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
The rejection of claims 1-20 under 35 U.S.C. §112(b) based on the former recitation “the first support comprises at least one of: (i) ... and (ii) ...” is withdrawn because claims 1 and 20 have been amended to separately recite catalyst alternatives (i) and (ii).
However, the previously identified indefiniteness concerning the molar ratios remains with respect to claims 1, 3, 4, and 20. The prior Office Action explained that the numerator and denominator of the ratios are each defined by “at least one” member selected from groups that can contain multiple different metals, without specifying whether the ratio is calculated from an individual selected metal or the combined molar amount of all selected metals
Since a new Final Office Actions follows, Applicants’ arguments will not be addressed.
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 1-20 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.
Claims 1, 3, 4, and 20 are indefinite because it remains unclear whether the recited molar ratios are based on (1) an individual selected metal, (2) the combined molar amount of all selected metals within the recited group, or (3) another calculation basis.
Claim 15 is rejected under 35 U.S.C. §112(d) as failing to further limit the subject matter of the claim from which it depends. Claim 15 depends on claim 12 and recites that “in step (VI), a second portion of the oxidant combusts at least a portion of the coke.” However, claim 12 does not recite or incorporate a step (VI). Step (VI) is introduced in claim 13, from which claim 15 does not depend. Accordingly, it is unclear what step of the process of claim 12 is intended to be further limited by the recitation “in step (VI).”
Claim 15 is further rejected under 35 U.S.C. §112(b) because the recitation “in step (VI)” lacks antecedent basis in claim 15 and the claims from which claim 15 depends, rendering the scope of the claim unclear.
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
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, 10-13 and 15-19 are rejected under 35 U.S.C. §103 as being unpatentable over Washburn et al. (US 2016/0318828 A1) in view of JP 4406541 B2.
Washburn teaches catalytic dehydrogenation of hydrocarbon feeds, including alkanes, by contacting the feed with a dehydrogenation catalyst comprising Pt and/or Cr to form an olefin-containing effluent and molecular hydrogen, and selectively combusting at least a portion of the molecular hydrogen with oxygen supplied by a solid oxygen carrier in the reaction zone to form water (Washburn, ¶¶[0035]–[0038], [0045]–[0052]; claims 9–12). Washburn expressly identifies Pt and Cr as suitable dehydrogenation elements and teaches Cr-containing commercial dehydrogenation catalysts. Washburn further teaches that removal of molecular hydrogen by selective combustion favors increased olefin production.
Washburn does not expressly teach the presently claimed second-catalyst alternative comprising 0.025–50 wt.% Cr based on the support and a support comprising SiO₂, ZrO₂, TiO₂, or a mixture thereof.
JP teaches alkane dehydrogenation using a chromium-containing dehydrogenation catalyst. JP teaches 10–20 wt.% Cr, preferably 12–18 wt.% Cr (¶¶[0025], [0028]), and teaches suitable catalyst supports including silica, zirconia, and titania (¶[0028]). JP's disclosed Cr concentrations fall within the very broad claimed Cr loading when expressed relative to the supporting material. JP specifically applies these chromium catalysts to alkane dehydrogenation.
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have employed the chromium-containing dehydrogenation catalyst taught by JP, including chromium supported on silica, zirconia, or titania, as the dehydrogenation catalyst in the process of Washburn because JP teaches such chromium catalysts and supports as suitable for alkane dehydrogenation, thereby providing a known catalyst for carrying out the same alkane-to-olefin dehydrogenation reaction performed by Washburn. Accordingly, the combination meets the second-catalyst/Cr alternative of claim 1; it is unnecessary for this rejection of claim 1 to establish the alternative Pt catalyst. Regarding claim 10, Washburn teaches chromium oxide dehydrogenation catalyst promoted with an alkali metal (Washburn, ¶[0007]), thereby teaching the claimed addition of an alkali-metal component to the second catalyst.
Regarding claims 11 and 12, Washburn teaches that the dehydrogenation catalyst may further comprise binder, matrix, and/or support materials comprising inorganic oxides, specifically silica and alumina, a Group 13 metal oxide (Washburn, ¶¶[0053]–[0054]).
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have included alumina as an additional support component in the JP chromium catalyst employed in modified Washburn because Washburn expressly teaches alumina as a conventional stable support/binder material for dehydrogenation catalysts. Alumina satisfies the Group 13 limitation of claim 11 and the “oxide” alternative of claim 12.
Regarding claim 13, Washburn expressly teaches that during dehydrogenation the SOC is reduced from a first oxidation state to a second state; alkane feed is thereafter curtailed or stopped, an oxidant-containing feed is introduced to reoxidize/replenish the SOC, oxidant flow is stopped, and dehydrogenation is repeated (Washburn, claims 16–17; ¶¶[0082]–[0086]). Washburn's claim 16 substantially recites this same SOC reduction/reoxidation sequence.
Regarding claim 15, Washburn teaches formation of carbon/coke deposits during alkane dehydrogenation and combustion/removal of the coke during regeneration. Washburn teaches providing oxidant in excess of that required to replenish SOC oxygen-storage capacity so that the excess oxidant increases the rate of coke removal; regeneration replenishes SOC oxidant capacity while removing accumulated coke (Washburn, ¶¶[0084]–[0086]). Thus, under the interpretation stated above, Washburn teaches the additionally recited coke-combustion limitation.
Regarding claim 16, Washburn teaches dehydrogenation and hydrogen combustion at 450-550°C, 0.1-10 bar, and WHSV >0.5 hr⁻¹ (claim 7), which overlap the claimed 300-750°C, 10–1000 kPa absolute, and 0.01–300 hr⁻¹ ranges. The claimed operating ranges therefore encompass operating conditions expressly taught by Washburn.
Regarding claim 17, Washburn teaches that the dehydrogenation component and SOC may be provided as particles in a physical mixture in the reaction zone (¶¶[0077]-[0079]; claim 13), thereby meeting the claimed mixed-particle arrangement.
Regarding claim 18, Washburn teaches both staged and layered composites of the dehydrogenation functionality and the hydrogen-combustion/SOC functionality within the reaction zone (¶[0078]).
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have repeated Washburn's disclosed layers of dehydrogenation catalyst and SOC along the direction of flow to provide alternating layers because Washburn expressly teaches layered placement of the two functionalities in the reaction zone and teaches that their arrangement and distribution is not critical provided that the functionalities are suitably proximate. Such repetition represents a predictable arrangement of Washburn's expressly disclosed catalyst and SOC layers.
Regarding claim 19, Washburn expressly teaches a “staged composite” in which the dehydrogenation component is positioned upstream of the SOC component (¶[0078]) and further teaches fixed-bed reactors having a plurality of beds of active materials whose compositions may be the same or different (¶[0087]). Thus, it would have been obvious to arrange the dehydrogenation catalyst and SOC in staged beds as claimed.
Claims 2-8 and 14 are rejected under 35 U.S.C. §103 as being unpatentable over Washburn et al. in view of JP 4406541 B2, as applied above, and further in view of Kauffman et al. (US 2015/0151283 A1).
The combination of Washburn and JP establishes the underlying process of claim 1.
Claims 2-8 select and further limit the first/Pt catalyst alternative.
Kauffman teaches a Pt-containing catalyst specifically for paraffin dehydrogenation in which the catalyst support contains La, Ce, Ba, Zr, and alumina. Kauffman teaches La₂O₃ and CeO₂ at 1–8 wt.% of support, ZrO₂ at 5–20 wt.% of support, and an eta-alumina support (¶¶[0003]–[0012], [0018]–[0024]). Kauffman's Example 1 specifically contains 81.5 wt.% Al₂O₃, 1.6 wt.% La₂O₃, 3.3 wt.% CeO₂, 1.5 wt.% BaO, and 12.1 wt.% ZrO₂, and the resulting support is impregnated with a Pt precursor and used for propane dehydrogenation (Examples 1–3, ¶¶[0052]–[0055]).
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have employed Kauffman's Pt-containing supported dehydrogenation catalyst as the Pt catalyst in the process of modified Washburn because Kauffman expressly teaches the catalyst for the same purpose of paraffin dehydrogenation to
corresponding olefins, with the disclosed support promoters providing a dehydrogenation catalyst having improved performance and stability.
Regarding claim 2, Kauffman teaches Li, Na, K, Rb, and Cs combined with the catalyst support, particularly at 0.5–3 wt.% of the catalyst, which is within the broad claimed amount of up to 5 wt.% when expressed relative to the support (¶[0033]).
Regarding claim 3, Kauffman's Example 1 provides, inter alia, La₂O₃ and CeO₂ together with ZrO₂. Based on the expressly disclosed amounts, the La:Zr and Ce:Zr molar ratios are approximately 0.10:1 and 0.20:1, respectively, both within the claimed 0.03:1-2.7:1 range.
Regarding claim 4, Kauffman teaches La₂O₃ and CeO₂ up to 8 wt.% of the support and Pt within the disclosed Pt catalyst composition. Its disclosed compositional ranges encompass selected-metal Pt molar ratios of at least 30:1 and within the claimed 30:1-5000:1 range; Kauffman expressly states that every concentration within its disclosed ranges is contemplated (¶[0021]). Selection of such expressly disclosed relative amounts would have been obvious for obtaining an operative Kauffman dehydrogenation catalyst.
Regarding claim 5, Kauffman expressly teaches the selected La and Ce components as oxides, including La₂O₃ and CeO₂ (¶¶[0019]–[0022]), thereby meeting the “oxide” alternative.
Regarding claim 6, Kauffman expressly teaches Ce and La as support components (¶¶[0019]–[0022]).
Regarding claim 7, Kauffman expressly teaches Zr and Al, including ZrO₂ and an alumina support, thereby meeting the claimed selection of Zr or Al.
Regarding claim 8, Kauffman's Example 1 expressly teaches a support comprising the claimed combination of rare-earth oxides La₂O₃/CeO₂ with Al₂O₃/ZrO₂.
Regarding claim 14, Kauffman establishes the claimed Pt-containing first catalyst as discussed above. Washburn further teaches that catalytic metal is typically activated before use by reducing the catalytic metal from a higher oxidation state to a lower oxidation state using conventional reduction methods (Washburn, ¶[0056]) and expressly identifies Pt-containing dehydrogenation catalysts (¶[0057]). It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have reduced oxidized Pt of the Pt-containing dehydrogenation catalyst with a conventional reducing gas, including H₂, before recommencing dehydrogenation following regeneration because such reduction restores the catalytic metal to its reduced, catalytically active state for the subsequent dehydrogenation cycle.
Claim 9 is rejected under 35 U.S.C. §103 as being unpatentable over Washburn et al. in view of JP 4406541 B2 and Kauffman et al., as applied to claim 8 above, and further in view of CN 105582918 A (“CN '918”).
Kauffman does not expressly disclose the particular CeZrO₂, CeAlO₃, BaCeO₃, or CePO₄ support compound required by claim 9.
CN '918 teaches Pt-containing catalysts for low-carbon alkane dehydrogenation comprising a Ce-Zr-O solid solution, including exemplified ceria-zirconia compositions supported with alumina, which correspond to the claimed CeZrO₂ alternative. The examples and Table 1 identify the Ce-Zr-containing catalyst compositions used for alkane dehydrogenation.
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have employed the Ce-Zr-O solid-solution support taught by CN '918 in the Pt-containing dehydrogenation catalyst of modified Washburn/Kauffman because CN '918 expressly teaches Ce-Zr-O support compositions for Pt-containing catalysts used for the same purpose of lower-alkane dehydrogenation, with a reasonable expectation that the resulting catalyst would perform the known dehydrogenation reaction.
Claim 20 is rejected under 35 U.S.C. §103 as being unpatentable over Washburn et al. in view of JP 4406541 B2, as applied to claim 1 above, and further in view of Blann et al. (WO 2020/046978). Washburn in view of JP teaches the hydrocarbon dehydrogenation process and the claimed Cr catalyst alternative substantially as discussed regarding claim 1, but does not expressly require that dehydrogenation occur in a first conversion zone and that the resulting effluent thereafter be fed to a second conversion zone containing the SOC.
Blann teaches a process in which hydrocarbon is dehydrogenated in a first fluidized-bed dehydrogenation zone and the resulting effluent is subsequently contacted in a second fluidized-bed zone with an oxygen-rich carrier to selectively combust molecular hydrogen, with the oxygen carrier thereafter regenerated (Blann, ¶¶[0009]–[0014], particularly ¶[0013]).
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have arranged the dehydrogenation and hydrogen-combustion operations of modified Washburn in separate first and second conversion zones as taught by Blann, with the dehydrogenation effluent from the first zone fed to the second zone containing the solid oxygen carrier, because Blann expressly teaches this reactor configuration for sequential hydrocarbon dehydrogenation and selective combustion of the resulting molecular hydrogen.
Conclusion
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.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to TAM M NGUYEN whose telephone number is (571)272-1452. The examiner can normally be reached Mon - Frid.
Examiner interviews are available via telephone, in-person, and video conferencing using a USPTO supplied web-based collaboration tool. To schedule an interview, applicant is encouraged to use the USPTO Automated Interview Request (AIR) at http://www.uspto.gov/interviewpractice.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Prem C Singh can be reached at 571-273-6381. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/TAM M NGUYEN/Primary Examiner, Art Unit 1771
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