DETAILED ACTION
STATUS OF THE APPLICATION
Receipt is acknowledged of Applicants’ Amendments and Remarks, filed 18 July 2023, in the matter of Application No. 18/354,571. Said documents have been entered on the record. The Examiner further acknowledges the following:
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claims 1-12, 19-24, and 41-42 are pending.
No claims have been amended.
No claims have been cancelled.
Thus, claims 1-12, 19-24, and 41-42 represent all claims currently under consideration.
Information Disclosure Statement (IDS)
The information disclosure statements submitted on 20 October 2023 are in compliance with the provisions of 37 CFR 1.97. Accordingly, the information disclosure statements are being considered by the Examiner.
Claim Objections
Claim 9 is objected to because of the following informalities:
“…N-(2-EthoxyEthyl)-3-MorpholinoPropan-1-Amine...” should read “…N-(2-ethoxyethyl)-3-morpholinopropan-1-amine...”
Claim 10 is objected to because of the following informalities:
“…in the amine...” should read “…in which the amine...”
“…with 0.5-20wt%...” should read “…comprises 0.5-20 wt%...”
Claim 41 is objected to because of the following informalities:
In lines 1-2, “…CO2, and a heterogeneous catalyst, and methanol…” should read “…CO2, a heterogeneous catalyst, and methanol…
In line 3, “…at least 1% of mass percent of the CO2...” should read “…at least 1% by mass of the CO2...”
Claim 42 is objected to because of the following informalities:
In lines 1-2, “…of capture solvent…” should read “…of the amine solvent…”
Appropriate correction is required.
Claim Interpretation
The term “amine sorbent” as recited in instant claims 1, 7, 9-10, 19, 24 will be interpreted in a manner consistent with the written description (Specification; page 6, lines 22-23) as a solvent containing an amine that is capable of retaining and releasing CO2.
The term “reducible metal oxide support” as recited in instant claims 1, 19, and 22 will be interpreted in a manner consistent with the written description (Specification; page 7, lines 30-31 and page 8, lines 1-7) as solid state materials that are strongly affected by the reversible oxidation state of the metal that include, but are not limited to CeO2, TiO2, VxOy, FexOy, CoxOy, HfO2, MnOx, PrOx, SmOx, MoO3, WO3, In2O3, and more complex solids, such as BaTiO3 and LaCoO3, and any combination thereof.
Claim Rejections - 35 USC § 102
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.
(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.
Claim 41 is rejected under 35 U.S.C. 102(a)(1) as being anticipated by Kothandaraman et al. (US 2021/0214287 A1; hereinafter “Kothandaraman”).
Regarding claim 41, Kothandaraman teaches a Parr reactor composition comprising CO2 captured by an amine solvent, wherein the CO2 activated in this fashion can be utilized to produce CO2-derived products, such as methanol (Kothandaraman; paragraphs [0161]-[0163]; Example 1). Of particular note, Kothandaraman teaches a reaction example wherein the composition comprises the heterogeneous catalyst Cu/ZnO/Al2O3, CO2/H2, and tetramethylethylenediamine (TMEA) amine solvent (20 mmol), wherein the reaction products include methanol (18% yield) produced from the captured CO2 via hydrogenation and ethyl formate (1% yield) (Kothandaraman; paragraph [0163]; Table 1). The yields of methanol and ethyl formate are calculated with respect to the amine (Kothandaraman; Table 1), and therefore these yields correspond to 3.6 mmol of methanol and 0.2 mmol ethyl formate and further correspond to a ratio of methanol produced from CO2 to ethyl formate of 18. Thus, Kothandaraman anticipates every limitation of the instant claim.
Claim Rejections - 35 USC § 103
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
Claims 1-12 and 41-42 are rejected under 35 U.S.C. 103 as being unpatentable over Kothandaraman et al. (US 2021/0214287 A1; hereinafter “Kothandaraman”), in view of Graciani et al. (ACS Catal. 2022, 12, 15097-15109; hereinafter “Graciani”) and further evidenced by Ra et al. (ACS Catal. 2020, 10, 11318-11345; IDS reference, Cite No. 5; hereinafter “Ra”).
Regarding claim 1 and claims 2 and 5 depending from claim 1, Kothandaraman teaches the integrated capture and conversion of CO2 to methane, methanol, or methanol and glycol comprising combining a hydrogenation catalyst, hydrogen, and CO2 with a condensed phase solution comprising an amine under conditions effective to form methane or methanol, and water (Kothandaraman; Title; Abstract; paragraph [0100]).
Kothandaraman further teaches that the amine may comprise a 1° amine group, a 2° amine group, a 3° amine group, or any combination thereof, and the CO2 may be adsorbed, absorbed, covalently, or ionically bound to the amine (Kothandaraman; paragraph [0010]).
In addition, Kothandaraman teaches that the hydrogenation catalyst may comprise known materials to catalyze hydrogenation such as the noble metals Pt, Pd, Rh, Ir, Ru, and Cu, and the catalysts may comprise catalysts supported on reducible metal oxide supports including In2O3, CeO2, TiO2, and ZrO2 (Kothandaraman; paragraph [0012]).
The method of Kothandaraman teaches that the conditions effective to form methanol include a temperature TM within a range of from 50-180 ºC (Kothandaraman; paragraphs [0005] and [0108]). This temperature range resides close to the range recited in the instant claim. MPEP § 2144.05(I) states that “a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close.”
The method of Kothandaraman teaches that the CO2 may be obtained from any suitable source such as landfill gases, wastewater treatment gases, manure gas sources, or other industrial processes (Kothandaraman; paragraph [0052]). The skilled artisan would therefore recognize that the method of Kothandaraman may employ post or pre combustion CO2, in a manner consistent with the instant claim. Furthermore, Kothandaraman teaches that the hydrogenation of CO2 to methanol is performed in the condensed phase amine at a lower temperature than is required for gas phase hydrogenation, and therefore the integrated capture and conversion process is more economically viable than existing technologies (Kothandaraman; paragraph [0052]; Fig. 10).
Kothandaraman further teaches that the conversion of CO2 to methanol is a one-pot, one-step process that may be a batch process or a continuous process, and that CO2 captured by the amine may be the limiting reactant and from 25-100 to 95-100 mol% of the captured CO2 may be consumed (Kothandaraman; paragraphs [0109], [0115], and [0117]). In addition, Kothandaraman teaches reaction examples wherein methanol is obtained in about 76% and 100% yields that correspond to selectivities of about 90% or greater, respectively (Kothandaraman; Table 1; entries 5-6). Thus, the yields (corresponding to conversion of captured CO2) and methanol selectivities of the method of Kothandaraman overlaps with the range of at least 40% methanol selectivity, a methanol selectivity of at least 50 mol%, a single pass conversion of CO2 of at least 75%, a single pass conversion of CO2 in the range of 75 to about 90%, and a single pass conversion of CO2 of 80-90%, as recited in instant claims 1-2 and 5, respectively. MPEP § 2144.05(I) states that “[i]n the case where the claimed ranges ‘overlap or lie inside ranges disclosed by the prior art’ a prima facie case of obviousness exists.”
Kothandaraman fails to explicitly teach (1) a reaction example comprising a noble metal on a reducible metal oxide support; and (2) wherein the C2+ alcohol selectivity, or the ethanol selectivity, is at least 4 mol%, as recited in instant claim 1.
Regarding point (1), although Kothandaraman teaches a genus of catalysts and reducible metal oxide supports that are consistent with the instant claim, as detailed above, Kothandaraman teaches reactions examples using Cu/ZnO/Al2O3 as the hydrogenation catalyst (Kothandaraman; Table 1).
However, Graciani teaches that although the catalyst most frequently used in the industry for methanol synthesis from CO2/CO/H2 is a Cu/ZnO/Al2O3 composite, this system requires complex activation steps, operates at relatively high pressures, suffers from severe deactivation through particle sintering, and is pyrophoric nature (Graciani; page 15097, Col. 1, paragraph 1). Graciani further teaches the conversion of CO2 to methanol and ethanol using Pt/TiO2, Pt/CeO2, and Pt/CeOx/TiO2 catalytic systems (Graciani; Title; page 15100, Figure 2). It is further known that the most widely used industrial Cu/ZnO catalysts have low activities and stabilities without modifiers for CO2 hydrogenation because they are easily deactivated by water under high-pressure reaction conditions, the use of reducible oxides such as CeO2 and TiO2 have been investigated as excellent promotors and supports for methanol synthesis, and CeO2 in particular enhances CO2 adsorption which greatly increases reaction rates, as evidenced by Ra (Ra; page 11325, Col. 2, paragraph 2).
Regarding point (2), Graciani teaches that along with the conversion of CO2 to methanol with Pt/TiO2, Pt/CeO2, and Pt/CeOx/TiO2 catalysts, some ethanol is also produced (Graciani; Title; Abstract; page 15097, Col. 2, paragraph 1; page 15100, Figure 2; page 15106, Col. 2, paragraph 6; page 15107, Col. 1, paragraph 1). Of particular note, Graciani teaches that upon the deposition of Pt on TiO2 and CeO2, there was a significant increase in the catalytic activity for methanol production, and the Pt/CeOx/TiO2 system displays a catalytic activity that is larger (1.6-2.8 times) than that seen under the same conditions for Cu/ZnO catalysts (Graciani; page 15099; Col. 2, paragraph 2).
Although Graciani does not explicitly teach wherein the C2+ alcohol selectivity, or the ethanol selectivity, is at least 4 mol%, as recited in instant claim 1, or wherein the selectivity of ethanol is 4 to 10 mol%, as recited in instant claim 2, the skilled artisan would recognize that this selectivity range can be achieved using the catalysts of Graciani by means of routine experimentation that is non-inventive in nature. MPEP § 2144.05(II) states that “[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation.
The prior art as taught by Kothandaraman, Graciani, and Ra reside in the closely overlapping technical field of methanol production from CO2 via heterogeneous catalysis, and are therefore deemed analogous art, as described in MPEP § 2141.01(a). In addition, the catalysts of Graciani are also disclosed within the genus of Kothandaraman, as detailed above, and Graciani teaches that Pt deposited on TiO2, CeO2, or CeOx/TiO2 displays a larger catalytic activity than Cu/ZnO catalysts for methanol production. Thus, the skilled artisan would be sufficiently motivated to substitute the Cu/ZnO/Al2O3 catalyst of the reaction example of Kothandaraman with the Pt/TiO2, Pt/CeO2, and/or Pt/CeOx/TiO2 catalysts of Graciani to realize a catalytic system that does not suffer from severe deactivation and utilizes reducible supports with known utility for methanol synthesis and greatly increase reaction rates, as evidenced by Ra, with a reasonable expectation of success. Such an endeavor would result in the simple substitution of one known element for another to obtain predictable results, as described in MPEP § 2143(I)(B). Finally, the skilled artisan would recognize that the catalysts of Graciani also produce a small amount of ethanol, in a manner consistent with the instant claim.
Therefore, it would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have substituted the catalyst of Kothandaraman with the catalyst of Graciani as evidenced by Ra to arrive at the claimed method. The motivation to do so would permit the skilled artisan to pursue, with a reasonable expectation of success, a method that uses a catalytic system that does not suffer from severe deactivation and utilizes reducible supports with known utility for methanol synthesis and greatly increased reaction rates, as described above.
Regarding claims 3-4 depending from claim 1, Kothandaraman teaches that the apparatus shown in Figures. 3A and 3B may be suitable for a continuous process. In a continuous process, the hydrogenation catalyst may be disposed in a fixed bed in the hydrogenation reactor 320, and both H2 and the condensed phase solution comprising the amine and CO2 flow through or across the fixed bed (Kothandaraman; paragraph [0117]; Figs. 3A and 3B). Thus, the skilled artisan would recognize that the method of Kothandaraman can be performed in a continuous flow operation for the conversion of CO2 occurring in a single pass and therefore, as with claim 1, it would have been prima facie obvious to arrive at the claimed method based on the teachings of Kothandaraman in view of Graciani and further evidenced by Ra. Furthermore, the claimed continuous process would have been obvious in view of the batch process of Kothandaraman (Kothandaraman; paragraph [0117]), as described in MPEP § 2144.04(V)(E).
Regarding claim 6 depending from claim 1, Kothandaraman teaches that the hydrogenation catalysts may comprise catalysts supported on materials such as carbon, Al2O3, In2O3, CeO2 and TiO2, SiO2, ZrO2, magnesium aluminum spinels (e.g., MgO—Al2O3), chromite (e.g., FeCr2O4), or any combination thereof (Kothandaraman; paragraph [0012]). Furthermore, Graciani teaches the use of Pt/TiO2, Pt/CeO2, and/or Pt/CeOx/TiO2 catalysts with improved catalyst characteristics and adjustable ethanol selectivities, as detailed above (Graciani; page 15097, Col. 2, paragraph 1; page 15100, Figure 2).
Regarding claims 7 and 9 depending from claim 1, Kothandaraman teaches that in some embodiments, the carbon dioxide binding organic liquid (CO2BOL) is N-(2-ethoxyethyl)-3-morpholinopropan-1-amine (EEMPA) (Kothandaraman; paragraphs [0083] and [0147]). Kothandaraman further teaches that EEMPA is a single component, water-lean post-combustion CO2 capture solvent (Kothandaraman; paragraphs [0083], [0147], and [0195]).
Regarding claim 8 depending from claim 1, Kothandaraman teaches that the CO2 may be obtained from any suitable source, including landfill gases, wastewater treatment gases, manure gas sources, or other industrial processes (Kothandaraman; paragraph [0052]).
Regarding claim 10 depending from claim 1, Kothandaraman teaches that a concentration of CO2 in the condensed phase comprising the amine may be from 1 wt % to 25 wt % CO2 (Kothandaraman; paragraph [0148]). This range significantly overlaps with the range recited in the instant claim. MPEP § 2144.05(I) states that “[i]n the case where the claimed ranges ‘overlap or lie inside ranges disclosed by the prior art’ a prima facie case of obviousness exists.”
Regarding claim 11 depending from claim 1, Kothandaraman teaches that in some embodiments the condensed phase is a solution comprising a solvent and a tertiary amine, and in an exemplary embodiment, CO2 is combined with a condensed phase comprising triethylamine and ethanol (Kothandaraman; paragraphs [0103], [0118], and [0164]; Table 1, entries 2-11).
Regarding claim 12 depending from claim 1, Kothandaraman teaches that Operando NMR analysis of hydrogenation of EEMPA captured CO2 solution showed in-situ formation of EEMPA N-formamide (Kothandaraman; paragraph [0197]; Figs. 27-28). Kothandaraman further teaches a test reaction wherein N-formylpiperidine was hydrogenated to get >80% conversion of formylpiperidine to methane and piperidine without addition of external CO2, which proved that both CO and N-formamide routes are possible in the solution phase (Kothandaraman; paragraph [0197]).
Regarding claim 42 depending from claim 41, the teachings of Kothandaraman from the 102 rejection above are incorporated herein.
Kothandaraman teaches that N-methylation of the amine solvent used for carbon capture occurs from a produced formamide intermediate and represents an undesired byproduct that cannot be further converted to methane or methanol, (Kothandaraman; paragraph [0145]; Fig. 10B). Furthermore, Kothandaraman teaches that subsequent catalyst selection, hydrogen stoichiometry, and temperature influence whether the formamide intermediate is hydrogenated to form an N-methylated product, methane, or methanol (Kothandaraman; paragraph [0145]). Finally, the skilled artisan would recognize the formamide intermediate as a tertiary amide ester (Kothandaraman; paragraph [0145]; Fig. 10B).
Kothandaraman fails to explicitly teach in which the catalyst suppresses N-methylation of capture solvent, as recited in instant claim 42. However, Kothandaraman in view of Graciani and Ra teaches the beneficial use of Pt/TiO2, Pt/CeO2, and/or Pt/CeOx/TiO2 catalysts of Graciani to pursue a catalytic system that does not suffer from severe deactivation and utilizes reducible supports with known utility for methanol synthesis and greatly increase reaction rates, as evidenced by Ra, with a reasonable expectation of success. These catalysts are commensurate in scope with the instantly claimed catalysts of the present application, wherein Pt catalysts on reducible metal oxides (such as TiO2 or CeO2) were found to suppress undesirable N-methylation of the capture solvent (Specification; page 3, lines 8-10). Thus, the catalysts of Kothandaraman in view of Graciani and Ra would intrinsically possess this same property. Therefore, as with claim 1, it would have been prima facie obvious to combine Kothandaraman, Graciani, and Ra to arrive at the claimed invention.
Claims 19-24 are rejected under 35 U.S.C. 103 as being unpatentable over Kothandaraman et al. (US 2021/0214287 A1; hereinafter “Kothandaraman”), in view of Graciani et al. (ACS Catal. 2022, 12, 15097-15109; hereinafter “Graciani”) and further evidenced by Ra et al. (ACS Catal. 2020, 10, 11318-11345; IDS reference, Cite No. 5; hereinafter “Ra”) as applied to claims 1-12 and 41-42 above, and further evidenced by Jiang et al. (Int. J. Greenh. Gas Control, 2021, 106, 103279, pages 1-12; IDS reference, Cite No. 35; hereinafter “Jiang”).
Regarding claim 19, claim 22 depending from claim 19, and claim 23 depending from claim 22, Kothandaraman teaches the integrated capture and conversion of CO2 to methane, methanol, or methanol and glycol comprising combining a hydrogenation catalyst, hydrogen, and CO2 with a condensed phase solution comprising an amine under conditions effective to form methane or methanol, and water (Kothandaraman; Title; Abstract; paragraph [0100]).
In one embodiment, Kothandaraman teaches an exemplary apparatus 300 for performing the method of FIG. 2 to convert CO2 into methanol that may be performed as a continuous process (Kothandaraman; paragraphs [0014] and [0116]-[0118], Figs. 3A and 3B). The apparatus comprises a condensed phase with amine and a gas flow comprising CO2 flowed into a CO2 absorber 310, and the condensed phase comprising the amine and the CO2 are subjected to a temperature, pressure, and time sufficient for the amine to capture the CO2 to form a condensed phase solution comprising the amine and CO2 (Kothandaraman; paragraph [0116] and Fig. 3A). Kothandaraman further teaches that conventionally, CO2 in the flue gas is captured in the absorber (Kothandaraman; paragraph [0049]). Next, the condensed phase solution flows into a hydrogenation reactor 320 and subjected to an effective temperature TM and pressure PM (Kothandaraman; paragraph [0116] and Figs. 3A and 3B). The condensed phased solution is flowed through a hydrogenation reactor over a Cu/ZnO/Al2O3 hydrogenation catalyst, and conditions effective to form methanol include a temperature TM of 50-180 ºC and a pressure PM of 1 MPa to 10 MPa comprising a molar ratio of added H2 to CO2 from 2:1 to 10:1 (Kothandaraman; paragraphs [0005], [0114], and [0116]-[0118]). This reaction temperature range resides close to the range recited in the instant claim. MPEP § 2144.05(I) states that “a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close.” Furthermore, a reaction pressure of 1 MPa to 10 MPa and a molar ratio of H2 to CO2 from 2:1 to 10:1 corresponds to a range of hydrogen pressure of about 7 to 91 bar, and this reaction pressure range overlaps with the range recited in the instant claim. MPEP § 2144.05(I) states that “[i]n the case where the claimed ranges ‘overlap or lie inside ranges disclosed by the prior art’ a prima facie case of obviousness exists.”
Although the reactor system of Kothandaraman does not explicitly teach the use of pumps, the skilled artisan would recognize that a continuous flow reactor system necessarily involves pumps and the requirement for pumping, as evidenced by Jiang, who teaches various process configurations for post-combustion carbon capture using a water-lean solvent and CO2 obtained from flue gas, in a manner consistent with the instant claim (page 4, Figure 4 and page 8, Table 3).
Although Kothandaraman teaches that the hydrogenation catalyst may comprise known materials to catalyze hydrogenation such as the noble metals Pt, Pd, Rh, Ir, Ru, and Cu, and the catalysts may comprise catalysts supported on reducible metal oxide supports including In2O3, CeO2, TiO2, and ZrO2 (Kothandaraman; paragraph [0012]), Kothandaraman fails to explicitly teach (1) a noble metal on a reducible metal oxide support; (2) wherein the solid catalyst comprises Pt disposed on a reducible metal oxide support; and (3) wherein the catalyst support comprises CeO2 and/or TiO2, as recited in instant claims 19 and 22-23. Instead, Kothandaraman teaches reaction examples using Cu/ZnO/Al2O3 as the hydrogenation catalyst for the process detailed above (Kothandaraman; paragraphs [0005] and [0118]; Example 4).
However, this deficiency is sufficiently addressed by Kothandaraman in view of Graciani and Ra as detailed above in the rejection of claim 1, wherein the skilled artisan would be sufficiently motivated to substitute the Cu/ZnO/Al2O3 catalyst of the reaction example of Kothandaraman with the Pt/TiO2, Pt/CeO2, and/or Pt/CeOx/TiO2 catalysts of Graciani to realize a catalytic system that does not suffer from severe deactivation and utilizes reducible supports with known utility for methanol synthesis and greatly increase reaction rates, as evidenced by Ra, with a reasonable expectation of success. MPEP § 2143(I)(B).
Finally, although the methanol production method of Kothandaraman teaches that trace CH4 was detected by gas chromatographic analysis (Kothandaraman; Example 1; paragraph [0164]), Kothandaraman fails to explicitly teach that the CO2 in solution is converted to C2+ alcohols and light hydrocarbons over the solids catalyst, as recited in instant claim 19. However, this deficiency is adequately addressed by Kothandaraman in view of Graciani and Ra as detailed above, wherein the catalysts of Graciani are known to also produce ethanol (Graciani; Title; Abstract; page 15097, Col. 2, paragraph 1; page 15100, Figure 2; page 15106, Col. 2, paragraph 6; page 15107, Col. 1, paragraph 1). Furthermore, the catalytic conversion of CO2 is known to also produce low-molecular weight (C1-C4) hydrocarbons and light olefins, as evidenced by Ra (Ra; Abstract; page 11319; Col. 1, paragraph 2 and Col. 2, paragraph 1; page 11320, Figs. 3-4).
Therefore, it would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have substituted the catalyst of Kothandaraman with the catalyst of Graciani as evidenced by Jiang and Ra to arrive at the claimed method. The motivation to do so would permit the skilled artisan to pursue, with a reasonable expectation of success, a method that uses a catalytic system that does not suffer from severe deactivation and utilizes reducible supports with known utility for methanol synthesis and greatly increased reaction rates, as described above.
Regarding claim 20 depending from claim 19, Kothandaraman teaches reaction examples wherein methanol is obtained in about 76% and 100% yields (Kothandaraman; Table 1; entries 5-6). Thus, the yields (corresponding to conversion of captured CO2) of the method of Kothandaraman overlaps with the range of a single pass conversion of CO2 of 80-90%, as recited in the instant claim. MPEP § 2144.05(I) states that “[i]n the case where the claimed ranges ‘overlap or lie inside ranges disclosed by the prior art’ a prima facie case of obviousness exists.”
Regarding claim 21 depending from claim 20, Kothandaraman teaches that the hydrogenation of CO2 occurs in a condensed phase solution (Kothandaraman; Title; Abstract; paragraph [0100]).
Regarding claim 24 depending from claim 20, Kothandaraman teaches that in some embodiments, the carbon dioxide binding organic liquid (CO2BOL) is N-(2-ethoxyethyl)-3-morpholinopropan-1-amine (EEMPA) (Kothandaraman; paragraphs [0083] and [0147]). Kothandaraman further teaches that EEMPA is a single component, water-lean post-combustion CO2 capture solvent (Kothandaraman; paragraphs [0083], [0147], and [0195]).
Claims 19-21 and 24 are rejected under 35 U.S.C. 103 as being unpatentable over Kothandaraman et al. (US 2021/0214287 A1; hereinafter “Kothandaraman”) as evidenced by Jiang et al. (Int. J. Greenh. Gas Control, 2021, 106, 103279, pages 1-12; IDS reference, Cite No. 35; hereinafter “Jiang”), in view of Ra et al. (ACS Catal. 2020, 10, 11318-11345; IDS reference, Cite No. 5; hereinafter “Ra”).
Regarding claim 19, Kothandaraman teaches the integrated capture and conversion of CO2 to methane, methanol, or methanol and glycol comprising combining a hydrogenation catalyst, hydrogen, and CO2 with a condensed phase solution comprising an amine under conditions effective to form methane or methanol, and water (Kothandaraman; Title; Abstract; paragraph [0100]).
In one embodiment, Kothandaraman teaches an exemplary apparatus 300 to convert CO2 into methane, methanol, ethane, ethanol and higher hydrocarbons that can be performed as a continuous process, (Kothandaraman; paragraphs [0155], [0158] and [0198]-[0199], Fig. 13A). The apparatus comprises a condensed phase with amine and a gas flow comprising CO2 flowed into a CO2 absorber 1310, and the condensed phase comprising the amine and the CO2 are subjected to a temperature, pressure, and time sufficient for the amine to capture the CO2 to form a condensed phase solution comprising the amine and CO2 (Kothandaraman; paragraph [0154] and Fig. 13A). Kothandaraman further teaches that conventionally, CO2 in the flue gas is captured in the absorber (Kothandaraman; paragraph [0049]). Next, the condensed phase solution flows into a hydrogenation reactor 1320 (Kothandaraman; paragraphs [0154]-[0155]; Figs. 13A and 13B). The condensed phased solution is flowed through a hydrogenation reactor over a Ru/Al2O3 hydrogenation catalyst and heated to a temperature of 120 ºC to 190 ºC, with a pressure of 1 MPa to 6 MPa and a molar ratio of H2 to CO2 from 4:1 to 10:1 (Kothandaraman; claims 1 and 20). This reaction temperature range overlaps with the range recited in the instant claim. Furthermore, a reaction pressure of 1 MPa to 6 MPa and a molar ratio of H2 to CO2 from 4:1 to 10:1 corresponds to a range of hydrogen pressure of about 8 to 54.5 bar, and this reaction pressure range overlaps with the range recited in the instant claim. MPEP § 2144.05(I) states that “[i]n the case where the claimed ranges ‘overlap or lie inside ranges disclosed by the prior art’ a prima facie case of obviousness exists.”
Although the reactor system of Kothandaraman does not explicitly teach the use of pumps, the skilled artisan would recognize that a continuous flow reactor system necessarily involves pumps and the requirement for pumping, as evidenced by Jiang, who teaches various process configurations for post-combustion carbon capture using a water-lean solvent and CO2 obtained from flue gas, in a manner consistent with the instant claim (page 4, Figure 4 and page 8, Table 3).
Although Kothandaraman teaches that the hydrogenation catalyst may comprise known materials to catalyze hydrogenation such as the noble metals Pt, Pd, Rh, Ir, Ru, and Cu, and the catalysts may comprise catalysts supported on reducible metal oxide supports including In2O3, CeO2, TiO2, and ZrO2 (Kothandaraman; paragraph [0012]), Kothandaraman fails to explicitly teach a noble metal on a reducible metal oxide support. Instead, Kothandaraman teaches reaction examples using Ru/Al2O3 and Ru/C as the hydrogenation catalyst for the process detailed above (Kothandaraman; claim 20; paragraphs [0149] and [0156]).
However, Ra teaches recent key developments and perspectives of catalytic hydrogenation (Ra; Title; Abstract). Of particular note, Ra teaches enhanced CO2 methanation rates via a pronounced support effect, wherein Ru/CeO2 enables greatly increased reaction rates and excellent CO2 conversion at significantly lower reaction temperatures compared to Ru/Al2O3 (Ra; page 11328; page 1, Col. 1, paragraph 2; Figure 9B):
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The prior art as taught by Kothandaraman and Ra reside in the closely overlapping technical field of methods for converting CO2 via heterogeneous catalysis. In addition, the prior art as taught by Kothandaraman and Jiang reside in the overlapping technical field of process configurations for post-combustion carbon capture using a single-component water-lean solvent. The prior art is therefore deemed analogous art, as described in MPEP § 2141.01(a). Furthermore, the Ru/CeO2 catalyst of Ra is also disclosed within the genus of Kothandaraman, as detailed above. Thus, the skilled artisan would be sufficiently motivated to substitute the Ru/Al2O3 catalyst of the reaction process of Kothandaraman detailed above with the Ru/CeO2 catalyst of Ra to pursue a catalytic system with increased reaction rates and enhanced CO2 conversions at lower temperature with a reasonable expectation of success. Such an endeavor would result in the simple substitution of one known element for another to obtain predictable results, as described in MPEP § 2143(I)(B).
Therefore, it would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have substituted the catalyst of Kothandaraman with the catalyst of Ra to arrive at the claimed method based on the method of Kothandaraman in view of the supportive teachings of Jiang. The motivation to do so would permit the skilled artisan to pursue, with a reasonable expectation of success, a method that uses a catalytic system with increased reaction rates and enhanced CO2 conversions at lower temperature, as described above.
Regarding claim 20 depending from claim 19, Kothandaraman teaches a continuous reaction system (fixed bed) example with a CO2 conversion of 52.1% (Kothandaraman; Table 8). Of particular note, Kothandaraman teaches that CO2 conversion can be increased at lower WHSV (higher contact time), and longer reaction times resulted in >90% conversion of CO2 (Kothandaraman; paragraphs [0196] and [0199]). Thus, the skilled artisan could reasonably arrive at a single pass CO2 conversion of 80-90% by adjusting the contact time and/or reaction time through means of routine experimentation that is non-inventive in nature. MPEP § 2144.05(II) states that “[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation.
Regarding claim 21 depending from claim 20, Kothandaraman teaches that the hydrogenation of CO2 occurs in a condensed phase solution (Kothandaraman; Title; Abstract; paragraph [0100]).
Regarding claim 24 depending from claim 20, Kothandaraman teaches that in some embodiments, the carbon dioxide binding organic liquid (CO2BOL) is N-(2-ethoxyethyl)-3-morpholinopropan-1-amine (EEMPA) (Kothandaraman; paragraphs [0083] and [0147]). Kothandaraman further teaches that EEMPA is a single component, water-lean post-combustion CO2 capture solvent (Kothandaraman; paragraphs [0083], [0147], and [0195]).
Claims 22-23 are rejected under 35 U.S.C. 103 as being unpatentable over Kothandaraman et al. (US 2021/0214287 A1; hereinafter “Kothandaraman”) as evidenced by Jiang et al. (Int. J. Greenh. Gas Control, 2021, 106, 103279, pages 1-12; IDS reference, Cite No. 35; hereinafter “Jiang”), in view of Ra et al. (ACS Catal. 2020, 10, 11318-11345; IDS reference, Cite No. 5; hereinafter “Ra”) as applied to claims 19-21 and 24 above, and further in view of Graciani et al. (ACS Catal. 2022, 12, 15097-15109; hereinafter “Graciani”).
Regarding claim 22 depending from claim 19 and claim 23 depending from claim 22, claim 19 is rendered obvious over Kothandaraman, Jiang, and Ra, as detailed above.
Although the genus of catalysts and supports taught by Kothandaraman include Pt as a solid catalyst and CeO2 and/or TiO2 as reducible metal oxide supports (Kothandaraman; paragraph [0012]), in a manner consistent with instant claims 22-23, Kothandaraman fails to explicitly teach use of Pt on a support comprising CeO2 and/or TiO2. Instead, Kothandaraman teaches reaction examples using Ru/Al2O3 and Ru/C as the hydrogenation catalyst for the process detailed above (Kothandaraman; claim 20; paragraphs [0149] and [0156]).
However, Graciani teaches that alcohols such as methanol and ethanol have proven to be promising alternative fuels due to their high energy density and compatibility with the current distribution systems, and therefore the use of stable and active catalysts that are also capable of producing higher alcohols and oxygenates, such as ethanol directly from CO2/H2 feeds, is crucial (Graciani; page 15097; paragraph 1; Col. 1). Graciani further teaches that Pt/TiO2 and Pt/CeO2 can generate methanol and ethanol from a CO2/H2 feed based on the addition of water, and Pt/CeOx/TiO2 as a catalyst can generate a significant yield (10-20%) of the C2 alcohol in the absence of water, and this selectivity can be increased with the addition of water (Graciani; page 15097, Col. 2, paragraph 1; page 15100, Figure 2).
The prior art as taught by Kothandaraman, Ra, and Graciani reside in the closely overlapping technical field of methods for converting CO2 via heterogeneous catalysis, and are therefore deemed analogous art, as described in MPEP § 2141.01(a). In addition, the catalysts of Graciani are also disclosed within the genus of Kothandaraman, as detailed above. Thus, the skilled artisan would be sufficiently motivated to substitute the Ru/CeO2 catalyst of the reaction process of Kothandaraman, Jiang, and Ra as detailed above with the Pt/TiO2, Pt/CeO2, and/or Pt/CeOx/TiO2 catalysts of Graciani to realize a catalytic system with an improved selectivity profile for methanol and ethanol for use as promising alternative fuels with a reasonable expectation of success. Such an endeavor would result in the simple substitution of one known element for another to obtain predictable results, as described in MPEP § 2143(I)(B).
Therefore, it would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have substituted the catalyst of Kothandaraman, Jiang, and Ra with the catalyst of Graciani arrive at the claimed method. The motivation to do so would permit the skilled artisan to pursue, with a reasonable expectation of success, a method that uses a catalytic system with known utility for methanol and ethanol synthesis for use as an alternative fuel source, as described above.
Based on the combined teachings of the references, the Examiner submits that a person of ordinary skill in the art would have had a reasonable expectation of success of arriving at the instantly claimed method and composition. Therefore, the invention as a whole would have been prima facie obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, and absent a clear showing of evidence to the contrary.
Conclusion
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/D.R./Examiner, Art Unit 1692
/AMY C BONAPARTE/Primary Examiner, Art Unit 1692