DETAILED ACTIONNotice 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 .
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 1 and 17 are rejected on the ground of nonstatutory double patenting as being unpatentable over claim 1 of U.S. Patent No. 12,371,335, herein known as ‘335. Although the claims at issue are not identical, they are not patentably distinct from each other because the system of claim 17 in the instant application is anticipated by the system disclosed in claim 1 of ‘335. Furthermore, the method of claim 1 in the instant application is rendered obvious by the system disclosed in claim 1 of ‘335, as the method recites all the functions of the system, and is thus considered an “obvious variation” of the system. See MPEP 804.II.B.
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 1, 3-4, 13, 15-17, and 19 are rejected under 35 U.S.C. 103 as being unpatentable over Han et al. (US 2020/0172394 A1) in view of Flytzani-Stephanopoulos et al. (US 8628744 B2) and Han et al. (CN 113562701 A, citations from corresponding US 2023/0092115 A1), herein known as Han’701.
With regard to Claim 1, Han teaches a method for producing ammonia (Abstract, method for the preparation of ammonia synthesis gas).
Han teaches electrolyzing water to form a first electrolysis stream comprising H2 and a second electrolysis stream comprising O2 (Paragraph 0011, a separate hydrogen stream and a separate oxygen stream by electrolysis of water).
Han teaches contacting a reformer feed stream comprising hydrocarbons (Paragraph 0011, reforming at least a part of the hydrocarbon feed stock), at least a portion of the second electrolysis stream comprising O2 (Paragraph 0010, the oxygen product from electrolysis of water is advantageously used for partial oxidation), and an oxidant stream comprising O2 and N2 (Paragraph 0016, the atmospheric air… is enriched with oxygen from the water electrolysis).
Han teaches forming a subsequent reformed stream comprising H2, CO, CO2, and N-2 (Paragraph 0011, a process gas stream comprising hydrogen, nitrogen, carbon monoxide and carbon dioxide).
Han teaches contacting at least a portion of the reformed stream through a water-gas shift reaction to form a shifted stream comprising H2, CO2, and N2 (Paragraph 0022, subjecting the process gas to one or more water gas shift reactions of CO to CO2).
Han teaches separating at least a portion of the shifted stream to form a captured stream comprising CO2 (Paragraph 0039, carbon dioxide…is removed from the water gas shift treated process gas stream…by absorption in N-methyldiethanolamine (MDEA), as known in the art).
Han teaches separating at least a portion of the shifted stream to form an ammonia production feed stream comprising H2 and N2 (Fig. 1, purified process gas stream 19).
Han teaches reacting an ammonia production mixture comprising at least a portion of the ammonia production feed stream comprising H2 and N2, and optionally at least a portion of the first electrolysis stream comprising H2, to form a product stream comprising ammonia (Paragraph 0009, hydrogen from the electrolysis can be used to adjust the hydrogen/nitrogen molar ratio in the ammonia synthesis gas…for the production of ammonia).
However, Han is silent to the use of a water-gas shift catalyst in the water-gas shift reaction.
Flytzani-Stephanopoulos discloses a sulfur-tolerant water-gas shift catalyst (Abstract). Flytzani-Stephanopoulos teaches a method of reacting CO with water to form a product with an increased amount of CO2 and decreased amount of CO (Col. 2, lines 19-21, a method of oxidizing carbon monoxide with water to produce carbon dioxide and hydrogen by a WGS reaction). Such a catalyst is present to catalyze, or speed up, the water-gas shift reaction, as commonly known in the art.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for Han to use a water-gas shift catalyst in the water-gas shift reaction, as taught by Flytzani-Stephanopoulos, to catalyze, or speed up, the water-gas shift reaction, as commonly known in the art.
However, Han is further silent to liquefying at least a portion of the second electrolysis stream comprising O2 to form liquid O2 and storing the liquid O2, and gasifying at least a portion of the stored liquid O2 to form a gasified O2 stream.
Han’701 discloses a device and method for recovering by-product oxygen from water-electrolysis hydrogen production (Abstract, A device and a method for recovering by-product oxygen from water-electrolysis hydrogen production using a low-temperature method are provided). This includes liquefying the oxygen (Paragraph 0010, the oxygen is cooled to a liquid state to obtain liquid oxygen), storing the liquid oxygen (Paragraph 0010, one stream of liquid is directly collected from a cold box to obtain liquid oxygen products), and gasifying at least a portion of the stored liquid oxygen (Paragraph 0010, the pressurized and cooled circulating argon enters the plate heat exchanger to gasify high-pressure liquid oxygen as a high-pressure heat source).
Han’701 notes that this is done to reduce the unit consumption of oxygen and overall carbon emissions (Paragraph 0004, so as to…greatly reduce the unit consumption of oxygen production of high-pressure oxygen and liquid oxygen required by users, and reduce the overall carbon emission of users; Paragraph 0014, The energy consumption of high-pressure gas oxygen per production unit is not higher than 0.13 KW·h/m3… thus reducing carbon emissions and realizing a win-win situation of enterprise economic benefits and environmental benefits).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for Han to liquefy, store, and gasify oxygen, as taught in Han’701, to reduce the unit consumption of oxygen and overall carbon emissions.
With regard to Claim 3, Han teaches a molar ratio of H2 to N2 present in the ammonia production mixture within the range of about 2.5:1 to about 3.5:1 (Paragraph 0017, the molar ratio of hydrogen to nitrogen in ammonia synthesis gas is required to be between 2.7-3.3).
With regard to Claim 4, Han teaches a molar ratio of a total amount of H2 present in the first electrolysis stream and H2 present in the shifted stream to a total amount of N2 present in the reformed stream within the range of at least about 2.5 (Paragraph 0020, at least a part of the hydrogen stream…is added to process gas stream…in an amount to provide a molar ratio of the hydrogen to the nitrogen of 2.7-3.3 in the ammonia synthesis gas).
With regard to Claim 13, Han teaches the electrolysis as being driven by renewable energy (Paragraph 0028, in a preferred embodiment of the invention, the electrolysis of water is powered by renewable energy).
With regard to Claim 15, Han teaches the oxidant stream comprising air (Paragraph 0011, reforming at least a part of the hydrocarbon feed stock with the oxygen enriched process air).
With regard to Claim 16, ‘under conditions sufficient’ is interpreted as any conditions where ammonia can be formed. Han teaches a method for producing ammonia (Abstract, method for the preparation of ammonia synthesis gas).
Therefore, Han teaches contacting the ammonia production mixture in a process under conditions sufficient to form ammonia.
With regard to Claim 17, Han teaches a system for producing ammonia (Abstract, method for the preparation of ammonia synthesis gas).
Han teaches an electrolyzer configured to electrolyze water to form a first electrolysis stream comprising H2 and a second electrolysis stream comprising O2 (Paragraph 0011, a separate hydrogen stream and a separate oxygen stream by electrolysis of water).
Han teaches a reformer configured to contact a reformer feed stream comprising hydrocarbons (Paragraph 0011, reforming at least a part of the hydrocarbon feed stock), at least a portion of the second electrolysis stream comprising O2 (Paragraph 0010, the oxygen product from electrolysis of water is advantageously used for partial oxidation), and an oxidant stream comprising O2 and N2 (Paragraph 0016, the atmospheric air… is enriched with oxygen from the water electrolysis).
Han teaches forming a subsequent reformed stream comprising H2, CO, CO2, and N-2 (Paragraph 0011, a process gas stream comprising hydrogen, nitrogen, carbon monoxide and carbon dioxide).
Han teaches a water-gas shift reactor configured to contact at least a portion of the reformed stream through a water-gas shift reaction to form a shifted stream comprising H2, CO2, and N2 (Paragraph 0022, subjecting the process gas to one or more water gas shift reactions of CO to CO2).
Han teaches a carbon capture unit configured to separate at least a portion of the shifted stream to form a captured stream comprising CO2 (Paragraph 0039, carbon dioxide…is removed from the water gas shift treated process gas stream…by absorption in N-methyldiethanolamine (MDEA), as known in the art).
Han teaches forming an ammonia production feed stream comprising H2 and N2 (Fig. 1, purified process gas stream 19).
Han teaches an ammonia production unit configured to react at least a portion of the ammonia production feed stream comprising H2 and N2, and optionally at least a portion of the first electrolysis stream comprising H2, to form a product stream comprising ammonia (Paragraph 0009, hydrogen from the electrolysis can be used to adjust the hydrogen/nitrogen molar ratio in the ammonia synthesis gas…for the production of ammonia).
However, Han is silent to the use of a water-gas shift catalyst in the water-gas shift reaction.
Flytzani-Stephanopoulos discloses a sulfur-tolerant water-gas shift catalyst (Abstract). Flytzani-Stephanopoulos teaches a method of reacting CO with water to form a product with an increased amount of CO2 and decreased amount of CO (Col. 2, lines 19-21, a method of oxidizing carbon monoxide with water to produce carbon dioxide and hydrogen by a WGS reaction). Such a catalyst is present to catalyze, or speed up, the water-gas shift reaction, as commonly known in the art.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for Han to use a water-gas shift catalyst in a water-gas shift reaction, as taught by Flytzani-Stephanopoulos, to catalyze, or speed up, the water-gas shift reaction, as commonly known in the art.
However, Han is further silent to an O2 liquefaction unit configured to liquefy at least a portion of the second electrolysis stream comprising O2 to form liquid O2, an O2 storage facility configured to store the liquid O2, and an O2 gasification unit configured to gasify at least a portion of the liquid O2 to form a gasified O2 stream and provide the gasified O2 to the reformer.
Han’701 discloses a device and method for recovering by-product oxygen from water-electrolysis hydrogen production (Abstract, A device and a method for recovering by-product oxygen from water-electrolysis hydrogen production using a low-temperature method are provided).
This includes an O2 liquefaction unit configured to liquefy oxygen (Paragraph 0010, the oxygen is cooled to a liquid state to obtain liquid oxygen), an O2 storage facility configured to store the liquid oxygen (Paragraph 0010, one stream of liquid is directly collected from a cold box to obtain liquid oxygen products), and an O2 gasification unit configured to gasify at least a portion of the stored liquid oxygen (Paragraph 0010, the pressurized and cooled circulating argon enters the plate heat exchanger to gasify high-pressure liquid oxygen as a high-pressure heat source).
Han’701 notes that this is done to reduce the unit consumption of oxygen and overall carbon emissions (Paragraph 0004, so as to…greatly reduce the unit consumption of oxygen production of high-pressure oxygen and liquid oxygen required by users, and reduce the overall carbon emission of users; Paragraph 0014, The energy consumption of high-pressure gas oxygen per production unit is not higher than 0.13 KW·h/m3… thus reducing carbon emissions and realizing a win-win situation of enterprise economic benefits and environmental benefits).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for Han to disclose an O2 liquefaction unit configured to liquefy oxygen, an O2 storage facility configured to store the liquid oxygen, and an O2 gasification unit configured to gasify at least a portion of the stored liquid oxygen, as taught in Han’701, to reduce the unit consumption of oxygen and overall carbon emissions.
With regard to Claim 19, Han teaches maintaining a molar ratio of a total amount of H2 present in the first electrolysis stream and H2 present in the shifted stream to a total amount of N2 present in the reformed stream within the range of at least about 2.5 (Paragraph 0020, at least a part of the hydrogen stream…is added to process gas stream…in an amount to provide a molar ratio of the hydrogen to the nitrogen of 2.7-3.3 in the ammonia synthesis gas).
Claims 2 and 18 are rejected under 35 U.S.C. 103 as being unpatentable over Han et al. (US 2020/0172394 A1) in view of Flytzani-Stephanopoulos et al. (US 8628744 B2) and Han’701, as applied to the claims above, and further in view of Kawasaki et al. (WO 2019043875 A1) and Ostuni et al. (US 2013/0108538 A1).
With regard to Claim 2, modified Han teaches all the limitations in the claims as set forth above.
In addition, modified Han teaches an amount of the gasified O2 contacted to form the reformed stream (Paragraph 0010, the oxygen product from electrolysis of water is advantageously used for partial oxidation).
Modified Han teaches an amount of the oxidant stream contacted to form the reformed stream (Paragraph 0016, the atmospheric air used in the method according to the invention is enriched with oxygen from the water electrolysis).
Modified Han teaches an amount of the reformer feed stream contacted to form the reformed stream (Paragraph 0011, reforming at least a part of the hydrocarbon feed stock).
However, modified Han is silent to selecting a ratio of an amount of the gasified O2, an amount of the oxidant stream, and an amount of the reformer feed stream.
Modified Han is also silent to maintaining a rate of formation of the product stream that is at least 50% of a maximum rate of formation of the product stream corresponding to a maximum rate of formation of the first electrolysis stream.
Kawasaki teaches selecting a ratio of an amount of the oxidant stream (Paragraph 0071, the amount of nitrogen-rich gas mixed with the refined gas or the reformed gas downstream of the reformer outlet is adjusted). This is done to optimize the ratio of hydrogen to nitrogen in the ammonia production feed stream (Paragraph 0071, the ratio of hydrogen concentration to nitrogen concentration in the ammonia synthesis feed gas becomes 2 to 4:1, which is suitable for ammonia synthesis).
Kawasaki teaches selecting a ratio of amount of the reformer feed stream (Paragraph 0062, the flow rate of the refined gas supplied to the reformer is adjusted). This is done to optimize the ratio of hydrogen to nitrogen in the ammonia production feed stream (Paragraph 0062, the ratio of hydrogen concentration to nitrogen concentration in the ammonia synthesis raw material gas becomes 2 to 4:1, which is a ratio suitable for the ammonia synthesis reaction).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to select an amount of the oxidant stream contacted to form the reformed stream and an amount of the reformer feed stream contacted to form the reformed stream, as taught in Kawasaki. One of ordinary skill in the art would have been motivated to optimize the ratio of hydrogen to nitrogen in the ammonia production feed stream in order to produce the desired ammonia product with minimal amounts of unreacted reagents.
However, Kawasaki is silent to selecting a ratio of an amount of the gasified O2, and maintaining a rate of formation of the product stream that is at least 50% of a maximum rate of formation of the product stream corresponding to a maximum rate of formation of the first electrolysis stream.
Ostuni teaches selecting a ratio of an amount of the gasified O2 (Paragraph 0023, the ammonia production is regulated by reducing or increasing the load of said electrolysis section). This is done to account for short term changes in cost or availability of feed (Paragraph 0013, One of the aims of the invention is to provide an ammonia process whose output can be regulated to follow short-term variations of cost and/or availability of a source feed).
Ostuni teaches maintaining a rate of formation of the product stream that is at least 50% of a maximum rate of formation of the product stream corresponding to a maximum rate of formation of the first electrolysis stream (Paragraph 0011, large ammonia plants, which are in any case unable to operate
below a 50%-60% of nominal capacity). This is because of the high operating cost of the ammonia plant (Paragraph 0011, there would be no incentive to run such a large plant at a low partial load).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to select a ratio of an amount of the gasified O2, as taught in Ostuni, to account for short term changes in cost or availability of feed.
It would also have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to maintain a rate of formation of the product stream that is at least 50% of a maximum rate of formation of the product stream corresponding to a maximum rate of formation of the first electrolysis stream, as taught in Ostuni, because of the high operating cost of the ammonia plant.
With regard to Claim 18, modified Han teaches all the limitations in the claims as set forth above.
In addition, modified Han teaches an amount of the gasified O2 contacted in the reformer (Paragraph 0010, the oxygen product from electrolysis of water is advantageously used for partial oxidation).
Modified Han teaches an amount of the oxidant stream contacted in the reformer (Paragraph 0016, the atmospheric air used in the method according to the invention is enriched with oxygen from the water electrolysis).
Modified Han teaches an amount of the reformer feed stream contacted in the reformer (Paragraph 0011, reforming at least a part of the hydrocarbon feed stock).
However, modified Han is silent to adjusting a ratio of an amount of the gasified O2, an amount of the oxidant stream, and an amount of the reformer feed stream.
Modified Han is also silent to maintaining a rate of formation of the product stream that is at least 50% of a maximum rate of formation of the product stream corresponding to a maximum rate of formation of the first electrolysis stream.
Kawasaki teaches adjusting a ratio of an amount of the oxidant stream (Paragraph 0071, the amount of nitrogen-rich gas mixed with the refined gas or the reformed gas downstream of the reformer outlet is adjusted). This is done to optimize the ratio of hydrogen to nitrogen in the ammonia production feed stream. (Paragraph 0071, the ratio of hydrogen concentration to nitrogen concentration in the ammonia synthesis feed gas becomes 2 to 4:1, which is suitable for ammonia synthesis).
Kawasaki teaches adjusting a ratio of amount of the reformer feed stream (Paragraph 0062, the flow rate of the refined gas supplied to the reformer is adjusted). This is done to optimize the ratio of hydrogen to nitrogen in the ammonia production feed stream (Paragraph 0062, the ratio of hydrogen concentration to nitrogen concentration in the ammonia synthesis raw material gas becomes 2 to 4:1, which is a ratio suitable for the ammonia synthesis reaction).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to adjust an amount of the oxidant stream contacted to form the reformed stream and an amount of the reformer feed stream contacted to form the reformed stream, as taught in Kawasaki. One of ordinary skill in the art would have been motivated to optimize the ratio of hydrogen to nitrogen in the ammonia production feed stream in order to produce the desired ammonia product with minimal amounts of unreacted reagents.
However, Kawasaki is silent to adjusting a ratio of an amount of the gasified O2, and maintaining a rate of formation of the product stream that is at least 50% of a maximum rate of formation of the product stream corresponding to a maximum rate of formation of the first electrolysis stream.
Ostuni teaches adjusting a ratio of an amount of the gasified O2 (Paragraph 0023, the ammonia production is regulated by reducing or increasing the load of said electrolysis section). This is done to account for short term changes in cost or availability of feed (Paragraph 0013, One of the aims of the invention is to provide an ammonia process whose output can be regulated to follow short-term variations of cost and/or availability of a source feed).
Ostuni teaches maintaining a rate of formation of the product stream that is at least 50% of a maximum rate of formation of the product stream corresponding to a maximum rate of formation of the first electrolysis stream (Paragraph 0011, large ammonia plants, which are in any case unable to operate below a 50%-60% of nominal capacity). This is because of the high operating cost of the ammonia plant (Paragraph 0011, there would be no incentive to run such a large plant at a low partial load).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to adjust a ratio of an amount of the gasified O2, as taught in Ostuni, to account for short term changes in cost or availability of feed.
It would also have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to maintain a rate of formation of the product stream that is at least 50% of a maximum rate of formation of the product stream corresponding to a maximum rate of formation of the first electrolysis stream, as taught in Ostuni, because of the high operating cost of the ammonia plant.
Claims 5-6, 8, and 20-21 are rejected under 35 U.S.C. 103 as being unpatentable over Han et al. (US 2020/0172394 A1) in view of Flytzani-Stephanopoulos et al. (US 8628744 B2) and Han’701, as applied to the claims above, and further in view of Hannemann et al. (WO 2021122584 A1, citations from corresponding US 2023/0020698 A1) and DE202010012734U1, hereby known as DE734.
With regard to Claim 5, modified Han teaches all the limitations in the claims as set forth above.
Modified Han is silent to combusting an oxy-fuel combustion mixture comprising a portion of the second electrolysis stream comprising O2, and a fuel feed stream comprising a combustible fuel to produce thermal energy, and converting at least a portion of the thermal energy to electrical energy.
Modified Han is silent to capturing at least a portion of CO2 formed by combusting the oxy-fuel combustion mixture.
Hannemann discloses combusting an oxy-fuel combustion mixture comprising a portion of the second electrolysis stream comprising O2 (Paragraph 0011, an oxyfuel combustion plant is further comprised, in which noncondensable off-gases from the chemical reactor and oxygen O2 from the electrolyzer are suppliable).
Hannemann discloses a fuel feed stream comprising a combustible fuel to produce thermal energy (Paragraph 0017, the heat generated during the combustion is dissipatable and is integrable into other parts of the power-to-X plant).
Hannemann notes that this is done for further decarbonization of the transport and energy sectors (Paragraph 0003, power-to-liquid/power-to-gas processes which may be a major element for decarbonization or defossilization of the transport and energy sector).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to combust an oxy-fuel combustion mixture comprising a portion of the second electrolysis stream comprising O2, a fuel feed stream comprising a combustible fuel to produce thermal energy, and capturing at least a portion of CO2 formed by combusting the oxy-fuel combustion mixture, as taught in Hannemann, in order for further decarbonization of the transport and energy sectors.
However, Hannemann is silent to converting at least a portion of the thermal energy to electrical energy.
DE734 discloses a process in which thermal energy is converted to electrical energy (Paragraph 0009, the thermal energy of the flue gas stream formed during combustion can be used to generate electrical energy in a gas turbine process and/or in a steam turbine process). This is done as an additional supply of energy to other units in the process, such as the compressor or electrolyzer (Paragraph 0013, A portion of the electrical energy generated…can be provided for internal use in the energy source generation plant…for example for the compression of material flows and/or for the electrolysis of water to generate the hydrogen flow in the electrolysis unit).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to convert at least a portion of the thermal energy to electrical energy, as taught in DE734, in order to add an additional supply of energy to other units in the process, such as the compressor or electrolyzer.
With regard to Claim 6, modified Han teaches all the limitations in the claims as set forth above.
Modified Han is silent to combusting an oxy-fuel combustion mixture comprising a portion of the second electrolysis stream comprising O2, a fuel feed stream comprising a combustible fuel, and a compressed CO2 stream comprising supercritical CO2 to form a high-pressure exhaust.
Modified Han is silent to expanding the high-pressure exhaust to produce electrical energy.
Modified Han is silent to compressing at least a portion of the expanded exhaust to form the compressed CO2 stream.
Hannemann teaches combusting an oxy-fuel combustion mixture comprising a portion of the second electrolysis stream comprising O2 and a fuel feed stream comprising a combustible fuel (Paragraph 0011, an oxyfuel combustion plant is further comprised, in which noncondensable off-gases from the chemical reactor and oxygen O2 from the electrolyzer are suppliable). Hannemann notes that this is done for further decarbonization of the transport and energy sectors (Paragraph 0003, power-to-liquid/power-to-gas processes which may be a major element for decarbonization or defossilization of the transport and energy sector).
Hannemann teaches compressing at least a portion of the expanded exhaust to form the compressed CO2 stream (Paragraph 0021, the H2/CO2 synthesis gas is compressed using a piston compressor to operating pressures above 10 bar). This is done to recycle the CO2 into the combustion process (Paragraph 0025, carbon dioxide CO2 which is formed as a result of the combustion of the off-gases is recycled into the stream of hydrogen H2 downstream of the electrolyzer).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to combust an oxy-fuel combustion mixture comprising a portion of the second electrolysis stream comprising O2 and a fuel feed stream comprising a combustible fuel, as taught in Hannemann, in order for further decarbonization of the transport and energy sectors.
It also would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to compress at least a portion of the expanded exhaust to form the compressed CO2 stream, as taught in Hannemann, in order for recycling of CO2 in the combustion process.
However, Hannemann is silent to a compressed CO2 stream comprising supercritical CO2 to form a high-pressure exhaust, and expanding the high-pressure exhaust to produce electrical energy.
DE734 discloses the mixture comprising a compressed CO2 stream comprising supercritical CO2 to form a high-pressure exhaust (Paragraph 0022, it is also possible to store carbon dioxide from the flue gas and/or an external carbon dioxide stream in a storage unit and supply it to the reactor unit as needed… the carbon dioxide stream can be compressed, preferably liquefied). DE734 notes that the recycling of CO2 can reduce emissions (Paragraph 0012, the flue gas stream generated…creates a closed carbon dioxide cycle, which reduces the burden on the environment by reducing carbon dioxide emissions).
DE734 discloses expanding the high-pressure exhaust to produce electrical energy (Paragraph 0015, to generate electrical power by using the flue gas stream formed during the combustion of the external energy carrier stream in the combustion chamber in the gas turbine process and/or the steam turbine process). This allows for an alternative source of electrical power to the electrolysis unit (Paragraph 0015, This is particularly advantageous…when the available electrical energy from a renewable energy source is not sufficient to supply sufficient power for the electrolysis unit).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to have a compressed CO2 stream comprising supercritical CO2 to form a high-pressure exhaust, as taught in DE734, in order for reduced emissions through the recycling of CO2.
It would also have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to expand the high-pressure exhaust to produce electrical energy, as taught in DE734, in order to provide an alternative source of electrical power to the electrolysis unit.
With regard to Claim 8, modified Han teaches all the limitations in the claims as set forth above.
However, modified Han is silent to the water-gas shift catalyst comprising a sulfur-tolerant water-gas shift catalyst.
Flytzani-Stephanopoulos teaches the water-gas shift catalyst comprising a sulfur-tolerant water-gas shift catalyst (Col. 1, lines 34-36, certain lanthanide oxysulfides and lanthanide oxysulfates can be used as sulfur-tolerant high-temperature catalysts for both the WGS reaction and the RWGS reaction). Flytzani-Stephanopoulos notes that this is done because sulfur containing compounds are not tolerated by commercial water-gas shift catalysts (Col. 1, lines 20-23, fuel gas streams derived from the reformation or gasification of fuels often contain sulfur compounds that are not tolerated by commercial high-temperature water-gas shift catalysts).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to have a sulfur-tolerant water-gas shift catalyst, as taught in Flytzani-Stephanopoulos, because sulfur containing compounds are not tolerated by commercial water-gas shift catalysts.
However, modified Han is silent to the reformer feed stream comprising a heavy feedstock, and the captured stream further comprising one or more sulfur-containing compounds.
Hannemann teaches the supplying of biomass into the oxyfuel combustion plant (Paragraph 0023, biomass is additionally supplied to the oxyfuel combustion plant). ‘Heavy feedstock’ can be interpreted as including biomass, as specified in Paragraph 0025 of the instant specification. Therefore, Hannemann teaches a heavy feedstock. It is known that biomass can offset CO2 emissions through its growth (Paragraph 0018, biomass and/or processed waste for CO2-neutral incineration is, alternatively or additionally, suppliable to the oxyfuel combustion plant).
Hannemann teaches a captured stream comprising one or more sulfur-containing compounds (Paragraph 0023, the carbon dioxide CO2 produced in the oxyfuel process is contaminated with sulfur, alkali-metal and halogen compounds). When using a heavy feedstock such as biomass as disclosed above, it would have been obvious to remove sulfur impurities to produce a purer product.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to have a reformer feed stream comprising a heavy feedstock, such as biomass, as taught in Hannemann, since it is known that biomass can offset CO2 emissions through its growth.
It would have also been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to have the captured stream further comprising one or more sulfur-containing compounds, as taught in Hannemann. When using a heavy feedstock such as biomass, as taught in Hannemann, it would have been obvious to remove sulfur impurities to produce a purer product.
With regard to Claim 20, modified Han teaches all the limitations in the claims as set forth above.
Modified Han is silent to a power plant configured to combust an oxy-fuel combustion mixture comprising a portion of the second electrolysis stream comprising O2, and a fuel feed stream comprising a combustible fuel to produce thermal energy, and converting at least a portion of the thermal energy to electrical energy.
Modified Han is silent to capturing at least a portion of CO2 formed by combusting the oxy-fuel combustion mixture.
Hannemann discloses a power plant configured to combust an oxy-fuel combustion mixture comprising a portion of the second electrolysis stream comprising O2 (Paragraph 0011, an oxyfuel combustion plant is further comprised, in which noncondensable off-gases from the chemical reactor and oxygen O2 from the electrolyzer are suppliable).
Hannemann discloses a fuel feed stream comprising a combustible fuel to produce thermal energy (Paragraph 0017, the heat generated during the combustion is dissipatable and is integrable into other parts of the power-to-X plant). Hannemann notes that this is done for further decarbonization of the transport and energy sectors (Paragraph 0003, power-to-liquid/power-to-gas processes which may be a major element for decarbonization or defossilization of the transport and energy sector).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to combust an oxy-fuel combustion mixture comprising a portion of the second electrolysis stream comprising O2, a fuel feed stream comprising a combustible fuel to produce thermal energy, and capturing at least a portion of CO2 formed by combusting the oxy-fuel combustion mixture, as taught in Hannemann, in order for further decarbonization of the transport and energy sectors.
However, Hannemann is silent to converting at least a portion of the thermal energy to electrical energy.
DE734 discloses a process in which thermal energy is converted to electrical energy (Paragraph 0009, the thermal energy of the flue gas stream formed during combustion can be used to generate electrical energy in a gas turbine process and/or in a steam turbine process). This is done as an additional supply of energy to other units in the process, such as the compressor or electrolyzer (Paragraph 0013, A portion of the electrical energy generated…can be provided for internal use in the energy source generation plant…for example for the compression of material flows and/or for the electrolysis of water to generate the hydrogen flow in the electrolysis unit).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to convert at least a portion of the thermal energy to electrical energy, as taught in DE734, in order to provide an additional supply of energy to other units in the process, such as the compressor or electrolyzer.
With regard to Claim 21, modified Han teaches all the limitations in the claims as set forth above.
Modified Han is silent to a power plant configured to combust an oxy-fuel combustion mixture comprising a portion of the second electrolysis stream comprising O2, a fuel feed stream comprising a combustible fuel, and a compressed CO2 stream comprising supercritical CO2 to form a high-pressure exhaust.
Modified Han is silent to expanding the high-pressure exhaust to produce electrical energy.
Modified Han is silent to compressing at least a portion of the expanded exhaust to form the compressed CO2 stream.
Hannemann teaches a power plant configured to combust an oxy-fuel combustion mixture comprising a portion of the second electrolysis stream comprising O2 and a fuel feed stream comprising a combustible fuel (Paragraph 0011, an oxyfuel combustion plant is further comprised, in which noncondensable off-gases from the chemical reactor and oxygen O2 from the electrolyzer are suppliable). Hannemann notes that this is done for further decarbonization of the transport and energy sectors (Paragraph 0003, power-to-liquid/power-to-gas processes which may be a major element for decarbonization or defossilization of the transport and energy sector).
Hannemann teaches compressing at least a portion of the expanded exhaust to form the compressed CO2 stream (Paragraph 0021, the H2/CO2 synthesis gas is compressed using a piston compressor to operating pressures above 10 bar). This is done to recycle the CO2 into the combustion process (Paragraph 0025, carbon dioxide CO2 which is formed as a result of the combustion of the off-gases is recycled into the stream of hydrogen H2 downstream of the electrolyzer).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to have a power plant configured to combust an oxy-fuel combustion mixture comprising a portion of the second electrolysis stream comprising O2 and a fuel feed stream comprising a combustible fuel, as taught in Hannemann, in order for further decarbonization of the transport and energy sectors.
It also would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to compress at least a portion of the expanded exhaust to form the compressed CO2 stream, as taught in Hannemann, in order for recycling of CO2 in the combustion process.
However, Hannemann is silent to a compressed CO2 stream comprising supercritical CO2 to form a high-pressure exhaust, and expanding the high-pressure exhaust to produce electrical energy.
DE734 discloses the mixture comprising a compressed CO2 stream comprising supercritical CO2 to form a high-pressure exhaust (Paragraph 0022, it is also possible to store carbon dioxide from the flue gas and/or an external carbon dioxide stream in a storage unit and supply it to the reactor unit as needed… the carbon dioxide stream can be compressed, preferably liquefied). DE734 notes that the recycling of CO2 can reduce emissions (Paragraph 0012, the flue gas stream generated…creates a closed carbon dioxide cycle, which reduces the burden on the environment by reducing carbon dioxide emissions).
DE734 discloses expanding the high-pressure exhaust to produce electrical energy (Paragraph 0015, to generate electrical power by using the flue gas stream formed during the combustion of the external energy carrier stream in the combustion chamber in the gas turbine process and/or the steam turbine process). This allows for an alternative source of electrical power to the electrolysis unit (Paragraph 0015, This is particularly advantageous…when the available electrical energy from a renewable energy source is not sufficient to supply sufficient power for the electrolysis unit).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to have a compressed CO2 stream comprising supercritical CO2 to form a high-pressure exhaust, as taught in DE734, in order for reduced emissions through the recycling of CO2.
It would also have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to expand the high-pressure exhaust to produce electrical energy, as taught in DE734, in order to provide an alternative source of electrical power to the electrolysis unit.
Claims 7 and 22 are rejected under 35 U.S.C. 103 as being unpatentable over Han et al. (US 2020/0172394 A1) in view of Flytzani-Stephanopoulos et al. (US 8628744 B2), Han’701, Hannemann et al. (WO 2021122584 A1, citations from corresponding US 2023/0020698 A1) and DE202010012734U1, hereby known as DE734, as applied to claims 5-6, 8, and 20-21 above, and further in view of Kapoor et al. (US 5714132 A).
With regard to Claim 7, modified Han’ teaches all the limitations in the claims as set forth above.
Modified Han’ is silent to separating a portion of the reformed stream comprising CO to form the fuel feed stream.
Kapoor discloses separating a portion of the reformed stream comprising CO to form the fuel feed stream (Col. 3, lines 3-6, subjecting the reactor effluent to a pressure swing adsorption process with an adsorbent which more strongly adsorbs carbon monoxide than hydrogen, thereby producing high purity carbon monoxide and a hydrogen-enriched stream). Kapoor notes that this is done to increase efficiency through recycling the remaining product into the process (Col. 3, lines 18-22, part or all of the gaseous product remaining after separation of hydrogen and carbon monoxide from the gaseous reactor effluent product is recycled to the reformer or partial oxidation reactor).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han’ to separating a portion of the reformed stream comprising CO to form the fuel feed stream, as taught in Kapoor, to increase the efficiency through recycling the remaining product into the process.
With regard to Claim 22, modified Han’ teaches all the limitations in the claims as set forth above.
Modified Han’ is silent to a CO separation unit configured to separate a portion of the reformed stream comprising CO to form the fuel feed stream.
Kapoor discloses a CO separation unit configured to separate a portion of the reformed stream comprising CO to form the fuel feed stream (Col. 3, lines 3-6, subjecting the reactor effluent to a pressure swing adsorption process with an adsorbent which more strongly adsorbs carbon monoxide than hydrogen, thereby producing high purity carbon monoxide and a hydrogen-enriched stream). Kapoor notes that this is done to increase efficiency through recycling the remaining product into the process (Col. 3, lines 18-22, part or all of the gaseous product remaining after separation of hydrogen and carbon monoxide from the gaseous reactor effluent product is recycled to the reformer or partial oxidation reactor).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han’ to have a CO separation unit configured to separate a portion of the reformed stream comprising CO to form the fuel feed stream, as taught in Kapoor, to increase the efficiency through recycling the remaining product into the process.
Claims 9 and 23 are rejected under 35 U.S.C. 103 as being unpatentable over Han et al. (US 2020/0172394 A1) in view of Flytzani-Stephanopoulos et al. (US 8628744 B2) and Han’701, as applied to the claims above, and further in view of Kang et al. (US 2018/0215618 A1).
With regard to Claim 9, modified Han teaches all the limitations in the claims as set forth above.
Modified Han is silent to contacting a partial-reformer feed stream comprising hydrocarbons, and steam with a partial-reforming catalyst under conditions suitable to form the reformer feed stream.
Modified Han is silent to the process wherein an average hydrocarbon chain length of the partial-reformer feed stream is greater than an average hydrocarbon chain length of the reformer feed stream.
Kang teaches contacting a partial-reformer feed stream comprising hydrocarbons, and steam in a partial-reforming process (Paragraph 0050, in the presence of steam, the desulfurized natural gas is pre-reformed in a pre-reformer to break down heavy hydrocarbons existing in the desulfurized natural gas into light hydrocarbons (e.g., methane)).
Kang teaches a partial-reforming catalyst under conditions suitable to form the reformer feed stream (Paragraph 0039, the pre-reformer catalyst is specifically designed for removing heavy hydrocarbons).
Kang teaches the process wherein an average hydrocarbon chain length of the partial-reformer feed stream is greater than an average hydrocarbon chain length of the reformer feed stream (Paragraph 0038, the natural gas is mixed with steam or water vapor and forwarded to pre-reformer 104 for breaking down long chain or heavy hydrocarbons in the natural gas into light hydrocarbons (e.g., methane) to produce a pre-reformed natural gas for use as fuel and process gas).
Kang notes that this is done to avoid carbon deposition or coking caused by long chain hydrocarbons (Paragraph 0038, avoiding carbon deposition or coking caused by heavier or higher hydrocarbons in reformer).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to have contacted a partial-reformer feed stream comprising hydrocarbons, and steam with a partial-reforming catalyst under conditions suitable to form the reformer feed stream, wherein an average hydrocarbon chain length of the partial-reformer feed stream is greater than an average hydrocarbon chain length of the reformer feed stream, as taught in Kang, in order to avoid carbon deposition or coking caused by long chain hydrocarbons.
With regard to Claim 23, modified Han teaches all the limitations in the claims as set forth above.
Modified Han is silent to a pre-reformer configured to contact a partial-reformer feed stream comprising hydrocarbons, and steam with a partial-reforming catalyst under conditions suitable to form the reformer feed stream.
Modified Han is silent to the process wherein an average hydrocarbon chain length of the partial-reformer feed stream is greater than an average hydrocarbon chain length of the reformer feed stream.
Kang teaches a pre-reformer configured to contact a partial-reformer feed stream comprising hydrocarbons, and steam in a partial-reforming process (Paragraph 0050, in the presence of steam, the desulfurized natural gas is pre-reformed in a pre-reformer to break down heavy hydrocarbons existing in the desulfurized natural gas into light hydrocarbons (e.g., methane)).
Kang teaches a partial-reforming catalyst under conditions suitable to form the reformer feed stream (Paragraph 0039, the pre-reformer catalyst is specifically designed for removing heavy hydrocarbons).
Kang teaches the process wherein an average hydrocarbon chain length of the partial-reformer feed stream is greater than an average hydrocarbon chain length of the reformer feed stream (Paragraph 0038, the natural gas is mixed with steam or water vapor and forwarded to pre-reformer 104 for breaking down long chain or heavy hydrocarbons in the natural gas into light hydrocarbons (e.g., methane) to produce a pre-reformed natural gas for use as fuel and process gas).
Kang notes that this is done to avoid carbon deposition or coking caused by long chain hydrocarbons (Paragraph 0038, avoiding carbon deposition or coking caused by heavier or higher hydrocarbons in reformer).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to have a pre-reformer configured to contact a partial-reformer feed stream comprising hydrocarbons, and steam with a partial-reforming catalyst under conditions suitable to form the reformer feed stream, wherein an average hydrocarbon chain length of the partial-reformer feed stream is greater than an average hydrocarbon chain length of the reformer feed stream, as taught in Kang, in order to avoid carbon deposition or coking caused by long chain hydrocarbons.
Claims 10 and 24 are rejected under 35 U.S.C. 103 as being unpatentable over Han et al. (US 2020/0172394 A1) in view of Flytzani-Stephanopoulos et al. (US 8628744 B2), Han’701, and Kang et al. (US 2018/0215618 A1), as applied to claims 9 and 23 above, and further in view of Abe et al. (US 2016/0149244 A1).
With regard to Claim 10, modified Han teaches all the limitations in the claims as set forth above.
Modified Han is silent to contacting a purification feed stream comprising hydrocarbons and a sulfur-containing impurity, and at least a portion of the first electrolysis stream comprising H2 with a hydro-desulfurization catalyst under conditions suitable to form the partial-reformer feed stream.
Modified Han is silent to the process wherein an amount of the sulfur-containing impurity present in the purification feed stream is greater than an amount of the sulfur-containing impurity present in the partial-reformer feed stream.
Kang teaches contacting a purification feed stream comprising hydrocarbons and a sulfur-containing impurity in a hydro-desulfurization process under conditions suitable to form the partial-reformer feed stream (Paragraph 0037, a hydrocarbon gas, e.g., natural gas, for use as process gas and fuel gas is pre-heated (not shown) and sent to hydrodesulfurization unit (HDS) 102 where sulfur in the natural gas is removed).
Kang teaches the process wherein an amount of the sulfur-containing impurity present in the purification feed stream is greater than an amount of the sulfur-containing impurity present in the partial-reformer feed stream (Paragraph 0039, the HDS unit (herein HDS 102) is used upstream of the pre-reformer in order to remove sulfur).
Kang notes that this process of removing sulfur is done to eliminate potential corrosion of equipment at low temperatures (Paragraph 0058, helps to eliminate corrosion of the equipment operated in the low temperature range).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to contact a purification feed stream comprising hydrocarbons and a sulfur-containing impurity in a hydro-desulfurization process under conditions suitable to form the partial-reformer feed stream, wherein an amount of the sulfur-containing impurity present in the purification feed stream is greater than an amount of the sulfur-containing impurity present in the partial-reformer feed stream, as taught by Kang, in order to eliminate potential corrosion of equipment at low temperatures.
However, Kang is silent to contacting at least a portion of the first electrolysis stream comprising H2 with a hydro-desulfurization catalyst.
Abe teaches a hydro-desulfurization process involving contacting H2 with the use of a hydro-desulfurization catalyst (Paragraph 0005, The operation of a hydro-desulfurizer involves hydrodesulfurization, a process of allowing sulfur to react with hydrogen in the presence of a catalyst (Ni-Mo or Co-Mo)). Abe notes that the catalyst is used due to the ability to adsorb the hydrogen sulfide produced from the hydrodesulfurization (Paragraph 0032, The adsorption catalyst is a sulfur adsorbent that adsorbs hydrogen sulfide resulting from hydrodesulfurization. Examples include ZnO and CuZn catalysts. These types of desulfurizing agents…remove a large amount of sulfur per unit area).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han in view of Kang to contact at least a portion of the first electrolysis stream comprising H2 and the use of a hydro-desulfurization catalyst, as taught by Abe, in order to adsorb the hydrogen sulfide produced from the hydrodesulfurization.
With regard to Claim 24, modified Han teaches all the limitations in the claims as set forth above.
Modified Han is silent to a purification unit configured to contact a purification feed stream comprising hydrocarbons and one or more sulfur-containing compounds, and at least a portion of the first electrolysis stream comprising H2 with a hydro-desulfurization catalyst under conditions suitable to form the partial-reformer feed stream.
Modified Han is silent to the process wherein an amount of sulfur-containing compounds present in the purification feed stream is greater than an amount of sulfur-containing compounds present in the partial-reformer feed stream.
Kang teaches a purification unit configured to contact a purification feed stream comprising hydrocarbons and one or more sulfur-containing compounds in a hydro-desulfurization process under conditions suitable to form the partial-reformer feed stream (Paragraph 0037, a hydrocarbon gas, e.g., natural gas, for use as process gas and fuel gas is pre-heated (not shown) and sent to hydrodesulfurization unit (HDS) 102 where sulfur in the natural gas is removed).
Kang teaches the process wherein an amount of sulfur-containing compounds present in the purification feed stream is greater than an amount of sulfur-containing compounds present in the partial-reformer feed stream (Paragraph 0039, the HDS unit (herein HDS 102) is used upstream of the pre-reformer in order to remove sulfur).
Kang notes that this process of removing sulfur is done to eliminate potential corrosion of equipment at low temperatures (Paragraph 0058, helps to eliminate corrosion of the equipment operated in the low temperature range).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to have a purification unit configured to contact a purification feed stream comprising hydrocarbons and one or more sulfur-containing compounds in a hydro-desulfurization process under conditions suitable to form the partial-reformer feed stream, wherein an amount of sulfur-containing compounds present in the purification feed stream is greater than an amount of sulfur-containing compounds present in the partial-reformer feed stream, as taught by Kang, in order to eliminate potential corrosion of equipment at low temperatures.
However, Kang is silent to contacting at least a portion of the first electrolysis stream comprising H2 with a hydro-desulfurization catalyst.
Abe teaches a hydro-desulfurization process involving contacting H2 with the use of a hydro-desulfurization catalyst (Paragraph 0005, The operation of a hydro-desulfurizer involves hydrodesulfurization, a process of allowing sulfur to react with hydrogen in the presence of a catalyst (Ni-Mo or Co-Mo)). Abe notes that the catalyst is used due to the ability to adsorb the hydrogen sulfide produced from the hydrodesulfurization (Paragraph 0032, The adsorption catalyst is a sulfur adsorbent that adsorbs hydrogen sulfide resulting from hydrodesulfurization. Examples include ZnO and CuZn catalysts. These types of desulfurizing agents…remove a large amount of sulfur per unit area).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han in view of Kang to contact at least a portion of the first electrolysis stream comprising H2 and the use of a hydro-desulfurization catalyst, as taught by Abe, in order to adsorb the hydrogen sulfide produced from the hydrodesulfurization.
Claims 11 and 12 are rejected under 35 U.S.C. 103 as being unpatentable over Han et al. (US 2020/0172394 A1) in view of Flytzani-Stephanopoulos et al. (US 8628744 B2) and Han’701, as applied to the claims above, and further in view of Bielenberg et al. (US 2022/0119720 A1).
With regard to Claims 11 and 12, modified Han teaches all the limitations in the claims as set forth above.
However, modified Han is silent to the second electrolysis stream comprising less than 10 wt% H2 (Claim 11) and a second electrolysis stream substantially free from H2 (Claim 12).
Bielenberg teaches a process for electrolysis wherein the second electrolysis stream comprises less than 10 wt% H2 and is substantially free from H2 (Paragraph 0028, an oxygen-containing stream generated by an electrolyzer can have an O2 content of 99.5 vol% or more, or 99.6 vol% or more, such as up to 100 vol%.). ‘Substantially free’ can be interpreted as an O2 content of up to 100 vol%. Therefore, Bielenberg teaches the range claimed by the invention.
Bielenberg notes that this is due to the high purity of oxygen generated by electrolysis relative to other methods (Paragraph 0028, oxygen generated by an electrolyzer can have a relatively high purity… in contrast to an oxygen-containing stream generated by an air separation unit). This is ideal for the molar ratio of oxygen to hydrogen in the electrolysis reaction (Paragraph 0027, in an idealized setting, the molar quantity of oxygen generated during electrolysis is half of the molar quantity of hydrogen generated during electrolysis).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to have the second electrolysis stream comprising less than 10 wt% H2 and a second electrolysis stream substantially free from H2, as taught in Bielenberg, in order to produce high purity oxygen as generated by electrolysis relative to other methods, which is ideal for the molar ratio of oxygen to hydrogen in the electrolysis reaction.
Claim 14 is rejected under 35 U.S.C. 103 as being unpatentable over Han et al. (US 2020/0172394 A1) in view of Flytzani-Stephanopoulos et al. (US 8628744 B2) and Han’701, as applied to the claims above, and further in view of Mikhajlov et al. (US 2020/0016578 A1).
With regard to Claim 14, modified Han teaches all the limitations in the claims as set forth above.
In addition, modified Han teaches contacting the reformer feed stream (Paragraph 0011, reforming at least a part of the hydrocarbon feed stock).
Modified Han teaches contacting at least a portion of the second electrolysis stream comprising O2 (Paragraph 0010, the oxygen product from electrolysis of water is advantageously used for partial oxidation).
Modified Han teaches contacting an oxidant stream comprising O2 and N2 (Paragraph 0016, the atmospheric air… is enriched with oxygen from the water electrolysis).
Modified Han teaches contacting steam in an auto-thermal reforming process (Paragraph 0005, ATR comprises…steam reforming of the hydrocarbon to form raw synthesis gas).
However, modified Han is silent to the use of an auto-thermal reforming catalyst.
Mikhajlov teaches an auto-thermal reforming catalyst for the conversion of natural or associated gas (Paragraph 0001, the production of synthesis gas from natural/associated gas in an autothermal reforming process in particular, to a catalyst). Such a catalyst is present to catalyze, or speed up, the auto-thermal reforming process, as commonly known in the art.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to use an auto-thermal reforming catalyst, as taught by Mikhajlov, to catalyze, or speed up, the auto-thermal reforming process, as commonly known in the art.
Claim 25 is rejected under 35 U.S.C. 103 as being unpatentable over Han et al. (US 2020/0172394 A1) in view of Flytzani-Stephanopoulos et al. (US 8628744 B2) and Han’701, as applied to the claims above, and further in view of Esposito (“Membraneless electrolyzers for low-cost hydrogen production in a renewable energy future”).
With regard to Claim 25, modified Han teaches all the limitations in the claims as set forth above.
Modified Han is silent to a membrane-less electrolyzer.
Esposito teaches membrane-less electrolyzers for production of hydrogen (Page 658, membraneless electrolyzers represent a promising technology for the production of H2). Esposito notes that membrane-less electrolyzers have multiple advantages, including durability, resilience, and tolerance to impurities (Page 654, potential to be durable devices with long operating lifetimes, high tolerance to impurities, and greater resilience to extreme operating conditions that would harm a membrane).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention for modified Han to use a membrane-less electrolyzer, as taught by Esposito, as membrane-less electrolyzers have multiple advantages, including durability, resilience, and tolerance to impurities.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure:
Balaji et al. (US 2022/0048776 A1) teaches a process for converting carbon dioxide into carbon monoxide, comprising a water splitting process wherein the oxygen output stream is liquified, stored, and re-gasified before use as feed.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to ABDUL-RAHMAN YUSUF WALEED SMARI whose telephone number is (571)270-7302. The examiner can normally be reached M-Th 7:30-5, F 7:30-4.
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/ABDUL-RAHMAN YUSUF WALEED SMARI/Examiner, Art Unit 1736
/ANTHONY J ZIMMER/Supervisory Patent Examiner, Art Unit 1736
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