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 .
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.
Claim(s) 1, 2, 4, 5, 7, 8, 11, 12 and 16-19 is/are rejected under 35 U.S.C. 103 as being unpatentable over García (US 2007/0227351 A1), and further in view of Gorzin (“Preparation of hierarchical HZSM-5 zeolites with combined desilication with NaAlO₂/tetrapropylammonium hydroxide and acid modification for converting methanol to propylene, 2007”)
With respect to claim 1, the claim requires “a method of making a hierarchically ordered crystalline microporous material, Garcia teaches the claimed method of making a hierarchically ordered crystalline microporous material (abstract).
Claim 1 requires "forming an aqueous suspension comprising: a parent crystalline microporous material." Garcia teaches suspending 0.79 g of parent H-Y zeolite in 50 mL of aqueous ammonium hydroxide (Garcia, para. [0337]).
Claim 1 further requires "an alkaline reagent." Garcia uses 0.37 M ammonium hydroxide in that suspension (Garcia, [0337]).
Claim 1 further requires "a supramolecular template." Garcia includes 0.55 g of cetyltrimethylammonium bromide (CTAB), a cationic surfactant that directs the MCM-41 mesostructure (Garcia, [0054]-[0055] and [0337]).
Claim 1 further requires "a silica source material, an alumina source material, or both." Garcia teaches that metal-oxide precursors, including silicates and aluminates, may be added to the pH-controlled synthesis medium to control final material properties (Garcia, [0067], [0233]). Garcia does not, however, demonstrate in Example 1 that an added source changes the product SAR by at least 0.5. Gorzin teaches contacting 30 g of a parent HZSM-5 with 300 mL of 0.2 M sodium aluminate solution; sodium aluminate is an external alumina source (Gorzin p. 41133, sec. 2.2.2).
Claim 1 further requires "hydrothermally treating the aqueous suspension to form the hierarchically ordered crystalline microporous material." Garcia hydrothermally treats the same parent-zeolite/ammonium-hydroxide/CTAB suspension at 150 degrees C for 10 hours and then recovers and calcines H-Y[MCM-41] (Garcia, [0337]).
Claim 1 further requires "the hierarchically ordered crystalline microporous material has a greater degree of mesoporosity than the parent crystalline microporous material." Garcia reports a 2.6 nm mesopore diameter for H-Y[MCM-41] and expressly compares the mesostructured products with their parent zeolites (Garcia, Table 1, [0340]; Figs. 6-8). Gorzin independently reports that pure-sodium-aluminate treatment increases external surface area from 30.1 to 70.6 m2/g before acid washing and to 122.9 m2/g after acid washing; mesopore volume after acid washing is 0.104 cm3/g versus 0.065 cm3/g for the parent (Gorzin, Table 1 and sec. 3.1.3, pp. 41135-41136).
Claim 1 further requires "the hierarchically ordered crystalline microporous material has a silica-to-alumina ratio (SAR) that is at least 0.5 different than the parent crystalline microporous material." Garcia does not teach "the hierarchically ordered crystalline microporous material has a silica-to-alumina ratio (SAR) that is at least 0.5 different than the parent crystalline microporous material." However, Gorzin reports a parent Si/Al ratio of 183 and a Si/Al ratio of 44 after pure-sodium-aluminate treatment, or 155 after the following acid wash; either reported product differs from the parent by much more than 0.5 (Gorzin, Table 1, p. 41135).
It would have been obvious to a person having ordinary skill in the art to add Gorzin's sodium aluminate to Garcia's aqueous parent-zeolite/base/surfactant suspension before hydrothermal treatment. Garcia teaches aluminates as suitable metal-oxide precursors that may be added to control the properties of the final material (Garcia, [0067], [0233], and [0239]). Gorzin provides the known reason and predictable result for that selection: sodium aluminate changes the Si/Al ratio and develops mesoporosity in a parent ZSM-5 during alkaline treatment (Gorzin, sec. 3.1.3 and Table 1, pp. 41135-41136).
Regarding claim 2, the method of claim 1 has been discussed above.
Claim 2 further requires “wherein the aqueous suspension comprises the alumina source material, and the alumina source material is chosen from aluminates, alumina, aluminum colloids, boehmites, pseudo-boehmites, aluminum hydroxides, aluminum salts, aluminum alkoxides, aluminum wire, alumina gels, zeolites, or combinations thereof. “ Garcia does not explicitly teach an alumina source material. However, Gorzin teaches use of sodium aluminate, NaAlO₂ (Gorzin, abstract).
Regarding claim 4, the method of claim 1 has been discussed above.
Claim 4 further requires “wherein the aqueous suspension has a weight ratio of the parent crystalline microporous material to the silica source material, the alumina source material, or both of from 100:1 to 1:1." Gorzin uses 30 g parent HZSM-5 with 300 mL of 0.2 M NaAlO2 solution (Gorzin, sec. 2.2.2, p. 41133). The solution contains 0.060 mol NaAlO2, or about 4.92 g based on a molecular weight of 81.97 g/mol, giving a parent-to-source weight ratio of about 6.1:1, within 100:1 to 1:1.
Regarding claim 5, the method of claim 1 has been discussed above
Claim 5 further requires "wherein the hierarchically ordered crystalline microporous material has a bimodal mesopore size distribution comprising a first peak and a second peak." Gorzin reports that the HZSM-5 sample treated with pure NaAlO2 has a narrow pore-size peak at about 3 nm and a broad peak at about 9 nm (Gorzin, Fig. 3(b) and sec. 3.1.3, pp. 41135-41136). Those two reported mesopore peaks satisfy the unrestricted first-peak and second-peak requirement of claim 5.
Regarding claim 7, Garcia teaches treating parent ZSM-5 with HF, then adds CTAB, raises pH with NH₄OH, and hydrothermally treats the suspension. Fluoride is therefore an ionic co-solute separate from the bromide counterion associated with CTAB (Garcia, Example 3).
Regarding claim 8, García teaches that the ionic co-solute is fluoride (Garcia, Example 3).
Regarding claim 11, García teaches use of CTAB, a cationic quaternary-ammonium surfactant (Garcia 183, Examples 1-3).
Regarding claim 12, García teaches use of CTAB contains a terminal C16 cetyl group, within the claimed C6–C24 range (Garcia, Examples 1-3).
Regarding claim 16, García teaches using 37 M of NH₄OH. That corresponds approximately to 1.3 wt% NH₃ equivalent and falls within 0.1–5 wt%; NH₄OH range that is claimed (Garcia, Examples 1-3).
Regarding claim 17, García teaches calcining the hydrothermally treated product at approximately 500–600 °C, specifically 550 °C in Example 1 (Garcia, Examples 1-3).
Regarding claim 18, García teaches use of parent H-Y, H-MOR, and ZSM-5 zeolites (Garcia, Examples 1-3).
Regarding claim 19, García teaches H Y supplies FAU, H MOR supplies MOR, and ZSM 5 supplies MFI (Garcia, Examples 1-3).
Claim(s) 3, 9, 10, 13, 15 is/are rejected under 35 U.S.C. 103 as being unpatentable over García (US 2007/0227351 A1), and Gorzin (“Preparation of hierarchical HZSM-5 zeolites with combined desilication with NaAlO₂/tetrapropylammonium hydroxide and acid modification for converting methanol to propylene, 2007”) as applied to claim 1 above, and further in view of Wang “Synthesis of mesoporous ZSM-5 catalysts using different mesogenous templates and their application in methanol conversion for enhanced catalyst lifespan,” 2014).
With respect to claim 3, the method of claim 1 has been discussed above.
Claim 3 further requires “wherein the aqueous suspension comprises the silica source material, and the silica source material is chosen from sodium silicate, fumed silica, precipitated silica, colloidal silica, silica gels, zeolites, dealuminated zeolites, rice husk, silicon hydroxides, silicon alkoxides, or combinations thereof.” Garcia and Gorzin do not teach "wherein the aqueous suspension comprises the silica source material, and the silica source material is chosen from sodium silicate, fumed silica, precipitated silica, colloidal silica, silica gels, zeolites, dealuminated zeolites, rice husk, silicon hydroxides, silicon alkoxides, or combinations thereof" in Garcia's hydrothermal suspension. However, Wang teaches use of 8.57 g of tetraethyl orthosilicate (TEOS) in an aqueous NaAlO2/NaOH/TPABr/TPOAC synthesis gel hydrothermally treated at 150 degrees C (Wang, secs. 2.1-2.2, p. 21481). TEOS is a silicon alkoxide within the claimed group.
It would have been obvious to a person having ordinary skill in the art before the effective filing date of the invention to have, by the method of Garcia, silica source material, and the silica source material chose from the group above as Wang teaches Wang confirms that TEOS is compatible with aqueous alkaline, alumina-containing, surfactant-containing hydrothermal ZSM-5 synthesis at the same 150 degrees C temperature used by Garcia (Wang, sec. 2.2, p. 21481). TEOS would predictably perform its conventional silica-source function.
Regarding claim 9, the method of claim 1 has been discussed above.
Claim 9 further requires “wherein the supramolecular template is a surfactant having one or more dimensions larger than dimensions of micropores of the parent crystalline microporous material.” Garcia does not explicitly teach the limitations claimed. However, Wang teaches dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (TPOAC) as a mesogenous surfactant for ZSM-5; its disclosed structure contains a C18 chain joined to a quaternary-ammonium/trimethoxysilyl-propyl group (Wang, Abstract, p. 21479; sec. 2.1, p. 21481)
It would have been obvious to substitute or supplement Garcia's CTAB with Wang's TPOAC because Wang uses TPOAC as a supramolecular template to generate mesopores in ZSM-5 and as part of the silica source, while improving mesopore-micropore interconnectivity (Wang, Abstract, p. 21479; Conclusion, p. 21489)
Regarding claim 10, the method of claim 9 has been discussed above.
Claim 10 further requires “wherein the supramolecular template comprises least one moiety as a head group or a tail group, chosen from organosilanes, hydroxysilyls, alkoxysilyls, aromatics, branched alkyls, sulfonates, carboxylates, phosphates, and combinations thereof.”
With respect to claim 13, the method of claim 1 has been discussed above.
Claim 13 further requires “wherein the supramolecular template comprises two quaternary ammonium groups wherein an alkyl group bridging the quaternary ammonium groups comprises 1-10 carbon atoms.”
Regarding claim 14, the method of claim 1 has been discussed above.
Claim 14 further requires, “wherein the supramolecular template comprises at least one quaternary ammonium group, and at least one head group moiety chosen from organosilanes, hydroxysilyls, alkoxysilyls, aromatics, branched alkyls, sulfonates, carboxylates, phosphates and combinations comprising one of the foregoing moieties.” Wang's TPOAC structure contains a quaternary-ammonium group and a trimethoxysilyl/alkoxysilyl organosilane head functionality (Wang, Abstract, p. 21479; sec. 2.1, p. 21481). For the reasons stated for claim 9, substituting TPOAC for CTAB would have been an obvious use of a known mesogenous template for its established function.
Regarding claim 15, the method of claim 1 has been discussed above,
Claim 15 further requires, wherein the supramolecular template comprises dimethyloctadecyl(3-trimethoxysilyl-propyl)-ammonium or a derivative of dimethyloctadecyl(3- trimethoxysilyl-propyl)-ammonium. Wang teaches use of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, TPOAC, having the structure [(CH3O)3SiC3H6N(CH3)2C18H37]Cl (Wang, Abstract, p. 21479; secs. 2.1-2.2, p. 21481).
Regarding claim 16, modified Garcia teaches the subject matter of claim 1 as discussed above.
Claim 16 further requires "wherein the alkaline reagent is provided at a concentration in the aqueous suspension of about 0.1 wt. % to 5 wt. % and is chosen from ammonia, ammonium hydroxide and urea." Garcia teaches use of 0.37 M ammonium hydroxide (Garcia, para. [0337]). That concentration corresponds to about 0.63 wt.% on an NH3 basis or about 1.30 wt.% on an NH4OH-equivalent basis for a dilute aqueous solution; either convention falls within about 0.1-5 wt.%.
Regarding claim 17, modified Garcia teaches the subject matter of claim 1 as discussed above. Claim 17 further requires "further comprising calcining the hierarchically ordered mesostructures." Garcia teaches filtering and washing the hydrothermal product, ramps it under nitrogen to 550 degrees C, and then calcines it in air for four hours (Garcia, para. [0337]). Garcia further teaches calcination to remove surfactant from the final material (Garcia, para. [0232]).
Regarding claim 18, modified Garcia teaches the subject matter of claim 1 as discussed above. Claim 18 further requires "wherein the parent crystalline microporous material comprises a zeolite or zeolite-type material." Garcia teaches use of parent H-Y, H-MOR, and NH4-ZSM-5 zeolites in Examples 1-3 (Garcia, [0337], [0339], and [0340]).
Regarding claim 19, modified Garcia teaches the subject matter of claim 1 as discussed above. Claim 19 further requires "wherein the parent crystalline microporous material is a zeolite having a framework chosen from AEI, BEA, CHA, FAU, MFI, MOR, LTL, LTA and MWW." Garcia teaches faujasite as FAU, mordenite as MOR, and ZSM-5 as MFI (Garcia, para. [0016]) and uses H-Y, H-MOR, and ZSM-5 parents in Examples 1-3 (Garcia, [0337], [0339], and [0340]).
Claim(s) 6 is/are rejected under 35 U.S.C. 103 as being unpatentable over García (US 2007/0227351 A1), and Gorzin (“Preparation of hierarchical HZSM-5 zeolites with combined desilication with NaAlO₂/tetrapropylammonium hydroxide and acid modification for converting methanol to propylene, 2007”) as applied to claim 1 above, and further in view of Song (“Synthesis and Characterization of Hierarchical ZSM-5 Zeolites with Outstanding Mesoporosity and Excellent
Catalytic Properties,” 2018).
With respect to claim 6, the method of claim 1 has been discussed above.
Claim 6 further requires "wherein the first peak is from 2 nm to 4 nm and the second peak is from 4 nm to 6 nm." Garcia and Gorzin do not teach "wherein the first peak is from 2 nm to 4 nm and the second peak is from 4 nm to 6 nm" because Gorzin's second peak is about 9 nm (Gorzin, Fig. 3(b) and sec. 3.1.3, pp. 41135-41136). However, Song's DFT mesopore-size distribution for hierarchical ZSM-5 sample MZ-2 shows a lower-diameter local peak in the approximately 2-3 nm region and a pronounced second peak at approximately 5 nm (Song 4,). The first depicted peak falls within 2-4 nm and the second depicted peak falls within 4-6 nm.
It would have been obvious to a person having ordinary skill in the art before the effective filing date of the invention to have, by the method of Garcia, the limitations claimed above as Song teaches that soft-template chemistry makes hierarchical-zeolite pore parameters adjustable and multiple and demonstrates that different template amounts alter the DFT mesopore-size distributions (Song 2-3, Introduction, Fig. 1(d), p. 4).
Claim(s) 20 is/are rejected under 35 U.S.C. 103 as being unpatentable over García (US 2007/0227351 A1), and Gorzin (“Preparation of hierarchical HZSM-5 zeolites with combined desilication with NaAlO₂/tetrapropylammonium hydroxide and acid modification for converting methanol to propylene, 2007”) as applied to claim 1 above, and further in view of Yoo (“Synthesis of mesoporous ZSM-5 zeolites through desilication and re-assembly processes," Microporous and Mesoporous Materials,” 2012)
With respect to claim 20, the method of claim 1 has been discussed above, wherein the hydrothermally treating of the aqueous suspension is under conditions effective to form oligomeric units of the parent crystalline microporous material, form shaped micelles of the supramolecular template, and induce assembly of the oligomeric units around the shaped micelles. Garcia teaches partially dissolving parent zeolite in a controlled-pH medium, adding CTAB, and hydrothermally treating the mixture to form a mesostructured zeolitic material (Garcia, [0142]-[0146] and [0337]-[0340]). Garcia does not expressly teach "wherein the hydrothermally treating of the aqueous suspension is under conditions effective to form oligomeric units of the parent crystalline microporous material, form shaped micelles of the supramolecular template, and induce assembly of the oligomeric units around the shaped micelles." However, Yoo teaches alkaline desilication and surfactant-induced reassembly of dissolved silicates, aluminosilicates, and zeolite crystal fragments originating from parent ZSM-5; Yoo attributes the approximately 3 nm mesopores to surfactant-induced micelle formation and states that the dissolved species reassemble by surfactant-induced micellization (Yoo, Abstract, p. 147).
It would have been obvious to operate Garcia's hydrothermal treatment to promote Yoo's known dissolution-micellization-reassembly mechanism because both references treat parent ZSM-5 in aqueous alkaline surfactant media to introduce secondary mesoporosity while retaining zeolitic character (Garcia, [0142]-[0146]; Yoo, Abstract, p. 147).
Conclusion
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/STARFARI TESHAWN MCCLAIN/ Examiner, Art Unit 1736
/DANIEL C. MCCRACKEN/ Primary Examiner, Art Unit 1736
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