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
Claims 9 and 12 are rejected under 35 U.S.C. 103 as being unpatentable over Kim (U.S. PG Pub. No. 2013/0030224) in view of Ziehe (WO 2004/078336 A1).
Kim, in paragraph 1, discloses preparing an alcohol by reacting carboxylic acid with hydrogen using a copper-based catalyst. In paragraph 72 Kim discloses converting butyric acid to butanol using the copper-based catalyst. In paragraph 52 Kim discloses that the catalyst includes SiO2 (silica), Al2O3 (alumina), or TiO2 (titania) as a support, as recited in amended claim 9. While Kim refers to the reaction as a hydrogenation, the removal of oxygen when the acid is converted to the corresponding alcohol renders the reaction a hydrodeoxygenation. In paragraph 127 Kim discloses that the reaction is carried out in a reactor into which the carboxylic acid and hydrogen are introduced in the presence of the catalyst meeting the limitations of the hydrodeoxygenation reaction unit and reaction system of claim 9. In paragraph 143 Kim indicates that the butanol selectivity can be as high as 98.6%.
The difference between Kim and the currently presented claims is that Kim does not disclose a dual-bed catalyst system having a hydrodeoxygenation reaction unit and a dehydration reaction unit, where the butanol can be dehydrated to an alpha-olefin in the dehydration reaction unit.
With respect to i), Ziehe, on page 1 lines 5-7 and page 2 line 20 through page 3 line 3, discloses a process for selectively producing α-olefins by dehydration of alcohols in the presence of γ-alumina, corresponding to the dehydration reaction recited in claim 9. On page 3 lines 5-9 Ziehe discloses that preferred alcohols include butanol, as produced in the reaction unit of Kim. Ziehe therefore discloses a dehydration reaction unit configured to supply an effluent from the hydrodeoxygenation reaction unit to a reaction system comprising a dehydration catalyst and to form an alpha-olefin, as recited in claim 9.
While Kim and Ziehe do not specifically performing a dehydration reaction at the WHSV recited in amended claim 9, it is noted that the claims only require that the dehydration reaction system is “configured” to have the WHSV. Since the WHSV of a system depends on the weight of feed and the weight of catalyst, the WHSV can be controlled by the operator of the system; any dehydration reaction system selectively producing α-olefins by dehydration of alcohols in the presence of γ-alumina can therefore be considered to be “configured” to have a WHSV within the range recited in amended claim 9.
It would have been obvious to one of ordinary skill in the art to perform the method of Kim in view of Ziehe in a dual bed catalyst system comprising a separate hydrodeoxygenation reaction unit and dehydration reaction unit, since Kim teaches a that the catalyst used for the hydrodeoxygenation reaction is highly selective for producing 1-butanol, and Ziehe teaches that the catalyst used for the dehydration reaction is highly selective for producing alpha-olefins, and carrying out the reactions in separate reaction units in a dual-bed system, meeting the limitations of claims 9 and 12 ensures high selectivity and minimizes the chance of undesired by-products.
Claims 9 and 11-12 are rejected under 35 U.S.C. 103 as being unpatentable over Endou (JP 6-116182 A) in view of Ziehe (WO 2004/078336 A1).
An English-language machine translation of Endou, which is attached, has been used in setting forth this rejection, and the paragraph numbers referred to herein are those of the English-language translation.
In paragraph 1 Endou discloses a method for hydrogenating organic carboxylic acids in the presence of a supported catalyst using SiO2 (silica) modified with a metal oxide as a catalyst. In paragraph 9 Endou discloses that the silica is modified with TiO2 (titania) or Al2O3 (alumina), meeting the limitations of the catalyst support in the reaction system of claim 9, since the “at least one” language indicates that the support can be a mixture of the recited species. In paragraph 9 Endou further discloses that the catalyst preferably comprises ruthenium (Ru) as a precious metal, and in paragraph 10 discloses that the catalyst can further include tin (Sn), meeting the limitations of the catalyst recited in amended claim 11. In paragraph 20 (Example 1) Endou specifically discloses an RuSn catalyst on a SiO2/TiO2 support. In paragraph 16 Endou discloses suitable organic carboxylic acids, including various monocarboxylic acids, and in paragraph 32 Endou discloses that the method leads to the production of the corresponding alcohols in high yield with high selectivity. While Endou refers to the reaction as a hydrogenation, the removal of oxygen when the acid is converted to the corresponding alcohol renders the reaction a hydrodeoxygenation. In paragraph 15 Endou discloses that the reaction can be carried out as a liquid-phase suspension or a fixed-bed reaction method in the presence of the acids, hydrogen, and catalyst; the vessel in which this reaction is carried out, such as a fixed-bed reactor, meets the limitations of the hydrodeoxygenation reaction unit of amended claim 9.
The difference between Endou and the currently presented claims is that Endou does not disclose a dual-bed catalyst system having a hydrodeoxygenation reaction unit and a dehydration reaction unit, where the butanol can be dehydrated to an alpha-olefin in the dehydration reaction unit.
With respect to i), Ziehe, on page 1 lines 5-7 and page 2 line 20 through page 3 line 3, discloses a process for selectively producing α-olefins by dehydration of alcohols in the presence of γ-alumina, corresponding to the dehydration reaction recited in claim 9. On page 3 lines 5-9 Ziehe discloses that preferred alcohols include various alcohols which correspond to the acids disclosed in paragraph 16 of Endou. Ziehe therefore discloses a dehydration reaction unit configured to supply an effluent from the hydrodeoxygenation reaction unit to a reaction system comprising a dehydration catalyst and to form an alpha-olefin, as recited in claim 9.
While Endou and Ziehe do not specifically performing a dehydration reaction at the WHSV recited in amended claim 9, it is noted that the claims only require that the dehydration reaction system is “configured” to have the WHSV. Since the WHSV of a system depends on the weight of feed and the weight of catalyst, the WHSV can be controlled by the operator of the system; any dehydration reaction system selectively producing α-olefins by dehydration of alcohols in the presence of γ-alumina can therefore be considered to be “configured” to have a WHSV within the range recited in amended claim 9.
It would have been obvious to one of ordinary skill in the art to perform the method of Endou in view of Ziehe in a dual bed catalyst system comprising a separate hydrodeoxygenation reaction unit and dehydration reaction unit, since Endou teaches a that the catalyst used for the hydrodeoxygenation reaction is highly selective for producing alcohols, and Ziehe teaches that the catalyst used for the dehydration reaction is highly selective for producing alpha-olefins from alcohols, and carrying out the reactions in separate reaction units in a dual-bed system, meeting the limitations of claims 9 and 11-12 ensures high selectivity and minimizes the chance of undesired by-products.
Claims 9-10 and 12 are rejected under 35 U.S.C. 103 as being unpatentable over Onyestyak (Onyestyak, G., Harnos, S., Kallo, D., “Improving the catalytic behavior of Ni/Al2O3 by indium in reduction of carboxylic acid to alcohol”, Catalysis Communications, 2011, 16, 184-188) in view of Ziehe (WO 2004/078336 A1).
In the experimental section on page 185, Onyestyak discloses carrying out the hydrogenation of octanoic acid in the presence of hydrogen and a catalyst at a temperature of 240 to 360° C, and in Figures 1-2 Onyestyak discloses the conversion of octanoic acid to octanol with the use of Al2O3-supported catalysts, as recited for the catalyst in the reaction system of claim 9. It is noted that while Onyestyak refers to this as a hydrogenation, the removal of oxygen when octanoic acid is converted to octanol renders the reaction a hydrodeoxygenation, as recited in claim 9.
Onyestyak does not disclose the further dehydration of octanol to an alpha-olefin, and does not specifically disclose a dual-bed catalyst system having a hydrodeoxygenation reaction unit and a dehydration reaction unit. This relates to claims 9-10.
With respect to i), Ziehe, on page 1 lines 5-7 and page 2 line 20 through page 3 line 3, discloses a process for selectively producing α-olefins by dehydration of alcohols in the presence of γ-alumina, corresponding to the dehydration reaction recited in claim 9.
Onyestyak discloses in the “Results and discussion” section on the right column of page 185 that the reaction is stopped at the conversion of octanoic acid to octanol, before conversion to octenes, dioctyl ether, and eventually octane. Figures 1B and 4B of Onyestyak teach that the catalysts of Onyestyak lead to a high proportion of dioctyl ether relative to octenes in this case, and it is unclear what proportion of the octenes are 1-octenes, as desired by Ziehe.
While Onyestyak and Ziehe do not specifically performing a dehydration reaction at the WHSV recited in amended claim 9, it is noted that the claims only require that the dehydration reaction system is “configured” to have the WHSV. Since the WHSV of a system depends on the weight of feed and the weight of catalyst, the WHSV can be controlled by the operator of the system; any dehydration reaction system selectively producing α-olefins by dehydration of alcohols in the presence of γ-alumina can therefore be considered to be “configured” to have a WHSV within the range recited in amended claim 9.
It would therefore be obvious to one of ordinary skill in the art to perform the method of Onyestyak and Ziehe in a dual-bed catalyst system, meeting the limitations of claims 9-10 and 12, where the hydrodeoxygenation reaction of Onyestyak and the dehydration reaction of Ziehe are performed in separate units or zones with separate catalysts within the same unit in order to achieve the high α-olefin selectivity of Ziehe without competing reactions catalyzed by the catalyst of Onyestyak.
Allowable Subject Matter
The amendments filed 1/13/26 incorporate the limitations of previous claim 8, indicated as containing allowable subject matter in the office action mailed 10/15/25, into claim 1. Amended claim 1 and its dependent claims require the reaction system filled with the dehydration reaction catalyst to have a WHSV of greater than 0.5 h-1 and less than 1.75 h-1. In the examples on page 7, Ziehe, discussed in the office action mailed 10/15/25, discloses operating the reactor with a hexanol flow rate of 2 ml/min, which equates to an hourly flow rate of about 98 ml/hr (density of hexanol = 0.814 g/ml). The reactor of Ziehe contains 7.2 to 9.9 grams of catalyst, leading to a WHSV of about 9.9 to about 14 h-1, far outside the claimed range. While Ziehe also teaches (example 4 in figure 2, see page 6 lines 20-26) an example with a flow rate of 1 ml/min, this leads to WHSV of about 5 to about 7, still well outside the claimed range. While dehydration processes using a WHSV in ranges overlapping the claimed range are known in the art, one of ordinary skill in the art would have no motivation to modify Ziehe to use the much lower WHSV range recited in the amended claims, since Ziehe teaches that the method using the disclosed WHSV leads to high selectivity for alpha-olefins. Amended claims 1-7 are therefore allowable over the prior art.
Response to Arguments
Applicant's arguments filed 1/13/26 have been fully considered but they are not persuasive. Applicant argues that claim 9 has been amended to include similar language as amended into claim 1, and also to include elements related to the composition of the carrier which are allegedly not taught or suggested in the cited references. However, as discussed in the above rejections, Onyestyak discloses Al2O3-supported catalysts, as recited in amended claim 9, and the newly applied Kim reference discloses SiO2, Al2O3, and TiO2 references for converting carboxylic acids into alcohols. Also as discussed in the rejection, even thought the cited references do not disclose performing the dehydration reaction at the WHSV recited in amended claim 9, the claim only requires that the dehydration reaction unit be “configured” to perform the reaction at the recited WHSV, and since the WHSV of a system depends on the weight of feed and the weight of catalyst, the WHSV can be controlled by the operator of the system; any dehydration reaction system selectively producing α-olefins by dehydration of alcohols in the presence of γ-alumina can therefore be considered to be “configured” to have a WHSV within the range recited in amended claim 9.
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). 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.
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/JAMES C GOLOBOY/Primary Examiner, Art Unit 1771