US20230201791A1 - Diesel reforming apparatus having a heat exchanger for higher efficiency steam reforming for solid oxide fuel cells (sofc) - Google Patents
Diesel reforming apparatus having a heat exchanger for higher efficiency steam reforming for solid oxide fuel cells (sofc) Download PDFInfo
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- US20230201791A1 US20230201791A1 US18/117,160 US202318117160A US2023201791A1 US 20230201791 A1 US20230201791 A1 US 20230201791A1 US 202318117160 A US202318117160 A US 202318117160A US 2023201791 A1 US2023201791 A1 US 2023201791A1
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- reforming unit
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- 238000002407 reforming Methods 0.000 title claims abstract description 72
- 239000000446 fuel Substances 0.000 title description 16
- 238000000629 steam reforming Methods 0.000 title description 6
- 239000007787 solid Substances 0.000 title description 4
- 238000002453 autothermal reforming Methods 0.000 claims abstract description 45
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 26
- 230000023556 desulfurization Effects 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims description 34
- 229910000510 noble metal Inorganic materials 0.000 claims description 13
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 239000002283 diesel fuel Substances 0.000 description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 16
- 239000003570 air Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000183024 Populus tremula Species 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- -1 carbon hydrocarbon Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
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- C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- C01B2203/0872—Methods of cooling
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- C01B2203/1041—Composition of the catalyst
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- C01B2203/1064—Platinum group metal catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
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Definitions
- Embodiments of the present disclosure generally relate to diesel reforming systems and specifically relate diesel reforming systems having improved efficiency for coupling with Solid Oxide Fuel Cells (SOFC).
- SOFC Solid Oxide Fuel Cells
- Fuel cells are power generation systems that convert the chemical reaction energy of hydrogen and oxidant contained in hydrocarbon-based materials such as hydrogen, methanol, and ethanol into direct electrical energy.
- the hydrogen for the fuel cell can be obtained through steam reforming from a hydrocarbon-based fuel such as methane, methanol, natural gas, gasoline and diesel.
- a fuel reformer can be classified into steam reforming, partial oxidation reforming and autothermal reforming according to a reforming method.
- Steam reformers are suitable for fuels with a high hydrogen content in the reformed gas and short carbon chains such as methane and natural gas.
- the steam reforming reaction is suitable for an SOFC system having a high operating temperature because the reformed gas contains a high temperature.
- the steam reformer consumes a large amount of heat to generate steam. There is a problem that the structure for heat recovery is complicated due to the heat consumption due to the endothermic reaction and that the manufacturing difficulty and the manufacturing cost of the reactor are increased due to these reasons.
- Embodiments of the present disclosure meet this need by efficiently controlling the arrangement conditions of the apparatus with constrained heat exchanger setup.
- the present diesel reformer embodiments provides efficient production of hydrogen by reforming diesel fuel supplied with a diesel autothermal reforming unit, a post-reforming unit disposed downstream of the autothermal reforming unit, a heat exchanger disposed downstream of the post-reforming unit, and a desulfurization unit.
- this sequential arrangement of system components in conjunction with temperature control and feed control maximizes reforming efficiency, which is highly desirable when coupling the diesel reformer to an SOFC system.
- a diesel reformer system comprising a diesel autothermal reforming unit; a post-reforming unit disposed downstream of the autothermal reforming unit; a heat exchanger disposed downstream of the post-reforming unit; and a desulfurization unit disposed downstream of the heat exchanger.
- a method of diesel reforming comprises: introducing one or more feed streams to a diesel autothermal reforming unit to at least partially convert the one or more feed streams to a diesel reformate, wherein the one or more feed streams comprising diesel fuel, air, and steam.
- SCR Steam to Carbon Ratio
- OCR Oxygen to Carbon Ratio
- the method also includes introducing the diesel reformate to a post-reforming unit disposed downstream of the diesel autothermal reforming unit, wherein the post-reforming unit selectively decomposes low carbon (C 2 -C 5 ) hydrocarbons in the diesel reformate into hydrogen and methane.
- the method includes passing post-reforming unit diesel reformate through a heat exchanger disposed downstream of the post-reforming unit and into a desulfurization unit disposed downstream of the heat exchanger, wherein the desulfurization unit removes sulfur compounds from the post-reforming unit diesel reformate.
- FIG. 1 is a schematic illustration of a diesel reforming system according to one or more embodiments of the present disclosure.
- Embodiments of the present disclosure are directed to a diesel reformer system and a method of diesel reforming.
- a diesel reformer system 1 is provided.
- the diesel reformer system 1 comprises a diesel autothermal reforming unit 120 , a post-reforming unit 130 disposed downstream of the autothermal reforming unit 120 , a heat exchanger 135 disposed downstream of the post-reforming unit 130 , and a desulfurization unit 140 disposed downstream of the heat exchanger 135 .
- the diesel autothermal reforming unit 120 , the post-reforming unit 130 , the heat exchanger 135 , and the desulfurizati on unit 140 are incorporated into a single reactor unit.
- the diesel reforming system 1 may conduct the following diesel reforming method as shown in FIG. 1 .
- the method may include introducing one or more feed streams to a diesel autothermal reforming unit 120 to at least partially convert the one or more feed streams to a diesel reformate 64 .
- the feed streams may comprise diesel fuel 14 , air 26 , and steam 48 .
- the diesel fuel 14 feed may be pumped from a diesel tank 10 by a pump 12 .
- the temperature of the feed streams may be from 10° C. to 50° C., or from 20° C. to 50° C., or from 20° C. to 40° C., or about 25° C.
- the pressure of the feed streams may be from 0.5 atm to 2 atm, or from 0.5 atm to 1.5 atm, or about 1 atm.
- the diesel fuel at the diesel tank 10 may be stored at room condition, about 25° C. and about 1 atm.
- the air 26 feed may be delivered from an air tank 20 by blower 22 .
- the diesel fuel 14 and air 26 feeds may be mixed upstream of the diesel autothermal reformer unit 120 at a mixing station 150 .
- the mixing station 150 may include a flow nozzle, which is utilized to pass the mixture 54 of diesel fuel and air to the reactor unit.
- the mixture 54 of diesel fuel and air may be fed upstream of a preheater 122 .
- the preheater 122 may be disposed at the top of the diesel autothermal reformer unit 120 .
- the preheater 122 may be a heating coil.
- the preheater 122 which may be used during the initial heat-up of the reforming catalyst with the air feed 26 , may heat the reforming catalyst in the diesel autothermal reformer unit 120 to a temperature of up to 300° C., or from 200° C. to 300° C., or from 250° C. to 300° C.
- the preheater 122 may heat the air feed 26 to a temperature of up to 450° C., or from 350° C. to 450° C., or from 400° C. to 450° C.
- the preheater 122 will not heat the mixture 54 of diesel fuel and air.
- the diesel fuel 14 will not be supplied during the heating of the reforming catalyst.
- the steam feed 48 it is contemplated that water is pumped from water tank 30 via pump 32 and is then converted into steam by heat exchanger 40 . As shown in the embodiment of FIG. 1 , the steam feed 48 is delivered downstream of preheater 122 . The steam feed 48 may be heated up to 150° C. In further embodiments, the heat exchanger 40 may heat the steam feed 48 from 100° C. to 150° C., or from 110° C. to 150° C., or from 120° C. to 150° C.
- the SCR is from 1.5 to 4, or from 2 to 3.
- the OCR is from 0.5 to 0.9, or from 0.6 to 0.8.
- the diesel autothermal reforming unit 120 utilizes high pressure and high temperature operating conditions.
- the diesel autothermal reforming unit 120 may have an operating temperature of at least 700° C., or from 750 to 1100° C., or from 750 to 850° C.
- the diesel autothermal reforming unit 120 may have an operating pressure of at least 0.5 bar, or from 0.5 to 1.5 bars, or from 1.0 to 1.5 bars, or about 1 bar at atmospheric condition.
- the diesel reformate 64 comprises various components, including syngas (i.e., hydrogen and carbon monoxide).
- syngas i.e., hydrogen and carbon monoxide
- the steam reforming reaction conducted by the diesel autothermal reforming unit 120 is as follows:
- the conversion of the methane to syngas in the diesel autothermal reforming unit 120 may be from 95% to 100%, or from 96% to 100%, or from 97% to 100% or from 98% to 100%, or from 99% to 100%, or from 99.5% to 100%, or from 99.9% to 100%, or about 100%.
- the diesel reformate 64 is introduced to a post-reforming unit 130 disposed downstream of the diesel autothermal reforming unit 120 .
- the post-reforming unit 130 selectively decomposes low carbon (C 2 -C 5 ) hydrocarbons in the diesel reformate 64 into a post-reforming unit diesel reformate stream 74 comprising hydrogen and methane.
- the post-reforming catalyst by the post-reforming catalyst, the low carbon hydrocarbon material (C 2 -C 5 ) in the diesel reformate 64 is reacted with hydrogen and vapor contained in the diesel reformate 64 to be selectively decomposed into hydrogen and methane.
- the inlet of the post-reforming unit 130 utilizes high temperature and high pressure operating conditions.
- the inlet of the post-reforming unit 130 may have an operating temperature range of from 650° C. to 850° C., or from 650° C. to 800° C., or from 700° C. to 850° C., or from 700° C. to 800° C., or about 750° C.
- the inlet of the post-reforming unit 130 may have an operating pressure of at least 0.5 bar, or from 0.5 to 1.5 bars, or from 1.0 to 1.5 bars, or about 1 bar at atmospheric condition.
- the outlet of the post-reforming unit 130 utilizes high temperature and high pressure operating conditions.
- the outlet of the post-reforming unit 130 may have an operating temperature range of from 450° C. to 800° C., or from 450° C. to 750° C., or from 450° C. to 700° C., or from 450° C. to 650° C., or from 450° C. to 600° C., or from 500° C. to 800° C., or from 500° C. to 750° C., or from 500° C. to 700° C., or from 500° C. to 650° C., or from 500° C. to 600° C., or from 550° C. to 800° C., or from 550° C.
- the outlet of the post-reformer 120 may have an operating pressure of at least 0.5 bar, or from 0.5 to 1.5 bars, or from 1.0 to 1.5 bars, or about 1 bar at atmospheric condition.
- the post-reforming unit diesel reformate 74 is passed through a heat exchanger 135 disposed downstream of the post-reforming unit 130 .
- the heat transfer amount of the heat exchanger 135 is optimized to make higher system efficiency by controlling the heat transfer amount (UA).
- the heat transfer amount (UA) is equal to (U), the heat transfer coefficient multiplied by (A) the heat transfer surface area.
- the heat transfer amount (UA) may be from 0.75 watts per kelvin (W/K) to 4.0 W/K, from 0.75 W/K to 3.5 W/K, from 0.75 W/K to 3.0 W/K, from 0.8 W/K to 4.0 W/K, from 0.8 W/K to 3.5 W/K, from 0.8 W/K to 3.0 W/K, 1.0 W/K to 4.0 W/K, from 1.0 W/K to 3.5 W/K, from 1.0 W/K to 3.0 W/K, from 0.75 W/K to 1.50 W/K, or from 0.80 W/K to 1.50 W/K, from 0.90 W/K to 1.50 W/K, from 1.00 W/K to 1.50 W/K, from 0.75 W/K to 1.40 W/K, from 0.80 W/K to 1.40 W/K, from 0.90 W/K to 1.40 W/K, from 1.00 W/K to 1.40 W/K, from 0.75 W/K to 1.30 W/K, from 0.
- the heated post-reforming unit diesel reformate 84 is delivered into a desulfurization unit 140 disposed downstream of the heat exchanger 135 , wherein the desulfurization unit removes sulfur compounds from the heated post-reforming unit diesel reformate 84 .
- the sulfur content of the heated post-reforming unit diesel reformate 84 may be equal or less than 10 ppm.
- the sulfur content of the heated post-reforming unit diesel reformate 84 may be equal or less than 9 ppm, or 8 ppm, or 7 ppm, or 6 ppm.
- the sulfur content of the desulfurized product 94 may be from 5 ppm to 10 ppm, or from 6 ppm to 10 ppm, or from 7 ppm to 10 ppm, or from 8 ppm to 10 ppm, from 5 ppm to 9 ppm, or from 6 ppm to 9 ppm, or from 7 ppm to 9 ppm, or from 5 ppm to 8 ppm from 5 ppm to 7 ppm, or from 6 ppm to 8 ppm.
- the desulfurized product 94 which is hydrogen rich, may be fed for use in an SOFC reactor or stack.
- the desulfurization unit 140 utilizes less severe operating conditions than the diesel autothermal reforming unit 120 .
- the desulfurization unit has an operating temperature at least 100° C. less than the operating temperature of the diesel autothermal reforming unit 120 .
- the operating temperature range of the desulfurization unit is from 300 to 500° C.
- the sulfur content of the desulfurized product 94 may be equal or less than 0.05 ppm.
- the sulfur content of the desulfurized product 94 may be equal or less than 0.04 ppm, or 0.03 ppm, or 0.02 ppm, or 0.01 ppm.
- the sulfur content of the desulfurized product 94 may be from 0.001 ppm to 0.05 ppm, or from 0.01 ppm to 0.05 ppm, or from 0.001 ppm to 0.03 ppm, or from 0.01 ppm to 0.03 ppm.
- Table 1 shows an example composition of the desulfurized product 94 .
- the diesel autothermal reforming unit 120 comprises a noble metal catalyst.
- the noble metal catalyst may include Pt, Rh, Ru and a mixture thereof.
- the catalysts may be supported or unsupported.
- the catalyst support may comprise alumina, silica, ceria, or combinations thereof. While various amounts of noble metal catalyst are considered suitable, the amount of the noble metal catalyst may be controlled according to a kind of hydrocarbon-based fuel to be reformed, an amount of the supplied fuel and the like.
- the internal and external partition walls of the diesel autothermal reforming unit may be formed of any material having high durability at a high temperature (about 800° C.) and an excellent heat transfer efficiency.
- the internal and external partition walls can be substantially formed of stainless steel.
- the diesel autothermal reforming unit comprises a porous support (including a support having through-pores along a fluid conveying direction) through which the fluid is passed and which impregnates the noble metal catalyst.
- the post-reforming unit 130 comprises a post-reforming catalyst formed of a transition metal, a noble metal, or a mixture thereof.
- the transition metal of the post-reforming catalyst includes Ni, Mg and a mixture thereof, and the noble metal thereof includes Pt, Rh, Pd, Ru and a mixture thereof.
- the post-reforming catalysts may be supported or unsupported. In supported catalyst embodiments, the catalyst support may comprise alumina, silica, ceria, or combinations thereof.
- the post-reforming unit 130 can be formed of a porous support (including a support having through-pores along a fluid conveying direction) through which the fluid is passed and which impregnates the post-reforming catalyst
- the desulfurizer 140 may be formed of a porous support (including a support having through-pores along a fluid conveying direction) through which the fluid is passed and which impregnates the desulfurizing catalyst.
- the desulfurization unit 140 comprises a ZnO catalyst.
- Example 1 Post-Reformer Outlet Temperature (° C.) 702 741 Heat Exchanger Steam Outlet Temperature (° C.) 345 216 Heat Exchanger Outlet/Desulfurizer Input Feed 138 302 Temperature (° C.) UA Value of Heat Exchanger (W/K) 4.77 1.25
- Example 1 As shown in Table 2, the Example 1 system and heat exchanger operated sub-optimally.
- the UA value of the heat exchanger was 4.77 W/K and the desulfurization input feed temperature was 138° C.
- the Example 2 system operated with a heat exchanger UA value of 1.25 W/K, which was almost 1 ⁇ 4 of Example 1. This was achieved in part through an OCR of 0.73 and an SCR of 2.2, which helped result in a desulfurization input temperature of 302° C.
- a first aspect of the present disclosure is directed to a diesel reformer system comprising a diesel autothermal reforming unit; a post-reforming unit disposed downstream of the autothermal reforming unit; a heat exchanger disposed downstream of the post-reforming unit; and a desulfurization unit disposed downstream of the heat exchanger.
- a second aspect of the present disclosure may include the first aspect, wherein the diesel autothermal reforming unit comprises a noble metal catalyst.
- a third aspect of the present disclosure may include either of the first or second aspects, wherein the diesel post-reforming unit comprises a noble metal catalyst, a transition metal catalyst, or combinations thereof.
- a fourth aspect of the present disclosure may include any of the first through third aspects, wherein the desulfurization unit comprises a ZnO catalyst.
- a fifth aspect of the present disclosure may include any of the first through fourth aspects, wherein the diesel autothermal reforming unit, the post-reforming unit, the heat exchanger, and the desulfurization unit are incorporated into a single reactor unit.
- a seventh aspect of the present disclosure may include the sixth aspect, wherein the desulfurization unit has an operating temperature at least 100° C. less than the operating temperature of the diesel autothermal reforming unit.
- An eighth aspect of the present disclosure may include either the sixth or seventh aspects, wherein the diesel reformate comprises syngas.
- a ninth aspect of the present disclosure may include any of the sixth through eighth aspects, wherein the operating temperature range of the diesel autothermal reforming unit is from 750 to 850° C.
- a tenth aspect of the present disclosure may include any of the sixth through ninth aspects, wherein the operating temperature range of the desulfurization unit is from 300 to 500° C.
- An eleventh aspect of the present disclosure may include any of the sixth through tenth aspects, wherein the SCR is from 2 to 3.
- a twelfth aspect of the present disclosure may include any of the sixth through eleventh aspects, wherein the OCR is from 0.6 to 0.8.
- a thirteenth aspect of the present disclosure may include any of the sixth through twelfth aspects, wherein the diesel autothermal reforming unit comprises a noble metal catalyst.
- a fourteenth aspect of the present disclosure may include any of the sixth through thirteenth aspects, wherein the diesel post-reforming unit comprises a noble metal catalyst, a transition metal catalyst, or combinations thereof.
- a fifteenth aspect of the present disclosure may include any of the sixth through fourteenth aspects, wherein the desulfurization unit comprises a ZnO catalyst.
- a sixteenth aspect of the present disclosure may include any of the sixth through fifteenth aspects, wherein the diesel autothermal reforming unit, the post-reforming unit, the heat exchanger, and the desulfurization unit are incorporated into a single reactor unit.
- compositional ranges of a chemical constituent in a composition or formulation should be appreciated as containing, in one or more embodiments, a mixture of isomers of that constituent. It should be appreciated that the examples supply compositional ranges for various compositions, and that the total amount of isomers of a particular chemical composition can constitute a range.
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Abstract
Description
- This application is a divisional of U.S. patent application Ser. No. 16/908,977, filed on Jun. 23, 2020, and entitled “Diesel Reforming Apparatus Having a Heat Exchanger for Higher Efficiency Steam Reforming For Solid Oxide Fuel Cells (SOFC)”, the entire contents of which are incorporated by reference in the present disclosure.
- Embodiments of the present disclosure generally relate to diesel reforming systems and specifically relate diesel reforming systems having improved efficiency for coupling with Solid Oxide Fuel Cells (SOFC).
- Fuel cells are power generation systems that convert the chemical reaction energy of hydrogen and oxidant contained in hydrocarbon-based materials such as hydrogen, methanol, and ethanol into direct electrical energy.
- Since a fuel cell uses hydrogen as a fuel, the hydrogen for the fuel cell can be obtained through steam reforming from a hydrocarbon-based fuel such as methane, methanol, natural gas, gasoline and diesel. Such a fuel reformer can be classified into steam reforming, partial oxidation reforming and autothermal reforming according to a reforming method.
- Steam reformers are suitable for fuels with a high hydrogen content in the reformed gas and short carbon chains such as methane and natural gas. In addition, the steam reforming reaction is suitable for an SOFC system having a high operating temperature because the reformed gas contains a high temperature. However, the steam reformer consumes a large amount of heat to generate steam. There is a problem that the structure for heat recovery is complicated due to the heat consumption due to the endothermic reaction and that the manufacturing difficulty and the manufacturing cost of the reactor are increased due to these reasons.
- Accordingly, there is a continual need for diesel reformers using diesel fuel, which yields improved system efficiency.
- Embodiments of the present disclosure meet this need by efficiently controlling the arrangement conditions of the apparatus with constrained heat exchanger setup. The present diesel reformer embodiments provides efficient production of hydrogen by reforming diesel fuel supplied with a diesel autothermal reforming unit, a post-reforming unit disposed downstream of the autothermal reforming unit, a heat exchanger disposed downstream of the post-reforming unit, and a desulfurization unit. Without being bound by theory, this sequential arrangement of system components in conjunction with temperature control and feed control maximizes reforming efficiency, which is highly desirable when coupling the diesel reformer to an SOFC system.
- According to one embodiment of the present disclosure, a diesel reformer system comprising a diesel autothermal reforming unit; a post-reforming unit disposed downstream of the autothermal reforming unit; a heat exchanger disposed downstream of the post-reforming unit; and a desulfurization unit disposed downstream of the heat exchanger.
- According to another embodiment, a method of diesel reforming is provided. The method comprises: introducing one or more feed streams to a diesel autothermal reforming unit to at least partially convert the one or more feed streams to a diesel reformate, wherein the one or more feed streams comprising diesel fuel, air, and steam. The one or more feed streams comprise: a Steam to Carbon Ratio (SCR) greater than 1, wherein SCR=Steam feed/total Carbon in diesel fuel feed, and an Oxygen to Carbon Ratio (OCR) less than 1, wherein OCR=O2 input from air feed/total Carbon in diesel fuel feed. The method also includes introducing the diesel reformate to a post-reforming unit disposed downstream of the diesel autothermal reforming unit, wherein the post-reforming unit selectively decomposes low carbon (C2-C5) hydrocarbons in the diesel reformate into hydrogen and methane. Moreover, the method includes passing post-reforming unit diesel reformate through a heat exchanger disposed downstream of the post-reforming unit and into a desulfurization unit disposed downstream of the heat exchanger, wherein the desulfurization unit removes sulfur compounds from the post-reforming unit diesel reformate.
- Additional features and advantages of the described embodiments will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the described embodiments, including the detailed description which follows and the claims.
- The following detailed description of specific embodiments of the present disclosure can be best understood when read in conjunction with the following drawing in which:
-
FIG. 1 is a schematic illustration of a diesel reforming system according to one or more embodiments of the present disclosure. - Reference will now be made in detail to various embodiments, some embodiments of which are illustrated in the accompanying drawings.
- Embodiments of the present disclosure are directed to a diesel reformer system and a method of diesel reforming. Referring to
FIG. 1 , a diesel reformer system 1 is provided. The diesel reformer system 1 comprises a dieselautothermal reforming unit 120, apost-reforming unit 130 disposed downstream of theautothermal reforming unit 120, aheat exchanger 135 disposed downstream of thepost-reforming unit 130, and adesulfurization unit 140 disposed downstream of theheat exchanger 135. In one embodiment as depicted inFIG. 1 , the dieselautothermal reforming unit 120, thepost-reforming unit 130, theheat exchanger 135, and the desulfurizati onunit 140 are incorporated into a single reactor unit. - In operation, the diesel reforming system 1 may conduct the following diesel reforming method as shown in
FIG. 1 . As shown inFIG. 1 , the method may include introducing one or more feed streams to a dieselautothermal reforming unit 120 to at least partially convert the one or more feed streams to adiesel reformate 64. The feed streams may comprisediesel fuel 14,air 26, andsteam 48. Thediesel fuel 14 feed may be pumped from adiesel tank 10 by a pump 12. - The temperature of the feed streams may be from 10° C. to 50° C., or from 20° C. to 50° C., or from 20° C. to 40° C., or about 25° C. The pressure of the feed streams may be from 0.5 atm to 2 atm, or from 0.5 atm to 1.5 atm, or about 1 atm. In some embodiments, the diesel fuel at the
diesel tank 10 may be stored at room condition, about 25° C. and about 1 atm. - Similarly, the
air 26 feed may be delivered from anair tank 20 byblower 22. As shown inFIG. 1 , thediesel fuel 14 andair 26 feeds may be mixed upstream of the dieselautothermal reformer unit 120 at amixing station 150. Themixing station 150 may include a flow nozzle, which is utilized to pass themixture 54 of diesel fuel and air to the reactor unit. In the embodiment ofFIG. 1 , themixture 54 of diesel fuel and air may be fed upstream of apreheater 122. - The
preheater 122 may be disposed at the top of the dieselautothermal reformer unit 120. In some embodiments, thepreheater 122 may be a heating coil. Thepreheater 122, which may be used during the initial heat-up of the reforming catalyst with theair feed 26, may heat the reforming catalyst in the dieselautothermal reformer unit 120 to a temperature of up to 300° C., or from 200° C. to 300° C., or from 250° C. to 300° C. Thepreheater 122 may heat theair feed 26 to a temperature of up to 450° C., or from 350° C. to 450° C., or from 400° C. to 450° C. In some embodiments, thepreheater 122 will not heat themixture 54 of diesel fuel and air. Thediesel fuel 14 will not be supplied during the heating of the reforming catalyst. - For the
steam feed 48, it is contemplated that water is pumped fromwater tank 30 viapump 32 and is then converted into steam byheat exchanger 40. As shown in the embodiment ofFIG. 1 , thesteam feed 48 is delivered downstream ofpreheater 122. Thesteam feed 48 may be heated up to 150° C. In further embodiments, theheat exchanger 40 may heat thesteam feed 48 from 100° C. to 150° C., or from 110° C. to 150° C., or from 120° C. to 150° C. - Various feed amounts are contemplated for the diesel reforming system 1 of
FIG. 1 . In one embodiment, the diesel reforming system 1 may have a Steam to Carbon Ratio (SCR) greater than 1, wherein SCR=Steam feed/total Carbon in diesel fuel feed. Furthermore, the diesel reforming system 1 may have an Oxygen to Carbon Ratio (OCR) less than 1, wherein OCR=O2 input from air feed/total Carbon in diesel fuel feed. In further embodiments, the SCR is from 1.5 to 4, or from 2 to 3. In further embodiments, the OCR is from 0.5 to 0.9, or from 0.6 to 0.8. Without being bound by theory, the present diesel reforming system 1 in combination with these OCR and SCR ranges have been surprisingly found to yield improved system efficiency. - The diesel autothermal reforming
unit 120 utilizes high pressure and high temperature operating conditions. For example, the dieselautothermal reforming unit 120 may have an operating temperature of at least 700° C., or from 750 to 1100° C., or from 750 to 850° C. Moreover, the dieselautothermal reforming unit 120 may have an operating pressure of at least 0.5 bar, or from 0.5 to 1.5 bars, or from 1.0 to 1.5 bars, or about 1 bar at atmospheric condition. - The
diesel reformate 64 comprises various components, including syngas (i.e., hydrogen and carbon monoxide). The steam reforming reaction conducted by the diesel autothermal reformingunit 120 is as follows: -
4CH4+O2+2H2O→10H2+4CO -
CnHm +aO2+(2n−2a)H2O→(2n−2a+(m/2))H2 +nCO2 (each n, m, and a is natural number) - The conversion of the methane to syngas in the diesel
autothermal reforming unit 120 may be from 95% to 100%, or from 96% to 100%, or from 97% to 100% or from 98% to 100%, or from 99% to 100%, or from 99.5% to 100%, or from 99.9% to 100%, or about 100%. - Referring again to
FIG. 1 , thediesel reformate 64 is introduced to apost-reforming unit 130 disposed downstream of the dieselautothermal reforming unit 120. Here, thepost-reforming unit 130 selectively decomposes low carbon (C2-C5) hydrocarbons in thediesel reformate 64 into a post-reforming unitdiesel reformate stream 74 comprising hydrogen and methane. In detail, by the post-reforming catalyst, the low carbon hydrocarbon material (C2-C5) in thediesel reformate 64 is reacted with hydrogen and vapor contained in thediesel reformate 64 to be selectively decomposed into hydrogen and methane. - The inlet of the
post-reforming unit 130 utilizes high temperature and high pressure operating conditions. For example, the inlet of thepost-reforming unit 130 may have an operating temperature range of from 650° C. to 850° C., or from 650° C. to 800° C., or from 700° C. to 850° C., or from 700° C. to 800° C., or about 750° C. Moreover, the inlet of thepost-reforming unit 130 may have an operating pressure of at least 0.5 bar, or from 0.5 to 1.5 bars, or from 1.0 to 1.5 bars, or about 1 bar at atmospheric condition. - The outlet of the
post-reforming unit 130 utilizes high temperature and high pressure operating conditions. For example, the outlet of thepost-reforming unit 130 may have an operating temperature range of from 450° C. to 800° C., or from 450° C. to 750° C., or from 450° C. to 700° C., or from 450° C. to 650° C., or from 450° C. to 600° C., or from 500° C. to 800° C., or from 500° C. to 750° C., or from 500° C. to 700° C., or from 500° C. to 650° C., or from 500° C. to 600° C., or from 550° C. to 800° C., or from 550° C. to 750° C., or from 550° C. to 700° C., or from 550° C. to 650° C., or from 550° C. to 600° C. Moreover, the outlet of the post-reformer 120 may have an operating pressure of at least 0.5 bar, or from 0.5 to 1.5 bars, or from 1.0 to 1.5 bars, or about 1 bar at atmospheric condition. - Next, the post-reforming
unit diesel reformate 74 is passed through aheat exchanger 135 disposed downstream of thepost-reforming unit 130. Without being bound by theory, the heat transfer amount of theheat exchanger 135 is optimized to make higher system efficiency by controlling the heat transfer amount (UA). The heat transfer amount (UA) is equal to (U), the heat transfer coefficient multiplied by (A) the heat transfer surface area. The heat transfer amount (UA) may be from 0.75 watts per kelvin (W/K) to 4.0 W/K, from 0.75 W/K to 3.5 W/K, from 0.75 W/K to 3.0 W/K, from 0.8 W/K to 4.0 W/K, from 0.8 W/K to 3.5 W/K, from 0.8 W/K to 3.0 W/K, 1.0 W/K to 4.0 W/K, from 1.0 W/K to 3.5 W/K, from 1.0 W/K to 3.0 W/K, from 0.75 W/K to 1.50 W/K, or from 0.80 W/K to 1.50 W/K, from 0.90 W/K to 1.50 W/K, from 1.00 W/K to 1.50 W/K, from 0.75 W/K to 1.40 W/K, from 0.80 W/K to 1.40 W/K, from 0.90 W/K to 1.40 W/K, from 1.00 W/K to 1.40 W/K, from 0.75 W/K to 1.30 W/K, from 0.80 W/K to 1.30 W/K, from 0.90 W/K to 1.30 W/K, from 1.00 W/K to 1.30 W/K, or about 1.25 W/K. In some embodiments, the heat transfer coefficient (U) may be from 6.0 to 8.5, from 6.5 to 8.5, from 7.0 to 8.5, from 7.5 to 8.5, from 8.0 to 8.5, or about 8.5. - The heated post-reforming
unit diesel reformate 84 is delivered into adesulfurization unit 140 disposed downstream of theheat exchanger 135, wherein the desulfurization unit removes sulfur compounds from the heated post-reformingunit diesel reformate 84. - In some embodiments, the sulfur content of the heated post-reforming
unit diesel reformate 84 may be equal or less than 10 ppm. The sulfur content of the heated post-reformingunit diesel reformate 84 may be equal or less than 9 ppm, or 8 ppm, or 7 ppm, or 6 ppm. The sulfur content of the desulfurizedproduct 94 may be from 5 ppm to 10 ppm, or from 6 ppm to 10 ppm, or from 7 ppm to 10 ppm, or from 8 ppm to 10 ppm, from 5 ppm to 9 ppm, or from 6 ppm to 9 ppm, or from 7 ppm to 9 ppm, or from 5 ppm to 8 ppm from 5 ppm to 7 ppm, or from 6 ppm to 8 ppm. - At which point, the desulfurized
product 94, which is hydrogen rich, may be fed for use in an SOFC reactor or stack. Thedesulfurization unit 140 utilizes less severe operating conditions than the dieselautothermal reforming unit 120. In one embodiment, the desulfurization unit has an operating temperature at least 100° C. less than the operating temperature of the dieselautothermal reforming unit 120. In another embodiment, the operating temperature range of the desulfurization unit is from 300 to 500° C. - In some embodiments, the sulfur content of the desulfurized
product 94 may be equal or less than 0.05 ppm. The sulfur content of the desulfurizedproduct 94 may be equal or less than 0.04 ppm, or 0.03 ppm, or 0.02 ppm, or 0.01 ppm. The sulfur content of the desulfurizedproduct 94 may be from 0.001 ppm to 0.05 ppm, or from 0.01 ppm to 0.05 ppm, or from 0.001 ppm to 0.03 ppm, or from 0.01 ppm to 0.03 ppm. Table 1 shows an example composition of the desulfurizedproduct 94. -
TABLE 1 Components H2 CO2 CO N2 CH4 H2O Sulfur content Composition 19.6% 10.6% 6.33% 39.0% 0.22% 24.2% less than 0.01 ppm - Turning now to more details on the system units depicted in
FIG. 1 , the dieselautothermal reforming unit 120 comprises a noble metal catalyst. Various catalysts suitable for performing the autothermal reforming reactions among the supplied fuel, water and air are contemplated herein. The noble metal catalyst may include Pt, Rh, Ru and a mixture thereof. The catalysts may be supported or unsupported. In supported catalyst embodiments, the catalyst support may comprise alumina, silica, ceria, or combinations thereof. While various amounts of noble metal catalyst are considered suitable, the amount of the noble metal catalyst may be controlled according to a kind of hydrocarbon-based fuel to be reformed, an amount of the supplied fuel and the like. - Various structural embodiments are contemplated for the diesel
autothermal reforming unit 120. The internal and external partition walls of the diesel autothermal reforming unit may be formed of any material having high durability at a high temperature (about 800° C.) and an excellent heat transfer efficiency. For example, the internal and external partition walls can be substantially formed of stainless steel. In another embodiment, the diesel autothermal reforming unit comprises a porous support (including a support having through-pores along a fluid conveying direction) through which the fluid is passed and which impregnates the noble metal catalyst. - In one or more embodiments, the
post-reforming unit 130 comprises a post-reforming catalyst formed of a transition metal, a noble metal, or a mixture thereof. In one or more embodiments, the transition metal of the post-reforming catalyst includes Ni, Mg and a mixture thereof, and the noble metal thereof includes Pt, Rh, Pd, Ru and a mixture thereof. Like the diesel autothermal reforming catalysts, the post-reforming catalysts may be supported or unsupported. In supported catalyst embodiments, the catalyst support may comprise alumina, silica, ceria, or combinations thereof. - Like the diesel
autothermal reforming unit 120, thepost-reforming unit 130 can be formed of a porous support (including a support having through-pores along a fluid conveying direction) through which the fluid is passed and which impregnates the post-reforming catalyst - Like the diesel
autothermal reforming unit 120, thedesulfurizer 140 may be formed of a porous support (including a support having through-pores along a fluid conveying direction) through which the fluid is passed and which impregnates the desulfurizing catalyst. In one embodiment, thedesulfurization unit 140 comprises a ZnO catalyst. - The following examples illustrate one or more additional features of the present disclosure. It should be understood that these examples are not intended to limit the scope of the disclosure or the appended claims in any manner.
- Experimental simulations of embodiments similar to
FIG. 1 were performed using the process simulator Aspen Plus™ from Aspen Technology, Inc. The following specific process features were used in the simulation: (1) Diesel fuel was modeled with 80 mol % n-dodecane and 20 mol % 1-methyl-naphthalene; (2) Fuel input was determined as reformate produces 1 kWe of electricity with operating voltage of Solid Oxide Fuel Cell (SOFC)=0.7 V, and fuel utilisation=75%; (3) the diesel autothermal reforming unit and post reforming unit reach thermodynamic equilibriums; (4) Heat loss after diesel autothermal reforming is simulated with a cooler (20 W); and (5) the heat exchanger is counter-current type. -
TABLE 2 Example Example 1 Example 2 Post-Reformer Outlet Temperature (° C.) 702 741 Heat Exchanger Steam Outlet Temperature (° C.) 345 216 Heat Exchanger Outlet/Desulfurizer Input Feed 138 302 Temperature (° C.) UA Value of Heat Exchanger (W/K) 4.77 1.25 - As shown in Table 2, the Example 1 system and heat exchanger operated sub-optimally. The UA value of the heat exchanger was 4.77 W/K and the desulfurization input feed temperature was 138° C. Conversely, the Example 2 system operated with a heat exchanger UA value of 1.25 W/K, which was almost ¼ of Example 1. This was achieved in part through an OCR of 0.73 and an SCR of 2.2, which helped result in a desulfurization input temperature of 302° C.
- A first aspect of the present disclosure is directed to a diesel reformer system comprising a diesel autothermal reforming unit; a post-reforming unit disposed downstream of the autothermal reforming unit; a heat exchanger disposed downstream of the post-reforming unit; and a desulfurization unit disposed downstream of the heat exchanger.
- A second aspect of the present disclosure may include the first aspect, wherein the diesel autothermal reforming unit comprises a noble metal catalyst.
- A third aspect of the present disclosure may include either of the first or second aspects, wherein the diesel post-reforming unit comprises a noble metal catalyst, a transition metal catalyst, or combinations thereof.
- A fourth aspect of the present disclosure may include any of the first through third aspects, wherein the desulfurization unit comprises a ZnO catalyst.
- A fifth aspect of the present disclosure may include any of the first through fourth aspects, wherein the diesel autothermal reforming unit, the post-reforming unit, the heat exchanger, and the desulfurization unit are incorporated into a single reactor unit.
- A sixth aspect of the present disclosure is directed to a method of diesel reforming comprising introducing one or more feed streams to a diesel autothermal reforming unit to at least partially convert the one or more feed streams to a diesel reformate, wherein the one or more feed streams comprising diesel fuel, air, and steam, and wherein the one or more feed streams comprise: a Steam to Carbon Ratio (SCR) greater than 1, wherein SCR=Steam feed/total Carbon in diesel fuel feed, and an Oxygen to Carbon Ratio (OCR) less than 1, wherein OCR=O2 input from air feed/total Carbon in diesel fuel feed; introducing the diesel reformate to a post-reforming unit disposed downstream of the diesel autothermal reforming unit, wherein the post-reforming unit selectively decomposes low carbon (C2-C5) hydrocarbons in the diesel reformate into hydrogen and methane; and passing post-reforming unit diesel reformate through a heat exchanger disposed downstream of the post-reforming unit and into a desulfurization unit disposed downstream of the heat exchanger, wherein the desulfurization unit removes sulfur compounds from the post-reforming unit diesel reformate.
- A seventh aspect of the present disclosure may include the sixth aspect, wherein the desulfurization unit has an operating temperature at least 100° C. less than the operating temperature of the diesel autothermal reforming unit.
- An eighth aspect of the present disclosure may include either the sixth or seventh aspects, wherein the diesel reformate comprises syngas.
- A ninth aspect of the present disclosure may include any of the sixth through eighth aspects, wherein the operating temperature range of the diesel autothermal reforming unit is from 750 to 850° C.
- A tenth aspect of the present disclosure may include any of the sixth through ninth aspects, wherein the operating temperature range of the desulfurization unit is from 300 to 500° C.
- An eleventh aspect of the present disclosure may include any of the sixth through tenth aspects, wherein the SCR is from 2 to 3.
- A twelfth aspect of the present disclosure may include any of the sixth through eleventh aspects, wherein the OCR is from 0.6 to 0.8.
- A thirteenth aspect of the present disclosure may include any of the sixth through twelfth aspects, wherein the diesel autothermal reforming unit comprises a noble metal catalyst.
- A fourteenth aspect of the present disclosure may include any of the sixth through thirteenth aspects, wherein the diesel post-reforming unit comprises a noble metal catalyst, a transition metal catalyst, or combinations thereof.
- A fifteenth aspect of the present disclosure may include any of the sixth through fourteenth aspects, wherein the desulfurization unit comprises a ZnO catalyst.
- A sixteenth aspect of the present disclosure may include any of the sixth through fifteenth aspects, wherein the diesel autothermal reforming unit, the post-reforming unit, the heat exchanger, and the desulfurization unit are incorporated into a single reactor unit.
- It should be understood that any two quantitative values assigned to a property may constitute a range of that property, and all combinations of ranges formed from all stated quantitative values of a given property are contemplated in this disclosure. It should be appreciated that compositional ranges of a chemical constituent in a composition or formulation should be appreciated as containing, in one or more embodiments, a mixture of isomers of that constituent. It should be appreciated that the examples supply compositional ranges for various compositions, and that the total amount of isomers of a particular chemical composition can constitute a range.
- It is noted that one or more of the following claims utilize the term “where” as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term “comprising.”
- Having described the subject matter of the present disclosure in detail and by reference to specific embodiments, it is noted that the various details described in this disclosure should not be taken to imply that these details relate to elements that are essential components of the various embodiments described in this disclosure, even in cases where a particular element is illustrated in each of the drawings that accompany the present description. Rather, the claims appended should be taken as the sole representation of the breadth of the present disclosure and the corresponding scope of the various embodiments described in this disclosure. Further, it should be apparent to those skilled in the art that various modifications and variations can be made to the described embodiments without departing from the spirit and scope of the claimed subject matter. Thus it is intended that the specification cover the modifications and variations of the various described embodiments provided such modification and variations come within the scope of the appended claims and their equivalents.
Claims (5)
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US18/117,160 US20230201791A1 (en) | 2020-06-23 | 2023-03-03 | Diesel reforming apparatus having a heat exchanger for higher efficiency steam reforming for solid oxide fuel cells (sofc) |
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US18/117,160 Pending US20230201791A1 (en) | 2020-06-23 | 2023-03-03 | Diesel reforming apparatus having a heat exchanger for higher efficiency steam reforming for solid oxide fuel cells (sofc) |
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US20210394151A1 (en) | 2021-12-23 |
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