DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Priority
Receipt is acknowledged of certified copies of papers required by 37 CFR 1.55.
Information Disclosure Statement
The information disclosure statement (IDS) submitted on 06/13/2024 has been considered by the examiner.
Election/Restrictions
Claims 1-7, 19-25 withdrawn from further consideration pursuant to 37 CFR 1.142(b), as being drawn to a nonelected invention, there being no allowable generic or linking claim. Applicant timely traversed the restriction (election) requirement in the reply filed on 12/09/2025.
Applicant's election with traverse of claims 8-18 in the reply filed on 12/09/2025 is acknowledged. The traversal is on the ground(s) that the proposed combination of the cited references Genkin and Quirino is not one that those of ordinary skill in the art would have been motivated to make since the methane steam reforming unit disclosed by Quirino has a different role and operates at different temperatures than the pre-reformer disclosed by Genkin.
This is not found persuasive because the methane steam reforming unit disclosed by Quirino heats the reforming tubes by both convection and radiation, which makes the heat transfer more effective. This increased efficiency would be the case at any operating temperature and with any reactants, and would thus motivate one of ordinary skill in the art to modify the pre-reformer of Genkin to the unit disclosed by Quirino.
The requirement is still deemed proper and is therefore made FINAL.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claim 8 rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Claim 8 recites the limitation "the shell-side" in line 4. There is insufficient antecedent basis for this limitation in the claim.
Claim Rejections - 35 USC § 103
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claims 8-18 are rejected under 35 U.S.C. 103 as being unpatentable over Genkin et al (US 20130243686 A1) in view of Quirino et al ("Modeling and Simulation of an Industrial Top-Fired Methane Steam Reforming Unit) and Ravikumar (US 20220267147 A1).
Regarding claim 8, Genkin discloses a process for producing hydrogen ([0068] meeting limitation “A process for the production of hydrogen”). The process comprises introducing reactants comprising steam and a hydrocarbon feed 47 into reactor 10, reacting the reactants in the presence of a reforming catalyst... and withdrawing the reformate from reactor 10 ([0069] meeting limitation “feeding a mixture of hydrocarbon and steam” and “to produce a crude synthesis gas”). The steam and hydrocarbon feed may be mixed and introduced together into the reactor 10 as a so-called mixed feed ([0070]). The process further comprises introducing oxygen-containing stream 22 and the reformate from reactor 10 into reactor 20, reacting the oxygen from the oxygen-containing stream and the reformate in the presence of a second reforming catalyst ([0077] meeting limitation “feeding the crude synthesis gas from the… reformer to an autothermal reformer along with an oxygen-containing gas to produce a reformed synthesis gas”). Reactor 20 is a reformer often called an "autothermal reformer" ([0080]).
Reformate from reactor 20 that has been cooled in heat recovery train 50 is passed to water-gas shift reactor 60 to shift the reformate and form additional H₂ ([0092] meeting limitation “feeding the reformed synthesis gas to a water-gas shift unit to produce a hydrogen- enriched gas”). The process further comprises recovering heat from the shifted reformate thereby cooling the shifted reformate ([0098]). The process further comprises removing H2O from the shifted reformate to form a water-depleted reformate ([0101]). The process further comprises separating the water-depleted reformatted into a CO₂ product stream and a pressure swing adsorber feed stream ([0103] meeting limitation “feeding the hydrogen-enriched gas to a carbon dioxide removal unit and separating the hydrogen-enriched gas into a crude hydrogen stream and a carbon dioxide stream”). The pressure swing adsorber feed stream is passed to pressure swing adsorption beds 100, i.e. purification unit, where the stream is separated into H₂ product stream 102 and pressure swing adsorption tail gas stream 104 i.e. off-gas ([0111] meeting limitation “feeding the crude hydrogen stream to a purification unit and separating the crude hydrogen stream into a hydrogen product stream and an off-gas stream”).
While Genkin discloses forming a reformate in reactor 10, Genkin does not disclose “a fired reformer containing a plurality of catalyst-containing reformer tubes”, “feeding a fuel to the shell-side of the fired reformer to provide heat for the steam reforming reactions taking place in the catalyst-containing reformer tubes” or “feeding a portion of the crude hydrogen stream and/or a portion of hydrogen product stream as fuel to the shell-side of the fired reformer”.
Quirino discloses an MSRU (methane steam reforming unit) composed of 72 CFTs (catalyst-filled tubes) which are fed by a mixture of the natural gas, steam and CO₂, producing the reformed gas (Pg. 11252 left column par. 2). The combustion in the 21 burners located at the top of the furnace provides heat (Pg. 11252 left column par. 2). The heat is distributed by convention and radiation mechanisms to the reforming tubes and to the refractory surface (Pg. 11252 left column par. 2). Figure 1 illustrates:
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The catalytic tube is fed natural gas and steam and reformed gas exits at the outlet meeting limitation “feeding a mixture of hydrocarbon and steam to a fired reformer containing a plurality of catalyst-containing reformer tubes to produce a crude synthesis gas”. Combustion air and fuel are fed to the burner and combustion gas is produced meeting limitation “feeding a fuel to the shell-side of the fired reformer to provide heat for the steam reforming reactions taking place in the catalyst-containing reformer tubes”.
Thus, prior to the effective filing date of the claimed invention it would have been obvious to one of ordinary skill in the art to use a fired reformer containing a plurality of catalyst-containing reformer tubes and feeding a fuel to the shell-side of the fired reformer to provide heat for the steam reforming reactions taking place in the catalyst-containing reformer tubes in the method of Genkin in order for the reformer to heat the reforming tubes by both convection and radiation, which makes the heat transfer more effective as taught by Quirino.
Ravikumar discloses a process for reforming for producing hydrogen and generating electricity, comprising: introducing a feed comprising a hydrocarbon stream to a reformer to produce unshifted synthesis gas; introducing the unshifted syngas to a water gas shift unit to produce a shifted syngas; removing CO2 from the shifted syngas to produce a FO2 depleted syngas and a CO2 product; introducing the CO2 depleted syngas to a pressure swing adsorption unit to produce a hydrogen product and an off-gas (abstract). The processes and systems … use a hydrogen enriched recycle stream that is derived from i) combining a portion of the off-gas from pressure swing adsorption of the shifted syngas and a portion of the hydrogen product from pressure swing adsorption… for use as fuel for combustion in a steam methane reformer ([0016]). This fuel which is enriched in hydrogen, and thus uses more hydrogen for combustion in the steam methane reformer, replaces amounts of natural gas fuel that would otherwise create carbon dioxide upon combustion ([0016]). A vessel for the steam methane reformer 110 can contain one or more tubes loaded with catalyst, where the interior of the tubes is the reaction side of the steam methane reformer 110, and each tube is fluidly connected with streams 1, 2, and 11; while, the outer surface of the tubes is considered to be on the heating side of the steam methane reformer 110 and is subjected to heat generated from combustion of a fuel that is fed to and combusted on the heating side of the steam methane reformer 110 ([0043]).
Using the hydrogen enriched recycle stream as fuel in place of a hydrocarbon fuel reduces the amount of carbon dioxide generated due to fuel combustion because a smaller amount of hydrocarbon fuel is used ([0018]). Combustion of hydrogen produces no carbon dioxide; thus, the flue gas that flows from the steam methane reformer contains less carbon dioxide (compared with using hydrocarbon-based fuels) ([0018]).
Thus, prior to the effective filing date of the claimed invention it would have been obvious to one of ordinary skill in the art to feed a portion of the hydrogen product stream as fuel to the shell-side of the fired reformer in the method of Genkin in order to reduce the amount of carbon dioxide generated by the process as taught by Ravikumar.
Regarding claim 9, Genkin in view of Quirino and Ravikumar discloses all the limitations in the claims as set forth above and Genkin further discloses Fig. 1:
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Where introducing reactants comprising steam and a hydrocarbon feed 47 into reactor 10, reacting the reactants in the presence of a reforming catalyst under reaction conditions sufficient to form a reformate comprising H2, CO, and unreacted hydrocarbon feed and steam, and withdrawing the reformate from reactor 10 ([0069] meeting limitation “a… reformer… operable to produce a crude synthesis gas from a feed stream containing a hydrocarbon and steam”).
The process further comprises introducing oxygen containing stream 22 and the reformate from reactor 10 into reactor 20, reacting the oxygen from the oxygen-containing stream and the reformate in the presence of a second reforming catalyst under reaction conditions sufficient to form additional H2 and CO in the reformate ([0079]). Reactor 20 is a reformer often called an “autothermal reformer” abbreviated “ATR” ([0080] meeting limitation “an autothermal reformer arranged to be fed with an oxygen-containing gas and a crude synthesis gas from the fired reformer, operable to produce a reformed synthesis gas”).
Reformate from reactor 20 that has been cooled in heat recovery train 50 is passed to water-gas shift reactor 60 to shift the reformate and form additional H2 ([0092] meeting limitation “a water-gas shift unit arranged to be fed with a reformed synthesis gas recovered from the autothermal reformer, operable to produce a hydrogen-enriched gas”).
The water-depleted reformate is passed from vapor-liquid separator 80 to CO2 removal system 90 where a CO2 product stream 92 is removed and a pressure swing adsorber feed stream is passed to pressure swing adsorption beds 100 ([0104] meeting limitation “a carbon dioxide removal unit arranged to be fed with a hydrogen-enriched gas from the water-gas shift unit, operable to produce a crude hydrogen stream and a carbon dioxide stream”).
The pressure swing adsorber feed stream is passed to pressure swing adsorption beds 100 where the stream is separated into H2 product stream 102 and pressure swing adsorption tail gas stream 104 ([0111] meeting limitation “a purification unit arranged to be fed with a crude hydrogen stream gas from the carbon dioxide removal unit, operable to produce a hydrogen product stream and an off-gas stream”).
While Genkin discloses forming a reformate in reactor 10, Genkin does not disclose “a fired reformer containing a plurality of catalyst-containing reformer tubes and having a shell side to which fuel is fed” and “wherein the plant is arranged such that a portion of the crude hydrogen stream from the carbon dioxide removal unit and/or a portion of hydrogen product stream from the purification unit is fed as a fuel to a shell-side of the fired reformer”.
Quirino discloses an MSRU (methane steam reforming unit) composed of 72 CFTs (catalyst-filled tubes) which are fed by a mixture of the natural gas, steam and CO₂, producing the reformed gas (Pg. 11252 left column par. 2). The combustion in the 21 burners located at the top of the furnace provides heat (Pg. 11252 left column par. 2). The heat is distributed by convention and radiation mechanisms to the reforming tubes and to the refractory surface (Pg. 11252 left column par. 2).
Thus, prior to the effective filing date of the claimed invention it would have been obvious to one of ordinary skill in the art to use a fired reformer containing a plurality of catalyst-containing reformer tubes and having a shell side to which fuel is fed in the method of Genkin in order for the reformer to heat the reforming tubes by both convection and radiation, which makes the heat transfer more effective as taught by Quirino.
Ravikumar discloses the processes and systems … use a hydrogen enriched recycle stream that is derived from i) combining a portion of the off-gas from pressure swing adsorption of the shifted syngas and a portion of the hydrogen product from pressure swing adsorption… for use as fuel for combustion in a steam methane reformer ([0016]). This fuel which is enriched in hydrogen, and thus uses more hydrogen for combustion in the steam methane reformer, replaces amounts of natural gas fuel that would otherwise create carbon dioxide upon combustion ([0016]).
Using the hydrogen enriched recycle stream as fuel in place of a hydrocarbon fuel reduces the amount of carbon dioxide generated due to fuel combustion because a smaller amount of hydrocarbon fuel is used ([0018]). Combustion of hydrogen produces no carbon dioxide; thus, the flue gas that flows from the steam methane reformer contains less carbon dioxide (compared with using hydrocarbon-based fuels) ([0018]).
Thus, prior to the effective filing date of the claimed invention it would have been obvious to one of ordinary skill in the art for the plant to be arranged such that a portion of the hydrogen product stream from the purification unit to be fed as a fuel to a shell-side of the fired reformer in the method of Genkin in order to reduce the amount of carbon dioxide generated by the process as taught by Ravikumar.
Regarding claims 10 and 11, Genkin in view of Quirino and Ravikumar discloses all the limitations in the claims as set forth above and Genkin further discloses the hydrocarbon feed may be formed from any suitable hydrocarbon feedstock known for producing hydrogen, for example, natural gas ([0071]).
Regarding claim 12, Genkin in view of Quirino and Ravikumar discloses all the limitations in the claims as set forth above and Ravikumar further discloses in an embodiment, a molar ratio of steam to methane in the total feed streams to the steam methane reformer can be … from about 3.0:1 to about 3.5:1, for a sulfur sensitive nickel-based catalyst in the steam methane reformer. 3.0:1 to about 3.5:1 is within the claimed range of 1.5-3.5 moles of steam per mole of hydrocarbon carbon.
Thus, prior to the effective filing date of the claimed invention it would have been obvious to one of ordinary skill in the art for the mixture of hydrocarbon and steam fed to the fired reformer to have a ratio of 1.5 to 3.5 moles of steam per mole of hydrocarbon carbon in the method of Genkin when using a sulfur sensitive nickel-based catalyst as taught by Ravikumar.
Regarding claim 13 and 14, Genkin in view of Quirino and Ravikumar discloses all the limitations in the claims as set forth above and Ravikumar further discloses the amount of hydrogen in the steam methane reformer fuel that is fed to the steam methane reformer 110 can be greater than 50 mol % based on a total moles of components in the fuel that is fed to the steam methane reformer 110 ({0018] and [0047]). Mole% and volume % are interpreted as effectively equivalent based on Avogadro’s Law.
As set forth in MPEP 2144.05, in the case where the claimed range “overlap or lie inside ranges disclosed by the prior art”, a prima facie case of obviousness exists, In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990). In the instant case, the range taught by Ravikumar (greater than 50 mol %) overlaps with the claimed range (at least 75% vol.). Therefore, the range in Ravikumar renders obvious the claimed range.
In the instant case, the range taught by Ravikumar (greater than 50 mol %) overlaps with the claimed range (at least 95% vol.). Therefore, the range in Ravikumar renders obvious the claimed range.
Regarding claim 15, Genkin in view of Quirino and Ravikumar discloses all the limitations in the claims as set forth above and Genkin further discloses the oxygen-containing stream 22 may be industrial grade oxygen ([0079]).
Regarding claim 16, Genkin in view of Quirino and Ravikumar discloses all the limitations in the claims as set forth above including Ravikumar discloses a process for reforming for producing hydrogen and generating electricity, comprises: introducing a feed comprising a hydrocarbon stream to a reformer to produce unshifted synthesis gas (syngas); introducing the unshifted syngas to a water gas shift unit to produce a shifted syngas; removing CO2 from the shifted syngas to produce a CO2 depleted syngas and a CO2 product; introducing the CO2 depleted syngas to a pressure swing adsorption unit to produce a hydrogen product and an off-gas (abstract). Typically a natural gas is reformed to produce hydrogen and carbon dioxide that is removed in a pre-combustion context, in that, the processes and systems separate carbon dioxide from a shifted syngas, and use a hydrogen enriched recycle stream that is derived from i) combining a portion of the off-gas from pressure swing adsorption of the shifted syngas and a portion of the hydrogen product from pressure swing adsorption… for use as fuel for combustion in a steam methane reformer ([0016]). Therefore Ravikumar discloses all of the hydrogen used as fuel in the fired reformer comes from a hydrogen enriched recycle stream. The source of hydrogen for both streams that make up the hydrogen enriched recycle stream is the reformer disclosed by Ravikumar. This is further illustrated in Fig. 1:
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A steam methane reformer 110 ([0019]) where hydrogen is produced. Splitting the hydrogen product 7 into a first hydrogen portion 7A and a second hydrogen portion 7B; and introducing the second hydrogen portion 7B to the steam methane reformer 110 ([0021]).
Thus, prior to the effective filing date of the claimed invention it would have been obvious to one of ordinary skill in the art for the autothermal reformer to be sized to provide essentially all of the hydrogen used as fuel in the fired reformer in the method of Genkin as taught by Ravikumar in order to reduce operating costs by avoiding the purchase of hydrogen gas.
Regarding claim 17, Genkin in view of Quirino and Ravikumar discloses all the limitations in the claims as set forth above and Ravikumar further discloses alternatively, the process can include sending the carbon dioxide product in the CO2 product stream 5 to storage or a pipeline for transport, for example, for use in enhanced oil recovery ([0080]).
Regarding claim 18, Genkin in view of Quirino and Ravikumar discloses all the limitations in the claims as set forth above and Genkin further discloses the process further comprises introducing a first portion 114 of the tail gas stream into at least one of reactor 10 and reactor 20 ([0112]). If the first portion is introduced into reactor 10, the first portion 114 of the tail gas stream may be mixed and introduced together with the steam and hydrocarbon feed into reactor 10 or introduced separately from the steam and hydrocarbon feed ([0112]).
Conclusion
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/N.L.Q./Examiner, Art Unit 1738
/MICHAEL FORREST/Primary Examiner, Art Unit 1738