DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claim Rejections - 35 USC § 103
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.
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 text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claims 1-3 and 5-6 are rejected under 35 U.S.C. 103 as being unpatentable over Hoffmann et al. (US Patent No. 3,953,367) in view of Bansode et al. (Catal. Sci. Technol. 2013, 3, pp. 767-778) and Gao et al. (Catal. Sci. Technol. 2015, 5, pp. 4365-4377).
With regard to claim 1, Hoffmann et al. teaches a Raney copper (i.e. skeletal copper) catalyst comprising up to 100 wt% copper, and optionally 2-45 wt% aluminum (Col. 2, lines 54-64). Hoffmann et al. teaches that such Raney copper catalysts can be used in a variety of chemical reactions and are most suitable for reactions conducted under continuous conditions or for extended times (Col. 2, line 65 – Col. 3, line 14). Hoffmann et al. does not teach the doping of Raney copper with barium, potassium, and yttrium oxides wherein copper accounts for 70-90 wt% of the composition (as per line 3) and the oxides are present such that there is a ratio of 1:0.02-0.08:0.01-0.04 Ba:K:Y elements (as per lines 3-4).
However, Bansode et al. discusses the reaction promotion effect of potassium and barium species in alumina-supported copper catalysts for CO2 hydrogenation (pp. 767, Abstract). Said catalyst, after pretreatment, comprises metallic copper as the active catalyst and either potassium or barium oxide as promoters (pp. 770, left col., lines 13-18 & pp. 771, right col., lines 5-10). Both potassium and barium were noted to form oxides as the active species (reading to the instantly claimed oxides, pp. 771, left col., lines 29-32). With respect to the copper chemistry, Bansode et al. teaches that potassium and barium are known promoters in CO2 hydrogenation (pp. 768, left col., lines 42-50). Bansode et al. posit that potassium species coat the metallic copper surface area to strongly modify surface acidity and generate unique reaction intermediates at the K-Cu interface (pp. 775, right col., lines 3-18) and barium species improve reduction of bulk copper species and can prevent copper particle agglomeration (pp. 771, left col., lines 8-16 & pp. 775, right col., lines 29-35). Both promote CO2 hydrogenation over metallic copper by acting as CO2-capturing components, providing additional active sites for reaction due to the oxides’ affinity for CO2 adsorption (pp. 771, right col., lines 21-28). As Bansode et al. describes barium and potassium promoters to achieve different effects on the copper-based catalysts, and specifically are related to the efficacy of the active metallic copper, not the support, a person of ordinary skill in the art would have found it obvious to apply barium oxide and potassium oxide as dopants/reaction promoters in the Raney copper catalyst taught by Hoffmann et al.
Furthermore, Gao et al. teaches that yttrium oxide doping of a supported copper catalyst, comprising metallic copper as the active catalyst, has a measured effect on the catalytic activity of the active copper species (pp. 4365, Abstract). Within the composition, yttrium oxide specifically promotes the relevant copper chemistry by increasing the active copper specific surface area (pp. 4365, left col., lines 18-27) by increasing the reduction of inactive Cu2+ to the active metallic form Cu0 (pp. 4372, right col., line 13-pp.4373, left col., line 17) which in turn improved catalytic activity of methanol synthesis via the increase in available active sites (pp. 4374, right col., lines 22-44). The amount of yttrium oxide included in relation to the catalyst composition was found to have a drastic effect on catalytic activity, as its inclusion increased catalytic activity while excessive amounts decreased catalytic activity by lowering active copper surface area (pp. 4376, left col., lines 10-19). A person of ordinary skill in the art would readily recognize the positive effect of yttrium oxide on the active copper species and be motivated to include yttrium oxide as a dopant in the composition described by Hoffmann et al. to increase active copper surface area for improved catalytic activity in a catalyst where the primary material in elemental copper. As Bansode et al. and Gao et al. teach that barium oxide, potassium oxide, and yttrium oxide promote CO2 hydrogenation through different mechanisms, a person of ordinary skill could readily envision combining the oxides as dopants to improve a Raney copper catalyst, as taught by Hoffmann et al., through a multifaceted approach.
With regard to the instantly claimed weight ratio of copper skeleton (as per line 3), Gao et al. explicitly provides evidence that there is an optimal range of yttrium oxide to be added to a catalyst composition before mass transport issues outweigh additional catalytic activity (approximately Y3+ : Cu2+ <0.05 in mols, see Abstract). In a catalyst composition comprising only skeletal copper (as taught by Hoffmann et al.) and the oxide dopants, the suggested molar ratio converted to mass is 0<x<8.15 wt% yttrium oxide. Bansode et al. teaches that potassium and barium species when added account for 5 wt% of the composition (pp. 768, Experimental) and that each dopant promotes different reaction products (pp. 775, left col., line 23- right col., line 2). A person of ordinary skill in the art would be motivated to optimize the combined amount of barium oxide, potassium oxide, and yttrium oxide because the promoters enhance specific product selectivity, enhance catalytic efficiency through different chemical mechanisms, and in excess can decrease catalytic efficiency by decreasing the available copper surface area. Based on the amount of each oxide suggested in the prior art and conventional knowledge, a person of ordinary skill in the art would have found it obvious to create a modified composition based on Hoffmann et al., Bansode et al. and Gao et al. comprising 70-90 wt% skeletal copper through routine experimentation and optimization of dopant composition.
With regard to the instantly claimed ratio of barium, potassium, and yttrium (as per lines 3-4), as stated above barium oxide and yttrium oxide promote methanol generation, while potassium oxide promotes carbon monoxide formation. A person of ordinary skill in the art, when adding barium oxide and potassium oxide for their general improvements to copper’s catalytic efficiency and stability, would select one to be in significant excess over the other, to achieve high selectivity of a single product instead of promoting equally two competing reactions. It would have been obvious to a person of ordinary skill in the art to use predominantly barium oxide and yttrium oxide as reaction promoters for methanol selectivity (see Bansode et al. pp. 773, Fig. 8 and Gao et al. pp. 4773-434, Section 3.3) and potassium oxide as a small additive to enhance copper reduction and surface properties (Bansode et al. pp. 775, right col., lines 3-18). Therefore, it would have been obvious to one having ordinary skill in the art at the time the invention was made to choose the instantly claimed ratio of elemental Ba:K:Y within the composition through routine experimentation and optimization, since it has been held that there the general conditions of a claim are disclosed in the prior art, discovering the optimum or workable ranges involves only routine skill in the art. See In re Boesch, 205 USPQ 215.
With regard to claims 2-3 and 5-6, the process limitations are noted. However, when the examiner has found the same or substantially similar product as in the applied prior art, the burden of proof is shifted to applicant to establish that their product is patentably distinct and not the examiner to show the same process of making. In re Brown, 173 USPQ 685 and In re Fessmann, 180 USPQ 324.
With regard to claim 4, Hoffmann et al. teaches that the Raney copper catalyst particles may be 0.001-0.5 inches, i.e. 25.4-12700 µm, in diameter which encompasses the instantly claimed range of 200-1000 µm (Col. 2, lines 61-64). Hoffmann et al. teaches that the particle size of the Raney copper can be altered based on the intended application for the catalyst, suggesting smaller particles (~50.8-2540 µm) for free-particle catalysts and larger particles (~508-12700 µm) for a fixed-bed reactor (Col. 6, line 61-Col. 7, line 3). Therefore, the prior art provides a suggestion that particle size as a variable affects the applicability of the produced catalyst. With respect to the encompassing and overlapping ranges previously discussed, the subject matter as a whole would have been obvious to one of ordinary skill in the art at the time of invention to select the portion of the prior art’s range which is within the range of the applicants’ claims because it has been held prima facie case of obviousness to select a value in a known range by optimization for the results. In re Aller, 105 USPQ 233. Additionally, the subject matter as a whole would have been obvious to one of ordinary skill in the art at the time invention was made to have selected the overlapping portion of the range disclosed by the reference because overlapping ranges have been held to be a prima facie case of obviousness. In re Malagari, 182 USPQ.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure:
Wainwright et al., Catalysis Today 1995, 23, pp. 29-42; which discusses the application of Raney copper catalysts for CO2 hydrogenation to methanol.
Yang et al., Catalysis Communications 2011, 12, pp. 1389-1395; which discusses copper-catalyzed steam reformation of methanol promoted by yttrium oxide.
Terzan et al., ACS Catal. 2020, 10(22), pp. 13415-13436; which discusses potassium-doped copper catalysts and barium-doped silver catalysts for propylene epoxidation.
Chinese Patent Publication No. CN115210214A; which discusses a catalyst composition comprising a Group IIB or VIB metal in elemental form and 1-3 additional metals in elemental or oxide form used for catalysis of amine alkylation.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to MORDECAI M LEAVITT whose telephone number is (571)272-6637. The examiner can normally be reached Monday-Friday 8AM-5PM.
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/MORDECAI M LEAVITT/Examiner, Art Unit 1742
/MONICA A HUSON/Primary Examiner, Art Unit 1742
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