Utilization of Landfill Gas

towards High-BTU Methane and

Low-Cost Hydrogen Fuel

by
Manolis M. Tomadakis
and Howell H. Heck

Florida Institute of Technology

Melbourne, FL 32901
 Outline
 Rationale
 Objectives
 Methodology
 Preliminary Results
 Anticipated Benefits
 Rationale
 H2S is among the components of landfill
gas, which contains primarily CO2 and CH4
 Photolytic decomposition of H2S provides
an alternative source of hydrogen fuel
 Removal of H2S from landfill gas would
help prevent odors, hazards and corrosion
 Removal of CO2 would increase the BTU
value of the remaining methane gas
 Objectives
1. Test the efficiency of molecular sieves 4A, 5A, 13X
in separating landfill gas towards high-BTU methane
and FSEC- quality H2S (>50% H2S and <1% CO2)
by Pressure Swing Adsorption (PSA)

2. Investigate the effect of the landfill gas H2S content

on the PSA process efficiency, by varying the H2S
feed volume fraction in the range 0-1 %
 Objectives (cont’d)
3. Determine the effect of pressure on CH4 and H2S
product recovery and purity, by varying the
system high pressure in the range 40-100 psig.

4. Examine the effect of near-equilibrium operation

of the PSA process on the percent utilized sieve
capacity and overall process efficiency, by
varying the gas feed flowrate.
Pressure Swing Adsorption System Layout
Pressure Swing Adsorption Apparatus
 Experimental Methodology
Column I

1. Pressurization to the desired adsorption

pressure by pure CH4
2. Adsorption - supplying a mixture of CH4,
CO2 and H2S
3. Blowdown to the initial pressure (~1 atm)
4. Desorption - purging with inert N2 at nearly
atmospheric pressure
 Experimental Methodology
Column II
1. Pressurization to the selected adsorption pressure
by the adsorption product of column I or a
directly supplied mixture of CO2/H2S
2. Adsorption at the desired high pressure
3. Blowdown to the initial pressure
4. Desorption by purging with inert N2 at nearly
atmospheric pressure
 Preliminary Testing
1. Molecular Sieves 13X and 4A were packed in
Columns I and II, respectively
2. A mixture of CH4-CO2-H2S was supplied to
Bed I to separate CH4
3. A mixture of CO2-H2S was supplied to
Bed II to separate CO2 and recover H2S
4. Adsorption and desorption in Beds I & II
were carried out at 100 psig & 0 psig,
respectively
Preliminary Experiments
Ratio of Outlet to Inlet Molar Flow
during Adsorption

0.9
Gout/Gin, dimensionless

0.8

Bed I
Bed II
0.7

0.6

0.5

0.4
0 10 20 30 40 50 60 70

time, min
Ratio of Inlet to Outlet Molar Flow
during Desorption

1.0

0.9
Gin/Gout, dimensionless

0.8

Bed I
0.7
Bed II

0.6

0.5

0.4
0 2 4 6 8 10 12 14 16 18 20 22 24 26

time, min
Gas Product Composition in Bed I
during Adsorption

100

90

80

70

60
Volume %

CH4
50

40

30 CO2

20 H2S

10

0
0 10 20 30 40 50 60

time, min
Gas Product Composition in Bed I
during Desorption
45

40

35

30
Volume %

25

20
H2S

15

10 CO2

0
0 5 10 15 20 25

time, min
Gas Product Composition in Bed II
during Adsorption

100

90

80 CO2

70

60
Volume %

50

40

30
H2 S
20

10

0
0 10 20 30 40 50 60 70

time, min
Gas Product Composition in Bed II
during Desorption

60

50

40
Volume %

30

H2 S
20

10

CO2
0
0 2 4 6 8 10 12 14

time, min
H2S/CO2 Molar Ratio in Bed II
Desorption Product

Current Product
5 Accumulated Product
H2S/CO2, dimensionless

0
0 2 4 6 8 10 12 14

time, min
 Sieve Capacity & Utilization

1. Column I adsorption loads:

0.9 kg CH4, 2.4 kg CO2, & 2 kg H2S/100 kg 13X
Column I sieve equilibrium capacities:
23 kg CO2 or 19 kg H2S per 100 kg 13X

2. Column II adsorption loads:

2.8 kg CO2 and 1.9 kg H2S per 100 kg 4A
Column II sieve equilibrium capacities:
18 kg CO2 or 14 kg H2S per 100 kg 4A
 Summary of Preliminary Results

1. A 50% CH4 feed over 13X ZMS resulted to

98%-99% product CH4 during adsorption

2. A 68% CO2 - 32 % H2S feed over 4A ZMS

resulted to 71% H2S and 29% CO2 product
during desorption

3. A 20-30% utilization of equilibrium sieve

capacity was encountered
 Expected Technical Results
of Proposed Study
Variation of the PSA product purity and recovery
(CH4%, H2S%, CO2%) and utilized % sieve
capacity with:

a) Type of utilized molecular sieve (4A, 5A, 13X)

b) H2S content of landfill gas (0-1%)
c) Maximum applied pressure (40-100 psig)
d) Landfill gas feed flowrate
 Anticipated Benefits
Development of environmentally acceptable
& financially sound end use for landfill gas,
providing both a high-BTU CH4 stream and
a low-cost H2S feed stream supply for the
FSEC renewable hydrogen fuel program