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 .
Priority
Acknowledgment is made of applicant’s claim for foreign priority under 35 U.S.C. 119 (a)-(d). The certified copy has been filed in parent Application No. CN202110018642.4, filed on 7 January 2021.
Information Disclosure Statement
The information disclosure statements (IDS’s) submitted on 7 July 2023, have been considered by the examiner.
Claim Objections
Claim 11 is objected to for a typographical error, where the limitation, “is characterized in that the reaction temperature of said gelatination is 10-40°C, preferably 15-35°C, the pH after the gelatination is controlled to 9-12,” should read as “is characterized in that the reaction temperature of said gelatination is 10-40°C, preferably 15-35°C, and the pH after the gelatination is controlled to 9-12.”
Claim 14 is objected to for a typographical error, where the limitation, “the time of said ageing,” in line 2 should be corrected t oread “the time of said aging.”
Claim 16 is objected to for a lack of clarity in writing. It is suggested the limitation, “based on the total charging molar ratios of SiO2:Al2O3:R2O(an alkali source, wherein R is an alkali metal, such as sodium and potassium):H2O = 1:(0.0025-0.025):(0.015-0.08):(30-80)” should instead read, “based on the total charging molar ratios of SiO2:Al2O3:R2O:H2O = 1:(0.0025-0.025):(0.015-0.08):(30-80), wherein R2O is an alkali source” to improve clarity.
Furthermore, the acronym SDA in the limitation, “template agent (SDA)/SiO2” is not defined in the claims or specification and should be defined when first used. For the purpose of examination, it is interpreted to refer to the term structure-defining additive/agent as an alternate term for template agent.
Claim Interpretation
In regard to claim 8, after a review of the relevant art, the closest conventional use of “carbonization method” was found to be the terms carbonization and carbonation interchangeably used to refer to mineral carbonation, a reaction of a metal oxide bearing material with CO2 to form insoluble carbonates (Sanna et. al., Section 1.2). These reactions are commonly conducted alongside industrial processes to sequester CO2, and have been reported extensively with silicate materials under alkaline aqueous conditions. For the purpose of examination, any chemical reaction where CO2 is introduced as a reagent under alkaline conditions which would reasonably result in the formation of carbonate side products is interpreted to be a carbonation or carbonization process.
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.
Claims 1-18 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.
Broader ranges or limitations followed by narrow ranges or limitations:
A broad range or limitation together with a narrow range or limitation that falls within the broad range or limitation (in the same claim) may be considered indefinite if the resulting claim does not clearly set forth the metes and bounds of the patent protection desired. See MPEP § 2173.05(c).
In the present instance:
Claim 1 recites the broad recitation "the total acid amount of said ZSM- 23 zeolite is 0.05-0.25 mmol/g,", and the claim also recites "preferably, 0.06-0.22 mmol/g, more preferably, 0.06-0.20 mmol/g" which are the narrower statements of the range/limitation.
Claim 1 recites the broad recitation "the strong acid content of said ZSM-23 zeolite is 5-33%," and the claim also recites "preferably, 7-33%, which are the narrower statements of the range/limitation.
Claim 2 recites the broad recitation "grain size of 100-700 nm and the claim also recites preferably 200-600 nm, which are the narrower statements of the range/limitation.
Claim 3 recites the broad recitation "a SiO and the claim also recites "a SiO which is the narrower statement of the range/limitation.
Claim 3 recites the broad recitation "a specific surface area of 200-400 m and the claim also recites "a specific surface area which is the narrower statement of the range/limitation.
Claim 3 recites the broad recitation "a pore volume of 0.25-0.50 cm and the claim also recites "a pore volume of which is the narrower statement of the range/limitation.
Claim 4 recites the broad recitation "a relative crystallinity of 95-130% after calcination," and the claim also recites "preferably a relative crystallinity which is the narrower statement of the range/limitation.
Claim 4 recites the broad recitation "a relative crystallinity of 93-120% after a hydrothermal treatment," and the claim also recites "preferably...a relative which is the narrower statement of the range/limitation.
Claim 5 recites the broad recitation "an amorphous silica-alumina and/or amorphous silica-alumina precursor," and the claim also recites "preferably, the amorphous silica-alumina and/or amorphous silica-alumina precursor is derived from an alkaline aluminum source," which is the narrower statement of the range/limitation.
Claim 7 recites the broad recitation "the molar ratio of silicon (as silica) :aluminum (as alumina) is 1:(0.10-0.85)," and the claim also recites " preferably 1:(0.20-0.79 which are narrower statements of the range/limitation.
Claim 7 recites the broad recitation "the molar ratio of said aluminum (as alumina) :the template agent is 1:(10-100)," and the claim also recites "preferably 1:(15-85) which are narrower statements of the range/limitation.
Claim 9 recites the broad recitation "the volume of the introduced CO and the claim also recites "preferably 70-90%" which is the narrower statement of the range/limitation.
Claim 10 recites the broad recitation "the remaining part of the solution of the silicon-containing compound as silica comprises 5-85wt%," and the claim also recites "preferably 30- 70wt%," which is the narrower statement of the range/limitation.
Claim 11 recites the broad recitation "the reaction temperature of said gelatination is 10-40°C," and the claim also recites "preferably 15-35°C," which is the narrower statement of the range/limitation.
Claim 14 recites the broad recitation "the time of said ageing is 5-60 minutes," and the claim also recites "preferably 10-30 minutes," which is the narrower statement of the range/limitation.
Claim 14 recites the broad recitation "the temperature of said aging is 10-40°C," and the claim also recites "preferably 15-35°C," which is the narrower statement of the range/limitation.
Claim 15 recites the broad recitation "said mixed solution is stirred at 10-35°C for 0.2-1.5 hours," and the claim also recites "preferably stirred at 10-25°C for 0.5-1 hours," which is the narrower statement of the range/limitation.
Claim 16 recites the broad recitation "SiO and the claim also recites preferably SiO which is the narrower statement of the range/limitation.
Claim 18 recites the broad recitation "the crystallization is performed at 150-200°C for 8-72 hours," and the claim also recites "preferably at 160-180°C for 10-48 hours," which is the narrower statement of the range/limitation.
Claim 18 recites the broad recitation "the drying is performed at 60-130°C for 2-12 hours," and the claim also recites "the drying is performed at 60-130°C for 2-12 hours, preferably at 80-120°C for 4-8 hours," which is the narrower statement of the range/limitation.
Claim 18 recites the broad recitation "the calcining is performed at 500-600°C for 2-8 hours," and the claim also recites “preferably at 530-570°C for 3-6 hours or 4-6 hours," which is the narrower statement of the range/limitation.
Claims 1-5, 7, 9-11, 14-16, and 18 are considered indefinite because there is a question or doubt as to whether the feature introduced by such narrower language is (a) merely exemplary of the remainder of the claim, and therefore not required, or (b) a required feature of the claims.
Lack of antecedent basis in the claims:
Claim 5 recites the limitation "The material" in line 9. There is insufficient antecedent basis for this limitation in the claim.
Claim 11 recites the limitation “said gelatination,” in line 2. There is insufficient antecedent basis for this limitation. In claim 9, the recited limitation, “introducing a CO2 gas for gelatination,” could imply that a gelatination step occurs in the preparation process claimed in claim 9 or provide context for a later step. However, it is never explicitly stated in the list of elements of claim 9 that gelatination is used.
Claim 16 recites the limitation “the total charging molar ratios of,” in line 3. There is insufficient antecedent basis for this limitation in the claim.
Indefinite language:
Regarding claim 5, the phrase "for example" renders the claim indefinite because it is unclear whether the limitation(s) following the phrase are part of the claimed invention. See MPEP § 2173.05(d).
Regarding claim 5, 9, & 16, the phrase "such as" renders the claim indefinite because it is unclear whether the limitations following the phrase are part of the claimed invention. See MPEP § 2173.05(d).
Regarding claim 8, the recitation, “in step (1), an amorphous silica-alumina precursor is prepared by carbonization method,” is considered indefinite because it is unclear what method the “carbonization method,” is within the claim, and the detailed description of the instant application does not describe the conditions of the method.
Regarding claim 9, the recitation, “introducing a CO2 gas for gelatination, when the volume of the introduced CO2 gas is 50-100%, preferably 70- 90% of the total volume of the introduced CO2 gas,” is indefinite because it is unclear how the volume of the introduced CO2 gas could be less than 100% as the limitation is currently defined. If applicant intends for CO2 to be a component of an introduced gas, it must be stated clearly that a gas is introduced which contains CO2, and may choose to specify a concentration or percentage of CO2 within the introduced gas.
Claims 6, 12, and 13 are rejected via their dependency on rejected claims 1 and 5.
Claim Rejections - 35 USC § 102
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 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Chen et. al. (Microporous and Mesoporous Materials, 252, 2017 pp. 146-153).
In regard to claim 1, Chen et. al. teaches a ZSM-23 zeolite (SNNa) with a total acid amount of 0.105 mmol/g and a strong acid content of 33% of the total acid amount when strong acids are characterized as having a desorption temperature above 350°C (SNNa in Table 3, pp. 150-151).
Regarding claims 2-3, Chen et. al. further teaches that the zeolite forms as needle-like crystals with dimensions of 500-1100 nm in length and 50-200 nm in diameter (left column, pp. 148), a SiO2:Al2O3 ratio of 80, 100, 120, 140 or 200 (Fig. 3b, pp. 149 and paragraph 3, right column, pp. 148), a specific surface area of 281 m2/g, and a pore volume of 0.35 cm3/g (SNNa in Table 2, pp. 150).
In regard to claim 4, Chen et. al. teaches ZSM-23 zeolite samples with 100% crystallinity relative to a reference sample (Fig. 4. & pp. 148, right column, paragraph 3). The process limitations in claim 4 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.
As each and every element of the claimed invention is taught in the prior art as recited above, the claims are anticipated by Chen et. al.
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 5-7, 9-12 and 14-18 are rejected under 35 U.S.C. 103 as being unpatentable over Chen et. al. as applied above for claim 1 and further in view of Wang et al. (Microporous and Mesoporous Materials, 134(1–3), 2010, pp. 203-209) and Chinese Patent Pub. CN104591213A (2015-05-06, machine translation provided and cited herein).
With regard to claim 5, Chen et. al. does not teach the order of mixing reagents as claimed. Wang et. al. teaches a method for preparing a ZSM-23 zeolite comprising forming a mixed solution containing a template agent, DMF, and an aluminum source, aluminum sulfate; adding to the mixed solution a second solution of an alkali source, sodium hydroxide, and silicon source, silica sol to form a gel material; and crystallizing, filtering, washing, and drying the material (Section 2.2, pp. 204). Wang et. al. discloses a clear benefit of DMF as a template agent as it both acts as a template agent and promotes nucleation and crystallization (Section 3.3, right column, pp. 206). Crystallization was conducted in 65 hours in Wang et. al.’s method, versus 132 hours in Chen et. al. This significant reduction in crystallization time provides ample justification to modify Chen et. al.’s synthesis with the teachings of Wang et. al. to hastened synthesis without compromising physical properties.
Further in regard to claim 5, neither Chen et. al. or Wang et. al. teaches the use of an aluminum-silica precursor as an aluminum source or reactant. However, CN ‘213A teaches a preparation of NaY zeolites (e.g. NaY-type molecular sieves) by mixing water, a silicon source, a directing agent, an alkali source, and a prepared amorphous silica-alumina precursor at 0-40°C and 9.5-12 pH to obtain a gel (paragraph [0020], pp. 9) followed by crystallization, filtering, and drying (paragraph [0021], pp. 9). CN ‘213A teaches that the method improves other synthesis methods by preventing agglomeration of silica particles which commonly occurs when adding a large amount of the silicon source at once (paragraph [0029], pp.15). Additionally, CN ‘213A teaches that zeolites prepared via the method had a large specific surface area, external surface area, and increased exposed pores (paragraph [0028], 13-14). One of ordinary skill in the art would note the improved physical characteristics of the NaY-type zeolites would impart desirable adsorption properties as taught by CN ‘213A.
As typical synthesis preparations between the ZSM-23 and NaY-type zeolites differ primarily in the ratio of reagents used, one of ordinary skill in the art would assume the application of improvements synthesis of one zeolite composition to yield similar improvements in another. Therefore, it would have been obvious to one of ordinary skill in the art at the relevant time to modify the teachings of Chen et. al. and Wang et. al. to prepare and use an amorphous silica-alumina precursor in place of aluminum sulfate to yield a ZSM-23 zeolite with improved physical characteristics.
With regard to claim 6, Chen et. al. teaches the use of pyrrolidine as a template agent (e.g. structure directing agent/SDA, abbreviated PYR in Section 2.1.2, left column, pp. 147).
With regard to claim 7, Chen et. al. teaches a ratio of SiO2:Al2O3 of 1:0.1 which is within the claimed molar ratio of silicon (as silica) : aluminum (as alumina) of 1:(0.10-0.85) and a ratio of 1:45 Al2O3:pyrrolidine which is within the claimed molar ratio of aluminum (as alumina) : template agent of 1:(10-100) (Section 2.1.2, left column, pp. 147).
With regard to claim 9, CN ‘213A teaches a preparation of an amorphous silica-alumina precursor comprising mixing a portion of a silicon-containing material with an alkaline aluminum material (paragraph [0024]), pp. 10), introducing CO2 to the solution, conducting a gelation at 5-80°C and a pH of 7-10 (paragraph [0024], pp. 11), adding the remainder of the silicon-containing material (paragraph [0024], pp. 10), and aging the gel to yield the amorphous silica-alumina precursor (paragraph [0024], pp. 12). CN ‘213A teaches the neutralization with CO2 with no other components, so it is the examiner’s position that the introduced gas is 100% CO2 by volume (paragraph [0024], pp. 11). CN ‘213A further teaches using a sodium aluminate solution with a 100 g/L Al2O3 concentration and a sodium silicate solution with a 140 g/L SiO2-NER58 concentration as reagents (Example 1, paragraph [0041], pp. 18).
With regard to claim 10, CN ‘213A teaches the addition of the silicon-containing material as a first aliquot of 0.17 L, and a second aliquot of 0.33 L (paragraph [0041], pp. 19). Therefore, the remainder of silicon-containing solution is 66% of the total added material. Since the working solution is homogenous, the second aliquot is 66 wt% the total material and is within the instantly claimed range of 5-85 wt%.
With regard to claim 11, CN ‘213A teaches the gelatination reaction of the amorphous silica-alumina precursor is conducted between a temperature of 5-80°C and a pH of 7-10 (paragraph 0024], pp. 11), which overlap the instantly claimed ranges of 10-40°C and a pH of 9-12.
With regard to claim 12, CN ‘213A teaches that the silicon-containing solution used to prepare the amorphous silica-alumina precursor is a sodium silicate solution (paragraph [0041], pp. 18).
With regard to claim 13, CN ‘213A teaches the use of CO2 gas to neutralize excess aluminum salts during the formation of the amorphous silica-alumina precursor (paragraph [0024], pp. 11). CN ‘213A further teaches that there is an optimal pH range (7-10, preferably 7.5-9) at which the reaction should be conducted, where the CO2 gas plays a key role as an acidic precipitant (paragraph [0024], pp. 11). Finding the optimal concentration of CO2 gas added to the reaction mixture to maintain a specific solution pH would be within the level of one of ordinary skill in the art. 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 CO2 gas concentration through process 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 claim 14, CN ‘213A broadly teaches that the aging of the precursor may be conducted at temperatures from room temperature (25°C) to 85°C and for a time of 0.2-8 hours (paragraph [0024], pp. 12) which overlaps the instantly claimed range of 10-40°C and encompasses the instantly claimed range of 5-60 minutes. With respect to the encompassing and overlapping ranges, 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.
With regard to claim 15, Chen et. al. teaches that the reaction mixture prior to crystallization is stirred for 1 hour (Section 2.1.2, left column, pp. 147). Stirring conditions beyond time are not specified, which is suggestive that stirring was completed at standard temperature and pressure, 25°C and 1 atm. Furthermore, examiner considers finding the best conditions necessary to mix a solution in step (1) to be routine optimization. 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 stirring temperature through process 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 claim 16, the claimed amount of reagents added are based on the final charging ratio of components in the zeolite. To make the ratio of reagents comparable to the prior art, which only describe initial reactant ratios, the appropriate range of added hydroxide (ROH) can be back-calculated by doubling the range of the R2O unit cell (where R = an alkali metal). The given charging ratio of 1 SiO2:0.030-0.080 R2O in the ZSM-23 zeolite is then equivalent to 1 SiO2:0.030-0.160 ROH in the reaction mixture. Chen et. al. teaches a ratio of 1 SiO2:0.083 NaOH, which is within the claimed range (Section 2.1.2, left column, pp. 147).
With regard to claim 17, Chen et. al. teaches using fumed silica as the silicon source and sodium hydroxide as an alkali source as claimed in the instant application (Section 2.1.2, left column, pp. 147).
With regard to claim 18, Chen et. al. teaches a crystallization of a formed gel conducted at 180°C for 48 hours (NS-2 in Section 2.1.2, right column, pp. 147), drying of zeolite products at 65°C for 12 hours, and calcination at 550°C for 3 hours after temperature ramping (Section 2.1.1, paragraph 2, pp. 147). These preparation conditions are within the instantly claimed ranges of 150-200°C for 8-72 hours, 60-130°C for 2-12 hours, and 500-600°C for 2-8 respectively.
Claims 8 is rejected under 35 U.S.C. 103 as being unpatentable over Chen et. al., Wang et. al., and CN104591213A as applied above for claim 5 and further in view of Sanna et. al. (Chem. Soc. Rev., 2014, 43, 8049-8080).
In regard to claim 8, the combined teachings of Chen et. al., Wang et. al., and CN ‘213A provide the conditions necessary for a carbonization reaction in solution as described by Sanna et. al. Specifically, the addition of CO2 as a part of an acid-precipitation reaction to form the precursor as described in CN ‘213A would result in the neutralization of CO2 as a carbonate (paragraph [0024], pp. 11). Further, CN ‘213A teaches the addition of a directing agent (the instantly claimed template agent) to the precursor solution (paragraph [0020], pp. 9). As claim 8 does not elaborate on further conditions for a carbonization reaction, all aspects of the claim are considered met by the teachings of Chen et. al., Wang et. al., and CN ‘213A.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure: Liu et. al. (Chin J Catal, 30(6), 2009, pp. 525–530).
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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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, CHRISTINA JOHNSON can be reached at (571) 272-1176. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/MORDECAI M LEAVITT/Examiner, Art Unit 1742 /CHRISTINA A JOHNSON/Supervisory Patent Examiner, Art Unit 1742