DETAILED ACTION
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claims 1-20 are pending in the instant application.
Priority
This application was filed on May 2nd, 2023.
Information Disclosure Statements
Applicants’ Information Disclosure Statement, filed on 05/02/2023, has been considered. Please refer to Applicant’s copy of the PTO-1449 submitted herewith.
Response to Restriction Requirement
Applicant’s election with traverse of elected species disclosed in claim 15 in the reply filed by Applicant’s representative Dr. Derek A. Lighter on 12/29/2025 is acknowledged. Applicant traverses the Restriction Requirement on the ground that the office action does not show a search burden and a search has not been conducted. Applicant’s traverse has been fully considered, but not persuasive. This application contains claims directed to the following patentably distinct species of methods for chemically reducing carbon dioxide (CO2) with a red mud catalyst composition wherein in the red mud catalyst composition contains different elements of Al, Fe, Mg, Na, P, Ti, V, Ca, Si, and K cited in claims 15 and 16. Each red mud catalyst composition is patentably distinct species and distinct method of using said catalyst composition for chemically reducing CO2. The species are independent or distinct because claims to the different species recite the mutually exclusive characteristics of such species. In addition, these species are not obvious variants of each other based on the current record. In this case, the species of the preparation methods are drawn to distinct methods for chemically reducing carbon dioxide (CO2) with different catalyst of the red mud. These species of methods require a different field of search (e.g., searching different CPC classes/subclasses or electronic resources, or employing different search queries); and/or the prior art applicable to one species would not likely be applicable to another species; and/or the species are likely to raise different non-prior art issues under 35 U.S.C. 101 and/or 35 U.S.C. 112, first paragraph. Therefore, it would be burdensome for the Office to search and examine all the species. Therefore, the restriction requirement is indeed appropriate, maintained, and made FINAL.
Status of the Claims
Claim 16 is withdrawn from further consideration by Examiner as being drawn to non-elected inventions under 37 CFR 1.142(b) responding to the restriction requirement. Claims 1-15 and 17-20 (in part) are under examination on the merits.
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 for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 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 1, 4-8, and 12-14 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Russkikh et al., ChemSusChem, (2020), v.13, p.2981-2987, evidenced by US11,426,708 (“the `708 patent”) and Hidayat et al., Material Science Forum, (2021), v.1029, p.147-152.
Applicant’s claim 1 is drawn to a method for chemically reducing carbon dioxide (CO2) with a red mud catalyst composition, comprising: introducing a gaseous mixture of CO2 and H2 into a reactor containing red mud catalyst particles of the red mud catalyst composition, wherein the red mud catalyst composition comprises at least 70 wt.% of the red mud catalyst particles based on a total weight of the red mud catalyst composition; reacting at least a portion of the CO2 and H2 in the gaseous mixture in the presence of the red mud catalyst composition at a temperature of 200 to 800 °C, and under a pressure ranging from 5 to 100 bar to form a gaseous product comprising a chemical reduction product of the CO2; wherein a volume ratio of the CO2 to the H2 in the gaseous mixture is in a range of 1:10 to 10:1; and wherein the gaseous product comprises 20 to 50 wt.% methane, 1 to 20 wt.% ethane, 0.5 to 10 wt.% propane, 0.01 to 1 wt.% methanol, 1 to 70 wt.% dimethyl ether (DME), and 1 to 50 wt.% carbon monoxide, each wt. % based on a total weight of the gaseous product.
Russkikh et al. discloses a method for hydrogenation reducing of carbon dioxide (CO2) with a red mud catalyst composition, or a K-promoted red mud catalyst composition. The unpromoted red mud catalyst composition is active in the hydrogenation of CO2 at all temperatures studied (Figures 3a-c), especially at relatively high temperatures: under the studied reaction conditions (30 bar, 9600 mLg-1h-1) raising the reaction temperature from 325 to 375 °C increased the conversion of CO2 from 25% to 42% and the selectivity to C2-C4 olefins from 4% to 15%. The reaction conditions: 350 °C, 30 bar, CO2:H2=1:3, and 9600 mLg-1h-1, see Figure 3 at p.2983.
Russkikh et al. is silent on the following limitations: the gaseous product comprises 0.01 to 1 wt.% methanol, and 1 to 70 wt.% dimethyl ether (DME). However, said limitations of obtained methanol and DME are the inevitable products from the same preparation methods disclosed by both claim 1 and Russkikh et al., wherein the method is drawn to reacting at least a portion of the CO2 and H2 in the gaseous mixture in the presence of the red mud catalyst composition at a temperature of 200 to 800 °C, and under a pressure ranging from 5 to 100 bar to form a gaseous product comprising a chemical reduction product of the CO2; wherein a volume ratio of the CO2 to the H2 in the gaseous mixture is in a range of 1:10 to 10:1. Further evidence of red mud catalyzed hydrogenation of CO2 to methanol was disclosed by the `708 patent (col. 2, lns. 4-9), and converting methanol to DME in the presence of red mud catalyst is also evidenced by Hidayat et al. Therefore, forming the claimed products of methanol and DME is inherited from the process disclosed by Russkikh et al. Accordingly, Russkikh et al. anticipates claims 1, and 4-7.
In terms of claim 8 wherein the red mud catalyst composition is a waste product from an aluminum extraction process, Russkikh et al. (Abstract) teaches red mud has been an unavoidable waste derived from the production of alumina in the Bayer process.
In terms of claim 12, the method of claim 1 wherein the red mud catalyst composition has: a hydrogen temperature-programmed reduction (H2-TPR) of 0.5 to 5 millimoles per gram (mmol/g);a temperature-programmed desorption of ammonia (NH3-TPD) of 0.001 to 0.1 mmol/g; a temperature-programmed desorption of carbon dioxide (C02-TPD) of 0.01 to 0.5 mmol/g, they are the inherited property of the red mud catalyst composition prepared by the method disclosed by Russkikh et al. because a product is inseparable from its property.
In terms of claim 13, wherein the red mud catalyst composition is an alkali modified red mud catalyst composition or an alkaline modified red mud catalyst composition, wherein the alkali modified red mud catalyst composition has an alkali content of from 0.001 to 10 wt. % based on the total weight of the red mud catalyst composition, and wherein the alkaline modified red mud catalyst composition has an alkaline content of from 0.001 to 10 wt. % based on the total weight of the red mud catalyst composition, Russkikh et al. (Table S2, Supplemental Information) teaches Red Mud sample promoted with 2 wt% of K (alkali modified).
In terms of claim 14, the method of claim 1 wherein the gaseous product further comprises ethylene, propylene, a hydrocarbon containing C4-C9, and aromatics, and wherein the C4-C9 hydrocarbon comprises butane, butene, butyne, pentane, pentene, pentyne, hexane, hexene, hexyne, cyclohexane, cyclohexene, heptane, heptene, heptyne, octane, octene, octyne, nonane, nonene, and nonyne, they are the inherited property of the red mud catalyst composition prepared by the method disclosed by Russkikh et al. because a product is inseparable from its property. In addition, Russkikh et al. disclosed the red mud catalyst composition is active in the hydrogenation of CO2 at all temperatures studied (Figures 3a-c), and the products include aromatics, C5+ hydrocarbon, and C2-C4 hydrocarbon. More importantly, Russkikh et al. teaches the hydrogenation of CO2 under the studied reaction conditions: 350 °C, 30 bar, CO2:H2=1:3, and 9600 mLg-1h-1, see Figure 3 at p.2983. Russkikh et al. is silent on the limitations: the C4-C9 hydrocarbon comprises butane, butene, butyne, pentane, pentene, pentyne, hexane, hexene, hexyne, cyclohexane, cyclohexene, heptane, heptene, heptyne, octane, octene, octyne, nonane, nonene, and nonyne. However, said limitations are the inevitable products from the same preparation methods disclosed by both claim 1 and Russkikh et al., wherein the method is reacting at least a portion of the CO2 and H2 in the gaseous mixture in the presence of the red mud catalyst composition at a temperature of 200 to 800 °C, and under a pressure ranging from 5 to 100 bar to form a gaseous product comprising a chemical reduction product of the CO2; wherein a volume ratio of the CO2 to the H2 in the gaseous mixture is in a range of 1:10 to 10:1.
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102 of this title, 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 set forth in Graham v. John Deere Co., 383 U.S. 1, 148 USPQ 459 (1966), that are applied 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 2-3, 9-11, and 17-20 are rejected under 35 U.S.C. 103 as being unpatentable over Russkikh et al. in view of the `708 patent, Ma et al., Adv. Mater. Sci. Eng., (2015), p1-6, Liu et al., Geodrrma, (2011), v.163, p.1-12, and 16-channel reactor of Flowrence® Technology_ Product Catalog_downed 03052026.
Russkikh et al. discloses a method for hydrogenation reducing of carbon dioxide (CO2) with a red mud catalyst composition, or a K-promoted red mud catalyst composition. The unpromoted red mud catalyst composition is active in the hydrogenation of CO2 at all temperatures studied (Figures 3a-c), especially at relatively high temperatures: under the studied reaction conditions (30 bar, 9600 mLg-1h-1) raising the reaction temperature from 325 to 375 °C increased the conversion of CO2 from 25% to 42% and the selectivity to C2-C4 olefins from 4% to 15%. The reaction conditions: 350 °C, 30 bar, CO2:H2=1:3, and 9600 mLg-1h-1, see Figure 3 at p.2983. Russkikh et al. is silent on the limitations: the gaseous product comprises 0.01 to 1 wt.% methanol, and 1 to 70 wt.% dimethyl ether (DME). However, said limitations of obtained methanol and DME are the inevitable products from the same preparation methods disclosed by both claim 1 and Russkikh et al., wherein the method is reacting at least a portion of the CO2 and H2 in the gaseous mixture in the presence of the red mud catalyst composition at a temperature of 200 to 800 °C, and under a pressure ranging from 5 to 100 bar to form a gaseous product comprising a chemical reduction product of the CO2; wherein a volume ratio of the CO2 to the H2 in the gaseous mixture is in a range of 1:10 to 10:1.
In terms of claim 2 wherein the reactor is at least one selected from the group consisting of a fixed-bed reactor, a trickle-bed reactor, a moving bed reactor, a rotating bed reactor, a fluidized bed reactor, and a slurry reactor, the `708 patent (col. 3, lns. 60-61) teaches the catalytic tests using the potassium-promoted red mud catalyst were conducted in a 16-channel Flowrence® Avantium setup. It is well-known that the 16-channel Flowrence® Avantium reactor is a high-throughput, 16-channel, parallel fixed-bed reactor system. It is designed for heterogeneous catalyst testing under real commercial plant conditions.
In terms of claim 3 wherein the reactor is a fixed-bed reactor in the form of a cylindrical reactor comprising: a top portion; a cylindrical body portion; a bottom portion; a housing having an open top and open bottom supportably maintained with the cylindrical body portion; wherein the red mud catalyst composition is supportably retained within the housing permitting fluid flow therethrough; at least one propeller agitator is disposed in the bottom portion of the reactor; wherein the bottom portion is cone shaped or pyramidal; and wherein a plurality of recirculation tubes fluidly connects the bottom portion of the cylindrical reactor with the cylindrical body portion of the cylindrical reactor, the `708 patent (col. 3, lns. 60-61) teaches the catalytic tests using the potassium-promoted red mud catalyst were conducted in a 16-channel Flowrence® Avantium setup. It is well-known that the 16-channel Flowrence® Avantium reactor is a high-throughput, 16-channel, parallel fixed-bed reactor system. It is designed for heterogeneous catalyst testing under real commercial plant conditions. The `708 patent (col. 3, lns. 60-61) using the Flowrence® Avantium fied-bed reactor would have rendered claim 3 obvious.
In terms of claim 9 wherein the red mud catalyst composition comprises 10 to 30 wt.% Al, 2 to 20 wt.% Fe, 0.02 to 1 wt.% Mg, 1 to 20 wt.% Na, 0.02 to 1 wt.% P, 0.2 to 8 wt.% Ti, 0.02 to 1 wt.% V, 1 to 5 wt.% Ca, 2 to 15 wt.% Si, and 0.02 to 1 wt.% K, each wt.% based on a total weight of the red mud catalyst composition by energy dispersive X-ray fluorescence (ED-XRF), Russkikh et al. (Table S1, Supplemental Information) teaches the elemental compositions of red mud particle samples b)-d) are most related to the claimed ranges of each elements, and would have rendered claim 9 obvious.
In terms of claim 10, Russkikh et al. does not teach the red mud catalyst composition comprises particles having a specific surface area in a range of 5 to 120 square meter per gram (m2/g). However, the difference is further taught and/or suggested by Ma et al. Ma et al. discloses the red mud has a specific surface area 8.12 m2/g (see TABLE 2 at p.3).
In terms of claim 11, Russkikh et al. does not teach the red mud catalyst composition comprises particles having a cumulative specific pore volume in a range of 0.01 to 0.1 cubic centimeter per gram (cm3/g). However, the difference is further taught and/or suggested by Ma et al. Ma et al. discloses the red mud has a total pore volume 0.115 cm3/g (see TABLE 2 at p.3).
In terms of claims 17-20, Liu et al. discloses heat treatment of red mud at various temperature from 200 to 1000 °C (see “3.1.2. Heat treatment” at p.4), and the `708 patent (col. 2, lns. 40-46) K-modified red mud was prepared by the incipient wetness impregnation with potassium carbonate (K2CO3) or potassium hydroxide (KOH) solutions. Therefore, claims 17-20 would have been obvious over the disclosure by Russkikh et al. in view of the `708 patent, and Liu et al.
Claim Objection
Claim 15 is objected to as being dependent upon a rejected base claim 1, but would be allowable if rewritten in independent form including all of the limitations of the base claim and any intervening claims.
Conclusions
Claims 1-14 and 17-20 are rejected.
Claim 15 is objected to.
Claim 16 is withdrawn.
Telephone Inquiry
Any inquiry concerning this communication or earlier communications from the examiner should be directed to Yong L. Chu, whose telephone number is (571)272-5759. The examiner can normally be reached on M-F 8:30am-5:00pm.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Amber R. Orlando can be reached on 571-270-3149. The fax phone number for the organization where this application or proceeding is assigned is (571) 273-8300.
/YONG L CHU/Primary Examiner, Art Unit 1731