Title of Invention	FUELL CELL SYSTEM WITH ELECTROCHEMICAL ANODE EXHAUST RECYCLING
Abstract	A method of operating a fuel cell system includes providing a fuel inlet stream into a fuel cell stack, operating the fuel cell stack to generate electricity and a hydrogen containing fuel exhaust stream, separating at least a portion of hydrogen contained in the fuel exhaust stream using a high temperature, low hydration ion exchange membrane cell stack, and providing the hydrogen separated from the fuel exhaust stream into the fuel inlet stream.

Title of Invention

FUELL CELL SYSTEM WITH ELECTROCHEMICAL ANODE EXHAUST RECYCLING

Abstract

A method of operating a fuel cell system includes providing a fuel inlet stream into a fuel cell stack, operating the fuel cell stack to generate electricity and a hydrogen containing fuel exhaust stream, separating at least a portion of hydrogen contained in the fuel exhaust stream using a high temperature, low hydration ion exchange membrane cell stack, and providing the hydrogen separated from the fuel exhaust stream into the fuel inlet stream.

Full Text	FUEL CELL SYSTEM WITH ELECTROCHEMICAL ANODE EXHAUST RECYCLING [0001] The present application claims benefit of United States provisional patent application serial number 60/701,977, filed July 25, 2005, which is incorporated herein by reference in entirety. BACKGROUND OF THE INVENTION [0002] The present invention relates generally to the field of gas separation and more particularly to fuel cell systems with electrochemical fuel exhaust fuel recovery, [0003] Fuel cells are electrochemical devices which can convert energy stored in fuels to electrical energy with high efficiencies. High temperature fuel cells include solid oxide and molten carbonate fuel cells. These fuel cells may operate using hydrogen and/or hydrocarbon fuels. There are classes of fuel cells, such as the solid oxide regenerative fuel cells, that also allow reversed operation, such that oxidized fuel can be reduced back to unoxidized fuel using electrical energy as an input. BRIEF DESCRIPTION OF THE DRAWINGS [0004] Figures 1 and 2 are schematic diagrams of fuel cell systems of the embodiments of the invention. SUMMARY [0005] The embodiments of the invention provide a fuel cell system with an electrochemical fuel cell stack fuel (i.e., anode) exhaust recycling. The fuel exhaust stream is sent to a hydrogen separation device which separates hydrogen from the fuel exhaust stream. The hydrogen separation device is an electrochemical pump separation unit, such as a proton exchange membrane type separation unit. The separated hydrogen is recycled into the fuel inlet stream. -1- DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0006] The first and second embodiments of the invention illustrate how the electrochemical pump separation unit is used together with a fuel cell system, such as a solid oxide fuel cell system. It should be noted that other fuel cell systems may also be used. [0007] In the system of the first embodiment, a fuel humidifier is used to humidify the fuel inlet stream provided into the fuel cell stack. In the system of the second embodiment, the fiiel humidifier may be omitted. A portion of the fuel cell stack fuel exhaust stream is directly recycled into the fuel inlet stream to humidify the fuel inlet steam. Another portion of the fuel cell stack fuel exhaust stream is provided into the separation unit, and the separated hydrogen is then provided into the fuel inlet stream. [0008] Figure 1 illustrates a fuel cell system 100 of the first embodiment. The system 100 contains a fuel cell stack 101, such as a solid oxide fuel cell stack (illustrated schematically to show one solid oxide fuel cell of the stack containing a ceramic electrolyte, such as yttria stabilized zirconia (YSZ), an anode electrode, such as a nickel-YSZ cermet, and a cathode electrode, such as lanthanum strontium manganite). [0009] The system also contains an electrochemical pump separation unit 1 which electrochemically separates hydrogen from the fuel exhaust stream. The electrochemical pump unit 1 may comprise any suitable proton exchange membrane device comprising a polymer electrolyte. The hydrogen diffuses through the polymer electrolyte under an application of a potential difference between anode and cathode electrodes located on either side of the electrolyte. Preferably, the electrochemical pump comprises a stack of carbon monoxide tolerant electrochemical cells, such as a stack of high-temperature, low-hydration ion exchange membrane cells. This type of cell includes a non-fluorinated ion exchange ionomer membrane, such as, for example, a polyben/imidazole (PBI) membrane, located between anode and cathode electrodes. The membrane is doped with an acid, such as sulfuric or phosphoric acid. -2- An example of such cell is disclosed in US published application US 2003/0196893 Al, incorporated herein by reference in its entirety. These cells generally operate in a temperature range of above 100 to about 200 degrees Celsius. Thus, the heat exchangers in the system 100 preferably keep the fuel exhaust stream at a temperature of about 120 to about 200 degrees Celsius, such as about 160 to about 190 degrees Celsius. [0010] The system 100 also contains the first conduit 3 which operatively connects a fuel exhaust outlet 103 of the fuel cell stack 101 to a first inlet 2 of the electrochemical pump separation unit 1. The system also contains a second conduit 7 which operatively connects an outlet 8 of the electrochemical pump separation unit 1 to a fuel inlet 105 of the fuel cell stack 101. Preferably, the system 100 lacks a compressor which in operation compresses the fuel cell stack fuel exhaust stream to be provided into the electrochemical pump separation unit 1. The system 100 also contains a third conduit 9 which removes the exhaust from the unit 1. The conduit 9 may be connected to a catalytic burner 107 or to an atmospheric vent. [0011] The system 100 further contains a fuel humidifier 119 having a first inlet operatively connected to a hydrocarbon fuel source, such as the hydrocarbon fuel inlet conduit 111, a second inlet operatively connected to the fuel cell stack fuel exhaust 103, a first outlet operatively connected to the fuel cell stack fuel inlet 105, and a second outlet operatively connected to a burner 107. In operation, the fuel humidifier 119 humidifies a hydrocarbon fuel inlet stream from conduit 111 containing the recycled hydrogen using water vapor contained in a fuel cell stack fuel exhaust stream. The fuel humidifier may comprise a polymeric membrane humidifier, such as a Nafion© membrane humidifier, an enthalpy wheel or a plurality of water adsorbent beds, as described for example in U.S. Patent Number 6,106,964 and in U.S. Application Serial Number 10/368,425, both incorporated herein by reference in their entirety. For example, one suitable type of humidifier comprises a water vapor and enthalpy transfer Nafion® based, water permeable membrane available from Perma Pure LLC. The humidifier passively transfers water vapor and enthalpy from the fuel exhaust stream into the fuel inlet stream to provide a 2 to 2.5 -3- steam to carbon ratio in the fuel inlet stream. The fuel inlet stream temperature may be raised to about 80 to about 90 degrees Celsius in the humidifier. [0012] The system 100 also contains a recuperative heat exchanger 121 which exchanges heat between the stack fuel exhaust stream and the hydrocarbon fuel inlet stream being provided from the humidifier 119. The heat exchanger helps to raise the temperature of the fuel inlet stream and reduces the temperature of the fuel exhaust stream so that it may be further cooled in the condenser and such that it does not damage the humidifier. [0013] If the fuel cells are external fuel reformation type cells, then the system 100 contains a fuel reformer 123. The reformer 123 reforms a hydrocarbon fuel inlet stream into hydrogen and carbon monoxide containing fuel stream which is then provided into the stack 101. The reformer 123 may be heated radiatively, convectively and/or conductively by the heat generated in the iiiel cell stack 101 and/or by the heat generated in an optional burner/combustor, as described in U.S. Patent Application Serial Number 11/002,681, filed December 2, 2004, incoiporated herein by reference in its entirety. Alternatively, the external reformer 123 may be omitted if the stack 101 contains cells of the internal reforming type where reformation occurs primarily within the fuel cells of the stack. [0014] Optionally, the system 100 also contains an air preheater heat exchanger 125. This heat exchanger 125 heats the air inlet stream being provided to the fuel cell stack 101 using the heat of the fuel cell stack fuel exhaust. If desired, this heat exchanger 125 maybe omitted. [0015] The system 100 also preferably contains an air heat exchanger 127. This heat exchanger 127 further heats the air inlet stream being provided to the fuel cell stack 101 using the heat of the fuel cell stack air (i.e., oxidizer or cathode) exhaust. If the preheater heat exchanger 125 is omitted, then the air inlet stream is provided directly into the heat exchanger 127 by a blower or other air intake device. The system also optionally contains a hydrogen cooler heat exchanger 129 which -4- cools the separated hydrogen stream provided from unit 1, using an air stream, such as an air inlet stream. [0016] The system may also contain an optional water-gas si lift reactor 128. The water-gas shift reactor 128 may be any suitable device which converts at least a portion of the water in the fuel exhaust stream into free hydrogen. For example, the reactor 128 may comprise a tube or conduit containing a catalyst which converts some or all of the carbon monoxide and water vapor in tine fuel exhaust stream into carbon dioxide and hydrogen. Thus, the reactor 128 increases the amount of hydrogen in the fuel exhaust stream. The catalyst may be any suitable catalyst, such as a iron oxide or a chromium promoted iron oxide catalyst. The reactor 128 may be located between the fuel heat exchanger 121 and the air preheater heat exchanger 125. [0017] The system 100 of the first embodiment operates as follows. A fuel inlet stream is provided into the fuel cell stack 101 through fuel inlet conduit 111. The fuel may comprise any suitable fuel, such as a hydrocarbon fuel, including but not limited to methane, natural gas which contains methane with hydrogen and other gases, propane or other biogas, or a mixture of a carbon fuel, such as carbon monoxide, oxygenated carbon containing gas, such as rnethanol, or other carbon containing gas with a hydrogen containing gas, such as water vapor, I-I2 gas or their mixtures. For example, the mixture may comprise syngas derived from coal or natural gas reformation. [0018] The fuel inlet stream passes through the humidifier 119 where humidity is added to the fuel inlet stream. The humidified fuel inlet stream then passes through the fuel heat exchanger 121 where the humidified fuel inlet stream is heated by the fuel cell stack fuel exhaust stream. The heated and humidified fuel inlet stream is then provided into a reformer 123, which is preferably an external reformer. For example,. reformer 123 may comprise a reformer described in U.S. Patent Application Serial Number 11/002,681, filed on December 2, 2004, incorporated herein by reference in its entirety. The fuel reformer 123 may be any suitable device which is capable of partially or wholly reforming a hydrocarbon fuel 10 form a carbon containing and free hydrogen containing fuel. For example, the fuel reformer 123 -5- may be any suitable device which can reform a hydrocarbon gas into a gas mixture of free hydrogen and a carbon containing gas. For example, the fuel reformer 123 may comprise a catalyst coated passage where a humidified biogas, such as natural gas, is reformed via a steam-methane reformation reaction to form free hydrogen, carbon monoxide, carbon dioxide, water vapor and optionally a residual amount of unreformed biogas. The free hydrogen and carbon monoxide are then provided into the fuel (i.e., anode) inlet 105 of the fuel cell stack 101. Thus, with respect to the fuel inlet stream, the humidifier 119 is located upstream of the heat exchanger 121 which is located upstream of the reformer 123 which is located upstream of the stack 101. [0019J The air or other oxygen containing gas (i.e., oxidizer) inlet stream is preferably provided into the stack 101 through a heat exchanger 127, where it is heated by the air (i.e., cathode) exhaust stream from the fuel cell stack, If desired, the air inlet stream may also pass through the hydrogen cooler heat exchanger 129" and/or through the air preheat heat exchanger 125 to further increase the temperature of the air before providing the air into the stack 101. [0020] Once the fuel and air are provided into the fuel cell stack 101, the stack 101 is operated to generate electricity and a hydrogen containing fuel exhaust stream. About 25% of the input fuel exits the fud exhau..;t outlet 103 of the stack. The fuel exhaust stream (i.e., the stack anode exhan;;l stream) is provided from the stack fuel exhaust outlet 103 into the electrochemical pump separation unit 1. At least a portion of hydrogen contained in the fuel exhaust stream is separated in the unit 1. The hydrogen separated from the fuel exhaust stream in the unit 1 is then provided back into the fuel inlet stream. Preferably, the hydrogen is provided back into the fuel inlet conduit 111 upstream of the humidifier 119. [0021] The fuel exhaust stream is provided into the unit 1 as follows. The fuel exhaust stream may contain hydrogen, water vapor, carbon monoxide, carbon dioxide, some unreacted hydrocarbon gas, such as methane and other reaction by-products and impurities. This exhaust stream is first provided into the heat exchanger 121, where its temperature is lowered, preferably to less than 200 degrees Celsius, while the temperature of the fuel inlet stream is raised. If the water-gas shift reactor 128 and -6- the air preheater heat exchanger 125 are present. Lhen the fuel exhaust stream is provided through the reactor 128 to convert al least a portion of the water vapor and a majority of the residual carbon monoxide into carbon dioxide and hydrogen. The fuel exhaust stream is then passed through the heat exchanger 125 to further lower its temperature while raising the temperature of the air inlet stream. The temperature may be lowered to 90 to 110 degrees Celsius for example. [0022] The fuel exhaust stream is then provided into inlet 2 of the electrochemical pump separation unit 1 via conduit 3. During the separation step in unit 1, at least a majority of the hydrogen, such as about 85% of the hydrogen in the fuel exhaust stream, diffuses through the electrolyte of the cells in the unit 1, while allowing the water vapor, carbon dioxide, carbon monoxide and remaining hydrocarbon gas in the fuel exhaust stream to be passed through conduit 9 to the humidifier 119. [0023J In the fuel humidifier 119, a portion of the water vapor in the fuel exhaust stream is transferred to the fuel inlet stream to humidify the fuel inlet stream. The fuel/hydrogen fuel inlet stream mixture is humidified to 80C to 90C dew point. The remainder of the fuel exhaust stream is then provided into the burner 107 along with the air (i.e., cathode) exhaust stream from the stack 101 to be burned and to provide low quality heat. The heat from the burner 107 may be used to heat the reformer 123 or it may be provided to other parts of the system 100 or to a heat consuming devices outside the system 100, such as a building heating system. [0024] The hydrogen separated from the fuel exhaust stream is then removed from unit 1 through outlet 8 and conduit 7 and provided into the hydrocarbon fuel inlet stream in the fuel inlet conduit 111. If desired, prior to being provided to the fuel inlet conduit, the hydrogen stream may be passed through a hydrogen cooler heat exchanger 129, where the hydrogen stream exchanges heat with an air stream, such as the air inlet .stream provided into the fuel cell stack 101. The temperature of the hydrogen stream is lowered in the heat exchanger 129 before being provided into the fuel inlet conduit, while the temperature of the air inlet stream is raised. Thus, the hydrocarbon fuel inlet stream is mixed with a low dew point, near ambient -7- temperature recycled hydrogen recovered from the anode tail gas with an electrochemical hydrogen pump 1. [0025] Thus, with respect 10 the fuel exhaust stream, the heat exchanger 121 is located upstream of the reactor 128, which is located upstream of the heat exchanger 125, which is located upstream of the pump unit 1, which is located upstream of the humidifier 119 and the fuel inlet conduit 111. [0026] Figure 2 illustrates a system 200 according to the second embodiment of the invention. The system 200 is similar to system 100 and contains a number of components in common. Those components which are common to both systems 100 and 200 arc numbered with the same numbers in Figures 1 and 2 and will not be described further. [0027] One difference between systems 100 and 200 is that system 200 preferably, but not necessarily lacks, the humidifier 119. Instead, a portion of the water vapor containing stack fuel exhaust stream is directly recycled into the stack fuel inlet stream. The water vapor in the fuel exhaust stream is sufficient to humidify the fuel inlci stream. [0028] The system 200 contains a fuel splitter device 201, such as a computer or operator controlled multi-way valve, for example a three-way valve, or another fluid splitting device. The device 201 contains an inlet 203 opcratively connected to the fuel cell stack fuel exhaust outlet 103, a first outlet 205 operatively connected to the unit 1 and a second outlet 207 operatively connected to the fuel cell stack fuel inlet 105. For example, the second outlet 207 may be operatively connected to the fuel inlet conduit 111, which is operatively connected to inlet 105. However, the second outlet 207 may provide a portion of the fuel exhaust stream into the fuel inlet stream further downstream. [0029] Preferably, the system 200 contains a blower or compressor 209 which provides the fuel exhaust stream into the fuel inlet stream. Specifically, the outlet 207 of the valve 201 is operatively connected to an inlet of a blower or compressor 209, while an-outlet of the blower or compressor 209 is connected to the hydrocarbon -8- fuel inlet conduit 111. In operation, the blower or compressor 209 controllably provides a desired amount of the fuel cell stack fuel exhaust stream into the fuel cell stack fuel inlet stream. [0030] The method of operating the system 200 is similar to the method of operating the system 100. One difference is that the fuel exhaust stream is separated into at least two streams by the device 201. The first fuel exhaust stream is recycled into the fuel inlet stream, while the second stream is directed into the separation unit 1 where at least a portion of hydrogen contained in the second fuel exhaust stream is electrochemically separated from the second fuel exhaust stream. The hydrogen separated from the second fuel exhaust stream is then provided into the fuel inlet stream. For example, between 50 and 70%, such as about 60% of the fuel exhaust stream may be provided 1o the blower or compressor 209, while the remainder may be provided toward the unit 1. [0031] Preferably, the fuel exhaust stream is first provided through the heat exchangers 121 and 125 and reactor 128 before being provided into the valve 201. The fuel exhaust stream is cooled to 200 degrees Celsius or less, such as to 120 to 180 degrees, in the heat exchanger 125 prior to being provided into the valve 201 where it is separated into two streams. This allows the use of a low temperature blower 209 to controllably recycle a desired amount of the first fuel exhaust stream into the fuel inlet stream, since such blower may be adapted to move a gas utreani which has a temperature of 200 degrees Celsius or less. [0032] The blower or compressor 209 may be computer or operator controlled and may vary the amount of the fuel exhaust stream being provided into the fuel inlet stream depending on the conditions described below. If desired, all or a portion of the hydrogen separated from unit 1 may be provided to a hydrogen using device, such as a PEM fuel cell in a vehicle or another hydrogen using device or to a hydrogen storage vessel. In this case, a selector valve may be placed in conduit 7 to either split the hydrogen stream between the fuel inlet conduit 111 and the hydrogen storage vessel or hydrogen using device, or to alternate the hydrogen flow between the fuel inlet conduit ll and the hydrogen storage vessel or hydrogen using device. The -9- blower or compressor and the optional selector valve may be operated by a computer or an operator to controllably vary the gas .flow based on one or more of the following conditions: i) detected or observed conditions of the system 100 (i.e., changes in the sys'.em operating conditions requiring a change in the amount of hydrogen in the fuel inlet stream); ii) previous calculations provided into the computer or conditions known to the operator which require a temporal adjustment of the hydrogen in the fuel inlet stream; iii) desired future changes, presently occurring changes or recent past changes in the operating parameters of the stack 101, such as changes in the electricity demrmd by the users of electricity generated by the slack, changes in price for electricity or hydrocarbon fuel compared to the price of hydrogen, etc, and/or iv) changes in the demand for hydrogen by the hydrogen user, such as the hydrogen using device, changes in price of hydrogen or hydrocarbon fuel compared to the price of electricity, etc. [0033] It is believed that by recycling at least a portion of the hydrogen from the fuel exhaust (i.e., tail) gas stream into the fuel inlet stream, a high efficiency operation of the fuel cell system is obtained. Furthermore, the overall fuel utilization is increased. The electrical efficiency (i.e., AC electrical efficiency) can range between about 50% and about 60%, such as between about 54% and about 60% for the methods of the firs I and second embodiments when the per pass fuel utilization rate is about 75% (i.e., about 75% of the fuel is utilized during each pass through the stack). An effective fuel utilization of about 94% to about 95% is obtained when the per pass utilization is about 75%, and about 85% of the fuel exhaust gas hydrogen is recycled back to the fuel cell stack by the separation unit 1. Even higher efficiency may be obtained by increasing the per pass fuel utilization rate above 75%, such as about 76-80%. At steady-state, the methods of the first and second embodiments eliminate the need for generating steam when steam methane reformation is used to create the feed gas to the fuel cell. The fuel exhaust stream contains enough water vapor to humidify the fuel inlet stream to the stack at steam to carbon ratios of 2 to 2.5. The increase in net fuel utilization and the removal of heat requirement to generate steam increases the overall electrical efficiency. In contrast, without -10- recycling hydrogen, the AC electrical efficiency is about 45% for a fuel utilization rate within the stack of about 75% to 80%. [0034] The fuel cell systems described herein may have other embodiments and configurations, as desired. Other components may be added if desired, as described, for example, in U.S. Application Serial Number 10/300,021, filed on November 20. 2002, in U.S. Provisional Application Serial Number 60/461,190, filed on April 9, 2003, and in U.S. Application Serial Number 10/446,704, filed on May 29, 2003 all incorporated herein by reference in their entirety. Furthermore, it should be understood that any system element or method step described in any embodiment and/or illustrated in any figure herein may also be used in systems and/or methods of other suitable embodiments described above, even if such use is not expressly described. [0035] The foregoing description of the invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed, and modifications and variations are possible in light of the above teaching; or may be acquired from practice of the invention. The description was chosen in order to explain the principles of the invention audits practical application. It is intended that the scope of the invention be defined by the claims appended hereto, and their equivalents. -11- WHAT IS CLAIMED IS: 1. A method of operating a fuel cell system, comprising: providing a fuel inlet stream into a fuel cell stack; operating the fuel cell stack to generate electricity and a hydrogen containing fuel exhaust stream; separating at least a portion of hydrogen contained in the fuel exhaust stream using a high temperature, low hydration ion exchange membrane cell stack; and providing the hydrogen separated from the fuel exhaust stream into the fuel inlet stream. 2. The method of claim 1, wherein the high temperature, low hydration ion exchange membrane cell stack comprises a stack of acid doped non-fluorinated ion exchange ionomer membrane cells. 3. The method of claim 2, wherein each membrane of the membrane cells comprises a polybenzimidaole (PB1) membrane, doped with sulfuric or phosphoric acid. 4. The method of claim 1, further comprising lowering a temperature of the fuel exhaust stream to between 120 C and 200 C prior to the step of separating at least a portion of hydrogen. 5. A fuel cell system, comprising: a fuel coll stack; a high temperature, low hydration ion exchange membrane cell stack; a first conduit which operatively connects a fuel exhaust outlet of the fuel cell stack to a first inlet of the high temperature, low hydration ion exchange membrane cell stack; and a second conduit which operatively connects an outlet of the a high temperature, low hydration ion exchange membrane cell stack to the fuel cell stack fuel inlet. -12- 6. The system of claim 5, wherein the high temperature, low hydration ion exchange membrane cell stack comprises a slack of acid doped non-fiuorinated ion exchange ionomer membrane cells. 7. The system of claim 6, wherein each membrane of the membrane cells comprises a polybenzimidazole (PBI) membrane doped with sulfuric or phosphoric acid. -13- A method of operating a fuel cell system includes providing a fuel inlet stream into a fuel cell stack, operating the fuel cell stack to generate electricity and a hydrogen containing fuel exhaust stream, separating at least a portion of hydrogen contained in the fuel exhaust stream using a high temperature, low hydration ion exchange membrane cell stack, and providing the hydrogen separated from the fuel exhaust stream into the fuel inlet stream.

Full Text

FUEL CELL SYSTEM WITH ELECTROCHEMICAL ANODE EXHAUST
RECYCLING
[0001] The present application claims benefit of United States provisional
patent application serial number 60/701,977, filed July 25, 2005, which is
incorporated herein by reference in entirety.
BACKGROUND OF THE INVENTION
[0002] The present invention relates generally to the field of gas separation
and more particularly to fuel cell systems with electrochemical fuel exhaust fuel
recovery,
[0003] Fuel cells are electrochemical devices which can convert energy stored
in fuels to electrical energy with high efficiencies. High temperature fuel cells
include solid oxide and molten carbonate fuel cells. These fuel cells may operate
using hydrogen and/or hydrocarbon fuels. There are classes of fuel cells, such as the
solid oxide regenerative fuel cells, that also allow reversed operation, such that
oxidized fuel can be reduced back to unoxidized fuel using electrical energy as an
input.
BRIEF DESCRIPTION OF THE DRAWINGS
[0004] Figures 1 and 2 are schematic diagrams of fuel cell systems of the
embodiments of the invention.
SUMMARY
[0005] The embodiments of the invention provide a fuel cell system with an
electrochemical fuel cell stack fuel (i.e., anode) exhaust recycling. The fuel exhaust
stream is sent to a hydrogen separation device which separates hydrogen from the fuel
exhaust stream. The hydrogen separation device is an electrochemical pump
separation unit, such as a proton exchange membrane type separation unit. The
separated hydrogen is recycled into the fuel inlet stream.
-1-

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0006] The first and second embodiments of the invention illustrate how the
electrochemical pump separation unit is used together with a fuel cell system, such as
a solid oxide fuel cell system. It should be noted that other fuel cell systems may also
be used.
[0007] In the system of the first embodiment, a fuel humidifier is used to
humidify the fuel inlet stream provided into the fuel cell stack. In the system of the
second embodiment, the fiiel humidifier may be omitted. A portion of the fuel cell
stack fuel exhaust stream is directly recycled into the fuel inlet stream to humidify the
fuel inlet steam. Another portion of the fuel cell stack fuel exhaust stream is provided
into the separation unit, and the separated hydrogen is then provided into the fuel inlet
stream.
[0008] Figure 1 illustrates a fuel cell system 100 of the first embodiment.
The system 100 contains a fuel cell stack 101, such as a solid oxide fuel cell stack
(illustrated schematically to show one solid oxide fuel cell of the stack containing a
ceramic electrolyte, such as yttria stabilized zirconia (YSZ), an anode electrode, such
as a nickel-YSZ cermet, and a cathode electrode, such as lanthanum strontium
manganite).
[0009] The system also contains an electrochemical pump separation unit 1
which electrochemically separates hydrogen from the fuel exhaust stream. The
electrochemical pump unit 1 may comprise any suitable proton exchange membrane
device comprising a polymer electrolyte. The hydrogen diffuses through the polymer
electrolyte under an application of a potential difference between anode and cathode
electrodes located on either side of the electrolyte. Preferably, the electrochemical
pump comprises a stack of carbon monoxide tolerant electrochemical cells, such as a
stack of high-temperature, low-hydration ion exchange membrane cells. This type of
cell includes a non-fluorinated ion exchange ionomer membrane, such as, for
example, a polyben/imidazole (PBI) membrane, located between anode and cathode
electrodes. The membrane is doped with an acid, such as sulfuric or phosphoric acid.
-2-

An example of such cell is disclosed in US published application US 2003/0196893
Al, incorporated herein by reference in its entirety. These cells generally operate in a
temperature range of above 100 to about 200 degrees Celsius. Thus, the heat
exchangers in the system 100 preferably keep the fuel exhaust stream at a temperature
of about 120 to about 200 degrees Celsius, such as about 160 to about 190 degrees
Celsius.
[0010] The system 100 also contains the first conduit 3 which operatively
connects a fuel exhaust outlet 103 of the fuel cell stack 101 to a first inlet 2 of the
electrochemical pump separation unit 1. The system also contains a second conduit 7
which operatively connects an outlet 8 of the electrochemical pump separation unit 1
to a fuel inlet 105 of the fuel cell stack 101. Preferably, the system 100 lacks a
compressor which in operation compresses the fuel cell stack fuel exhaust stream to
be provided into the electrochemical pump separation unit 1. The system 100 also
contains a third conduit 9 which removes the exhaust from the unit 1. The conduit 9
may be connected to a catalytic burner 107 or to an atmospheric vent.
[0011] The system 100 further contains a fuel humidifier 119 having a first
inlet operatively connected to a hydrocarbon fuel source, such as the hydrocarbon fuel
inlet conduit 111, a second inlet operatively connected to the fuel cell stack fuel
exhaust 103, a first outlet operatively connected to the fuel cell stack fuel inlet 105,
and a second outlet operatively connected to a burner 107. In operation, the fuel
humidifier 119 humidifies a hydrocarbon fuel inlet stream from conduit 111
containing the recycled hydrogen using water vapor contained in a fuel cell stack fuel
exhaust stream. The fuel humidifier may comprise a polymeric membrane
humidifier, such as a Nafion© membrane humidifier, an enthalpy wheel or a plurality
of water adsorbent beds, as described for example in U.S. Patent Number 6,106,964
and in U.S. Application Serial Number 10/368,425, both incorporated herein by
reference in their entirety. For example, one suitable type of humidifier comprises a
water vapor and enthalpy transfer Nafion® based, water permeable membrane
available from Perma Pure LLC. The humidifier passively transfers water vapor and
enthalpy from the fuel exhaust stream into the fuel inlet stream to provide a 2 to 2.5
-3-

steam to carbon ratio in the fuel inlet stream. The fuel inlet stream temperature may
be raised to about 80 to about 90 degrees Celsius in the humidifier.
[0012] The system 100 also contains a recuperative heat exchanger 121 which
exchanges heat between the stack fuel exhaust stream and the hydrocarbon fuel inlet
stream being provided from the humidifier 119. The heat exchanger helps to raise the
temperature of the fuel inlet stream and reduces the temperature of the fuel exhaust
stream so that it may be further cooled in the condenser and such that it does not
damage the humidifier.
[0013] If the fuel cells are external fuel reformation type cells, then the system
100 contains a fuel reformer 123. The reformer 123 reforms a hydrocarbon fuel inlet
stream into hydrogen and carbon monoxide containing fuel stream which is then
provided into the stack 101. The reformer 123 may be heated radiatively,
convectively and/or conductively by the heat generated in the iiiel cell stack 101
and/or by the heat generated in an optional burner/combustor, as described in U.S.
Patent Application Serial Number 11/002,681, filed December 2, 2004, incoiporated
herein by reference in its entirety. Alternatively, the external reformer 123 may be
omitted if the stack 101 contains cells of the internal reforming type where
reformation occurs primarily within the fuel cells of the stack.
[0014] Optionally, the system 100 also contains an air preheater heat
exchanger 125. This heat exchanger 125 heats the air inlet stream being provided to
the fuel cell stack 101 using the heat of the fuel cell stack fuel exhaust. If desired, this
heat exchanger 125 maybe omitted.
[0015] The system 100 also preferably contains an air heat exchanger 127.
This heat exchanger 127 further heats the air inlet stream being provided to the fuel
cell stack 101 using the heat of the fuel cell stack air (i.e., oxidizer or cathode)
exhaust. If the preheater heat exchanger 125 is omitted, then the air inlet stream is
provided directly into the heat exchanger 127 by a blower or other air intake device.
The system also optionally contains a hydrogen cooler heat exchanger 129 which
-4-

cools the separated hydrogen stream provided from unit 1, using an air stream, such as
an air inlet stream.
[0016] The system may also contain an optional water-gas si lift reactor 128.
The water-gas shift reactor 128 may be any suitable device which converts at least a
portion of the water in the fuel exhaust stream into free hydrogen. For example, the
reactor 128 may comprise a tube or conduit containing a catalyst which converts some
or all of the carbon monoxide and water vapor in tine fuel exhaust stream into carbon
dioxide and hydrogen. Thus, the reactor 128 increases the amount of hydrogen in the
fuel exhaust stream. The catalyst may be any suitable catalyst, such as a iron oxide or
a chromium promoted iron oxide catalyst. The reactor 128 may be located between
the fuel heat exchanger 121 and the air preheater heat exchanger 125.
[0017] The system 100 of the first embodiment operates as follows. A fuel
inlet stream is provided into the fuel cell stack 101 through fuel inlet conduit 111.
The fuel may comprise any suitable fuel, such as a hydrocarbon fuel, including but
not limited to methane, natural gas which contains methane with hydrogen and other
gases, propane or other biogas, or a mixture of a carbon fuel, such as carbon
monoxide, oxygenated carbon containing gas, such as rnethanol, or other carbon
containing gas with a hydrogen containing gas, such as water vapor, I-I2 gas or their
mixtures. For example, the mixture may comprise syngas derived from coal or
natural gas reformation.
[0018] The fuel inlet stream passes through the humidifier 119 where
humidity is added to the fuel inlet stream. The humidified fuel inlet stream then
passes through the fuel heat exchanger 121 where the humidified fuel inlet stream is
heated by the fuel cell stack fuel exhaust stream. The heated and humidified fuel inlet
stream is then provided into a reformer 123, which is preferably an external reformer.
For example,. reformer 123 may comprise a reformer described in U.S. Patent
Application Serial Number 11/002,681, filed on December 2, 2004, incorporated
herein by reference in its entirety. The fuel reformer 123 may be any suitable device
which is capable of partially or wholly reforming a hydrocarbon fuel 10 form a carbon
containing and free hydrogen containing fuel. For example, the fuel reformer 123
-5-

may be any suitable device which can reform a hydrocarbon gas into a gas mixture of
free hydrogen and a carbon containing gas. For example, the fuel reformer 123 may
comprise a catalyst coated passage where a humidified biogas, such as natural gas, is
reformed via a steam-methane reformation reaction to form free hydrogen, carbon
monoxide, carbon dioxide, water vapor and optionally a residual amount of
unreformed biogas. The free hydrogen and carbon monoxide are then provided into
the fuel (i.e., anode) inlet 105 of the fuel cell stack 101. Thus, with respect to the fuel
inlet stream, the humidifier 119 is located upstream of the heat exchanger 121 which
is located upstream of the reformer 123 which is located upstream of the stack 101.
[0019J The air or other oxygen containing gas (i.e., oxidizer) inlet stream is
preferably provided into the stack 101 through a heat exchanger 127, where it is
heated by the air (i.e., cathode) exhaust stream from the fuel cell stack, If desired, the
air inlet stream may also pass through the hydrogen cooler heat exchanger 129" and/or
through the air preheat heat exchanger 125 to further increase the temperature of the
air before providing the air into the stack 101.
[0020] Once the fuel and air are provided into the fuel cell stack 101, the stack
101 is operated to generate electricity and a hydrogen containing fuel exhaust stream.
About 25% of the input fuel exits the fud exhau..;t outlet 103 of the stack. The fuel
exhaust stream (i.e., the stack anode exhan;;l stream) is provided from the stack fuel
exhaust outlet 103 into the electrochemical pump separation unit 1. At least a portion
of hydrogen contained in the fuel exhaust stream is separated in the unit 1. The
hydrogen separated from the fuel exhaust stream in the unit 1 is then provided back
into the fuel inlet stream. Preferably, the hydrogen is provided back into the fuel
inlet conduit 111 upstream of the humidifier 119.
[0021] The fuel exhaust stream is provided into the unit 1 as follows. The fuel
exhaust stream may contain hydrogen, water vapor, carbon monoxide, carbon dioxide,
some unreacted hydrocarbon gas, such as methane and other reaction by-products and
impurities. This exhaust stream is first provided into the heat exchanger 121, where
its temperature is lowered, preferably to less than 200 degrees Celsius, while the
temperature of the fuel inlet stream is raised. If the water-gas shift reactor 128 and
-6-

the air preheater heat exchanger 125 are present. Lhen the fuel exhaust stream is
provided through the reactor 128 to convert al least a portion of the water vapor and a
majority of the residual carbon monoxide into carbon dioxide and hydrogen. The fuel
exhaust stream is then passed through the heat exchanger 125 to further lower its
temperature while raising the temperature of the air inlet stream. The temperature
may be lowered to 90 to 110 degrees Celsius for example.
[0022] The fuel exhaust stream is then provided into inlet 2 of the
electrochemical pump separation unit 1 via conduit 3. During the separation step in
unit 1, at least a majority of the hydrogen, such as about 85% of the hydrogen in the
fuel exhaust stream, diffuses through the electrolyte of the cells in the unit 1, while
allowing the water vapor, carbon dioxide, carbon monoxide and remaining
hydrocarbon gas in the fuel exhaust stream to be passed through conduit 9 to the
humidifier 119.
[0023J In the fuel humidifier 119, a portion of the water vapor in the fuel
exhaust stream is transferred to the fuel inlet stream to humidify the fuel inlet stream.
The fuel/hydrogen fuel inlet stream mixture is humidified to 80C to 90C dew point.
The remainder of the fuel exhaust stream is then provided into the burner 107 along
with the air (i.e., cathode) exhaust stream from the stack 101 to be burned and to
provide low quality heat. The heat from the burner 107 may be used to heat the
reformer 123 or it may be provided to other parts of the system 100 or to a heat
consuming devices outside the system 100, such as a building heating system.
[0024] The hydrogen separated from the fuel exhaust stream is then removed
from unit 1 through outlet 8 and conduit 7 and provided into the hydrocarbon fuel
inlet stream in the fuel inlet conduit 111. If desired, prior to being provided to the
fuel inlet conduit, the hydrogen stream may be passed through a hydrogen cooler heat
exchanger 129, where the hydrogen stream exchanges heat with an air stream, such as
the air inlet .stream provided into the fuel cell stack 101. The temperature of the
hydrogen stream is lowered in the heat exchanger 129 before being provided into the
fuel inlet conduit, while the temperature of the air inlet stream is raised. Thus, the
hydrocarbon fuel inlet stream is mixed with a low dew point, near ambient
-7-

temperature recycled hydrogen recovered from the anode tail gas with an
electrochemical hydrogen pump 1.
[0025] Thus, with respect 10 the fuel exhaust stream, the heat exchanger 121 is
located upstream of the reactor 128, which is located upstream of the heat exchanger
125, which is located upstream of the pump unit 1, which is located upstream of the
humidifier 119 and the fuel inlet conduit 111.
[0026] Figure 2 illustrates a system 200 according to the second embodiment
of the invention. The system 200 is similar to system 100 and contains a number of
components in common. Those components which are common to both systems 100
and 200 arc numbered with the same numbers in Figures 1 and 2 and will not be
described further.
[0027] One difference between systems 100 and 200 is that system 200
preferably, but not necessarily lacks, the humidifier 119. Instead, a portion of the
water vapor containing stack fuel exhaust stream is directly recycled into the stack
fuel inlet stream. The water vapor in the fuel exhaust stream is sufficient to humidify
the fuel inlci stream.
[0028] The system 200 contains a fuel splitter device 201, such as a computer
or operator controlled multi-way valve, for example a three-way valve, or another
fluid splitting device. The device 201 contains an inlet 203 opcratively connected to
the fuel cell stack fuel exhaust outlet 103, a first outlet 205 operatively connected to
the unit 1 and a second outlet 207 operatively connected to the fuel cell stack fuel
inlet 105. For example, the second outlet 207 may be operatively connected to the
fuel inlet conduit 111, which is operatively connected to inlet 105. However, the
second outlet 207 may provide a portion of the fuel exhaust stream into the fuel inlet
stream further downstream.
[0029] Preferably, the system 200 contains a blower or compressor 209 which
provides the fuel exhaust stream into the fuel inlet stream. Specifically, the outlet
207 of the valve 201 is operatively connected to an inlet of a blower or compressor
209, while an-outlet of the blower or compressor 209 is connected to the hydrocarbon
-8-

fuel inlet conduit 111. In operation, the blower or compressor 209 controllably
provides a desired amount of the fuel cell stack fuel exhaust stream into the fuel cell
stack fuel inlet stream.
[0030] The method of operating the system 200 is similar to the method of
operating the system 100. One difference is that the fuel exhaust stream is separated
into at least two streams by the device 201. The first fuel exhaust stream is recycled
into the fuel inlet stream, while the second stream is directed into the separation unit 1
where at least a portion of hydrogen contained in the second fuel exhaust stream is
electrochemically separated from the second fuel exhaust stream. The hydrogen
separated from the second fuel exhaust stream is then provided into the fuel inlet
stream. For example, between 50 and 70%, such as about 60% of the fuel exhaust
stream may be provided 1o the blower or compressor 209, while the remainder may be
provided toward the unit 1.
[0031] Preferably, the fuel exhaust stream is first provided through the heat
exchangers 121 and 125 and reactor 128 before being provided into the valve 201.
The fuel exhaust stream is cooled to 200 degrees Celsius or less, such as to 120 to 180
degrees, in the heat exchanger 125 prior to being provided into the valve 201 where it
is separated into two streams. This allows the use of a low temperature blower 209 to
controllably recycle a desired amount of the first fuel exhaust stream into the fuel inlet
stream, since such blower may be adapted to move a gas utreani which has a
temperature of 200 degrees Celsius or less.
[0032] The blower or compressor 209 may be computer or operator controlled
and may vary the amount of the fuel exhaust stream being provided into the fuel inlet
stream depending on the conditions described below. If desired, all or a portion of the
hydrogen separated from unit 1 may be provided to a hydrogen using device, such as
a PEM fuel cell in a vehicle or another hydrogen using device or to a hydrogen
storage vessel. In this case, a selector valve may be placed in conduit 7 to either split
the hydrogen stream between the fuel inlet conduit 111 and the hydrogen storage
vessel or hydrogen using device, or to alternate the hydrogen flow between the fuel
inlet conduit ll and the hydrogen storage vessel or hydrogen using device. The
-9-

blower or compressor and the optional selector valve may be operated by a computer
or an operator to controllably vary the gas .flow based on one or more of the following
conditions: i) detected or observed conditions of the system 100 (i.e., changes in the
sys'.em operating conditions requiring a change in the amount of hydrogen in the fuel
inlet stream); ii) previous calculations provided into the computer or conditions
known to the operator which require a temporal adjustment of the hydrogen in the fuel
inlet stream; iii) desired future changes, presently occurring changes or recent past
changes in the operating parameters of the stack 101, such as changes in the
electricity demrmd by the users of electricity generated by the slack, changes in price
for electricity or hydrocarbon fuel compared to the price of hydrogen, etc, and/or iv)
changes in the demand for hydrogen by the hydrogen user, such as the hydrogen using
device, changes in price of hydrogen or hydrocarbon fuel compared to the price of
electricity, etc.
[0033] It is believed that by recycling at least a portion of the hydrogen from
the fuel exhaust (i.e., tail) gas stream into the fuel inlet stream, a high efficiency
operation of the fuel cell system is obtained. Furthermore, the overall fuel utilization
is increased. The electrical efficiency (i.e., AC electrical efficiency) can range
between about 50% and about 60%, such as between about 54% and about 60% for
the methods of the firs I and second embodiments when the per pass fuel utilization
rate is about 75% (i.e., about 75% of the fuel is utilized during each pass through the
stack). An effective fuel utilization of about 94% to about 95% is obtained when the
per pass utilization is about 75%, and about 85% of the fuel exhaust gas hydrogen is
recycled back to the fuel cell stack by the separation unit 1. Even higher efficiency
may be obtained by increasing the per pass fuel utilization rate above 75%, such as
about 76-80%. At steady-state, the methods of the first and second embodiments
eliminate the need for generating steam when steam methane reformation is used to
create the feed gas to the fuel cell. The fuel exhaust stream contains enough water
vapor to humidify the fuel inlet stream to the stack at steam to carbon ratios of 2 to
2.5. The increase in net fuel utilization and the removal of heat requirement to
generate steam increases the overall electrical efficiency. In contrast, without
-10-

recycling hydrogen, the AC electrical efficiency is about 45% for a fuel utilization
rate within the stack of about 75% to 80%.
[0034] The fuel cell systems described herein may have other embodiments
and configurations, as desired. Other components may be added if desired, as
described, for example, in U.S. Application Serial Number 10/300,021, filed on
November 20. 2002, in U.S. Provisional Application Serial Number 60/461,190, filed
on April 9, 2003, and in U.S. Application Serial Number 10/446,704, filed on May
29, 2003 all incorporated herein by reference in their entirety. Furthermore, it should
be understood that any system element or method step described in any embodiment
and/or illustrated in any figure herein may also be used in systems and/or methods of
other suitable embodiments described above, even if such use is not expressly
described.
[0035] The foregoing description of the invention has been presented for
purposes of illustration and description. It is not intended to be exhaustive or to limit
the invention to the precise form disclosed, and modifications and variations are
possible in light of the above teaching; or may be acquired from practice of the
invention. The description was chosen in order to explain the principles of the
invention audits practical application. It is intended that the scope of the invention be
defined by the claims appended hereto, and their equivalents.
-11-

WHAT IS CLAIMED IS:
1. A method of operating a fuel cell system, comprising:
providing a fuel inlet stream into a fuel cell stack;
operating the fuel cell stack to generate electricity and a hydrogen containing
fuel exhaust stream;
separating at least a portion of hydrogen contained in the fuel exhaust stream
using a high temperature, low hydration ion exchange membrane cell stack; and
providing the hydrogen separated from the fuel exhaust stream into the fuel
inlet stream.
2. The method of claim 1, wherein the high temperature, low hydration ion
exchange membrane cell stack comprises a stack of acid doped non-fluorinated ion
exchange ionomer membrane cells.
3. The method of claim 2, wherein each membrane of the membrane cells
comprises a polybenzimidaole (PB1) membrane, doped with sulfuric or phosphoric
acid.
4. The method of claim 1, further comprising lowering a temperature of the fuel
exhaust stream to between 120 C and 200 C prior to the step of separating at least a
portion of hydrogen.
5. A fuel cell system, comprising:
a fuel coll stack;
a high temperature, low hydration ion exchange membrane cell stack;
a first conduit which operatively connects a fuel exhaust outlet of the fuel cell
stack to a first inlet of the high temperature, low hydration ion exchange membrane
cell stack; and
a second conduit which operatively connects an outlet of the a high
temperature, low hydration ion exchange membrane cell stack to the fuel cell stack
fuel inlet.
-12-

6. The system of claim 5, wherein the high temperature, low hydration
ion exchange membrane cell stack comprises a slack of acid doped non-fiuorinated
ion exchange ionomer membrane cells.
7. The system of claim 6, wherein each membrane of the membrane cells
comprises a polybenzimidazole (PBI) membrane doped with sulfuric or phosphoric
acid.
-13-

A method of operating a fuel cell system includes providing a fuel inlet stream into a fuel cell stack, operating the fuel cell stack to generate electricity and a hydrogen containing fuel exhaust stream, separating at least a portion of hydrogen contained in the fuel exhaust stream using a high temperature, low hydration ion exchange membrane cell stack, and providing the hydrogen separated from the fuel exhaust stream into the fuel inlet stream.

Documents:

http://ipindiaonline.gov.in/patentsearch/GrantedSearch/viewdoc.aspx?id=WYwFo8r79xqon1tDWqmCcA==&loc=wDBSZCsAt7zoiVrqcFJsRw==

« Previous Patent

Next Patent »

Patent Number

278707

Indian Patent Application Number

366/KOLNP/2008

PG Journal Number

54/2016

Publication Date

30-Dec-2016

Grant Date

28-Dec-2016

Date of Filing

25-Jan-2008

Name of Patentee

BLOOM ENERGY CORPORATION

Applicant Address

1252 ORLEANS DRIVE SUNNYVALE, CALIFORNIA

Inventors:

#	Inventor's Name	Inventor's Address
1	MCELROY JAMES	C/O BLOOM ENERGY CORPORATION, 1252 ORLEANS DRIVE, SUNNYVALE, CALIFORNIA 94089-1137
2	VENKATARAMAN SWAMINATHAN	C/O BLOOM ENERGY CORPORATION, 1252 ORLEANS DRIVE, SUNNYVALE, CALIFORNIA 94089-1137

PCT International Classification Number

H01M 8/04

PCT International Application Number

PCT/US2006/028614

PCT International Filing date

2006-07-24

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	60/701977	2005-07-25	U.S.A.