U.S. patent number 3,794,116 [Application Number 05/257,965] was granted by the patent office on 1974-02-26 for situ coal bed gasification.
This patent grant is currently assigned to The United States of America as represented by the United States Atomic. Invention is credited to Gary H. Higgins.
United States Patent |
3,794,116 |
Higgins |
February 26, 1974 |
SITU COAL BED GASIFICATION
Abstract
Deeply buried relatively thick coal bed formations are fractured
explosively. Reactant input conduits communicating with upper
portions of the fragmented coal zone and product withdrawal
conduits communicating with lower portions thereof are provided.
The uppermost layer of the fragmented zone is ignited as by
injection of oxygen and fuel gas from a surface plant while the
product conduits are closed off to raise the operating pressure in
the fragmented zone to balance hydrostatic pressure so that the
fragmented zone comprises effectively a pressurized reaction
vessel. Water or steam together with regulated amounts of oxygen
are then introduced while reaction products are withdrawn at a rate
at which operating pressure is maintained so that a relatively
higher temperature reaction zone layer is reacted in the upper
layer to travel progressively downward. A graduated lower
temperature region precedes the higher temperature zone. Various
gasification reactions occur in the reaction zones with the net
overall products being methane and CO.sub.2 with relatively little
up to varying amounts of carbon monoxide and hydrogen appearing in
the reaction product gas. Processing to remove CO.sub.2 and react
the carbon monoxide and hydrogen if deemed necessary is done at the
surface yielding a high caloric value fuel gas suitable for
pipeline or for synthesis uses.
Inventors: |
Higgins; Gary H. (Livermore,
CA) |
Assignee: |
The United States of America as
represented by the United States Atomic (Washington,
DC)
|
Family
ID: |
22978534 |
Appl.
No.: |
05/257,965 |
Filed: |
May 30, 1972 |
Current U.S.
Class: |
166/259;
48/DIG.6; 166/247; 48/202 |
Current CPC
Class: |
E21B
43/247 (20130101); Y10S 48/06 (20130101) |
Current International
Class: |
E21B
43/16 (20060101); E21B 43/247 (20060101); E21b
043/24 (); E21b 043/26 () |
Field of
Search: |
;299/2,4
;166/247,259 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Purser; Ernest R.
Attorney, Agent or Firm: Horan; John A. Robertson; F. A.
Perona; John
Claims
What I claim is:
1. A process for in-situ gasification of a subterranean coal
deposit to produce synthetic natural gas comprising:
selecting a coal deposit formation having a relatively thick coal
bearing interval distributed therealong and situated beneath the
water table at a depth yielding a hydrostatic pressure of at least
about 500 psi;
emplacing and detonating explosive charges in said coal bearing
interval of said formation to provide a deep bed of broken coal
disposed in a closed cavity defined by undisturbed portions of the
formation;
providing at least one reactant input conduit communicating with
the uppermost layers of the broken coal bed in said cavity together
with at least one product withdrawal conduit communicating with
lowermost portions of the coal bed in said cavity;
injecting oxygen through said input conduit and igniting upper
layer portions of said coal bed while raising the operating
pressure in said cavity to balance said hydrostatic pressure;
then injecting water through said input conduit to react with said
ignited coal layer together with sufficient oxygen to supply heat
needed in the reaction while withdrawing reaction product gas
through said product withdrawal conduit to form a reaction zone
comprising an upper high temperature layer region merging into a
lower region having gradually decreasing temperatures therein,
which reaction zone progresses downwardly through said coal bed so
that a product gas containing methane is delivered to said
withdrawal conduit; and
separating said methane from said product gas withdrawn from said
product withdrawal conduit.
2. A process as defined in claim 1 wherein the coal in said coal
bearing interval has a composite thickness of at least about 50
feet.
3. A process as defined in claim 1 wherein the temperature in the
high temperature region of said reaction zone is in the range of
about 600.degree.K to about 1500.degree.K.
4. A process as defined in claim 1 wherein the temperature in the
high temperature region of said reaction zone is in the range of
about 650.degree.K to about 1,100.degree.K.
5. A process as defined in claim 4 wherein said product gas
comprises a mixture including methane and CO.sub.2.
6. A process as defined in claim 4 wherein said product gas
comprises a mixture including methane, CO.sub.2, CO and H.sub.2,
wherein said product gas is processed in a surface methanator to
complete the methanation reaction and wherein residual CO.sub.2 is
removed from the product gas to yield high quality synthetic
natural gas.
7. A process as defined in claim 4 wherein the operating pressure
in said cavity is in the range of about 500 to about 1,000 psi.
8. A process as defined in claim 7 wherein the temperature in the
high temperature region is of the order of 700.degree.K.
Description
BACKGROUND OF THE INVENTION
This invention was made under or in the course of Contract No.
W-7405-ENG-48 with the United States Atomic Energy Commission.
The domestic economy is faced with an ever growing deficit in
energy reserves and particularly in domestic supplies of liquid and
gaseous petroleum fuels. The shortage of natural gas is becoming
acute so that serious efforts are being directed toward obtaining
imports or to produce synthetic natural gas (SNG) in large surface
plants using mined coal or a variety of imported petroleum
fractions. In any case the cost of such supplies will be several
times the cost of natural gas which has existed in the past. Major
portions of the cost of the gas produced by surface coal
gasification plants are represented by mining costs and the cost of
the surface installation itself. Mining costs increase drastically
when deep lying coal deposits are used instead of shallow deposits
which can be strip mined. Various environmental problems accompany
operation of such plants as involved in strip mining and shipping
as well as sulfur removal, pollution from fly ash, waste disposal
and others.
Attempts have been made since the mid-nineteenth century to produce
fuel gas by in-situ coal bed gasification techniques (c.f. Homer
Lowery (Editor), The Chemistry of Coal Utilization, Supplemental
Volume 1968, J. Wylie Press, chapter 21). Most of these attempts
have been directed to shallow deposits of subbituminous coals in
eastern Germany, in Russia around Moscow and in Alabama by the U.
S. Bureau of Mines. In these procedures air at about atmospheric
pressure is pumped down a hole or shaft, directed across one or
more burning coal beds and collected in another shaft or drill
hole. There have been many variations in geometry of the holes but
in every case most of the coal is converted to CO.sub.2 with just
enough H.sub.2 and CO to make a very low quality heating gas. These
product gases typically have heating values of 100-300 BTU/ft.sup.3
while pure methane (natural gas) has a heating value of nearly 1000
BTU/ft.sup.3 and is suited to economical pipeline distribution.
Analyses of the burning fronts carried out through tunnels driven
parallel to the burning galleries and connected to them with small
horizontal drill holes show that most of the CH.sub.4 and much of
the H.sub.2 and CO is burned near the exit region. This occurs
since inlet air bypasses the hot front of combustion and combines
with the exit gases burning most of the gas as it combines. Even
so, several plants have been operated with this process
continuously over the past forty years producing low quality gas
from coal which is otherwise unsuitable for use because of its high
ash content.
Similar techniques are not practical for use with deeply buried
coal deposits since the cost of sinking shafts and driving the
necessary tunnels would be prohibitive. Also, the gas would be of
such low quality and caloric content that transmission by pipeline
would not be economically feasible. Accordingly, it may be seen
that a need exists for a procedure with which such deposits can be
economically converted into a high quality fuel gas, i.e.,
synthetic natural gas.
SUMMARY OF THE INVENTION
The invention relates generally to coal gasification and, more
particularly, to an improved process for use in the in-situ
gasification of deeply buried thick coal beds to provide high
quality synthetic fuel gas.
In practicing the present invention there is selected a relatively
thick deeply buried coal deposit having a coal bearing interval
with a thickness or composite thickness of at least about 50 feet
and situated far below the water table. A large volume of the
deposit is fractured by any suitable means. From the standpoint of
economy explosive fracturing is generally preferred since the
explosive may be emplaced by means of drill holes appropriately
spaced. Moreover, selected drill holes may be provided with
suitable casings to be used as reactant input conduits. Product
output conduits may be provided as drill holes formed by slant
drilling methods extending from the surface to communicate with the
lowermost fractured portions of the fractured material. Suitable
casing, e.g., with perforated lower ends may then be used to
conduct the product gases to a surface processing facility. In some
instances, the output conduit might be provided by a strategically
placed shaft with radiating galleries.
In commencing operations a mixture of oxygen and fuel gas is
introduced through the reactant input conduits and is ignited so as
to heat the upper layer of fragmented coal to reaction, i.e.,
ignition temperature. Generally, the output conduits are closed off
at this time so that the pressure in the cavity defined by the
fractured volume of material is built up to an operating range of
the order of 500 to 1000 psi. The operating pressure may be
selected so as to balance the hydrostatic pressure of the ground
water thereby preventing ingress of water while the hydrostatic
head may serve to eliminate or minimize leakage from the cavity.
Moreover, operation at such an elevated pressure promotes
methanation reactions in the fractured coal bed so as to yield a
high caloric value product gas.
When the desired operating pressure is attained the product output
conduits are opened and reactant water in an appropriate form
together with oxygen are introduced to contact the ignited upper
coal layer. Withdrawal of product gas is then correlated with
reactant input to maintain operating pressure. Thereupon, the
ignited layer spreads downward with a temperature in the range of
about 600.degree. to 1,500.degree.K and preferably in a range of
about 650.degree. to 1,100.degree.K, developing therein as the
water and oxygen react with the upper coal layer. Heat carried by
the flowing reaction gases heats up the bed downwardly from the hot
layer zone to a lower temperature than exists in the hot zone and
further reactions productive of methane occur therein. It is to be
noted that use of a downwardly progressing reaction assures a
stable burning or reaction zone which eliminates by passing. A
product gas comprising methane, water vapor, possibly with some CO
and H.sub.2, as well as CO.sub.2 is formed as a result of the
foregoing reactions. The latter gas may be removed and the water
vapor condensed in a surface facility and the CO and H.sub.2 may be
reacted catalytically if desired to produce methane. In any event
there is obtained a high caloric content gas suitable for fuel or
for use in chemical syntheses.
The process has several advantageous features in that no ash or
mining debris is produced at the surface. Also mining costs are
eliminated and the cost of surface facilities is drastically
reduced since expensive large-scale reactors or converters are not
needed.
Accordingly, it is an object of the invention to provide procedure
for in-situ gasification of a coal deposit.
Still another object of the invention is to provide in-situ
gasification of a deeply buried coal deposit using elevated
pressures and temperatures.
Another object of the invention is to provide for the economical
in-situ gasification of a coal deposit to yield a high caloric
value fuel gas.
Other objects and advantageous features of the invention will be
apparent in the following description and accompanying drawing, of
which:
FIG. 1 is a vertical sectional view of a subterranean formation
having a relatively thick coal bearing interval suitable for
practice of the invention;
FIG. 2 is an illustrative blasting hole pattern for emplacement of
explosive for shattering the coal bearing interval shown in FIG.
1;
FIG. 3 is a schematic illustration of a plant arrangement for
conducting gasification of coal shattered by detonation of
explosives in the interval of FIG. 1; and
FIG. 4 is an enlarged view of the shattered coal interval shown in
FIG. 3 together with a temperature profile and corresponding
reactions which occur in various portions of the reaction zone.
DESCRIPTION OF THE INVENTION
Coal deposits are widely distributed in the North American
continent as well as elsewhere throughout various regions of the
earth. For purposes of the invention those found between about 600
and 3000 feet below the ground surface are of particular interest.
The Western United States is particularly well endowed with coal
deposits which have appropriate physical and chemical
characteristics. An estimated 1.5.times.10.sup.12 tons of coal
reserves exist therein (c.f. The Economy, Energy and the
Environment, Joint Economic Committee of Congress of the United
States, Sept. 1, 1970). Processing of only 30 percent of these
coals would yield the equivalent of about 10,000 trillion cubic
feet of gas or about 30 times presently known producible
reserves.
For purposes of describing the invention reference will be made to
a particular deposit existing in the Central Powder River Basin of
eastern Wyoming about 20 miles west of Gillette. In this formation,
there generally exists five separate coal beds each averaging about
50 feet in thickness although one portion has a continuous 205 foot
thick seam of coal. In one area therein coal sufficient to produce
a potential of 700 trillion cubic feet of gas exists in an area of
9 by 18 square miles. These coals are too deep to mine economically
so that in situ gasification would utilize resources not otherwise
available.
A typical section of such a deposit is shown in FIG. 1 of the
drawing wherein coal seams 11 interspersed with shale layers 12 in
a relatively closely spaced formation interval is shown. The
indicated interval is overlain by overburden 13 comprising
interspersed layers of sandstone and shale in which the water table
14 exists some level beneath the ground surface. A formation is
generally selected for which the uppermost coal layer is at a depth
beneath the water table sufficient to provide a hydrostatic
pressure in the range of about 500 to about 1,000 psi or somewhat
more. In this respect hydrostatic pressure is about 435 psi for
each 1,000 feet below the water table. It is considered that the
interval selected should average at least about a 20 percent coal
content in order that a satisfactory reaction rate be sustained.
The interval may comprise a continuous bed or interspersed
coal-country rock layers.
To prepare the selected coal bearing interval, the coal seams and
interspersed shale layers, if present, are shattered with
explosives. The area extent is selected to encompass sufficient
coal to provide more or less continuous operation for a
considerable time, e.g., one year or more. It is preferred to
shatter the coal in as large a unit as can be processed at one time
so as to minimize the amount of coal left between the areas to be
processed. One half square mile area or more may be processed at
one time. Explosives such as the ammonium nitrate-aluminum-diesel
or stove oil mixtures or ammonium nitrate fuel oil mixture (ANFO-Al
or ANFO) widely used in the mining and construction industries may
be used as may nuclear explosives developed for plowshare
applications. Conventional blasting explosives may be emplaced by
means of, for example, 24 inch drill holes 19 shown in FIG. 1 and,
for example, with about a 60 foot spacing in a concentric hexagonal
pattern as shown in FIG. 2 of the drawing. Those drill holes to be
used for injecting reactants may be cased with steel tubing prior
to blasting and stemmed, e.g., with drillable plugs or with
removable packers to a sufficient height to contain the detonation.
Casing may be used in the remaining drill holes to prevent ingress
of water if needed or may simply be stemmed with water tight
material. The explosives may be emplaced and detonated
sequentially, e.g., from the central hole outwardly to minimize
possibility of fracturing overlying strata. The explosive charge
size is selected to give adequate breakage but less than enough to
give a "lifting" type detonation which might unduly disturb the
formation. Conventional loading and firing systems may be used.
Breakage of the order of 600 tons of coal per ton of explosive may
be obtained. A lesser number of nuclear devices may be used for
which the spacing and device size may be determined using published
information (c.f. UCRL-50929, "Aids for Estimating Effects of
Underground Nuclear Explosions," T. R. Butkovich et al., Sept. 8,
1970).
Once the desired quantity of coal has been broken, the detonated
area may be arranged, as shown schematically in FIG. 3, for
carrying out the gasification process. The shattered or broken coal
bed 21 may be considered to be disposed in a closed vessel or
cavity defined by surrounding undisturbed portions of the original
formation. One or more of the cased drill holes 17 (one only shown)
may be drilled out to serve as reactant input conduits. Conduit
holes 17 may be connected to an oxygen supply plant 22 and to
receive water from a water processing plant 23. A sufficient number
of drill holes are utilized, or other means, e.g., spray devices
can be used to assure reasonably uniform distribution of the water
to uppermost layer of the bed 21 of broken coal. Oxygen will be
distributed merely by injection. At least one product output
conduit 24 (one only shown) is provided to communicate with the
bottom of the broken coal bed 21 for conducting product gases
(CH.sub.4, CO, CO.sub.2, H.sub.2, H.sub.2 O, etc.) to a surface gas
purification plant 26. It is conceivable that the outlet conduit
could also be provided as a lined shaft with galleries (not shown)
being mined beneath the broken coal bed and lined. A centrally
located shaft could be used with several satellite gasification
chambers. The gas purification plant 26 may be of conventional
design similar to those used in surface gasification plant
technology. In the event that the product gas comprises principally
methane and CO.sub.2 as occurs with certain modes of operation the
plant 26 may comprise merely a CO.sub.2 removal unit using, for
example, absorption of the CO.sub.2 in water and a water
condensation unit to yield gas suitable for pipeline delivery.
Excess water which may accummulate or condense in lower portions of
the cavity may also be withdrawn through a conduit 24 using a pump
(not shown). Under other operating conditions, as when the
gasification reaction hot zone approaches lower portions of the
coal bed, methanation may not be complete and CO and H.sub.2 may
appear in the product gases. In this event an auxiliary catalytic
methanation circuit of conventional design may be included in the
gas purification plant.
Absorber water containing CO.sub.2 may be circulated to the water
processing plant 23 wherein the CO.sub.2 may be stripped as in a
stripping tower, or by bubbling air therethrough. This water and
that withdrawn from the cavity may then be recirculated to react
with the coal bed. The initial water supply and makeup water need
not be fresh potable water but may be brackish water provided from
a collection and storage system.
In commencing operation a flammable mixture, e.g., oxygen and fuel
gas, e.g., natural gas, may be introduced and ignited to heat the
uppermost layers of the coal bed to reaction temperature, i.e.,
preferably in the range of about 650.degree. to about 1100.degree.K
and still more preferably in the range of about 650.degree. to
about 850.degree.K. Other ignition procedures used in fire drive
secondary oil field techniques may also be used. During this
operation the product output conduit 24 is closed off so that the
cavity pressure is raised to the operating range, i.e., about 500
to 1,000 psi or more. Thereafter, the product output conduit 24 is
opened whereupon a gasification reaction zone having a temperature
profile as shown in FIG. 4 of the drawing is established. The
relative amounts of water and oxygen are generally regulated to
maintain the peak reaction temperature in the uppermost coal bed
layers at a level where water gas reactions and some methanation
reactions occur. More complete methanation then occurs in the
cooler zone ahead of the peak temperature region. As the reaction
proceeds over a period of time the reaction zone progresses
downwardly leaving heated ash and residual debris behind. Water and
oxygen entering therethrough absorbs residual heat therefrom to
provide a portion of the heat required in the gasification
reaction.
It is to be noted that the downward gasification procedure provides
for a very stable reaction front, which minimizes bypassing of
unreacted coal, as compared to upward or lateral burning. Also, the
reacted and unreacted shale and the coal ash are effective
catalysts for the carbon monoxide-water reaction as well as being
powerful scavengers of sulfur oxides, hydrogen sulfide and acid
vapors such as may be created when using brackish water. The rock
has low thermal conductivity so that heat loss does not occur to an
appreciable extent. Likewise fly ash and heavy metal contaminants
should be trapped in the long vertical column of rock and ash. A
low pollution product synthetic natural gas is thereby
produced.
COAL GASIFICATION PROCESS CHEMISTRY
Coal is an organic compound which contains essentially no free
carbon in the natural state. It is made up of a series of molecules
containing three or four six-carbon-rings in a phenanthrene-like
structure. The phenantherene-like structure is partially hydrogen
saturated so it is strained into "boat-like" shapes. Nitrogen and
sulfur (non-pyrite) are contained within the rings while oxygen is
mostly in the hydroxy form. These elements thus cross link the
basic ring structures into phenolformaldehyde-like polymers.
Because of the ring strain the whole structure is so loose that
water molecules can occupy space between loosely parallel rings
forming hydrogen bonds with the unsaturated carbon atoms giving the
whole structure additional stability. This water comprises 10-30
percent of the weight of coal in place and is chemically part of
the coal.
Coals are classified into a complex sequence depending on their
hydrogen-carbon ratio, coking properties, ash content, behavior
when heated and sulfur content. It is sufficient for present
purposes to consider four broad categories; anthacites, bitumins,
sub-bitumins, and lignites. In this order these classifications are
characterized by generally increasing hydrogen-carbon ratios,
generally decreasing heats of combustion and generally increasing
oxygen content. The method of gasification described herein appears
more readily applicable to those coals in the sub-bituminous and
lignite classifications and which have hydrogen-carbon ratios
approaching one in the newly mined coal. This type of coal has a
large amount of fixed hydrocarbon and has a more favorable heat
balance during in situ gasification.
Since each coal will have a slightly different chemical makeup, a
universally applicable set of reactions cannot easily be written.
For present purposes gasification of coal from the Central Powder
River basin as representative of widely distributed coal deposits
will be considered. This coal has a heating value of about 9000
BTU/lb and chemical properties as shown in Table I. There are
generally five coal beds in the area each averaging 50 ft in
thickness although one drill hole (sec. 29 T49NR75W) indicated 205
ft of continuous coal in one bed. ##SPC1##
The "formula" for the coal indicated in Table 1 is CH.sub.1.16
O.sub.0.35 N.sub.0.015 S.sub.0.005 which can be simplified to
CH.sub.1.16 O.sub.0.35 for the thermodynamic calculations. This
coal has a gram-formal weight of 18.76; this should not be confused
with its molecular weight which is likely nearer one or two
thousand. In the following calculation the "mole" used is assumed
to be the simple one shown above.
In order to calculate heat balances and chemical reactions it is
necessary to know the enthalpy H.degree..sub.298 and the entropy
S.degree..sub.298 of the coal compound. The enthalpy or heat of
formation of coal can be determined from the heat of combustion and
the known heats of formations of the reactant oxygen and combustion
products. From this calculation, H.degree..sub.298 of this coal is
found to be -30.627 K cal mole.sup.-.sup.1.
Estimating the entropy of formation is more difficult and may be
attempted by making assumptions about the chemical structure of
coal. By comparison with a number of organic compounds whose
compositions are similar, the entropy of the coal can be estimated
to be between 5 and 15 cal deg.sup.-.sup.1 mole.sup.-.sup.1. Use of
the Latimer rule for estimating entropy, ##SPC2##
(3/2 R lnM.sub.i -0.94), yields a value of 10.24 cal
deg.sup.-.sup.1 mole.sup.-.sup.1 for the coal in question. This
very important property may be measured more accurately by
conventional experimental methods. However, it will be appreciated
that there may be some shift in optimum operating temperatures if
the true value is much different than that assumed, however, an
assumed value can be used to evaluate the heat and equilibrium
reactions which may occur. Its choice does not affect the heat
balance significantly. A value of 10.1 cal deg.sup.-.sup.1
mole.sup.-.sup.1 is assumed in the following.
The reactions occurring during gasification of coal can now be
examined and attention is directed to four categories, i.e.,
combustion, pyrolysis, reaction with water, and with hydrogen as
shown in Table 2. These are the compounds which contact the coal at
various locations in the active reaction zone. Neither CO.sub.2 nor
CO react with coal at lower temperatures and these reactions are
omitted in Table 2.
The estimated .DELTA.H for reaction and the free energy, .DELTA.F,
are shown in Table 2 for temperatures of 500.degree. and
1000.degree.K. Following the usual convention, a negative value of
.DELTA.H means heat is released and a positive .DELTA.H means heat
is consumed. Negative values of .DELTA.F imply reactions favor the
product or right side of the chemical equation, while positive
values of .DELTA.F indicate that the reactants or left side
compounds are favored. Thus a reaction with positive .DELTA.H and
negative .DELTA.F will proceed to completion while consuming heat.
##SPC3##
The thermodynamic quantities in Table 2 show that coal decomposes
or reacts with water (reactions 1 and 2) only if heat is supplied
at temperatures above 500.degree.K. Therefore, in this coal and in
the absence of oxygen or hydrogen (reactions 3 and 4) the coal will
not continue to react and no "runaway" burn can occur. The reaction
which produces methane (reaction 2) directly from coal requires
heat to be supplied and appears to be somewhat more favored at
these temperatures than is pyrolysis (reaction 1), so that that the
direct conversion of coal to methane with water is possible if
enough O.sub.2 is supplied to provide the necessary heat via
reaction 4. If, on the other hand, reaction 1 occurs faster, then
methane is produced through reactions 1 and carbon is then reacted
with water (reaction 5), a portion of the CO reacted further with
water (reaction 8), to produce enough hydrogen to balance reaction
9 with the same net result. Two competitive reactions may also be
considered. This second path of methane production, i.e., from
carbon, can be inhibited if reaction 3 depletes all the hydrogen
(although methane is produced anyway by other reactions) or if
reaction 10 occurs and depletes all the CO before 8 and 9 can
occur. It appears from experiments done in surface methanators that
the rates of reaction of 8 and 9 are favored under some conditions
while 10 is favored under others. However, if 10 does occur then,
when the higher temperature zone reaches the product carbon,
reaction 7 will start the whole cycle over until the product gas is
H.sub.2 and CO. This can be combined at the surface to form methane
with the proper catalyst as in conventional practice. The secondary
reactions which occur between C, CH.sub.4, CO.sub.2, H.sub.2 and
H.sub.2 O shown in Table 2 are reproduced from a similar table in
Homer Lowery (Editor), The Chemistry of Coal Utilization,
Supplemental Vol. 1968, J. Wylie Press, Chapter 21.
Several other conclusions can be drawn from this table. No oxygen
can survive, even at modest temperatures, since reactions 4, 5 and
11 are all exothermic with strongly negative free energies.
Reactions 1, 2 and 7 consume energy at high temperature while 6 and
9 or 10 produce energy at lower temperatures. This combination
causes the heat to be "spread" through the reaction zone, and helps
or assures that the combustion zone will "skip" across barren shale
zones without external attempts at ignition as the reaction zone
proceeds downwardly.
All the information in Tables I and 2 can be combined to do an
overall energy balance if the initial reaction temperature is
selected. In the following illustrative example it is proposed that
water and oxygen are added just sufficient to maintain reaction 2
of Table 2 at 700.degree.K. The ambient temperature is assumed to
be 300.degree.K and the coal composition is as shown in Table 1.
Under these conditions, the heat required is that to increase the
coal, ash, and water from ambient temperature to the reaction
temperature, to vaporize the water and to sustain the reaction. The
heat supplied must come from combustion of coal. For this
calculation it is convenient to express the thermodynamic
quantities on a unit weight basis as shown in Table 3.
The calculation above, while approximate since several of the heat
capacities have been estimated, can be used in preliminary design
of the facility. Optimized conditions can be determined with more
precision using computer simulation and/or by varying operating
conditions. The calculation leaves the products at 700.degree.K but
a significant part of this heat will be recovered during the flow
of hot gases through the cooler unreacted coal beyond the reaction
zone and during the flow of input oxygen and water through the ash
and spent material leading up to the reaction zone permitting use
of lesser amounts of O.sub.2 once operation is established. The
water use has been calculated as if all of the water remains in the
coal. It is most likely some will vaporize in the hot downstream
gases and appear as liquid condensate at the base of the broken
zone. In this case it is pumped to the surface and re-injected as
needed.
TABLE 3
1. 1 g coal-in-place = 0.936 coal + 0.064 g ash
2. 1 g coal + 1.9 g O.sub.2 .fwdarw. 2.34 g CO.sub.2 + 0.56 g
H.sub.2 O (g)
.DELTA.H = -5291 cal/g coal
3. 1 g coal + 0.513 g H.sub.2 O (g) .fwdarw. 0.475 g CH.sub.4 +
1.038 g CO.sub.2
.DELTA.H = 529 cal/g coal
4. 1 g coal at 300.degree.K .fwdarw. 1 g coal at 700.degree.K
.DELTA.H = +255/cal/g
5 1 g H.sub.2 O (l) .fwdarw. 1 g H.sub.2 O (g) (T =
393.degree.K)
.DELTA.H = +575 cal/g
Let x equal the coal-in-place to be burned to provide heat and
assume 1 g of coal-in-place is converted to methane. The equation
for heat balance is as follows:
.936 .times. 5291 x -255x = 255 + 529 .times. .936 + .936 .times.
575 [.513 - .936 .times. .56x]
x = 0.206
Thus essentially 0.2 grams of coal-in-place must be burned for each
gram of coal-in-place converted with water. Table 4 summarizes the
products and reactants per ton of coal-in-place.
TABLE 4
Reactants Coal-in-place 1 metric ton Oxygen 0.304 tons Water 0.306
tons 306 liters Products Methane 0.370 ton 19.8 MCF Carbon dioxide
1.175 ton 22.9 MCF Ash 0.064 ton Nitrogen 0.0072 ton 0.22 MCF S*
0.0058 ton 0 *It is not predictable whether sulfur will appear as
SO.sub.2 or H.sub.2 S, but CS.sub.2 is not found at low
temperatures. Either SO.sub.2 or H.sub.2 S will likely react with
the shales and be absorbed before reaching the product line so that
a low pollutant content gas is produced.
The heating value of the coal used is 9000 BTU per lb or 19.8
million BTU per metric ton. The heating value of the methane
produced is 18.6 million BTU so the heating value of the coal has
been largely conserved by this process even though only 46.4
percent of the carbon is converted to methane.
The small loss is the heat left in hot ashes, shale and gas. The
shales between coal beds will use some heat, but under the
assumption that all product heat is supplied from the coal and the
products are left at the reaction temperature this loss does not
reduce the reaction efficiency. In a very real sense, the heat
balance assumed in arriving at Table 4 is belived to be overly
pessimistic from the standpoint of efficiency and that an even more
favorable result will be attained in practice.
Process
more particularly, starting with the broken coal system depicted in
FIG. 2 and assuming methane as a product, the thermodynamics
described in the previous section may be used to select best
operating conditions of the coal gasification process. The process
to be described is thus useful for comparison with other coal
gasification schemes and for approximate economic analyses.
The schematic plant arrangement as shown in FIG. 3 may be used. The
oxygen plant can be a standard cryogenic unit including a high
pressure injection pump. The water processing plant may simply
consist of a storage, CO.sub.2 stripping unit if recycle water is
to be used, and pumping system including a high pressure injection
pump. The gas purification plant may be of conventional design
adapted to remove SO.sub.2 if such appears in the product. However,
it seems most likely that SO.sub.2 will be formed in the ground,
however, if that is the case then it will be absorbed in the shale
by reaction with carbonates so that no sulfur oxide gases will be
present in the produced gas. This is a very important and
environmentally favorable consequence of the in situ processes as
contrasted with surface coal gasification methods. Removal of
CO.sub.2 can be accomplished by water scrubbing or by expansion
cooling. Also simple high pressure potassium carbonate scrubbing
may be an economic procedure for CO.sub.2 removal and would be
effective in removing sulfur compounds as well, should they be
present. The solution can be reconditioned and recycled.
The plant size depends on the quantity of gas to be produced,
which, in turn, depends on pipeline proximity. For example, with
100 BCF per year as the desired rate and assuming that each broken
coal unit as shown in FIG. 3 is processed in one year and contains
over 5 million metric tons of coal in place, the total requirements
are shown in Table 5.
TABLE 5
Annually Daily Gas Produced 100 BCF 274 MMCF Coal Consumed 5.05
million metric tons 13.8 thousand metric tons Oxygen Consumed 1.53
million metric tons 4.19 thousand metric tons Water Consumed 1.54
billion liters 4.23 million liters Drill Holes .about.240 0.6
(e.g., 24 inch with 60 foot spacing) Explosive approximately 9
kilotons (ANFO-Al)
This process requires the coal to be burned from the top downward
in the explosive fractured region alone. This is required to assure
maximum stability of the burning front and thus avoid one of the
major problems encountered in previous in situ gasification
attempts where coal was bypassed by the input gases. Subsequent
units to be processed should be separated far enough so that no gas
bypass can occur in a previously burned out region. However, once
ground subsidence has occurred, it may be possible to later process
the remnant coal. This makes it desirable to process large areas
simultaneously as indicated in FIG. 2. The region shown in the
lower portion of FIG. 2 is approximately to the scale of a 100 BCF
per year operation.
In addition, it appears that the in situ process is conducted under
very favorable kinetic conditions. FIG. 4 shows a conceptual
vertical section through the reacting coal region along with the
chemical reactions and approximate temperature distribution. In the
inlet region water is being vaporized and heated up. As soon as the
gases reach the coal, oxygen and the water react very quickly
producing the high temperature peak. In the downstream region
carbon monoxide and water react at lower temperature to produce
carbon dioxide, methane and heat. This heat causes the extended
intermediate temperature zone. Finally, at the lowest temperature
water vaporization and condensation occur. The thickness of the
very high temperature zone probably does not exceed 10 meters.
Assuming gas production rates from Table 5 and the area from FIG. 2
it is found that the superficial gas velocity in the broken coal is
0.1 ft/minute and with a reasonable average porosity in the broken
coal the actual gas velocity should be 15 to 20 cm min.sup.-.sup.1.
The reaction zone should be about 10 m thick so that the time
available for reaction in the high temperature zone is thus of the
order of one hour.
Data from experiments conducted in the 1100.degree.-1300.degree.K
range indicate the reaction kinetics are pseudo first order and
follow an Arrehenious temperature dependence. Based on the observed
rates at the higher temperatures, rates for complete reaction at
700.degree.K are estimated to be on the order of one hour
comparable to the residence time computed herein. Accordingly,
maximum operating temperatures in the present process may be
decreased as compared to conventional processes where high reaction
rates are required for economic operation.
An economic analysis indicates that the capital cost requirements
are between 15 and 30 percent of surface plants of similar
capacity. Operating costs are very comparable to surface plants so
that a profitable sales price for the product is considerably
smaller (from 27-92 percent less) than for gas from surface plants.
Since these costs are not as dependent on interest rates, there is
considerably less overall risk for the investor or investment cost
for exploitation of the process.
The drilling costs which are the major operating costs have been
estimated assuming purchased rigs (nine) operated by permanent
crews on a year-round basis. This results in considerably lower
"per foot" drilling costs. In this analysis the use of ammonium
nitrate explosives was assumed. The same amount of coal could be
broken by c.a. nine 100-kt nuclear explosions. In this case,
explosives would be more costly and drilling lest costly. On
balance and to the accuracy of these analyses, the resulting total
cost might be up to 6 cents per MCF less using nuclear explosives,
depending on the amount of seismic damage. Only about 9-kt of
chemical explosives are required because they are emplaced so as to
avoid "lifting" the ground. When underground methanation is not
complete, then construction and operation of a surface methanator
to complete or accomplish this function would increase the gas
price by about 18 cents per MCF.
Although the invention has been hereinbefore described and
illustrated in the accompanying drawing with respect to specific
steps of the method thereof, it will be appreciated that various
modifications and changes may be made therein without departing
from the true spirit and scope of the invention, and thus it is not
intended to limit the invention except by the terms of the
following claims.
* * * * *