2011 Synthesis

y
Gas Seminar Margarita
g
Methanator
November 24, 2011

Methanator
Function: Remove CO/CO2 to trace levels (< 5 ppmv)
Hydrogen in Refineries
Some H2 applications involve catalysts sensitive to CO
T i l ttargett <50 ppm CO+CO2,
Typical
Sometimes <10 ppm CO+CO2
Ammonia Plants
CO and CO2 can form carbamates in the
NH3 synthesis loop causing P problems

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Page 2

Methanator Reactions

CO + 3H2

CH4 + H2O

H = - 88,700 BTU / lb-mole

= - 206 k-joules
k joules / g
g-mol
mol

CO2 + 4H2

Steam

HTS
Effl
Effluent
t

CH4 + 2H2O

H = - 71,000 BTU / lb-mole

= - 165 k-joules / g-mol

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Page 3

Methanator T
360 F

200 C

300 F

O2

240 F

CO
CO2

180 F

100 C

120 F
60 F
0F

0C
0.0

0.5

1.0

1.5

2.0

2.5

3.0

Mole % of Component In Feed Gas

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Page 4

Catalyst Activity
1.4

NH3

Re
elative A
Activity

1.2

H2

1.0
0.8
0.6
0.4
0.2
0.0
400
(204)

450

500
(260)

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

550

600
(316)

650

700
(371)

Temperature F (C)

750

800

850

(427)
Page 5

Methanator Design
1.30

Relative C
R
Catalyst V
Volume

1.20

CO and CO2 and Required Catalyst Volume

CO=0.10

CO=0.20

CO=0.30

1.10
1.00
0.90

TEMP=600 F ((316 C))

0.80
0.70
0 60
0.60
0.50

0.00

0.05

0.10

0.15

0.20

0.25

0.30

Mole Percent CO2

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Page 6

Methanator Temp Profile

Tem
mperatture, C

300

290

280
9 Mos.
15 Mos.
22 Mos.

270
0

20

40

60

80

100

% Bed Depth
Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Page 7

Methanator Operation
4500
4000

PPM CO+
P
+CO2

3500

80%

3000
60%

2500
2000

40%

1500
1000

20%

% of T
Temperrature R
Rise

100%

500
0
0%

20%

40%

60%

80%

0%
100%

% of Bed
Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Page 8

Operating Conditions

H2 Pl
Plants:
t

Tin .. 500F (260C)

Ti
T ... 20-35F (10-20C)
Pin .. 150-500
150 500 psig (10
(10-35
35 Bar)

NH3 Plants: Tin 550

550F
F (285
(285C)
C)
T ... 20-35F (10-20C)
Pin .. 150-500 psig (10-35 Bar)
Minimum Recommended T = 450
450F
F (230
(230C)
C)
Ni(CO)4 Forms at T < 350F (175C)

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Page 9

Nickel Carbonyl Ni(CO)4

8.00E-07

3.00E-04
ppm@900 K
ppm@1000 K

7.00E-07

ppm@1200 K

2.50E-04

ppm@700 K
6.00E-07

2.00E-04
5 00E 07
5.00E-07

4.00E-07

1.50E-04

3.00E-07
1.00E-04
2.00E-07
5.00E-05
1.00E-07

0.00E+00

0.00E+00
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

CO partial pressure, bar

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Page 10

Nickel Carbonyl

Ni(CO)4 Formation: ppm at 200 psig

Temperature
p
150F (65C)
200F (93C)
300F (149C)
400F (204C)

Mole % CO
0.2%
1.0%
3.2%
0.3
190
20,000
0.0
3
320
0.0
0
0.5
0.0
0
0.0

Note: Toxic Threshold for Ni(CO)4 is 1 ppb

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Page 11

Catalyst Reduction
Reduce
R
d
att > 600F (315C) for
f best
b t activity
ti it
Dry gas (<2% H2O) recommended for activation
Effect of Water Content (mol %)
on catalyst activity

Reduction Gas
Dry
6%
Dry
6%

Process Gas Relative Activity

Dry
100%
Dry
73%
6%
75%
6%
66%

If inlet temp < 500F (260C)

10-15% Pre-Reduced Catalyst on Top
Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Page 12

Pre-Reduced Catalyst

Pre-Reduced Catalyst An Advantage

oPlant Cannot Reach Normal Reduction
Temperatures
oPlant Has Wet Reduction Gas
oOperating Temperature is < 500F (260C)
oRapid Startup With New Catalyst Desired
SCI Offers Reduced and Stabilized Catalyst
oMETH 134RS 3-6 mm
Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Page 13

Methanator Deactivation
Loss off Activity
L
A ti it D
Due tto P
Poisons
i
Most Common Source
CO2 Removal Solution Carryover
oArsenic (Vetro Coke)
oSulfur (Sulfinol)
Hydrotreat to Break Ring
Adsorb in Layer of ZnO
oPhysical Masking (Potassium Carbonate)
oMEA - No effect
oDEA No effect

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Page 14

Methanation Catalyst

METH 130 Ext. 5.5 mm

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

METH 134 Sph. 3-6 mm

Page 15

Q&A

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Page 16