DETAILED ACTION
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
This communication is in response to application filed 3/12/2025.
Claims 1-15 are pending.
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.
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.
Claim(s) 1-12 and 14-15 is/are rejected under 35 U.S.C. 103 as being unpatentable over Pretz (EP 3699163) in view of Peterson (US 7153479).
With respect to claim 1, Pretz (EP 3699163) is directed to a hydrocarbon dehydrogenation processing using oxygen-carrier and oxygen-carrier reactivation and regeneration. A feed stream comprising one or more hydrocarbons is reacted in a dehydrogenation reactor in the presence of a solid catalyst which is an oxygen-carrier material to produce a product. [0017]+; [0041]. The dehydrogenation reaction produces hydrogen which reacts with the oxygen from the catalyst to form water and reduce the oxygen content in the oxygen-carrier material. [0070] The particulate solid from the dehydrogenation reactor is separated from the product and passed to a combustion unit. [0037]-[0040] Catalyst may move through the regenerator upward co-currently with gases or downward countercurrent to the gases. [0039] (“Another possible configuration, designed instead to enable an average catalyst flow downward and an average gas flow upward, comprises a fast fluidized, turbulent, or bubbling bed. Regardless of configuration, heat for the regenerator's combustion comes from a combination of (1) combustion of the deposited coke, i.e., the coke itself supplies heat as a result of the oxidation reaction, which further, and cyclically, combusts more coke; and (2) combustion of a supplemental fuel.”) The combustion unit comprises a gas inlet for oxygen-containing gas and fuel. [0039] The catalyst is subject to regeneration burning coke and fuel. After combustion the catalyst may be passed directly to the dehydrogenation reactor, [0042], or first through a conditions step of the regenerator. [0041]
Pertz teaches where the catalyst flows down through the regeneration unit and oxygen and fuel gases are both passed into the regenerator and move upwards in a countercurrent flow pattern [0039], but is silent regarding the relative locations of the fuel and oxygen inlets, i.e. the fuel inlet located beneath the oxygen-containing gas inlet as claimed.
Peterson (US 7153479) is directed to fluid catalyst regeneration. Peterson teaches a regeneration process and apparatus which operates in a downflow with respect to catalyst, countercurrent mode. “In the regenerator 120 (see FIGS. 2 and 3), there is a standpipe 118 and plug valve 200. Spent catalyst flows down the standpipe 118 and passes through the catalyst plug valve 200. After passing through the plug valve 200, the catalyst changes direction and flows upwardly through the annulus 202 of the spent catalyst centerwell 204 using a fluidization gas introduced via line 125 to distribution ring 204b positioned in the centerwell 204 below the valve 200. The fluidization medium or gas can be, for example, steam, an inert gas, and fuel gas.” Col. 8, lines 51+. “An oxygen-containing gas is preferably not used as the fluidization gas here in order to avoid, or at least minimize, combustion within the centerwell 204. The catalyst is diverted outwardly into the dense phase bed 122 from the circular slot 206 defined by the upper terminus of the centerwell 204 and an outer periphery of annular plate 208. The annular plate 208 is secured about the standpipe 118 and preferably has an outer diameter at least that of the centerwell 204. In this manner the catalyst is distributed radially outwardly into the dense phase catalyst bed 122 well below its upper surface 209.” Col. 8, lines 51+. Slurry may be added to ensure sufficient heat of combustion. Id. “The dense fluidized bed 122 is aerated by air provided by an air grid that preferably takes the form of air distribution ring 210. The ring 210 has a diameter between the outer diameter of the centerwell 204 and the outer diameter of the dense phase bed 122 in the regenerator 120. As the aeration air travels upward from perforations or nozzles 211 into the dense phase bed 122, the slurry oil and the carbon on the catalyst are burned to form CO.sub.2. It is important to introduce the slurry oil/catalyst mixture into the dense phase bed 122 in relatively close proximity to the air and below the upper surface 209 of the bed 122 to ensure good combustion and heat generation within the bed 122.” Col. 9, line 12+. The inlet of the air 210 is above the inlet 204 of the fuel gas 123 or slurry oil 126. Figures 2, 5; col. 8-9.
Therefore, before the filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to utilize a downflow regenerator with air inlet above the fuel inlet in the process of Prez as taught by Peterson because both are directed to catalyst regeneration and both teach using a downflow, countercurrent regenerator, Prez teaches regeneration in a downflow, countercurrent regenerator using both air or oxygen and fuel but is silent regarding the relative inlet positioning which information Peterson supplies, and combination of the inlet positioning of Peterson with the process of Prez would do no more than combine elements known in the art in a known way to perform their respect function and combust coke and fuel in the regenerator. Where the oxygen is contacted with the catalyst particles first, it would have been expected that the oxygen would increase the oxygen content on or in the carrier as discussed with respect to the downstream conditions step [0041], and therefore the oxygen would react with the fuel gas flowing up through the oxygen containing-catalyst as designed to do in the combustor.
With respect to claim 2, in view of the teaching of Prez with respect to the conditioning unit, it is expected that in an area of the regeneration unit above the oxygen gas inlet, the oxygen content in at least a portion of the oxygen-carrier material of the particulate solid increases. Additionally, this would be inherent where the same process is occurring.
With respect to claim 3, “As the aeration air travels upward from perforations or nozzles 211 into the dense phase bed 122, the slurry oil and the carbon on the catalyst are burned to form CO.sub.2.”
With respect to claim 4, “where the target product is an olefin (as distinguished from a di-olefin), that the C3-C4 hydrocarbon feed comprises the corresponding, i.e., same carbon number, starting paraffin, preferably in rich amount. As the term is used herein, "rich amount" means a feed comprising at least 50 percent by weight (wt%) of such paraffin, preferably at least 80 wt%, and most preferably at least 90 wt%.” [0019]
With respect to claim 5, the focus of Prez is production of C3-C4 olefins/diolefins from propane and butane. However, C2 may be in the feed [0018] and ethylene may be produced [0077], though not the focus of this disclosure.
With respect to claim 6, Prez mentions any supplemental fuel may be used. Hydrogen, or light gas from product effluent which includes hydrogen [0032], may be used as fuel. [0079]; see also [0006].
With respect to claim 7, coke is deposited on the particulate solid that passes from the dehydrogenation reactor to the combustion unit, and at least a portion of the coke is reacted with oxygen in the combustion unit.
With respect to claim 8, Pretz teaches generally contact with oxygen, regeneration by combustion followed by conditioning with oxygen, optional stripping, and return to the reactor. A portion of the particulate solid from the combustion unit, or directly from the dehydrogenation unit if regeneration is bypassed, is passed through a conditioning unit for contact with an oxygen-containing gas in the regeneration unit such that the content of oxygen in at least a portion of the oxygen-carrier material of the particulate solid is increased. [0041] “It is within the general understanding of the art that the combination of recycled and at least partially reactivated catalyst may be optimized based preferably upon a combination of feedback from the output of the dehydrogenation reactor and testing of sampled catalyst.” While Pretz does not explicitly teach sending the catalyst serially from the reactor to the condition unit, then to the regenerator, then back to the reactor, it would have been obvious to one of ordinary skill in the art at the time of filing to optimize the flow of catalyst through oxygen conditioning and regeneration to achieve the desired activity of the reactivated catalyst looped to the reactor as taught by Pretz.
With respect to claim 9, the conditioning unit flows concurrently. [0041]
With respect to claim 10, the regeneration unit comprises fuel, oxygen, and optional additional oxygen after combustion, optional stripping before or after each of the oxygen and fuel and optional stripping downstream of the oxygen conditioning to remove free oxygen.
With respect to claim 11, “a portion of the at least partially deactivated catalyst may also or alternatively be cycled back to the regenerator combustor directly without reactivation, with reactivation, or with partial reactivation, via a recycle loop.” [0042].
With respect to claim 12, “a portion of the at least partially deactivated catalyst may also or alternatively be cycled back to the regenerator combustor directly without reactivation, with reactivation, or with partial reactivation, via a recycle loop. The recycled catalyst can be removed at different heights in the reactivation section as desired. It is within the general understanding of the art that the combination of recycled and at least partially deactivated catalyst feed to the combustor may be optimized based upon feedback from the output of the combustor.” Par. [0042]. It would have been obvious and within the skill of one in the art to remove along any height, which would include each of fuel, striping or oxygen zones, of the reactor to achieve the desired heat and activity balance in the system.
With respect to claim 14, the catalyst includes both oxygen-carrier and dehydrogenation catalyst material, [0048]-[0051], and the alkane dehydrogenation is catalytic. Pretz, Abstract (“catalyst which has an activity for dehydrogenating the C3-C4 hydrocarbon feed”).
With respect to claim 15, the dehydrogenation catalyst material and the oxygen-carrier material may be the same particle or may include one or more. Pretz [0050]-[0051].
Claim(s) 13 is/are rejected under 35 U.S.C. 103 as being unpatentable over Pretz (EP 3699163) in view of Peterson (US 7153479) as applied to claims 1-12 and 14-15 above, further in view of Sharma (US 20210245146).
With respect to claim 13, Pretz discloses the limitations discussed above, including wherein one catalyst may be used and provides oxygen to the dehydrogenation reactor, ie an oxygen carrier. Pretz fails to disclose wherein the dehydrogenation of the one or more alkanes is by non-catalytic thermal dehydrogenation.
However, thermal dehydrogenation in the presence of a solid oxygen carrier is known in the art. Sharma is directed to oxygen carriers which are used in dehydrogenation reactions for conversion of paraffins to olefins. [0055] The dehydrogenation reactions may take place in the presence of the oxygen carrier by either thermal cracking or by contact with a dehydrogenation catalyst. [0055] In both, the “paraffin is converted to a olefin and the resulting hydrogen reacts with the hydrogen-selective oxygen carrier material to produce water and a reduced transition metal in the hydrogen-selective oxygen carrier material.” [0055] The reduced hydrogen-selective oxygen carrier material may be subject to regeneration in combustion and reoxidized in air. [0055] Therefore, before the filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to modify Pretz by utilizing a non-catalytic oxygen carrier of Sharma because both are directed to paraffin dehydrogenation, regeneration, and replenishing oxygen of an oxygen carrier, Sharma teaches the oxygen carrier may be used and regenerated in either a thermal or catalyst-assisted dehydrogenation process, and substitution of one would do no more than produce predictable results – conversion of the paraffin to olefin, water, and hydrogen, regeneration of the catalyst for looping, with an expected change in product when the catalyst is replaced with the oxygen carrier of Sharma.
Conclusion
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/BRANDI M DOYLE/Examiner, Art Unit 1771
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