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 .
Election/Restrictions
Applicant’s election of Group I, claims 1-15, in the reply filed on 01/28/2026 is acknowledged. Claims 16-29 are withdrawn. Because applicant did not distinctly and specifically point out the supposed errors in the restriction requirement, the election has been treated as an election without traverse (MPEP § 818.01(a)).
Claim Rejections - 35 USC § 102
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 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.
(a)(2) the claimed invention was described in a patent issued under section 151, or in an application for patent published or deemed published under section 122(b), in which the patent or application, as the case may be, names another inventor and was effectively filed before the effective filing date of the claimed invention.
Claims 1, 2, 4, and 12-15 are rejected under 35 U.S.C. 102(a)(1)/(a)(2) as being anticipated by Buchbinder et al. (US020220203340A1).
Regarding claim 1, Examiner notes the claim includes multiple instances of the term “optionally”. While not indefinite, use of the word “optionally” does not constitute necessary aspects required by the claim and are not considered as required in the following rejection over Buchbinder.
Buchbinder teaches a process for preparing a calcined catalyst comprising Pt supported on alumina, where after the catalyst components have been combined with the desired alumina support, the catalyst composite is dried prior to performing a calcination at a temperature from about 320 °C to about 600 °C for a period typically of about 0.5 to 10 hours in air (Abstract; [0007]-[0008]; [0028]; [0041]). Performing a calcination in air is equivalent to performing the initial calcination under oxidizing conditions according to the instant invention (see claims 1-3 describe oxidizing conditions), meeting the limitation of performing “an initial calcination comprising exposing the synthesized catalyst to a …first oxidizing gas under oxidation conditions to produce an initial calcined catalyst”.
Buchbinder further teaches the catalyst displays platinum levels below 0.0999 wt.% on a volatile-free basis ([0007]) while teaching examples of catalysts displaying volatile-free Pt content of 0.02, 0.03, and 0.04 % (Table 1).
Buchbinder teaches following the calcination treatment in air (i.e. an initial calcination in oxidizing gas), the catalyst can be subjected to propane dehydrogenation reaction conditions that include heating a temperatures from about 400 to about 900 °C in a hydrogen and propane atmosphere for residence times of 30 seconds to 5 minutes ([0030]-[0033]; [0047]). Performing a step that includes heating the catalyst at a temperature from about 400 to about 900 °C for 30 seconds to 5 minutes in a reducing environment of hydrogen and propane is equivalent to “reduction conditions” as described in at least claim 1 of the instant invention. This step taught by Buchbinder is therefore equivalent to a reducing treatment. Further, because Buchbinder teaches this step is performed after an initial oxidizing calcination treatment, it is equivalent to a “cycle calcination” and meets the required limitation of “wherein: at least one of the cycle calcination and the final calcination is carried out, …or, when carried out, the cycle calcination ends with the second reducing gas”
As stated above, Buchbinder teaches reducing conditions that include heating at temperatures from about 400 to about 900 °C in a hydrogen and propane atmosphere for residence times of 30 seconds to 5 minutes ([0030]-[0033]; [0047]) and oxidation conditions that include performing a calcination at a temperature from about 320 °C to about 600 °C for a period typically of about 0.5 to 10 hours in air (Abstract; [0007]-[0008]; [0028]). These conditions therefore meet the “reduction conditions used in the initial calcination” and the “oxidizing conditions used in the initial calcination” as claimed.
Regarding claim 2, Buchbinder teaches the first calcination is performed in air that contains O2 (Abstract; [0007]-[0008]; [0028]; [0039]).
Regarding claim 4, Buchbinder teaches the initial oxidizing calcination is generally performed at a temperature from about 320 °C to about 600 °C while the reducing calcination under propane and hydrogen is generally conducted from about 400 to about 900 °C ([0028]; [0032]). Buchbinder further teaches an example where the oxidizing calcination is performed at 524 °C while the reducing treatment is performed at 620 °C ([0041]; [0047]). This meets the limitation of performing the cycle reduction at a greater temperature than the initial oxidizing conditions.
Regarding claim 12, Buchbinder teaches the catalyst displays platinum levels below 0.0999 wt.% on a volatile-free basis ([0007]) while teaching examples of catalysts displaying volatile-free Pt content of 0.02, 0.03, and 0.04 % (Claim 1; Table 1).
Regarding claim 13, Buchbinder teaches the process of claim 1, where Buchbinder teaches operations consistent with an initial oxidation calcination followed by a cycle calcination under reducing conditions (Abstract; [0007]-[0008]; [0028]; [0030]-[0033]; [0047]).
Buchbinder further teaches following the second calcination under reducing conditions a regeneration cycle is performed where the catalyst is fed to a regenerator that is operated with O2 containing gas such as air at temperatures in the range of 600-800 °C and for durations of about 2 minutes ([0039]).
Buchbinder performing a further treatment after a second calcination, where the treatment is performed with O2 containing gas such as air at temperatures in the range of 600-800 °C and for durations of about 2 minutes, is consistent with “a final calcination” where the final calcination is described in claim 1 as being “heating the catalyst at a temperature in a range from 350°C to 850°C for a time period in a range from 30 seconds to 10 hours, and a calcined catalyst is obtained at the end of the cycle calcination or at the end of the final calcination.”
Regarding claim 14, Buchbinder teaches the oxidizing gas used in the initial calcination is performed in air ([0041]).
Regarding claim 15, Buchbinder teaches the reducing gas in the dehydrogenation reaction (i.e. cycle calcination) following the initial calcination is feed with H2/propane and maintained through the reaction ([0031]-[0032]; [0036]; [0047]).
Claim 10 is rejected under 35 U.S.C. 102(a)(1)/(a)(2) as being anticipated by Buchbinder et al. (US020220203340A1), with evidentiary support provided by Cocco et al. (Introduction to Fluidization, Ameri. Inst. Chem. Eng. 2014).
Regarding claim 10, Buchbinder anticipates the process of claim 1 and the claim further requires “the synthesized catalyst is in the form of particles that have a size and particle density that is consistent with a Geldart A definition of a fluidizable solid.”
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[AltContent: textbox (Figure 1. Reproduced Figure 4 from Cocco displaying the groups of Geldart regions for fluidizable solids.)] Buchbinder teaches the catalysts prepared are able to be sent to fluidized bed reactors and have a diameter of 20-200 microns and a bulk density of 0.7-1.1 g/cm3 (i.e. 700 to 1100 kg/m3) ([0014]-[0015]). While Buchbinder does not explicitly describe the particles as having “a size and particle density that is consistent with a Geldart A definition of a fluidizable solid,” Geldart A fluidizable solids, as evidenced by Cocco, display particles in the range from about 30 µm to 125 µm and particle densities on the order of 1500 kg/m3, consistent with the range presented in Figure 4 reproduced below (Pg. 23, left col.; Figure 4).
Accordingly, the fluidizable solid catalyst particles taught by Buchbinder are consistent with Geldart A fluidizable solids and meet the limitation required by the claim.
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 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.
Claim 3 and 6 are rejected under 35 U.S.C. 103 as being unpatentable over Buchbinder et al. (US020220203340A1).
Regarding claim 3, Buchbinder anticipates the process of claim 1 and Buchbinder further teaches the first calcination is an oxidizing calcination and is performed at a temperature from about 320 °C to about 600 °C for a period typically of about 0.5 to 10 hours in air (Abstract; [0007]-[0008]; [0028]). In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. MPEP 2144.05 (I). In the instant case, the range taught by Buchbinder (temperature from about 320 °C to about 600 °C for a period typically of about 0.5 (i.e. 30 mins) to 10 hours) overlaps with the claimed range (400 to 600 °C from 5 minutes to 1 hour). Therefore, the range in Buchbinder renders obvious the claimed range.
Regarding claim 6, Buchbinder anticipates the process of claim 1 and Buchbinder further teaches the catalyst is prepared from an aqueous mixture ([0041]; [0044]; [0045]). Buchbinder teaches the catalyst is dried at a temperature from about 100 °C to about 320 °C prior to calcination at about 320 to 600 °C ([0028]). The limitation “volatile compounds” was interpreted in view of the instant specification that describes “since the synthesized catalyst has not been subjected to a temperature of 350 °C or more, the synthesized catalyst can include one or more volatile compounds adsorbed thereon and/or one or more compounds that could form volatile compound(s) and desorb at higher temperatures such as when the synthesized catalyst is heated to a temperature of 350°C or more under an oxidizing atmosphere, a reduction atmosphere, or other atmosphere such as an inert atmosphere” [0025].
Accordingly, because the synthesized catalyst of Buchbinder is not subjected to a heating step prior to calcination that exceeds 350 °C and is synthesized with water, the calcination step of Buchbinder, which exceeds 350 °C would serve to remove adsorbed H2O and meet the limitation “wherein the one or more volatiles compounds comprise adsorbed H2O.”
Claims 5, 7-9 and 11 are rejected under 35 U.S.C. 103 as being unpatentable over Buchbinder et al. (US020220203340A1) in view of Rytter et al. (US6313063B1).
Regarding claim 5, Buchbinder anticipates the process of claim 1 and the claim further requires “a sum of the time periods in the reduction conditions used in the initial calcination, the optional cycle calcination, and the optional final calcination is greater than a sum of the time periods in the oxidizing conditions used in the initial calcination, the optional cycle calcination, and the optional final calcination.” Buchbinder effectively teaches an oxidation, reduction, oxidation cycle and is silent regarding the reduction cycle periods being greater than the sum of the oxidation cycles.
Rytter teaches a process of preparing a Pt supported dehydrogenation catalyst that is exposed to a reduction oxidation reduction (ROR) pretreatment that is carried out with a reduction of the catalyst with hydrogen, a subsequent oxidation in air, and a finally a second reduction in hydrogen where the pretreatment temperatures range from 500 to 700 °C (col. 5, lines 44-50). Rytter teaches the initial reduction is carried out for a period of 1 minute to 10 hours, usually for about 2 hours, the subsequent oxidation is carried out for a period of 1 minute to 10 hours, usually for about 2 hours and that the final reduction is carried out under similar conditions as the initial reduction (col. 5, lines 51-62). Accordingly, two reduction cycles at about 2 hours and one oxidation for about 2 hours would provide a longer reduction cycle than oxidation cycle, meeting the limitation required by the claim.
Advantageously, performing the ROR treatment taught by Rytter leads to improved performance in dehydrogenation reactions, where in propane dehydrogenation, the same level of propene selectivity is achieved as catalysts not treated while substantially increasing the propene yield (col. 11, lines 35-41).
Thus, prior to the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to perform reduction oxidation reduction treatment with longer reduction cycles than oxidization cycles in the process of Buchbinder in order to substantially increase the propene yields while achieving the same propane selectivity as catalysts not subjected to the treatment, as taught by Rytter.
Regarding claim 7, Buchbinder anticipates the process of claim 1 and the claim further requires limitations to which Buchbinder is silent.
Rytter teaches a process of preparing a Pt supported catalyst that is calcined at temperatures from about 700-1200 °C (Abstract; col. 4, line 1). Rytter teaches the catalyst comprises a group IV metal, including Sn, at a concentration from 0.05 to 7.0 percent by weight and a hydrotalcite-like compound (MgAI(OH)16CO3•4 H2O) as a support with a molar ratio of Mg to AI of about 2.5 to 6.0 (col. 2, lines 52-57; col. 3, lines 28-30; col. 4, lines 1-5). Rytter teaches the Mg/Al support is present at balance relative to the metals supported thereon, teaching a general range for the Mg/Al support of 83% to 99.85% (calculations shown below) and an example where the Mg(Al)O support is present at 98.6 wt.% (col. 4, lines 1-5; col. 8, lines 27-33). Magnesium (Mg) is a Group 2 element. From the Mg/Al ratio and Mg/Al support weight percent concentration, the Mg element concentration in the calcined support Mg(Al)O can be calculated as a range from 29.9 wt.% to 36.1wt.% (calculations shown below).
Regarding the limitation “all weight percent values are based on the non-volatile weight of the catalyst, the term “non-volatile weight” is described in the specification as the weight percentage in the catalyst following treatment at 900 °C (see at least [0025]). In this regard, Rytter teaches the catalyst can be calcined at temperatures ranging from 700-1200 °C (col. 3, lines 7-11; col. 3, lines 32-44). Accordingly, the weight percentages expressed in Rytter are consistent with the “non-volatile weight” in the instant invention.
In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. MPEP 2144.05 (I). In the instant case, the range taught by Rytter (Sn, at a concentration from 0.05 to 7.0 percent by weight; Mg element concentration from 29.9 wt.% to 36.1 wt.%) overlaps with the claimed range (catalyst comprises up to 10 wt.% promoter Sn; at least 0.5 wt.% of a Group 2 element). Therefore, the range in Rytter renders obvious the claimed range.
Calculation of Mg/Al general range:
Group VIII metal catalyst range of 0.05 to 5.0 percent by weight;
Group IVA metal is 0.05 to 7.0 percent;
Group IA 0.05 to 5 percent by weight;
Low end = Group VIII + Group IV + IA = 0.05 +0.05 + 0.05 = 0.15; 100-0.15 = 99.85% High End = Group VIII + Group IV + IA = 5 + 7 + 5 = 17; 100-17 = 83%
Calculation of Mg weight percent:
Mg molar mass = 24.305 g/mol
Al molar mass = 26.982 g/mol
O molar mass = 16 g/mol
Ratio of Mg content in Mg(Al)O = 24.305 / (24.305 + 26.982 + 16) = 0.361
Low end = 83% * 0.361 = 29.9 % Mg
High end = 99.85% * 0.361 (low end of Mg/Al ratio) = 36.1% Mg.
Advantageously, incorporating Pt and Sn on the mixed Mg(Al)O support according to Rytter provides a catalyst that displays very high activity in dehydrogenation reactions while displaying high specific surface area and improved stability towards sintering (col. 4, lines 17-25; col. 4, lines 37-44).
Thus, prior to the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to include a promoter including Sn and a group 2 element of Mg in the process of Buchbinder in order to provide a catalyst with very high activity in dehydrogenation reactions that displays high surface area and improves stability towards sintering, as taught by Rytter.
Regarding claim 8, Buchbinder anticipates the process of claim 1 and Buchbinder in view of Rytter teach the process of claim 7. The claim further requires limitations to which Buchbinder is silent.
Rytter teaches a process of preparing a Pt supported catalyst where the support is a hydrotalcite-like compound (MgAI(OH)16CO3•4 H2O) that is calcined to provide a mixed oxide support of Mg(Al)O (col. 2, lines 52-57; col. 3, lines 28-30).
Advantageously, the mixed oxide material consisting essentially of Mg and Al can be calcined at high temperatures of 700 to 1200 °C while still providing improved catalyst stability with acceptable reduction in surface area of the catalyst (col. 3, lines 8-24).
Thus, prior to the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to include Mg as a mixed oxide comprising Mg in the process of Buchbinder in order to provide a catalyst support that can be calcined at high temperatures while providing improved catalyst stability with acceptable reduction in surface area of the catalyst, as taught by Rytter.
Regarding claim 9, Buchbinder anticipates the process of claim 1 and Buchbinder in view of Rytter teach the process of claim 7. The claim further requires limitations to which Buchbinder is silent.
Rytter teaches a process of preparing a Pt supported catalyst where the support is a hydrotalcite-like compound (MgAI(OH)16CO3•4 H2O) that is calcined to provide a mixed oxide support of Mg(Al)O and the catalyst can further contain Sn (col. 2, lines 52-57; col. 3, lines 28-30; col. 4, lines 1-5).
Advantageously, incorporating Pt and Sn on the mixed Mg(Al)O support according to Rytter provides a catalyst that displays very high activity in dehydrogenation reactions while displaying high specific surface area and improved stability towards sintering (col. 4, lines 17-25; col. 4, lines 37-44).
Thus, prior to the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to include a promoter including Sn, a group 2 element of Mg, and a group XIII element Al in the process of Buchbinder in order to provide a catalyst with very high activity in dehydrogenation reactions that displays high surface area and improves stability towards sintering, as taught by Rytter.
Regarding claim 11, Buchbinder anticipates the process of claim 1 and Buchbinder further teaches performing dehydrogenation catalysis with the calcined catalyst and propane where the calcined catalyst displays a propylene selectivity of 92.0 % ([0031]-[0032]; Table 3). In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. MPEP 2144.05 (I). In the instant case, the value taught by Buchbinder (propylene selectivity of 92.0 %) overlaps with the claimed range (propylene selectivity of [Symbol font/0xB3] 90%). Therefore, the value in Buchbinder renders obvious the claimed range.
The claim further requires “a propylene yield of [Symbol font/0xB3] 48%” to which Buchbinder discloses a propane conversion and is silent regarding a propylene yield.
Rytter teaches the supported catalyst is used in the dehydrogenation of propane to propene (i.e. propylene) and displays propene yields of 51.6, 55.1, 55.5, and 55.1 % (Table 1).
Advantageously, the increased stability and surface area of the Mg(Al)O support taught by Rytter provides increases in the yield of propene (col. 11, lines 42-47).
Thus, prior to the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to provide a propene yield of 51.1-55.5% in the process of Buchbinder in order to utilize a catalyst with increased stability and surface area as taught by Rytter.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure. Lafyatis et al. (US20190002771A1); Lafyatis teaches a process of preparing a catalyst that includes multiple oxidation and reduction steps (Abstract; [0048]; [0050]). Matsui et al. (Sci. Tech. Adv. Mat. 2006, 7, 524–530); Matsui teaches the effect of reduction-oxidation treatment on the catalyst activity of tin oxide supported platinum catalysts (Title).
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/JORDAN W TAYLOR/Examiner, Art Unit 1738