed reactor to get maximum yield of H2 product.
 The use of HT CO shift conversion is state of the art in
almost every hydrogen plant.
 The application of the low temperature CO shift
conversion is normally installed downstream of the HT shift
at already reduced CO content in the feed gas
 Presently, most plants use a combination of conventional
High/Low Temperature Shift (HTS/LTS) or
High/Medium/Low Temperature Shift (HTS/MTS/LTS)
technology.
 Another option is a combination of HTS/LTS/Selectoxo
technology.

7
HTS
 Operating Condition: Temperature- 350°C-420°C
 Pressure-32.2 kg/cm2G
 Reaction: CO + H2O = H2 + CO2
 Catalyst: Iron oxide
 CO content: 13% to 3%

LTS
 Operating Condition: Temperature- 220°C-260°C
 Pressure-31.2 kg/cm2G
 CuO+ ZnO
 CO content: 3% to <0.3%

8
CO2 Absorption

9
Why CO2 absorption?
To avoid catalyst poisoning
Produced CO2 in this section is a raw-material of urea
manufacturing.

Choice of Solvent:
Pressure: Must be of raw syngas pressure.
Concentration: Required CO2 concentration of treated
syngas. Raw syngas CO2 conc depends on feedstock.
Poisons: O2, CO, CO2, HCN in raw syngas can irreversibly
react with the solvent. Such poisoning may require expensive
pretreatments if solvent loss is not tolerated.
Utilities: Availability of LP steam for regeneration of solvent
and driving the pumps.

10
 CO2 removal processes
• Water scrubbing, monoethanolamine (MEA ) and absorption with
hot potassium carbonate are widely used process.

WATER SCRUBBING:
- Simple, - H 2 dissolves with CO2
-Inexpensive - H 2 loss is significant

MEA ABSORPTION:
- Slightly above ambient temperature
- Pressure up to 600 psig
- Regeneration involves both pressure release and reboiling
- Heat duties are some-what higher than water scrubbing
-Corrosion protection requires above 230oF (Inhibitor)

Reactions: 2 HOCH2CH2NH2 + H2O + CO2 = (HOCH2CH2NH3)2CO3

(HOCH2CH2NH3)2CO3 + H2O + CO2 = 2 HOCH2CH2NH2 + 2HCO3

11
 HOT POTASSIUM CARBONATE

- High capacity for CO 2

- Regeneration involves pressure release (Temp ↑)
- Activated by additives e.g., glycol, sucrose, dextrose,
Ethylene Glycol, methyl alcohol formaldehyde and lactose
to increase the rate of CO2 absorption.
- The identity of additives are proprietary under the
name of BENFIELD, GIMMARCO-VETROCOKE, CATACARB,
CARSOL and so on.
Reaction: K 2 CO3 + CO2 +H 2 O = 2KHCO3

12
Name of Process Temperature Pressure
Benfield (Hot Potassium carbonate) >100 0C 400 psig
Giammarco-Vetrocoke (Hot 50-1000C 75 atm
potassium carbonate activated by and
As2O3, glycine and various ethanol higher
amines)
Catacarb (Hot potassium Temperature 300-400
carbonate activated by amine depends on purity psig
borate)
Mono Ethanol Amine 27-60 0C absorption <400 psig
100-140 0C
regeneration
Dual-Solvent Process (MEA-TEA) 60-90 0C 25-27 atm
Rectisol Process (organic solvents < 0 0C -
mostly methanol)
13
Absorption tower design of CO2 removal is similar to general
absorption tower design. Difference with the general absorption
tower design is in size and the types of internals used to improve
vapor-liquid contact.
Regeneration:
Pressure Reduction
 Simplest; desorption by releasing pressure

 Dissolved CO2 is loaded under pressure is released in several stage

 If inert waste N2 from air-separation unit is available, then this can

be used indefinitely to strip the solvent most indefinitely.
Otherwise hot regeneration is required.
Regeneration by heating
 Additional heat exchange surface requires for cooling the solvent
before admission to the absorber if the absorber is to operate at
low pressure.
14
• Benfield solution: 29% K2CO3, 2.9% DEA and 0.9% V2O5
with remaining water.

15
 MEA process

Inhibited MEA

16
Selexol UOP process

17
 Catacarb single stage low heat desig

Potassium carbonate with DEA, potassium borate, and potassium

metavanadate
18
Methanation

19
 Operating Condition: Temperature- 363°C-392°C
 Pressure-26 kg/cm2G
 Reaction: CO2 + 4H2 = CH4+ 2H2O
 CO + 3H2 = CH4+ H2O
 Catalyst: Nickel
 Synthesis gas which is leaving from absorber consists a
total of 0.45% carbon oxide is purified by methanation
process with Nickel catalyst in the methanator.
 Since these will cause poison the ammonia synthesis
catalyst the concentration must be reduced to less than
10 ppm.
 In the Methanator the Carbon oxide is converted back
to methane over a nickel catalyst in a reaction, which is
reversed to that of steam reforming.
20
21
 Linde has a well-proven technology for hydrogen
manufacture by catalytic steam reforming of light
hydrocarbons in combination with Linde´s highly
efficient pressure swing adsorption process.
The basic process steps
1. Hydrodesulfurization of feed stock
2. Steam reforming
3. Heat recovery from reformed and from combustion
flue gas to produce process and export steam
4. Single stage adiabatic high temperature CO-shift
conversion
5. Final hydrogen purification by pressure swing
adsorption
22
23
 PSA means Pressure Swing Adsorption
 Pressure – elevated pressures, normally 5-8Bar are
needed for the process
 Swing – 2 vessels working in counterphase in terms of
pressurising and depressurising
 Adsorption – The PSA principle is used for separation of
atmospheric air, where product gases are separated
from others by adsorption process
CMS
filling with its ion-exchange bed traps O2 molecules and allows N2
molecules to stream through.
Zeolite
with it‘s ion-exchange beds traps N2 molecules and allows O2
molecules to stream through.
24
25
 The process involves feeding raw hydrogen into the
bottom of the nitrogen wash column and high
pressure nitrogen into the top of the wash unit. Both
streams are cooled down against the product gas, and
any trace impurities, such as methane, argon and
carbon monoxide, are then removed and recycled as
fuel gas. Finally, high pressure nitrogen is added to the
process stream to achieve the perfect balance of
hydrogen and nitrogen.
Advantages
 Optimized process for purifying and producing
ammonia synthesis gas
 Precision equipment delivers perfect 3:1 balance of
H2:N2
26