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.
Claims 1-3, 5, 10 are rejected under 35 U.S.C. 103 as being unpatentable over Canos et al. (US 10,676,367 B2) in view of Chen et al. (CN 108862307).
Regarding claim 1, Canos et al. teaches the synthesis of a CHA material which comprises of the steps of adding a copper source, a polyamine, a silicon source (Y tetravalent element), an aluminum source (X trivalent element), an alkaline cation source, an organic structure determining agent, CHA zeolite, and water (claim 1; column 7, line 25- column 8, line 67). The mixture remains under agitation for the time required to evaporate the excess water and the desired gel concentration is achieved (corresponding to subjecting the gel to hydrothermal reaction) (column 7, lines 36-40; column 8, lines 12-14, 54-56). The gel is transferred to an autoclave and crystallized, the solid product is rinsed and filtered, and then calcined (corresponding to separating slurry, drying, and calcining) (column 7 lines 42-45; column 8, lines 16-20, 57-61). Canos et al. does not teach the molecular sieve as MOR, CHA/MOR composite or CHA-MOR mixed molecular sieve.
However, Chen et al. teaches an SSZ-13 (CHA)/MOR eutectic molecular sieve. The eutectic molecular sieve refers to a co-crystallized product formed from two or more molecular sieves, the molecular sieves often have properties that are different from the individual molecular sieves or corresponding mechanical mixtures (paragraph [0007]). The SSZ-13/MOR eutectic molecular sieve has advantages such as ordered pore structure, good hydrothermal stability, adjustable surface acid center, and adjustable ratio of SSZ-13 to MOR, which results in a wide range of application properties (paragraph [0007]).
Therefore, it would have been prima facia obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have combined the teaching of Canos et al. with Chen et al. and to use the SSZ-13/MOR sieve taught as the molecular sieve in the composition taught by Canos et al. for the purpose as described by Chen et al. to optimize the molecular sieve structure for the desired application.
Regarding claim 2, Canos et al. teaches the alkali cation selected from Na and K (column 4, lines 64-67), and NaOH was specifically used (column 7, line 34; column 8, lines 8, 49), silicon source can be selected from silicon oxide, colloidal silica, fumed silica (column 3, lines 65-67), the aluminum source can be selected from any aluminum salt, any hydrated aluminum oxide, any aluminum alkoxide (column 4, lines 10-14). The ratios of the alkali source: silicon source: aluminum source: structure directing agent: active metal complex is (0.01-0.8):(1):(0.01-0.07):(0.1-0.6):(0.001-1) (column 3, lines 33-60) overlapping ranges are prima facia obvious. Additionally, it is possible to add CHA crystals to the synthesis mixture, which act as seeds facilitating the synthesis in a quantity of up to 25% by weight with respect to the total quantity of oxides (column 5, lines 24-28). This would result in a range of 0-0.04:1 in relation alkali source: silicon source: aluminum source: structure directing agent: active metal complex of (0.8):(1):(0.07):(0.6):(1) or a range of 0-0.17:1 in relation to alkali source: silicon source: aluminum source: structure directing agent: active metal complex is (0.01):(1):(0.01):(0.1):(0.001). Overlapping ranges are prima facia obvious.
Regarding claim 3, Canos et al. teaches any copper source can be used, and preferably the source is selected from a nitrate, sulfate, and oxalate salts (column 4, lines 55-58), and any polyamine capable of forming a complex with copper atoms can be used, preferably the polyamine is tetraethylenepentamine (column 5, lines 1-10).
Regarding claim 5, Canos et al. teaches NaOH (column 7, line 34; column 8, lines 8, 49), aluminum hydroxide (column 4, lines 10-14), and colloidal silica (column 3, lines 65-67). For the organic structure directing agent, Canos et al. teaches the novel use of the more economical tetraethylammonium (column 3, lines 17-20), in comparison to N,N,N-trimethyl-1-adamantylammonium hydroxide and benzyltrimethylammonium hydroxide that is known in the art as the preferred organic structure directing agent for a CHA zeolite (column 2, lines 38-67).
However, Chen et al. teaches the use of N,N,N-trimethyl-1-adamantylammonium hydroxide as the structure directing agent for the synthesis of the SSZ-13/MOR molecular sieve (paragraph [0031]).
Therefore, it would have been prima facia obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have combined the teaching of Canos et al. with Chen et al. and use N,N,N-trimethyl-1-adamantylammonium hydroxide as the organic structure directing agent in the composition taught by Canos et al. An express suggestion to substitute one equivalent component or process for another is not necessary to render such substitution obvious. In re Fout, 675 F.2d 297, 213 USPQ 532 (CCPA 1982).
Regarding claim 10, Canos et al. teaches the synthesis of a CHA material which comprises of the steps of adding a copper source, a polyamine, a silicon source (Y tetravalent element), an aluminum source (X trivalent element), an alkaline cation source, an organic structure determining agent, CHA zeolite, and water (claim 1; columns 8-9). The mixture remains under agitation for the time required to evaporate the excess water and the desired gel concentration is achieved (corresponding to subjecting the gel to hydrothermal reaction) (column 7, lines 36-40; column 8, lines 12-14, 54-56). The gel is transferred to an autoclave and crystallized, the solid product is rinsed and filtered, and then calcined (corresponding to separating slurry, drying, and calcining) (column 7 lines 42-45; column 8, lines 16-20, 57-61). Canos et al. does not teach the molecular sieve as having an intergrowth structure of an active metal containing M-CHA and M-MOR molecular sieve.
However, Chen et al. teaches an SSZ-13 (CHA)/MOR eutectic molecular sieve. The eutectic molecular sieve refers to a co-crystallized product formed from two or more molecular sieves, the molecular sieves often have properties that are different from the individual molecular sieves or corresponding mechanical mixtures (paragraph [0007]). The SSZ-13/MOR eutectic molecular sieve has advantages such as ordered pore structure, good hydrothermal stability, adjustable surface acid center, and adjustable ratio of SSZ-13 to MOR, which results in a wide range of application properties (paragraph [0007]). The SSZ-13/MOR eutectic molecular sieve was synthesized by adding an inorganic base, water, templating agent, an aluminum source, and a silicon source together, mixing and crystallizing, washing, separating, drying, and calcining (paragraph [0010]).
Therefore, it would have been prima facia obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have combined the teaching of Canos et al. with Chen et al. and to use the SSZ-13/MOR sieve taught as the molecular sieve in the composition that contains an active metal as taught by Canos et al. for the purpose as described by Chen et al. to optimize the molecular sieve structure for the desired application.
Claim 4 is rejected under 35 U.S.C. 103 as being unpatentable over Canos et al. (US 10,676,367 B2) and Chen et al. (CN 108862307) as applied to claims 1-3, 5, 10 above, and further in view of Ramakrishna et al. (US 20190284115 A1).
Regarding claim 4, Canos et al. does not teach adding at least of the MOR sieve, CHA/MOR composite molecular sieve, or CHA-MOR mixed molecular sieve into an alkaline solution.
However, Ramakrishna et al. teaches desilicating an acid mordenite in a basic solution, which produces a lesser Si to Al ratio and a more mesoporous zeolite (paragraphs [0048] and [0055]). The mordenite is treated in the basic solution for 15 mins to 2 hours at a temperature between 40-95 °C (paragraph [0055]). Overlapping ranges are prima facia obvious.
Therefore, it would have been prima facia obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have combined the teaching of Canos et al. with Ramakrishna et al. and to use additional step of desilicating the mordenite in the composition taught by Canos et al. for the purpose as described by Ramakrishna et al. to optimize the molecular sieve by having a lesser Si to Al ratio and a more mesoporous zeolite.
Claim 6 is rejected under 35 U.S.C. 103 as being unpatentable over Canos et al. (US 10,676,367 B2) and Chen et al. (CN 108862307) as applied to claims 1-3, 5, 10 above, and further in view of Qiao et al. (CN 108014842 A) (reference is made to the machine translation).
Regarding claim 6, Canos et al. teaches an agitation step for 2 hours, (column 7, line 29) and a crystallization process between 130-175 °C between 2 and 15 days (column 5, lines 11-20). Canos et al. does not teach a temperature for the agitation step.
However, Qiao et al. teaches the synthesis of a Cu-SSZ-13/ZSM-5 composite molecular sieve, in which aluminum sulfate, water, a copper complex (the copper salt and tetraethylenepentamine are premixed), lithium hydroxide, silica sol and diethylamine are stirred for 2 hours, and then subjected to hydrothermal treatment at 80 °C for 11.8 h. The resulting product was then crystallized at 160 °C for 100 h (paragraph [0048]).
Therefore, it would have been prima facia obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have combined the teaching of Canos et al. with Qiao et al. and to use additional step of heating and stirring before crystallization in the composition taught by Canos et al. Where 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)). See MPEP 2144.05.
Claims 7-9 are rejected under 35 U.S.C. 103 as being unpatentable over Canos et al. (US 10,676,367 B2) and Chen et al. (CN 108862307) as applied to claims 1-3, 5, 10 above, and further in view of Li et al. (CN 112158857 B).
Regarding claim 7-9, Canos et al. teaches crystallizing the gel (corresponding to composite molecular sieve), filtering, rinsing with water, drying at 100 °C, and calcining (column 7, lines 42-46). Canos et al. does not teach an active metal content regulator.
However, Li et al. teaches a CHA-OFF-ERI molecular sieve synthesis, where after the gel is prepared (corresponding to composite molecular sieve), the resulting product (sieve) was filtered and washed with water. The resulting product (corresponding to composite molecular sieve) was stirred with an aqueous solution of an ammonium salt and stirred at 60-80 °C for 4-12 hours. Overlapping ranges are prima facia obvious. The solid was separated, washed with water, dried and calcined (paragraphs [0014]-[0018]). The ammonium salt is at least one of ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, and ammonium acetate (paragraph [0032]). Li et al. teaches an “ammonium exchange” since the molecular sieve cannot not be used as a SCR (selective catalytic reduction) catalyst support since it contains K and Na. The ammonium salt exchanges with the alkali metals in the molecular sieve to obtain an ammonium type molecular sieve precursor. After drying and calcination an H-type molecular sieve is obtained, which can be used to prepare molecular sieve SCR catalysts (paragraph [0033]).
Therefore, it would have been prima facia obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have combined the teaching of Canos et al. with Li et al. and to use additional step of adding the ammonium salt in the composition taught by Canos et al. for the purpose as described by Li et al. to optimize the molecular sieve structure for further use as a SCR catalyst.
Conclusion
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/H.E.K./ Examiner, Art Unit 1742
/JEFFREY M WOLLSCHLAGER/ Primary Examiner, Art Unit 1742
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