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 .
Finality
Applicant's request for reconsideration of the finality of the rejection of the last Office action is persuasive and, therefore, the finality of that action is withdrawn. New ground(s) of rejection presented in this office action.
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 13, 15, 18, 19, 21, and 23 are rejected under 35 U.S.C. 103 as being unpatentable over Arnold et al. (US 8,519,210, 2013) in view of Sang et al. (Journal of Nanoparticle Research, 2014; cited on IDS filed August 2, 2023), Garcia-Martinez (US 2012 0024776; cited on IDS filed August 2, 2023), and Majeed and Saleh (Iraqi Journal of Chemical and Petroleum Engineering, 2016).
Arnold discloses a process for oxidative dehydrogenation (ODH) of ethane (alkane) to ethylene (olefin) comprising contacting an ethane feed and an oxygen-containing gas in the presence of an ODH catalyst in a reaction zone (column 3, ¶ 2). Arnold discloses the ODH catalyst can comprise Ni (nickel) and Bi (bismuth) (column 3, ¶ 3). Arnold discloses that the catalyst can be formed on a support such as silica (column 7, ¶ 3). Arnold discloses that the oxygen-containing gas can comprise oxygen and inert gas such as helium (column 8, ¶¶ 6-7). Arnold discloses that the reaction temperature can be about 500 ͦC and the pressure can be in the moderate range of about 0.1 to 20 barG (10 to 2000 kPa) (column 15, ¶ 3).
Arnold does not disclose a hierarchical silica composite which is a stereoregular MCM-41 ordered arrangement of uniformly-sized mesopores with diameters in a range of 10-50 nm and mesopore walls having a thickness of 3 to about 5 nm and a stereoregular ZSM-5 ordered arrangement of uniformly-sized micropores with diameters of less than 2 nm located within the mesopore walls of the stereoregular MCM-41.
Sang discloses a method for catalytic cracking of endothermic hydrocarbon fuels using HZSM-5/MCM-41 composite molecular sieves (abstract). Sang discloses that the HZSM-5 can be uniformly dispersed in the MCM-41 and that the microporous-mesoporous hierarchical composites shows a high catalytic activity, high selectivity to light olefins, and a long lifetime for n-decane catalytic cracking by providing a proper activity, shorter channels, and a higher specific surface area for reaction (abstract).
Garcia-Martinez discloses a silica composite (mesostructured zeolites) comprising an inorganic material such as ZSM-5 (zeolite) (claim 7; ¶ 16) and a mesostructure such as MCM-41 (claim 14) for use as a catalyst for producing a petrochemical product such as olefins (abstract; claim 50). Garcia-Martinez discloses that the mesopores can have an ordered arrangement (stereoregular) (¶ 129) and a narrow pore size distribution (uniformly sized) (claim 10; ¶ 200), with diameters in a range of 2-60 nm (¶ 82) and with a pore wall thickness in a range of 1-5 nm (claim 9). Garcia-Martinez discloses that the catalytic material can comprise nickel (¶ 310) and can be impregnated on the silica composite (¶ 24).
Majeed discloses a micro-mesoporous composite (abstract). Majeed discloses that the zeolite (ZSM-5) micropores can be less than 2 nm and mesopores can be 2-50 nm (page 71, column 2, ¶ 3). Majeed discloses that the composite can be multiporous (hierarchical) (page 73, column 1, ¶ 2) and can have ordered structure (stereoregular) (page 76, column 2, ¶ 2).
It would have been obvious to a person of ordinary skill in the art before the effective filing date of the claimed invention to use the hierarchical silica composite of Sang, Garcia-Martinez, and Majeed as a silica support of Arnold in order to improve the efficiency of the ODH catalyst. A person of ordinary skill in the art would have been motivated to make these modifications and reasonably would have expected success because Sang teaches that ZSM-5/MCM-41 microporous-mesoporous hierarchical composites can show a high catalytic activity by providing a higher specific surface area for the reaction; Garcia-Martinez teaches that MCM-41 can have a stereoregular, uniformly sized mesopores with diameters in the range of 2-60 nm and with a pore wall thickness in the range of 1-5 nm and can be effectively used for producing olefins; and Majeed teaches that ZSM-5 micropores can have a diameter of less than 2 nm. The combination of the teachings of Sang, Garcia-Martinez, and Majeed reads on the hierarchical silica composite of instant claim 13. The diameter and pore wall thickness of the mesopores of Garcia-Martinez encompass those instantly claimed. In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. Further, a person of ordinary skill in the art would have been motivated to adjust the diameter and pore wall thickness of the mesopore depending on the specific requirements of the target applications. The diameter and pore wall thickness of a mesopore are clearly result effective parameters that a person of ordinary skill in the art would routinely optimize. Optimization of parameters is a routine practice that would be obvious for a person of ordinary skill in the art to employ and reasonably would expect success. It would have been customary for an artisan of ordinary skill to determine the optimal diameter and pore wall thickness of the mesopore in order to best achieve the desired catalytic activity. Similarly, the reaction pressure of Arnold encompasses that instantly claimed. In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. Further, a person of ordinary skill in the art would have been motivated to adjust the reaction pressure depending on the specific requirements of the target applications. The reaction pressure is a clearly result effective parameters that a person of ordinary skill in the art would routinely optimize. Optimization of parameters is a routine practice that would be obvious for a person of ordinary skill in the art to employ and reasonably would expect success. It would have been customary for an artisan of ordinary skill to determine the optimal reaction pressure in order to best achieve the desired catalytic activity. “[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.” See MPEP § 2144.05. Further, a person of ordinary skill in the art would have been motivated to use uniformly-sized micropores in order to achieve precise shape selectivity and maintain homogeneous active sites across the catalysts. Further, a person of ordinary skill in the art would have been motivated to utilize a hierarchical silica composite as a silica support because the hierarchical silica composite can enhance the surface area and mass transfer for the catalytic reaction. Because the advantages of hierarchical silica support are intrinsic to the material itself, its utility as a superior catalyst support is not restricted solely to the specific reactions exemplified in those references. Further, none of the cited references teach away from utilizing a hierarchical silica support for an ODH process. Therefore, a person of ordinary skill in the art seeking to optimize a catalytic support for an ODH process would naturally look to known composite taught in closely related catalytic process such as hydrocarbon conversion catalysis, and would have found it obvious to apply the hierarchical silica support to an ODH reaction with a reasonable expectation of success.
Arnold does not disclose that the amount of the active catalytic material is in a range of 10-20 wt.% or 10 wt.% relative to the total weight of the catalyst.
In addition to the teachings of Garcia-Martinez discussed above, Garcia-Martinez discloses that the amount of catalytic material can be 0-99.5% of the total weight of the composite (¶ 79).
It would have been obvious to a person of ordinary skill in the art before the effective filing date of the claimed invention to impregnate 10 wt.% of the catalytic material of Arnold into the hierarchical silica composite of Sang, Garcia-Martinez, and Majeed to optimize the amount of the catalytic material according to the specific requirements of the application. A person of ordinary skill in the art would have been motivated to make these modifications and reasonably would have expected success because Garcia-Martinez discloses that an amount of catalytic material can be 0-99.5% of the total weight of the catalyst. The amount of the active catalytic material of Garcia-Martinez encompasses that instantly claimed. In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. Further, a person of ordinary skill in the art would have been motivated to adjust the amount of the catalytic material depending on the specific requirements of the target applications. The weight amount of the catalytic material is clearly a result effective parameter that a person of ordinary skill in the art would routinely optimize. Optimization of parameters is a routine practice that would be obvious for a person of ordinary skill in the art to employ and reasonably would expect success. It would have been customary for an artisan of ordinary skill to determine the optimal the amount of the catalytic material in order to best achieve the desired catalytic activity. “[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.” See MPEP § 2144.05.
Claims16 and 17 are rejected under 35 U.S.C. 103 as being unpatentable over Arnold, Sang, Garcia-Martinez, and Majeed as applied to claims 13, 15, 18, 19, 21, and 23 above, and further in view of Wang (王) et al. (CN100473635, 2009; all citations from the machine translation).
In addition to the teachings of Sang discussed above, Sang discloses that the catalytic reaction can be carried out with a nitrogen flow of 30 mL min-1 and a feeding rate of n-decane of 0.1 mL min-1 at atmospheric pressure and 500 ͦC (abstract; page 4, column 1, ¶2). This indicates an atmospheric pressure of 101.325 kPa (page 3, column 2; Nesbitt, 2007). Sang discloses that catalyst pretreatment method using nitrogen at a flow rate of 30 mL min-1 and 500 ͦC for 1 hour (page 2755, column 1, ¶ 2).
Arnold, Garcia-Martinez, and Majeed are discussed above.
None of Arnold, Sang, Garcia-Martinez, and Majeed discloses that inert gas flow rate of 50-150 mL min-1, alkane flow rate of 0.5-1.0 mmol min-1, and that pretreatment of the catalysis with an inert gas at an inert gas flow rate of 50-150 mL min-1.
Wang discloses methods of-1 when N2:O2:C2H6 = 17:3:10 (volume ratio) (page 5, Example 8). Wang discloses that catalyst pretreatment can be performed with mixed gas of oxygen and nitrogen at a flow rate of 10-1000 ml min -1 and a temperature of 400-700 ℃ for 1-60 minutes (claim 5).
It would have been obvious to a person of ordinary skill in the art before the effective filing date of the claimed invention to apply the reaction conditions of Wang to the method of Arnold, Sang, Garcia-Martinez, and Majeed in order to produce ethylene from alkane more efficiently. A person of ordinary skill in the art would have been motivated to make these modifications and reasonably would have expected success because Wang teaches the detailed experimental conditions for improved catalytic activity depending on the specific requirement of the target applications. The pretreatment conditions of Wang encompasses or overlaps with those instantly claimed. In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. Further, a person of ordinary skill in the art would have been motivated to optimize the reaction conditions such as flow rates of inert gas and alkane depending on the requirements of applications. The reaction conditions are clearly a result effective parameter that a person of ordinary skill in the art would routinely optimize. Optimization of reaction conditions is a routine practice that would be obvious for a person of ordinary skill in the art to employ and reasonably would expect success. It would have been customary for an artisan of ordinary skill to determine the optimal conditions in order to best achieve the desired catalytic activity as the conditions such as temperature and flow rate determine catalytic activity and selectivity as taught by Wang. “[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.” See MPEP § 2144.05.
Claim 22 is rejected under 35 U.S.C. 103 as being unpatentable over Arnold, Sang, Garcia-Martinez, and Majeed as applied to claims 13, 15, 18, 19, 21, and 23 above, and further in view of Vermeiren et al. (US 2008 0050308; cited on IDS filed August 2, 2023).
Arnold, Sang, Garcia-Martinez, and Majeed are discussed above.
None of Arnold, Sang, Garcia-Martinez, and Majeed discloses that the silica composite has a silicon to aluminum molar ratio in a range of 1,000:1 to 3,000:1.
Vermeiren discloses zeolite materials such as aluminosilicate (¶ 45) having silicon/metal ratio from 22.5 to 15,000 (22.5:1 to 15,000:1) (¶ 43). Vermeiren teaches that the zeolite can be ZSM-5 (¶ 80). Vermeiren discloses that dealumination of zeolites improves process performance such as selectivity, product quality, catalyst stability, and reduced surface activity (¶ 4).
It would have been obvious to a person of ordinary skill in the art before the effective filing date of the claimed invention to modify the silica composite of Arnold, Sang, Garcia-Martinez, and Majeed to have a low aluminum content such as 1,000:1 as taught by Vermeiren. A person of ordinary skill in the art would have been motivated to make these modifications and reasonably would have expected success because Vermeiren teaches that silica composites can be made with low aluminum content for improving performance and reducing surface activity. Further, a person of ordinary skill in the art would have been motivated to make this modification in order to improve catalyst stability and to prevent unwanted side reactions. The silicon to aluminum ratio of the prior art overlap with that instantly claimed. In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. The silicon to aluminum ratio is clearly a result effective parameter that a person of ordinary skill in the art would routinely optimize. Optimization of parameters is a routine practice that would be obvious for a person of ordinary skill in the art to employ and reasonably would expect success. It would have been customary for an artisan of ordinary skill to determine the optimal silicon to aluminum ratio in order to best achieve the desired catalytic activity as the ratio determine catalytic activity by controlling acidity, selectivity, and stability of the catalysts . “[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.” See MPEP § 2144.05. Accordingly, applying the teachings of Vermeiren to the method of Arnold, Sang, Garcia-Martinez, and Majeed to achieve low aluminum content represents a predictable use of prior art elements according to their established functions and therefore renders claim 22 obvious.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to JONG HWAN BAEK whose telephone number is (571)272-0670. The examiner can normally be reached Mon - Thu, 9 am - 3 pm ET.
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/JONG HWAN BAEK/Examiner, Art Unit 1618
/Nissa M Westerberg/Primary Examiner, Art Unit 1618
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