Adsorption-Desorption in coal Bed

Storage Mechanisms
Gas can exist in a coal seam in two ways. It can be present as free gas within the natural
porosity of the coal (joints and fractures), and it can be present as an adsorbed layer on the
internal surfaces of the coal. The fine micropore structure of coal has a very high storage
capacity for methane. Methane molecules adsorb to the micropore walls. Because the bulk
porosity of the coal cleat system is small (less than five percent) and the initial gas saturation
in the coal cleats is typically low (less than ten percent), most of the gas-in-place in coals
(greater than ninety percent) is adsorbed in the coal matrix. The adsorbed gas volume is
significant even in coals that have gas saturated cleat systems at initial reservoir conditions.

For most coal seams, the quantity of gas held in the coal is primarily a function of coal rank,
ash content, moisture content, and the pressure of the coal seam. The adsorbed capacity of a
coal seam varies non-linearly as a function of pressure. This relationship is best described
using a Langmuir isotherm. To estimate coalbed methane gas-in-place, you must determine
both the gas content of the coal as it exists at initial reservoir conditions (pressure and
temperature) and the desorption isotherm, which describes how methane will be released as
pressure is reduced. Both variables must be obtained from core analysis. The gas content of
coal generally is determined by directly measuring the amount of gas desorbed from a coal
after recovery. This measurement defines the amount of gas in the coal at initial reservoir
pressure and temperature. The desorption isotherm is determined by grinding the coal to a
fine mesh and systematically measuring the amount of gas that the coal can contain at various
pressures. The isotherm, therefore, defines the upper limit gas concentration (i.e., maximum
adsorptive capacity) as a function of pressure. The isotherm is quantified by determining the
Langmuir parameters from the test data. Determining the gas content and the desorption
isotherm by core testing is extremely important for estimating the gas-in-place and for
estimating well reserves. The desorption isotherm and gas content are necessary for analyzing
coalbed methane reservoirs and simulating recovery of methane from coalbed methane wells.
Water is stored in coals in two ways: as bound water in the coal matrix and as free water in
the coal cleat system. The bound water in coals is formed as a byproduct of the coalification
process. Matrix bound water is not mobile and has not been shown to significantly affect
methane recovery from coal.

The free water contained in the cleat system is mobile at high water saturations (greater than
thirty percent). Many blanket coal deposits are active aquifer systems and thus are 100
percent water saturated in the cleat system. Coals that are not aquifers may have initial water
saturations less than 100 percent. The minimum mobile water saturation of the coal cleat
system is determined by relative permeability testing of cleated coal samples. Data published
in the literature suggest that a typical irreducible water saturation for a well cleated coal is in
the range of twenty to fifty percent of the interconnected cleat volume.

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Gas Storage in the Coal Matrix
Gas is stored in coal primarily by sorption on matrix surfaces, although a small fraction of
gas may be stored as free gas in the fracture system. Gas adsorption on coal is a physical (as
opposed to chemical) phenomenon. During physical sorption, fluid molecules experience a
net attraction to a solid surface. Because of the attraction, the density of the fluids near the
pore walls is increased, which increases the bulk density of the fluid in the sorbed state. The
increased density means that at low pressure, greater volumes of gas can be stored by
sorption than by compression.

The Langmuir Isotherm

A variety of models have been used to describe the sorption process.The most common
model in use for coal is the Langmuir isotherm, which relates the capacity for coal to store
gas to the external pressure of the gas. As the name implies, an isotherm is evaluated at a
constant temperature (reservoir temperature). A form of the Langmuir isotherm that can be
used for both single component and multicomponent gases is given by the equation below.

[
G S =V L ( 1−f a−f m )
BP
]
1+ BP
where:
Gs = Gas storage capacity, scf/ton
VL = Dry, ash-free Langmuir storage capacity,
scf/ton
fq = Ash content, weight fraction
fm = Moisture content, weight fraction
B = Langmuir constant, psi-1
P = Pressure, psia
Another form of this equation uses the constant PL, referred to as the Langmuir pressure,
with b =PL-1. At low pressures, the relationship between storage capacity and pressure is
linear and is referred to as a Henry’s Law isotherm. At very high pressures, all of the storage
sites will be occupied if sufficient molecules are available, and the storage capacity will reach
its maximum value equal to the Langmuir storage capacity. If sufficient number of molecules
is not available, some storage sites will remain unoccupied. When the coal has the capacity to
adsorb more gas than is available, the coal is considered to be undersaturated. P L is defined as
the pressure that gives a gas content equal to one-half of the monolayer capacity. The
equation can be derived thermodynamically or from the kinetic theory of gases. At low
pressures attainable in the laboratory but difficult to attain in a coalseam in the field, (1 +
BP)≈1, VL, the Langmuir pressure is defined as the maximum volume of gas that can be
adsorption per unit mass of coal at inifinite pressure.

To determine, the PL and VL, the Langmuir equation can be written in the form of following
equation:
P 1 P
= +
V V max B V max

2
Thus, a plot of P/V vs. P gives a straight line with an intercept of 1/VmaxB and a slope of
1/Vmax.

Factors Affecting the Sorption Isotherm

These factors include ash content, moisture content, temperature, and gas composition. Each
of
these factors is discussed below.
Ash Content. The ash content has been included in the above Equation because non-coal
components
act as a diluent and reduce the gas storage capacity of coal. This term is also required because
storage capacity measurements generally are performed on a coal sample with an ash content
different from the average ash content of the reservoir. In coal samples that have a significant
sulphur content, the ash content is not equal to the mineral matter content of the coal. This is
because the procedure used to determine the ash content by burning the sample also vaporizes
sulfur.
Moisture Content: Water competes for the sorption sites with other molecular species and
reduces the storage capacity of non-water molecules. Moisture content is included in the
Equation because laboratory results often present the Langmuir volume on a dry, ash-free
basis. The accuracy of the available method to correct a sorption isotherm measured at one
moisture content to a different moisture content is subject to debate because only four
measurements were used to develop a correlation.
Thus, isotherms should be measured at the in-situ moisture content. Accepted practice is to
perform
sorption isotherm measurements at the equilibrium moisture content. The equilibrium
moisture content, which is defined by ASTM standards, is assumed to be the same as the in-
situ moisture
content. Moisture content has been shown to decrease methane storage capacity until the
critical moisture content is reached. Moisture contents above this critical moisture level are
generally believed to result in no further decreases in the methane storage capacity. This
critical moisture level often is assumed to be the same as the equilibrium moisture content.
Temperature: For a given coal sample, the sorption isotherm is strongly affected by changes
in temperature. Theory indicates that the Langmuir storage capacity (VL) is unaffected by
temperature.
This implies that the total number of storage sites is insensitive to changes in temperature.
However,
temperature affects the value of the Langmuir constant (b). As temperature increases, the
Langmuir constant will decrease. This means that at a fixed pressure, the amount of gas
stored will decrease as temperature increases.
Gas Composition: The term “coalbed methane” is commonly used when in reality gas
produced from coal often contains significant amounts of carbon dioxide, nitrogen, water and
heavier molecular weight hydrocarbons. Methane isotherms can result in estimates of pure
methane storage capacity that are less than the estimates of the total gas content.

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Measuring Sorption Isotherms
Measuring sorption isotherms involves two procedures:
1) selecting and preparing samples according to ASTM standards, and
2) performing isotherm tests. Each of these procedures are described in the sections below.

Selecting and Preparing Samples. The procedures for selecting and preparing samples for
isotherm testing are described below.
1. Selecting Samples. Samples for isother. Samples are dried and crushed during preparation.
A sieve analysis should be performed to determine the particle size distribution of the sample.
A minimum of 300 grams of crushed sample should be prepared for the various
measurements. The preparation procedure is described in the ASTM standards.
Performing Isotherm Tests.
1. Interconnected reference cell and sample cells are put into a temperature controlled
system
2. Volume of the reference cell and the sample cells are determined using Boyel’s law
Helium expansion.
3. Coal sample is charged into the sample cell
4. Helium is charged again to determine the void volume and the coal density.
5. The reference cell is charged to a pressure greater than the estimated stabilized
pressure
6. Valve between sample cell and reference cell is opened and let the pressure to
stabilize
7. Pressure is increase this way from atmospheric to the reservoir pressure in 6-8 steps.
8. In each step pressure variation with time is noted and final pressure of each step is
noted.
9. Volume of adsorbed gas is then calculated using the Boyel’s equation

Gas storage capacity is evaluated at the equilibrium endpoints for each pressure step. Total
gas capacity is the sum of the individual end point gas capacities. The change in gas storage
capacity at endpoints can be calculated using the equation below:

∆ G s=32.068 {
V r −1
mc
( B gr 2−B gr 1 ) −
−1 V rv −1
mc
( }
B grv 2−Bgrv 1)
−1

Where,
∆ G s=¿ Change in gas storage capacity, scf/ton
V r =¿ Reference cell volume, cm3
mc= mass of coal , grams
Bgr2 = Gas formation volume factor at the final reference cell pressure
Bgr1 = Gas formation volume factor at the initial reference cell pressure
Vrv = Sample cell void volume, cm3
Bgrv2 = Gas formation volume factor at the final sample cell pressure
Bgrv1 = Gas formation volume factor at the initial sample cell pressure

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The formation volume factor Bg can be determined by the equation below,
P z ( T + 459.69 )
Bg = sc …( Eq 17)
P z sc ( T sc + 459.69 )
Where,
Bg = Gas formation volume factor
Psc = Pressure at standard condition, psia
z = Real gas deviation factor
T = Temperature, ̊ F
P = Pressure, psia
Zsc = Real gas deviation factor at standard conditions
Tsc = Temperature at standard conditions, ̊ F
Desorption Test:
1. Calibration of the apparatus to determine the sample cell void volume.
2. Charging the reference cell to a pressure greater than the expected final pressure of
the sample cell at the current isotherm step.
3. Opening a valve between the reference cell and sample cell thereby allowing the
pressures to equalize.
4. Monitoring the sample cell pressure to determine when the pressure stabilizes and
adsorption is complete at the current step.
5. Repeating steps 2 through 5 until the final sample cell pressure is reached.
6. Measuring a desorption isotherm if desired
G 'S
GS =
Correction in Gas Content
( )1− f
ρ :
ρs
Where G's = Uncorrected laboratory estimate of gas storage capacity, scf/ton
ρf = Density of gas in the free state at the measurement pressure and temperature, g/cm3
ρs = Apparent density of the gas in the sorbed state, g/cm3

Desorption Testing of Conventional Core (Steps)

1. Cut the coal core into one foot long sections.
2. Place the coal core into tightly fitting plastic sleeves.
3. Insert the sleeved core into desorption canisters of known weight.
4. Weigh the filled canisters.
5. Place the canisters in water baths regulated at reservoir temperature.
6. Determine the desorbed gas volume as a function of time.
7. Periodically collect gas samples for composition determination.
8. Terminate the test.
9. Determine the residual gas volume.