06 methanator

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2011 S nthesis Gas Seminar Mar arita

MethanatorNovember 24, 2011


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Methanator

Function: Remove CO/CO2 to trace levels (< 5 ppmv)

Hydrogen in RefineriesSome H2 applications involve catalysts sensitive to CO

yp ca arge < ppm + 2,

Sometimes


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Methanator Reactions

Steam

2 4 2

H = - 88,700 BTU / lb-moleHTS

- - - uen

2 4 2

H = - 71,000 BTU / lb-mole

= - 165 k-joules / g-mol

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011 Page 3


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MethanatorT

300 F

360 F

2 C

240 F

300 F

O2 CO

180 F

1 C

CO2

60 F

120 F

0 F

0.0 0.5 1.0 1.5 2.0 2.5 3.0

C


Mole of Component In Feed Gas


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Catalyst Activity

1.2

1.4

NH3

0.8

1.0

ctivity H2

0.6

lative

0.2

0.4R

0.0

400 450 500 550 600 650 700 750 800 850


Temperature F (C)


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Methanator Design

1.20

1.30

CO=0.10 CO=0.20 CO=0.30

22

1.00

1.10

olume

0.90

atalyst

TEMP=600 F (316 C)

0.70

.

Relative

0.50

.

0.00 0.05 0.10 0.15 0.20 0.25 0.30


Mole Percent CO2


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Methanator Temp Profile

300

290ure,

280p

era

Te

9 Mos.

15 Mos.

22 Mos.

270

0 20 40 60 80 100



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Methanator Operation

4000

100%

ise

3000

+CO2

60% ature

2000

PM

CO

40% empe

100020% %

of

0

0% 20% 40% 60% 80% 100%

0%


% of Bed


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Operating Conditions

an s: n ..

T ... 20-35F (10-20C)

.. - -

T ... 20-35F (10-20C)

- -..

=

Ni(CO)4 Forms at T < 350F (175C)



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Nickel Carbonyl Ni(CO)4

7.00E-07

8.00E-07 3.00E-04

ppm@900 K

ppm@1000 K

m 1200 K

6.00E-07

2.00E-04

2.50E-04

ppm@700 K

4.00E-07

. -

1.50E-04

2.00E-07

3.00E-07

1.00E-04

0.00E+00

1.00E-07

0.00E+00

5.00E-05


0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

CO partial pressure, bar


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Nickel Carbonyl

Ni(CO)Ni(CO)44 Formation:Formation: ppm at 200 psigppm at 200 psig

Mole % COTem erature 0.2% 1.0% 3.2%

150F (65C) 0.3 190 20,000

200F (93C) 0.0 3 320300F (149C) 0.0 0 0.5

400F (204C) 0.0 0 0.0

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



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Catalyst Reduction

e uce at > or est act v ty

Dry gas (


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Pre-Reduced Catalyst

Pre-Reduced Catalyst An Advantage

Temperatures

oOperating Temperature is < 500F (260C)

oMETH 134RS 3-6 mm



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Methanator Deactivation

oss o c v y ue o o sons

Most Common Source

oArsenic (Vetro Coke)oSulfur (Sulfinol)

Hydrotreat to Break Ring

Adsorb in Layer of ZnOoPhysical Masking (Potassium Carbonate)

oMEA - No effect

o e ec



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Methanation Catalyst

METH 134 Sph. 3-6 mmMETH 130 Ext. 5.5 mm



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Q&A


06 methanator

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