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 .
Note from Examiner
The art unit location of your Application at the USPTO has changed. To aide in correlating any papers for this application, all further correspondence regarding this application should be directed to Examiner Judith Kamm in Art Unit 1611.
Election/Restrictions
Applicant’s election without traverse of Group I, claims 1-9, drawn to a catalyst, in the reply filed on 09/10/2025 is acknowledged.
Applicant’s further election without traverse of ZnCr2O4 as the species of spinel structure catalyst and Zn-ZSM-5@Silicalite-1 as the species of molecular sieve shell in the reply filed on 09/10/2025 is acknowledged.
Claims 10-19 are withdrawn from further consideration pursuant to 37 CFR 1.142(b) as being drawn to a nonelected invention, there being no allowable generic or linking claim. Election was made without traverse in the reply filed on 09/10/2025.
Claims 1-9 are under current examination.
Priority
This application is a national stage entry of PCT/CN2021/108678, filed 07/27/2021. Foreign priority has been claimed to CN 202010752882.2, filed 07/30/2020. Receipt is acknowledged of certified copies of papers required by 37 CFR 1.55.
Information Disclosure Statement
The information disclosure statement (IDS) submitted on 01/27/2023 is in compliance with the provisions of 37 CFR 1.97. Accordingly, the information disclosure statement has been considered by the Examiner.
Specification
Applicant is reminded of the proper language and format for an abstract of the disclosure.
The abstract should be in narrative form and generally limited to a single paragraph on a separate sheet within the range of 50 to 150 words in length. The abstract should describe the disclosure sufficiently to assist readers in deciding whether there is a need for consulting the full patent text for details.
The language should be clear and concise and should not repeat information given in the title. It should avoid using phrases which can be implied, such as, “The disclosure concerns,” “The disclosure defined by this invention,” “The disclosure describes,” etc. In addition, the form and legal phraseology often used in patent claims, such as “means” and “said,” should be avoided.
The abstract of the disclosure is objected to because it is more than 150 words in length and includes implied phrases such as “The present invention relates to”. A corrected abstract of the disclosure is required and must be presented on a separate sheet, apart from any other text. See MPEP § 608.01(b).
The spacing of the lines of the specification is such as to make reading difficult. New application papers with lines 1 1/2 or double spaced (see 37 CFR 1.52(b)(2)) on good quality paper are required.
Claim Objections
Claim 5 is objected to because of the following informalities: it is suggested that “a surface modifying material selected from one or more of…silica, resin, biomass” should read “a surface modifying material selected from one or more of…silica, resin, and biomass”. Further, a line appears over the period at the end of claim 5; this line should be omitted.
Appropriate correction is required.
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.
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 1-5 and 9 are rejected under 35 U.S.C. 103 as being unpatentable over Liu et al. (CN 109701604 A, published May 3rd, 2019), hereafter “Liu”, in view of Zhang et al. (“One-pass selective conversion of syngas to para-xylene” Chem. Sci. 2017, 8, 7941-7946; included on IDS submitted 01/27/2023), hereafter “Zhang”.
Regarding instant claims 1-3 and 5, Liu teaches a core-shell multifunctional catalyst system wherein the core layer is a metal oxide and the shell layer is a molecular sieve; the catalyst is used for the conversion of syngas to produce aromatics and light hydrocarbons (see entire document, particularly Abstract and claim 1). The metal component of the metal oxide is selected from at least one of Cr, Zr, Mn, Ce, La, Mo, Ti, In, Ga, and Zn (claims 2-3), preferably selected from Zn and Cr (paragraph [0016]); Liu exemplifies catalysts comprising Zn-Cr oxide (see examples beginning at paragraph [0049]). Liu further teaches that the shell is selected from one or more of ZSM-5, ZSM-11, Silicalite-1, and Silicalite-2 (claim 6). Liu exemplifies core-shell catalysts with a Zn-Cr oxide core, an HZSM-5 inner shell, and a Silicalite-1 outer shell (see paragraphs [0075], [0079], [0081]).
Regarding instant claim 4, Liu teaches that the mass ratio of core metal oxide to shell molecular sieve is in the range of 8:1 to 1:8 (claim 9), overlapping the claimed range. Per MPEP 2144.05 I., “In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990)”.
Liu does explicitly teach the elected core spinel-structure ZnCr2O4 (instant claims 1-2 and 9). Liu does not explicitly teach the elected species of molecular sieve of Zn-ZSM-5@Silicalite-1 (instant claims 1, 3, and 5).
Zhang teaches a hybrid catalyst, Cr/Zn-Zn/Z5@S1, for the one-pass conversion of syngas to value-added aromatics, especially para-xylene (see entire document, particularly Abstract). Para-xylene is a significant value-added chemical that can be synthesized from syngas, as it has important use in producing terephthalic acid and other chemicals (see “Introduction”, paragraph 1). The Cr/Zn component of Zhang has a ZnCr2O4 spinel structure (pg. 7942, column 1, paragraph 2) which converts syngas to methanol which then undergoes a series of reaction steps over the core-shell-structured Zn/Z5@S1 zeolite component (see paragraph bridging pg. 7943-7944). The Zn/Z5@S1 is a zinc doped H-ZSM-5 zeolite encapsulated with a silicalite-1 zeolite shell (pg. 7942, column 1, paragraph 2). The ion exchange of the Z5 zeolite with Zn generates Lewis acid sites, replacing the previous strong acid sites, leading to high para-xylene selectivity (see paragraph bridging pg. 7943-7944 and Table 1). The combination of the two components in the hybrid catalyst enabled a well-organized tandem catalysis process, performing syngas to methanol and methanol to para-xylene exclusively; sealing the exposed active sites of the Z5 zeolite with a silicalite-1 shell depressed the formation of unwanted xylene isomers (see “Conclusions” at pg. 7945).
It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the instant invention to use the spinel ZnCr2O4 catalyst suggested by Zhang in the core-shell particles of Liu. One of ordinary skill in the art would have been motivated to do so in order to incorporate a Zn-Cr oxide form that can effectively convert syngas to methanol and operate in tandem with ZSM-5@Silicalite-1 zeolites for the efficient and selective one-step production of value-added para-xylene from syngas. It would further have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the instant invention to use the Zn-substituted ZSM-5/Silicalite-1 suggested by Zhang as the molecular sieve in the core-shell particles of Liu. One of ordinary skill in the art would have been motivated to do so to achieve a catalyst with less acidic active sites and enhanced para-xylene selectivity in the conversion of methanol from syngas to value-added aromatics.
There is a reasonable expectation of success as the catalysts of Liu are taught to selectively produce aromatics from syngas (Abstract and paragraph [0047]) with the metal oxide core having syngas conversion activity and the molecular sieve shell having aromatic synthesis activity (paragraph [0035]). Liu further envisions Zn-Cr oxide cores (paragraph [0016]) and examples) and shells with a combination of ZSM-5 and Silicalite-1 (claim 6 and paragraphs [0075], [0079], [0081]), and teaches that that ZnZSM-5 multifunctional catalysts are known in the art for selective conversion of syngas to aromatics (paragraph [0005]).
Claim 6 is rejected under 35 U.S.C. 103 as being unpatentable over Liu in view of Zhang as applied to claims 1-5 and 9 above, and further in view of Yang et al. (WO 2019/062815 A1, published April 4, 2019), hereafter “Yang”.
The teachings of the modified Liu are described above.
Liu and Zhang do not teach that the weight ratio of the molecular sieve catalyst to the surface modifying material is 100:1-2:1 (instant claim 6).
Yang teaches core/shell catalysts with a core of HZSM-5 molecular sieve or modified HZSM-5, with Hs replaced by Zn, and a shell of Silicalite-1 which is used in combination with a methanol catalyst for the selective conversion of syngas to p-xylene (see entire document, particularly Abstract and Claims). Yang teaches that the weight ratio of core to shell is from 100:1 to 1:100, preferably from 5:1 to 1:1, but that there is no particular choice as to the amount of shell used, as long as the core can be coated (see Claims and pg. 5, paragraph 7).
It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the instant invention to modify the core-shell catalyst of Liu in view of Zhang with the weight ratio of molecular sieve to Silicalite-1 of 5:1 to 1:1, suggested by Yang, overlapping the claimed range. One of ordinary skill would have been motivated to routinely optimize the weight ratio in order to ensure that the molecular sieve is coated and to achieve a weight ratio known in the art for core-shell catalysts useful in the selective conversion of syngas to p-xylene. There is a reasonable expectation of success as the catalyst of the modified Liu comprises a metal oxide core with an inner Zn-ZSM-5 shell and an outer Silicalite-1 shell and is useful for the selective conversion of syngas to value-added aromatic products.
Further, per MPEP 2144.05 I., “In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990)” and per MPEP 2144.05 II. A. “"[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." In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955)”.
Claims 7-8 are rejected under 35 U.S.C. 103 as being unpatentable over Liu in view of Zhang as applied to claims 1-5 and 9 above, and further in view of Chai et al. (WO 2018/121324 A1, published July 5th, 2018), hereafter “Chai”.
The teachings of the modified Liu are described above.
Liu and Zhang do not teach that there is a binder layer between the core and the shell (instant claim 7) which is made of a silicon-containing material selected from silica sol, APTES, APTMS, γ-glycidoxypropyl trimethoxysilane, and γ-(methacryloxy)propyl trimethoxysilane (instant claim 8).
Chai teaches core/shell catalysts with a metal oxide core and molecular sieve catalyst shell, such as H-ZSM-5, which are used for preparing products from syngas (see entire document, particularly Abstract, Claims, and pg. 4, paragraph 2). Chai teaches that a silicon-containing binding or “tie layer” between the core and the shell greatly increases the proportion of shell catalyst in the core/shell catalyst and provides a simple way of successfully synthesizing the core-shell catalyst (see paragraph bridging pgs. 2-3). Chai exemplifies silica sol as a binder, which adheres the shell catalyst to the core (pg. 6, paragraph 1).
It would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the instant invention to modify the core-shell catalyst of Liu in view of Zhang with the silica sol binder layer suggested by Chai. One of ordinary skill would have been motivated to do so with a reasonable expectation of success to incorporate a layer that ensures adherence of a molecular sieve catalyst shell, such as ZSM-5 zeolite, to a metal oxide core and achieves a desired proportion of shell catalyst in the final core-shell catalyst, as suggested by Chai. There is a reasonable expectation of success as the catalyst of the modified Liu similarly comprises a metal oxide core with a molecular sieve shell comprising ZSM-5 for the conversion of syngas to value-added products, and Liu suggests that the ratio of core metal oxide to shell molecular sieve can be adjusted (claim 9).
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to JUDITH M KAMM whose telephone number is (703)756-4575. The examiner can normally be reached M-F 8:00 am-4:30 pm EST.
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/BETHANY P BARHAM/Supervisory Patent Examiner, Art Unit 1611
/J.M.K./Examiner, Art Unit 1611
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