DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Response to Amendment
Applicant’s amendment filed on July 29, 2026 has been received and considered. Claims 13, 27, and 32 are canceled. Claims 1-12, 14-26, and 28-31 are under consideration.
Response to Arguments
Applicant's arguments filed on July 29, 2026 have been fully considered.
With respect to the rejection of “method” claims 9-11, 13, 28-30 and 32 under 35 U.S.C. 102(a)(1) as being anticipated by Ambrosini et al. (US 10,107,268), Applicant (on page 9) argues,
“Ambrosini '268, as understood, discloses a solar power system and materials capable of storing heat energy by thermochemical. Ambrosini '268 uses a hot air discharge to drive a turbine.
In contrast, independent claim 9 has been amended to the reduction step discharges a pure nitrogen stream.
Further in contrast, independent claims 21 and 28 have been amended to produce a pure other gas.”
The argument is persuasive, and, therefore, the rejection has been withdrawn. However, upon further consideration, a new ground(s) of rejection is made in view of the newly discovered prior art to Ikeda et al. (Chemical Engineering Science 147 (2016) 166-172). In particular, Ikeda et al. discloses the use of synthetic air, which is 21 vol.% O2 and the balance N2 (see 2. Experimental). When a reduced metal oxide is oxidized in the presence of the synthetic air, oxygen is removed from the synthetic air, and a pure nitrogen product stream is produced.
With respect to the further rejection of the “system” claims 21-25 and 27 under 35 U.S.C. 102(a)(1) as being anticipated by Ambrosini et al., the arguments are not found persuasive. Note that the “system” claims are considered apparatus claims. The newly added limitations with respect to the use of an input gas stream “comprising oxygen and one other gas” (interpreted as the input gas stream containing only oxygen and one other gas) for producing an oxygen depleted product stream that is “pure in the other gas” (interpreted as the product stream only containing the one other gas) do not impart further patentability (structural limitations) to the apparatus claims. The input gas stream is merely a material to be worked upon by the apparatus during an intended operation; it is not an element of the apparatus. See MPEP §§ 2114, 2115. The system of Ambrosini et al. would have been capable of performing the intended use as claimed.
With respect to the rejection of claims 9-11, 21-26, and 28-31 under 35 U.S.C. 102(a)(1) as being anticipated by Lange et al. (DE 10 2014213987 A1), Applicant (on page 10) argues,
“Lange, as understood, discloses a solar power system for synthesizing nitrogen. The disclosed redox materials are simple metal oxides.
In contrast, independent claims 9 21 and 28 have been amended to specify that the redox materials are mixed ionic and electronic conducting oxides that are not disclosed by Lange.
Applicant submits that one or more of the features recited by Applicant in independent claims 9, 21 and 28 including the mixed ionic oxides are not taught or suggested by Lange.”
The argument is persuasive, and, therefore, the rejection has been withdrawn. However, the claimed feature of a mixed ionic and electronic conducting oxide was previously recited in dependent claims 13, 27, and 32 (now canceled), and these claims were previously rejected under 35 U.S.C. 103 as being unpatentable over Lange et al. in view of Vieten et al. (J. Mater. Chem. A. 2016, 4, 13652). Vieten et al. specifically teaches a mixed ionic and electronic conducting oxide (i.e., SrFe0.95Cu0.05O3-δ or Ca0.8Sr0.2MnO3-δ; see Abstract, and Results and discussion) as a suitable redox material for producing a nitrogen product stream.
With respect to the rejection of claims 1, 2, 4-6, and 14-18 under 35 U.S.C. 103 as being unpatentable over Lange et al. in view of Michalsky (Dissertation: “Thermochemical Production of Ammonia Using Sunlight, Air, Water and Biomass”, 2012), Applicant (on page 13) argues,
“Michalsky is used by the Examiner to disclose the claimed ammonia subsystem.
Applicant submits that Michalsky fails to disclose the redox oxide as now claimed by the Applicant and fails to cure the deficiencies of Lange.
In addition, Michalsky is improperly combined with Lange as Michalsky uses biomass that would fundamentally change the operation of Lange.”
The Office respectfully disagrees.
Firstly, as addressed above, the claimed feature of a redox material comprising “a mixed ionic and electronic conducting oxide” was taught by the secondary reference to Vieten et al.
Secondly, contrary to Applicant’s assertion, Michalsky does not use biomass. In fact, Michalsky teaches away from the use of biomass for the production of ammonia. Michalsky (see page 189, under 8.1 Abstract) states,
“For achieving food security, ammonia is an irreplaceable fertilizer supplying a growing global demand for food and biofuel. It has attached current attention due to alternative used for hydrogen storage and combustion fuel blends. Motivated by a prospective solar thermochemical synthesis of NH3 at ambient pressure and without biomass or a fossil fuel, this study characterizes the heterogenous reactions of manganese, calcium, or strontium nitrides with H2.” (with emphasis added).
Michalsky (see page 208, under 8.5 Conclusions) also states,
“To produce ammonia at atmospheric pressure with a solar thermochemical reaction cycle that does not require a chemical reducing agent (such as solid coal or solid or gasified biomass), the reactions of some binary metal nitrides formed by manganese, calcium, or strontium respectively with H2 were studied in this work.” (with emphasis added).
Applicant’s remaining arguments (on pages 13-15) are based upon the asserted deficiencies in the prior art as addressed above. Thus, the Examiner’s same comments apply.
With respect to the rejection of claims 9-11, 21-25, and 28-30 on the grounds of nonstatutory double patenting over claims 1-16 of Ambrosini et al. (US 10,107,268), the rejection has been withdrawn in view of the amendments to claims 9, 21, and 28.
Claim Objections
Claims 1, 9, 21, and 28 are objected to because of the following informalities:
In claim 1, the new limitations directed to “the metal oxide” (at lines 21-24) should be deleted and re-inserted/indented under “a nitrogen production sub-system” (at lines 2-10) because the metal oxide is a component of the nitrogen production sub-system.
In claim 1, the phrase “is a” (at line 22, before “selected”) should be deleted.
In claim 1, the formula “AxA’1-xByB’1-yO3-δ” (at lines 22-33) should be rewritten using subscripts for “x”, “1-x”, “y”, “1-y”, and “3-δ”.
In claim 9, the phrase “is a” (at line 11, before “selected”) should be deleted.
In claim 9, the formula “AxA’1-xByB’1-yO3-δ” (at lines 11-12) should be rewritten using subscripts for “x”, “1-x”, “y”, “1-y”, and “3-δ”.
In claim 21, the phrase “is a” (at line 12, before “selected”) should be deleted.
In claim 21, the formula “AxA’1-xByB’1-yO3-δ” (at line 13) should be rewritten using subscripts for “x”, “1-x”, “y”, “1-y”, and “3-δ”.
In claim 28, the phrase “is a” (at line 12, before “selected”) should be deleted.
In claim 28, the formula “AxA’1-xByB’1-yO3-δ” (at lines 12-13) should be rewritten using subscripts for “x”, “1-x”, “y”, “1-y”, and “3-δ”.
Appropriate correction is required.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 9-12, 14-26, and 28-31 are 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.
Regarding claim 9, the limitation “oxidizing the reduced metal oxide in the presence of an input stream comprising oxygen and nitrogen to remove the oxygen and produce the metal oxide and a pure nitrogen product stream” (at lines 4-6; with emphasis added) is unclear. The term “comprising” is inclusive or open-ended and does not exclude additional, unrecited elements (such as other gases in addition to oxygen and nitrogen). However, the recitation of a “pure” nitrogen product stream suggests that the input stream must “consist of” only oxygen and nitrogen. See MPEP § 2111.03, I and II.
Also, the relationship between “the nitrogen of the input stream” (at line 8) and “a pure nitrogen product stream” previously set forth in the claim (at line 6) is unclear.
Regarding claim 11, the further limitation “wherein the input stream is air” is unclear because “air” is made up of oxygen, nitrogen, and other gases, including argon. As such, it is unclear as to how a “pure nitrogen product stream” (interpreted as a stream which only contains nitrogen) can be produced from an input stream of “air”.
Regarding claim 12, the further limitation “wherein the metal oxide is selected from the group of oxides of Mn, Co, Fe, V, W, Mo, Cr and Cu” is unclear because claim 9 (at lines 10-13) sets forth that the metal oxide must be “a mixed ionic and electronic conducting oxide selected from the group having the formula AxA’1-xByB’1-yO3-δ, where A = La, Sr, Ca, Ba, Y and B = Mn, Fe, Co, Ti, Ni, Cu, Zr, Al, Y, Cr, V, Nb, Mo, and 0 ≤ x ≤ 1, 0 ≤ y ≤ 1 and 0 ≤ δ ≤ 1”. Based on Applicant’s disclosure, the MIEC metal oxide recited in claim 9 and the metal oxide recited in claim 12 are alternative metal oxide embodiments (see specification, paragraph [0024] versus paragraph [0025]). It is further noted that tungsten (W) is not a member of the closed group of elements set forth in claim 9.
Regarding claim 14, the relationship between “the nitrogen of the input stream” (at line 8) and “an enriched nitrogen product stream” set forth in the claim (at lines 5-6) is unclear.
Regarding claim 21, the limitation “the mass of reduced metal oxide is oxidized in the oxidation reactor in the presence of an input stream comprising oxygen and one other gas to produce an oxygen depleted product stream pure in the other gas” (at lines 8-10; with emphasis added) is unclear. The term “comprising” is inclusive or open-ended and does not exclude additional, unrecited elements (such as other gases in addition to the oxygen and the one other gas). However, the recitation of an oxygen depleted product stream “pure in the other gas” suggests that the input stream must “consist of” only the oxygen and the one other gas. See MPEP § 2111.03, I and II.
Regarding claim 24, the limitation, “wherein the one or more other gases are one or more inert gases” renders the claim indefinite because claim 21 previously set forth that the input stream includes only “one other gas” (at line 9).
Regarding claim 26, the further limitation “wherein the metal oxide is selected from the group of oxides of Mn, Co, Fe, V, W, Mo, Cr and Cu” is unclear because claim 21 (at lines 12-14) sets forth that the metal oxide must be “a mixed ionic and electronic conducting oxide selected from the group having the formula AxA’1-xByB’1-yO3-δ, where A = La, Sr, Ca, Ba, Y and B = Mn, Fe, Co, Ti, Ni, Cu, Zr, Al, Y, Cr, V, Nb, Mo, and 0 ≤ x ≤ 1, 0 ≤ y ≤ 1 and 0 ≤ δ ≤ 1”. Based on Applicant’s disclosure, the MIEC metal oxide recited in claim 21 and the metal oxide recited in claim 26 are alternative metal oxide embodiments (see specification, paragraph [0024] versus paragraph [0025]). It is further noted that tungsten (W) is not a member of the closed group of elements set forth in claim 21.
Regarding claim 28, the limitation, “oxidizing the reduced metal oxide in the presence of an input gas stream comprising oxygen and another gas to remove the oxygen and produce the metal oxide and an enriched product stream depleted of oxygen and pure in the other gas” (at lines 5-8) is unclear. Firstly, the term “comprising” is inclusive or open-ended and does not exclude additional, unrecited elements (such as other gases in addition to the oxygen and the another gas). However, the recitation “pure in the other gas” suggests that the input stream must “consist of” only oxygen and the another gas. See MPEP § 2111.03, I and II. Secondly, the word “enriched” (recited at lines 1, 7 and 10) refers to something that has been made richer or increased in quantity. However, the word “pure” refers to something which is not mixed with any other substance or material. Therefore, the use of both words for describing the “product stream” is unclear. Thirdly, the recitation of “the other gas” (at line 8) lacks proper antecedent basis, since “another gas” was previously set forth in the claim (at line 6).
Regarding claim 30, the limitation “wherein the other gases are one or more inert gases” renders the claim indefinite because claim 28 sets forth that the input gas stream merely comprises “another gas” (singular, at line 6).
Regarding claim 31, the limitation “wherein the metal oxide comprises Mn, Co, Fe, V, W, Mo, Cr and Cu” is unclear. Firstly, claim 28 (at lines 11-14) sets forth that the metal oxide must be “a mixed ionic and electronic conducting oxide selected from the group having the formula AxA’1-xByB’1-yO3-δ, where A = La, Sr, Ca, Ba, Y and B = Mn, Fe, Co, Ti, Ni, Cu, Zr, Al, Y, Cr, V, Nb, Mo, and 0 ≤ x ≤ 1, 0 ≤ y ≤ 1 and 0 ≤ δ ≤ 1”. Based on Applicant’s disclosure, the MIEC metal oxide recited in claim 28 and the metal oxide recited in claim 31 are alternative metal oxide embodiments (see specification, paragraph [0024] versus paragraph [0025]). Secondly, it is noted that tungsten (W) is not a member of the closed group of elements set forth in claim 28. Thirdly, the limitation that the metal oxide “comprises Mn, Co, Fe, V, W, Mo, Cr and Cu” refers to a metal oxide that contains all eight of the listed elements. No such metal oxide is suggested by the disclosure, and furthermore, in the case of the MIEC metal oxide set forth in claim 28, the metal oxide is limited to a maximum of four elements A, A’, B, and B’.
The remaining claims are also rejected because they depend from a rejected base claim.
Claim Rejections - 35 USC § 102
The following is a quotation of the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
Claims 21-25 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Ambrosini et al. (US 10,107,268 B1).
The instant “system” claims are considered apparatus claims.
Regarding claim 21, Ambrosini et al. discloses a system (see FIG. 1) for producing an oxygen depleted product stream, comprising:
a reduction reactor (i.e., a solar receiver reduction reactor 16 defining a particle reduction chamber 26; see column 5, lines 4-19) comprising a heat source (i.e., a source of concentrated sunlight 33 directed into the chamber 26 via an aperture or window 28);
an oxidation reactor (i.e., a re-oxidation reactor 20; see column 5, lines 44-63);
a mass of metal oxide (i.e., particles 34 of metal oxide (MOx); see column 7, lines 55-63) within the reduction reactor;
wherein the mass of metal oxide (MOx) is heated by the heat source 33 and reduced in the reduction reactor 16 to produce a mass of reduced metal oxide (i.e., particles 34 of reduced metal oxide (MOx-δ));
wherein the mass of reduced metal oxide (MOx-δ) is oxidized in the oxidation reactor 20 in the presence of an input stream 38 comprising oxygen and one or more other gases (i.e., air 38, which contains oxygen, nitrogen, and other gases including argon) to produce an oxygen depleted product stream enriched in the one or more other gasses (i.e., the oxygen in the air 38 reacts with the reduced metal oxide (MOx-δ) in the re-oxidation reactor 20 to re-oxidize the reduced metal oxide to its original metal oxide form (MOx), and a discharge gas 40 comprising oxygen-depleted air, which is a nitrogen-enriched product stream containing nitrogen and other gases including argon, is removed from the re-oxidation reactor 20); and
wherein the metal oxide is a mixed ionic and electronic conducting oxide selected from the group having the formula AxA′1-xByB′1-yO3-δ, where A = La, Sr, Ca, Ba, Y and B = Mn, Fe, Co, Ti, Ni, Cu, Zr, Al, Y, Cr, V, Nb, Mo, and 0≤x≤1, 0≤y≤1 and 0≤δ≤1 (see column 8, lines 18-24).
The newly added limitations with respect to the use of an input gas stream “comprising oxygen and one other gas” (interpreted as the input gas stream containing only oxygen and one other gas) for producing an oxygen depleted product stream “pure in the other gas” (interpreted as the product stream only containing the one other gas) do not impart further patentability (structural limitations) to the apparatus claim. The input gas stream is merely a material to be worked upon by the apparatus during an intended operation; it is not an element of the apparatus. See MPEP §§ 2114, 2115. The system of Ambrosini et al. would have been structurally capable of performing the intended use as claimed.
Regarding claim 22, Ambrosini et al. discloses that the heat source is concentrated solar energy (i.e., concentrated sunlight 33; see column 5, lines 6-19).
Regarding claim 23, Ambrosini et al. discloses that the reduction reactor 16 is the solar heating zone (i.e., the zone heated by concentrated sunlight 33) of the falling particle solar receiver or other receiver configurations (i.e., the particles 34 to be heated may flow via gravity or they may be mechanically or otherwise conveyed; see column 7, line 64, to column 8, line 6).
Regarding claim 24, Ambrosini et al. discloses that the one or more other gases are one or more inert gases (i.e., the discharge gas 40 comprises nitrogen, which is an inert gas).
Regarding claim 25, Ambrosini et al. discloses that the mass of metal oxide is a mass of metal oxide particles (i.e., particles 34 of metal oxide).
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.
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, 2 and 4-6 are rejected under 35 U.S.C. 103 as being unpatentable over Lange et al. (DE 10 2014213987 A1) in view of Michalsky (Dissertation: “Thermochemical Production of Ammonia Using Sunlight, Air, Water and Biomass”, 2012) and Vieten et al. (J. Mater. Chem. A. 2016, 4, 13652).
The instant “system” claims are considered apparatus claims.
Regarding claim 1, Lange et al. discloses a system for producing ammonia (i.e., an apparatus for producing ammonia; see FIG. 1 and translation) comprising:
a nitrogen production sub-system, comprising:
a reduction reactor (i.e., a reduction chamber 5) comprising a heat source (i.e., concentrated solar radiation 4 as a heat source);
a nitrogen production reactor (i.e., an oxidation tank 2 for producing a nitrogen-enriched product stream from a supply of compressed air 1); and
a mass of metal oxide (i.e., a metal oxide, such as cobalt oxide) within the reduction reactor 5;
wherein the mass of metal oxide is heated by the heat source 4 and reduced in the reduction reactor 5 to produce a mass of reduced metal oxide (i.e., cobalt oxide (Co3O4) is heated by the concentrated solar radiation 4, which releases oxygen (O2) and produces reduced cobalt oxide (CoO)); and
wherein the mass of reduced metal oxide is oxidized in the nitrogen production reactor 2 in the presence of an input stream comprising oxygen and nitrogen (i.e., air 1, which comprises oxygen and nitrogen) to remove the oxygen and produce a nitrogen enriched product stream (i.e., the oxygen in the air 1 reacts with the reduced cobalt oxide (CoO) to produce the cobalt oxide (Co3O4); the air is thus depleted in oxygen, and a nitrogen-enriched product stream is discharged from the oxidation tank 2); and
an ammonia production subsystem, comprising:
an ammonia production reactor 8, wherein hydrogen (i.e., supplied from an electrolyzer 6) and the nitrogen product stream produced in the nitrogen production sub-system are reacted in the ammonia production reactor 8 under high temperature and high pressure to synthesize ammonia (NH3).
Lange et al. fails to disclose that the ammonia production subsystem comprises the claimed ammonia production subsystem, which comprises:
an ammonia production reactor; a nitridation reactor; and a mass of metal nitride in the ammonia production reactor; wherein the mass of metal nitride is reacted with the hydrogen (i.e., from the electrolyzer 6) in the ammonia production reactor to produce a mass of nitrogen-deficient metal nitride and ammonia; and wherein the mass of nitrogen-deficient metal nitride is reacted with the nitrogen product stream produced in the nitrogen production sub-system (i.e., the product stream from the oxidation tank 2) to form the mass of metal nitride.
Michalsky discloses an ammonia production system (i.e., an apparatus for synthesizing ammonia, see Figure 8.10 (A) on page 207; also, generally, Chapter 8, from pages 189-209), the system comprising:
an ammonia production reactor (i.e., an “Ammonia formation” reactor);
a nitridation reactor (i.e., a “Nitrogen reduction” reactor); and
a mass of metal nitride in the ammonia production reactor (i.e., a metal nitride comprising, for instance, manganese nitride, Fe-doped manganese nitride, calcium nitride, or strontium nitride; see sections 8.3.1, 8.3.2, and 8.3.3 on pages 193-195);
wherein the mass of metal nitride is reacted with hydrogen in the ammonia production reactor to produce a mass of nitrogen-deficient metal nitride and ammonia (i.e., the Ammonia formation reactor is connected to a source of hydrogen (H2), see FIG. 8.10(A), and the metal nitride is reacted with the hydrogen in the Ammonia formation reactor to produce a nitrogen-deficient metal nitride and ammonia (NH3)); and
wherein the mass of nitrogen-deficient metal nitride is reacted with nitrogen to form the mass of metal nitride (i.e., the nitrogen-deficient metal nitride that was produced by the Ammonia formation reactor is subsequently regenerated in the Nitrogen reduction reactor, wherein the Nitrogen reduction reactor is connected to a source of nitrogen (N2), see FIG. 8.10(A), and the nitrogen-deficient metal nitride is reacted with the nitrogen in the Nitrogen reduction reactor to reform the metal nitride).
It would have been obvious for one of ordinary skill in the art before the effective filing date of the claimed invention to substitute the ammonia production system of Michalsky for the ammonia production subsystem in the system of Lange et al. because the ammonia production system would have enabled the ammonia to be produced from the hydrogen and the nitrogen product stream under ambient pressure, instead of the high pressures required by the conventional ammonia synthesis process, as taught by Michalsky (see 8.1 Abstract and 8.2 Introduction at page 189-191).
Lange et al. further discloses that the metal oxide of the nitrogen production system can be selected from a variety of metal oxides (see translation). Lange et al., however, fails to disclose that the metal oxide specifically comprises a mixed ionic and electronic conducting oxide selected from the group having the formula AxA′1-xByB′1-yO3-δ, where A=La, Sr, Ca, Ba, Y and B=Mn, Fe, Co, Ti, Ni, Cu, Zr, Al, Y, Cr, V, Nb, Mo, and 0≤x≤1, 0≤y≤1 and 0≤δ≤1.
Vieten et al. discloses a nitrogen production system (i.e., a thermochemical air separation process using non-stoichiometric perovskites, AMO3; see FIG. 1), comprising:
a reduction reactor containing a mass of metal oxide (i.e., a reactor for reducing the metal oxide AMO3, according to the upper reaction equation as shown) comprising a heat source (i.e., a source of concentrated solar power (CSP)); and
a nitrogen production reactor (i.e., a reactor for reacting the metal oxide AMO3-δ with oxygen, according to the lower reaction equation as shown);
wherein the mass of metal oxide (AMO3) is heated by the heat source (CSP) and reduced in the reduction reactor to produce a mass of reduced metal oxide (AMO3-δ);
wherein the mass of reduced metal oxide (AMO3-δ) is oxidized in the nitrogen production reactor in the presence of an input stream comprising oxygen and introduce (i.e. air N2 O2 Ar as the input stream) to remove the oxygen and produce a nitrogen enriched product stream (i.e., oxygen depleted air as the product stream); and
wherein, specifically, the metal oxide is a mixed ionic and electronic oxide selected from SrFe0.95Cu0.05O3-δ or Ca0.8Sr0.2MnO3-δ (see Abstract; Results and discussion).
It would have been obvious for one of ordinary skill in the art before the effective filing date of the claimed invention to also substitute the metal oxide of Vieten et al. for the metal oxide in the system of Lange et al. because the metal oxide, SrFe0.95Cu0.05O3-δ or Ca0.8Sr0.2MnO3-δ, was shown to exhibit an outstanding gravimetric oxygen storage capacity, with the redox reactions being completed very quickly in <1 min in air and with highly reversibility, which would allow for the air separation process based on thermochemical cycling to be performed in a competitive manner, as taught by Vieten et al. (see Abstract and Conclusions).
Regarding claim 2, Lange et al. further discloses that the heat source is concentrated solar energy (i.e., concentrated solar radiation 4; see FIG. 1, translation).
Regarding claim 4, Lange et al. further discloses that the input stream is air (i.e., compressed air 1 is fed to the oxidation tank 2; see FIG. 1, translation).
Regarding claim 5, Michalsky discloses that the metal nitride is a redox active metal or transition metal nitride (i.e., manganese nitride, Fe-doped manganese nitride, calcium nitride, or strontium nitride; see sections 8.3.1, 8.3.2, and 8.3.3 on pages 193-195).
Regarding claim 6, Michalsky further discloses that the metal nitride can comprise metals (interpreted as plural metals) selected from the groups consisting of redox active metals including Cr, Fe, Mn, Mo, V, W, Co, Cu, Ge, and Ni, and non-redox active metals including Ba, Ga, Li, Mg, Na, Sr, Sn and Zn (i.e., Fe-doped manganese nitride, see section 8.3.2, on page 194).
Claim 3 is rejected under 35 U.S.C. 103 as being unpatentable over Lange et al. (DE 10 2014213987 A1) in view of Michalsky (Dissertation: “Thermochemical Production of Ammonia Using Sunlight, Air, Water and Biomass”, 2012) and Vieten et al. (J. Mater. Chem. A. 2016, 4, 13652), as applied to claim 1 above, and further in view of Felinks et al. (DE 102013209658 A1).
Lange et al. discloses that the reduction reactor 5 is the solar heating zone of a particle solar receiver (i.e., the zone in which the particles of cobalt oxide are heated by the concentrated solar radiation 4, see FIG. 1). Lange et al., however, fails to disclose that the particle solar receiver is specifically a falling particle solar receiver.
Felinks et al. discloses a nitrogen production system (see FIG. 2 and translation, in particular, at the underlined portions) comprising:
a reduction reactor (i.e., a “Reduktion” reactor for a forward reaction step of the thermochemical cycle; see FIG. 1) comprising a heat source (i.e., concentrated solar radiation);
a nitrogen production reactor (i.e., an “Oxidation” reactor for a reverse reaction step of the thermochemical cycle; see FIG. 1); and
a mass of metal oxide within the reduction reactor (i.e., a metal oxide MOox supplied the Reduktion reactor);
wherein the mass of metal oxide (MOox) is heated by the heat source and reduced in the reduction reactor to produce a mass of reduced metal oxide (MOred); and
wherein the mass of reduced metal oxide (MOred) is oxidized in the nitrogen production reactor in the presence of an input stream comprising oxygen and nitrogen (i.e., an input of “Luft” (air) to the Oxidation reactor, which comprises oxygen and nitrogen) to remove the oxygen (i.e., by reaction of the oxygen in the air with the reduced metal oxide MOred, which produces the metal oxide MOox and simultaneously depletes the oxygen in the air) and produce a nitrogen enriched product stream (i.e., an “Inertgas” (inert gas) stream comprising oxygen-depleted air, which is a nitrogen-enriched product stream).
Specifically, Felinks et al. discloses that the reduction reactor is the solar heating zone of a falling particle solar receiver (i.e., the metal oxide MOox particles are heated by concentrated solar energy as they flow by gravity through the Reduktion reactor, from an upper inlet which receives the metal oxide MOox particles to a lower outlet which discharges the reduced metal oxide MOred particles, see FIG. 2; the heating by the concentrated solar radiation can be achieved by means of a solar tower, see translation).
It would have been obvious for one of ordinary skill in the art before the effective filing date of the claimed invention to configure the reduction reactor as the solar heating zone of a falling particle solar receiver in the modified system of Lange et al. because such reactor configuration would have been suitable for enabling the circulation of the metal oxide particles in a closed loop, between the reduction reactor and the nitrogen production reactor, for conducting the thermochemical cycle, as taught by Felinks et al.
Claims 7 and 8 are rejected under 35 U.S.C. 103 as being unpatentable over Lange et al. (DE 10 2014213987 A1) in view of Michalsky (Dissertation: “Thermochemical Production of Ammonia Using Sunlight, Air, Water and Biomass”, 2012) and Vieten et al. (J. Mater. Chem. A. 2016, 4, 13652), as applied to claim 1 above, and further in view of Daisley et al. (Journal of Energy Chemistry 39 (2019) 170-175).
Regarding claim 7, Michalsky fails to disclose that the metal nitride further comprises one or more elements selected from the group consisting of P, B, Si, S and C.
Daisley et al. discloses a metal nitride that further comprises the element carbon (C) (i.e., a nickel molybdenum carbonitride represented by the formula Ni2Mo3CxNy; see Abstract, Table 1, FIG. 5, and discussion beginning with “Ammonia Synthesis Testing:” on page 171), wherein the metal nitride is active for ammonia synthesis at 400 °C.
It would have been obvious for one of ordinary skill in the art before the effective filing date of the claimed invention to substitute the metal nitride (Ni2Mo3CxNy) of Daisley et al. for the metal nitride in the modified system of Lange et al. because the metal nitride (Ni2Mo3CxNy) would be active for ammonia synthesis at 400 °C, while also being effectively regenerated by nitrogen, as taught by Daisley et al.
Regarding claim 8, Michalsky fails to disclose that the metal nitride is selected from the group consisting of Co-Mn, Co-Mo, Co-W, Cu-Ba, Cu-Li, Cu-Mg, Cu-Sr, Ge-Cr, Ge-Fe, Ge-Mn, Ge-Na, Ni-Fe, Ni-Mn, Ni-Mo, Ni-W, Ni-Na, Ni-Sr, Sn-Cr, Sn-Mn, Zn-Cr, Zn-Mn, and Zn-Mo.
Daisley et al. discloses a Ni-Mo metal nitride (i.e., a nickel molybdenum carbonitride having the formula Ni2Mo3CxNy; see Abstract, Table 1, FIG. 5, discussion beginning with “Ammonia Synthesis Testing:” on page 171) which is active for ammonia synthesis at 400 °C.
It would have been obvious for one of ordinary skill in the art before the effective filing date of the claimed invention to substitute the metal nitride (Ni2Mo3CxNy) of Daisley et al. for the metal nitride in the modified system of Lange et al. because the metal nitride (Ni2Mo3CxNy) would be active for ammonia synthesis at 400 °C, while also being effectively regenerated by nitrogen, as taught by Daisley et al.
Claim 8 is rejected under 35 U.S.C. 103 as being unpatentable over Lange et al. (DE 10 2014213987 A1) in view of Michalsky (Dissertation: “Thermochemical Production of Ammonia Using Sunlight, Air, Water and Biomass”, 2012) and Vieten et al. (J. Mater. Chem. A. 2016, 4, 13652), as applied to claim 1 above, and further in view of Gregory et al. (Catal Lett (2011) 141:22-26).
Michalsky fails to disclose that the metal nitride is selected from the group consisting of Co-Mn, Co-Mo, Co-W, Cu-Ba, Cu-Li, Cu-Mg, Cu-Sr, Ge-Cr, Ge-Fe, Ge-Mn, Ge-Na, Ni-Fe, Ni-Mn, Ni-Mo, Ni-W, Ni-Na, Ni-Sr, Sn-Cr, Sn-Mn, Zn-Cr, Zn-Mn, and Zn-Mo.
Gregory et al. (see Abstract) discloses a Co-Mo metal nitride, wherein the metal nitride demonstrates specific utility for the production of ammonia. The reaction of the metal nitride (Co3Mo3N) with hydrogen produces a nitrogen-deficient metal nitride (Co6Mo6N) and ammonia, and the reaction of the nitrogen-deficient metal nitride (Co6Mo6N) with nitrogen (i.e., using H2/N2 at lower temperature or N2 (alone) at higher temperature) regenerates the nitrogen-deficient metal nitride (Co6Mo6N) to form the metal nitride (Co6Mo6N).
It would have been obvious for one of ordinary skill in the art before the effective filing date of the claimed invention to substitute the Co-Mo metal nitride of Gregory et al. for the metal nitride in the modified system of Lange et al. because the Co-Mo metal nitride would have exhibited significant production of ammonia during its reaction with hydrogen, while also being effectively regenerated by nitrogen, as taught by Gregory et al.
Claims 9-12 and 28-31 are rejected under 35 U.S.C. 103 as being unpatentable over Ambrosini et al. (US 10,107,268 B1) in view of Ikeda et al. (Chemical Engineering Science 147 (2016) 166-172).
Regarding claim 9, Ambrosini et al. (see FIG. 1) discloses a method for producing nitrogen, comprising:
a) reducing a metal oxide (i.e., particles 34 of a metal oxide undergo a reduction reaction in a particle reduction chamber 26 of a solar receiver reduction reactor 16, where a metal oxide MOx is reduced to MOx-δ; see column 5, lines 4-19; column 7, lines 55-63) by heating the metal oxide (i.e., the particles 34 are heated by concentrated sunlight 33 directed into the chamber 26 via an aperture or window 28) to produce a reduced metal oxide (MOx-δ);
b) oxidizing the reduced metal oxide (i.e., the reduced metal oxide is re-oxidized in a re-oxidation reactor 20, where the reduced metal oxide (MOx-δ) is re-oxidized to its original metal oxide form (MOx); see column 5, lines 44-63; column 8, lines 7-14) in the presence of an input stream comprising oxygen and nitrogen (i.e., a stream of air 38, which comprises oxygen and nitrogen) to remove the oxygen (i.e., by reaction the reduced metal oxide (MOx-δ) with the oxygen in the air 38) and produce the metal oxide (MOx) and a nitrogen product stream (i.e., a discharge gas 40 comprising oxygen-depleted air, which is a nitrogen product stream);
c) using the metal oxide produced in step b) in step a) (i.e., the particles of re-oxidized metal oxide (MOx) are discharged from the re-oxidation reactor 20 and transported back to the reduction reactor 16 via a particle transport means 44, so that the metal oxide (MOx) may again undergo the reduction reaction; see column 6, lines 51-62); and
d) discharging the nitrogen produced in step b), which comprises the nitrogen of the input stream, for further use (i.e., the oxygen-depleted air or nitrogen product stream, as the discharge gas 40, is sent to a further use, which includes the driving of a turbine 54; see column 7, lines 17-29);
wherein the metal oxide is a mixed ionic and electronic conducting oxide selected from the group having the formula AxA′1-xByB′1-yO3-δ, where A = La, Sr, Ca, Ba, Y and B = Mn, Fe, Co, Ti, Ni, Cu, Zr, Al, Y, Cr, V, Nb, Mo, and 0≤x≤1, 0≤y≤1 and 0≤δ≤1 (see column 8, lines 18-24).
As well-known in art, atmospheric air (excluding water vapor) is approximately 78.084% nitrogen, 20.946% oxygen, and less than 1% of all other gases, including argon. Therefore, an input stream 38 of atmospheric air will produce a nitrogen product stream 40 that also contains other gases in addition to nitrogen. As such, Ambrosini et al. fails to disclose that the nitrogen product stream 40 is a “pure” nitrogen product stream. However, Ambrosini et al. (at column 5, lines 50-54) discloses,
“In this exemplary embodiment, the ROx input gas 38 is air, however, in other embodiments, the ROx input gas may be air, oxygen, oxygen enriched air or gas, carbon dioxide, or other gas capable of facilitating a thermochemical oxidation reaction.”
Ikeda et al. further discloses a method for removing oxygen from a mixture containing nitrogen and oxygen, wherein the method comprises: oxidizing a reduced metal oxide in the presence of an input stream of “synthetic air” comprising oxygen and nitrogen to remove the oxygen and produce a metal oxide and a “pure” nitrogen product stream (i.e., during the step of oxygen sorption in the reversible oxygen sorption/desorption cycle using the perovskite-type metal oxide SrFeO3-δ, the reduced metal oxide was oxidized in the presence of an input stream of synthetic air (21 vol% O2 +N2 balance) to remove the oxygen from the input stream and produce a metal oxide and a “pure” nitrogen product stream, since the input stream was made up of only O2 and N2; see 2. Experimental). In addition, Ikeda et al. performed the same method using an input stream of “atmospheric air” comprising oxygen and nitrogen, instead of the synthetic air, so as to further demonstrate “actual oxygen separation from atmospheric air” using the metal oxide (see 2. Experimental; also, 3.3 Operation of small-scale HT-PSA apparatus using SrFeO3-δ sorbent).
It would have been obvious for one of ordinary skill in the art before the effective filing date of the claimed invention to substitute “synthetic air (21 vol% O2 +N2 balance)” for the atmospheric air of the input stream in the method of Ambrosini et al. because synthetic air would have been considered another gas that was suitable for facilitating the thermochemical oxidation reaction, as taught by Ikeda et al. Furthermore, one of ordinary skill in the art would have considered the synthetic air to be an equivalent to atmospheric air, and therefore, it would have been prima facie obvious to substitute one for the other, and the results would have been predictable to one of ordinary skill in the art. As such, a “pure” nitrogen product stream would be produced by oxidizing the reduced metal oxide in the presence of an input stream comprising synthetic air in the modified method of Ambrosini et al.
Regarding claim 10, Ambrosini et al. discloses that the heating is by concentrated solar energy (i.e., concentrated sunlight 33; see column 5, lines 6-19).
Regarding claim 11, Ambrosini et al. discloses that the input stream is air 38 (see FIG. 1; column 5, line 50-21). In addition, Ikeda et al. discloses that the input stream is air (i.e., a synthetic air; see 2. Experimental).
Regarding claim 12, Ambosini et al. discloses that a suitable metal oxide can comprise metals selected from Mn, Co, Fe, V, Mo, Cr, and Cu (see column 8, lines 18-24). Ikeda et al. also discloses that metal oxides that enable reversible oxygen sorption/desorption include perovskite-type oxides ABO3-δ, and, in particular, Fe-based perovskite-type oxides (see 1. Introduction and 2. Experimental). Therefore, it would have been obvious for one of ordinary skill in the art before the effective filing date of claimed invention to provide a metal oxide selected from the group of oxides of Mn, Co, Fe, V, Mo, Cr, and Cu for the metal oxide in the modified method of Ambrosini et al. because such metal oxides would have been effective for enabling the thermochemical oxidation reaction, as taught by Ambrosini et al. and Ikeda et al.
Regarding claim 28, Ambrosini et al. (see FIG. 1) discloses a method for producing an enriched product stream, comprising:
a) reducing a metal oxide (i.e., particles 34 of a thermochemically active, metal oxide undergo a reduction reaction within a particle reduction chamber 26 of a solar receiver reduction reactor 16, where a metal oxide (MOx) is converted to a reduced metal oxide (MOx-δ); see column 5, lines 4-19; column 7, lines 55-63) by heating the metal oxide (i.e., the particles 34 are heated by concentrated sunlight 33 directed into the particle reduction chamber 26 via an aperture or window 28) to produce a reduced metal oxide (MOx-δ);
b) oxidizing the reduced metal oxide (i.e., the reduced metal oxide is oxidized within a re-oxidation reactor 20, where the reduced metal oxide (MOx-δ) is re-oxidized to its original metal oxide form (MOx); see column 5, lines 44-63; column 8, lines 7-14) in the presence of an input gas stream comprising oxygen and other gases gas (i.e., air 38, which comprises oxygen and other gases including nitrogen and argon) to remove the oxygen (i.e., by reaction of the reduced metal oxide (MOx-δ) with the oxygen in the air) and produce the metal oxide (MOx) and an enriched product stream depleted of oxygen and enriched in the other gases (i.e., a discharge gas 40 comprising oxygen-depleted air, which is enriched in the other gases);
c) using the metal oxide produced in step b) in step a) (i.e., the particles 34 of metal oxide (MOx) are discharged from the re-oxidation reactor 20 and transported back to the reduction reactor 16 via a particle transport means 44, so that the metal oxide (MOx) may again undergo the reduction reaction; see column 6, lines 51-62); and
d) discharging the enriched product stream produced in step b) for further use (i.e., the hot gas stream 40 is used to drive a turbine 54; see column 7, lines 17-29);
wherein the metal oxide comprises a mixed ionic and electronic conducting (MIEC) oxide selected from the group having the formula AxA′1-xByB′1-yO3-δ, where A = La, Sr, Ca, Ba, Y and B = Mn, Fe, Co, Ti, Ni, Cu, Zr, Al, Y, Cr, V, Nb, Mo, and 0≤x≤1, 0≤y≤1 and 0≤δ≤1 (see column 8, lines 18-24).
As well-known in art, atmospheric air (excluding water vapor) is approximately 78.084% nitrogen, 20.946% oxygen, and less than 1% of all other gases, including argon. Therefore, an input gas stream 38 of atmospheric air will produce an enriched product stream 40 that is depleted of oxygen and enriched in the other gases, including nitrogen and argon.
Ambrosini et al. fails to disclose that the input gas stream 38 comprises oxygen and “another gas” (interpreted as a single other gas), so as to produce an enriched product stream 40 that is depleted of oxygen and “pure” in the other gas (interpreted as only containing the single other gas). However, Ambrosini et al. (at column 5, lines 50-54) discloses,
“In this exemplary embodiment, the ROx input gas 38 is air, however, in other embodiments, the ROx input gas may be air, oxygen, oxygen enriched air or gas, carbon dioxide, or other gas capable of facilitating a thermochemical oxidation reaction.”
Ikeda et al. further discloses a method for producing an enriched product stream, wherein the method comprises: oxidizing a reduced metal oxide in the presence of an input gas stream of “synthetic air” comprising oxygen and nitrogen as “another gas” to remove the oxygen and produce a metal oxide and an enriched product stream depleted of oxygen and “pure” in the other gas (i.e., during the step of oxygen sorption in the reversible oxygen sorption/desorption cycle using the perovskite-type metal oxide SrFeO3-δ, the reduced metal oxide was oxidized in the presence of an input gas stream of synthetic air (21 vol% O2 +N2 balance) to remove the oxygen from the input gas stream and produce a metal oxide and an enriched product stream depleted of oxygen and “pure” in nitrogen as the other gas, since the input gas stream was made up of only O2 and N2; see 2. Experimental). In addition, Ikeda et al. performed the same method using an input stream of “atmospheric air” comprising oxygen and nitrogen, instead of the synthetic air, so as to further demonstrate “actual oxygen separation from atmospheric air” using the metal oxide (see 2. Experimental; 3.3 Operation of small-scale HT-PSA apparatus using SrFeO3-δ sorbent).
It would have been obvious for one of ordinary skill in the art before the effective filing date of the claimed invention to substitute “synthetic air (21 vol% O2 +N2 balance)” for the atmospheric air used in the input gas stream in the method of Ambrosini et al. because the synthetic air would have been considered another gas that was suitable for facilitating the thermochemical oxidation reaction, as taught by Ikeda et al. Furthermore, one of ordinary skill in the art would have considered the synthetic air to be an equivalent to atmospheric air, and therefore, it would have been prima facie obvious to substitute one for the other, and the results would have been predictable to one of ordinary skill in the art. As such, an enriched product stream depleted of oxygen and “pure in the other gas” (i.e., pure in nitrogen) would be produced by oxidizing the reduced metal oxide using the input gas stream of synthetic air in the modified method of Ambrosini et al.
Regarding claim 29, Ambrosini et al. discloses that the heating is by concentrated solar energy (i.e., concentrated sunlight 33; see column 5, lines 6-19).
Regarding claim 30, Ambrosini et al. discloses that the other gases are one or more inert gases (i.e., the nitrogen and argon are inert gases). Ikeda et al. further discloses that the other gases are one or more inert gases (i.e., the synthesis air contains nitrogen as the single another gas, and nitrogen is an inert gas; see 2. Experimental).
Regarding claim 31, Ambosini et al. discloses that the metal oxide can comprise metals selected from Mn, Co, Fe, V, Mo, Cr, and Cu (see column 8, lines 18-24). Ikeda et al. also discloses metal oxides including perovskite-type oxides ABO3-δ, and, in particular, Fe-based perovskite-type oxides (see 1. Introduction; 2. Experimental). Therefore, it would have been obvious for one of ordinary skill in the art before the effective filing date of claimed invention to provide a metal oxide selected from the group of oxides of Mn, Co, Fe, V, Mo, Cr, and Cu for the metal oxide in the modified method of Ambrosini et al. because such metal oxides were known to be effective for the thermochemical reaction, as taught by Ambrosini et al. and Ikeda et al.
Claims 14-18 are rejected under 35 U.S.C. 103 as being unpatentable over Lange et al. (DE 10 2014213987 A1) in view of Michalsky (Dissertation: “Thermochemical Production of Ammonia Using Sunlight, Air, Water and Biomass”, 2012).
Regarding claim 14, Lange et al. discloses a method for producing ammonia (see FIG. 1 and translation) comprising:
a) reducing a metal oxide (i.e., reducing a redox material comprising a metal oxide, such as cobalt oxide) by heating the metal oxide with solar irradiance (i.e., heating cobalt oxide (Co3O4) in a reduction chamber 5 using concentrated solar radiation 4 as a heat source) to produce a reduced metal oxide (i.e., reduced cobalt oxide (CoO)) and oxygen (O2);
b) oxidizing the reduced metal oxide (i.e., the reduced cobalt oxide (CoO) is then oxidized in an oxidation tank 2) in the presence of an input stream comprising oxygen and nitrogen (i.e., air 1) to remove the oxygen and produce the metal oxide (i.e., the oxygen in the air 1 is reacted with the reduced cobalt oxide (CoO) to produce the cobalt oxide (Co3O4), which removes the oxygen from the air) and an enriched nitrogen product stream (i.e., a product stream, enriched in nitrogen, is discharged from the oxidation tank 2);
c) using the metal oxide produced in step b) in step a) (i.e., the cobalt oxide (Co3O4) is transported back to the reduction chamber 5, so that the cobalt oxide (Co3O4) can again be reduced to the cobalt oxide (CoO));
d’) discharging the nitrogen produced in step b), which comprises the nitrogen of the input stream, to an ammonia synthesis reactor 8; and
e’) reacting the nitrogen (N2) with hydrogen (i.e., H2 from an electrolyzer 6) in the ammonia synthesis reactor 8 to produce ammonia (NH3).
Lange et al. fails to disclose that the method further comprises:
d) discharging the enriched nitrogen product stream produced in step b), which comprises the nitrogen of the input stream, to a nitridation reactor;
e) nitriding a nitrogen-depleted metal nitride with the nitrogen in the nitridation reactor to produce a metal nitride;
f) reacting the metal nitride with hydrogen in an ammonia production reactor to produce ammonia and the nitrogen depleted metal nitride of step e); and
g) discharging the ammonia from the ammonia production reactor.
Michalsky discloses a method for producing ammonia (see Figure 8.10 (A) on page 207; also, generally, Chapter 8, from pages 189-209), comprising:
d) supplying nitrogen to a nitridation reactor (i.e., supplying nitrogen from a nitrogen source (N2) to a “Nitrogen reduction” reactor; Figure 8.10(A));
e) nitriding a nitrogen-depleted metal nitride with nitrogen in the nitridation reactor to produce a metal nitride (i.e., a nitrogen-deficient metal nitride is reacted with the nitrogen (N2) in the Nitrogen reduction reactor to produce a corresponding metal nitride; wherein the metal nitride comprises, for instance, manganese nitride, Fe-doped manganese nitride, calcium nitride, or strontium nitride; see sections 8.3.1, 8.3.2, and 8.3.3 on pages 193-195);
f) reacting the metal nitride with hydrogen in an ammonia production reactor to produce ammonia and the nitrogen depleted metal nitride of step e) (i.e., the metal nitride is then reacted with hydrogen supplied from a hydrogen source (H2) in an “Ammonia formation” reactor, wherein ammonia (NH3) is produced and the metal nitride is converted back into the nitrogen-depleted metal nitride); and
g) discharging the ammonia from the ammonia production reactor (i.e., the ammonia (NH3) is discharged from the Ammonia formation reactor for separation of the ammonia from unreacted nitrogen and hydrogen; Figure 8.10(A)).
It would have been obvious for one of ordinary skill in the art before the effective filing date of the claimed invention to substitute the process steps d) through g) of Michalsky for the process steps d’) and e’) in the method of Lange et al. because the process steps would have enabled the ammonia to be produced from the hydrogen and nitrogen using ambient pressure, instead of the high pressures required by the conventional ammonia synthesis process, as taught by Michalsky (see 8.1 Abstract and 8.2 Introduction, at pages 189-191).
Regarding claim 15, Lange et al. further discloses that the heating is by concentrated solar energy (i.e., concentrated solar radiation 4; see FIG. 1, translation).
Regarding claim 16, Michalsky further discloses that the metal nitride is a redox active metal or transition metal nitride (i.e., manganese nitride, Fe-doped manganese nitride, calcium nitride, or strontium nitride; see sections 8.3.1, 8.3.2, and 8.3.3 on pages 193-195).
Regarding claim 17, Lange et al. further discloses that the input stream is air (i.e., compressed air 1 is fed to the oxidation tank 2; see FIG. 1, translation).
Regarding claim 18, Michalsky further discloses that the metal nitride can comprise metals (interpreted as plural metals) selected from the groups consisting of redox active metals including Cr, Fe, Mn, Mo, V, W, Co, Cu, Ge, and Ni, and non-redox active metals including Ba, Ga, Li, Mg, Na, Sr, Sn and Zn (i.e., Fe-doped manganese nitride; see section 8.3.2, on page 194).
Claims 19 and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Lange et al. (DE 10 2014213987 A1) in view of Michalsky (Dissertation: “Thermochemical Production of Ammonia Using Sunlight, Air, Water and Biomass”, 2012), as applied to claim 14 above, and further in view of Daisley et al. (Journal of Energy Chemistry 39 (2019) 170-175).
Regarding claim 19, Michalsky fails to disclose that the metal nitride further comprises one or more elements selected from the group consisting of P, B, Si, S and C.
Daisley et al. discloses a metal nitride that further comprises the element carbon (C) (i.e., a nickel molybdenum carbonitride represented by the formula Ni2Mo3CxNy; see Abstract, Table 1, FIG. 5, and discussion beginning with “Ammonia Synthesis Testing:” on page 171), wherein the metal nitride is active for ammonia synthesis at 400 °C.
It would have been obvious for one of ordinary skill in the art before the effective filing date of the claimed invention to substitute the metal nitride (Ni2Mo3CxNy) of Daisley et al. for the metal nitride in the modified method/system of Lange et al. because the metal nitride (Ni2Mo3CxNy) would be active for ammonia synthesis at 400 °C, while also being effectively regenerated by nitrogen, as taught by Daisley et al.
Regarding claim 20, Michalsky fails to disclose that the metal nitride is selected from the group consisting of Co-Mn, Co-Mo, Co-W, Cu-Ba, Cu-Li, Cu-Mg, Cu-Sr, Ge-Cr, Ge-Fe, Ge-Mn, Ge-Na, Ni-Fe, Ni-Mn, Ni-Mo, Ni-W, Ni-Na, Ni-Sr, Sn-Cr, Sn-Mn, Zn-Cr, Zn-Mn, and Zn-Mo.
Daisley et al. discloses a Ni-Mo metal nitride (i.e., a nickel molybdenum carbonitride represented by the formula Ni2Mo3CxNy; see Abstract, Table 1, FIG. 5, and discussion beginning with “Ammonia Synthesis Testing:” on page 171), wherein the metal nitride is active for ammonia synthesis at 400 °C.
It would have been obvious for one of ordinary skill in the art before the effective filing date of the claimed invention to substitute the metal nitride (Ni2Mo3CxNy) of Daisley et al. for the metal nitride in the modified method of Lange et al. because the metal nitride (Ni2Mo3CxNy) would be active for ammonia synthesis at 400 °C, while also being effectively regenerated by nitrogen, as taught by Daisley et al.
Claim 20 is rejected under 35 U.S.C. 103 as being unpatentable over Lange et al. (DE 10 2014213987 A1) in view of Michalsky (Dissertation: “Thermochemical Production of Ammonia Using Sunlight, Air, Water and Biomass”, 2012), as applied to claim 14 above, and further in view of Gregory et al. (Catal Lett (2011) 141:22-26).
Michalsky fails to disclose that the metal nitride is selected from the group consisting of Co-Mn, Co-Mo, Co-W, Cu-Ba, Cu-Li, Cu-Mg, Cu-Sr, Ge-Cr, Ge-Fe, Ge-Mn, Ge-Na, Ni-Fe, Ni-Mn, Ni-Mo, Ni-W, Ni-Na, Ni-Sr, Sn-Cr, Sn-Mn, Zn-Cr, Zn-Mn, and Zn-Mo.
Gregory et al. (see Abstract) discloses a Co-Mo metal nitride, wherein the metal nitride demonstrates specific utility for the production of ammonia. The reaction of the metal nitride (Co3Mo3N) with hydrogen produces a nitrogen-deficient metal nitride (Co6Mo6N) and ammonia, and the reaction of the nitrogen-deficient metal nitride (Co6Mo6N) with nitrogen (i.e., using H2/N2 at lower temperature or N2 (alone) at higher temperature) regenerates the nitrogen-deficient metal nitride (Co6Mo6N) to form the metal nitride (Co6Mo6N).
It would have been obvious for one of ordinary skill in the art before the effective filing date of the claimed invention to substitute the Co-Mo metal nitride of Gregory et al. for the metal nitride in the modified method of Lange et al. because the Co-Mo metal nitride would have exhibited significant production of ammonia during its reaction with hydrogen, while also being effectively regenerated by nitrogen, as taught by Gregory et al.
Claims 21-26 are rejected under 35 U.S.C. 103 as being unpatentable over Lange et al. (DE 10 2014213987 A1) in view of Vieten et al. (J. Mater. Chem. A. 2016, 4, 13652).
The instant “system” claims are considered apparatus claims.
Regarding claim 21, Lange et al. discloses a system for producing an oxygen depleted product stream (see FIG. 1 and translation), comprising:
a reduction reactor (i.e., a reduction chamber 5) comprising a heat source (i.e., concentrated solar radiation 4);
an oxidation reactor (i.e., an oxidation tank 2); and
a mass of metal oxide (i.e., a redox material comprising a metal oxide, such as cobalt oxide) within the reduction reactor 5;
wherein the mass of metal oxide is heated by the heat source 4 and reduced in the reduction reactor 5 to produce a mass of reduced metal oxide (i.e., cobalt oxide (Co3O4) is heated by the concentrated solar radiation 4 and converted into cobalt oxide (CoO) in its reduced form); and
wherein the mass of reduced metal oxide (CoO) is oxidized in the oxidation reactor 2 in the presence of an input stream comprising oxygen and other gasses (i.e., air 1, which contains oxygen, nitrogen, and other gases) to produce an oxygen depleted product stream enriched in the other gasses (i.e., the oxygen in the air 1 is reacted with the reduced cobalt oxide (CoO) to form the cobalt oxide (Co3O4), which depletes the oxygen in the air and produces a product gas stream enriched in nitrogen and the other gases, including argon).
Lange et al. discloses that the metal oxide of the nitrogen production system can be selected from a variety of metal oxides (see translation). Lange et al., however, fails to disclose that the metal oxide specifically comprises a mixed ionic and electronic conducting oxide selected from the group having the formula AxA′1-xByB′1-yO3-δ, where A=La, Sr, Ca, Ba, Y and B=Mn, Fe, Co, Ti, Ni, Cu, Zr, Al, Y, Cr, V, Nb, Mo, and 0≤x≤1, 0≤y≤1 and 0≤δ≤1.
Vieten et al. discloses a nitrogen production system (i.e., a thermochemical air separation process using non-stoichiometric perovskites, AMO3; see FIG. 1), comprising:
a reduction reactor containing a mass of metal oxide (i.e., a reactor for reducing the metal oxide AMO3, according to the upper reaction equation as shown) comprising a heat source (i.e., a source of concentrated solar power (CSP)); and
a nitrogen production reactor (i.e., a reactor for reacting the metal oxide AMO3-δ with oxygen, according to the lower reaction equation as shown);
wherein the mass of metal oxide (AMO3) is heated by the heat source (CSP) and reduced in the reduction reactor to produce a mass of reduced metal oxide (AMO3-δ);
wherein the mass of reduced metal oxide (AMO3-δ) is oxidized in the nitrogen production reactor in the presence of an input stream comprising oxygen and introduce (i.e. air N2 O2 Ar as the input stream) to remove the oxygen and produce a nitrogen enriched product stream (i.e., oxygen depleted air as the product stream); and
wherein, specifically, the metal oxide is a mixed ionic and electronic oxide selected from SrFe0.95Cu0.05O3-δ or Ca0.8Sr0.2MnO3-δ (see Abstract; Results and discussion).
It would have been obvious for one of ordinary skill in the art before the effective filing date of the claimed invention to substitute the metal oxide of Vieten et al. for the metal oxide in the system of Lange et al. because the metal oxide, SrFe0.95Cu0.05O3-δ or Ca0.8Sr0.2MnO3-δ, was shown to exhibit an outstanding gravimetric oxygen storage capacity, with the redox reactions being completed very quickly in <1 min in air and with highly reversibility, which would allow for the air separation process based on thermochemical cycling to be performed in a competitive manner, as taught by Vieten et al. (see Abstract and Conclusions).
The recitations with respect to the use of an input gas stream “comprising oxygen and one other gas” for producing an oxygen depleted product stream “pure in the other gas” do not impart further patentability (structural limitations) to the apparatus claim. The input gas stream is merely a material to be worked upon by the apparatus during an intended operation; it is not an element of the apparatus. See MPEP §§ 2114, 2115. The modified system of Lange et al. would be structurally capable of performing the intended use as claimed.
Regarding claim 22, Lange et al. discloses that the heat source is concentrated solar energy (i.e., concentrated solar radiation 4; see translation).
Regarding claim 23, Lange et al. discloses that the reduction reactor 5 is the solar heating zone (i.e., the zone receiving the concentrated solar radiation 4) of “other receiver configurations”.
Regarding claim 24, Lange et al. discloses that the one or more other gases are one or more inert gases (i.e., nitrogen is an inert gas).
Regarding claim 25, Lange et al. discloses that the mass of metal oxide is a mass of metal oxide particles (i.e., particles of cobalt oxide are transported between the reduction chamber 5 and the oxidation tank 2 in a closed loop).
Regarding claim 26, Vieten et al. discloses that the metal oxide is selected from oxides of Mn, Fe, and Cu (i.e., SrFe0.95Cu0.05O3-δ or Ca0.8Sr0.2MnO3-δ).
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure:
“The Atmosphere” (retrieved from website: www.noaa.gov/jetstream/atmosphere) is cited for describing the chemical makeup of atmospheric air.
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
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Any inquiry concerning this communication or earlier communications from the examiner should be directed to JENNIFER A LEUNG whose telephone number is (571)272-1449. The examiner can normally be reached Monday - Friday 9:30 AM - 4:30 PM EST.
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/JENNIFER A LEUNG/Primary Examiner, Art Unit 1774
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