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 .
Claim Status
The claims of 06/01/2026 is acknowledged.
Claims 1-17 are pending.
Priority
The instant application claims foreign priority to EP application no. 22190843.7 filed on 08/17/2022. Receipt is acknowledged of certified copies of papers required by 37 CFR 1.55.
Acknowledgment is made of applicant's claim for foreign priority based on application no. 22190843.7 filed in EP on 08/17/2022. It is noted, however, that while applicant has filed a translation of the application on 08/15/2023, the translation does not include a statement that the translation of the certified copy is accurate as required by 37 CFR 1.55.
Should applicant desire to obtain the benefit of foreign priority under 35 U.S.C. 119(a)-(d) prior to declaration of an interference, a certification statement of the English translation of the foreign application must be submitted in reply to this action. 37 CFR 41.154(b) and 41.202(e).
Failure to provide a certification statement may result in no benefit being accorded for the non-English application.
Information Disclosure Statement
The information disclosure statement (IDS) submitted on 08/15/2023 are in compliance with the provisions of 37 CFR 1.97. Accordingly, the information disclosure statement has been considered by the examiner.
Election/Restrictions
Applicant’s election without traverse of Group I, claims 1-12, in the reply filed on 06/01/2026 is acknowledged.
The election/restriction requirement is deemed proper and is therefore made FINAL.
Claims 13-17 are withdrawn from further consideration pursuant to 37 CFR 1.142(b) as being drawn to a nonelected invention, there being no allowable generic or linking claim. Election was made without traverse in the reply filed on 06/01/2026.
Claims 1-12 are under examination.
Claim Rejections - 35 USC § 112(b)
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claim 5 is rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Claim 5 recites the limitation "the hydrodesulfurization unit" in the body of the claim. Claim 5 depends on claim 2 which depends on claim 1. Claims 1 and 2 do not recite the limitation of “a hydrodesulfurization”. There is insufficient antecedent basis for this limitation in the claim.
“The hydrodesulfurization unit” recited in claim 5 will be interpreted as the same as “a hydrodesulfurization step” recited in claim 4.
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.
Claims 1-2, 6-7, and 10-12 are rejected under 35 U.S.C. 103 as being unpatentable over Vicari et al. (WO2020048809, published 03/12/2020, original found in IDS dated 08/15/2023, translated version provided in PTO-892).
Vicari et al. teaches a process for preparing methanol from synthesis gas, in which the carbon compounds in the streams separated off in the isolation of the methanol are converted to carbon dioxide and, with avoidance of emission thereof, reused in the preparation of methanol (see first paragraph, page 1 of translation). The direct recycling of purge gases and off gases to the methanol synthesis reactor is disadvantageous since this results in accumulation of inert gases, for instance nitrogen and argon, but also methane or by-products such as dimethyl ether, in the synthesis circuit (see third paragraph, page 3 of translation). The process is based on the continuously operated methanol synthesis by the low-pressure process where synthesis gas is converted at a pressure of 5 to 10 MPa abs in the presence of a methanol synthesis catalyst to a methanol-containing reaction mixture and subsequently worked up stepwise for isolation of the methanol. The stepwise workup separates off various streams that still comprise components off value or unconverted feedstocks or by-products, for example carbon monoxide, carbon dioxide, dimethyl ether, methane or further by-products. The core of the invention is the physical reuse of the carbon in these components of value for further synthesis of methanol with simultaneous avoidance of carbon dioxide emission (see last paragraph, page 3 of translation). FIG. 4, shown below, shows a block diagram of a general embodiment in which additional hydrogen is supplied via stream (XVI) (see paragraph 8, page 10 of translation). A process for preparing methanol includes: (a) producing a synthesis gas (II) comprising carbon monoxide, carbon dioxide and hydrogen from a carbonaceous feedstock (I) in a synthesis gas production unit (A), (b) feeding the synthesis gas (II) from stage (a) to a methanol synthesis unit (B) and converting it at a temperature of 150 to 300° C. and a pressure of 5 to 10 MPa abs in the presence of a methanol synthesis catalyst to a reaction mixture containing methanol, water, carbon monoxide, carbon dioxide, hydrogen, dimethyl ether and methane, condensing a methanol- and water-enriched crude methanol stream (III) out of said reaction mixture, and conducting the crude methanol stream (III) and a gaseous stream (IV) comprising carbon monoxide, carbon dioxide, hydrogen and methane out of the methanol synthesis unit (B), (c) expanding the crude methanol stream (III) from stage (b) in an expansion unit (C) to a pressure of 0.1 to 2 MPa abs, and obtaining an expansion gas (V) comprising carbon dioxide and methane and a degassed
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crude methanol stream (VI) enriched with methanol and water, (d) separating a carbon dioxide- and dimethyl ether-comprising low boiler stream (VII) by distillation from the degassed crude methanol stream (VI) from stage (c) in a distillation apparatus (D), and obtaining a methanol- and water-enriched bottom stream (VIII), and (e) separating a water-containing high boiler stream (IX) from the bottom stream (VIII) from stage (d) in a further distillation apparatus (E), and obtaining methanol by distillation as stream (X), and which comprises (f) feeding the carbon monoxide, carbon dioxide, dimethyl ether and methane components of value in streams (IV) and in at least one of the two streams (V) and (VII) to a combustion unit (F) and combusting them therein with supply of an oxygenous gas (XI) having an oxygen content of 30% to 100% by volume, forming carbon dioxide-containing flue gas (XII), (g) separating a carbon dioxide-enriched stream (XIV) from the carbon dioxide-containing flue gas (XII) from stage (f) in a carbon dioxide recovery unit (G) to form an offgas stream (XIII), and (h) recycling the carbon dioxide-enriched stream (XIV) separated off in the carbon dioxide recovery unit (G) from stage (g) to the synthesis gas production unit (A) of stage (a) and/or to the methanol synthesis unit (B) of stage (b) (see pages 10-13 of translation).
The teachings of Vicari et al. differ from that of the instantly claimed invention in that Vicari et al. does not expressly teach wherein the streams of the process contain hydrocarbons and wherein the thermal separation process separates hydrocarbons as a byproduct stream as required by instant claim 11.
Nevertheless, it would have been prima facie obvious for one of ordinary skill in the art to combine the teachings of various streams of the process containing methane and the expansion unit (C) and the low boiler column (D) because the expansion unit (C) removes expansion gas at a lower pressure and the low boiler column separates methanol and water, and the combination of the two units would result in the combination of those outcomes. One of ordinary skill in the art would have a reasonable expectation of success because Vicari et al. suggests the possible combination of these elements in various embodiments.
Regarding instant claim 1, Vicari et al. teaches making a synthesis gas (II) from comprising carbon monoxide, carbon dioxide, and hydrogen from a carbonaceous feedstock (I) in a synthesis gas production unit (A), corresponding to instant step (a). Regarding the limitation of hydrocarbon-containing, Vicari et al. teaches particular preference is given to methane-containing streams (see 2nd paragraph, Column 7). The hydrogen (XVI), is combined with the syngas (II) produced, corresponding to instant step (c). The hydrogen (XVI) is derived from the electrolysis of water by solar, wind or water energy, corresponding to instant step (b) (see paragraph 3, column 20). The combined syngas (II) and additional hydrogen (XVI) are then sent to a methanol synthesis unit (B), corresponding to instant step (d). Another stream sent to methanol synthesis unit (B) is recovered hydrogen stream (IVb), corresponding to a recycle gas stream of instant step (d). From the methanol synthesis unit (B), gas stream (IVa), corresponding to the instant residual gas stream, and crude methanol stream (III), corresponding to the instant raw methanol stream, are produced. The gas stream (IVa), corresponding to the instant residual gas stream, is sent to pressure swing adsorption unit (H) and split into recovered hydrogen stream (IVb), corresponding to the instant recycle stream, and gas stream (IV), corresponding to the instant purge gas stream of instant step (e). The gas stream (IV), corresponding to the instant purge gas stream, is fed to combustion unit (F) where oxygen containing gas (XI) is also fed and combusted, corresponding to instant step (f), to afford a flue gas stream (XII), corresponding to the instant synthesis gas stream of instant step (f).
Regarding instant claim 2, the pressure swing adsorption unit (H), corresponds to the instant hydrogen recovery unit which is prior to the combustion unit (F), corresponding to instant step (f), produces gas stream (IV), corresponding to the instant hydrocarbons-enriched purge gas stream, and recovered hydrogen stream (IVb), which corresponds to the instant hydrogen-rich stream.
Regarding instant claim 6, the recovered hydrogen stream (IVb), corresponding to the instant hydrogen-rich stream, is fed to the gas stream entering the methanol synthesis unit (B), corresponding to supplying the instant hydrogen-rich stream to the instant hydrocarbon-containing synthesis gas stream before the reacting step according to instant step (d).
Regarding instant claim 7, the combustion unit (F) combusts the gas stream from upstream in the presence of an oxidant which corresponds to the instant reforming step including a partial oxidation.
Regarding instant claim 10, the flue gas (XII) comprising carbon dioxide and other off value components is fed to the carbon dioxide recovery unit (G), corresponding to the instant carbon capture unit.
Regarding instant claim 11, crude methanol stream (III), corresponding to the instant raw methanol stream, is fed to an expansion unit (C) separates the crude methanol stream (III) into expansion gas (V), corresponding to the instant hydrocarbons as a byproduct stream, and degassed crude methanol (VI) which is fed to low boiler column (D) which produced pure methanol (X) and high boiler stream from (D), corresponding to water. The combined steps of (C) and (D) correspond to the instant thermal separation process.
Regarding instant claim 12, flue gas (XII), corresponding to the instant synthesis gas stream, is fed to the carbon dioxide recovery unit (G) and fed upstream to the methanol synthesis unit (B), corresponding to the instant methanol synthesis reactor, through stream (XIV).
Claim 3 is rejected under 35 U.S.C. 103 as being unpatentable over U.S. Vicari et al. (WO2020048809, published 03/12/2020, original found in IDS dated 08/15/2023, translated version provided in PTO-892), as applied to claim 1 above, and further in view of Gioele et al. (NPL, published 02/08/2019, PTO-892).
The teachings of Vicari et al. were discussed above. Additionally, the hydrogen can be removed from stream (IV) using any apparatuses suitable for separating hydrogen from a gas stream comprising carbon monoxide, carbon dioxide, hydrogen and methane. Corresponding apparatuses are common knowledge to the person skilled in the art, for example pressure swing adsorption or permeation. Preferably, in the process of the invention, the hydrogen is separated off in the hydrogen recovery unit (A) by pressure swing adsorption (see third paragraph, column 19).
The teachings of Vicari et al. differ from that of the instantly claimed invention in that Vicari et al. does not teach wherein the hydrogen recovery unit comprises a membrane unit wherein the hydrocarbons-enriched purge gas stream is produced on the retentate side of the membrane unit and the hydrogen-rich stream is produced on the permeate side of the membrane unit.
Gioele et al. teaches the environmental and economic performances of a membrane reactor for hydrogen production from raw biogas. Potential benefits of the innovative technology are compared against reference hydrogen production processes based on steam (or autothermal) reforming, water gas shift reactors and a pressure swing adsorption unit. Results show that the adoption of the membrane reactor increases the system efficiency by more than 20 percentage points with respect to the reference cases. Focusing on the economic results, hydrogen production cost shows lower value with respect to the reference cases (4 euros /kgH2 vs 4.2 euros /kgH2) at the same hydrogen delivery pressure of 20 bar. Between landfill and anaerobic digestion cases, the latter has the lower costs as a consequence of the higher methane content (see Abstract).
It would have been obvious before the effective filing date of the claimed invention for one of ordinary skill in the art to substitute the teachings of Vicari et al. with the teachings of Gioele et al. by substituting the pressure swing adsorption (H), as taught by Vicari et al., with a membrane reactor, as taught by Gioele et al., to arrive at the instantly claimed invention. It would have been prima facie obvious for one of ordinary skill in the art to substitute the pressure swing adsorption with the membrane reactor because, as taught by Gioele et al., the substitution of a pressure swing adsorption unit for a membrane reactor increases the system efficiency by more than 20 percentage points with respect to the reference cases. One of ordinary skill in the art would have a reasonable expectation of success because the roles of a pressure swing adsorption unit and a membrane unit are known in the prior art for their roles in hydrogen recovery, as supported by Gioele et al., and the substitution would result in the predictable outcome of hydrogen recovery.
Claims 1-4 and 6-8 are rejected under 35 U.S.C. 103 as being unpatentable over Schulz et al. (US 2022/0162143 A1, published 05/26/2022, IDS dated 08/15/2023) in view of U.S. Patent No. 9,637,432 B2 (‘432, published 05/02/2017, PTO-892).
Schulz et al. teaches a process for synthesis of methanol wherein a CO2 stream consisting predominantly of carbon dioxide and an H stream consisting predominantly of hydrogen are supplied to a methanol reactor arrangement for conversion to methanol (see 0012). In the process proposed, a tail gas stream comprising unreacted hydrogen is obtained from the methanol reactor arrangement, and the unreacted hydrogen is returned at least partly to the methanol reactor arrangement. The tail gas stream may, as well as the unreacted hydrogen, also include unreacted carbon dioxide, and also carbon monoxide formed in the methanol reactor arrangement, especially by the reverse water-gas shift reaction. The tail gas stream for the methanol synthesis may likewise include inert constituents such as nitrogen, methane and noble gases, and also by-products such as dimethyl ether (see 0013). FIG. 4 (shown below) shows a CO2 stream 2 consisting essentially of carbon dioxide, an H stream 3 consisting essentially of hydrogen, and a return stream 4 likewise consisting essentially of hydrogen are pressurized by a feed gas compressor arrangement 5 and then fed to a first reactor stage 6a of a methanol reactor arrangement 7. This feed gas compressor arrangement 5 is in multistage form. It is apparent that the CO2 stream 2, the H stream 3 and the return stream 4 are each supplied upstream of a different compressor stage 21 a-c. The CO2 stream 2 is fed in at ambient pressure, and therefore is to be pressurized by all compressor stages 21 a-c of the feed gas compressor arrangement 5 for attainment of the target pressure for the methanol synthesis, and it is consequently supplied directly to the first compressor stage 21 a. The H stream 3 is fed in at a somewhat higher pressure and is therefore fed in downstream of the first compressor stage 21 a and upstream of the second compressor stage 21 b in the processing operation. Finally, the return stream 4 is fed in at the highest pressure, and therefore between the second compressor stage 21 b and the third compressor stage 21 c in the processing operation. Likewise fed into the first reactor stage 6a is a recycle stream 13. In this first reactor stage 6a consisting of a single isothermal reactor, partial conversion of the carbon dioxide and of the hydrogen to methanol takes place. The CO2 stream 2 is obtained from the flue gas from a power plant (not shown here). The H stream 3 is obtained from an electrolysis plant for obtaining hydrogen (likewise not shown here), wherein the H stream 3 in this example could also be obtained at ambient pressure. The return stream 4 is obtained from a hydrogen recovery arrangement 8 of the plant, which is supplied for this purpose with a tail gas stream 9 from the methanol reactor arrangement 7, which includes unreacted reactants from the methanol synthesis and therefore unreacted hydrogen in particular. Connected downstream of the first reactor stage 6a in the processing operation is a second reactor stage 6b of the methanol reactor arrangement 7, which second reactor stage 6b here likewise consists of a single isothermal reactor. The methanol reactor arrangement 7 has a methanol separation arrangement 10 which, through condensation of crude methanol, is set up to obtain the tail gas stream 9 and a crude methanol stream 12. The methanol separation arrangement 10 in turn consists here of a first methanol separation apparatus 11 a connected between the first reactor stage 6a and the second reactor stage 6b in the processing operation, and a second methanol separation apparatus 11b connected downstream of the second reactor stage 6b in the processing operation. The gas mixture comprising methanol and unreacted tail gas from the first reactor stage 6a is fed to the first methanol separation apparatus 11a, and a first crude methanol substream 14a, consisting essentially of crude methanol, and a first stage tail gas stream 15a comprising the unreacted tail gases from the first reactor stage 6a are obtained from this methanol separation apparatus 11a. The first stage tail gas stream 15a is fed to the second reactor stage 6b for methanol synthesis. Correspondingly, the gas mixture from the second reactor stage 6b is fed to the second methanol separation apparatus 11b, and a second crude methanol substream 14b and a second stage tail gas stream 15b are obtained therefrom. The first crude methanol substream 14a and the second crude methanol substream 14b are combined to give the crude methanol stream 12, which is in turn fed to a distillation 16 to obtain the methanol 1. The second stage tail gas stream 15b is divided into the tail gas stream 9, which is of course fed to the hydrogen recovery arrangement 8, and the recycle stream 13. In this way, both the tail gas stream 9 and the recycle stream 13 are obtained from the methanol separation arrangement 10. The recycle stream 13 is fed to a recycle compressor arrangement 17 for increasing the pressure and then to the first reactor stage 6a. Since the tail gas stream 9 from the second reactor stage 6b is thus obtained directly downstream here, the second reactor stage 6b can be referred to as tail gas-obtaining reactor stage 20 (see 0050-0056). The hydrogen recovery apparatus 8 comprises both a membrane apparatus 22 and a pressure swing adsorption apparatus 18. Specifically, the tail gas stream 9 is fed to the membrane apparatus 22. A hydrogen-enriched membrane hydrogen stream 23 and a correspondingly low-hydrogen membrane tail stream 24 are obtained from the membrane apparatus 22. The membrane tail stream 24 is fed to the pressure swing adsorption apparatus 18, such that a PSA hydrogen stream 25 consisting essentially of hydrogen and the purge stream 19 are obtained therefrom in turn. The PSA hydrogen stream 25 is combined here with the membrane hydrogen stream 23 to give the return stream 4. But it would also be possible to guide only the membrane hydrogen stream 23 as return stream 4 and the PSA hydrogen stream 25 separately as further return stream to the feed gas compressor arrangement 5. It is thus
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possible to return a very high proportion of the hydrogen in the tail gas stream 9 overall (see 0060).
Schulz et al. differs from that of the instantly claimed invention in that Schulz et al. does not teach (f) reacting the purge gas stream in the presence of oxygen as oxidant in a reforming step to afford a synthesis gas stream and wherein the hydrocarbon-containing carbon dioxide stream is treated in a hydrodesulfurization unit for removal of sulfur compounds before the combining according to step (c) as required by instant claim 4 and wherein the methanol synthesis reactor includes a water-cooled reactor stage and produces steam and the steam is utilized as process steam for the reforming step according to step (f) as required by instant claim 8.
‘432 teaches a method and system for producing methanol that employs steam methane reforming (SMR) and/or autothermal (ATR) synthesis gas production system, together with a partial oxidation system (see Abstract). Steam methane reforming (SMR) is a catalytic conversion of natural gas, including methane and light hydrocarbons, to synthesis gas containing hydrogen and carbon monoxide by reaction with steam. The reactions are endothermic, requiring significant amount of energy input. The methanol production process generally involves directing a compressed synthesis gas comprising hydrogen, carbon monoxide and carbon dioxide at an elevated temperature and pressure to a methanol converter reactor containing one or more beds of a methanol synthesis catalyst such as a copper and zinc oxide catalyst. The methanol synthesis process is usually operated in a loop where a portion of the compressed synthesis gas is converted to methanol each pass through the methanol converter reactor. Most of the unconverted gas is recycled to the methanol converter. A small portion is purged to prevent the buildup of inerts such as nitrogen, argon and methane (see paragraph 1, column 1). FIG. 2 shows a hydrocarbon containing feed stream 182 to be reformed is preferably natural gas but may be any suitable combustible fluid examples of which include methane, propane and coke oven gas, or a process stream containing reformable hydrocarbons. Since natural gas typically contains unacceptably high levels of sulfur species, and where other feed material contains unacceptably high levels of sulfur species, desulfurization is required to prevent poisoning of catalyst used in an autothermal reforming step and/or in methanol synthesis. To facilitate the desulfurization, a small amount of hydrogen or hydrogen-containing gas 191 is added to the feed stream 182. Stream 182 is then preheated in heat exchanger 192, that serves as a fuel preheater. The resulting heated stream 183 undergoes sulfur removal in desulfurization unit 190. The desulfurized natural gas feed stream 184 is mixed with superheated steam 185, heated to around 900° F. (e.g. heat exchanger 194) and pre-reformed in an adiabatic pre-reformer 150, which converts higher hydrocarbons to methane, hydrogen, carbon monoxide, and carbon dioxide. In the partial oxidation, the hydrocarbon containing stream 182 and the oxygen in the oxidant stream 110 are introduced into a partial oxidation reactor, and they react with each other. The synthesis gas 142 produced by partial oxidation or autothermal reforming in unit 120 generally contains hydrogen, carbon monoxide, carbon dioxide, water and other constituents such as unconverted methane. The hot synthesis gas is cooled in heat exchange sections 104 and 105 and treated to remove substances that should not be present when the stream is fed to reactor 405 in the methanol synthesis section. Section 104 typically includes a quench and/or process gas boiler that cools the synthesis gas 142 to less than about 760° F. Streams 125 and 129 represent the cooling water input and water/steam output from section 104, respectively. This initially cooled synthesis gas 143 is successively further cooled in heat exchange section 105, which removes heat from the gas by indirect heat exchange such as via the hydrocarbon feed heater 192, an economizer, feedwater heater, or air and/or water-based synthesis gas coolers (see paragraph 1,
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column 7 and FIG. 2). In addition, purge streams 430A, 430B comprising unreacted hydrogen and methane slip are recycled from the methanol synthesis and purification system 400 to the conventional synthesis gas generation system 300 or partial oxidation or autothermal reforming based synthesis gas generation system 100 or both. This particular coupling arrangement, schematically shown in FIG. 1, is most suitable for the retrofit of existing natural gas-based methanol production plants having a conventional synthesis gas production system, and where the partial oxidation or autothermal reforming based synthesis gas generation system is constructed as a retrofit to the existing methanol production plant and integrated therein (see 3rd
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paragraph, column 5 and FIG. 1).
It would have been obvious before the effective filing date of the claimed invention for one of ordinary skill in the art to modify the teachings of Schulz et al. with the teachings of ‘432 by treating the carbon dioxide stream 2, as taught by Schulz et al., with the desulfurization unit 190, as taught by ‘432, and treat the purge gas stream 19, as taught by Schulz et al., with the partial oxidation unit 120, as taught by ‘432, to arrive at the instantly claimed invention. One of ordinary skill in the art would have been motivated to combine the teachings of Schulz et al. by adding the desulfurization unit because, as taught by ‘432, desulfurization is required to prevent poisoning of catalyst used in an autothermal reforming step and/or in methanol synthesis. One of ordinary skill in the art would have been motivated to combine the teachings of Schulz et al. by adding a partial oxidation system to the method because, as taught by ‘432, efficiency and productivity of the methanol plant are optimized by using the partial oxidation based reforming system. One of ordinary skill in the art would have been motivated to feed the steam generated from the methanol reactor cooling into the reforming step because, as taught by ‘432, moderate amounts of steam are typically required to prevent the catalyst from coking. One of ordinary skill in the art would have a reasonable expectation of success because a desulfurization unit is considered an industry standard for methanol synthesis. One of ordinary skill in the art would have a reasonable expectation of success because partial oxidation reactors are commonly used in methanol synthesis loops. One of ordinary skill in the art would have a reasonable expectation of success because recovery of steam is a standard practice for energy recovery.
Regarding instant claim 1, FIG. 4 of Schulz et al. shows carbon dioxide stream 2 is combined with methane-containing recycle stream 13, corresponding to the instant recycle stream, corresponding to instant step (a). Hydrogen stream 3 is obtained by electrolysis, corresponding to instant step (b). Hydrogen stream 3 is combined with streams 2 and 13, corresponding to instant step (c) and fed to a methanol reactor arrangement 7, corresponding to instant step (d), which produces a tail gas stream which is split into tail gas streams 9 and 15a/b and a crude methanol substream, corresponding to instant raw methanol stream. The tail gas stream 9 is fed to membrane 22 and PSA 18 and finally purge stream 19, corresponding to the instant purge gas stream of instant step (e). The tail gas 15a/b is fed to recycle stream 13, corresponding to the instant recycle stream of step (e). The purge stream 19 of Schulz et al. can then be used in combination with the ATR 120, as taught by ‘432 and corresponding to the instant reforming step, in the presence of oxidant stream 110 containing oxygen, corresponding to instant step (f).
Regarding instant claims 2 and 3, tail gas 9 is fed to the membrane 22, as taught by Schulz et al. and corresponding to the instant hydrogen recovery unit, producing purge stream 19, corresponding to the instant hydrocarbons-enriched purge gas stream and return stream 4, corresponding to the instant hydrogen-rich stream. Regarding the instant limitations of a hydrogen-rich stream on the permeate side and the hydrocarbons-enriched purge gas stream on the retentate side, the membrane apparatus 22, as taught by Schulz et al., is preferably set up to separate off hydrogen which would produce a hydrogen-rich stream on the permeate side and other gases on the retentate side.
Regarding instant claim 4, the desulfurization unit 11, as taught by ‘432, corresponds to the instant hydrodesulfurization unit.
Regarding instant claims 6 and 7, return stream 4, as taught by Schulz et al., corresponds to the instant hydrogen-rich stream which is added to feed stream before reacting and the ATR 120, as taught by ‘432, is a partial oxidation reactor and corresponds to the instant reforming step.
Regarding instant claim 8, FIG. 1 from ‘432 shows an unreacted hydrogen stream 430A, corresponding to the instant steam, being recycled back to unit 100 and FIG. 2 from ‘432 shows a superheated steam 185 being added to the line to be fed to the partial oxidation unit 120, corresponding to the instant reforming step (f)
Claim 5 is rejected under 35 U.S.C. 103 as being unpatentable over Schulz et al. (US 2022/0162143 A1, published 05/26/2022, IDS dated 08/15/2023) in view of U.S. Patent No. 9,637,432 B2 (‘432, published 05/02/2017, PTO-892), as applied to claims 1 and 4 above, and further in view of Benson et al. (NPL, published 2018, PTO-892).
Regarding claim interpretation, instant claim 5 lacks antecedent basis and is being interpreted as depending from instant claim 4 which does not have lack of antecedent basis.
The combined teachings of Schulz et al. and ‘432 were discussed above.
The combined teachings of Schulz et al. and ‘432 differ from that of the instantly claimed invention in that the combined teachings of Schulz et al. and ‘432 does not teach wherein the hydrogen-rich stream is utilized for the hydrogenation in the hydrodesulfurization unit.
Benson et al. teaches a more profitable and efficient way to capture hydrogen’s full value is by capturing and purifying hydrogen from offgas and repurposing it for industrial use. Several recovery technologies are available to do this. Growing demand makes hydrogen recovery a more attractive option. Industry trends, including fuel desulfurization, will increase the need for hydrogen and for more profitable sources of gas (see paragraphs 2-3, page 55).
It would have been obvious before the effective filing date of the claimed invention for one of ordinary skill in the art to combine the teachings of Schulz et al. and ‘432 with the teachings of Benson et al. by using the recycled hydrogen from the membrane, as taught by Schulz et al. in the hydrodesulfurizer, as taught by ‘432, to arrive at the instantly claimed invention. One of ordinary skill in the art to be motivated to recycle the hydrogen to the desulfurization because, as taught by Benson et al., it is more profitable and efficient to purify hydrogen from off gas for industry trends like desulfurization. One of ordinary skill in the art would have a reasonable expectation of success because several recovery technologies, such as membranes, as supported by Benson et al. (see Closing Thoughts section), are available to do this.
Claims 1 and 9 are rejected under 35 U.S.C. 103 as being unpatentable over Schulz et al. (US 2022/0162143 A1, published 05/26/2022, IDS dated 08/15/2023) in view of Topsoe et al. (WO2022079010A1, published 04/21/2022, IDS dated 08/15/2023)
The teachings of Schulz et al. were discussed above.
The teachings of Schulz et al. differ from that of the instantly claimed invention in that Schulz et al. does not teach (f) reacting the purge gas stream in the presence of oxygen as oxidant in a reforming step to afford a synthesis gas stream, and wherein an electrolytically produced oxygen stream is provided and the oxygen of the electrolytically produced oxygen stream is utilized as oxidant in the reforming step according to step (f), as required by instant claim 9.
Topsoe et al. teaches a method for producing a hydrocarbon product stream. A first feed comprising hydrogen is provided to the syngas stage. Suitably, the first feed consists essentially of hydrogen. One source of the first feed of hydrogen can be one or more electrolyzers. In addition to hydrogen the first feed may for example comprise steam, nitrogen, argon, carbon monoxide, carbon dioxide, and/or hydrocarbons (see lines 18-26, page 3). A second feed comprising carbon dioxide is also provided to the syngas stage. The first and second feeds could be mixed before being added to the syngas stage (see lines 23-24, page 4). A third feed comprising oxygen may be provided to the syngas stage. This third feed will typically include a minor amount of steam (e.g. 5-10%). The source of third feed, oxygen, can be at least one air separation unit (ASU) and/or at least one membrane unit. The source of oxygen can also be at least one electrolyzer unit. A part or all of the first feed, and a part or all of the third feed may come from at least one electrolyzer (see lines 1-10, page 5). A fourth feed comprising hydrocarbons may be provided to the syngas stage (A). A hydrocarbon-containing off-gas stream (from the synthesis stage) may be fed to the syngas stage as said fourth feed comprising hydrocarbons. The source of fourth feed can be part or all of a stream comprising hydrocarbons produced in the synthesis stage. The fourth feed may additionally comprise other components such as CO2 and/or CO and/or H2 and/or steam and/or other components such as nitrogen and/or argon. A number of recycle streams may be added to various points of the synthesis gas stage - there may either be mixed or added separately - in other words this fourth feed may be several separate or mixed streams (see lines 11-27, page 5). In some cases, the hydrocarbon-containing off-gas stream contains minor amount of poisons, such as sulfur. In this case, the hydrocarbon-containing off-gas stream may be subjected to the step or steps of purification such as desulfurization (see lines 17-19, page 6). The syngas stage may comprise an RWGS section, a methanation section or an autothermal reforming (ATR) section, or combinations thereof (see lines 8-9, page 7). In an ATR reactor, partial combustion of the hydrocarbon containing feed by sub-stoichiometric amounts of oxygen is followed by steam reforming of the partially combusted hydrocarbon feed stream in a fixed bed of steam reforming catalyst (see lines 22-25, page 7). The syngas stream from the ATR is cooled in a cooling train normally comprising a waste heat boiler(s) (WHB) and one or more additional heat exchangers. The cooling medium in the WHB is (boiler feed) water which is evaporated to steam (see lines 6-12, page 8). In an embodiment, the synthesis stage is a methanol (MeOH) synthesis stage. This stage comprises a MeOH synthesis section where syngas from the syngas stage is first converted to a raw MeOH stream, followed by a purification section where said raw MeOH stream is purified to obtain a MeOH product stream. The MeOH synthesis stage generates a purge gas stream, which typically contains hydrogen, carbon dioxide, carbon monoxide and methane (see lines 23-29, page 17). At least a portion of said MeOH purge gas stream may be fed to the syngas stage as said fourth feed comprising hydrocarbons. The MeOH purge gas stream may be purified prior to feeding it to the syngas stage. Suitably, to avoid excessive build-up of inert components that may be present in the MeOH purge gas, only a portion of said MeOH purge gas stream may be fed to the syngas stage; and another portion of the MeOH purge gas may be purged and/or used as fuel (see lines 30-35, page 17).
It would have been obvious before the effective filing date of the claimed invention to combine the teachings of Schulz et al. with the teachings of Topsoe et al. by recycling the purge gas stream 19, as taught by Schulz et al., using the syngas stage, as taught by Topsoe et al., to arrive at the instantly claimed invention. It would have been prima facie obvious for one of ordinary skill in the art to combine the teachings because, as taught by Topsoe et al., at least a portion of said MeOH purge gas stream may be fed to the syngas stage as said fourth feed comprising hydrocarbons. One of ordinary skill in the art would have a reasonable expectation of success because the purge gas stream 19, as taught by Schulz et al., is suitable for the intended purpose of recycling methanol purge gas streams, as taught by Topsoe et al.
Regarding instant claims 1 and 9, Regarding instant claim 1, FIG. 4 of Schulz et al. shows carbon dioxide stream 2 is combined with methane-containing recycle stream 13, corresponding to the instant recycle stream, corresponding to instant step (a). Hydrogen stream 3 is obtained by electrolysis, corresponding to instant step (b). Hydrogen stream 3 is combined with streams 2 and 13, corresponding to instant step (c) and fed to a methanol reactor arrangement 7, corresponding to instant step (d), which produces a tail gas stream which is split into tail gas streams 9 and 15a/b and a crude methanol substream, corresponding to instant raw methanol stream. The tail gas stream 9 is fed to membrane 22 and PSA 18 and finally purge stream 19, corresponding to the instant purge gas stream of instant step (e). The tail gas 15a/b is fed to recycle stream 13, corresponding to the instant recycle stream of step (e). The purge stream 19 of Schulz et al. can then be used in combination with the syngas stage, as taught by Topsoe et al., comprising an ATR reactor, partial combustion of the hydrocarbon containing feed by sub-stoichiometric amounts of oxygen is followed by steam reforming of the partially combusted hydrocarbon feed stream in a fixed bed of steam reforming catalyst, as taught by Topsoe et al., wherein the source of oxygen can also be at least one electrolyzer unit, corresponding to the instant reforming step (f) with oxygen provided electrolytically.
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.
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Claims 1-2, 6-7, and 9 are provisionally rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1-2, 6, 10-11, and 13 of copending Application No. 18/234114 (‘114).
This is a provisional nonstatutory double patenting rejection because the patentably indistinct claims have not in fact been patented.
Applicant should note that a notice of allowance, dated 05/26/2026, has been mailed.
Although the claims at issue are not identical, they are not patentably distinct from each other because ‘114 recites:
1. A process for producing synthesis gas, comprising: (a) providing a hydrocarbon-containing input gas stream; (b) providing an electrolytically produced hydrogen stream; (c) supplying at least a portion of the electrolytically produced hydrogen stream to the hydrocarbon-containing input gas stream to obtain a hydrogen- containing input gas stream; and (d) reacting the hydrogen-containing input gas stream in the presence of oxygen as oxidant in a reforming step thereby producing a synthesis gas stream.
2. The process according to Claim 1, wherein the reforming step comprises an autothermal reforming (ATR) or a partial oxidation (POX) of the hydrogen-containing input gas stream.
6. The process according Claim 1, wherein the process comprises providing an electrolytically produced oxygen stream, wherein the electrolytically produced oxygen stream is used as oxidant in step (d).
10. A process for producing methanol comprising the process for producing synthesis gas according to Claim 1, further comprising the step of reacting the synthesis gas stream over a solid methanol synthesis catalyst to afford raw methanol, wherein the raw methanol comprises at least methanol (CH3OH) and water.
11. The process according to Claim 10, wherein the raw methanol is separated into pure methanol and water in a thermal separation process.
10. A process for producing methanol comprising the process for producing synthesis gas according to Claim 1, further comprising the step of reacting the synthesis gas stream over a solid methanol synthesis catalyst to afford raw methanol, wherein the raw methanol comprises at least methanol (CH3OH) and water.
11. The process according to Claim 10, wherein the raw methanol is separated into pure methanol and water in a thermal separation process.
12. The process according to Claim 10, wherein the water separated in the thermal separation process is used as starting material for the electrolytically produced hydrogen.
13. The process according to Claim 10, wherein reacting the synthesis gas stream over the solid methanol synthesis catalyst to afford raw methanol generates a residual gas stream containing synthesis gas unconverted into raw methanol, wherein a portion of the residual gas stream is separated as a purge gas stream and wherein the purge gas stream is supplied to a hydrogen recovery apparatus to produce a non-electrolytically produced hydrogen stream and - the non-electrolytically produced hydrogen stream is at least partially supplied to the hydrocarbon-containing input gas stream in addition to the electrolytically produced hydrogen stream to obtain the hydrogen- containing input gas stream according to step (c) and/or - the non-electrolytically produced hydrogen stream is at least partially supplied to the synthesis gas stream obtained according to step (d).
‘114 differs from that of the instantly claimed invention in that ‘114 is only drawn to a process to produce syn gas and not a combination of a process to produce syngas and methanol.
It would have been obvious for one of ordinary skill in the art to combine the claims of ‘114 by producing the synthesis gas of claim 1, as recited by ‘114, with the process for methanol production of claim 10 and 13, as recited by ‘114, to arrive at the instantly claimed invention. It would have been prima facie obvious to combine the process to make synthesis gas with the process to make methanol because the process to make methanol, as recited by ‘114, requires synthesis gas. One of ordinary skill in the art would have a reasonable expectation of success the combination would have resulted in the predictable outcome of methanol production.
Claims 3-4 and 8 are provisionally rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1-2, 6, 10-11, and 13 of copending Application No. 18/234114 (‘114), as applied to claim 1 above, and further in view of Schulz et al. (US 2022/0162143 A1, published 05/26/2022, IDS dated 08/15/2023) in further view of U.S. Patent No. 9,637,432 B2 (‘432, published 05/02/2017, PTO-892).
The claims of ‘114 were discussed above.
The claims of ‘114 differ from that of the instantly claimed invention in that ‘114 does not recite wherein the hydrogen recovery unit comprises a membrane unit wherein the hydrocarbons-enriched purge gas stream is produced on the retentate side of the membrane unit and the hydrogen-rich stream is produced on the permeate side of the membrane unit as required by instant claim 3 and wherein the methanol synthesis reactor includes a water-cooled reactor stage wherein the cooling by the water-cooled reactor stage produces steam and the steam is utilized as process steam for the reforming step according to step (f) as required by instant claim 8.
The teachings of Schulz et al. were discussed above.
The teachings of ‘432 were discussed above.
It would have been obvious before the effective filing date of the claimed invention to combine the claims of ’114 with the teachings of Schulz et al. by recovering hydrogen with the membrane unit 22, as taught by Schulz et al.,
It would have been prima facie obvious for one of ordinary skill in the art to be motivated to feed the steam generated from the methanol reactor cooling into the reforming step because, as taught by ‘432, autothermal reforming is a variant of the partial oxidation process, but which uses a catalyst to permit reforming to occur at lower temperatures than the partial oxidation process and moderate amounts of steam are typically required to prevent the catalyst from coking. One of ordinary skill in the art would have a reasonable expectation of success because recovery of steam is a standard practice for energy recovery.
Claim 5 is provisionally rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1-2, 6, 10-11, and 13 of copending Application No. 18/234114 (‘114) in view of Schulz et al. (US 2022/0162143 A1, published 05/26/2022, IDS dated 08/15/2023) in further view of U.S. Patent No. 9,637,432 B2 (‘432, published 05/02/2017, PTO-892), as applied to claim 4 above, and further in view of Benson et al. (NPL, published 2018, PTO-892).
Regarding claim interpretation, instant claim 5 lacks antecedent basis and is being interpreted as depending from instant claim 4 which does not have lack of antecedent basis.
The combined claims and teachings of ‘114, Schulz et al., and ‘432 were discussed above.
The combined claims and teachings of ‘114, Schulz et al., and ‘432 differ from that of the instantly claimed invention in that the combined claims and teachings of ‘114, Schulz et al., and ‘432 do not teach wherein the hydrogen-rich stream is utilized for the hydrogenation in the hydrodesulfurization unit.
The teachings of Benson et al. were discussed above.
It would have been obvious before the effective filing date of the claimed invention for one of ordinary skill in the art to be motivated to combine the teachings of ‘114, Schulz et al. and ‘432 with the teachings of Benson et al. by using the recycled hydrogen from the membrane, as taught by Schulz et al. in the hydrodesulfurizer, as taught by ‘432, to arrive at the instantly claimed invention. It would have been prima facie obvious for one of ordinary skill in the art to be motivated to recycle the hydrogen to the desulfurization because, as taught by Benson et al., it is more profitable and efficient to purify hydrogen from offgas for industry trends like desulfurization. One of ordinary skill in the art would have a reasonable expectation of success because several recovery technologies, such as membranes, as supported by Benson et al. (see Closing Thoughts section), are available to do this.
Claims 10 and 12 are provisionally rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1-2, 6, 10-11, and 13 of copending Application No. 18/234114 (‘114), as applied to claim 1 above, and further in view of Vicari et al. (WO2020048809, published 03/12/2020, original found in IDS dated 08/15/2023, translated version provided in PTO-892).
The claims of ‘114 were discussed above.
The claims of ‘114 differ from that of the instantly claimed invention in that the claims of ’114 do not recite wherein the hydrocarbon-containing carbon dioxide stream is provided by a carbon capture unit and wherein the synthesis gas stream produced according to step (f) is reacted in the methanol synthesis reactor in addition to the hydrocarbon-containing synthesis gas stream.
The teachings of Vicari et al. were discussed above.
It would have been obvious before the effective filing date of the claimed invention to combine the teachings of ‘114 with the teachings of Vicari et al. by feeding the flue gas (XII), corresponding to the instant synthesis gas stream, to the carbon dioxide recovery unit (G), corresponding to the instant carbon capture unit, and fed upstream to the methanol synthesis unit (B), corresponding to the instant methanol synthesis reactor, through stream (XIV), as taught by Vicari et al., to arrive at the instantly claimed invention. It would have been prima facie obvious for one of ordinary skill in the art to upcycle the synthesis gas stream, as taught by Vicari et al., because it avoids carbon dioxide emissions. One of ordinary skill in the art would have a reasonable expectation of success because upcycling off value streams is routine process optimization.
Conclusion
No claim is found allowable.
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/KRISTEN W BRADY/ Examiner, Art Unit 1692
/SCARLETT Y GOON/ Supervisory Patent Examiner, Art Unit 1693
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