DETAILED ACTION
Claims 1-11 are pending
Claims 1-11 are rejected
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 Objections
Claims 1-2 are objected to because of the following informalities:
In order to provide further clarity, it is suggested to amend “the silicon-titanium molar ratio” to “a silicon-titanium molar ratio” in claim 1 - line 7.
In order to provide further clarity and consistency, it is suggested to amend “ an alkali metal hydroxide modification solution” to “the alkali metal hydroxide modification solution” in claim 1 - line 12.
In order to provide further clarity and consistency, it is suggested to amend “the modification solution” to “the alkali metal hydroxide modification solution” in claim 1 - line 14 and claim 2 - line 3.
In order to provide further clarity, it is suggested to amend “the modified TS-1 zeolite wet material” to “a modified TS-1 zeolite wet material” in claim 1 - line 23.
In order to provide further clarity, it is suggested to amend “concentration” to “low concentration” in claim 1 - line 26.
Appropriate correction is required.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 5-10 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention
Each of claims 5-6 and 9 recites the term, “the final calcining temperature is 400-550℃” which lacks antecedent basis. It is unclear whether or not the final calcining temperature refers to the calcining in the post-treatment of claim 1. The examiner interprets this phrase as “the final calcining temperature in the post-treatment is 400-550℃”. Clarification is required
Regarding dependent claim 7, these claims do not remedy the deficiencies of parent claim 5 noted above, and is rejected for the same rationale.
10. Regarding dependent claim 8, these claims do not remedy the deficiencies of parent claim 6 noted above, and is rejected for the same rationale.
11. Regarding dependent claim 10, these claims do not remedy the deficiencies of parent claim 9 noted above, and is rejected for the same rationale.
12. Each of Claims 7-8 and 10 recites the term, “the fourth step” which lacks antecedent basis. The examiner interprets this phrase as “the third step”. Clarification is required.
Claim Rejections - 35 USC § 103
13. 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 pre-AIA 35 U.S.C. 103(a) which forms the basis for all obviousness rejections set forth in this Office action:
(a) A patent may not be obtained though the invention is not identically disclosed or described as set forth in section 102, if the differences between the subject matter sought to be patented and the prior art are such that the subject matter as a whole would have been obvious at the time the invention was made to a person having ordinary skill in the art to which said subject matter 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 pre-AIA 35 U.S.C. 103(a) 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.
14. Claim(s) 1-4 and 11 are rejected under 35 U.S.C. 103 as being unpatentable over Miao et al., Gas-Phase Epoxidation of Propylene with Hydrogen Peroxide Vapor: Effect of Modification with NaOH on TS‑1 Titanosilicate Catalyst in the Presence of Tetra-propylammonium Bromide (Miao) in view of Robson et al. Verified Syntheses of Zeolitic Materials (Robson) and Hani et al. Acid Washing Of “Zeolite A”: Performance Assessment And Optimization (Hani).
15. Regarding claims 1 and 3, Miao teaches a TS‑1 Treatment by a mixed alkaline used in propylene epoxidation) with hydrogen peroxide to synthesize propylene oxide (PO) (Miao, Abstract);
wherein the mixed alkaline is NaOH−TPABr (i.e. alkaline metal modified) (Miao, Abstract);
wherein sodium ions are on their neighboring silicon hydroxyls as counter cations (i.e. alkali metal ions are reserved on the silicon hydroxyl of the modified TS-1 zeolite) (Miao, p. 11748, right column, Conclusion).
Miao further teaches that the mixed alkaline treated TS-1 (i.e. an alkali metal ion modified titanium silicate zeolite for TS-1) has special Ti sites with characteristic IR absorption in between 960−980 cm−1 (Miao, p. 11740, left column, last paragraph), which falls within the claimed range.
Miao further teaches the mixed alkaline treated TS-1 (i.e. an alkali metal ion modified titanium silicate zeolite for TS-1) has a Si/Ti ratio of 33.3 (170-2 h), 33.3 (170-4 h), 33.4 (170-8 h), 33.6 (170-16 h), and 33.3 (170-24 h) (Miao, p. 11741, Table 1), which fall within the claimed range.
Miao further teaches a relative crystallinity of the mixed alkaline treated TS-1s have a relative crystallinity of ~85% (170-2 h), ~85% (170-8 h), and >90% % (170-16 h) (Miao, p. 11741, Figure 1 (right column)), which fall within the recited range (See annotated Fig. 1 below).
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351
465
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Annotated Fig. 1
Miao further teaches a hydrothermal modification was carried out with by creating modification solution containing NaOH (i.e. an alkali metal hydroxide) and TPABr (i.e. containing tetrapropylammonium cations (TPA+)) (i.e. first step: preparing an alkali metal hydroxide modification solution containing TPA+ ions) (Miao, p. 11740, right column, paragraph 2);
wherein the concentration of TPABr (i.e. concentration of TPA+ ions) 0.05−0.50 mol/L (Miao, p. 11740, right column, paragraph 2), which falls within the claimed range;
wherein the concentration of NaOH (i.e. concentration of alkali metal hydroxide) is 0.10−0.30 mol/L (Miao, p. 11740, right column, paragraph 2), which overlaps with the claimed range.
As set forth in MPEP 2144.05, in the case where the claimed range “overlap or lie inside ranges disclosed by the prior art”, a prima facie case of obviousness exists, In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990).
Miao further teaches parent TS-1 and the modification solution were added into an autoclave at a ratio (i.e. volume ratio) of 1/5−1/30 (i.e. 1 g/5 mL - 1 g/30 mL) (Miao, p. 11740, right column, paragraph 2), which overlaps the claimed range.
As set forth in MPEP 2144.05, in the case where the claimed range “overlap or lie inside ranges disclosed by the prior art”, a prima facie case of obviousness exists, In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990).
Although there is no disclosure that the test method is conformity with volume ratio units of ml/g, given that Miao discloses a ratio of TS-1 and the modification solution as is presently claimed and absent evidence of criticality in how the ratio is measured, it is the Examiner's position that the ratio of parent TS-1 and the modification solution as disclosed by Miao meets the claim limitation.
Miao further teaches hydrothermal treatment was performed at 170 °C (Miao, p. 11740, right column, paragraph 2) over a period of 16 hours (Miao, p. 11741, Table 1) (i.e. second step: conducting a degree controlled hydrothermal treatment on the TS-1 zeolite matrix), which fall within the claimed ranges.
Miao further teaches after the hydrothermal treatment (i.e. third step: conducting post-treatment on the hydrothermally modified TS-1 zeolite), filtration was used to recover the solid product (i.e. solid-liquid separation) (Miao, p.11740, right column, paragraph 2)
wherein the solid product was subjected to washing, drying, and calcination treatments (Miao, p.11740, right column, paragraph 2)
wherein a weakly acidic surface of the mixed alkaline treated TS-1 is neutralized by NA+- ions (Miao, p.11747, left column, paragraph 2)
However, Miao does not teach a solid-liquid separation is washed by using a 0.001-0.05 mol/L concentration alkali metal hydroxide solution and the washing solution is neutralized with acid.
With respect to the difference, Robson teaches hydrothermal synthesis methods of zeolites (Robson, p. 27, Summary)
wherein a SSZ-24 zeolite product has a KOH solution washing step (i.e. alkali metal hydroxide) with a concentration of 0.01 M, which falls within with the claimed range (Robson, p. 136, Product Recovery (3)).
Robson expressly teaches the alkaline wash helps prevent unreacted silica from coming out of solution (Robson, p. 136, Notes(d)).
Miao and Robson are analogous art as they are all drawn to hydrothermal synthesis methods of zeolites.
In light of the motivation for an alkaline wash as disclosed by Robson, it therefore would have been obvious to one of ordinary skill in the art to include a washing step of 0.01 M KOH solution in the TS‑1 Treatment by a mixed alkaline of Miao, in order to achieve prevention of unreacted silica from coming out of solution, and thereby arrive at the claimed invention.
Miao in view of Robson further does not teach the degree of washing is satisfactory when no precipitate appears after the washing solution is neutralized with acid.
With respect to the difference, Hani teaches industrial manufacture of zeolite A wherein the zeolite requires extensive washing cycles and time (Hani, Abstract)
wherein an acid washing method for neutralization and precipitation removal of highly alkaline zeolite A (i.e. the degree of washing is satisfactory when no precipitate appears after the washing solution in neutralized with acid) (Hani, p. 262, left column, second paragraph).
Hani expressly teaches neutralization of residual NaOH in the cake is done by a suitable acid (Hani, p. 261, right column, paragraph 2)
wherein an excessive amount of wash water used and an intensive energy is required to reach a pH value < 9.5 (Hani, p. 261, left column, paragraph 2)
wherein a modified cost-effective acid washing method has been developed for neutralization (Hani, p. 261, right column, paragraph 2) to achieve a significant reduction of wash water in complexation and precipitation removal (Hani, p. 262, left column, paragraph 2).
Miao, Robson, and Hani are analogous art as they are all drawn to a method of preparing zeolites.
In light of the motivation for neutralization of residual NaOH is done by a suitable acid as disclosed by Hani, it therefore would have been obvious to one of ordinary skill in the art to include an acid washing method for neutralization and precipitation removal in the TS‑1 Treatment by a mixed alkaline of Miao in view of Robson, in order to achieve a significant reduction of wash water in complexation and precipitation removal, and thereby arrive at the claimed invention.
Given Miao in view of Robson and Hani teaches a TS‑1 Treatment by a mixed alkaline with the steps in the process that are identical or substantially identical with those of the presently claimed, therefore, it is clear that the TS‑1 Treatment by a mixed alkaline of Miao in view of Robson and Hani would necessarily and inherently meet the claimed “an index value of the framework titanium content is ≥0.40;”
Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977). See MPEP 2112.01 (I).
16. Regarding claims 2 and 4, Miao further teaches the hydrothermal modification was carried out with a modification solution containing NaOH (i.e. an alkali metal hydroxide) and TPABr (i.e. containing tetrapropylammonium cations (TPA+)) (Miao, p. 11740, right column, paragraph 2);
wherein the concentration of TPABr (i.e. concentration of TPA+ ions) 0.05−0.50 mol/L, and the concentration of NaOH (i.e. concentration of alkali metal hydroxide) is 0.10−0.30 mol/L, which overlap with the claimed ranges (Miao, p. 11740, right column, paragraph 2).
Miao further teaches parent TS-1 and the modification solution were added into an autoclave at a ratio (i.e. volume ratio) of 1/5−1/30 (i.e. 1 g/5 mL - 1 g/30 mL) (Miao, p. 11740, right column, paragraph 2), which overlaps the claimed range.
As set forth in MPEP 2144.05, in the case where the claimed range “overlap or lie inside ranges disclosed by the prior art”, a prima facie case of obviousness exists, In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990).
Miao further teaches hydrothermal treatment was performed at 170 °C (Miao, p. 11740, right column, paragraph 2) over a period of 16 hours (Miao, p. 11741, Table 1), which fall within the claimed ranges.
17. Regarding claim 11, Miao further teaches the mixed alkaline treated TS-1 (i.e. an alkali metal ion modified titanium silicate zeolite for TS-1) has a Si/Ti ratio of 33.3 (170-2 h), 33.3 (170-4 h), 33.4 (170-8 h), 33.6 (170-16 h), and 33.3 (170-24 h) (Miao, p. 11741, Table 1), which fall within the claimed range.
Miao further teaches a relative crystallinity of the mixed alkaline treated TS-1s have a relative crystallinity of >90% % (170-16 h) (Miao, p. 11741, Figure 1 (right column)), which falls within the claimed range (See annotated Fig. 1 and article 15 above).
Given Miao in view of Robson and Hani teaches a TS‑1 Treatment by a mixed alkaline with the steps in the process that are identical or substantially identical with those of the presently claimed, therefore, it is clear that the TS‑1 Treatment by a mixed alkaline of Miao in view of Robson and Hani would necessarily and inherently meet the claimed “an index value of the framework titanium content is ≥0.45;”
Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977). See MPEP 2112.01 (I).
18. Claims 5 and 7 are rejected under 35 U.S.C. 103 as being unpatentable over Miao in view of Robson and Hani as applied to claim 1 above, and further in view of Liu et al, Study on the calcination of titanium silicalite zeolite (TS-1) (Liu) and Wang et al., Effect of TS‑1 Treatment by Mixed Alkaline on Propylene Epoxidation (Wang).
19. Regarding claim 5, Miao further teaches the solid product was subjected to washing, drying, and calcination treatments (Miao, p. 11740, right column, paragraph 2)
wherein there is a 0.01 M KOH (i.e. the alkali metal hydroxide used for washing is potassium hydroxide) solution washing step (Robson, p. 136, Product Recovery (3)), which falls within the claimed range.
However, Miao does not teach the drying temperature 80-120℃.
With respect to the difference, Robson teaches drying is accomplished in a laboratory oven at ~100 °C (Robson, p. 7, Product Recovery (paragraph 3)), which falls within the claimed range.
Robson expressly teaches it is good technique have a dried sample at a constant 50% humidity to achieve a stable product for handling in laboratory air (Robson, p. 7, Product Recovery (paragraph 3)).
In light of the motivation for a dried sample at a constant 50% humidity as disclosed by Robson, it therefore would have been obvious to one of ordinary skill in the art to include a drying step at ~100 °C in the TS‑1 Treatment by a mixed alkaline of Miao, in order to achieve a stable product for handling in laboratory air, and thereby arrive at the claimed invention.
Miao in view of Robson and Hani further does not teach the final calcining temperature is 400-550℃.
With respect to the difference, Liu teaches the calcination process of titanium silicalite zeolite TS-1 prepared by the hydrothermal method (Liu, Abstract)
wherein the calcined TS-1 crystal morphology was integrated under 823 K (i.e. calcinated 550 °C) (Liu, Abstract), which falls within with the claimed range.
Liu expressly teaches the crystal morphology after calcination at 823 K showing that no morphology transformed wherein controlling the calcination at 823 K (i.e. 550 °C) leads to a relatively unruptured crystal (Liu, p. 319, first paragraph).
Miao, Robson, Hani, and Liu are analogous art as they are all drawn to synthesis methods of zeolites.
In light of the motivation for controlling the crystal morphology via calcination as disclosed by Liu, it therefore would have been obvious to one of ordinary skill in the art to include a calcination at 823 K (i.e. 550 °C) in the TS‑1 Treatment by a mixed alkaline of Miao in view of Robson and Hani, in order to TS-1 zeolite with a relatively unruptured crystal, and thereby arrive at the claimed invention.
Miao in view of Robson and Hani further in view of Liu further does not teach the constant temperature time at the final calcining temperature is more than 3 hours.
With respect to the difference, Wang teaches, the crystalline product was obtained by strong centrifugation, washed with deionized water to neutral, dried at 393 K (i.e. 121.85 oC; ~100oC) for 6 h, and finally calcined at 823 K for 6 h in air (Wang, p. 26 – Synthesis of TS-1).
Given Wang teaches the calcination condition being 823 K for 6 h in air, it is clear that the calcination condition would be sufficient to form the TS-1 after drying.
Miao, Robson, Hani, Liu and Wang are analogous art as they are all drawn to synthesis methods of zeolites.
In light of the motivation for calcination condition being 823 K for 6 h in air as disclosed by Wang, it therefore would have been obvious to one of ordinary skill in the art to calcinate the solid product of Miao in view of Robson and Hani further in view of Lui with the calcination condition, i.e., 823 K for 6 h in air, in order to sufficiently form the TS-1 after drying, and thereby arrive at the claimed invention.
Miao in view of Robson and Hani further in view of Liu and Wang do not teach the drying time is decided based on the dry basis content of the sample not less than 90%.
Given Miao in view of Robson and Hani further in view of Liu and Wang teaches the TS‑1 Treatment by a mixed alkaline with the steps in the process that are identical or substantially identical with those of the presently claimed wherein the solid product was subjected to drying (Maio, p. 11740, right column, paragraph 2), therefore, it is clear that the TS‑1 Treatment by a mixed alkaline of Miao in view of Robson and Hani further in view of Liu and Wang would necessarily and inherently meet the claimed “the drying time is decided based on the dry basis content of the sample not less than 90%.”
Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977). See MPEP 2112.01 (I).
20. Regarding claim 7, Robson further teaches the SSZ-24 zeolite product has a KOH solution washing step (i.e. i.e. the alkali metal hydroxide used for washing is potassium hydroxide) with a concentration of 0.01 M, which falls within with the claimed range (Robson, p. 136, Product Recovery (3)).
21. Claims 6 and 8 are rejected under 35 U.S.C. 103 as being unpatentable over Miao in view of Robson and Hani as applied to claim 2 above, and further in view of Liu and Wang.
22. Regarding claims 6 and 8, Miao further teaches the solid product was subjected to washing, drying, and calcination treatments (Miao, p. 11740, right column, paragraph 2)
wherein there is a 0.01 M KOH (i.e. the alkali metal hydroxide used for washing is potassium hydroxide) solution washing step (Robson, p. 136, Product Recovery (3)), which falls within the claimed range.
Robson further teaches drying is accomplished in a laboratory oven at ~100 °C (Robson, p. 7, Product Recovery (paragraph 3)), which falls within the claimed range.
Liu further teaches the calcination process of titanium silicalite zeolite TS-1 prepared by the hydrothermal method (Liu, Abstract);
wherein the calcined TS-1 crystal morphology was integrated under 823 K (i.e. calcinated 550 °C) (Liu, Abstract)
wherein calcination at 823 K occurs for 6 h in air (Wang, p. 26 – Synthesis of TS-1) which falls within with the claimed range.
Miao in view of Robson and Hani further in view of Liu and Wang do not teach the drying time is decided based on the dry basis content of the sample not less than 90%.
Given Miao in view of Robson further in view of Liu teaches the TS‑1 Treatment by a mixed alkaline with the steps in the process that are identical or substantially identical with those of the presently claimed wherein the solid product was subjected to drying (Maio, p. 11740, right column, paragraph 2), therefore, it is clear that the TS‑1 Treatment by a mixed alkaline of Miao in view of Robson and Hani further in view of Liu and Wang would necessarily and inherently meet the claimed “the drying time is decided based on the dry basis content of the sample not less than 90%.”
Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977). See MPEP 2112.01 (I).
23. Claims 9-10 are rejected under 35 U.S.C. 103 as being unpatentable over Miao in view of Robson and Hani as applied to claim 3 above, and further in view of Liu and Wang.
Regarding claims 9-10, Miao further teaches the solid product was subjected to washing, drying, and calcination treatments (Miao, p. 11740, right column, paragraph 2)
wherein there is a 0.01 M KOH (i.e. the alkali metal hydroxide used for washing is potassium hydroxide) solution washing step (Robson, p. 136, Product Recovery (3)), which falls within the claimed range.
Robson further teaches drying is accomplished in a laboratory oven at ~100 °C (Robson, p. 7, Product Recovery (paragraph 3)), which falls within the claimed range.
Liu further teaches the calcined TS-1 crystal morphology was integrated under 823 K (i.e. calcinated 550 °C) (Liu, Abstract)
wherein calcination at 823 K occurs for 6 h in air (Wang, p. 26 – Synthesis of TS-1) which falls within with the claimed range.
Miao in view of Robson and Hani further in view of Liu and Wang do not teach the drying time is decided based on the dry basis content of the sample not less than 90%.
Given Miao in view of Robson and Hani further in view of Liu and Wang teaches the TS‑1 Treatment by a mixed alkaline with the steps in the process that are identical or substantially identical with those of the presently claimed wherein the solid product was subjected to drying (Miao, p. 11740, right column, paragraph 2), therefore, it is clear that the TS‑1 Treatment by a mixed alkaline of Miao in view of Robson and Hani further in view of Liu and Wang would necessarily and inherently meet the claimed “the drying time is decided based on the dry basis content of the sample not less than 90%.”
Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977). See MPEP 2112.01 (I).
Conclusion
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/R.F.L./Examiner, Art Unit 1732
/KELING ZHANG/Primary Examiner, Art Unit 1732
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