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 .
Response to Amendment
The amendment filed on 10/15/2025 has been entered. Claims 22-24, 26-42 are pending in the application. Claim 25 is cancelled. Applicant’s amendments to the claims have overcome each objection and each 112(b) rejection previously set forth in the office action mailed 08/19/2025.
Response to Arguments
Applicant's arguments filed 10/15/2025 have been fully considered but they are not persuasive.
Applicant argues top of page 10 that because Genkin diverts a proportion of the tail gas to the feed, Genkin cannot meet the fueling duties of the process and must import natural gas or another fuel gas to the process. This implies that Genkin does not meet the claim limitation “the fuel gas is fed, as the sole fuel, to one or more fired heaters used to heat one or more process streams within the process”.
However, Genkin discloses combusting a third portion 106 of the tail gas stream, i.e. fuel gas, in a boiler 120, i.e. fired heater, to generate a portion of the steam introduced into reactor 10 ([0114]). As depicted in FIGS 1 and 2, a third portion 106 of the tail gas and an oxygen-containing stream 124 are introduced into boiler 120 where combustible gases in the third portion of the tail gas are combusted to form combustion products 122, which are withdrawn from the boiler 120 ([0114]). Steam is formed by indirect heat exchange between heated feed water 86 and the combustion products 122 ([0114] meeting limitation “used to heat one or more process streams within the process”). Steam may then be added to the hydrocarbon mixture from desulfurizer 30, as shown in FIG. 1, or added to the mixed feed from saturator 35, as shown in FIG. 2 ([0114]). Figures 1 and 2 illustrate a third portion 106 of the tail gas, i.e. fuel gas, is the sole fuel fed to the boiler.
Applicant argues in middle of page 10 Rytter suggests that instead of using the rest gas as fuel, recycling the rest gas instead to the autothermal reformer provides “maximum carbon efficiency”.
However, Rytter is not relied upon for the claim limitation of “the fuel gas is fed, as the sole fuel, to one or more fired heaters used to heat one or more process streams within the process”, Genkin is. Rytter is relied upon for teaching steam reforming in a gas-heated reformer.
Applicant argues on top of page 11 that Speth does not disclose the claimed steam to carbon ratio of 2.8:1 to 3.5:1, and one would have no motivation to turn to Speth’s ammonia-producing process.
However, this argument is moot because the new ground of rejection does not rely on the Speth reference.
Applicant argues on bottom of page 12- top of page 13 that McKenna does not disclose feeding the fuel gas, as the sole fuel, to one or more fired heaters used to heat one or more process streams within the process.
However, McKenna is not relied upon for that claim limitation, Genkin is. McKenna is relied upon for teaching the steam to carbon ratio in the range 2.8:1 to 3.5:1.
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 22-24, 26-28, 31-38, 42 are rejected under 35 U.S.C. 103 as being unpatentable over Genkin et al (US 20130243686 A1, as cited in IDS 04/12/2024), in view of McKenna et al (WO 2011/077107, as cited in IDS 11/04/2022) and Rytter et al (WO 2019162236, as cited in IDS 04/12/2024).
Regarding claim 22, Genkin discloses a process for producing hydrogen ([0068]). 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]). 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]). 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]). 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 i.e., crude hydrogen gas stream ([0103]). 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 i.e. fuel gas ([0111]). The process may further comprise combusting a third portion 106 of the tail gas stream, i.e. fuel gas, in a boiler 120, i.e. fired heater, to generate a portion of the steam introduced into reactor 10 ([0114]). As depicted in FIGS 1 and 2, a third portion 106 of the tail gas and an oxygen-containing stream 124 are introduced into boiler 120 where combustible gases in the third portion of the tail gas are combusted to form combustion products 122, which are withdrawn from the boiler 120 ([0114]). Steam is formed by indirect heat exchange between heated feed water 86 and the combustion products 122 ([0114] meeting limitation “used to heat one or more process streams within the process”). Steam may then be added to the hydrocarbon mixture from desulfurizer 30, as shown in FIG. 1, or added to the mixed feed from saturator 35, as shown in FIG. 2 ([0114]). Figures 1 and 2 illustrate a third portion 106 of the tail gas, i.e. fuel gas, is the sole fuel fed to the boiler.
Genkin is silent to “having a steam to carbon ratio in the range 2.8:1 to 3.5:1” and “steam reforming in a gas-heated reformer”
McKenna discloses a process for the conversion of a hydrocarbon to CO2 and electrical power comprising subjecting a gas mixture comprising a hydrocarbon feed stream and steam to an integrated reforming process… to generate a reformed gas mixture (abstract). The hydrocarbon stream is mixed with steam: this steam introduction may be effected by direct injection of steam and/or by saturation of the feedstock by contact of the latter with a stream of heated water (Pg. 3 lines 24-26). The amount of steam introduced may be such as to give a steam ratio of 1 to 3 moles of steam per gram atom of hydrocarbon carbon in the feedstock (Pg. 3 lines 27-28).
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 McKenna (1 to 3:1) overlaps with the claimed range (2.8 to 3.5: 1). Therefore, the range in McKenna renders obvious the claimed range.
Rytter discloses a method of producing hydrogen comprising: receiving a feed gas comprising hydrocarbons and performing reforming processes so as to generate hydrogen from the feed gas; wherein the reforming processes comprise both a gas-heated reforming process and an auto thermal reforming process and heat generated by the autothermal reforming process is supplied to the gas-heated reforming process (abstract). Rytter further discloses gas heated reforming (GHR) utilizes hot gas, e.g. off-gas from autothermal reforming, to provide heat for reforming of a feed gas (Pg. 7 lines 1-2).
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 modify the pre-reactor of Genkin to be a gas-heated reformer as taught by Rytter in order to utilize hot off-gas from autothermal reforming to provide heat for reforming which increases the overall heat efficiency of the process.
Regarding claim 23, Genkin in view of McKenna and Rytter discloses all the limitations in the claims as set forth above and McKenna further discloses the hydrocarbon feedstock may be… natural gas (Pg. 3 lines 5-6). It is preferably methane, associated gas or natural gas containing a substantial proportion, e.g. over 85% v/v methane (Pg. 3 lines 7-8). Over 85% v/v methane is within the claimed range of greater than 50% by volume.
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 hydrocarbon to be a methane-containing gas stream containing greater than 50% by volume of methane in the method of Genkin in view of McKenna and Rytter as taught by McKenna in a preferred embodiment.
Regarding claim 24, Genkin in view of McKenna and Rytter discloses all the limitations in the claims as set forth above and Genkin further discloses the hydrocarbon feed may be “pretreated” in desulfurizer 30 to remove sulfur components prior to introducing into the reactor 10 ([0072]).
Regarding claim 26, Genkin in view of McKenna and Rytter discloses all the limitations in the claims as set forth above and McKenna further discloses the heated natural gas mixture in line 20 is mixed with steam fed from line 22 at a steam to carbon ratio of about 1.5 (Pg. 12 lines 10-11). Alternatively, steam may be provided by feeding the heated natural gas stream to a saturator fed with a stream of heated water under pressure (Pg. 12 lines 12-13). Following the one or more shift stages, the hydrogen enriched reformed gas is cooled to a temperature below the dew point so that the steam condenses (Pg. 7 line 40 – Pg. 8 line 1). Preferably, the condensed water is fed to a steam generator such as a steam stripper or saturator to provide at least a portion of the steam required for steam reforming (Pg. 8 lines 5- 7).
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 gaseous mixture comprising the hydrocarbon and steam to be formed by contacting the hydrocarbon with water in a saturator to form a saturated gas mixture in the method of Genkin in view of McKenna and Rytter in order to efficiently utilize the condensed water after the shift stages as taught by McKenna.
Regarding claim 27, Genkin in view of McKenna and Rytter discloses all the limitations in the claims as set forth above and Genkin further discloses the step of recovering heat from the reformate from reactor 20 may comprise generating steam by indirect heat exchange between feed water and reformate from reactor 20 in heat recovery train 50 ([0088]).
Regarding claim 28, Genkin in view of McKenna and Rytter discloses all the limitations in the claims as set forth above and Genkin further discloses the oxygen-containing stream may have an oxygen concentration of 85% to 100% oxygen.
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 Genkin (85% to 100%) overlaps with the claimed range (at least 90% vol). Therefore, the range in Genkin renders obvious the claimed range.
Regarding claim 31, Genkin in view of McKenna and Rytter discloses all the limitations in the claims as set forth above and Genkin further discloses the water-depleted reformate may be separated by liquid absorption… by any known acid gas removal system such as amine-based systems ([0105]).
Regarding claim 32, Genkin in view of McKenna and Rytter discloses all the limitations in the claims as set forth above and McKenna further discloses where the CO2 recovery uses a physical or amine wash solvent as sorbent, a portion of the LP steam generated in the HRSG (heat recovery and steam generator unit) may, if desired, be used to heat and thereby desorb CO2 out of the sorbent (Pg. 11 lines 23-25). The physical or amine wash, i.e. one stream of the carbon dioxide separation unit, may then be heated in a re-boiler in exchange with the reformed gas, i.e. heated in heat exchange with the hydrogen-enriched reformed gas stream (Pg. 11 lines 26-27).
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 one or more streams of the carbon dioxide separation unit are heated in heat exchange with the hydrogen-enriched reformed gas stream in the method of Genkin in view of McKenna and Rytter in order to desorb CO2 out of the sorbent as taught by McKenna.
Regarding claim 33, Genkin in view of McKenna and Rytter discloses all the limitations in the claims as set forth above and Genkin further discloses the process further comprises separating the pressure swing adsorber feed stream… thereby forming H2 product stream and a pressure swing adsorption tail gas stream ([0107]).
Regarding claim 34, Genkin in view of McKenna and Rytter discloses all the limitations in the claims as set forth above and Rytter further discloses a method of producing hydrogen, the method comprising: receiving a feed gas comprising hydrocarbons; and performing reforming processes so as to generate hydrogen in dependence on the feed gas (Pg. 2 lines 18-20). The method further comprises compressing and optionally, liquifying the separated hydrogen (Pg.2 lines 36-37). Preferably, the method further comprises separating carbon dioxide from the shifted gas (Pg. 3 line 1). Preferably, the method further comprises compressing and, optionally, liquifying the separated carbon dioxide (Pg. 3 lines 3-4). Electric power demand at 18.5 MW for compressors is delivered as renewable energy (Pg. 13 lines 31-32). Rytter further discloses hydrogen pressure requirement varies with application, but high pressure or liquid hydrogen will be needed for storage and in transportation applications (Pg. 11 lines 5-6).
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 wherein the carbon dioxide recovered from the carbon dioxide separation unit and the purified hydrogen gas recovered from the purification unit are each compressed in electrically-driven compressors in the method of Genkin in view of McKenna and Rytter in order to store and transport the hydrogen and carbon dioxide as taught by Rytter.
Regarding claim 35, Genkin in view of McKenna and Rytter discloses all the limitations in the claims as set forth above and Rytter further discloses a small portion of the hydrogen rich stream 103 is added to the pretreated natural gas 41 and fed to the prereformer 4 (Pg. 12 line 2-4). Rytter further discloses preferably, the method further comprises…supplying at least part of any product that is generated in at least one of the one or more of the further processing plants that the hydrogen production plant is integrated with to the hydrogen production plant such that the supplied product can be used by the hydrogen production plant (Pg. 3 lines 29, 32-35).
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 a portion of the crude hydrogen or purified hydrogen to be fed to the hydrocarbon in the process of Genkin in view of McKenna and Rytter in order to integrate processes in the preferred embodiment taught by Rytter.
Regarding claim 36, Genkin in view of McKenna and Rytter discloses all the limitations in the claims as set forth above and Rytter further discloses preferably, the process of separating hydrogen from the shifted gas comprises generating a rest gas i.e. fuel gas; and the method further comprises using at least part of the rest gas (Pg. 4 lines 37-38). The present embodiment comprises using the energy rich components of the rest gas(Pg. 15 lines11-12). For example, the rest gas may be used as a fuel in fired heater(s) for the preheating of the feed gas at one or more of the stages that process the feed gas (Pg. 15 lines 12-14). The feed gas, that may be natural gas, may be heated at one or more of: immediately prior to its input into the pre-treatment 3, i.e. heat the hydrocarbon and/or the gaseous mixture of hydrocarbon and steam, immediately prior to its input into the pre-reformer 4 and immediately prior to its input into the GHR 1, i.e. the reformed gas stream recovered from the pre-reforming stage upstream of the autothermal reforming stage (Pg. 15 lines 14-16). The rest gas may also be used as a fuel for generating steam 102 that is added before the pre-reformer, i.e. generate steam for the process (Pg. 15 lines 16-17).
While Rytter does not explicitly disclose “two fired heaters” or “second fired heater that functions as a boiler”, Rytter does disclose the rest gas may be used as a fuel in fired heater(s) (Pg. 15 lines 12-14), and it would be obvious to a skilled artisan to fuel any number of fired heaters needed for
the process to operate efficiently. Rytter also discloses the rest gas may also be used as a fuel for generating steam 102 (Pg. 15 lines 16-17), and it would be obvious to a skilled artisan to generate steam
in a boiler.
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 there to be two fired heaters fueled at least in part by the fuel gas
recovered from the purification unit; a first fired heater that heats the hydrocarbon and/or the gaseous mixture of hydrocarbon and steam, and a second fired heater that functions as a boiler to generate steam for the process in the process of Genkin in view of McKenna and Rytter in order to increase process efficiency by utilizing energy rich components as taught by Rytter.
Regarding claim 37, Genkin in view of McKenna and Rytter discloses all the limitations in the claims as set forth above and while Rytter does not explicitly disclose the fuel gas split to the first and second fired heaters in the ranges of 10-90% vol to 90-10% vol respectively, it would be obvious to a skilled artisan that the energy load of heating the hydrocarbon feed stream and the reformed gas stream is higher than the energy load of boiling water, since Rytter discloses the temperature of gas output from the gas-heated reformer is in the range 400-800 °C (Pg. 4 line 1) compared to generating steam at 100 °C.
Regarding claim 38, Genkin in view of McKenna and Rytter discloses all the limitations in the claims as set forth above including Rytter discloses the rest gas may also be used as a fuel for generating steam 102 that is added before the pre-reformer, i.e. gaseous mixture fed to the gas-heated reformer (Pg. 15 lines 16-17).
Regarding claim 42, Genkin in view of McKenna and Rytter discloses all the limitations in the claims as set forth above and Rytter further discloses preferably, the method further comprises supplying at least part of any product that is generated in the hydrogen production plant to at least one of the one or more of the further processing plants i.e. downstream chemical synthesis process, that the hydrogen production plant is integrated with such that the supplied product can be used by the at least one of the one or more of the further processing plants (Pg. 3 lines 29-32). Rytter further discloses preferably in use, all, or part of, the separated hydrogen is used to reduce carbon dioxide emission from an auxiliary processing plant (Pg. 4 lines 33-34).
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 pure hydrogen stream to be used in a downstream power process, heating process, a downstream chemical synthesis process or used to upgrade hydrocarbons in the method of Genkin in view of McKenna and Rytter in order to reduce carbon dioxide emissions from an auxiliary processing plant as taught by Rytter.
Claim 29 is rejected under 35 U.S.C. 103 as being unpatentable over Genkin et al (US 20130243686 A1, as cited in IDS 04/12/2024), in view of McKenna et al (WO 2011/077107, as cited in IDS 11/04/2022) and Rytter et al (WO 2019162236, as cited in IDS 04/12/2024), and in further view of Erlandsson (US 20190031604 A).
Regarding claim 29, Genkin in view of McKenna and Rytter discloses all the limitations in the claims as set forth above but is silent to “wherein the water-gas shift stage comprises an isothermal shift stage.”
Erlandsson discloses a process for the production of formaldehyde-stabilised urea comprising the steps of: (a) generating a synthesis gas comprising hydrogen, nitrogen, carbon monoxide, carbon dioxide and steam in a synthesis gas generation unit, (b) subjecting the synthesis gas to one or more stages of water-gas shift in one or more water-gas shift reactors to form a shifted gas; (c) recovering carbon dioxide from the shifted gas in a carbon dioxide removal unit to for a carbon dioxide-depleted synthesis gas (abstract). Before recovery of carbon dioxide, the crude synthesis gas is subjected in step (b) to one or more stages of water-gas shift to produce a shifted synthesis gas with the desired gas composition ([0020]). The reaction may be carried out in one or more stages ([0021]). The, or each, stage may be the same or different and may be selected from high temperature shift, low temperature shift, medium temperature shift, isothermal shift and sour shift ([0021]). In a preferred embodiment, the water-gas shift stage comprises a… isothermal shift stage with or without a low temperature shift stage ([0024]). The carbon monoxide concentration inlet the downstream shift reactor may be in the range of 2 - 5 vol % on a dry basis and the carbon dioxide concentration may be in the range of 13 - 17 vol % on a dry basis ([0026]). The downstream shift reactor converts still more carbon monoxide to carbon dioxide, and a shifted gas stream, e . g . from a low temperature shift reactor, may contain 0.1 - 0.5 vol % carbon monoxide on a dry basis and 15 - 20 vol % carbon dioxide on a dry basis ([0026]). A carbon dioxide removal unit is used to recover carbon dioxide from the shifted synthesis gas in step ( c ) ([0033]). The carbon dioxide removed by the carbon dioxide removal unit may be captured, treated to remove contaminants such as hydrogen, and stored ([0033]).
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 water-gas shift stage to comprise an isothermal shift stage in the method of Genkin in view of McKenna and Rytter in order to produce additional carbon dioxide for capture and storage as taught by Erlandsson.
Claim 30 is rejected under 35 U.S.C. 103 as being unpatentable over Genkin et al (US 20130243686 A1, as cited in IDS 04/12/2024), in view of McKenna et al (WO 2011/077107, as cited in IDS 11/04/2022) and Rytter et al (WO 2019162236, as cited in IDS 04/12/2024), and in further view of Zhou et al (CN 103771338 A, machine translation used for citations).
Regarding claim 30, Genkin in view of McKenna and Rytter discloses all the limitations in the claims as set forth above but is silent to “wherein there are two or three stages of cooling and separation of process condensate from the hydrogen-enriched reformed gas before passing the de-watered hydrogen-enriched reformed gas to the carbon dioxide separation unit”.
Zhou discloses a water-gas shift process and in particular to a water-gas shift method containing light oil and a water-gas shift system containing light oil ([0002]). The light oil-containing water-gas shift method according to an embodiment of the present invention comprises ([0008]): (1) introducing the light oil-water-containing coal gas into a shift converter… so as to obtain a mixed gas containing carbon dioxide, hydrogen, water vapor and gaseous light oil ([0009]); (2) subjecting the mixed gas to a first cooling process to obtain a first gas-liquid mixture of water, light oil, carbon dioxide, hydrogen water vapor and gaseous light oil ([0010]); (3) subjecting the first gas-liquid mixture to a first gas-liquid separation to obtain a first liquid mixture containing water and liquid light oil and a first coal gas containing carbon dioxide and hydrogen ([0011]); (4) subjecting the first liquid mixture to an oil-water separation treatment to obtain water and liquid light oil ([0012]). (5) subjecting the first gas obtained in step (3) to a second cooling treatment to obtain a second gas-liquid mixture of water, light oil, carbon dioxide, hydrogen, water vapor and gaseous light oil ([0018]). (7) subjecting the second gas obtained in step (6) to a third cooling treatment to obtain a third gas-liquid mixture of water, light oil and carbon dioxide, hydrogen water vapor and gaseous light oil; and (8) subjecting the third gas-liquid mixture to a third gas-liquid separation treatment to obtain a third liquid mixture containing water and liquid light oil and a third gas containing carbon dioxide and hydrogen ([0019]) Thus, the residual water vapor and light oil in the second coal gas can be fully condensed to further improve the purity of the second coal gas ([0019])
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 have two or three stages of cooling and separation of process condensate from the hydrogen-enriched reformed gas before passing the de-watered hydrogen-enriched reformed gas to the carbon dioxide separation unit in the process of Genkin in view of McKenna and Rytter in order to fully condense and separate the condensate and to improve purity as taught by Zhou.
Claims 39-40 are rejected under 35 U.S.C. 103 as being unpatentable over Genkin et al (US 20130243686 A1, as cited in IDS 11/07/2022), in view of McKenna et al (WO 2011/077107, as cited in IDS 11/04/2022) and Rytter et al (WO 2019162236, as cited in IDS 04/12/2024), and in further view of Wu (CN 110790227 A, machine translation used for citations).
Regarding claim 39, Genkin in view of McKenna and Rytter discloses all the limitations in the claims as set forth above but is silent to “wherein steam generated in the second fired heater is provided via a steam drum coupled to an isothermal shift converter”
Wu discloses an isothermal conversion hydrogen production method for a water-coal slurry gasification device in view of the current status of the prior art, which can effectively avoid overheating of the gas-cooled reactor and the by-production of medium-pressure superheated steam ([0011]). The second crude coal gas, i.e. reformed gas mixture, merges with the primary air-cooled shift gas after heat recovery to form a mixed gas, which enters the isothermal shift furnace for shift reaction ([0016]). The mixed gas first enters the first reaction chamber of the isothermal conversion furnace to undergo a medium-temperature conversion reaction to generate a primary isothermal conversion gas; the boiler i.e. second fired heater, water in the first steam drum enters the first heat exchange tube in the first reaction chamber to remove the reaction heat and produce medium-pressure saturated steam as a byproduct ([0018]). The system has short process, less equipment, low investment and small system pressure drop ([0052]).
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 steam generated in the second fired heater to be provided via a steam drum coupled to an isothermal shift converter in the method of Genkin in view of McKenna and Rytter in order to reduce equipment, investment and system pressure drop as disclosed by Wu.
Regarding claim 40, Genkin in view of McKenna, Rytter and Wu discloses all the limitations in the claims as set forth above including Genkin discloses a saturator that forms the gaseous mixture comprising the hydrocarbon and steam by contacting the hydrocarbon with water (see [0090]), Wu discloses second fired heater and steam drum coupled to an isothermal shift converter as claimed, discussed above. Since it would be obvious to a person having ordinary skill in the art to use a saturator, second fired heater and steam drum coupled to an isothermal shift converter individually, it would be obvious to use them together to generate steam in the method of Genkin in view of Speth, Rytter and Wu. See MPEP 2144.06.
Claim 41 are rejected under 35 U.S.C. 103 as being unpatentable over Genkin et al (US 20130243686 A1, as cited in IDS 11/07/2022), in view of McKenna et al (WO 2011/077107, as cited in IDS 11/04/2022), Rytter et al (WO 2019162236, as cited in IDS 04/12/2024), and Wu (CN 110790227 A, machine translation used for citations), and in further view of Ariyapadi et al (US 20130047509 A1).
Regarding claim 41, Genkin in view of McKenna, Rytter and Wu discloses all the limitations in the claims as set forth above does not disclose “wherein the saturator generates 50-60% or 55-65% of the steam, the second fired heater raises 20-25% of the steam and the steam drum coupled to the isothermal shift converter raises the balance”.
Ariyapadi discloses systems and methods for producing synthetic gas (abstract). As illustrated, the syngas cooler 305 can include three heat exchangers 310, 320, and 330 arranged in series ([0040]). Any one or all of the heat exchangers 310, 320, 330 can be shell-and-tube type heat exchangers ([0040]). The raw syngas via line 106 can be cooled in the first heat exchanger ("first zone") 310 to provide a cooled raw syngas via line 315 having a temperature of from about 260 °C to about 820 °C ([0040]). The cooled raw syngas exiting the first heat exchanger 310 via line 315 can be further cooled in the second heat exchanger ("second zone") 320 to provide a cooled raw syngas via line 325 having a temperature of from about 260 °C to about 704 °C ([0040]). The cooled raw syngas exiting the second heat exchanger 320 via line 325 can be further cooled in the third heat exchanger ("third zone") 330 to provide a cooled raw syngas via line 116 having a temperature of from about 260 °C to about 430 °C ([0040]). Although not shown, the syngas cooler 305 can be or include a single boiler. The heat transfer medium (e.g., boiler feed water) via line 108 can be heated within the third heat exchanger 330 to provide the cooled syngas via line 116 and a condensate via line 338. ([0041]). The condensate 338 can be introduced (“flashed”) to one or more steam drums or separators 340 to separate the gas phase (“steam”) from the liquid phase (“condensate”) ([0040]). The condensate via line 346 from the separator 340 can be introduced to the first heat exchanger ("boiler") 310 and indirectly heated against the syngas introduced via line 106 to provide at least partially vaporized steam which can be introduced to the separator 340 via line 344 ([0041]). Steam via line 342 can be introduced to the second heat exchanger ("superheater") 320 and heated against the incoming syngas via line 315 to provide the superheated steam or superheated high pressure steam via line 114 ([0041]). The saturator 420 can be used to increase the moisture content of the filtered syngas in line 415 before the syngas is introduced to the gas shift device 430 via line 424 ([0050]). The saturator 420 can have a heat requirement, and about 70 percent to 75 percent of the heat requirement can be sensible heat provided by the cooled syngas in line 415, as well as medium to low grade heat available from other portions of the SNG system 300 ([0051]). About 25 percent to 30 percent of the heat requirement can be supplied by indirect steam reboiling ([0051]).
While Ariyapadi does not explicitly disclose the ranges claimed for the amount of steam generated by each apparatus (saturator, second fired heater, steam drum), Ariyapadi does disclose the heat requirement of the saturator is a variable that can be modified by adjusting the sensible heat provided by the cooled syngas by adjusting the temperature of the cooled syngas. Ariyapadi further discloses that the heating duty of the three heat exchangers or boilers is a variable that can be modified by adjusting the temperature of the cooled raw syngas. The precise heat requirement of the saturator, second fired heater, and steam drum would have been considered a result effective variable by one having ordinary skill in the art at the time the invention was made. As such, without showing unexpected results, the claimed ranges cannot be considered critical. Accordingly, one of ordinary skill in the art at the time the invention was made would have optimized, by routine experimentation, the percentage of steam the saturator, second fired heater, and the steam drum coupled to the isothermal shift converter would generate in the process of Genkin in view of McKenna, Rytter and Wu to obtain the desired balance between the construction cost and the operation efficiency (In re Boesch, 617 F.2d. 272, 205 USPQ 215 (CCPA 1980)), since it has been held that where the general conditions of the claim are disclosed in the prior art, discovering the optimum or workable ranges involves only routine skill in the art. (In re Aller, 105 USPQ 223).
Double Patenting
The nonstatutory double patenting rejection is based on a judicially created doctrine grounded in public policy (a policy reflected in the statute) so as to prevent the unjustified or improper timewise extension of the “right to exclude” granted by a patent and to prevent possible harassment by multiple assignees. A nonstatutory double patenting rejection is appropriate where the conflicting claims are not identical, but at least one examined application claim is not patentably distinct from the reference claim(s) because the examined application claim is either anticipated by, or would have been obvious over, the reference claim(s). See, e.g., In re Berg, 140 F.3d 1428, 46 USPQ2d 1226 (Fed. Cir. 1998); In re Goodman, 11 F.3d 1046, 29 USPQ2d 2010 (Fed. Cir. 1993); In re Longi, 759 F.2d 887, 225 USPQ 645 (Fed. Cir. 1985); In re Van Ornum, 686 F.2d 937, 214 USPQ 761 (CCPA 1982); In re Vogel, 422 F.2d 438, 164 USPQ 619 (CCPA 1970); In re Thorington, 418 F.2d 528, 163 USPQ 644 (CCPA 1969).
A timely filed terminal disclaimer in compliance with 37 CFR 1.321(c) or 1.321(d) may be used to overcome an actual or provisional rejection based on nonstatutory double patenting provided the reference application or patent either is shown to be commonly owned with the examined application, or claims an invention made as a result of activities undertaken within the scope of a joint research agreement. See MPEP § 717.02 for applications subject to examination under the first inventor to file provisions of the AIA as explained in MPEP § 2159. See MPEP § 2146 et seq. for applications not subject to examination under the first inventor to file provisions of the AIA . A terminal disclaimer must be signed in compliance with 37 CFR 1.321(b).
The filing of a terminal disclaimer by itself is not a complete reply to a nonstatutory double patenting (NSDP) rejection. A complete reply requires that the terminal disclaimer be accompanied by a reply requesting reconsideration of the prior Office action. Even where the NSDP rejection is provisional the reply must be complete. See MPEP § 804, subsection I.B.1. For a reply to a non-final Office action, see 37 CFR 1.111(a). For a reply to final Office action, see 37 CFR 1.113(c). A request for reconsideration while not provided for in 37 CFR 1.113(c) may be filed after final for consideration. See MPEP §§ 706.07(e) and 714.13.
The USPTO Internet website contains terminal disclaimer forms which may be used. Please visit www.uspto.gov/patent/patents-forms. The actual filing date of the application in which the form is filed determines what form (e.g., PTO/SB/25, PTO/SB/26, PTO/AIA /25, or PTO/AIA /26) should be used. A web-based eTerminal Disclaimer may be filled out completely online using web-screens. An eTerminal Disclaimer that meets all requirements is auto-processed and approved immediately upon submission. For more information about eTerminal Disclaimers, refer to www.uspto.gov/patents/apply/applying-online/eterminal-disclaimer.
Claims 22-24, 28-29, 31, 33-37, 42 provisionally rejected on the ground of nonstatutory double patenting as being unpatentable over claims 28-30, 34, 40, 42-44, 47-48, 54 of copending Application No. 17/998,103 in view of Rytter et al (WO 2019162236, as cited in IDS 04/12/2024).
Regarding claim 22, copending application ‘103 discloses a process for the production of hydrogen comprising the steps of:
(i) subjecting a gaseous mixture comprising a hydrocarbon and steam, and having a steam to carbon ratio of at least 0.9:1 to adiabatic pre-reforming in a pre-reformer followed by autothermal reforming with an oxygen-rich gas in an autothermal reformer to generate a reformed gas mixture,
(ii) increasing the hydrogen content of the reformed gas mixture by subjecting it to one or more water-gas shift stages in a water-gas shift unit to provide a hydrogen-enriched reformed gas,
(iii)cooling the hydrogen-enriched reformed gas and separating condensed water therefrom,
(iv)passing the de-watered hydrogen-enriched reformed gas to a carbon dioxide separation unit to provide a carbon dioxide gas stream and a crude hydrogen gas stream, and
(v) passing the crude hydrogen gas stream from the carbon dioxide removal unit to a purification unit to provide a purified hydrogen gas and a fuel gas, wherein the fuel gas is fed to one or more fired heaters used to heat one or more process streams within the process (claim 28).
Copending application ‘103 claim of a steam to carbon ratio of at least 0.9:1 overlaps with the claimed range of 2.8:1 to 3.5:1.
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 copending application ‘103 (at least 0.9:1) overlaps with the claimed range (2.8:1 to 3.5:1). Therefore, the range in copending application ‘103 renders obvious the claimed range.
Copending application ‘103 is silent to “steam reforming in a gas-heated reformer”.
Rytter discloses a method of producing hydrogen comprising: receiving a feed gas comprising hydrocarbons and performing reforming processes so as to generate hydrogen from the feed gas; wherein the reforming processes comprise both a gas-heated reforming process and an auto thermal reforming process and heat generated by the autothermal reforming process is supplied to the gas-heated reforming process (abstract). Rytter further discloses gas heated reforming (GHR) utilizes hot gas, e.g. off-gas from autothermal reforming, to provide heat for reforming of a feed gas (Pg. 5 lines 24-25).
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 modify the pre-reactor of copending application ‘103 to be a gas-heated reformer as taught by Rytter in order to utilize hot off-gas from autothermal reforming to provide heat for reforming which increases the overall heat efficiency of the process.
Regarding claim 23, copending application ‘103 discloses wherein the hydrocarbon is a methane-containing gas stream, preferably containing >50% vol of methane (claim 29).
Regarding claim 24, copending application ‘103 discloses wherein the hydrocarbon is desulphurised (claim 30).
Regarding claim 28, copending application ‘103 discloses wherein the oxygen-rich gas comprises at least 90% vol 02, preferably at least 95% vol 02, more preferably at least 98% vol 02 (claim 34).
Regarding claim 31, copending application ‘103 discloses wherein the carbon dioxide removal stage is performed using a physical wash system or a reactive wash system, preferably a reactive wash system, especially an amine wash system (claim 40).
Regarding claim 33, copending application ‘103 discloses wherein the purification unit is a pressure swing adsorption unit or a temperature swing adsorption unit, preferably a pressure swing adsorption unit (claim 42).
Regarding claim 34, copending application ‘103 discloses wherein the carbon dioxide recovered from the carbon dioxide removal unit and the purified hydrogen gas recovered from the purification unit are each compressed in electrically-driven compressors (claim 43).
Regarding claim 35, copending application ‘103 discloses wherein a portion of the crude hydrogen or pure hydrogen is fed to the hydrocarbon (claim 44).
Regarding claim 36, copending application ‘103 discloses wherein there are two fired heaters fueled by the fuel gas recovered from the purification unit; a first fired heater that heats the hydrocarbon and/or the gaseous mixture of hydrocarbon and steam, and a second fired heater that functions as a boiler to generate steam for the process (claim 47).
Regarding claim 37, copending application ‘103 discloses wherein the fuel gas split to the first and second fired heaters in the ranges of 10-90% vol to 90-10% vol respectively, preferably 40-50% vol to the first fired heater and 60-50% vol to the second fired heater (claim 48).
Regarding claim 42, copending application ‘103 discloses wherein the pure hydrogen stream is used in a downstream power process, heating process, a downstream chemical synthesis process or used to upgrade hydrocarbons (claim 54).
This is a provisional nonstatutory double patenting rejection.
Claims 22, 33 provisionally rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1-2, 4, 14-15 of copending Application No. 18/041,628 in view of Genkin et al (US 20130243686 A1, as cited in IDS 11/07/2022) and McKenna et al (WO 2011/077107, as cited in IDS 11/04/2022).
Regarding claim 22, copending application ‘628 discloses a process for the production of hydrogen comprising the steps of: (a) generating a synthesis gas comprising hydrogen, carbon monoxide, carbon dioxide and steam in a synthesis gas generation unit; (b) increasing the hydrogen content of the synthesis gas and decreasing the carbon monoxide content by subjecting it to one or more water-gas shift stages in a water-gas shift unit to provide a hydrogen-enriched gas, (c) cooling the hydrogen-enriched gas and separating condensed water therefrom, (d) passing the resulting de-watered hydrogen-enriched gas to a carbon dioxide separation unit to provide a carbon dioxide gas stream and a hydrogen gas stream, wherein the synthesis gas from step (a) is fed without adjustment of the carbon monoxide content to a water gas shift reactor, operated adiabatically or with cooling (claim 1). Copending application ‘628 further discloses wherein the synthesis gas generation comprises one or more steps selected from adiabatic pre-reforming, catalytic steam reforming in a fired- or gas-heated reformer, autothermal reforming, and catalytic partial oxidation, applied to a gaseous or vapourised hydrocarbon such as natural gas, naphtha or a refinery off-gas (claim 2, meeting “A process for the production of hydrogen comprising the steps of: (i) subjecting a gaseous mixture comprising a hydrocarbon and steam… to steam reforming in a gas-heated reformer followed by autothermal reforming”). Copending application ‘628 further discloses wherein the process further comprises passing the hydrogen gas stream to a purification unit to provide a purified hydrogen gas (claim 14).
Copending application ‘628 is silent to “having a steam to carbon ratio in the range 2.8:1 to 3.5:1” “with an oxygen-rich gas in an autothermal reformer to generate a reformed gas mixture” and “to provide…a fuel gas, wherein the fuel gas is fed to one or more fired heaters used to heat one or more process streams within the process”.
McKenna discloses a process for the conversion of a hydrocarbon to CO2 and electrical power comprising subjecting a gas mixture comprising a hydrocarbon feed stream and steam to an integrated reforming process… to generate a reformed gas mixture (abstract). The hydrocarbon stream is mixed with steam: this steam introduction may be effected by direct injection of steam and/or by saturation of the feedstock by contact of the latter with a stream of heated water (Pg. 3 lines 24-26). The amount of steam introduced may be such as to give a steam ratio of 1 to 3 moles of steam per gram atom of hydrocarbon carbon in the feedstock (Pg. 3 lines 27-28).
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 McKenna (1 to 3:1) overlaps with the claimed range (2.8 to 3.5: 1). Therefore, the range in McKenna renders obvious the claimed range.
Genkin discloses 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]). Reactor 20 is a reformer often called an “autothermal reformer” ([0080] meeting limitation “with an oxygen-rich gas in an autothermal reformer to generate a reformed gas mixture”). Autothermal reformers are well-known in the art ([0080]).
Genkin further discloses the process may further comprise combusting a third portion 106 of the tail gas stream, i.e. fuel gas, in a boiler 120, i.e. fired heater, to generate a portion of the steam introduced into reactor 10 ([0114]). As depicted in FIGS 1 and 2, a third portion 106 of the tail gas and an oxygen-containing stream 124 are introduced into boiler 120 where combustible gases in the third portion of the tail gas are combusted to form combustion products 122, which are withdrawn from the boiler 120 ([0114]). Steam is formed by indirect heat exchange between heated feed water 86 and the combustion products 122 ([0114] meeting limitation “used to heat one or more process streams within the process”). Steam may then be added to the hydrocarbon mixture from desulfurizer 30, as shown in FIG. 1, or added to the mixed feed from saturator 35, as shown in FIG. 2 ([0114]). Figures 1 and 2 illustrate a third portion 106 of the tail gas, i.e. fuel gas, is the sole fuel fed to the boiler.
Regarding claim 42, copending application ‘628 discloses wherein the purification unit is a pressure-swing adsorption unit or a temperature swing adsorption unit (claim 15).
This is a provisional nonstatutory double patenting rejection.
Claims 22, 34 provisionally rejected on the ground of nonstatutory double patenting as being unpatentable over claims 8, 12, 17 of copending Application No. 18/719,581 in view of Genkin et al (US 20130243686 A1, as cited in IDS 11/07/2022).
Regarding claim 22, copending Application No. 18/719,581 discloses a process for the production of hydrogen, comprising the steps of 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, i.e. steam reforming in a gas-heated reformer; feeding the crude synthesis gas from the fired reformer to an autothermal reformer along with an oxygen-containing gas to produce a reformed synthesis gas, i.e. a reformed gas mixture; feeding the reformed synthesis gas to a water-gas shift unit to produce a hydrogen-enriched gas; 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; 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, i.e. fuel gas (claim 8). Copending Application No. 18/719,581 further discloses wherein the mixture of hydrocarbon and steam fed to the fired reformer has a ratio of 1.5 to 3.5 moles of steam per mole of hydrocarbon carbon (claim 12).
Copending Application No. 18/719,581 is silent to “cooling the hydrogen-enriched reformed gas and separating condensed water therefrom to provide a de-watered hydrogen-enriched reformed gas” and “wherein the fuel gas is fed to one or more fired heaters used to heat one or more process streams within the process”.
Genkin discloses a hydrogen production process comprising ([0008]) introducing reactants comprising steam and a hydrocarbon feed into a first reactor ([0009]); introducing an oxygen-containing stream and the reformate from the first reactor into a second reactor ([0010]) recovering heat from the reformate from the second reactor thereby cooling the reformate ([0011]); reacting the cooled reformate in the presence of a shift catalyst ([0012]); recovering heat from the shifted reformate thereby cooling the shifted reformate ([0013]); removing H2O from the shifted reformatted to form a water-depleted reformate ([0014]); separating the water-depleted reformate into a CO2 product stream and a pressure swing adsorber feed stream ([0015]); separating the pressure swing adsorber feed stream… thereby forming a H2 product stream and a pressure swing adsorption tail gas stream, i.e. fuel gas ([0016]). A third portion of the tail gas stream is combusted in a boiler thereby forming combustion products and generating heat for forming a portion of the steam in the reactants from feed water ([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 to cool the hydrogen-enriched reformed gas and separate condensed water therefrom to provide a de-watered hydrogen-enriched reformed gas and for the fuel gas to be fed to one or more fired heaters used to heat one or more process streams within the process in the process of copending Application No. 18/719,581 in order to recover heat and make the process more efficient as taught by Genkin.
This is a provisional nonstatutory double patenting rejection.
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
/N.L.Q./Examiner, Art Unit 1738
/MICHAEL FORREST/Primary Examiner, Art Unit 1738