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 .
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on 03/16/2026 has been entered.
Response to Amendment
The amendment filed on 03/16/2026 has been entered. Claims 28-30, 32-45, 48-55 are pending in the application.
Response to Arguments
Applicant's arguments filed 03/16/2026 have been fully considered but they are not persuasive. Applicant argues on bottom of page 8 to top of page 9 that the claimed process has several advantages.
Applicant argues on page 9 that a key feature which is non-obvious from the prior art is the need to balance the steam ratio and the fuel demand of the process.
Applicant's arguments fail to comply with 37 CFR 1.111(b) because they amount to a general allegation that the claims define a patentable invention without specifically pointing out how the language of the claims patentably distinguishes them from the references.
Claim 28 recites “a steam to carbon ratio of 0.9:1 to 3.5:1” and Speth discloses the steam/carbon ratio in the reforming section may be 2.6-0.1, such as 1.2, 1.0 ([0046]). 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 a steam to carbon ratio of 0.9:1 to 3.5:1 in the method of Genkin in order to reduce feed plus steam flow through the reforming section as taught by Speth.
Applicant argues on top of page 10 that Christiansen in combination with the secondary references, including Rytter, does not suggest the particular arrangement of a pre-reformer coupled to the autothermal reformer and operating at the selected steam to carbon ratio, using all the fuel gas for the one or more fired heaters and thereby minimizes CO2 emissions from the process.
However, the fact that the inventor has recognized another advantage which would flow naturally from following the suggestion of the prior art cannot be the basis for patentability when the differences would otherwise be obvious. See Ex parte Obiaya, 227 USPQ 58, 60 (Bd. Pat. App. & Inter. 1985).
Genkin discloses a pre-reformer ([0073]) coupled to an autothermal reformer ([0077] and [0080]). Speth discloses the steam/carbon ratio in the reforming step is less than 2.6 ([0010]) in order to reduce feed plus steam flow through the reforming section ([0011]). Rytter discloses 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 feed stream, 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). 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 a steam to carbon ratio of 0.9:1 to 3.5:1 in the method of Genkin in order to reduce feed plus steam flow through the reforming section as taught by Speth. Further, 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 fuel gas to be fed to one or more fired heaters used to heat one or more process streams within the process; there are two fired heaters that are fueled at least in part by the fuel gas recovered from the purification unit; a first fired heater heats the hydrocarbon feed stream and a reformed gas stream recovered from the pre-reforming stage upstream of the autothermal reforming stage; and a second fired heater is a boiler that generates steam for the process in the process of Genkin in order to increase process efficiency by utilizing energy rich components as taught by Rytter.
Therefore, the claimed features, including the particular arrangement described by applicant on page 9, are taught by the combination of prior art as discussed further below.
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
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 28-30, 33-34, 36, 40, 42-44, 48-49, 54 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 Speth et al (US 20190382277 A1, as cited in IDS 11/07/2025) and Rytter et al (WO 2019/162236 A, as cited in IDS 04/12/2024).
Regarding claim 28, 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 “comprising the steps of: (i) subjecting a gaseous mixture comprising a hydrocarbon and steam”). The steam and hydrocarbon feed may be mixed and introduced together into the reactor 10 as a so-called mixed feed ([0070]). Reactor 10 is a so-called “prereformer” and may be adiabatic ([0073] meeting limitation “to adiabatic pre-reforming in a pre-reformer”). 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 “followed by autothermal reforming with an oxygen-rich gas in an autothermal reformer to generate a reformed gas mixture”). 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 “(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”). The process further comprises recovering heat from the shifted reformate thereby cooling the shifted reformate ([0098] meeting limitation “(iii)cooling the hydrogen-enriched reformed gas”). The process further comprises removing H2O from the shifted reformate to form a water-depleted reformate ([0101] meeting limitation “separating condensed water therefrom to provide a de-watered hydrogen-enriched reformed gas”). 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] meeting limitation “(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”). 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] meeting limitation “(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”). The process may further comprise combusting a third portion 106 of the tail gas stream in a boiler to generate a portion of the steam introduced into reactor 10 ([0114]).
Genkin is silent to “having a steam to carbon ratio in a range of 0.9:1 to 3.5:1” and “the fuel gas is fed to one or more fired heaters used to heat one or more process streams within the process; there are two fired heaters that are fueled at least in part by the fuel gas recovered from the purification unit; a first fired heater heats the hydrocarbon feed stream and a reformed gas stream recovered from the pre-reforming stage upstream of the autothermal reforming stage; and a second fired heater is a boiler that generates steam for the process”.
Speth discloses reforming a hydrocarbon feed in a reforming step thereby obtaining a synthesis gas ([0005]), shifting the synthesis gas ([0006]). The steam/carbon ratio in the reforming step is less than 2.6 ([0010]). The steam/carbon ratio in the reforming section may be 2.6-0.1, such as 1.2, 1.0 ([0046]). A steam/carbon ratio of less than 2.6 has several advantages in relation to the present invention, for example, reducing steam/carbon ratio on a general basis leads to reduced feed plus steam flow through the reforming section and the downstream cooling and synthesis gas preparation sections ([0011]).
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 Speth (less than 2.6) overlaps with the claimed range (0.9:1 to 3.5:1). Therefore, the range in Speth renders obvious the claimed range.
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 a steam to carbon ratio of 0.9:1 to 3.5:1 in the method of Genkin in order to reduce feed plus steam flow through the reforming section as taught by Speth.
Rytter 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; wherein the reforming processes comprise both a gas-heated reforming process and an autothermal reforming process (abstract). The method further comprises: performing a water-gas-shift on the gas output from the reforming processes; and separating hydrogen from the shifted gas (Pg. 2 lines 33-34).
Rytter further discloses 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 lines 11-12). 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 meeting limitation “the fuel gas is fed to one or more fired heaters used to heat one or more process streams within the process”). 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 (Pg. 15 lines 14-15 meeting limitation “a first fired heater heats the hydrocarbon feed stream”), immediately prior to its input into the pre-reformer 4 and immediately prior to its input into the GHR 1 (Pg. 15 lines 15-16 meeting limitation “and a reformed gas stream recovered from the pre-reforming stage upstream of the autothermal reforming stage”). The rest gas may also be used as a fuel for generating steam 102 that is added before the pre-reformer (Pg. 15 lines 16-17 meeting limitation “and a second fired heater is a boiler that generates steam for the process”). Rytter’s disclosure of fired heater(s) reads on the claim limitation of two fired heaters as it would be obvious to a skilled artisan to fuel any number of fired heaters needed for the process to operate efficiently.
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 fuel gas to be fed to one or more fired heaters used to heat one or more process streams within the process; there are two fired heaters that are fueled at least in part by the fuel gas recovered from the purification unit; a first fired heater heats the hydrocarbon feed stream and a reformed gas stream recovered from the pre-reforming stage upstream of the autothermal reforming stage; and a second fired heater is a boiler that generates steam for the process in the process of Genkin in order to increase process efficiency by utilizing energy rich components as taught by Rytter.
Regarding claim 29, Genkin in view of Speth and Rytter discloses all the limitations in the claims as set forth above and Genkin further discloses the hydrocarbon feed comprises CH4 ([0071], meeting limitation “wherein the hydrocarbon is a methane-containing gas stream containing >50% by volume of methane”).
Regarding claim 30, Genkin in view of Speth 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 33, Genkin in view of Speth 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]). Heated feed water from heat recovery train 50 is passed to steam drum 40 and steam is withdrawn and mixed with the hydrocarbon feed to form a mixed feed for reacting in reactor 10 ([0088] meeting limitation “by cooling the reformed gas mixture with water”). Genkin also discloses combusting a third portion 106 of the tail gas stream i.e. fuel gas, in a boiler i.e. fired heater, to generate a portion of the steam introduced into reactor 10 ([0114] meeting limitation “wherein the gaseous mixture comprising the hydrocarbon and steam is formed by mixing the hydrocarbon with steam generated by the one or more fired heaters”).
Regarding claim 34, Genkin in view of Speth 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% by volume). Therefore, the range in Genkin renders obvious the claimed range.
Regarding claim 36, Genkin in view of Speth and Rytter discloses all the limitations in the claims as set forth above and Genkin further discloses the shift reactor may be a so-called high temperature shift (HTS), low temperature shift (LTS), medium temperature shift (MTS), or combination ([0093]).
Regarding claim 40, Genkin in view of Speth 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 42, Genkin in view of Speth 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 43, Genkin in view of Speth and Rytter discloses all the limitations in the claims as set forth above and Rytter further discloses 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 Speth and Rytter in order to store and transport the hydrogen and carbon dioxide as taught by Rytter.
Regarding claim 44, Genkin in view of Speth 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 Speth and Rytter in order to integrate processes in the preferred embodiment taught by Rytter.
Regarding claim 48, Genkin in view of Speth 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 Genkin discloses reaction conditions in reactor 10, i.e. prereformer, include a temperature ranging from 430 to 570 °C ([0076]) and in reactor 20, i.e. autothermal reformer, ranging from 940 °C to 1040 °C ([0082]) compared to generating steam at 100 °C.
Regarding claim 49, Genkin in view of Speth and Rytter discloses all the limitations in the claims as set forth above and Speth further discloses the CO2 wash following the HT/MT/LT shifts requires heat for regeneration of the CO2 absorption solution ([0058]). This heat is normally provided as sensible heat from the process gas but this is not always enough ([0058]). Typically, an additional steam fired reboiler, i.e. second fired heater, is providing any missing heat ([0058]).
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 steam generated in the second fired heater to be used to heat a CO2 absorbent liquid in the carbon dioxide separation unit in the method of Genkin in view of Speth and Rytter in order to provide missing heat as taught by Speth.
Regarding claim 54, Genkin in view of Speth 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 Speth and Rytter in order to reduce carbon dioxide emissions from an auxiliary processing plant as taught by Rytter.
Claim 32 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 Speth et al (US 20190382277 A1, as cited in IDS 11/07/2025) and Rytter et al (WO 2019/162236 A, as cited in IDS 04/12/2024), in further view of Abbott et al (US 9206044 B2, as cited in IDS 06/12/2025).
Regarding claim 32, Genkin in view of Speth and Rytter discloses all the limitations in the claims as set forth above including the steam/carbon ratio in the reforming section may be 2.6-0.1 (Speth [0046]).
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 Speth (2.6-0.1) overlaps with the claimed range (0.9:1 to below 2.4:1). Therefore, the range in Speth renders obvious the claimed range.
Genkin in view of Speth and Rytter discloses additional hydrogen gas may be obtained by the catalytic reaction of carbon monoxide and steam (Genkin [0092]). This reaction is exothermic and is commonly referred to as the water-gas shift reaction or shit reaction (Genkin [0092]). However, Genkin in view of Speth and Rytter does not explicitly state “the process includes adding steam to the reformed gas mixture”.
Abbott discloses a process for increasing the hydrogen content of a synthesis gas generated from a carbonaceous feedstock (Col.1 lines 6-9). If the synthesis gas, i.e. reformed gas mixture, does not contain enough steam for the water-gas shift process, steam may be added to the synthesis gas, for example by live steam addition or saturation or a combination of these (Col. 2 lines 64-67).
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 process to include adding steam to the reformed gas mixture in the process of Genkin in view of Speth and Rytter in order to increase hydrogen production as taught by Abbott.
Claim 35, 37, 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 Speth et al (US 20190382277 A1, as cited in IDS 11/07/2025) and Rytter et al (WO 2019/162236 A, as cited in IDS 04/12/2024), in further view of Morar et al (“Review: Important contributions in development and improvement of the heat integration techniques”).
Regarding claim 35, it is noted that Genkin discloses reactor 20 is a reformer often called and “autothermal reformer” ([0080]) which is by name designed to optimize heat reuse within the process in order to achieve a process that is considered “autothermal”, or not requiring any external heat input to operate. The reactor conditions in the reactor 20 include a temperature ranging from 940 to 1040° C ([0082]). Given this high temperature range and the reactor is an autothermal reformer, heat must necessarily be added from elsewhere in the process of Genkin.
Genkin in view of Speth and Rytter does not disclose “the oxygen-rich gas is heated before being fed to the autothermal reformer in heat exchange with steam generated by cooling of the reformed gas”.
The reuse of excess process heat, however, is a routine convention in the field of chemical engineering, also known as process heat integration. As detailed in the introduction of Morar, the design of a heat exchanger network for a chemical process is a routine step in the design of a chemical process that results from analysis of the energy balance of the process, or in other words, determining where energy enters and leaves the process, and ensuring that the amount leaving the process is equal to the amount that enters to maximize energy usage within the process- by this analysis, it is readily apparent where in the process excess energy may be directed in order to ensure maximum process efficiency and reduce the heating and cooling duty of the process, thereby reducing process operation costs. Morar even discloses that “…it is possible to save an important part from the necessary energy required by a plant through specific actions and therefore resulting saving related to capital and operational costs up to 15-45%”. Such an energy balance analysis considers where process units require heat, such as in the case of an endothermic reaction requiring energy in order to proceed, and, by the use of heat exchangers, byproduct heat from one process gas stream may be used to provide heat to another, effectively ‘recycling’ heat from one process step to another.
Accordingly, given that Genkin clearly discloses the use of an autothermal reformer, prior to the effective filing date of the claimed invention it would have been obvious to design a heat exchange network that would effectuate heat transfer between the oxygen-rich gas before being fed to the autothermal reformer with steam generated by cooling of the reformed gas, as such heat integration would reduce the heating duty of Genkin in view of Speth and Rytter, thereby improving the energy efficiency of the production of hydrogen and reducing the cost of the process associated with temperature control.
Regarding claim 37, it is noted that Genkin discloses the shift reactor may be a so-called high temperature shift, low temperature shift, or combination ([0093]). A combination may include a sequence of high temperature shift, cooling by indirect heat exchange, and low temperature shift ([0097]). While Genkin does not disclose which process stream is in heat exchange to cause the cooling, Genkin discloses the reaction conditions in reactor 10, i.e. pre-reformer, include temperature ranging from 430 to 570°C ([0076]).
Genkin in view of Speth and Rytter does not disclose “wherein the hydrocarbon is heated in heat exchange with a shifted gas stream recovered from the high-temperature shift stage”.
The reuse of excess process heat, however, is a routine convention in the field of chemical engineering, also known as process heat integration. As detailed in the introduction of Morar, the design of a heat exchanger network for a chemical process is a routine step in the design of a chemical process that results from analysis of the energy balance of the process, or in other words, determining where energy enters and leaves the process, and ensuring that the amount leaving the process is equal to the amount that enters to maximize energy usage within the process- by this analysis, it is readily apparent where in the process excess energy may be directed in order to ensure maximum process efficiency and reduce the heating and cooling duty of the process, thereby reducing process operation costs. Morar even discloses that “…it is possible to save an important part from the necessary energy required by a plant through specific actions and therefore resulting saving related to capital and operational costs up to 15-45%”. Such an energy balance analysis considers where process units require heat, such as in the case of an endothermic reaction requiring energy in order to proceed, and, by the use of heat exchangers, byproduct heat from one process gas stream may be used to provide heat to another, effectively ‘recycling’ heat from one process step to another.
Accordingly, given that Genkin clearly discloses the cooling by indirect heat exchange of a shifted gas stream recovered from the high-temperature shift stage, prior to the effective filing date of the claimed invention it would have been obvious to design a heat exchange network that would effectuate heat transfer between the hydrocarbon and a shifted gas stream recovered from the high-temperature shift stage, as such heat integration would reduce the heating duty of Genkin in view of Speth and Rytter, thereby improving the energy efficiency of the production of hydrogen and reducing the cost of the process associated with temperature control.
Regarding claim 41, it is noted that Speth discloses the CO2 wash following the HT/MT/LT shifts requires heat for regeneration of the CO2 absorption solution ([0058]). This heat is normally provided as sensible heat from the process gas but this is not always enough ([0058]). Typically, an additional steam fired reboiler is providing any missing heat ([0058]). Optionally adding steam to the process gas can replace or reduce the size of this additional steam fired reboiler and simultaneously ensures reduction of byproduct formation in the HT/MT/LT shift section ([0058]).
Genkin in view of Speth and Rytter does not disclose “wherein one or more streams in the carbon dioxide separation unit are heated in heat exchange with steam generated in the one or more fired heaters”.
The reuse of excess process heat, however, is a routine convention in the field of chemical engineering, also known as process heat integration. As detailed in the introduction of Morar, the design of a heat exchanger network for a chemical process is a routine step in the design of a chemical process that results from analysis of the energy balance of the process, or in other words, determining where energy enters and leaves the process, and ensuring that the amount leaving the process is equal to the amount that enters to maximize energy usage within the process- by this analysis, it is readily apparent where in the process excess energy may be directed in order to ensure maximum process efficiency and reduce the heating and cooling duty of the process, thereby reducing process operation costs. Morar even discloses that “…it is possible to save an important part from the necessary energy required by a plant through specific actions and therefore resulting saving related to capital and operational costs up to 15-45%”. Such an energy balance analysis considers where process units require heat, such as in the case of an endothermic reaction requiring energy in order to proceed, and, by the use of heat exchangers, byproduct heat from one process gas stream may be used to provide heat to another, effectively ‘recycling’ heat from one process step to another.
Accordingly, given that Speth clearly discloses the CO2 wash following the HT/MT/LT shifts requires heat for regeneration of the CO2 absorption solution, prior to the effective filing date of the claimed invention it would have been obvious to design a heat exchange network that would effectuate heat transfer between the one or more carbon dioxide separation unit streams and steam generated in the one or more fired heaters, as such heat integration would reduce the heating duty of Genkin in view of Speth and Christensen, thereby improving the energy efficiency of the production of hydrogen and reducing the cost of the process associated with temperature control.
Claim 38 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 Speth et al (US 20190382277 A1, as cited in IDS 11/07/2025) and Rytter et al (WO 2019/162236 A, as cited in IDS 04/12/2024), in further view of McKenna et al (WO 2011/077106 A1, as cited in IDS 11/07/2022).
Genkin in view of Speth and Rytter discloses all the limitations in the claims as set forth above but are silent to “wherein steam generated in the one or more fired heaters is used to generate electrical power for the process”.
McKenna discloses a process for reducing the CO2 emissions from a combined cycle power generation process utilizing a gaseous hydrocarbon feed comprising the steps of: …subjecting a mixture comprising the first portion of hydrocarbon feed and steam to adiabatic steam reforming …autothermally reforming the pre-reformed gas mixture… increasing the hydrogen content of the reformed gas mixture… cooling the hydrogen-enriched reformed gas…passing the de-watered hydrogen-enriched reformed gas to one or more stages of carbon dioxide separation to generate a carbon dioxide stream and a hydrogen-containing stream, mixing the hydrogen-containing stream with the second portion of the gaseous hydrocarbon feed to form a hydrogen-containing fuel stream, and combusting the hydrogen-containing fuel stream with an oxygen containing gas in a gas turbine to generate electrical power and an exhaust gas mixture, and passing the exhaust gas mixture to a heat recovery steam generation system to provide steam for one or more steam turbines to generate additional electrical power (Pg. 1 lines 29-36 to Pg. 2 lines 1-16).
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 steam generated in the one or more fired heaters to be used to generate electrical power for the process in the method of Genkin in view of Speth and Rytter in order to reduce the CO2 emissions and make the process more energy efficient as taught by McKenna.
Claim 39 is 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 Speth et al (US 20190382277 A1, as cited in IDS 11/07/2025) and Rytter et al (WO 2019/162236 A, 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 39, Genkin in view of Speth and Rytter discloses all the limitations in the claims as set forth above but is silent to “wherein there are at least two 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 at least two 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 Speth and Rytter in order to fully condense and separate the condensate and to improve purity as taught by Zhou.
Claim 45 is 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 Speth et al (US 20190382277 A1, as cited in IDS 11/07/2025) and Rytter et al (WO 2019/162236 A, as cited in IDS 04/12/2024), in further view of Pham et al (US 20130097929 A1).
Regarding claim 45, Genkin in view of Speth and Rytter discloses all the limitations in the claims as set forth above but is silent to “wherein a supplemental fuel is added to the fuel gas fed to the one or more fired heaters and the amount of the supplemental fuel is less than 5% vol of the total fuel provided”.
Pham discloses a process for producing a hydrogen-containing product gas with reduced carbon dioxide emissions (abstract). The process comprises introducing a process stream 8 comprising steam and at least one hydrocarbon selected from the group consisting of methane, ethane, propane, butane, pentane, and hexane into a plurality of catalyst-containing reformer tubes 14 in a reformer furnace 10, reacting the process stream inside ([0040]). The reformate stream is passed to high temperature shift reactor 30 ([0045]). The reformate stream may be separated into the CO2 product stream, the hydrogen-containing product gas, and the pressure swing adsorption tail gas by first separating the reformate stream to form a CO2-depleted stream 107 and the CO2 product stream 105, then separating at least a portion of the CO2-depleted stream 107 by pressure swing adsorption to form the hydrogen-containing product gas 125 and the pressure swing adsorption tail gas 135 ([0052]). Fuel gas 155 is passed to burners 12, i.e. fired heater. Fuel gas comprises the pressure swing adsorption tail gas 135 and the supplemental fuel 145. The process comprises combusting fuel gas 155 comprising the pressure Swing adsorption tail gas 135 and supplemental fuel 145 in the reformer furnace external to the plurality of catalyst-containing reformer tubes at a firing rate to supply energy for reacting the process stream inside the plurality of catalyst-containing reformer tubes 14 ([0061]). The supplemental fuel provides 5% to 15% of the firing rate ([0062]). The amount of CO2 emissions in the flue gas 23 can be adjusted by the amount of hydrogen in the fuel gas 155 and the percentage of the total firing rate provided by the supplemental fuel 145 ([0064]).
While Pham does not explicitly disclose the amount of the supplemental fuel is less than 5% vol, this is not considered to confer patentability to the claims. Pham discloses that it was known in the art at the time of the invention that amount of CO2 emission in the flue gas can be adjusted by the percentage of the total firing rate provided by the supplemental fuel. Therefore, the amount of CO2 emissions in the flue gas is a variable that can be modified, among others, by varying the total firing rate provided by the supplemental fuel. For that reason, the amount of supplemental fuel 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 amount of supplemental fuel 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 amount of supplemental fuel in the process of Genkin in view of Speth and Rytter to obtain the desired amount of CO2 emissions (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).
Claim 50-52 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 Speth et al (US 20190382277 A1, as cited in IDS 11/07/2025), and Rytter et al (WO 2019/162236 A as cited in IDS 04/12/2024), and in further view of Lywood et al (US 4910228, as cited in IDS 11/16/2022) and Morar et al (“Review: Important contributions in development and improvement of the heat integration techniques”).
Regarding claim 50, Genkin in view of Speth, 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 used to superheat steam recovered from a steam drum coupled to a waste-heat boiler heated by the reformed gas mixture”.
Lywood discloses in a conventional reforming process, heat is usually recovered from the hot reformed gas and from the flue gases from the furnace heating the reformer tubes, where a fired furnace is employed, by a steam power system wherein boiler feed water is heated, high pressure steam is raised and usually superheated, and then the high pressure steam is expanded in a turbine with the recovery of power, e.g. for export as electricity or for compression of the make-gas (Col. 6 lines 27-35). Often it can be arranged that the exhaust from the turbine is at a suitable pressure for use as process steam, i.e. for use in the reforming process (Col. 6 lines 35-38).
While Lywood does not disclose “steam generated in the second fired heater is used”, the reuse of excess process heat, is a routine convention in the field of chemical engineering, also known as process heat integration. As detailed in the introduction of Morar, the design of a heat exchanger network for a chemical process is a routine step in the design of a chemical process that results from analysis of the energy balance of the process, or in other words, determining where energy enters and leaves the process, and ensuring that the amount leaving the process is equal to the amount that enters to maximize energy usage within the process- by this analysis, it is readily apparent where in the process excess energy may be directed in order to ensure maximum process efficiency and reduce the heating and cooling duty of the process, thereby reducing process operation costs. Morar even discloses that “…it is possible to save an important part from the necessary energy required by a plant through specific actions and therefore resulting saving related to capital and operational costs up to 15-45%”. Such an energy balance analysis considers where process units require heat, such as in the case of an endothermic reaction requiring energy in order to proceed, and, by the use of heat exchangers, byproduct heat from one process gas stream may be used to provide heat to another, effectively ‘recycling’ heat from one process step to another.
Accordingly, given that Lywood clearly discloses a waste-heat boiler heated by reformed gas coupled to a steam drum (Col. 11 line 1-2) from which steam is then superheated (Col. 6 lines 27-35), prior to the effective filing date of the claimed invention it would have been obvious to design a heat exchange network that would effectuate heat transfer between the steam from the steam drum with steam generated in the second fired heater, as such heat integration would reduce the heating duty of Genkin in view of Speth and Rytter, thereby improving the energy efficiency of the production of hydrogen and reducing the cost of the process associated with temperature control.
Regarding claim 51, Genkin in view of Speth, Rytter, Lywood and Morar discloses all the limitations in the claims as set forth above including in a conventional reforming process, heat is usually recovered from the hot reformed gas and from the flue gases from the furnace heating the reformer tubes, where a fired furnace is employed, by a steam power system wherein boiler feed water is heated, high pressure steam is raised and usually superheated, and then the high pressure steam is expanded in a turbine with the recovery of power, e.g. for export as electricity or for compression of the make-gas (Lywood Col. 6 lines 27-35). Often it can be arranged that the exhaust from the turbine is at a suitable pressure for use as process steam, i.e. for use in the reforming process (Lywood Col. 6 lines 35-38). Use as process steam is interpreted as used to pre-heat the oxygen-rich gas.
Regarding claim 52, Genkin in view of Speth, Rytter, Lywood and Morar discloses all the limitations in the claims as set forth above including high pressure steam is raised and usually superheated, and then the high pressure steam is expanded in a turbine with the recovery of power (Lywood Col. 6 lines 31-34).
Claim 53 is 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 Speth et al (US 20190382277 A1, as cited in IDS 11/07/2025), Rytter et al (WO 2019/162236 A as cited in IDS 04/12/2024), Lywood et al (US 4910228, as cited in IDS 11/16/2022), and Morar et al (“Review: Important contributions in development and improvement of the heat integration techniques”), and in further view of Abbott et al (US 9206044 B2, as cited in IDS 06/12/2025).
Regarding claim 53, Genkin in view of Speth, Rytter, Lywood and Morar discloses all the limitations in the claims as set forth above including the steam/carbon ratio in the reforming section may be 2.6-0.1 (Speth [0046]).
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 Speth (2.6-0.1) overlaps with the claimed ratio (2.4:1). Therefore, the range in Speth renders obvious the claimed range.
Genkin discloses additional hydrogen gas may be obtained by the catalytic reaction of carbon monoxide and steam (Genkin [0092]). This reaction is exothermic and is commonly referred to as the water-gas shift reaction or shit reaction (Genkin [0092]). However, Genkin in view of Speth, Rytter, Lywood and Morar does not explicitly state “a portion of the steam from the waste-heat boiler is added to the reformed gas”.
Abbott discloses a process for increasing the hydrogen content of a synthesis gas generated from a carbonaceous feedstock (Col.1 lines 6-9). If the synthesis gas, i.e. reformed gas mixture, does not contain enough steam for the water-gas shift process, steam may be added to the synthesis gas, for example by live steam addition or saturation or a combination of these (Col. 2 lines 64-67).
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 process to include adding a portion of the steam from the waste-heat boiler to the reformed gas in the process of Genkin in view of Speth, Rytter, Lywood and Morar in order to increase hydrogen production as taught by Abbott.
Claim 55 is 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 Speth et al (US 20190382277 A1, as cited in IDS 11/07/2025) and Rytter et al (WO 2019/162236 A as cited in IDS 04/12/2024) and in further view of Christensen et al (WO 2020221642 A1).
Regarding claim 55, Genkin in view of Speth and Rytter discloses all the limitations in the claims as set forth above but does not disclose “wherein all of the fuel gas is fed to the fired heaters”.
Christensen discloses a plant and process for producing a hydrogen rich gas…comprising the steps of reforming a hydrocarbon feed in a reforming step thereby obtaining a synthesis gas… shifting said synthesis gas in a shift configuration… removal of CO2 upstream hydrogen purification unit, such as a pressure swing adsorption unit (PSA), and recycling off-gas from hydrogen purification unit and mix it with natural gas upstream prereformer feed preheater (abstract). This syngas stream (7) is then fed to a hydrogen purification unit 125, e.g. a PSA-unit, from 10 which a high purity H2 stream 8 and an off-gas recycle stream 9 is produced (Pg. 20 lines 8-10). This off-gas recycle stream 9 serves as fuel for a fired heater 135 and optionally also as fuel for steam superheaters (Pg. 20 lines 10-12 meeting limitation “all of the fuel gas is fed to the fired heaters”). The fired heater 135 provides for the indirect heating of hydrocarbon feed 1 and hydrocarbon feed 2 (Pg. 20 lines 12-13). Figure 1 shows off-gas recycle stream 9 flowing into fired heater 135 only. Christensen further discloses the recycling of off-gas increases the hydrogen recovery and thereby the feed consumption is reduced (Pg. 5 lines 16-18).
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 all of the fuel gas to be fed to one or more fired heaters used to heat one or more process streams within the process of Genkin in view of Speth and Rytter in order to increase hydrogen recovery and reduce feed consumption as taught by Christensen.
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 28-30, 34, 40, 42-44, 47-48, 54 provisionally rejected on the ground of nonstatutory double patenting as being unpatentable over claims 22-24, 28-29, 31, 33-37, 42 of copending Application No. 17/997,968 in view of Christensen (“Adiabatic prereforming of hydrocarbons – an important step in syngas production”, hereinafter “Christensen 2”) and Rytter et al (WO 2019/162236 A as cited in IDS 04/12/2024).
Regarding claim 28, copending application ‘968 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 2.6:1 to steam reforming in a gas-heated 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 22).
Regarding the limitation “having a steam to carbon ratio in a range of 0.9:1 to 3.5:1”, copending application ‘968 claim 22 discloses a steam to carbon ratio of at least 2.6:1 which is within the claimed range.
Copending application ‘968 is silent to “adiabatic pre-reforming in a pre-reformer” and “there are two fired heaters that are fueled at least in part by the fuel gas recovered from the purification unit; a first fired heater heats the hydrocarbon feed stream and a reformed gas stream recovered from the pre-reforming stage upstream of the autothermal reforming stage; and a second fired heater is a boiler that generates steam for the process”.
Christensen 2 discloses adiabatic prereforming is a well-established process in modern syngas production and implies both economic and operational benefits (abstract).
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 adiabatic pre-reforming in a pre-reformer in the process of copending application ‘968 in order to have both economic and operational benefits as taught by Christensen 2.
Rytter 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; wherein the reforming processes comprise both a gas-heated reforming process and an autothermal reforming process (abstract). The method further comprises: performing a water-gas-shift on the gas output from the reforming processes; and separating hydrogen from the shifted gas (Pg. 2 lines 33-34).
Rytter further discloses 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 lines 11-12). 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 meeting limitation “the fuel gas is fed to one or more fired heaters used to heat one or more process streams within the process”). 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 (Pg. 15 lines 14-15 meeting limitation “a first fired heater heats the hydrocarbon feed stream”), immediately prior to its input into the pre-reformer 4 and immediately prior to its input into the GHR 1 (Pg. 15 lines 15-16 meeting limitation “and a reformed gas stream recovered from the pre-reforming stage upstream of the autothermal reforming stage”). The rest gas may also be used as a fuel for generating steam 102 that is added before the pre-reformer (Pg. 15 lines 16-17 meeting limitation “and a second fired heater is a boiler that generates steam for the process”). Rytter’s disclosure of fired heater(s) reads on the claim limitation of two fired heaters as it would be obvious to a skilled artisan to fuel any number of fired heaters needed for the process to operate efficiently.
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 fuel gas to be fed to one or more fired heaters used to heat one or more process streams within the process; there are two fired heaters that are fueled at least in part by the fuel gas recovered from the purification unit; a first fired heater heats the hydrocarbon feed stream and a reformed gas stream recovered from the pre-reforming stage upstream of the autothermal reforming stage; and a second fired heater is a boiler that generates steam for the process in the process of copending application ‘968 in order to increase process efficiency by utilizing energy rich components as taught by Rytter.
Regarding claim 29, copending application ‘968 discloses wherein the hydrocarbon is a methane-containing gas stream, preferably containing >50% vol of methane (claim 23).
Regarding claim 30, copending application ‘968 discloses wherein the hydrocarbon is desulphurised (claim 24).
Regarding claim 34, copending application ‘968 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 28).
Regarding claim 40, copending application ‘968 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 31).
Regarding claim 42, copending application ‘968 discloses wherein the purification unit is a pressure swing adsorption unit or a temperature swing adsorption unit, preferably a pressure swing adsorption unit (claim 33).
Regarding claim 43, copending application ‘968 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 34).
Regarding claim 44, copending application ‘968 discloses wherein a portion of the crude hydrogen or pure hydrogen is fed to the hydrocarbon (claim 35).
Regarding claim 47, copending application ‘968 discloses wherein there are two fired heaters fuelled 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 36).
Regarding claim 48, copending application ‘968 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 37).
Regarding claim 54, copending application ‘968 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 42).
This is a provisional nonstatutory double patenting rejection.
Claims 28, 42 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 Baratto et al (US 20200055738 A1, as cited in IDS 11/07/2022) and Rytter et al (WO 2019/162236 A as cited in IDS 04/12/2024).
Regarding claim 28, 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 adiabatic pre-reforming in a pre-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 a range of 0.9:1 to 3.5:1” “with an oxygen-rich gas in an autothermal reformer to generate a reformed gas mixture”, “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” and “there are two fired heaters that are fueled at least in part by the fuel gas recovered from the purification unit; a first fired heater heats the hydrocarbon feed stream and a reformed gas stream recovered from the pre-reforming stage upstream of the autothermal reforming stage; and a second fired heater is a boiler that generates steam for the process”.
Baratto discloses conversion of a charge of desulphurized natural gas and steam with oxygen-enriched air or with oxygen to form a synthesis gas containing hydrogen, CO and CO2 ([0012]). The step of natural gas conversion into synthesis gas comprises primary reforming followed by secondary reforming ([0053]). In some embodiments, more preferably, the conversion step comprises a catalytic autothermal reforming (ATR) ([0053]). A pure ATR, or ATR in combination with a prereformer may advantageously operate with a steam/carbon ratio … more preferably not greater than 1 ([0055]). Baratto further discloses a part 14 of said CO2-depleted syngas 12 is used as fuel in a furnace in the front end, for example in a charge heater ([132]).
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 Baratto (not greater than 1) overlaps with the claimed range (0.9:1 to 3.5:1). Therefore, the range in Baratto renders obvious the claimed range.
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 a steam to carbon ratio in a range of 0.9:1 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 in the process of copending application ‘628 as taught by the preferred embodiments taught by Baratto.
Rytter 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; wherein the reforming processes comprise both a gas-heated reforming process and an autothermal reforming process (abstract). The method further comprises: performing a water-gas-shift on the gas output from the reforming processes; and separating hydrogen from the shifted gas (Pg. 2 lines 33-34).
Rytter further discloses 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 lines 11-12). 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 meeting limitation “the fuel gas is fed to one or more fired heaters used to heat one or more process streams within the process”). 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 (Pg. 15 lines 14-15 meeting limitation “a first fired heater heats the hydrocarbon feed stream”), immediately prior to its input into the pre-reformer 4 and immediately prior to its input into the GHR 1 (Pg. 15 lines 15-16 meeting limitation “and a reformed gas stream recovered from the pre-reforming stage upstream of the autothermal reforming stage”). The rest gas may also be used as a fuel for generating steam 102 that is added before the pre-reformer (Pg. 15 lines 16-17 meeting limitation “and a second fired heater is a boiler that generates steam for the process”). Rytter’s disclosure of fired heater(s) reads on the claim limitation of two fired heaters as it would be obvious to a skilled artisan to fuel any number of fired heaters needed for the process to operate efficiently.
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 fuel gas to be fed to one or more fired heaters used to heat one or more process streams within the process; there are two fired heaters that are fueled at least in part by the fuel gas recovered from the purification unit; a first fired heater heats the hydrocarbon feed stream and a reformed gas stream recovered from the pre-reforming stage upstream of the autothermal reforming stage; and a second fired heater is a boiler that generates steam for the process in the process of copending application ‘628 in order to increase process efficiency by utilizing energy rich components as taught by Rytter.
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 28, 43 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) and Rytter et al (WO 2019/162236 A as cited in IDS 04/12/2024).
Regarding claim 28, 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. adiabatic pre-reforming in a pre-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”, “wherein the fuel gas is fed to one or more fired heaters used to heat one or more process streams within the process” and “there are two fired heaters that are fueled at least in part by the fuel gas recovered from the purification unit; a first fired heater heats the hydrocarbon feed stream and a reformed gas stream recovered from the pre-reforming stage upstream of the autothermal reforming stage; and a second fired heater is a boiler that generates steam for 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.
Rytter 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; wherein the reforming processes comprise both a gas-heated reforming process and an autothermal reforming process (abstract). The method further comprises: performing a water-gas-shift on the gas output from the reforming processes; and separating hydrogen from the shifted gas (Pg. 2 lines 33-34).
Rytter further discloses 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 lines 11-12). 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 meeting limitation “the fuel gas is fed to one or more fired heaters used to heat one or more process streams within the process”). 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 (Pg. 15 lines 14-15 meeting limitation “a first fired heater heats the hydrocarbon feed stream”), immediately prior to its input into the pre-reformer 4 and immediately prior to its input into the GHR 1 (Pg. 15 lines 15-16 meeting limitation “and a reformed gas stream recovered from the pre-reforming stage upstream of the autothermal reforming stage”). The rest gas may also be used as a fuel for generating steam 102 that is added before the pre-reformer (Pg. 15 lines 16-17 meeting limitation “and a second fired heater is a boiler that generates steam for the process”). Rytter’s disclosure of fired heater(s) reads on the claim limitation of two fired heaters as it would be obvious to a skilled artisan to fuel any number of fired heaters needed for the process to operate efficiently.
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 fuel gas to be fed to one or more fired heaters used to heat one or more process streams within the process; there are two fired heaters that are fueled at least in part by the fuel gas recovered from the purification unit; a first fired heater heats the hydrocarbon feed stream and a reformed gas stream recovered from the pre-reforming stage upstream of the autothermal reforming stage; and a second fired heater is a boiler that generates steam for the process in the process of copending application No. 18/719,581 in order to increase process efficiency by utilizing energy rich components as taught by Rytter.
This is a provisional nonstatutory double patenting rejection.
Claims 28-30, 34, 40 provisionally rejected on the ground of nonstatutory double patenting as being unpatentable over claims 8, 12, 17 of copending Application No. 18/710,046 in view of Genkin et al (US 20130243686 A1, as cited in IDS 11/07/2022) and Rytter et al (WO 2019/162236 A as cited in IDS 04/12/2024).
Regarding claim 28, copending application ‘046 claims 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 … adiabatic pre-reformer followed by autothermal reforming with an oxygen-rich gas in an autothermal reformer to generate a reformed gas mixture (claim 1 meeting limitation “a process for the production of hydrogen comprising the steps of: (i) subjecting a gaseous mixture comprising a hydrocarbon and steam”, “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 (claim 1 meeting limitation “(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”).
Regarding the limitation “having a steam to carbon ratio in the range of 0.9:1 to 3.5:1”, ‘046 claims wherein the steam to carbon ratio in the gaseous mixture is in the range 0.9: to 5:1.
Copending application ‘046 does not claim “(iii) cooling the hydrogen-enriched reformed gas and separating condensed water therefrom to provide a de-watered hydrogen-enriched reformed gas, (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 separation 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; there are two fired heaters that are fueled at least in part by the fuel gas recovered from the purification unit; a first fired heater heats the hydrocarbon feed stream and a reformed gas stream recovered from the pre-reforming stage upstream of the autothermal reforming stage; and a second fired heater is a boiler that generates steam for the process”.
Genkin discloses a process for producing hydrogen ([0068]). The process further comprises recovering heat from the shifted reformate thereby cooling the shifted reformate ([0098] meeting limitation “cooling the hydrogen-enriched reformed gas”). The step of recovering heat from the reformate from reactor 20 may comprise heating a hydrocarbon feedstock by indirect heat exchange ([0087]). The process further comprises removing H2O from the shifted reformate to form a water-depleted reformate ([0101] meeting limitation “separating condensed water therefrom to provide a de-watered hydrogen-enriched reformed gas”). H2O removed from the shifted reformate may be used to form boiler feed water with makeup water 84 added ([0102]). 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] meeting limitation “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”). 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] meeting limitation “passing the crude hydrogen gas stream from the carbon dioxide separation unit to a purification unit to provide a purified hydrogen gas and a fuel gas”). The process may further comprise combusting a third portion 106 of the tail gas stream in a boiler to generate a portion of the steam introduced into reactor 10 ([0114] meeting limitation “wherein the fuel gas is fed to one or more fired heaters used to heat one or more process streams within the process”).
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 separating condensed water therefrom to provide a de-watered hydrogen-enriched reformed gas, (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 separation 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 in the process of copending application ‘046 in order to heat a hydrocarbon feedstock by indirect heat exchange, use separated H2O as boiler feed water, to produce a CO2 product stream, to produce a H2 product stream and to generate a portion of the steam introduced into the pre-reformer as taught by Genkin.
Rytter 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; wherein the reforming processes comprise both a gas-heated reforming process and an autothermal reforming process (abstract). The method further comprises: performing a water-gas-shift on the gas output from the reforming processes; and separating hydrogen from the shifted gas (Pg. 2 lines 33-34).
Rytter further discloses 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 lines 11-12). 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 meeting limitation “the fuel gas is fed to one or more fired heaters used to heat one or more process streams within the process”). 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 (Pg. 15 lines 14-15 meeting limitation “a first fired heater heats the hydrocarbon feed stream”), immediately prior to its input into the pre-reformer 4 and immediately prior to its input into the GHR 1 (Pg. 15 lines 15-16 meeting limitation “and a reformed gas stream recovered from the pre-reforming stage upstream of the autothermal reforming stage”). The rest gas may also be used as a fuel for generating steam 102 that is added before the pre-reformer (Pg. 15 lines 16-17 meeting limitation “and a second fired heater is a boiler that generates steam for the process”). Rytter’s disclosure of fired heater(s) reads on the claim limitation of two fired heaters as it would be obvious to a skilled artisan to fuel any number of fired heaters needed for the process to operate efficiently.
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 fuel gas to be fed to one or more fired heaters used to heat one or more process streams within the process; there are two fired heaters that are fueled at least in part by the fuel gas recovered from the purification unit; a first fired heater heats the hydrocarbon feed stream and a reformed gas stream recovered from the pre-reforming stage upstream of the autothermal reforming stage; and a second fired heater is a boiler that generates steam for the process in the process of copending application ‘046 in order to increase process efficiency by utilizing energy rich components as taught by Rytter.
Regarding claim 29, copending application ‘046 claims wherein the hydrocarbon is a methane-containing gas stream containing >50% vol of methane (claim 2).
Regarding claim 30, copending application ‘046 claims wherein the hydrocarbon is desulphurised (claim 3).
Regarding claim 34, copending application ‘046 claims wherein the oxygen-rich gas comprises at least 90% by volume O2 (claim 6).
Regarding claim 40, copending application ‘046 claims wherein carbon dioxide removal in the carbon dioxide separation unit is performed using a physical wash system or a reactive wash system (claim 10).
This is a provisional nonstatutory double patenting rejection.
Conclusion
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/N.L.Q./Examiner, Art Unit 1738
/MICHAEL FORREST/Primary Examiner, Art Unit 1738
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