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 .
Terminal Disclaimer
The terminal disclaimer filed on 7/28/2026 disclaiming the terminal portion of any patent granted on this application which would extend beyond the expiration date of US 12,084,622 and US 12,012,562 has been reviewed and is accepted. The terminal disclaimer has been recorded.
Response to Arguments
Applicant's argument that the previous rejection failed to address the requirement of at least 2.0 wt% C17–C18 together with FBP ≤300°C is persuasive; therefore, the previous Office Action rejections are withdrawn by the examiner.
A new Non-Final Office follows.
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.
Claims 1-3, 5-6, 10, and 15-17 are rejected under 35 U.S.C. §103 as being unpatentable over Lilga et al. (US 2017/0369804 A1) in view of Cantrell et al. (US 2012/0197053 A1), Kuechler et al. (US 2006/0199984 A1), and Peters et al. (US 2014/0051897 A1).
Regarding independent claims 1 and 15, Lilga teaches a two-step oligomerization process in which ethylene is converted in a first oligomerization stage to predominantly C4-C8 olefins, including butenes, hexenes and octenes, which are further oligomerized to higher-molecular-weight fuel-range hydrocarbons; Lilga further teaches hydrogenation of the resulting olefinic fractions to paraffin/isoparaffin fuel blendstocks (Lilga ¶¶ [0021]-[0022], [0068]-[0070], [0084]-[0086]).
Lilga does not expressly teach all of the claimed intermediate-separation and final jet-blend limitations.
Cantrell expressly teaches a first oligomerization reactor, a separator configured to remove unreacted olefin from the first oligomerization product, and a second oligomerization reactor receiving the resulting unreacted-olefin-reduced product; the feed may comprise primarily ethylene, the first oligomerization product may comprise primarily butene, and the second reactor converts the first-stage oligomers to longer-chain olefins (Cantrell ¶¶ [0015]-[0020]). Cantrell therefore provides the claimed serial first-oligomerization/separation/further-oligomerization architecture. Cantrell also demonstrates an ethylene feed containing 99.5 wt% ethylene, 7.7 ppm methane, 420.9 ppm ethane and less than 1 ppm CO, followed by purification before oligomerization (Cantrell ¶¶ [0174]-[0176], Table A). Cantrell's primary oligomerization converts that purified ethylene feed to butene and heavier olefins and sends the product to a secondary oligomerization reactor (Cantrell ¶¶ [0176]-[0177], Tables C–D).
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to modify the two-stage oligomerization process of Lilga to incorporate the intermediate separator and serial reactor arrangement taught by Cantrell, because Cantrell expressly teaches removing unreacted/light material from the first oligomerization product before further oligomerization, thereby providing an olefin-enriched intermediate suitable for conversion to higher oligomers.
It would further have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to employ the purified ethylene feed taught by Cantrell in Lilga's process, thereby providing an ethylene stream having at least 50 wt% ethylene and no greater than 1000 wppm methane, because Cantrell expressly demonstrates 99.5 wt% ethylene and only 7.7 ppm methane.
Kuechler teaches oligomerization-derived jet-fuel compositions containing more than 90 wt% non-normal olefins and subsequently hydrogenates those compositions with hydrogen over Ni or Pd catalyst. Hydrogenation does not significantly change the non-normal character, and the hydrogenated products are almost completely aliphatic with very low aromatic content (Kuechler ¶¶ [0115]-[0119]).
More particularly, Kuechler Table 5 reports:
Distillate 1: C17 = 2.15 wt%, C18 = 1.46 wt%, C19 = 1.24 wt%, C20 = 0.96 wt%;
Distillate 2: C17 = 2.53 wt%, C18 = 1.73 wt%, C19 = 1.07 wt%, C20 = 0.70 wt%.
Thus, Distillates 1 and 2 contain respectively 3.61 wt% and 4.26 wt% C17–C18, while their C19–C20 contents are only 2.20 wt% and 1.77 wt%; Kuechler further reports no products above C21 and the Table 5 distributions total 100 wt%.
Kuechler's hydrogenated Distillate 2 has T10 = 165°C, FBP = 293°C, and freeze point = −62°C, thereby expressly demonstrating that an oligomerized/hydrogenated composition may retain greater than 2 wt% C17–C18 while having a final boiling point below 300°C. Kuechler further teaches blending hydrogenated oligomerization product with petroleum-derived JP-8, and expressly observes that the distillation endpoint of the blend is lower than the endpoint of the neat synthetic distillate (Kuechler ¶ [0120], Table 7).
Peters teaches blending synthesized paraffinic kerosene with conventional jet fuel and expressly discloses synthetic blendstock proportions of 30, 35, 40, 45, and 50%, which overlap the claimed 30-99 vol% hydrotreated component and 1-70 vol% mineral jet fraction. Peters further teaches that varying the synthetic/conventional blend and oligomer distribution is used to tune the final jet-fuel distillation characteristics (Peters ¶¶ [0132]-[0140]).
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to use the hydrogenated, highly non-normal oligomerization product taught by Kuechler as the hydrotreated jet-fuel component of Lilga and blend it with conventional mineral jet fuel in a proportion taught by Peters, because Kuechler expressly identifies such hydrogenated oligomerization products as jet-fuel blendstocks and Peters expressly teaches selecting the synthetic/mineral blend ratio to obtain the required aviation-fuel boiling characteristics. For example, selecting the expressly taught 50% synthetic/50% conventional-jet blend of Peters in combination with Kuechler's Distillate 2 provides a blend within the claimed 30–99/1–70 vol% ranges. Kuechler's Distillate 2 itself contains 4.26 wt% C17–C18, has FBP 293°C, T10 165°C, and freeze point −62°C, while Kuechler demonstrates that blending such synthetic material with petroleum jet lowers rather than raises the distillation endpoint. Accordingly, the combination teaches or renders obvious the limitations of claims 1 and 15 relating to a hydrotreated highly branched/isoparaffinic jet component, ≤5 wt% C19+ hydrocarbons, the claimed synthetic/mineral blend proportions, T10 ≤205°C, FBP ≤300°C, freeze point ≤−40°C, and ≥2 wt% C17–C18 hydrocarbons.
For claim 15, Cantrell also teaches that an olefin-production stream may contain hydrogen and carbon monoxide and teaches substantially complete removal of non-olefin gas species before oligomerization. Cantrell's Example 1 actually reduces CO to less than 1 ppm. It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to operate Cantrell's known gas-cleanup operation sufficiently to reduce residual CO and H2 to no greater than 20 wppm each before oligomerization, because Cantrell expressly teaches removal of those non-olefin gas species and substantially complete purification of the olefin stream.
Regarding claim 2, Kuechler teaches compositions containing at least 90 wt% non-normal olefins/non-normal saturates and embodiments containing 60–90 wt% such non-normal material. Kuechler further teaches that hydrogenation substantially preserves the non-normal character while producing material that is almost completely aliphatic. Because Kuechler's products have very low normal-paraffin, aromatic and naphthenic contents, the disclosed non-normal aliphatic material renders obvious a product comprising at least 60 wt% combined isoolefins/isoparaffins.
Regarding claims 3 and 16, Kuechler's disclosed ≥ 90 wt% non-normal compositions likewise encompass and render obvious at least 70 wt% combined isoolefin/isoparaffin content.
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to select the highly non-normal Kuechler hydrogenation product for use as the synthetic component of Lilga, thereby obtaining the claimed ≥ 60 wt% or ≥ 70 wt% branched olefin/paraffin content because such compositions are expressly taught as desirable aviation-fuel blendstocks.
Claims 5 and 17 further require the C4+ stream to contain no greater than 5 wt% methane, ethylene and ethane combined.
Cantrell teaches a first oligomerization product comprising primarily butene, separation of unreacted olefin before the second oligomerization, and an ethylene feed containing only 7.7 ppm methane and 420.9 ppm ethane.
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to operate Cantrell's intermediate separation sufficiently to provide the C4+-rich product with no greater than 5 wt% methane, ethylene and ethane combined, because Cantrell expressly removes unreacted olefin from the predominantly butene product and begins with an ethylene feed containing only trace methane and ethane.
Claim 6 narrows the same residual lights concentration to no greater than 2000 wppm.
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to increase the separation efficiency of Cantrell's known intermediate separator to reduce residual methane, ethylene and ethane to no greater than 2000 wppm, because the residual concentration of the separated light components is a result-effective variable controlled by the operating severity of the separation.
Cantrell expressly teaches separating a C2–C30 olefin stream from the second oligomerization product and recycling at least a portion of that olefin stream to the second oligomerization reactor; it likewise teaches recycling unreacted olefins removed by a downstream separator to the second oligomerization reactor (Cantrell ¶¶ [0021]-[0022]).
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to recycle the unconverted C4+ portion of the second oligomerization product to the second oligomerization stage of Lilga, as taught by Cantrell, to further convert unreacted olefins and increase production of higher-molecular-weight fuel-range hydrocarbons.
Claims 7-8, 11-14, and 18-19 are rejected under 35 U.S.C. §103 as being unpatentable over Lilga in view of Cantrell, Kuechler, and Peters as applied above, and further in view of Kuzma et al. (US 2016/0362352 A1).
The processes of Lilga in view of Cantrell, Kuechler, and Peters are as discussed above.
Kuzma expressly concerns conversion of methanol to olefins and recovery of ethylene from the resulting MTO effluent. Kuzma teaches that MTO effluent contains methane, ethylene and ethane and that separation is used to recover an ethylene-rich stream (Kuzma ¶¶ [0004]-[0009]). Kuzma further teaches MTO products including ethylene and propylene; methane and ethane are identified as MTO by-products whose concentrations vary with feedstock, reactor, reaction conditions and catalyst (Kuzma ¶¶ [0027]-[0031]).
Regarding claims 7 and 18, Cantrell demonstrates a purified ethylene stream having CO < 1 ppm and teaches removal of non-olefin gas contaminants, while Kuzma teaches an MTO recovery arrangement in which ethylene and ethane are recovered together before further separation.
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have modified the process of Lilga by operating the known MTO ethylene-recovery/purification train so that the ethylene product retains at least 2000 wppm ethane while CO and H2 are reduced to no greater than 5 wppm each, because Kuzma expressly permits recovery of an ethylene/ethane fraction and Cantrell demonstrates purification of oxygenate-derived ethylene to trace contaminant levels.
Regarding claims 8 and 19, Kuzma expressly teaches that separation zone 140 recovers ethylene 40 and an additional hydrocarbon product 42 comprising “propylene and higher olefins” (Kuzma ¶ [0042]).
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to combine the propylene/higher-olefin fraction recovered by Kuzma with the C4+ first-stage oligomerization product of Lilga/Cantrell before the second oligomerization reactor, because both are suitable olefin feeds for conversion to higher fuel-range oligomers and combining them permits recovery and conversion of the available propylene/C4+ material rather than discarding it.
Regarding claim 11, Kuzma expressly teaches converting methanol to an MTO effluent comprising ethylene, propylene, methane, ethane and higher hydrocarbons and subsequently separating the effluent to recover ethylene and other olefin products. Ethylene concentrations of at least approximately 10, 20, or 30 mole% are disclosed, while methane is expressly present and may be several mole percent (Kuzma ¶¶ [0027]-[0031]).
Kuzma also teaches carbon monoxide as a component that may be present in the oxygenate feed/MTO system and teaches that MTO by-product concentrations depend upon feed composition, reactor configuration, reaction conditions and catalyst. Cantrell independently establishes that oxygenate-to-olefin reactor products conventionally contain carbon monoxide and hydrogen before purification.
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to use the MTO process of Kuzma as the source of Lilga's ethylene and propylene/C4+ feeds and to separate the raw MTO stream using the known purification operations of Kuzma and Cantrell, because Lilga expressly identifies methanol-derived ethylene as a suitable feed and Kuzma teaches the corresponding industrial MTO-production and separation process.
The concentrations of methane, ethane, CO and H2 in the raw olefin stream are operating-dependent concentrations. Selecting an MTO effluent containing at least 1000 wppm methane and ethane and at least 100 wppm CO and H2 before purification would have been an obvious selection of the known raw oxygenate-derived olefin composition, followed by removal of those species to obtain the desired ethylene feed.
Regarding claim 12, Kuzma expressly teaches forming a light hydrocarbon fraction containing ethylene and ethane, with subsequent ethane separation being optional downstream processing (Kuzma ¶ [0039]).
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to terminate or control the ethylene/ethane separation so that at least 90% of the ethane present in the raw stream remains with the recovered ethylene, where high-purity ethane removal is unnecessary for subsequent oligomerization, because Kuzma expressly teaches recovering ethylene and ethane together and the degree of their subsequent separation is controlled by the fractionation operation.
Regarding claim 13, Kuzma expressly teaches contacting methanol with a zeolite catalyst such as an aluminosilicate to produce light olefins including ethylene (Kuzma ¶ [0005]) and further describes crystalline aluminosilicate zeolite catalysts for MTO conversion (¶ [0024]).
Accordingly, the aluminosilicate catalyst alternative recited in claim 13 is expressly taught by Kuzma; no further modification is required for that alternative.
Regarding claim 14, Kuzma expressly teaches separating the MTO effluent in separation zone 140 to recover ethylene and an additional product comprising propylene and higher olefins.
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to recover that propylene/higher-olefin stream as the claimed propylene/C4+ stream, because Kuzma expressly teaches production of that stream during the same MTO separation used to recover the ethylene stream.
Claim 9 is rejected under 35 U.S.C. §103 as being unpatentable over Lilga in view of Cantrell, Kuechler, and Peters as applied to claim 1 above, and further in view of Anina et al. (EP 2684857 A1).
The references applied to claim 1 are as discussed above.
Lilga/Cantrell do not expressly require that the first oligomerization catalyst be homogeneous.
Anina expressly characterizes its process as a “homogeneous catalyzed ethylene oligomerization technology” and teaches transferring a homogeneous catalyst system with solvent to a reactor wherein dissolved ethylene is oligomerized to linear alpha olefins (Anina ¶¶ [0007]-[0010]).
Cantrell expressly teaches that the second oligomerization catalyst may comprise a solid acid, specifically silica-alumina or ZSM-5, and thus teaches a heterogeneous second-stage catalyst (Cantrell ¶¶ [0015]-[0019]).
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to employ Anina's homogeneous ethylene-oligomerization catalyst in the first oligomerization stage of Lilga/Cantrell while retaining Cantrell's solid heterogeneous catalyst in the second oligomerization stage, because Anina teaches homogeneous catalysts as suitable for selective conversion of ethylene to C4+ alpha-olefin intermediates, while Cantrell teaches solid-acid catalysts for converting those intermediates to longer-chain olefins.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to TAM M NGUYEN whose telephone number is (571)272-1452. The examiner can normally be reached Mon - Frid.
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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Prem C Singh can be reached at 571-273-6381. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/TAM M NGUYEN/Primary Examiner, Art Unit 1771
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