Fuel cell system having biogas desulfurizer assembly with manganese oxide desulfurizer material
09847543 · 2017-12-19
Assignee
Inventors
- Jin-Yun Wang (Cheshire, CT, US)
- Mohammad Farooque (Danbury, CT, US)
- David Xu (Medfield, MA, US)
- Zachary Sanders (Pardeeville, WI, US)
Cpc classification
B01J43/00
PERFORMING OPERATIONS; TRANSPORTING
B01D2257/553
PERFORMING OPERATIONS; TRANSPORTING
H01M8/04014
ELECTRICITY
B01D2257/306
PERFORMING OPERATIONS; TRANSPORTING
C12M47/18
CHEMISTRY; METALLURGY
Y02E60/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
H01M8/0662
ELECTRICITY
B01J43/00
PERFORMING OPERATIONS; TRANSPORTING
H01M8/04014
ELECTRICITY
Abstract
A desulfurizer material for desulfurizing fuel supplied to a fuel cell system, the desulfurizer material comprising one or more manganese oxide materials having an octahedral molecular sieve (OMS) structure, and the desulfurizer material being resistant to moisture and being capable of removing organic sulfur containing compounds and H.sub.2S. The desulfurizer material is used in a desulfurizer assembly which is used as part of a fuel cell system.
Claims
1. A fuel cell system comprising: a biogas fuel supply assembly; a desulfurizer assembly configured to receive biogas fuel from the biogas fuel supply assembly and to desulfurize the biogas fuel, the desulfurizer assembly comprising one or more desulfurizer beds; and a fuel cell stack including an anode side and a cathode side, the anode side of the fuel cell stack receiving the desulfurized biogas fuel from the desulfurizer assembly; wherein each of the one or more desulfurizer beds comprises a desulfurizer material configured to desulfurize biogas fuel conveyed through said one or more desulfurizer beds, and wherein the desulfurizer material in at least one of the one or more desulfurizer beds comprises a manganese oxide material that has an octahedral molecular sieve (OMS) structure and is doped with Fe, wherein the manganese oxide material comprises OMS-2 having a 2×2 tunnel structure, and wherein an amount of the Fe in the desulfurizer material is greater than 0% (mole) and less than 50% (mole) of a total metal content of the desulfurizer material.
2. The fuel cell system in accordance with claim 1, wherein: the desulfurizer assembly comprises a plurality of desulfurizer beds, including a first desulfurizer bed and a second desulfurizer bed, and the first desulfurizer bed and the second desulfurizer bed comprises different desulfurizer materials.
3. The fuel cell system in accordance with claim 1, further comprising a cleanup assembly configured to process the biogas fuel before the biogas fuel is conveyed to the fuel cell assembly, the cleanup assembly comprising an H.sub.2S removal unit for removing H.sub.2S from the biogas fuel.
4. The fuel cell system in accordance with claim 3, wherein: the biogas fuel supply comprises a biogas digester; and the fuel cell system further comprises a heating assembly configured to heat the biogas digester using waste heat from the fuel cell stack.
5. The fuel cell system in accordance with claim 4, wherein the heating assembly is configured to pre-heat the desulfurized fuel using one of anode exhaust and cathode exhaust, and the heating assembly is further configured to receive water and to humidify the desulfurized fuel with the received water.
6. The fuel cell system in accordance with claim 3, wherein the fuel cell system is configured to operate on two or more fuels of different compositions and the fuel cell system further comprises: a second fuel supply assembly for supplying a second fuel, having a different composition from the first fuel, to the desulfurizer assembly, wherein the second fuel is not conveyed through the cleanup assembly.
7. The fuel cell system in accordance with claim 6, wherein the biogas fuel supply assembly comprises a biogas digester and the fuel cell system further comprises a heating assembly configured to heat the biogas digester so as to maintain the temperature in the biogas digester at a predetermined temperature.
8. The fuel cell system according to claim 6, further comprising a control assembly for controlling at least one of: (a) flow rates of first fuel and second fuel through the biogas fuel supply assembly and the second supply assembly, respectively; and (b) flow of the biogas fuel and the second fuel through the one or more desulfurizer beds in the desulfurizer assembly.
9. The fuel cell system in accordance with claim 3, wherein the cleanup assembly further comprises a moisture conditioning unit for removing moisture from the biogas fuel.
10. The fuel cell system in accordance with claim 9, wherein the cleanup assembly further comprises a siloxane removal unit for removing siloxanes from the biogas fuel.
11. The fuel cell system in accordance with claim 6, wherein the second fuel is natural gas.
12. The fuel cell system in accordance with claim 1, wherein the manganese oxide material of the desulfurizer material in said at least one of the one or more desulfurizer beds is further doped with a second doping metal selected from the group consisting of K, Mg, Co, Ag, Cu, Zn, Ni, and mixtures thereof.
13. The fuel cell system in accordance with claim 1, wherein the manganese oxide material is resistant to moisture and capable of removing organic sulfur containing compounds and H.sub.2S.
14. The fuel cell system in accordance with claim 1, wherein the OMS-2 has a tunnel size of about 4.6 Å.
15. The fuel cell system in accordance with claim 1, wherein the biogas fuel supply assembly is configured to supply biogas fuel having a relative humidity of at least 10% to the desulfurizer assembly.
16. The fuel cell system in accordance with claim 1, wherein the biogas fuel supply assembly is configured to supply biogas fuel having a relative humidity of at least 30% to the desulfurizer assembly.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The above and other features and aspects of the present invention will become more apparent upon reading the following detailed description in conjunction with the accompanying drawings, in which:
(2)
(3)
(4)
(5)
(6)
DETAILED DESCRIPTION
(7) The present invention is directed to desulfurizing materials for removal of sulfur-containing compounds from a variety of fuel gases and suitable for use with both wet and dry fuel gases. The present invention is also directed to fuel cell systems which include a fuel polishing and desulfurizing assemblies capable of polishing and desulfurizing fuels with high water content and capable of processing dual fuels, including a dry fuel and a wet fuel, without requiring a separate fuel processing train.
(8) In accordance with the present invention, the desulfurizing materials comprise octahedral molecular sieves (OMS), and in particular undoped and doped manganese oxide containing materials with OMS structure. The oxidation state of the Mn in the OMS structures is typically between +3 and +4.
(9) Manganese oxide OMS desulfurizer materials have mixed covalent properties, high surface area and high stability which differentiate manganese oxide OMS materials from MnO.sub.2 and permanganates. The mixed valence of the manganese oxide OMS desulfurizer materials provides an excellent mechanism for oxidation-reduction and an ion-exchange capability which allows for modification of the properties of these materials. In addition, the manganese oxide OMS desulfurizer materials are resistant to moisture in the fuel being desulfurized so that they are capable of desulfurizing fuel with or without moisture present therein.
(10) As mentioned above, the manganese oxide OMS desulfurizer materials may be undoped or doped. In certain embodiments, the manganese oxide OMS desulfurizer materials are doped by using one or more transition metals in the framework of the crystal structures or by inserting transition metal or non-transition metal ions into the tunnels of the OMS structure by ion-exchange. For example, most cations, such as Fe, Cu, Ag, Mg, and Co, etc. may be used as the doping materials for doping the manganese oxide OMS desulfurizer materials. The doping transition metals generally improve the sulfur capacity of the manganese oxide OMS desulfurizer materials, and can be added in amounts of 0-50% (mole) of the total metal content of the desulfurizer materials. Illustrative examples of doped manganese oxide OMS desulfurizer materials include, but are not limited to Cu-OMS-2, Co-OMS-2 and Fe-OMS-2. In other embodiments, multiple metal species may be used for doping the manganese oxide OMS desulfurizer materials, including transition metals, alkali, and alkali earth metals. For example, two different metals may be used to dope the manganese oxide desulfurizer materials, including at least one of a transition metal, an alkali metal and an alkali earth metal, with the amount of the first doping metal being about 0-50% (mole) of the total metal content and the amount of the second doping metal being about 0-25% (mole) of the total metal content of the desulfurizer materials. Illustrative examples of manganese oxide OMS desulfurizer materials doped with two or more metals include, but are not limited to, manganese oxide OMS materials doped with K, Mg, Fe, Co, Ag, Cu, Zn, Ni and mixtures thereof.
(11) The manganese oxide OMS desulfurizer materials of the present invention are used to remove sulfur from a variety of fuels, including natural gas, biogas, such as anaerobic digester gas (ADG), and other types of fuel. Moisture resistance of the manganese oxide OMS desulfurizer materials allows them to be used for desulfurizing fuels having high moisture content, as well as fuels with low moisture content. Generally, the manganese oxide OMS desulfurizer materials remove sulfur-containing compounds from the fuel through oxidation and/or catalytic oxidative desulfurization and are effective for organic sulfur compounds and H.sub.2S. In addition to being used for desulfurizing different fuels, these manganese oxide OMS desulfurizer materials can be used as polishing media for biogas after bulk H.sub.2S is removed from the biogas.
(12) Different doped and undoped OMS desulfurizer materials were tested for their capacity to remove dimethyl sulfide (DMS) from fuel and were compared to various commercially available desulfurizers. The tests were conducted at ambient conditions and the fuel conveyed through the desulfurizer materials being tested included 70% methane and 30% CO.sub.2. The water content in the fuel was 3,000 ppm, DMS content in the fuel was 16 ppm and the gas hourly space velocity (GHSV) was 6,600 h.sup.−1 during all tests. Table 1 summarizes the test results and
(13) TABLE-US-00001 TABLE 1 Desulfurizer DMS Capacity material/sorbent (% wt) S MnO.sub.2 0 Activated Carbon 0.04 Cu-Activated Carbon 0.08 Cu-Zeolites 0.02 6% KMnO.sub.4/Zeolites 0.21 OMS-1 0.24 OMS-2 0.46 Cu-OMS-2 0.42 Co-OMS-2 0.48 Fe-OMS-2 1.43
(14) As can be seen from
(15) In addition to higher capacity, manganese oxide OMS desulfurizer materials have substantially higher moisture resistance than the conventionally used products. Almost all of the conventionally used products were seriously affected by moisture, including Cu-Zeolite which is the best DMS sorbent for use with natural gas. In contrast, Fe-doped OMS-2 material was only slightly affected by the moisture content in the fuel, thus providing the moisture resistance required for desulfurizing biogas.
(16)
(17) As shown in
(18) It is understood that other fuels, such as other biogas fuels, wet and/or dry natural gas, coal-bed methane, etc., may be used by the fuel cell system 100, and that in certain embodiments, the biogas bulky cleanup assembly 126 may be omitted or bypassed by the fuel, depending on the needs for the particular fuel gas. In addition, depending on the fuel used by the system 100, another suitable fuel supply may be used instead of the biogas digester to provide the fuel to the bulky cleanup assembly, and/or the desulfurizer. Waste heat from the fuel cell may be provided, if needed, to preheat the fuel before supplying the fuel to the bulky cleanup assembly 126 or to the desulfurizer 124.
(19) The illustrative biogas bulky cleanup assembly 126 shown in
(20) After the biogas fuel is cleaned by the biogas cleanup assembly 126, the biogas fuel is conveyed to the desulfurizer (polishing) assembly 124 of the present invention for removal of sulfur-containing compounds from the biogas. The desulfurizer assembly 124 includes at least one desulfurizing bed comprising the manganese oxide OMS desulfurizer material described above. In some embodiments, the desulfurizer assembly may include two or more desulfurizing beds, with each of the beds having the same or different manganese oxide OMS desulfurizer materials. In addition, in some embodiments with two or more desulfurizing beds, at least one of the beds includes manganese oxide OMS desulfurizer materials, while another one or more of the beds may include other OMS or non-OMS materials. The at least one desulfurizing bed of the desulfurizer assembly 124 is disposed in a housing, and in the embodiments of the desulfurizer assembly including multiple desulfurizing beds, each bed may be disposed in a separate housing, or two or more beds may be disposed in series in a common housing. In other embodiments, the desulfurizer assembly 124 may be arranged as a lead-lag desulfurizer assembly having multiple desulfurizing beds and switching between the operational and standby desulfurizing beds. An exemplary lead lag desulfurizer assembly construction is disclosed in U.S. Pat. No. 7,063,732, assigned to the same assignee herein. As discussed above, the manganese oxide OMS desulfurizer material removes sulfur-containing compounds from the fuel, including organic sulfur-containing compounds and H.sub.2S, and is resistant to moisture present in the fuel.
(21) After desulfurization in the desulfurizer assembly 124, the desulfurized biogas fuel is conveyed through the heat recovery unit 118 where it is pre-heated using waste heat from cathode exhaust and/or oxidizer. The heat recovery unit 118 also functions as a humidifier and receives water for humidifying the desulfurized biogas fuel. Pre-heated and humidified biogas fuel is then conveyed to the pre-processing assembly 116 in which the biogas fuel may be de-oxidized in the de-oxidizer 122 to remove oxygen in the biogas and at least partially reformed in a pre-reforming unit 120. The biogas fuel is thereafter conveyed to the anode side 112 of the fuel cell 110.
(22) As shown in
(23) The system shown in
(24) As shown in
(25) As shown in
(26) As in the system of
(27) As shown in
(28) In the embodiment shown in
(29) Referring again to
(30) After desulfurization in the desulfurizer assembly 124, the desulfurized fuel, including desulfurized first fuel and/or desulfurized second fuel, is conveyed through the heat recovery unit 118 where it is pre-heated using waste heat from cathode exhaust and/or oxidizer. The heat recovery unit 118 also functions as a humidifier and receives water for humidifying the desulfurized fuel. Pre-heated and humidified fuel is then conveyed to the pre-processing assembly 116 in which the fuel may be de-oxidized in the de-oxidizer 122 and at least partially reformed in a pre-reforming unit 120. The fuel is thereafter conveyed to the anode side 112 of the fuel cell 110.
(31) The above described system of
(32) In all cases it is understood that the above-described arrangements are merely illustrative of the many possible specific embodiments which represent applications of the present invention. Numerous and varied other arrangements can be readily devised in accordance with the principles of the present invention without departing from the spirit and the scope of the invention.