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 .
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on 24 March 2026 has been entered.
Claim Status
Claim 17 is new.
Claims 1-17 are pending for examination below.
Response to Arguments
Applicant's arguments filed 24 March 2026 have been fully considered but they are not persuasive.
Applicant argues on pages 7-9 of the Remarks that there is evidence that 8 and 10 MR zeolites may perform differently in MTO vs STO, thus it is not obvious to use any 8-MR catalyst in the STO process to achieve the expected to desired results, as which is the Examiner’s position in the rejection.
In response, the Examiner respectfully disagrees that the provided references provide evidence against the general use of 8-MR zeolites in the reaction of Pollefeyt. Pollefeyt explicitly teaches a hybrid catalyst which contains a metal oxide catalyst component physically mixed with a microporous catalyst component (paragraph [0023]), where the metal oxide catalyst component converts the synthesis gas feed stream to oxygenated hydrocarbons, and the microporous catalyst component converts the oxygenates to hydrocarbons (paragraph [0011]). Pollefeyt further explicitly teaches the zeolite should have 8-MR pore openings, and that in embodiments it can have a CHA (chabazite) or ERI (erionite) structure (paragraph [0023]). Thus, the arguments providing evidence that catalysts known to be useful for MTO reactions may not predictably perform as well for STO reactions are not a direct comparison to the prior art relied upon, given that the primary reference Pollefeyt discloses a hybrid catalyst system where one catalyst is responsible for the reaction of syngas to methanol and the other is responsible for the reaction of methanol to olefins. Accordingly, in this scenario, a catalyst known to be useful for MTO reactions would be considered relevant to one of ordinary skill in the art and a modifying reference to Pollefeyt. Forbus and Wunder each teach a natural zeolite having 8-MR pore sizes which is suitable for MTO, and thus it remains obvious to use the natural zeolite of Forbus or Wunder in the process of Pollefeyt, absent any evidence that one of ordinary skill in the art, reading Pollefeyt, would not find it obvious to use any 8-MR zeolite which is suitable for MTO. None of Applicant’s references cited in the Remarks provide evidence that one of ordinary skill in the art would expect the zeolites of Forbus and Wunder to fail to function as the desired MTO component in the process of Pollefeyt, because the comparative references are not commensurate with Pollefeyt. This is because Pollefeyt has a designated physically separate MTO component which is an 8-MR ring zeolite and physically separate syngas to oxygenates component, whereas none of the cited art discusses such a catalyst combination. As such, the combination of Pollefeyt and Forbus or Wunder remains obvious.
Applicant argues on pages 9-11 of the Remarks that regardless of the references used and location of the iron, iron is present in natural erionite, and because of the iron, one of ordinary skill in the art would not think the natural zeolites are suitable for conversion to olefins because iron is a known Fischer-Tropsch active element which one would expect to result in heavy hydrocarbons under STO conditions.
In response, the Examiner respectfully disagrees with the overall conclusion that natural zeolites are not suitable. Whether or not iron is present, Pollefeyt explicitly teaches that the zeolite having 8-MR rings is a physically separate component which is only for converting oxygenates to olefins, as the metal oxide component is used for converting the synthesis gas to the oxygenates (paragraph [0011]). As can be seen from Forbus and Wunder, it is well known in the art that natural zeolites are in fact suitable for converting oxygenates to olefins, as desired by Pollefeyt. With regard to the conditions, Pollefeyt teaches temperatures of 300-500°C and pressures of 10 to 30 bar (paragraphs [0029]-[0030]). Forbus teaches temperatures of 200-500°C and pressures of 50 to 500 psi (3.4 to 34 bar) (column 2, lines 33-35), and Wunder teaches temperatures of 300-500°C (column 3, lines 35-36) and is silent regarding the pressure. The temperatures of Forbus and Wunder overlap the temperatures of Pollefeyt and the pressure of Forbus overlaps the pressure of Pollefeyt. Thus, the presence or absence of iron in the natural zeolites is moot, because the argument that the natural zeolite is not suitable for producing light olefins at the STO conditions is not persuasive. This is because natural zeolites are explicitly used in producing olefins in Forbus and Wunder at similar conditions to Pollefeyt, and Pollefeyt explicitly teaches that the 8-MR component is only for converting oxygenates to olefins.
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.
Claims 1-3, 9-15, and 17 are rejected under 35 U.S.C. 103 as being unpatentable over Pollefeyt et al. (WO 2020/005701) in view of Forbus et al. (US 4,449,961) or Wunder et al. (US 4,481,376).
With regard to claims 1-3 and 15, Pollefeyt teaches a method for preparing C2 and C3 olefins (instant claim 15) (paragraph [0006]), comprising the following:
a) introducing a feed stream comprising synthesis gas comprising hydrogen gas and a carbon-containing gas selected from the group consisting of carbon monoxide, carbon dioxide, and mixtures thereof (paragraph [0001]) into a reaction zone of a reactor; and
b) converting the feed stream into a product stream comprising C2 and C3 olefins in the reaction zone in the presence of a hybrid catalyst (paragraph [0006]).
Pollefeyt further teaches that the hybrid catalyst comprises a metal oxide catalyst component comprising chromium and zinc (mixed metal oxide) and a microporous catalyst component comprising 8-MR pore openings (paragraph [0023]), where the microporous component of the hybrid catalyst converts oxygenates including methanol to the desired hydrocarbons (paragraph [0011])
Pollefeyt is silent with regard to the microporous component being derived from a natural mineral (instant claim 1) which is i) Chabazite, Erionite, or Levyne (instant claim 2) or ii) Heulandite, Phillipsite, Stilbite, or Natrolite (instant claim 3), and also does not specifically teach iii) a combined C2 and C3 selectivity of greater than 40 mol%.
With regard to i) Forbus teaches a process for producing light olefins (instant claim 15) from methanol (column 1, lines 16-18) comprising reacting the methanol over a catalyst comprising 8-membered ring zeolite materials including erionite (instant claim 2) (column 2, lines 26-28). Forbus further teaches that erionite can be natural erionite (instant claims 1 and 2) (column 3, lines 9-12). Forbus additionally teaches that the reaction further comprises adding a diluent comprising synthesis gas (column 2, lines 30-32), where the presence of the combination of 8-membered ring zeolite, methanol, and synthesis gas provides selective conversion of methanol to olefins and enhanced catalyst lifetimes (column 2, lines 18-22). While Pollefeyt teaches a process comprising the simultaneous steps of syngas to methanol and methanol to olefins (paragraph [0011]) and Forbus only teaches the second step of methanol to olefins, where the syngas is present as a diluent (column 2, lines 18-22 and 31), it is clear from the teaching of Pollefeyt that the 8-MR zeolite is the part of the hybrid catalyst which converts methanol to olefins (paragraph [0011]), thus Pollefeyt and Forbus are analogous art for this portion of the process.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the natural erionite of Forbus in the hybrid catalyst of Pollefeyt because Pollefeyt and Forbus each teach conversion of a stream comprising oxygenates including methanol and synthesis gas over an 8-MR pore opening zeolite catalyst to light olefins, and Forbus further teaches that 8-membered ring zeolite catalysts including natural erionite provide the benefits of selective conversion to olefins and enhanced catalyst lifetimes in the methanol to olefin conversion in the presence of syngas (column 2, lines 19-21 and 32).
With regard to ii) Wunder teaches a process for producing lower olefins (instant claim 15) from methanol (column 1, lines 1-3) comprising reacting the methanol over a catalyst comprising hafnium or zirconium on natural natrolite (instant claims 1 and 3) (column 1, lines 59-64). Wunder also teaches that the catalyst provides the benefits of a selective conversion to ethylene and propylene with long operating times between regenerations (column 3, lines 48-51).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the catalyst comprising natural natrolite of Wunder in the process of Pollefeyt, because Pollefeyt and Wunder each teach oxygenate conversion to light olefins over a catalyst comprising an 8-MR zeolite, and Wunder teaches that the catalyst comprising hafnium or zirconium on natural natrolite provides the benefits of a selective conversion to ethylene and propylene with long operating times between regenerations (column 3, lines 48-51).
With regard to C2 and C3 selectivity iii), Pollefeyt teaches that the purpose of the syngas to olefins process is to produce C2 and C3 olefins (paragraph [0006]), Forbus teaches that the methanol to olefins reaction using natural erionite is selective to light olefins (column 2, lines 19-20) and Wunder teaches that the desire for the methanol to olefins process comprising natural natrolite is an increase in the selectivity of lower olefins (column 2, lines 28-29). Therefore, because Pollefeyt in view of Forbus or Wunder teaches the similar process comprising a similar catalyst hybrid catalyst comprising natural erionite (Forbus) or natural natrolite (Wunder), where each process has the similar goal of being selective to lower olefins including C2 and C3 olefins, one of ordinary skill in the art would reasonably expect the process to have the similar result of a combined C2 and C3 selectivity of greater than 40 carbon mol% as claimed, absent any evidence to the contrary.
With regard to claims 9 and 10, Pollefeyt teaches that the conditions include a temperature of from 400 to 500°C (paragraph [0029]) which is within the range of 300 to 500°C of instant claim 9 and overlaps the range of 400 to 470°C of instant claim 10, rendering the range prima facie obvious.
With regard to claim 11, Pollefeyt teaches the reaction conditions include a pressure of at least about 20 bar (paragraph [0030]), which overlaps the range of 20 to 70 bar of instant claim 11, rendering the range prima facie obvious.
With regard to claim 12, Pollefeyt is silent with regard to the gas hourly space velocity. However, the gas hourly space velocity is a process parameter with affects the conversion and selectivity of the reactants, and thus can be optimized. Therefore, it would have been obvious to one having ordinary skill in the art to have determined the optimum value of a GHSV of greater than 500 hr-1 as claimed, through routine experimentation in the absence of a showing of criticality. See MPEP 2144.05(II).
With regard to claim 13, Pollefeyt teaches that the ratio of metal oxide catalyst to microporous catalyst is 0.1:1 to 10:1 (paragraph [0024]), which overlaps the range of 1:1 to 10:1 of instant claim 13, and renders the range prima facie obvious.
With regard to claim 14, Pollefeyt in view of Forbus or Wunder does not explicitly teach that the product has a C2/C-3 molar ratio of greater than or equal to 1.0. However, Pollefeyt teaches that the process is to produce C2 and C3 olefins, Forbus teaches that the reaction is selective conversion to light olefins (column 2, lines 19-20) and Wunder teaches that the desire is an increase in the selectivity of lower olefins (column 2, lines 28-29). Therefore, because Pollefeyt in view of Forbus or Wunder teaches the similar process comprising a similar catalyst with the similar goal of producing lower olefins, one of ordinary skill in the art would reasonably expect the process to have the similar result of a C2/C3 molar ratio of greater than or equal to 1.0 as claimed, absent any evidence to the contrary.
With regard to claim 17, the claim recites that the natural mineral “may be” ion exchanged. Thus, the limitation in claim 17 is optional, and the method of Pollefeyt in view of Forbus or Wunder renders obvious the claim.
Alternatively, Forbus teaches ion exchange of the natural zeolite with ammonium ions (column 3, lines 58-60) where the ammonium ions are present as ammonium salts in an aqueous solution (column 12, Example VIII).
Claims 4 and 5 are rejected under 35 U.S.C. 103 as being unpatentable over Pollefeyt et al. (WO 2020/005701) in view of Forbus et al. (US 4,449,961) or Wunder et al. (US 4,481,376) as applied to claim 1 above as evidenced by mindat.org (Erionite) or mindat.org (Natrolite).
With regard to claims 4 and 5, Pollefeyt in view of Forbus or Wunder teaches the natural erionite and natural natrolite above. Forbus and Wunder do not explicitly teach the silica to alumina ratio of the natural erionite or natural natrolite. However, these are naturally occurring structures, and thus have a known formula. Mindat.org teaches that the formula for Erionite is Ca3K2Na2[Al10Si26O72] · 30H2O (page 2) and that the formula for Natrolite is Na2Al2Si3O10 · 2H2O (page 1). The SiO2 to Al2O3 ratio calculated from these formulas are 5.2 and 3 for erionite and natrolite, respectively. These are each within the ranges of less than or equal to 50 and less than or equal to 10 of instant claims 4 and 5.
Claims 6-8 are rejected under 35 U.S.C. 103 as being unpatentable over Pollefeyt et al. (WO 2020/005701) in view of Forbus et al. (US 4,449,961) or Wunder et al. (US 4,481,376) as applied to claim 1 above, and further in view of O’Connor et al. (US 2014/0000157).
With regard to claims 6-8, Pollefeyt in view of Forbus or Wunder teaches the hybrid catalyst above comprising gallium in the metal oxide component (paragraph [0015]) where the metal oxide component converts the hydrogen and carbon oxides to oxygenated hydrocarbons (paragraph [0009]).
Pollefeyt does not explicitly teach that the metal oxide component comprises a support comprising zirconia, or that the amount of metal in the metal oxide component is 0.1 to 10 wt% per the total amount of the metal oxide component
O’Connor teaches a process for conversion of carbon dioxide and hydrogen to oxygenated hydrocarbons (Abstract). O’Connor teaches that the catalyst comprises a metal on a support material which can be zirconia (instant claim 7) (paragraph [0034]) where the metal includes chromium, zinc, and gallium (instant claim 8) (paragraphs [0034], [0041]). O’Connor further teaches that the inclusion of the zirconia support provides oxygen storage capacity which can enhance the catalytic activity of the system (paragraph [0034]).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use a support comprising zirconium for the catalyst comprising chromium, zinc, and gallium of Pollefeyt, because Pollefeyt and O’Connor each teach conversion of carbon oxides and hydrogen to oxygenated hydrocarbons with a catalyst comprising metals including zinc, chromium, and gallium, and O’Connor further teaches that inclusion of the zirconia support provides oxygen storage capacity which can enhance the catalytic activity of the system (paragraph [0034]).
While Pollefeyt in view of O’Connor does not specifically teach the amount of metal when the support is used, this is a process parameter which would determine the cost of the catalyst as well as affecting the activity. Thus, the amount of metal in the metal oxide component comprising a support is a process parameter, and can be optimized. Therefore, it would have been obvious to one having ordinary skill in the art to have determined the optimum value of an amount of metal of 0.1 to 10 wt% per the total amount of metal oxide component, as claimed in instant claim 6, through routine experimentation in the absence of a showing of criticality. See MPEP 2144.05(II).
Claim 16 is rejected under 35 U.S.C. 103 as being unpatentable over Pollefeyt et al. (WO 2020/005701) in view of Forbus et al. (US 4,449,961) or Wunder et al. (US 4,481,376) as applied to claim 1 above, and further in view of Dakka et al. WO 2020/150067).
With regard to claim 16, Pollefeyt in view of Forbus or Wunder teaches the method above.
Pollefeyt in view of Forbus or Wunder is silent with regard to steaming the catalyst.
Dakka teaches a method for conversion of synthesis gas to olefins (paragraph [0016]). Dakka further teaches that the acidic catalyst which converts oxygenates to olefins can have a zeolitic structure (paragraph [0057]) and that after extrusion the zeolite is optionally steamed (paragraphs [0063], [0065]).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to steam the catalyst of Forbus or Wunder before using in the method of Pollefeyt, because each of Forbus, Wunder, and Dakka teach a zeolitic framework for an oxygenate conversion catalyst, and Dakka further teaches that when the catalyst is used in the conversion of syngas to olefins, it is known to steam the catalyst before use (paragraphs [0063], [0065]).
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to ALYSSA L CEPLUCH whose telephone number is (571)270-5752. The examiner can normally be reached M-F, 8:30 am-5 pm, EST.
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/Alyssa L Cepluch/Examiner, Art Unit 1772
/Renee Robinson/Primary Examiner, Art Unit 1772
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