Theory and Operation

of Methanation Catalyst

By:

Gerard B. Hawkins
Managing Director, CEO
 Contents

 Introduction and Theoretical

Aspects
 Catalyst Reduction and Start-up
 Normal Operation and
Troubleshooting
 Shutdown and Catalyst Discharge
 Nickel Carbonyl Hazard
 Introduction

 Carbon oxides are poisons for many

hydrogenation reactions
 Used on older plants (without PSA)
 CO2 removal followed by methanation
 Uses nickel-based catalyst
 Theoretical Aspects
Strongly exothermic reactions:
CO + 3H2 CH4 + H2O H = 206 kJ/mol
-89 BTU/lbmol
CO2 + 4H2 CH4 + 2H2O H = -165 kJ/mol
-71 BTU/lbmol
(Reverse of steam reforming)

Temperature rise:

74OC (133OF) for each 1% of CO converted

60OC (108OF) for each 1% of CO2 converted
 Typical Process Conditions
270°C

Inlet 518°F
Outlet
Composition (%) Composition (%)

CO 0.2 CO
CO2 0.1 CO2 }<5ppmv
H2 93.9 H2 93.5
CH4 3.3 CH4 3.6
H2O 2.5 H2O 2.9

291°C
556°F
Methanator Vessel
 Mechanism of Reaction
 Equilibrium concentrations of carbon oxides
10-4 ppmv
 Governed by Kinetics
 CO inhibits methanation of CO2
 Two stage reaction:

i) CO2 reverse - shifts to CO

CO2 + H2 CO + H2O
ii) CO methanates
CO + 3H2 CH4 + H2O

Intrinsic reaction rates very high (diffusion limited

at higher temperature
 Catalyst Composition
 Iron originally studied
 Ruthenium good at low temperature
(“ultra-methanation”)
 Nickel conventionally used
 Support matrix with 20-40% (wt) nickel
 Promotors to reduce sintering
 Small pellets (5 mm x 3 mm)
 Contents

 Introduction and Theoretical Aspects

 Catalyst reduction and start-up
 Normal operation and troubleshooting
 Shutdown and Catalyst Discharge
 Nickel Carbonyl Hazard
 Catalyst Reduction
NiO + H2 Ni + H2O ∆H = +3 kJ/mol
+1 BTU/lbmol
NiO + CO Ni + CO2 ∆ H = -30 kJ/mol
-13 BTU/lbmol

BUT  little temperature rise from reduction itself

 metallic nickel will lead to methanation during
THEREFORE reduction
 reduction gas should not contain carbon oxides
(<15)
 need to heat catalyst to 400-450oC (750-840oF)
for maximum activity
 Pre-Reduced Catalyst
 Now available

 Simplifies start-up

 Maximises activity at low temperatures

 Contents

 Introduction and Theoretical Aspects

 Catalyst Reduction and Start-up
 Normal Operational and
troubleshooting
 Shutdown and Catalyst Discharge
 Nickel Carbonyl Hazard
Methanation Catalyst Temperature
Profile

 Over designed originally, high catalyst

activity
 Most reaction in top of bed
 Catalyst lives 10-15 years
 Methanation Reaction Profile

320
Temperature °C (°F)

(608)

310
(590)

300
(572)

290
(554)

280
(536) 0 1 2 3 4
(2) (4) (6) (8) (10) (12)

Bed depth m (ft)

 Normal Operation
 Conversion of carbon oxides depends on
outlet temperature
 If CO inlet increases, exit temperature also
increases, reaction rate increases and exit
carbon oxide level decreases
• this may allow a reduction in inlet
temperature
 Methanation Catalyst Ageing
Temperature

Top Bed Depth Bottom

- ageing mechanism is gradual poisoning

- profile moves down the bed
 Abnormal Conditions
1. Gradual steady rise across whole bed
• inadequate reduction?
• poisoning
2. Sudden movement of reaction zone with no change
in slope
• poisoning of top?
• Poor reduction of top?
3. Normal temperature profile, high outlet carbon
oxides
• channelling through bed?
• mechanical problems? (by pass valve; heat
exchanger)
• analytical problems?
 Unusual Operating Conditions

1. High CO levels
• LTS by-passed
• total concentration of carbon oxides <3%
• inlet temperature 210-250oC (410-480oF)
• if necessary, lower rate through HTS and increase
S/C ratio
2. High Water Levels
• normal level 2-3% H2O in inlet gas
• if >3%, can lead to high CO2 in exit gas
• may need to increase bed inlet temperature
• operating experience up to 7% H2O
 Plant Mal-Operation
 Normal maximum exit temperature is 450OC
(480OF)

 Excursions to 600OC (1100OF) for several hours

can be tolerated

 In this event of a temperature runaway, the vessel

must be protected:
• isolate on inlet side
• blow down to atmospheric
• purge with nitrogen to aid cooling
• exclude air to avoid exothermic oxidation
 Catalyst Poisons
 S is a poison but normally present unless LTS by-
passed
 Most poisons originate from CO2 removal system
 Carry-over of a small amount of liquid not
generally serious
 Large volumes will have a serious effect

Common Poisons Effect

K2CO3 Blocks pores; removable
As2O3 Serious, irreversible poisoning
Sulpholane Decomposes to S; poison
 CO2 Removal Systems
Process Chemical
Benfield Aqueous potassium carbonate
Vetrocoke Aqueous potassium carbonate
plus arsenious oxide
Benfield DEA Aqueous potassium carbonate
With 3% di-ethanolamine
Sulphinol Sulpholane, water
di-2-propanolamine
MEA, DEA Mono- or di-ethanolamine
in aqueous solution
MDEA Aqueous solution of methyl
di-ethanolamine and activators
Rectisol Methanol
Catacarb Aqueous potassium carbonate
with borate additive
Selexol Dimethyl ether of polyethylene
glycol
Effect
Blocks pores of catalyst by evaporation of K2CO3
Blocks pores of catalyst by evaporation of K2CO3 .
As2O3 is also a poison; 0.5% of As on the catalyst
will reduce its activity by 50%
Blocks pores of catalyst by evaporation of K2CO3 .
(DEA is harmless)
Sulpholane will decompose and cause sulphur
poisoning
None
None
None
Blocks pores of catalyst by evaporation of K2CO3
None
 Contents

 Introduction and Theoretical Aspects

 Catalyst Reduction and Start-up
 Normal Operation and Troubleshooting
 Shutdown and Catalyst Discharge
 Nickel Carbonyl Hazard
 Shutdown
 If process gas temperature > 200OC
(390OF), can be left in atmosphere of
process gas for short periods
 Below 200OC (390OF), must be purged with
an inert to prevent carbonyl formation
 Reduced catalyst pyrophoric; oxidation
very exothermic
• spread catalyst thinly on ground
• have water hoses available
• transport in metal skips/metal/sided
trucks
 Catalyst Back-washing for K2CO3
Removal
 Considerations
• catalyst strength
• water quality and temperature
• reactor cooling and purging
• plant isolations
 Methanator Back-washing - Effect
on Performance

 Catalyst performance fully regained

• CO + CO2 slip < 6 ppm
 Catalyst strength unaffected by repeated
washings
 No effect on catalyst pressure drop
 Contents

 Introduction and Theoretical

Aspects
 Catalyst Reduction and Start-up
 Normal Operation and
troubleshooting
 Shutdown and Catalyst Discharge
 Nickel Carbonyl Hazard
 Nickel Carbonyl Ni(CO)4
• Colorless, mobile liquid flammable in air,
insoluble in water
• Boiling point 43°C (109°F)
• Vapor pressure:

(°C) (°F) v p (bar) v p (psi)

-12 10 0.10 1.4

18 64 0.25 3.6
24 75 0.51 7.4
43 109 1.01 14.6

EXTREMELY TOXIC!
 Toxicity of Ni(CO)4

 4 ppm v/v for 1 minute gives severe toxic

effects
 2 ppm v/v short time leads to illness
 target value (daily average concentration)
0.001 ppm v/v

Ni + 4 CO Ni(CO)4
 Guidelines
1. Under normal operating conditions, concentrations
are too low to be a problem
• steam reformer has high CO, high Ni, but high
temperatures
• after LTS, temperatures low, but low Co, low Ni
2. Under abnormal operating conditions
(eg start-up or shut-down) it is possible to get
conditions favourable for the formation of
Ni(CO)4

Keep temperatures above 200°C

(390°F) to avoid formation of Ni(CO)4
 Nickel Carbonyl Formation
Conditions for the formation of 0.001 ppmv
Partial Pressure of CO (bar)

0.5 30 bar
0.2
Favorable
0.1
1 bar
0.05

0.02

0.01 Not Favorable

0.005

0.002

0.001
0 100 200 300 400
(32) (212) (392) (572) (752)

Temperature °C (°F )
 Conclusions

 Reviewed methanation reactions and catalyst

 Described normal operation
 Described abnormal conditions
 Poisoning
 Mentioned catalyst back-washing
 Reviewed nickel carbonyl hazard