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
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 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.
Claims 1-2, 4-5, 8, 18, 19, and 21 are rejected under 35 U.S.C. 103 as being unpatentable over Elliott (US4164551), and further in view of Willis (US3898319).
Regarding claim 1, Elliott discloses a type Y zeolite synthesis by creating a zeolite precursor
solution with sodium silicate, aluminum sulfate, water (solvent), and additional components (col 3, lines
41-46). The molar ratio of the solution is 1 Al2O3:3.1 Na2O:9.1 SiO2: 143 H2O (col 3, line 57). The
solution is heated to 212 °F (100 °C), the type Y zeolite product is recovered by filtration, and the mother
liquor is obtained (col 3, lines 58-65). The weight percent of SiO2 in the mother liquor is 8.8% and Al2O3
is <0.1% (col 3, lines 65-67). We will convert these mass% to moles and get a molar ratio.
Mol SiO2 = 8.8 g/60.1 g/mol = 0.15 mol
Mol Al2O3 = 0.05 g/101.96 g/mol = 4.9*10^-4 mol
Al/SiO2 molar ratio = 4.9*10^-4/0.15 = 0.0033
The molar ratio of the precursor solution is 1 molAl2O3/9.1 mol SiO2 = 0.11. Therefore, we see
that the mother liquor has a different alumina to silica molar ratio.
The mother liquor filtrate is combined with aluminum sulfate to produce a silica alumina
hydrogel (col 4, lines 3-6). The hydrogel is mixed with other components to make a second zeolite
precursor solution (col 4, lines 12-19). The molar ratio of the second solution is 1 Al2O3:3.3 Na2O:9.1
SiO2: 142 H2O (col 4, line 22). Therefore, we see that the alumina to silica molar ratio is the same for the
first and second solutions. Finally, the second solution is heated to 100 °C to form type Y zeolite (col 4,
line 19-20).
Elliott discloses the molar ratio of the second solution is 1 Al2O3:3.3 Na2O:9.1SiO2: 142 H2O (col 4, line 22). This is outside the amended Na2O:Al2O3 molar ratio range of 8:1 to 12:1.
Willis discloses a hydrothermal process that utilizes solid reactive silica derived from waste liquors from previous zeolite synthesis for preparing zeolite Y (col 1, lines 2-6). The SiO2 concentration of spent liquors from a previous zeolite Y reaction mixture is adjusted and then contacted with carbon dioxide so that amorphous solid silica is precipitated (col 2, lines 5-14). The precipitated silica is used to form a reaction mixture having a composition of mole ratios expressed in one of the ranges of Table I (col 2, lines 15-18). The reaction mixture is then crystallized to form zeolite Y (col 2, lines 20-22). The reaction mixture is the same as the present inventions’ recycled precursor solution because both are subsequently crystallized to create zeolite-Y particles.
There are four separate ranges in Table I. Looking at range 3 we can pick ratios of Na2O/SiO2 = 0.65, SiO2/Al2O3 = 14, and H2O/Na2O = 30. We can create a system of equations to find the molar composition of a reaction mixture with these ratios. The molar ratio of Na2O:Al2O3 is 9.1 which satisfies the amended range of claim 1.
Na2O = 0.65*SiO2
Al2O3 = SiO2/14
H2O = 30*Na2O = 30*0.65*SiO2 = 19.5*SiO2
Na2O:SiO2:Al2O3:H2O = 0.65SiO2:SiO2:(1/14)SiO2:19.5SiO-2
Divide by SiO2
Na2O:SiO2:Al2O3:H2O = 0.65:1:1/14:19.5
Multiply by 14
Na2O:SiO2:Al2O3:H2O = 9.1:14:1:273
Therefore, it would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention, to adjust the zeolite precursor solution and recycled zeolite precursor solution to have a Na2O:Al2O molar ratio from 8:1 to 12:1 because such molar compositions of a zeolite-Y precursor are known and conventional in the art. Willis discloses the zeolite-Y is made with spent liquors from a reaction mixture used to prepare zeolite Y (col 2, lines 5-7) which is the same approach as the Elliott reference. As a result, one having ordinary skill in the art would have had a reasonable expectation of success to synthesize zeolite-Y particles from recycled mother liquor having a molar composition of Na2O:SiO2:Al2O3:H2O in a ratio of 9.1:14:1:273.
Regarding claim 2, Elliott discloses the molar ratio of the second solution 1 Al2O3:3.3 Na2O:9.1 SiO2: 142 H2O (col 4, line 22) and the first solution 1 Al2O3:3.1 Na2O:9.1 SiO2: 143 H2O (col 3, line 57). We see that both solutions have the same alumina to silica molar ratio. The precursor and recycled precursor composition of Elliott could be substituted with Willis to satisfy the Na2O:Al2O3 ratio of claim 1.
Regarding claim 4, Elliott discloses an alumina source in the first solution of aluminum sulfate Al2(SO4)3 and sodium aluminate NaAlO2 (col 3, lines 45-50).
Regarding claim 5, Elliott discloses a silica source in the first solution of sodium silicate Na2SiO3 (col 3, lines 43-44).
Regarding claim 8, Elliott does not disclose a structure directing agent in the first solution.
Regarding claim 18, Elliott discloses a surface area of 868 m2/g (col 4, lines 26-27).
Regarding claim 19, Elliott discloses a crystallinity of 101% (col 4, lines 25-26).
Regarding claim 21, Elliott discloses the molar ratio of the second solution is 1 Al2O3:3.3 Na2O:9.1SiO2: 142 H2O (col 4, line 22). This is outside the claimed range of 8-12 Na2O:1 Al2O3:8-16 SiO2:200-400 H2O.
Willis discloses a hydrothermal process that utilizes solid reactive silica derived from waste liquors from previous zeolite synthesis for preparing zeolite Y (col 1, lines 2-6). The SiO2 concentration of spent liquors from a previous zeolite Y reaction mixture is adjusted and then contacted with carbon dioxide so that amorphous solid silica is precipitated (col 2, lines 5-14). The precipitated silica is used to form a reaction mixture having a composition of mole ratios expressed in one of the ranges of Table I (col 2, lines 15-18). The reaction mixture is then crystallized to form zeolite Y (col 2, lines 20-22). The reaction mixture is the same as the present inventions’ recycled precursor solution because both are subsequently crystallized to create zeolite-Y particles.
There are four separate ranges in Table I. Looking at range 3 we can pick ratios of Na2O/SiO2 = 0.65, SiO2/Al2O3 = 14, and H2O/Na2O = 30. We can create a system of equations to find the molar composition of a reaction mixture with these ratios. The molar ratio of Na2O:SiO2:Al2O3:H2O is 9.1:14:1:273 which satisfies the amended range of claim 1.
Na2O = 0.65*SiO2
Al2O3 = SiO2/14
H2O = 30*Na2O = 30*0.65*SiO2 = 19.5*SiO2
Na2O:SiO2:Al2O3:H2O = 0.65SiO2:SiO2:(1/14)SiO2:19.5SiO-2
Divide by SiO2
Na2O:SiO2:Al2O3:H2O = 0.65:1:1/14:19.5
Multiply by 14
Na2O:SiO2:Al2O3:H2O = 9.1:14:1:273
Therefore, it would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention, to adjust the zeolite precursor solution and recycled zeolite precursor solution to have a Na2O:Al2O3:SiO2:H2O molar ratio of 8-12:1:8-16:200-400 because such molar compositions of a zeolite-Y precursor are known and conventional in the art. Willis discloses the zeolite-Y is made with spent liquors from a reaction mixture used to prepare zeolite Y (col 2, lines 5-7) which is the same approach as the Elliott reference. As a result, one having ordinary skill in the art would have had a reasonable expectation of success to synthesize zeolite-Y particles from recycled mother liquor having a molar composition of Na2O:SiO2:Al2O3:H2O in a ratio of 9.1:14:1:273.
Claims 3, 6, 7, and 9-13 are rejected under 35 U.S.C. 103 as being unpatentable over Elliott in view of Willis as applied to claims 1-2, 4, 5, 8, and 18, 19, and 21 above, and further in view of Dwyer et al. (US4818509).
Regarding claim 3, modified Elliott discloses combining the mother liquor filtrate with aluminum sulfate to produce a silica alumina hydrogel and using it to make more type zeolite Y (col 4, lines 3-6). Modified Elliott does not disclose agitating the recycled mixture containing the hydrogel for at least 10 hours.
Dwyer et al. discloses a multiple stage crystallization process for making zeolites. The slurry
starts in an auxiliary low-temperature induction tank (81a) before it moves to the first crystallization
step (154a) (col 13, line 26-32). The auxiliary tank used for induction holds the precursor slurry for 10
hours (col 13 line 26-28) and has high shear agitation capability (col 7, line 37-39).
Therefore, it would have been obvious to one having skill in the art before the effective filing date of the claimed invention, to further modify Elliott by combining the agitation and holding time of Dwyer et al. with Elliott’s process in order to prevent the formation of continuous gel and the setting of gel which would immobilize the crystallizer contents (col 6, line 19-23).
Regarding claim 6, modified Elliott discloses forming a first solution which contains a basic compound sodium hydroxide, a silica source sodium silicate, an alumina source sodium aluminate, and a solvent that is water (col 3, lines 43-54). This solution is agitated (col 3, line 58), but Elliott fails to disclose how long agitation goes on for.
Dwyer et al. discloses a multiple stage crystallization process for making zeolites. The slurry
starts in an auxiliary low-temperature induction tank (81a) before it moves to the first crystallization
step (154a) (col 13, line 26-32). The auxiliary tank used for induction holds the precursor slurry for 10 hours (col 13 line 26-28) and has high shear agitation capability (col 7, line 37-39).
Therefore, it would have been obvious to one having skill in the art before the effective filing date of the claimed invention, to further modify Elliott by combining the holding time of Dwyer et al. with Elliott’s process in order to prevent the formation of continuous gel and the setting of gel which would immobilize the crystallizer contents (col 6, line 19-23).
Regarding claim 7, modified Elliott discloses a solvent in the first solution that is water (col 3, line 44-45).
Regarding claim 9, modified Elliott discloses a heating process of 100 °C for 16 hours (col 3, lines 58-59). Modified Elliott does not disclose increasing the first temperature of 100 °C to a second temperature and holding it for another period of time.
Dwyer et al. discloses a multiple stage crystallization process for making zeolites. The slurry
starts in an auxiliary low-temperature induction tank (81a) before it moves to the first crystallization
tank (154a) followed by a second crystallization tank if necessary (158a) (col 13, lines 23-35). The heating begins in the first stage auxiliary low-temperature tank where the temperature varies from sub-
ambient to 180 °F (82 °C) and is held for 4-16 hours (col 7, lines 65-68). After the holding tank, the
temperature is increased in the first crystallization vessel in a range of 180-250 °F (82-121°C) and is held
for 2-72 hours (col 8, lines 22-30).
Therefore, it would have been obvious to one having skill in the art before the effective filing
date of the claimed invention, to further modify Elliott by combining the optimized heating process of Dwyer et al. with Elliott’s process in order to favor nucleation for the first heating step and then increase the rate of crystallization at the second temperature so the remaining components in the reaction mix can be consumed (col 7, lines 12-23).
Regarding claim 10, modified Elliott discloses a heating process of 100 °C for 16 hours (col 3, line 63) but does not disclose the heating process under elevated pressure, elevated humidity, or both, relative to ambient conditions.
Dwyer et al. discloses a multiple stage crystallization process for making zeolites. The slurry
starts in an auxiliary low-temperature induction tank (81a) before it moves to the first crystallization
tank (154a) followed by a second crystallization tank (158a) (col 13, lines 23-35). The first crystallization
tank is held at 30-35 psig (col 13, lines 33-34) and the second tank is held at 130 psig (col 13, lines 35-
36).
Therefore, it would have been obvious to one having skill in the art before the effective filing
date of the claimed invention, to further modify Elliott by combining the elevated pressures of Dwyer et al. with Elliott’s process because elevated pressure in zeolite crystallization is conventional.
Regarding claim 11, modified Elliott discloses the method of making the zeolite-Y particle but does not disclose crystallizing the first or second solution in an autoclave.
Dwyer et al. discloses that zeolite crystallization is commonly conducted in large autoclaves (col 5, lines 20-21). Therefore, it would have been obvious to one having skill in the art before the effective filing date of the claimed invention, to use an autoclave to crystallize the first and second solution in Elliott because autoclaves are conventional and well known in the art of crystallizing precursor solutions to form zeolites.
Regarding claim 12, modified Elliott discloses a heating process of 100 °C for 11.5 hours of the second solution (col 4, lines 19-20). Modified Elliott does not disclose increasing the first temperature of 100 °C to a second temperature and holding it for another period of time.
Dwyer et al. discloses a multiple stage crystallization process for making zeolites. The slurry
starts in an auxiliary low-temperature induction tank (81a) before it moves to the first crystallization
tank (154a) followed by a second crystallization tank if necessary (158a) (col 13, lines 23-35). The heating begins in the first stage auxiliary low-temperature tank where the temperature varies from sub-ambient to 180 °F (82 °C) and is held for 4-16 hours (col 7, lines 65-68). After the holding tank, the temperature is increased in the first crystallization vessel in a range of 180-250 °F (82-121°C) and is held
for 2-72 hours (col 8, lines 22-30).
Therefore, it would have been obvious to one having skill in the art before the effective filing
date of the claimed invention, to further modify Elliott by combining the optimized heating process of Dwyer et al. with Elliott’s process in order to favor nucleation for the first heating step and then increase the rate of crystallization at the second temperature so the remaining components in the reaction mix can be consumed (col 7, lines 12-23).
Regarding claim 13, modified Elliott discloses a second heating process of 100 °C for 11.5 hours (col 4, lines 19-20) but does not disclose the heating process under elevated pressure, elevated humidity, or both, relative to ambient conditions.
Dwyer et al. discloses a multiple stage crystallization process for making zeolites. The slurry
starts in an auxiliary low-temperature induction tank (81a) before it moves to the first crystallization
tank (154a) followed by a second crystallization tank (158a) (col 13, lines 23-35). The first crystallization
tank is held at 30-35 psig (col 13, lines 33-34) and the second tank is held at 130 psig (col 13, lines 35-
36).
Therefore, it would have been obvious to one having skill in the art before the effective filing
date of the claimed invention, to further modify Elliott by combining the elevated pressures of Dwyer et al. with Elliott’s process because elevated pressure in zeolite crystallization is conventional.
Claim 15-16 is rejected under 35 U.S.C. 103 as being unpatentable over Elliott in view of Willis as applied to claims 1-2, 4-5, 8, 18, 19, and 21 above, and further in view of Koegler et al. (CN1331747C).
Regarding claim 15, modified Elliott discloses the method of making zeolite-Y particles but does not disclose an average particle size.
Koegler et al. discloses preparing Y zeolite with a particle size range of 100 nm to 500 nm;
entirely encompassing the claimed range (paragraph 0049). 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.
Therefore, it would have been obvious to one having skill in the art before the effective filing
date of the claimed invention, to further modify Elliott by combining the optimized particle size taught in Koegler et al. with Elliott’s process because a zeolite with small crystal size has advantages when used in hydrocarbon conversion processes for example effective diffusion characteristics (paragraph 0026).
Regarding claim 16, modified Elliott discloses the method of making zeolite-Y particles but does not disclose an average pore size.
Koegler et al. discloses preparing Y zeolite with a pore size of 7-8 angstroms (0.7-0.8 nm)
(paragraph 0027). These pore sizes fall outside the claimed range. 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
ranges through process optimization, since it has been held that the general conditions of the claims 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.
Therefore, it would have been obvious to one having skill in the art before the effective filing date of the claimed invention, to further modify Elliott by combining the optimized pore size taught in Koegler et al. with Elliott’s process because catalysts with ideal pore sizes can facilitate the transport of reactants to the active sites of the catalyst (paragraph 0006).
Claim 17 is rejected under 35 U.S.C. 103 as being unpatentable over Elliott in view of Willis as applied to claims 1-2, 4-5, 8, 18, 19, and 21 above, and further in view of Zheng et al. (CN107867699).
Regarding claim 17, modified Elliott discloses the method of making zeolite-Y particles but does not disclose a total pore volume.
Zheng et al. discloses a total pore volume of the structure microporous Y zeolite that is 0.17-1.0
ml/g; entirely encompassing the claimed range (paragraph 012). 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.
Therefore, it would have been obvious to one having skill in the art before the effective filing
date of the claimed invention, to further modify Elliott by combining the optimized pore volume taught in Zheng et al. with Elliott’s process because microporous catalysts provide abundant active sites (paragraph 0004).
Claim 20 is rejected under 35 U.S.C. 103 as being unpatentable over Elliott in view of Willis as applied to claims 1-2, 4-5, 8, 18, 19, and 21 above, and further in view of Alexander et al. (US20240367987).
Regarding claim 20, modified Elliott discloses the method of making and washing zeolite-Y particles (col 4, lines 1-2). Modified Elliott does not disclose drying the zeolite-Y or calcinating it.
Alexander et al. discloses creating a mixture comprising CTAB and Y-zeolite and precipitating
solids (paragraph 0035). The solids are washed, filtered, and calcined (paragraph 0035).
Therefore, it would have been obvious to one having skill in the art before the effective filing
date of the claimed invention, to further modify Elliot by combining the drying and calcination step of Alexander et al. with Elliott’s process to control the size of the mesopores in the Y zeolite (paragraph 0038).
Response to Arguments
Applicant’s arguments with respect to claims 1-21 have been considered but are moot because the new ground of rejection does not rely on any reference applied in the prior rejection of record for any teaching or matter specifically challenged in the argument. Applicant argues that Elliott does not teach the molar composition of the recycled zeolite precursor solution as recited in the amended claims. The examiner agrees but new grounds of rejection has been made in view of Willis (US3898319).
Conclusion
THIS ACTION IS MADE FINAL. Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to DAVID A CALDERON whose telephone number is (571)272-9866. The examiner can normally be reached Monday-Friday 8-5PM.
Examiner interviews are available via telephone, in-person, and video conferencing using a USPTO supplied web-based collaboration tool. To schedule an interview, applicant is encouraged to use the USPTO Automated Interview Request (AIR) at http://www.uspto.gov/interviewpractice.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Christina Johnson can be reached at 5712721176. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
Information regarding the status of published or unpublished applications may be obtained from Patent Center. Unpublished application information in Patent Center is available to registered users. To file and manage patent submissions in Patent Center, visit: https://patentcenter.uspto.gov. Visit https://www.uspto.gov/patents/apply/patent-center for more information about Patent Center and https://www.uspto.gov/patents/docx for information about filing in DOCX format. For additional questions, contact the Electronic Business Center (EBC) at 866-217-9197 (toll-free). If you would like assistance from a USPTO Customer Service Representative, call 800-786-9199 (IN USA OR CANADA) or 571-272-1000.
/DAVID ANDREW CALDERON/Examiner, Art Unit 1742 /CHRISTINA A JOHNSON/Supervisory Patent Examiner, Art Unit 1742
Prosecution Insights