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 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, 2, and 5–13 are rejected under 35 U.S.C. §103 as being unpatentable over Garforth et al. (EP 2649121 B1) in view of Streed et al. (US 3,702,818), and further in view of Pierre et al. (EP 0214717 A1).
Garforth discloses a process for hydrodepolymerization/hydrocracking of polymeric waste material comprising plastic wastes such as PE and PP (¶¶[0013], [0016], [0018], [0020]) by contacting the polymeric waste with a hydrocracking catalyst comprising a metal hydrogenation function and an acidic cracking function, wherein conventional hydrogenation components include Pt, Pd, Ni, Co/Mo and Ni/Mo and conventional acidic supports include alumina, amorphous silica-alumina and zeolites (¶[0005]). Garforth further teaches catalysts comprising metals such as Fe or Ni and zeolitic materials (¶¶[0067]–[0069], [0072]), treatment in the presence of hydrogen at pressures including about 35–60 bar (claims 1 and 6), temperatures including 150–400°C (¶[0042]), and separation of the resulting hydrocracked product into gaseous and liquid hydrocarbon products (Figs. 1–2). These pressure and temperature ranges overlap the presently claimed 20–500 bar and 200–550°C ranges. The teachings of Garforth relied upon in the previous rejection are summarized in the prior Office Action.
Garforth does not expressly teach that the hydrogenation catalyst and acidic depolymerization catalyst are separate catalysts physically mixed together, that the acidic compound is specifically Zeolite Beta, or that the hydrogenation catalyst and depolymerization catalyst are present at the claimed 100:1 to 1:3 weight ratio.
Streed teaches hydrocracking catalysts containing hydrogenation components and acidic zeolitic cracking components and expressly teaches that the hydrogenation component may be introduced into the zeolite catalyst by ion exchange, impregnation, or as a physical mixture (col. 6, lines. 50–67).
Pierre teaches that the hydrocracking catalyst comprises Zeolite Beta as the acidic component together with a hydrogenation-dehydrogenation component, including metals such as Cr, Mo, W, Co, and Ni, and further teaches that the hydrogenation component may be exchanged onto, impregnated into, or physically admixed with the Zeolite Beta. (See pages 4-5 and 9)
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 hydrocracking catalyst system of Garforth by providing the hydrogenation catalyst and acidic depolymerization catalyst as physically mixed components, as taught by Streed, and by employing Zeolite Beta as the acidic depolymerization catalyst, as taught by Pierre, because Pierre expressly teaches Zeolite Beta as an effective acidic hydrocracking component having useful cracking and hydroisomerization properties and expressly teaches combining it with hydrogenation components, including by physical admixture.
Regarding the claimed 100:1 to 1:3 weight ratio, Garforth expressly teaches that the balance between the acidic and metal functions is critical to hydrocracking catalyst performance (¶[0005]). Thus, once the hydrogenation and acidic functions are provided as separate physically mixed catalyst components in accordance with Streed and Pierre, their relative quantities would necessarily be selected to provide an effective balance of hydrogenation and cracking activities. The claimed range is broad, encompassing hydrogenation-catalyst-rich mixtures through mixtures containing three parts depolymerization catalyst per part hydrogenation catalyst.
Accordingly, it would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have selected and adjusted the relative amounts of the physically mixed hydrogenation catalyst and depolymerization catalyst, including a weight ratio within the broadly claimed range of 100:1 to 1:3, through routine optimization of the known balance between hydrogenation and acidic cracking activity to obtain effective hydrocracking of the feedstock. Garforth's statement that the optimum balance cannot be determined ab initio does not teach away from such optimization, but rather indicates that the optimum balance is selected experimentally for the particular catalyst and process.
Regarding claim 2, Garforth teaches conventional hydrocracking catalysts in which the hydrogenating metal is supported on an acidic carrier that itself provides the cracking function, including alumina and silica-alumina (¶[0005]). Thus, Garforth teaches an embodiment in which the inorganic carrier of the hydrogenating component itself provides the depolymerizing/acidic function.
Regarding claim 5, Garforth teaches hydrocracking catalysts comprising metal hydrogenation components, including embodiments containing about 10-75 wt.% metal (¶¶[0067]–[0069], [0072]), thereby encompassing or overlapping the claimed 0.5-25 wt.% active hydrogenation species at least over the 10*-5 wt.% portion of the claimed range. Pierre additionally confirms that hydrogenation-metal amount is selected according to catalytic activity, teaching about 1 wt.% or less Pt, about 7 wt.% Ni and about 2.1-21 wt.% W.
Regarding claim 6, Garforth does not expressly disclose the claimed catalyst/feed ratio of 1:500 to 1:10. However, catalyst quantity relative to the material being catalytically hydrocracked necessarily must be selected in carrying out Garforth's catalytic hydrocracking process. It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have selected an effective catalyst-to-feed ratio, including a ratio within the broadly claimed range of 1:500 to 1:10, through routine optimization to provide sufficient catalytic activity for hydrocracking of the polymeric waste.
Regarding claim 7, Garforth teaches hydrocracking at about 150-400°C (¶[0042]), which overlaps the claimed 200-550°C range.
Regarding claim 8, Garforth teaches polymeric waste comprising plastic materials including PE, PP and other waste plastics (¶¶[0013], [0016], [0018], [0020]), thereby meeting the requirement that the polymeric waste comprise at least one of the recited plastic materials.
Regarding claim 9, Garforth does not expressly disclose the claimed numerical volatile content measured according to the recited test. Garforth, however, expressly teaches operating its blending chamber at reduced pressure in order to remove volatile components and fumes from the polymeric waste material (¶[0028]). It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have operated the expressly taught volatile-removal step to obtain a suitably devolatilized polymeric waste feed, including a volatile content below 10 wt.%, because Garforth expressly identifies removal of volatile components from the feed as a desired operation.
Regarding claim 10, Garforth teaches processing waste plastics and mechanically handling the plastic feed before hydrocracking. The claimed shredded-material bulk-density range of 50-500 g/L and pellet bulk-density range of 300-700 g/L are broad physical feed-form parameters. It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have selected the size and physical form of the polymeric waste, including shredded material or pellets having an effective bulk density within the claimed ranges, to facilitate feeding and handling of the polymeric material in Garforth's continuous process.
Regarding claim 11, Garforth expressly teaches polymeric waste containing polyolefins, including PE and PP (¶¶[0013], [0016], [0018], [0020]). Selection of a PE- and/or PP-rich feed containing greater than 50 wt.% polyolefin therefore falls within Garforth's disclosed waste-plastic feedstocks.
Regarding claim 12, Garforth expressly provides a dechlorination reaction chamber upstream of subsequent processing and teaches processing PVC-containing waste feeds (¶¶[0029]–[0034]). It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have operated Garforth's expressly taught dechlorination treatment to reduce the chlorine content to an effective low level, including less than 1 wt.%, thereby reducing the amount of chlorine carried into the subsequent hydrocracking operation.
Regarding claim 13, Garforth employs hydrocracking under hydrogen in the presence of a catalyst having a hydrogenation function. It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have operated the hydrogenation/hydrocracking process to provide a hydrodepolymerization product having a reduced degree of unsaturation, including a bromine number below 20 or less than 10 mol.% aromatic protons, because the hydrogenation function is employed to hydrogenate unsaturated hydrocarbon species during hydrocracking. Pierre similarly explains that hydrocracking involves hydrogenation followed by cracking and further hydrogenation.
Claim 4 is rejected under 35 U.S.C. §103 as being unpatentable over Garforth in view of Streed and Pierre, as applied to claim 1 above, and further in view of Rana et al. (US 9,919,293 B1).
Garforth, Streed and Pierre do not expressly disclose that the inorganic carrier of the hydrogenating component has the claimed pore volume of 0.2-4 mL/g. Rana teaches a hydrocracking catalyst having a pore volume of about 0.25-1.5 mL/g, which lies within the claimed range (Rana's Abstract).
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 inorganic catalyst carrier employed in the modified Garforth process to have a pore volume within the range taught by Rana, including within the claimed 0.2–4 mL/g range, because Rana teaches such pore volumes as suitable for hydrocracking catalysts.
Claim 15 is rejected under 35 U.S.C. §103 as being unpatentable over Garforth in view of Streed and Pierre, and further in view of Narayanaswamy et al. (US 2018/0002609 A1).
Garforth, Streed, and Pierre teach or suggest the polymer-waste hydrocracking catalyst and process limitations discussed above, including use of a physical mixture comprising a hydrogenation component and Zeolite Beta acidic component. Garforth itself recognizes that depolymerized thermoplastic products may be used as petrochemical feedstocks, including feed to a naphtha steam cracker for production of ethylene and coproducts.
Narayanaswamy expressly teaches feeding a mixed-plastics-derived stream and hydrogen to a hydrocracker to produce a hydrocracked stream, and then feeding the hydrocracked stream to a steam cracker to produce C1-C4 gaseous hydrocarbons and light gas olefins. See Abstract; ¶¶[0005], [0011]–[0013]; Fig. 1. Narayanaswamy's Figure 1 specifically shows the sequence pyrolysis 100 → hydrocracker 110 → splitter 120 → steam cracker 140, and ¶[0013] states that the C8-and-lighter hydrocracker-derived stream 27 is fed to steam cracker 140, which produces light gas olefins.
It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have further modified the process of Garforth, as modified by Streed and Pierre, by introducing the hydrodepolymerization product into a steam cracker as taught by Narayanaswamy, because Narayanaswamy expressly teaches steam cracking a plastics-derived hydrocracked product to produce light olefins such as ethylene and propylene. Narayanaswamy further explains that steam crackers are primarily used to produce ethylene.
Response to Arguments
Applicant's arguments have been fully considered but are not persuasive.
Applicant argues that Garforth and Streed fail to teach or suggest the claimed catalyst because Garforth does not disclose a physical mixture of separate hydrogenation and depolymerization catalysts, the claimed 100:1 to 1:3 weight ratio, the catalyst-to-feed ratio, the volatile and chlorine limitations, or the claimed product properties. Applicant further argues that substituting Streed's catalyst arrangement into Garforth would require reconstruction of Garforth's process and that Garforth's discussion of balancing acidic and metal functions does not identify catalyst weight ratio as a result-effective variable. The arguments are not persuasive in view of the rejection as presently modified. The rejection does not require Garforth alone to disclose every claimed limitation. Garforth teaches hydrocracking polymeric waste using a catalyst having both a metal hydrogenation function and an acidic cracking function and expressly recognizes that the balance between the acidic and metal functions is critical to catalyst performance. Applicant itself quotes this disclosure in its remarks. Streed further teaches that the hydrogenation component of a hydrocracking catalyst may be introduced into the zeolite catalyst by ion exchange, impregnation, or as a physical mixture. Thus, physical admixture is not an unsupported reconstruction of the hydrocracking process but a known manner of providing the hydrogenation and acidic cracking functions in a hydrocracking catalyst.
Applicant's newly amended claims further require the acidic depolymerization compound to be Zeolite Beta. Pierre et al. (EP 0214717 A1), newly applied in the present rejection, expressly teaches a hydrocracking catalyst comprising Zeolite Beta as the acidic component together with a hydrogenation-dehydrogenation component, including Cr, Mo, W, Co and Ni, and further teaches that the hydrogenation component may be physically admixed with Zeolite Beta. Pierre therefore directly addresses Applicant's argument that the cited art fails to suggest Zeolite Beta or its use in a physically admixed hydrocracking catalyst.
Applicant's argument that modifying Garforth according to Streed would constitute a complete reconstruction or change Garforth's principle of operation is also not persuasive. The proposed modification retains Garforth's same fundamental hydrocracking functions—hydrogenation and acidic cracking—and merely employs a known physical-mixture configuration for providing those functions. Pierre independently confirms that physical admixture of a hydrogenation component with Zeolite Beta is suitable for hydrocracking. Accordingly, the modification does not eliminate or defeat Garforth's hydrocracking principle of operation.
Regarding the 100:1 to 1:3 weight ratio, Applicant argues that Garforth's statement concerning the balance of acidic and metal functions does not expressly identify catalyst weight ratio as the parameter to be adjusted. The argument is acknowledged but is not persuasive. Garforth expressly identifies the relative balance of the two catalytic functions as important to hydrocracking performance. Once those same functions are supplied by separate physically mixed catalyst components, as suggested by Streed and Pierre, adjustment of the relative quantities of those components is a predictable means of adjusting their relative catalytic contributions. The claimed range of 100:1 to 1:3 is also exceptionally broad, extending from a hydrogenation-catalyst-rich mixture to a mixture containing three parts depolymerization catalyst per part hydrogenation catalyst. Accordingly, it would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have selected and adjusted the relative amounts of the physically mixed hydrogenation catalyst and depolymerization catalyst, including amounts within the claimed 100:1 to 1:3 range, to obtain an effective balance of the known hydrogenation and acidic cracking functions. Garforth's statement that the optimum balance cannot be determined ab initio does not teach away from such selection; rather, it indicates that the optimum balance is determined for the particular catalyst and process.
Applicant also argues that there is no evidentiary basis for the catalyst-to-feed ratio and requests evidentiary support for the Examiner's statement that catalyst-to-feed ratio governs conversion and process severity. Applicant's argument is noted. The rejection, however, is based on selecting an effective amount of the hydrocracking catalyst required to carry out Garforth's catalytic conversion, rather than on an assertion that Garforth expressly discloses the claimed numerical ratio. The claimed range of 1:500 to 1:10 encompasses a broad range of catalyst amounts. Accordingly, it would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have selected an effective quantity of hydrocracking catalyst relative to the polymeric feed, including a catalyst-to-feed ratio within the claimed range, to obtain the desired catalytic hydrocracking conversion.
Applicant further argues that Garforth and Streed are silent concerning a feed having less than 10 wt.% volatiles and less than 1 wt.% chlorine. The argument does not account for Garforth's express feed-treatment teachings relied upon in the present rejection. Garforth teaches operation under reduced pressure to remove volatile components and fumes and teaches dechlorination of the polymeric waste before subsequent processing. Thus, the claimed numerical limits represent degrees of the expressly taught removal of undesirable feed components. It would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have operated Garforth's volatile-removal and dechlorination treatments to reduce these components to effective low concentrations, including the claimed levels.
Applicant's arguments concerning claim 4 are likewise not persuasive. Applicant argues that Garforth, Streed and Rana collectively fail to disclose Zeolite Beta, the physical mixture, the catalyst weight ratio, catalyst/feed ratio, volatile and chlorine limitations, and product properties. As explained above, those limitations are addressed by the combined teachings of Garforth, Streed and newly applied Pierre. Rana is additionally relied upon for the particular limitation of claim 4, namely the inorganic carrier pore volume, and teaches hydrocracking catalyst pore volumes overlapping the claimed 0.2-4 mL/g range. Thus, Applicant's argument against the former Garforth/Streed/Rana combination does not address the rejection as presently formulated with Pierre.
Applicant's arguments concerning claim 15 are also not persuasive. Applicant argues that Garforth, Streed and Narayanaswamy fail to teach Zeolite Beta, the physical mixture, the 100:1 to 1:3 ratio, and the catalyst/feed ratio. As discussed above, Pierre is now relied upon for Zeolite Beta and further corroborates physical admixture of the hydrogenation and acidic components. Narayanaswamy is relied upon for the additional steam-cracking limitation. Narayanaswamy expressly teaches feeding a plastics-derived stream together with hydrogen to a hydrocracker and then feeding the resulting hydrocracked stream to a steam cracker to produce C1–C4 hydrocarbons and light gas olefins (Abstract; ¶¶[0005], [0011]–[0013]; Fig. 1). Narayanaswamy specifically explains that the hydrocracked product is subjected to steam cracking to maximize light gas olefins and that steam crackers are primarily used to produce ethylene.
Accordingly, it would have been obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have further modified the process of Garforth, as modified by Streed and Pierre, by introducing the resulting hydrodepolymerization product into a steam cracker as taught by Narayanaswamy in order to produce valuable light olefins.
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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.
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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/TAM M NGUYEN/Primary Examiner, Art Unit 1771
