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 Status
Claims 10-22 are pending.
Claims 1-9 have been cancelled.
Claims 10-22 have been newly added.
Thus, claims 10-22 represent all claims currently under consideration.
Priority
Domestic Priority data as claimed by Applicant:
This application is a 371 of PCT/JP2022/021648 (05/26/2022)
Foreign Applications:
JAPAN 2021-112315 (07/06/2021)
Receipt is acknowledged of certified copies of papers required by 37 CFR 1.55.
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.
Claims 10, 17, and 21 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Yamaguchi et al. (JP2019104003A; published 06-27-2019; English language machine translation obtained from IDS of 03-13-2024).
Regarding claims 10, 17, and 21, Yamaguchi discloses a reaction method and reaction apparatus comprising a trickle bed reactor that causes a chemical reaction by passing a raw material solution and a reaction gas through a column packed with an immobilized catalyst, characterized in that a first column and a second column are arranged in parallel, and the supply of the raw material solution or reaction gas to each of the first column and the second column is switched alternately at predetermined levels. The immobilized catalyst packed in the first column and the second column is supported on a carrier having an average particle size of 20 μm to 3 mm (Title; claims 1 and 9; 0001, 0008). The alternate feeding of gaseous starting material and liquid starting material is consistent with the definition of “alternately flowed” provided in the present application (Specification; 0045).
The reaction apparatus 1 as detailed in Figure 1 of Yamaguchi comprises a column 3 packed with an immobilized palladium catalyst on a spherical alumina support and configured to receive a raw material solution from storage unit 11 and a reaction gas from storage unit 12. The first channel 4 and the second flow path 5 are channels for supplying the raw material solution and the reaction gas to the first column 3a and the second column 3b through means of pump 13 and mass controller 14, respectively. The gas and liquid obtained from this chemical reaction then flow through third channel 6 to the gas-liquid separation tank 15. Subsequently, the liquid is sent to the outside via the liquid discharge channel 16 provided with a needle valve 20, and the waste gas is discharged via the gas discharge channel 17 provided through the back pressure valve 21 (Figure 1; 0025-0027, 0030-0032, and 0035).
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The switching unit 7 is positioned between the first flow path 4 and the second flow path 5 and the first column 3a and the second column 3b, and includes a first position (see Fig. 2a) in which the first flow path 4 and the first column 3a are connected via the first connecting flow path 9, and the second flow path 5 and the second column 3b are connected via the second connecting flow path 10, or a second position (see Fig. 2b) in which the first flow path 4 and the second column 3b are connected via the second connecting flow path 10, and the second flow path 5 and the first column 3a are connected via the first connecting flow path 9. The switching unit 7 is switched between the first and second positions by control means 8 at predetermined intervals to alternately supply the raw material solution 18 and the reaction gas 19 to the first column 3a and the second column 3b (Figure 2; 0028-0029 and 0033).
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Example 1 of Yamaguchi discloses a hydrogenation reaction of benzonitrile to produce benzylamine, wherein the raw material solution 18 is a benzonitrile solution, the reaction gas 19 is hydrogen gas, and the first column 3a and the second column 3b are packed with an immobilized palladium catalyst on an alumina support. The pump 13 supplies the benzonitrile solution to the first column 3a via the first channel 4. Simultaneously, hydrogen gas is supplied to the second column 3b via the second channel 5. The switching unit 7 is switched between the first and second positions (see Fig. 2) every 5 second to alternately supply benzonitrile solution and hydrogen gas to the first column 3a and the second column 3b. The benzonitrile solution and hydrogen gas are brough into contact with the reaction surface of each layer via the palladium catalyst packed in the columns 3a/3b, and a chemical reaction is carried out. HPLC analysis of the liquid discharge channel 16 indicated that the collection rate of benzylamine was 88% (Example 1; 0047-0048; Figures 1-2).
Thus, the reaction method and apparatus of Yamaguchi teaches every limitation of instant claims 10 and 21. Furthermore, Example 1 of Yamaguchi teaches every limitation of instant claim 17 wherein the first starting material is hydrogen gas and the second starting material is benzonitrile.
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.
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.
Claims 10-15, 17-18, and 21-22 are rejected under 35 U.S.C. 103 as being unpatentable over Yamaguchi et al. (JP2019104003A; published 06-27-2019; English language machine translation obtained from IDS of 03-13-2024).
Regarding claims 10-13, 17-18, and 21, the teachings of Yamaguchi were discussed in the previous rejections of claims 10, 17, and 21 and are incorporated herein.
Further regarding claims 11-13, Yamaguchi does not explicitly teach wherein each feed rate for the gaseous and/or liquid starting materials are either equal to the volume of the reaction field or greater than the volume of the reaction field, in terms of the volume of the gaseous starting material at the reaction temperature and/or in terms of the volume of the liquid starting material, as recited in claims 11-13.
However, Yamaguchi does teach that in the reaction method, by alternately switching the supply of the raw material solution or reaction gas to the first and second column at predetermined intervals, the raw material solution and reaction gas flow alternately through the first and second columns. As a result, within each column, the raw material solution and reaction gas flowing through it form alternating layers in the direction of their flow, and the raw material solution and reaction gas come into contact at the boundaries of each layer that act as reaction surfaces, where chemical reactions occur between the raw material solution and the reaction gas (0009 and 0011). Therefore, the skilled artisan would recognize from these teachings that the feed rate of the gaseous and liquid starting materials would need to provide a volume of at least equal to the volume of the reaction field in order to form the alternating layers as taught by Yamaguchi.
In addition, Examples 1-4 of Yamaguchi teach liquid flow rates ranging from 20.0 mL/min to 100 mL/min, and gas flow rates ranging from of 2.87 mL/min to 1.67 L/min (0047, 0052, 0057, 0062; Examples 1-4). Therefore, the skilled artisan would recognize from the teachings of Yamaguchi that the liquid and gas flow rates could be adjusted and optimized accordingly through means of pump 13 and mass controller 14 to arrive at the claimed invention with a reasonable expectation of success through means of routine optimization (0030 and 0032; Figure 1). See MPEP § 2144.05(II).
Therefore, it would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have arrived at the claimed invention based on the teachings of Yamaguchi and through means of routine optimization that is non-inventive in nature, as described above.
Regarding claims 14-15 and 22, Yamaguchi does not explicitly teach a reaction method and system wherein the liquid starting material that has been flowed through the reaction/reaction field is recovered and reflowed. However, Examples 1-2 and 4 of Yamaguchi does teach that the recovered liquid product mixture is subjected to HPLC purification to separate the desired products from their respective components (0048, 0053, 0063, Examples 1-2 and 4). As such, the skilled artisan would reasonably deduce that any reisolated liquid starting material recovered from the process of Yamaguchi could be recycled to the reactor to improve the efficiency of the overall process with a reasonable expectation of success.
Regarding claim 18, Example 1 of Yamaguchi teaches the use of a benzonitrile solution and hydrogen gas for the production of benzylamine was 88% (Example 1; 0047-0048; Figures 1-2). This embodiment teaches every limitation of instant claim wherein the first starting material is hydrogen gas and the second starting material is benzonitrile.
Claim 16 is rejected under 35 U.S.C. 103 as being unpatentable over Yamaguchi et al. (JP2019104003A; published 06-27-2019; English language machine translation obtained from IDS of 03-13-2024) as applied to claims 10-15, 17-18, and 21-22 above, and further in view of Liu (US 2002/0198419 A1; published 12-26-2002).
Regarding claim 16, claim 10 is rendered obvious over Yamaguchi as detailed above.
Although Yamaguchi teaches that the catalyst of the trickle bed reactor is not particularly limited as long as it is an immobilized catalyst with an average particle size of 20 μm to 3 mm that allows the desired reaction to proceed smoothly (0045, claim 1), Yamaguchi does not teach wherein the reaction field is a honeycomb substrate, and the solid catalyst is held on the honeycomb substrate, as recited in claim 16.
However, Liu teaches three-phase chemical hydrogenation reactions involving the processing of gas-liquid reactant feed streams over “mini-structured” solid catalyst beds formed of channeled honeycomb monoliths incorporating solid catalysts. The process is carried out with hydrogen gas and at least one hydrocarbon selected from the group consisting of unsaturated hydrocarbons and aromatic hydrocarbons (Abstract; claims 1-3, 6, 17-18).
Liu further teaches that conventional packed catalyst beds are affected by blocked flow, wherein hydrogen gas streams (20) and liquid droplets (22) enter a packed catalyst bed and move downwardly through a cluster of catalyst pellets (24). The spreading liquid tends to fill voids among the catalyst pellets and is preferentially trapped by capillary forces in inter-pellet void spaces (26) of appropriate size and shape. This effectively reduces catalyst utilization, and at the same time increases the chance of secondary reactions, such as coking, that can occur in stagnant liquid zones due to the relative unavailability of hydrogen. This is a fundamental disadvantage that is inherent in packed bed reactors including trickle bed reactors (0033-0034, Fig. 2, Example 1).
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Liu teaches that in contrast to packed bed reactors, a key advantage of reactors incorporating honeycomb or other structured catalysts is that bulk gas and liquid flows, even though divided into dimensions similar to the passages between catalyst pellets in a packed bed reactor, are much more resistant to trapping and stagnation. As shown in Fig.3 of Liu, this results from the fact that liquids (22) coming into contact with the channel walls (25) of the catalyst tend to spread on channel surfaces, leaving free channel space available for gas streams (20) to pass through the catalyst bed. Thus, liquid entrapment is unlikely and a more uniform distribution of gases and liquids over the surfaces of the available catalyst is realized. At the same time, surface reactions and the tensile forces applied by the gas flow on the liquid film on the wall further facilitate liquid exchange, i.e., mass transfer from the bulk of the liquid onto the catalyst surface (0035, Fig. 3).
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In addition to the well recognized low-pressure-drop advantage of honeycomb monolith catalysts, Liu further teaches that the conversion activity of toluene to methylcyclohexane of the structured catalyst significantly exceeds the activity of the crushed catalyst at all reactor temperatures below 180 ºC, and it is only at temperatures above this point that the activity of the trickle bed reactor becomes competitive (0005, 0022, 0080, Fig. 4).
The illustrative examples of Liu demonstrate the advantages of the present invention for hydrogenation and hydrotreating reactions. The tabular data in Tables 1-3 suggest that the structured catalysts of Example III (structured monolithic catalyst of honeycomb configuration) demonstrate 1-octene hydrogenation activities that are from one to two orders of magnitude higher than the corresponding activities calculated for the pellet bed catalysts of Examples I (packed bed/trickle reactor) and II (ideal packed bed), and the hydrogenation conversion rates and catalytic activities are unexpectedly high (0064-0065, Tables 1-3, Examples 1-3).
The process of Liu and Yamaguchi are analogous because they both teach three-phase teach hydrogenation methods comprising hydrogen gas, a liquid unsaturated hydrocarbon, and a solid catalyst. Furthermore, both Liu and Yamaguchi teach the use of trickle bed reactors, and Liu teaches several key advantages for the use of structured monolithic honeycomb catalyst beds compared to the packed catalyst beds of conventional trickle bed reactors. As such, the skilled artisan would be sufficiently motivated to predictably substitute the catalyst bed of the trickle bed reactor of Yamaguchi with the structured monolithic honeycomb catalyst bed of Liu to pursue an improved method and reactor with a low-pressure-drop, reduced block flow that can cause coking to occur, improved mass transfer, and improved conversion rates and catalyst activity with a reasonable expectation of success. See MPEP § 2143(I)(B).
Therefore, it would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have substituted the catalyst bed of Yamaguchi with the structured monolithic honeycomb catalyst bed of Liu to arrive at the invention. The motivation to do so would permit the skilled artisan to pursue, with a reasonable expectation of success, a reaction method and system with a low-pressure-drop, reduced block flow that can cause coking to occur, improved mass transfer, and improved conversion rates and catalyst activity, as described above.
Claims 19-20 are rejected under 35 U.S.C. 103 as being unpatentable over Yamaguchi et al. (JP2019104003A; published 06-27-2019; English language machine translation obtained from IDS of 03-13-2024) as applied to claims 10-15, 17-18, and 21-22 above, and further in view of Degirmenci et al. (“Design of catalytic micro trickle bed reactors”; Phys. Sci. Rev. 2016, 20150018, pages 1-29; published 04-30-2016).
Regarding claims 19-20, claims 10 and 13 are rendered obvious over Yamaguchi, as detailed above.
Yamaguchi does not teach wherein the first starting material is oxygen or air, and the second starting material is an oxygen-oxidizable or air-oxidizable compound. However, Yamaguchi does teach that the illustrative aspects of the present invention is not intended to limit the technical scope of the present invention, and embodiments in which some of the components of each section are replaced, deleted, or other components are added may also be embodiments of the present invention (0007).
In addition, Degirmenci teaches the design of micro trickle bed reactors and reviews the four main classes of trickle bed reactor configurations (Title; page 2, paragraph 5 and page 3, paragraph 1). Degirmenci further teaches that trickle bed reactors are known to facilitate a variety of gas-liquid-solid reactions in addition to hydrogenation, including oxidation reactions of organic compounds in the presence of oxygen (page 2, paragraphs 1-2; page 22, paragraphs 6-7; page 24, paragraph 4 and Figure 17).
The teachings of Degirmenci and Yamaguchi are analogous because they both reside in the overlapping technical field of processes involving trickle bed reactors for gas-liquid-solid reactions, in a manner consistent with the invention of instant claims 19-20. As such, the skilled artisan would be sufficiently motivated to predictably modify the trickle bed reactor method of Yamaguchi to incorporate the teachings of Degirmenci to arrive at a process wherein the first starting material is oxygen or air, and the second starting material is an oxygen-oxidizable or air-oxidizable compound to pursue a broadened scope of valuable oxidation products with a reasonable expectation of success. See MPEP § 2143(I)(A).
Therefore, it would have been prima facie obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the reaction method of Yamaguchi to incorporate the teachings of Degirmenci to arrive at the claimed invention. The motivation to do so would permit the skilled artisan to pursue, with a reasonable expectation of success, a reaction method and system with a broadened scope capable of producing valuable oxidation products, as described above.
Based on the combined teachings of the references, the Examiner submits that a person of ordinary skill in the art would have had a reasonable expectation of success of arriving at the instantly claimed reaction method and system. Therefore, the invention as a whole would have been prima facie obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, and absent a clear showing of evidence to the contrary.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure. Letourneur et al. (US 2002/0119082 A1; published 08-29-2002) discloses a method for maintaining a ratio of gas volume to liquid volume in a segmented gas/liquid flow along a reactor containing monolithic catalyst beds in series (Abstract; claim 1). Although the process of Letourneur discloses alternately flowing gas and liquid reactants (Figure 2), Letourneur does not appear to render obvious the claims because of the definition of “alternately flowed” provided in the present application, wherein liquid feed processing is not carried out during gas feed processing and gas feed processing is not carried out during liquid feed processing (Specification; 0045).
Any inquiry concerning this communication or earlier communications from the Examiner should be directed to Derek Rhoades whose telephone number is (703)-756-5321. The Examiner can normally be reached Monday–Thursday, 7:30 am–5:00 pm EST; Friday, 7:30 am–4:00 pm EST.
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If attempts to reach the examiner by telephone are unsuccessful, the Examiner’s supervisor, Scarlett Goon can be reached on 571-270-5241. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/D.R./Examiner, Art Unit 1692
/AMY C BONAPARTE/Primary Examiner, Art Unit 1692
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