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Presented to
ALL-CRAFT Columbia, Mo
July,2005
Adsorption
Solid placed in B
then,
PAVA
>
PAB(VA + VB)
Extent of adsorption
dependent on,
1.
Temperature
2.
3.
1. Temperature
Lower temperature, greater adsorption,
Higher temperature, lower adsorption.
Simplify to realistic temperature for vehicular use,
constant temperature, (isothermal), of 298K
for experimental studies.
2.
BPL
Dow Resin
MCM-41
Zeolite
Uptake (mg/g)
80
60
40
20
0
0
100
200
300
400
Pressure (psia)
500
600
However,
Some high methane uptake claims made for
cavity based crystalline salts.
Ni++ Cu++ salts
1,4-Benzenedicarboxylate
(BDC)
[Fm-3m, a=25.6690(3)]
Porous Carbons
Highly disordered carbon, unlike diamond or
graphite
Described as like a pile of potato chips
Chips, small crystallites with graphite like
structure
Space between chips are the pores
Pore Definitions (IUPAC)
Micropore
2 - 20
Mesopore
20 - 50
Macropore
> 50
Adsorption
Pore wall of carbon atoms provides attractive
force for the adsorbate molecules.
Influence of both walls in narrow pores
so adsorption potential is greater.
Rule of thumb,
Narrow pored adsorbents, good for gas
adsorption, small molecules.
Larger pored materials, better for liquids
and larger sized molecules.
BPL
PVDC
Uptake (mg/g)
200
150
100
50
0
0
100 200 300 400 500 600 700 800 900 1000 1100
Pressure (psia)
Gas Storage
Adsorption uptakes usually expressed as
mass uptake,
e.g. Grams adsorbate / gram adsorbent
Porous carbons differ greatly in density.
Storage vessels have finite volume.
For storage, uptake must be considered
from a volume perspective.
Container Volume
Micropore
Macropore
Carbon
Void
Macro
32%
Carbon
12%
Void
42%
AX-21 Carbon
Micro
44%
Carbon
46%
Void
8%
Macro
2%
PVDC Carbon
Micro
14%
Carbon
12%
Micro
44%
Macro
32%
Carbon
46%
Void
42%
Void
8%
Macro
2%
AX-21 Carbon
PVDC Carbon
BPL
PVDC
Uptake (mgs/mL)
200
150
100
50
0
0
100 200 300 400 500 600 700 800 900 1000 1100
Pressure (psia)
Mass
250
AX-21
BPL
PVDC
Uptake (mg/g)
200
150
100
50
0
0
250
AX-21
BPL
PVDC
Uptake (mgs/mL)
200
150
100
50
Volume
100 200 300 400 500 600 700 800 900 1000 1100
Pressure (psia)
Volumetric Storage
Maximise micropore volume in vessel
Minimise void space in vessel
Density of molecules in macropore nearly
the same as the gas phase,
so carbon adsorbent should have as few
macropores as possible.
Some mesopore structure needed to aid
kinetics of adsorption / desorption.
CH4 Delivery
AGLARG ANG Vessel vs. CNG Vessel
250
CNG
AGLARG ANG
V/V Delivered
200
150
100
50
0
0
10
15
Pressure (MPa)
20
0.18
0.16
0.14
0.12
0.10
0.08
M
e
th
a
n
e
d
e
n
sity (g/mL)
0.06
0.04
0.02
0.00
)
PSI
(
e
300r
ssu
e
r
P
200
400
100
0
140
120
100
80
Por
60
eS
40
ize
20
[A]
= 0.66
Macro
32%
Carbon
12%
Void
42%
AX-21 Carbon
Micropore Volume
Various methods in use for determination of
micropore volume.
Most common, Dubinin-Radushkevich (1947) plot
using the low pressure 77K nitrogen isotherm.
Has also been applied to 273K CO2 isotherms.
Very different conditions to relatively high
pressure methane at 298K.
These methods only give overall micropore
volume but give no clue or indication of the range
of micropore widths.
1. Tank
Should possess good box (envelope)
characteristics.
Must be suitable for packing monoliths.
Internal web structure, not only for strength,
but for good heat exchange.
Multiple tanks, switchable and programmed to
operate as isothermally as possible.
2. Guard Bed
Impurities in natural gas can build up in the
micropores and over many fill / empty cycles
can result in a decrease in storage capacity.
Water is particularly difficult to desorb.
3. Monolith
Carbon adsorbent should be capable of being
produced as monoliths to minimise void space.
If a binder is used, it should not block
micropores.
Binder should also occupy minimal volume.
4. Micropore Volume
Methane isotherm should be used to determine
micropore volume.
It should be in excess of 0.7 mL / mL of monolith,
since it is unlikely to be all optimal pore.
5.
Carbon Preparation
Directed towards methods that create new
micropore, not to conventional activation
methods which merely enlarge existing pore.
X-ray P51
Rosalind Franklin