Note: Descriptions are shown in the official language in which they were submitted.
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METHOD AND APPARATUS FOR SEQUESTERING CARBON DIOXIDE FROM A
SPENT GAS
Gary E. METIUS
James M. MCCLELLAND, JR.
CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present patent application/patent is a continuation-in-part of co-
pending U.S.
Patent Application No. 12/762,618, filed on April 19, 2010, and entitled
"Method and
Apparatus for Sequestering Carbon Dioxide From a Spent Gas," which claims the
benefit of
priority of U.S. Provisional Patent Application No. 61/170,999, filed on April
20, 2009, and
entitled "Method and Apparatus for Sequestering Carbon Dioxide From a Top Gas
Fuel," the
contents of both of which are incorporated in full by reference herein.
FIELD OF THE INVENTION
[0002] The present invention relates generally to a method and apparatus for
the direct
reduction of iron oxide to metallic iron, among other processes. More
specifically, the
present invention relates to a method and apparatus for sequestering carbon
dioxide from a
spent gas in association with such processes.
BACKGROUND OF THE INVENTION
[0003] A need exists in many industrial processes for an effective and
efficient method for
removing carbon dioxide from a secondary fuel source, such as a top gas fuel
source, in a
direct reduction process. In other words, a need exists in many industrial
processes for an
effective and efficient method for removing carbon dioxide from an otherwise
waste fuel
source, allowing it to be used as a primary fuel source without emissions
problems. In some
cases, government policy has required such carbon dioxide removal, and the
need for carbon
dioxide emissions control will only increase in the future. Direct reduction
involves the
reduction of iron oxide ores into metalized iron pellets, lumps, or compacts,
where the iron
oxide is reduced by a gas containing hydrogen and/or carbon monoxide,
resulting in a carbon
dioxide byproduct.
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BRIEF SUMMARY OF THE INVENTION
[0004] In one exemplary embodiment of the present invention, a method for
sequestering
carbon dioxide from a top gas fuel, includes: given a top gas divided into a
process gas and a
top gas fuel: mixing the process gas with a hydrocarbon and feeding a
resulting reformer
feed gas into a carbon dioxide and steam reformer for reforming the reformer
feed gas and
forming a reducing gas; and feeding the top gas fuel into a carbon dioxide
scrubber for
removing at least some carbon dioxide from the top gas fuel and forming a
reformer fuel gas
after the addition of a hydrocarbon that is fed into the carbon dioxide and
steam reformer.
The method also includes compressing the process gas and the top gas fuel. The
method
further includes generating steam from the top gas. The method still further
includes
scrubbing the top gas to remove dust. Optionally, the top gas is obtained from
a reduction
furnace. Optionally, the method still further includes mixing the reducing gas
with oxygen
and a hydrocarbon to form a bustle gas and feeding the bustle gas into the
reduction furnace.
The carbon dioxide scrubber also produces carbon dioxide lean gas. The method
still further
includes mixing the carbon dioxide lean gas with the reducing gas. Optionally,
the method
still further includes preheating the carbon dioxide lean gas before mixing it
with the
reducing gas or using it as fuel. The carbon dioxide and steam reformer also
produces flue
gas. The method still further includes generating steam from the flue gas.
Optionally, the
method still further includes using the flue gas to preheat another gas.
Optionally, the top gas
and the bustle gas are associated with a direct reduction process for
converting iron oxide to
metallic iron.
[0005] In another exemplary embodiment of the present invention, an apparatus
for
sequestering carbon dioxide from a top gas fuel, includes: one or more
conduits for dividing
a top gas into a process gas and a top gas fuel; one or more conduits for
mixing the process
gas with a hydrocarbon and feeding a resulting reformer feed gas into a carbon
dioxide and
steam reformer for reforming the reformer feed gas and forming a reducing gas;
and one or
more conduits for feeding the top gas fuel into a carbon dioxide scrubber for
removing at
least some carbon dioxide from the top gas fuel and forming a reformer fuel
gas after the
addition of a hydrocarbon that is fed into the carbon dioxide and steam
reformer. The
apparatus also includes one or more gas compressors for compressing the
process gas and the
top gas fuel. The apparatus further includes a low-pressure steam boiler for
generating steam
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from the top gas. The apparatus still further includes a wet scrubber for
scrubbing the top gas
to remove dust. Optionally, the top gas is obtained from a reduction furnace.
Optionally, the
apparatus still further includes one or more conduits for mixing the reducing
gas with oxygen
and a hydrocarbon to form a bustle gas and feeding the bustle gas into the
reduction furnace.
The carbon dioxide scrubber also produces carbon dioxide lean gas. The
apparatus still
further includes one or more conduits for mixing the carbon dioxide lean gas
with the
reducing gas. Optionally, the apparatus still further includes a preheater for
preheating the
carbon dioxide lean gas before mixing it with the reducing gas or using it as
fuel. The carbon
dioxide and steam reformer also produces flue gas. The apparatus still further
includes a low-
pressure steam boiler for generating steam from the flue gas. Optionally, the
apparatus still
further includes one or more conduits for using the flue gas to preheat
another gas.
Optionally, the top gas and the bustle gas are associated with a direct
reduction process for
converting iron oxide to metallic iron.
[0006] In a further exemplary embodiment of the present invention, a method
for
sequestering carbon dioxide from a waste gas and reusing it as a recycled gas
without
emissions concerns, includes: given a gas source divided into a process gas
and a waste gas:
mixing the process gas with a hydrocarbon and feeding a resulting feed gas
into a reformer
for refolining the feed gas and forming a reducing gas; and feeding at least a
portion of the
waste gas into a carbon dioxide scrubber for removing at least some carbon
dioxide from the
waste gas and forming a carbon dioxide lean gas that is mixed with the
reducing gas.
Optionally, the method also includes feeding at least a portion of the waste
gas into the
carbon dioxide scrubber for removing at least some carbon dioxide from the
waste gas and
forming a fuel gas after the addition of a hydrocarbon that is fed into the
reformer.
[0007] The carbon dioxide sequestration processes of the present invention
provide an
efficient loop by which carbon monoxide and hydrogen not used in a primary
process and
expelled as waste gas may be recaptured, while minimizing unwanted emissions.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] The present invention is illustrated and described herein with
reference to the various
drawings, in which like reference numbers are used to denote like method
steps/apparatus
components, as appropriate, and in which:
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[0009] FIG. 1 is a process/schematic diagram of the method/apparatus for
sequestering
carbon dioxide from a top gas fuel of the present invention; and
[0010] FIG. 2 is a process/schematic diagram of the direct reduction process
of the present
invention.
DETAILED DESCRIPTION OF THE INVENTION
[0011] Referring to FIG. 1, in one exemplary embodiment of the present
invention, the
apparatus for sequestering carbon dioxide from a top gas fuel 10 inherently
includes a vertical
shaft-type reduction furnace 12 or the like. In this example, the reduction
furnace 12 includes
a feed hopper (not illustrated) into which iron oxide pellets, lumps, or
compacts are fed at a
predetermined rate. The iron oxide pellets, lumps, or compacts descend by
gravity into the
reduction furnace 12 from the feed hopper through a feed pipe (not
illustrated), which also
serves as a gas seal pipe. At the bottom of the reduction furnace 12 is a
discharge pipe (not
illustrated), which further serves as a gas seal pipe. A discharge feeder (not
illustrated), such
as an electric vibrating feeder or the like, is disposed below the discharge
pipe and receives
the metallic iron pellets, lumps, or compacts, thereby establishing a system
for the
gravitational descent of the burden through the reduction furnace 12.
[0012] At approximately the midpoint of the reduction furnace 12 is a bustle
and tuyere
system (not illustrated), through which the hot reducing gas is introduced at
a temperature of
between about 700 degrees C and about 1050 degrees C. The hot reducing gas
flows
upwards through a reduction region of the reduction furnace 12, counter to the
flow of the
pellets, lumps, or compacts, and exits the reduction furnace 12 through a gas
off-take pipe
(not illustrated) located at the top of the reduction furnace 12. The feed
pipe extends below
the gas off-take pipe, this geometric arrangement creating a spent gas
disengaging plenum
that permits spent gas to disengage from the stock line and flow freely to the
gas off-take
pipe. The hot reducing gas, in flowing from the bustle and tuyere system to
the gas off-take
pipe, serves to heat the iron oxide pellets, lumps, or compacts and reduce
them to metallic
iron pellets, lumps, or compacts (i.e. via direct reduction). The hot reducing
gas contains
hydrogen, nitrogen, carbon monoxide, carbon dioxide, methane, and water vapor
that reduce
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the iron oxide pellets, lumps, or compacts and produce a spent gas, or top
gas, containing
carbon dioxide and water vapor.
[0013] Referring to FIG. 2, the direct reduction processes utilized herein
control the
reduction conditions, temperatures, and chemistries at the point where the
bustle gas enters
the reduction furnace 12 by adjusting the carbon dioxide lean gas, natural
gas, and oxygen
additions to the reducing gas just prior. These direct reduction processes are
described
generally in U.S. Patent No. 3,748,120, entitled "Method of Reducing Iron
Oxide to Metallic
Iron," U.S. Patent No. 3,749,386, entitled "Method for Reducing Iron Oxides in
a Gaseous
Reduction Process," U.S. Patent No. 3,764,123, entitled "Apparatus for
Reducing Iron Oxide
to Metallic Iron," U.S. Patent No. 3,816,101, entitled "Method for Reducing
Iron Oxides in a
Gaseous Reduction Process," U.S. Patent No. 4,046,557, entitled "Method for
Producing
Metallic Iron Particles," and U.S. Patent No. 5,437,708, entitled "Iron
Carbide Production in
Shaft Furnace," the contents of all of which are incorporated in full by
reference herein.
[0014] The reduction furnace burden acts as a large adiabatic reactor and
promotes
equilibrium reactions in the zone of the bustle gas injection. As the bustle
gas enters the
reduction furnace 12 and passes through the burden, the gas reacts to its
equilibrium
composition and temperature, which is observed on the burden thermocouples at
the upper
portion of the reduction furnace 12.
[0015] The carburizing reactions are affected by the following reducing gas
stream factors:
1. Initial reducing gas hydrogen:carbon monoxide ratio;
2. Initial reducing gas methane content;
3. Initial reducing gas temperature;
4. Natural gas addition to reducing gas;
5. Oxygen addition to reducing gas;
6. Carbon dioxide lean gas addition to reducing gas;
7. Final bustle gas reductant:oxidant ratio; and
8. Final bustle gas pressure
[0016] Under normal operating conditions, the initial reducing gas quality is
closely
controlled and becomes the primary stability factor for the direct reduction
process. As the
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reducing gas flows towards the reduction furnace 12, natural gas is added
based on the
methane content analysis of the final bustle gas. This provides a stabilizing
adjustment for
any variation in the methane content of the initial reducing gas, and affects
the carburizing
potential of the final bustle gas. Oxygen is added to the reducing gas to
increase the
temperature of the final bustle gas and improve the kinetics of the iron ore
reduction process.
[0017] Optionally, the operating conditions used include preheating the
natural gas addition,
reducing gas methane content equal to or less than about 12 percent, and
oxygen addition
flow/ton equal to or less than about 30 Nm3/t.
[0018] During use of the direct reduction apparatus, gas exits the reducing
gas source 40 and
a first sensor performs a gas analyses and measures the temperature of the
gas. Natural gas is
then mixed with the gas at the natural gas inlet. Oxygen is then mixed with
the gas and
natural gas mixture at the oxygen inlet, thereby forming the bustle gas. The
second sensor
performs a gas analysis and measures the temperature of the bustle gas, prior
to the bustle gas
entering the reduction furnace 12.
[0019] Referring again to FIG. 1, in accordance with the present invention,
the top gas from
the gas off-take pipe of the reduction furnace 12 flows through another pipe
(not illustrated)
to a low-pressure steam boiler 14. This allows for the efficient generation of
steam for use
elsewhere in the process, such as in the carbon dioxide removal step described
in greater
detail herein below. Boiler feed water is fed to the low-pressure steam boiler
14 and, as
alluded to herein above, the steam generated is recirculated through the
process or used
elsewhere.
[0020] The top gas is then directed to a wet scrubber 20 that is provided to
cool the top gas
and remove dust, with a water output. The wet scrubber 20 may be of any
conventional type
known to those of ordinary skill in the art, such as a venturi with a packed
tower (not
illustrated), with the top gas flowing downwards through the venturi and then
upwards
through the packing counterflow to cooling water.
[0021] The top gas exits the wet scrubber 20 in two streams by the influence
of a valve (not
illustrated). The first stream represents process gas and the second gas
represents top gas fuel
(i.e. waste). The ratio of these streams is defined by the available heat in a
carbon dioxide
and steam reformer 24 coupled to the first stream, which is typically
constant, resulting in an
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exemplary ratio of 1:1 (with the use of recycled carbon dioxide lean gas), 2:1
(without the use
of recycled carbon dioxide lean gas), etc.
[0022] The process gas from the wet scrubber 20 is fed to a compressor 22 and
compressed to
a desired pressure, and then fed to a mixer (not illustrated), where the
process gas is mixed
with natural gas. This reformer feed gas is then fed into the carbon dioxide
and steam
reformer 24. The carbon dioxide and steam reformer 24 includes fuel-fired
burners (not
illustrated), producing heated flue gas containing nitrogen, carbon dioxide,
and water via
combustion and a plurality of catalytic reformer tubes (not illustrated), the
later of which
utilize reformer feed gas and heat from the combustion to form reducing gas
which is fed
back into the reduction furnace 12 after the introduction of oxygen, natural
gas, and carbon
dioxide lean gas, resulting in bustle gas.
[0023] The top gas fuel from the wet scrubber 20 is also fed to a compressor
26 and
compressed to a desired pressure, prior to introduction into a carbon dioxide
scrubber 28.
The carbon dioxide scrubber 28 has an input of low-pressure steam, optionally
obtained from
any of the low-pressure steam boilers 14, 32 of the apparatus for sequestering
carbon dioxide
from a top gas fuel 10, and outputs of boiler feed water, sulfur, and carbon
dioxide. The
boiler feed water may be input into any of the low-pressure steam boilers 14,
32 of the
apparatus for sequestering carbon dioxide from a top gas fuel 10. Another
output of the
carbon dioxide scrubber 28 is carbon dioxide lean gas, which when mixed with
natural gas
becomes, in part, the reformer fuel gas that is fed into the carbon dioxide
and steam reformer
24.
[0024] The carbon dioxide scrubber 28 may include any type of alkanolamine,
such as MEA,
MDEA, or the like, or any type of hot potassium scrubbing system known to
those of
ordinary skill in the art. The low-pressure steam is used to regenerate the
solution used in the
carbon dioxide scrubber 28, and exits as the boiler feed water. During the
carbon dioxide
scrubbing process, the sulfur and carbon dioxide are sequestered from the top
gas fuel. The
top gas fuel minus the sulfur and carbon dioxide exits the carbon dioxide
scrubber 28 as the
carbon dioxide lean gas. Again, a portion of the carbon dioxide lean gas is
mixed with
natural gas to form the reformer fuel gas, and is introduced into the carbon
dioxide and steam
reformer 24 via the fuel-fired burners. The remainder of the carbon dioxide
lean gas is
recycled and mixed with the reducing gas, which is fed back into the reduction
furnace 12
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after the introduction of oxygen and natural gas, thereby forming the bustle
gas. Optionally,
later portion of the carbon dioxide lean gas, or the entire stream, is
introduced into a preheater
30 prior to mixing with the existing reducing gas or using it as fuel.
[0025] In one exemplary embodiment of the present invention, this carbon
dioxide lean
gas/reducing gas stream ultimately represents about 20 percent of the bustle
gas supply to the
reduction furnace 12, while the carbon dioxide and steam reformer reducing gas
stream
ultimately represents about 80 percent of the bustle gas supply to the
reduction furnace 12,
although other percentages are contemplated herein.
[0026] A flue gas off-take pipe (not illustrated) is provided on the carbon
dioxide and steam
reformer 24 for removing the flue gas containing nitrogen, carbon dioxide, and
water after
combustion. The flue gas flows through one or several heat exchangers,
including a low-
pressure steam boiler 32. Again, this allows for the efficient generation of
steam for use
elsewhere in the process, such as in the carbon dioxide removal step described
in greater
detail herein above. Boiler feed water is fed to the low-pressure steam boiler
32, optionally
from the carbon dioxide scrubber 28, and, as alluded to herein above, the
steam generated is
recirculated through the process or used elsewhere. The low-pressure steam
boiler 32 may
thus be coupled to the optional preheater 30.
[0027] Variations to the above-described processes and apparatuses may also
be
implemented, without departing from the fundamental concepts of the present
invention. For
example, the carbon dioxide scrubber 28 used may be a pressure swing
adsorption (PSA)
unit, a vacuum pressure swing adsorption (VPSA) unit, or a membrane separator,
as
circumstances dictate. The MDEA unit may be used without steam, and be direct
fired using
natural gas and/or an export fuel, providing direct heat exchange MDEA with
the top gas
and/or flue gas. The captured carbon dioxide may be used for enhanced oil
recovery,
enhanced biogrowth for biofuel production, the production of iron
carbonate/silicate
structural bricks (Fe fines + CO2 + ground steelmaking slag), etc. The
captured carbon
dioxide may also be refornied and the resulting reformed gas used in the
direct reduction
process. An Oxygen-fired reformer/heater may be used to concentrate the flue
gas carbon
dioxide. A shift reactor may be used to convert carbon monoxide and water to
carbon
dioxide and H2, then the reformer may be fired with the H2 to make water. Flue
gas carbon
dioxide may be captured from concentrated flue gas. Water may be captured from
the flue
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gas for use in arid locations. Finally, a direct-fired heater may be used for
reheating the lean
(stripped) top gas fuel and/or process gases.
[0028] Although the present invention has been illustrated and described
herein with
reference to preferred embodiments and specific examples thereof, it will be
readily apparent
to those of ordinary skill in the art that other embodiments and examples may
perform similar
functions and/or achieve like results. All such equivalent embodiments and
examples are
within the spirit and scope of the present invention, are contemplated
thereby, and are
intended to be covered by the following claims. In this respect, the above
detailed
description of the present invention is to be considered non-limiting and all-
encompassing to
the greatest extent possible.
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