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 .
DETAILED ACTION
Claims 1 and 3-16 of G. Pollefeyt, et al., US 18/547,530 (08/23/2023) are pending. Claims 3-14 are withdrawn as directed to non-elected Group(s). Claims 1 and 14-16 are under examination on merits and are rejected.
Election/Restrictions
Pursuant to the restriction requirement, Applicant elected Group I, without traverse, in the reply filed on 04/23/2026. Applicant cancelled claim 2 and incorporate the subject matter of the claim 2 into claim 1 in the reply filed on 04/23/2026. Claims 3-16 drawn to Groups II-VI are withdrawn from consideration pursuant to 37 CFR 1.142(b). The restriction requirement is maintained as FINAL.
Maintained 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.
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.
35 USC § 103 Rejection over Kirilin and Molinier
Note: The rejection are modified after reconsideration of teachings from the cited prior art.
Claims 1, 14 and 16 are rejected under 35 U.S.C. 103 as being unpatentable over A. Kirilin, et al, WO2020236431A1(2020)(“Kirilin”) in view of M. Molinier, et al, US 20070244000A1 (2007)(“Molinier”)1. Kirilin is effective prior art under 35 USC § 102(a)(1) because: (1) it is published before the effective filling date of the instant application and (2) names other inventors. Applicant may consider an exception under 35 U.S.C. 102(b)(1) to remove Kirilin as prior art.
A. Kirilin, et al, WO2020236431A1(2020)(“Kirilin”)
Kirilin teaches a method for preparing C2 to C5 paraffins including introducing a feed stream of hydrogen gas and a carbon-containing gas selected from carbon monoxide, carbon dioxide, and mixtures thereof into a reaction zone of a reactor. Converting the feed stream into a product stream that includes C2 to C5 paraffins in the reaction zone in the presence of a hybrid catalyst. The hybrid catalyst including a microporous catalyst component; and a metal oxide catalyst component. Kirilin at abstract.
Kirilin teaches that the metal oxide catalyst component converts the feed stream to oxygenated hydrocarbons, and the microporous component converts the intermediated oxygenated products to hydrocarbons. Kirilin at page 4, [0015], line 1-4.
Kirilin teaches that the hybrid catalyst can be prepared by any method known to skilled artisan. Kirilin at page 9, [0031]-[0032].
Kirilin teaches examples of hybrid catalyst such as Example 5 that comprises a metal oxide catalyst component comprising gallium oxide and zirconia; and a microporous catalyst component SSZ-13 that is a molecular sieve having 8-MR pore openings; and the hybrid catalyst in Example 5 is prepared by physical mixing of the metal oxide catalyst component and a microporous catalyst. Kirilin at page 21-23, Example 5.
Per Example 5, Kirilin also teaches a process comprising introducing a feed stream comprising hydrogen gas and carbon monoxide into a reaction zone of a reactor; and converting the feed stream into a product stream comprising Ethane, propane (47%), C4 paraffins at 400 ºC under the pressure of 30 bar in the reaction zone in the presence of the formed Example 5 hybrid catalyst. Kirilin Table 10 at page 22 [0087], and Table 1 at page 14 for the conditions of Condition 7-8.
Difference Between Kirilin and the Claims 1, 14 and 16
The Kirilin process differs from the instant claim 1 in that Kirilin does not teach to use the claimed method to prepare the claimed hybrid catalyst having a binder selected from alumina, zirconia, or both.
M. Molinier, et al, US 20070244000A1 (2007)(“Molinier”)
Similar as Kirilin, Molinier also teaches to prepare hydrocarbon from hydrogen gas and a carbon-containing gas with hybrid catalyst comprising metal oxide and molecular sieve. Molinier at abstract.
Molinier teaches that amorphous materials such as alumina, silica, titania can be used as a binder to prepare hybrid catalyst comprising of a molecular sieve and at least one metal oxide. Molinier at page 7, [0079]. Molinier teaches that hybrid catalyst comprising a molecular sieve and at least one metal oxide can be prepared through forming a slurry by extruding. Molinier at page 8, [0086], line 3-4.
Molinier also teaches that catalyst used for transforming syngas into alcohol is particularly preferred to be resistant to mechanical attrition. Molinier at page 7, [0079],
Obviousness Rationales of Claims 1, 14 and 16
Claims 1 and 16 are obvious because one ordinary skilled artisan seeking propane from hydrogen and carbon monoxide is motivated to modify the Kirilin method by:
(i). prepare a metal oxide catalyst component comprising Ga2O3 and ZrO2.
(ii). mixing the metal oxide catalyst component with the microporous catalyst component SSZ-13;
(iii). adding a solution of alumina as a binder to the above mentioned mixture to form a paste,
(iv). extruding the paste to produce the formed hybrid catalyst; and
(v). replacing the Kirilin Example 5 with the proposed catalyst to transfer H2 and CO into propane as taught by Kirilin.
thus arrive at a process meeting each and every limitation of claims 1 and 16, therefore, claims 1 and 16 are obvious.
One ordinary skilled artisan has a motivation to do so with a reasonable expectation of success because:
(i). by including a binder can maintain the metal oxide (Ga2O3 /ZrO2 ) component and microporous catalyst component SSZ-13 staying together so that once oxygenated hydrocarbons are formed under the catalyzation of the metal oxide (Ga2O3 /ZrO2 ) will be quickly transformed into C2 to C5 paraffins under the catalyzation of the microporous catalyst component SSZ-13.
(ii) Molinier teaches that alumina is one of often used binder for hybrid catalyst preparation.
Claim 14 is obvious because Kirilin teaches to conduct the production at 400 ºC which anticipates the claim 350-480ºC.
Applicant’s Argument
Applicant first argues on the ground that:
The alleged motivation to modify Kirilin is defective because Kirilin has no need for its alleged benefits. The "hybrid catalyst" of Example 5 of Kirilin is a "dual pellet formulation" (e.g., a mixture of particles), which has no need for increased physical stability. Kirilin has no apparent need or desire to keep its metal oxide component and its microporous component together in a single particle. [0085] of Kirilin recites that "[t]he microporous catalyst component ... and the metal oxide catalyst component... were mixed... and shaken for 30 sec." No mention of a further calcination or method to form the mixture of particles into single particles is included in Kirilin. Thus, Kirilin is a mere physical mixture. Kirilin has no need for increased "physical stability" and the skilled person would not have modified Kirilin with the teachings of Molinier.
Paragraph 2 at page 7 in the Remarks filed on 08/10/2026.
This argument has been fully considered but not persuasive. As mentioned in the previous Office action that Kirilin teaches that his hybrid catalyst comprises a metal oxide catalyst component and a microporous component. Kirilin at abstract and page 2, [0009]. Kirilin also teaches that the metal oxide catalyst component converts the feed stream to oxygenated hydrocarbons, and the microporous component converts the intermediated oxygenated products to hydrocarbons. Kirilin at page 4, [0015], line 1-4. Therefore, one of ordinary skill in the art has a motivation to including a binder to maintain both the metal oxide catalyst component and the microporous component together staying together so that once oxygenated hydrocarbons are formed under the catalyzation of the metal oxide will be quickly transformed into C2 to C5 paraffins under the catalyzation of the microporous catalyst component. Molinier teaches that amorphous materials such as alumina, silica, titania can be used as a binder to prepare hybrid catalyst comprising of a molecular sieve and a metal oxide. Therefore, there is a prima facie case of obviousness to modify the Kirilin process in view of the teaching from Molinier.
Applicant’s Argument Regarding Unexpected Results
Applicant argues on unexpected results on the ground that:
Even if a prima facie case of obviousness has been presented, the present specification includes detailed unexpected results for both the presence of the binder and the specific binder selection.
The last line at page 6 to line 2 at page 7 in the Remarks filed on 08/10/2026.
Relevant Sections of the MPEP
A greater than expected result and evidence of unobvious or unexpected advantageous properties are evidentiary factors pertinent to the legal conclusion of obviousness of the claims at issue. MPEP § 716.02(a)(I)/(II). However, the burden is on Applicant to establish that the evidence relied upon demonstrates that the differences in results are in fact unexpected and unobvious and of both statistical and practical significance. MPEP § 716.02(b). Evidence of unexpected properties may be in the form of a direct or indirect comparison of the claimed invention with the closest prior art which is commensurate in scope with the claims. MPEP § 716.02(b)(III).
Furthermore, whether the unexpected results are the result of unexpectedly improved results or a property not taught by the prior art, the objective evidence of nonobviousness must be commensurate in scope with the claims which the evidence is offered to support; that is, the showing of unexpected results must be reviewed to see if the results occur over the entire claimed range. MPEP § 716.02(d). The nonobviousness of a broader claimed range can be supported by evidence based on unexpected results from testing a narrower range if one of ordinary skill in the art would be able to determine a trend in the exemplified data which would allow the artisan to reasonably extend the probative value thereof. MPEP § 716.02(d)(I).
Further, an affidavit or declaration under 37 CFR 1.132 also must compare the claimed subject matter with the closest prior art to be effective to rebut a prima facie case of obviousness. MPEP § 716.02(e).
The Results Proffered in the Specification
The following Table summarizes comparative data from the Table 2 in the specification
PNG
media_image1.png
673
643
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Greyscale
Specification at page 21-22, [0078], Table 2.
The Proffered Results Do Not Overcome the § 103 Rejection Because Applicant Has Not Met Its Burden of Demonstrating that the Proffered Result Is Unexpected
The specification states that:
[0079] As shown in Table 2, the comparison of Examples 1-2 versus Comparative Examples 1-2 demonstrates the improved performance of the single pellet formulation compared to dual pellet mixtures when loading larger particles into the reactor. Whereas dual pellet mixtures suffer from transport limitations, the single pellet formulation retains identical performance between large and small particles loaded in the reactor. Additionally, higher olefin selectivity and C2/C3 ratios are obtained for the single pellet formulation while maintaining low oxygenate selectivity, leading to higher absolute ethylene yields. Single pellet formulations also show a wider window of operability, particularly lowering the operating temperature. As shown in Comparative Example 2 with Condition 2, dual pellet formulations suffer from high oxygenate selectivity when operated at 400 °C.
Specification at page 22, [0079].
It needs to be noted that the particle size of the metal oxide catalyst component in the Example 1-2 catalysts are much smaller (smaller than 75 µm) than those in the Comparative Example 1-2 (177-400µM), thus, the metal oxide particles used in the Example 1-2 catalysts have larger surface area than those used in the Comparative Example 1-2, therefore, it is expected that the Example 1-2 catalysts have better catalytic performance than those of the comparative Example 1-2 catalysts because reactants can be easily catalyzed by catalyst has larger surface area.
Applicant does not provide a persuasive explanation why that the catalytic performance difference between the Example 1-2 catalysts and the Comparative Example 1-2 is caused by the presence of binder rather than because the metal oxide catalyst in the Example 1-2 catalysts is much smaller than the metal oxide catalyst in the comparative Example 1-2 catalysts?
The specification also states that:
[0080] The comparison of Examples 3-4 versus Comparative Examples 3-4 shows the importance of the used binder. Al2O3 and ZrO2 binder give comparable performance, whereas TiO2 and SiO2 binder respectively lead to olefin hydrogenation or poisoning of the catalyst.
Specification at page 23, [0080].
It needs to be noted that the comparative Example 4 is conducted at a different condition as those for the Example 3-4. Also, the concentration of SAPO-34 in the comparative Example 4 (3.2 g of metal oxide with 0.724 g of uncalcined SAPO-34) much less than those in the Example 3 (3.35 g of metal oxide with 1.25 g of calcined SAPO-34) and in the Example 4 (5 g of metal oxide with 2.5 g of calcined SAPO-34). Applicant does not provide a persuasive explanation that why the catalytic difference between Example 3-4 catalysts and Comparative Example 4 catalyst is caused by the presence of different binder rather than the Example 3-4 catalysts has higher percent of SAPO-34 which is a catalyst catalyzes the intermediate oxygenated hydrocarbon to hydrocarbon?
The Example 4 catalyst and the comparative Example 3 catalyst have a same amount of metal oxide (5 g) and a same amount of SAPO-34 (2.5 g of calcined SAPO-34), they have different binders (ZrO2 vs TiO2). Molinier teaches that catalyst comprising zirconium oxide and SAPO molecular catalyze syngas (H2, CO/CO2) into oxygenated hydrocarbon. See Molinier at page 2, left col. line 3-10. Therefore, it is not unexpected that the Example 4 catalyst comprising ZrO2 as a binder has better catalytic activity than that of the compare Example 3 catalyst.
Applicant has provided no explanation of how those difference is unexpected and unobvious and of both statistical and practical significance. MPEP § 716.02(b). Applicant has therefore not met its burden. MPEP § 716.02(b). The burden is on Applicant to establish that the evidence relied upon demonstrates that the differences in results are in fact unexpected and unobvious and of both statistical and practical significance. MPEP § 716.02(b).
The Proffered Results Do Not Overcome the § 103 Rejection Because the Proffered Results are Not Commensurate in Scope with the Claims
Whether the unexpected results are the result of unexpectedly improved results or a property not taught by the prior art, the objective evidence of nonobviousness must be commensurate in scope with the claims which the evidence is offered to support; that is, the showing of unexpected results must be reviewed to see if the results occur over the entire claimed range. MPEP § 716.02(d). Herein, the relatively small number of the binder (AlOOH and Zirconia sol) and/or molecular sieve having 8-MR (SAPO-34) is clearly not commensurate in scope with the large genera of binder and molecular sieve having 8-MR claimed by the claim 1.
35 USC § 103 Rejection over a Combination of Molinier, Wang and Liu
Note: the Rejection is modified after reconsideration of teaching from the recited prior art.
Claims 1 and 14-16 are rejected under 35 U.S.C. 103 as being unpatentable over M. Molinier, et al, US20070244000A1 (2007)(“Molinier”) in view of M. Wang, et al, 394 Journal of Catalysis 181-192 (available online 08/25/2020) (‘Wang”) and X. Liu, et al. 54.2 Chemical Communications 140-143,(2018) (“Liu”).
M. Molinier, et al, US 20070244000A1 (2007)(“ Molinier”)
Molinier teaches a process for production of olefin product high in ethylene and propylene content using synthesis gas (syngas2) as a feed. The syngas is converted to an intermediate composition high in methanol and dimethyl ether using a catalyst of at least two catalyst components, the first including at least one metal oxide and the second including at least one molecular sieve. The intermediate composition is then contacted with an olefin forming catalyst to form the olefin product. Molinier at abstract.
Molinie teaches that the methanol and dimethyl ether composition is converted to olefins by contacting the methanol and dimethyl ether composition with an olefin forming catalyst. Molinie at page 8, [0096]. Regarding the olefin forming catalyst, Molinier teaches that one or a combination of SAPO-34 and ALPO-18 is most preferred. Molinier at page 9, [0099]. Molinie teaches that the olefin product that is produced is high in prime olefin (i.e. ethylene and propylene). Molinier at page 2, [0023], line 8.
Regarding the methanol and dimethyl ether forming catalyst, Molinier teaches that:
According to one aspect of the invention, there is provided a methanol and dimethyl ether forming catalyst comprising a mixture of at least two catalyst components. The first of the catalyst components includes at least one oxide of at least one element selected from the group consisting of copper, silver, zinc, boron, magnesium, aluminum, vanadium, chromium, manganese, gallium, palladium, osmium, and zirconium, and the second of the catalyst components includes at least one MCM or SAPO molecular sieve.
Molinier at page 1, [0013], emphasis added.
Thus, Molinier teaches one of ordinary skill in the art that a hybrid catalyst for transforming syngas into hydrocarbon can comprise of SAPO molecular sieve and metal oxides of Zinc, gallium and zirconium. Molinie teaches that:
the zeolite molecular sieve and the metal oxide are formed into a slurry and the slurry dried to form the alcohol forming catalyst of the invention. Binder and other materials are, optionally, used in forming the slurry. The binder materials used are preferably those that are resistant to high stress conditions such as temperature and mechanical stress conditions that occur in various hydrocarbon conversion processes. It is particularly preferred that the alcohol forming catalyst be resistant to mechanical attrition, that is, the formation of fines which are small particles, e.g., particles having a size of less than 20 microns. Examples of suitable binders that can be used include amorphous materials such as alumina, silica, titania, and various types of clays.
Molinier at page 7, [0079], emphasis added.
Molinie also teaches that:
the slurry of the molecular sieve and metal oxide is fed to a forming unit that produces a dried catalyst composition. Non-limiting examples of forming units include spray dryers, pelletizers, extruders, etc. Typically, the forming unit is maintained at a temperature sufficient to remove most of the liquid (e.g., water) from the slurry.
Molinier at page 8, [0086], emphasis added.
Molinie teaches that:
The conversion of syngas to the methanol and dimethyl ether intermediate can be accomplished over a wide range of temperatures. Lower to mid-temperature ranges are preferred. In one embodiment, the syngas is contacted with the catalysts at a temperature in the range of from about 150° C. to about 550° C., preferably in a range of from about 175° C. to about 450° C., more preferably in a range of from about 200° C. to about 400° C.
Molinier at page 8, [0088], emphasis added.
Molinier teaches working examples, such as Example 8 as follows:
Example 8
[0200] 2 ml of catalyst C were loaded in a reactor and tested for syngas conversion under the following conditions: T=300°C., P=750 psi, GHSV=5000, feed composition: 60% H2, 25% CO, 5% CO2, 10% N2. Average conversions and selectivity over a 20-hour period were as follows:
[0201] COx conversion=2.1%
[0202] Methanol selectivity=63.1%
[0203] Methane selectivity=0%
[0204] DME selectivity=7.8%
[0205]Other C2s, C3s, C4s, and C5+=balance
[0206] As indicated, the amount of methanol remains the major product from the syngas conversion, but ca. 8% DME is also obtained in the product.
Molinier at page 12, Example 8.
Per Example 3, Molinier teaches that the catalyst C is 50% SAPO-11/50% (60% CuO/30% ZnO/10% Mn2O3 (nominal). Molinier at page 11, Example 3.
Thus, the Molinier process such as Example 8 comprising:
(i). introducing a feed stream comprising hydrogen gas, carbon monoxide, and carbon dioxide into a reaction zone of a reactor
(ii). converting the feed stream into a product stream comprising the methanol and dimethyl ether in the presence of a formed hybrid catalyst 50% SAPO-11/50% (60% CuO/30% ZnO/10% Mn2O3).
Difference between Molinier and the Claims
The Molinier that differs from the instant claim 1 in that:
(i). Molinier does not specify to include gallium oxide and zirconia into his a metal oxide catalyst component, however, Molinier teaches that the metal oxide catalyst component includes at least one oxide of at least one element selected from the group consisting of copper, silver, zinc, boron, magnesium, aluminum, vanadium, chromium, manganese, gallium, palladium, osmium, and zirconium. Molinier at page 1, [0013].
(ii). Molinier does not specify to include a binder in his hybrid catalyst, however, Molinier teaches that binder is optionally used for his hybrid catalyst preparation. Molinier at page 7, [0079]
(iii). Molinier does not teach C2 to C4 hydrocarbons are formed in the same reaction zone in the presence of the formed hybrid catalyst, rather Molinier teaches that the olefin product is formed in the presence of an olefin forming catalyst.
M. Wang, et al, 394Journal of Catalysis 181-192 (available online 08/25/2020) (‘Wang”)
Wang teaches that:
Another newly developed route for direct transformation of syngas to C2-C4= is bifunctional catalysis, coupling methanol/ketene synthesis and C-C coupling reactions in one catalyst. This idea is inspired by one of the commercialized processes for the production of C2-C4= which separates methanol synthesis from syngas and methanol (or dimethyl ether, DME) to C2-C4= (MTO). Typical bifunctional catalysts are composed of mixed oxides and zeolites, which are responsible for CO activation and C-C coupling reactions, respectively.
Wang at page 181, right col, paragraph 2 to page 182, left col. line 6.
Wang also teaches that his group has developed a series of bifunctional catalysts composed of ZnO-ZrO2 oxide and SAPO-343 (or SSZ-13) zeolite that bridged methanol synthesis and the MTO reaction, which was named the SMO route (syngas via methanol intermediate to olefin), and the selectivity for C2-C4= could reach 87% at a CO conversion of 10%, or 77% by increasing CO conversion to 29%, wherein methanol and dimethyl ether were confirmed to be the key reaction intermediates. Wang at page 182, left col. line 12-18.
To summarize, Wang teaches:
(1). Synthesis of olefin from syngas can conducted through a bifunctional catalysis, which is an improvement of the two step synthesis (syngas to methanol/dimethyl ether, and methanol/dimethyl ether to olefins); and
(2). hybrid catalyst comprising SAPO-34 and ZnO-ZrO2 is a bifunctional catalyst that can transform syngas into C2-C4= with 77%-87% selectivity.
X. Liu, et al. 54.2 Chemical Communications 140-143,(2018) (“Liu”).
Liu teaches a bifunctional catalyst composed of ZnGa2O4 and SAPO-34, which catalyzes the direct conversion of CO2 to C2-C4 olefins with a selectivity of 86% and a CO2 conversion of 13% at 370°C. The oxygen vacancies on ZnGa2O4 surfaces are responsible for CO2 activation, forming a methanol intermediate, which is then converted into C2-C4 olefins in SAPO-34. Liu at abstract, emphasis added.
Thus, Liu teaches that hybrid catalyst comprising SAPO-34 and ZnO-Ga2O3 is another bifunctional catalyst that can transformation of CO2 into C2-C4= with 86%% selectivity.
Obviousness Rationales of Claims 1 and 14-16
One of ordinary skill in the art would have arrive at the claimed invention before the effective filling date of the instant application in view of the teachings from Liu, Wang and Molinier.
One of ordinary skill in the art seeking preparation of olefins from syngas is motivated to prepare a bifunctional hybrid catalyst comprising SAPO-34 (as a molecular sieve component) and ZnO-ZrO2-Ga2O3 (as metal oxides component), and then use the prepared hybrid catalyst to replace the catalyst C in the Molinier Example 8 to transform syngas into olefin.
One of ordinary skill in the art has a motivation to do so with a reasonable expectation of success for the following reasons:
(ii). Molinier teaches that a hybrid catalyst for transforming syngas into hydrocarbon can comprise of SAPO molecular sieve and metal oxides of zinc, gallium and zirconium.,
(ii). the Molinier method is a two-step method comprising first converting of syngas into syngas to methanol/dimethyl ether with a methanol/dimethyl ether forming catalyst, and methanol/dimethyl ether to olefins with an olefins forming catalyst,
(iii). Wang teaches that the Molinier two-step method can be improved by a bifunctional catalysis method, hybrid catalyst comprising SAPO-34 and ZnO-ZrO2 is a bifunctional catalyst with high olefin selectivity; and,
(iv). Liu teaches hybrid catalyst comprising SAPO-34 and ZnO-Ga2O3 is another bifunctional catalyst.
One of ordinary skill in the art is so motivated because the proposed method can direct transformation of both CO and CO2 in the syngas to olefins high selectivity.
One of ordinary skill in the art is also motivated to include alumina as a binder in the proposed hybrid catalyst by adding alumina to a slurry of SAPO-34 and ZnO-ZrO2-Ga2O3 and extruding of the mixture as taught by Molinier. Molinier at page 8, [0086]. Thus, arrive at a method meeting each and every limitation of claim 1, therefore, claim 1 is obvious. One of ordinary skill in the art has a motivation to include alumina as a binder because Molinier teaches that the hybrid catalyst for hydrocarbon preparation should be resistant to mechanical attrition and alumina is one often used binder. Adding a binder can increase the physical stability of the hybrid catalyst and resistance to mechanical attrition.
Claim 15 is obvious because wang teaches that the selectivity for C2-C4= is 77%-87% for catalyst ZnO-ZrO2/SPAO-34, Liu teaches that the selectivity for C2-C4= is 85% for catalyst ZnO-Ga2O3/SPAO-34, Molinie teaches that the olefin product that is produced is high in ethylene and propylene. Molinier at page 2, [0023], line 8. Therefore, there is a reasonable expectation that the proposed catalyst has a selectivity for C2-C3= more than 70%, which meets the limitation of “C2-C3 olefin selectivity/paraffin selectivity ratio of from 2 to 20”. Once a reference teaching product appearing to be substantially identical is made the basis of a rejection, and the examiner presents evidence or reasoning to show inherency, the burden of production shifts to the applicant. MPEP § 2112(V) (citing In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433-34 (CCPA 1977).
Claim 16 is obvious because the metal oxide in the proposed hybrid catalyst is ZnO-ZrO2-Ga2O3, which is substantially free of silica.
Applicant’s Arguments
Applicant first argues on the ground that the Examiner does not provide a prima facie case of obviousness for the rejection. Page 9 in the Remarks filed on 08/10/2026.
These arguments have been fully considered but not persuasive. As mentioned in the rejection above that
(i)..Molinier teaches a two steps method for preparation of olefins from syngas and each of the two steps with a catalyst;
(ii) both of Wang and Liu teaches that preparation of olefins from syngas can be conducted with a bifunctional catalyst. Wang teaches that catalyst comprising SAPO-34 and ZnO-ZrO2 can be used as the bifunctional catalyst, and Liu teaches that catalyst comprising SAPO-34 and ZnO-Ga2O3 can be used as the bifunctional catalyst;
(iii). Molinier that a hybrid catalyst for transforming syngas into hydrocarbon can comprise of SAPO molecular sieve and metal oxides of Zinc, gallium and zirconium, and a binder. And the catalyst is particularly preferred to be resistant to mechanical attrition
Therefore, one of ordinary skill in the art seeking preparation of olefins from syngas is motivated to replace the Molinier catalyst with the proposed bifunctional catalyst to arrive at the instant claim 1, therefore, a prima facie case of obviousness is provided.
Applicant also argues that:
Wang includes no mention of a binder. It is unclear to the Applicant whether the Office is alleging that Wang does include a binder or that it would be obvious to modify Wang to include a binder. If the Office believes that Wang does include a binder, the Applicant requests the Office provide a citation. If the Office believes it would be obvious to modify Wang to include a binder, initially, the Applicant notes that no explanation for such a modification has been presented, as required per MPEP 2143 ("The Supreme Court in KSR noted that the analysis supporting a rejection under 35 U.S.C. 103 should be made explicit"). Should the Office consider making such an allegation in the future, the Applicant reminds the Office that such an allegation would constitute a new ground of rejection which was not necessitated by an amendment and for which a Final Rejection would not be appropriate. The Applicant also points the Office to the above distinctions of a formed hybrid catalyst comprising the claimed binder vs a mixture of powders, and the unexpected results derived therefrom.
Paragraph 1 at page 10 in the Remarks filed on 08/18/2026.
These arguments are not persuasive. As detail discussed in rejection above that while Wang does not teach to include a binder in his hybrid catalyst, Molinier teaches that the hybrid catalyst for hydrocarbon preparation is particularly preferred to be resistant to mechanical attrition, and a binder such as alumina can be included into his hybrid catalyst. Therefore, one of ordinary skill has a motivation to add a binder to the proposed hybrid catalyst to increase resistance to mechanical attrition. It is noted that while the rejection is reorganized, the ground of rejection is not changed, and citing a different portion of a reference to elaborate upon that which has been cited previously is not a new ground of rejection. MPEP1207.03(a).II.
Applicant’s argument unexpected result has been addressed as above.
Maintained Non-Statutory Double Patenting Rejections
The nonstatutory double patenting rejection is based on a judicially created doctrine grounded in public policy (a policy reflected in the statute) so as to prevent the unjustified or improper timewise extension of the “right to exclude” granted by a patent and to prevent possible harassment by multiple assignees. A nonstatutory double patenting rejection is appropriate where the conflicting claims are not identical, but at least one examined application claim is not patentably distinct from the reference claim(s) because the examined application claim is either anticipated by, or would have been obvious over, the reference claim(s). See, e.g., In re Berg, 140 F.3d 1428, 46 USPQ2d 1226 (Fed. Cir. 1998); In re Goodman, 11 F.3d 1046, 29 USPQ2d 2010 (Fed. Cir. 1993); In re Longi, 759 F.2d 887, 225 USPQ 645 (Fed. Cir. 1985); In re Van Ornum, 686 F.2d 937, 214 USPQ 761 (CCPA 1982); In re Vogel, 422 F.2d 438, 164 USPQ 619 (CCPA 1970); In re Thorington, 418 F.2d 528, 163 USPQ 644 (CCPA 1969).
Non-Statutory Double Patenting Rejections over US12,227,465B2 and Molinier
Claims 1 and 16 are rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1-2, 7-8, of US patent No.12,227,465B2, which is the US patent of the WO2020236431A1 cited above for 103 rejection, in view of M. Molinier, et al, US 20070244000A1 (2007)(“Molinier”).
Conflicting Claims
The conflicting claims 1-2 and 7-8 respectively claims:
A method for preparing C2 to C5 paraffins comprising:
introducing a feed stream comprising hydrogen gas and a carbon-containing gas selected from the group consisting of carbon monoxide, carbon dioxide, and mixtures thereof into a reaction zone of a reactor; and
converting the feed stream into a product stream comprising C3 to C5 paraffins in the reaction zone in the presence of a hybrid catalyst, the hybrid catalyst comprising:
a microporous catalyst component; and
a metal oxide catalyst component comprising a metal component present on a metal oxide support material, wherein the metal oxide support material comprises at least one oxide of a metal selected from Group 4 of the IUPAC periodic table of elements,
wherein the product stream has a C3/C2 carbon molar ratio greater than or equal to 4.0.
The method of claim 1, wherein the microporous catalyst component is a molecular sieve having 8-MR pore openings.
7. The method of any one of claims 1 to 6, where in the metal component of the metal oxide catalyst component is selected from the group consisting of zinc, gallium, indium, lanthanum, chromium and mixtures thereof.
8. The method of any one of claims 1 to 7, wherein the metal oxide support material comprises titania or gallium.
Difference Conflicting Claims and Claims 1 and 16
The combination of conflicting claims 1-2 and 7-8 differs from claims 1 and 16 in that the conflicting claims does not claim the claimed method to prepare the claimed hybrid catalyst having a binder selected from alumina, zirconia, or both as the instant claim 1 claims.
M. Molinier, et al, US 20070244000A1 (2007)(“Molinier”)
Molinier has been discussed as above in the 103 rejection.
Obviousness Rationales of Claims 1 and 16
Claims 1 and 16 are obvious for the same reason as detail discussed in the 103 rejection above.
Applicant’s Argument
Applicant’s argument has been addressed above for the argument on the 103 rejection based on Kirilin and Molinier.
Non-Statutory Double Patenting Rejections over US 12,454,496B2 and Molinier
Claims 1 and 14-16 are rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1 and 8-9 of US patent No.12,454,496 B2, in view of M. Molinier, et al, US 20070244000A1 (2007)(“Molinier”).
Conflicting Claims
The conflicting claims 1 and 8-9 respectively claims:
1. A process for preparing C2 to C3 hydrocarbons comprising:
introducing a feed stream comprising hydrogen gas and a carbon-containing gas selected from the group consisting of carbon monoxide, carbon dioxide, and mixtures thereof into a reaction zone of a reactor; and
converting the feed stream into a product stream comprising C2 to C3 hydrocarbons in the reaction zone in the presence of a hybrid catalyst, the hybrid catalyst comprising:
a mixed metal oxide catalyst component; and
a microporous catalyst component comprising 8-MR pore openings having a size less than or equal to 5.1 {acute over (Å)} and a cage defining ring size less than or equal to 7.45 {acute over (Å)}, wherein:
a C2/C3 carbon molar ratio of the product stream is greater than or equal to 0.7.
7. The process of claim 1, wherein the mixed metal oxide catalyst component comprises a metal oxide support material comprising zirconia.
8. The process of claim 7, wherein the mixed metal oxide catalyst component comprises gallium supported on zirconia.
9. The process of claim 1, wherein the reaction zone operates at a temperature from 370° C. to 470° C.
Difference between Conflicting Claims and Claims 1, 14-16
The combination of conflicting claims 1 and 8-9 differs from claim 1 in that the conflicting claims does not claim the claimed method to prepare the claimed hybrid catalyst having a binder selected from alumina, zirconia, or both as the instant claim 1 claims.
M. Molinier, et al, US 20070244000A1 (2007)(“Molinier”)
Molinier has been discussed as above in the 103 rejection.
Obviousness Rationales of Claims 1 and 16
Claims 1 and 16 are obvious for the same reason as detail discussed in the 103 rejection above.
Claim 14 is obvious because the conflicting claim 9 claims the reaction zone operates at a temperature from 370°C. to 470°C, which anticipates the claimed 350°C. to 480°C.
Claim 15 is obvious because the conflicting claim 15 claims the C2 to C3 hydrocarbons consist essentially of olefins.
Applicant’s Argument
Applicant’s argument has been addressed above for the argument on the 103 rejection based on Kirilin and Molinier.
Provisional Non-Statutory Double Patenting Rejections over Co-pending Application 18/995,437
Claims 1 and 16 are provisionally rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1, 2 and 12 in the claim set filed on 01/16/2025 of co-pending Application No. 18/995,437 (US20260158475A1).
The conflicting claims 1-2 and 12 respectively claims:
A process for preparing C2 to C4 hydrocarbons comprising:
introducing a feed stream comprising hydrogen gas and a carbon-containing gas selected from the group consisting of carbon monoxide, carbon dioxide, and mixtures thereof into a reaction zone of a reactor; and
converting the feed stream into a product stream comprising C2 to C4 hydrocarbons in the reaction zone in the presence of a formed hybrid catalyst, the formed hybrid catalyst comprising:
a metal oxide catalyst component comprising gallium oxide and zirconia, wherein the zirconia has a macroporosity fraction that is less than 0.3;
a microporous catalyst component that is a molecular sieve having 8-MR (Membered Ring) pore openings; and
a binder comprising alumina, zirconia, or mixtures thereof.
A process for preparing a formed hybrid catalyst, the process comprising:
mixing a metal oxide catalyst component and a microporous catalyst component, wherein:
the metal oxide catalyst component comprises gallium oxide and zirconia, wherein the zirconia has a macroporosity fraction that is less than 0.3; and
the microporous catalyst component comprises a molecular sieve having 8-MR (Member Ring) pore openings;
adding a binder to the metal oxide catalyst component and the microporous catalyst component to form a paste, wherein the binder is a colloidal solution, suspension, or gel of a binder precursor comprising oxides or hydroxides of aluminum, oxides or hydroxides of zirconium, or mixtures thereof; and
extruding the paste to produce the formed hybrid catalyst.
12. The process of claim1, wherein the binder comprises pure alumina.
Claims 1 and 16 are obvious because the combination of conflicting claims 1-2 and 12 meets each and every limitation of claims 1 and 16, therefore, claims 1 and 16 are obvious.
Provisional Non-Statutory Double Patenting Rejections over Co-pending Application 18/995,527
Claims 1 and 14,16 are provisionally rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1, 9,11 and 14 in the claim set filed on 01/16/2025 of co-pending Application No. 18/995,527 (US20260250581A1).
The conflicting claims 1, 9,11 and 14 respectively claims:
A process for preparing C2 to C4 hydrocarbons comprising: introducing a feed stream comprising hydrogen gas and a carbon-containing gas selected from the group consisting of carbon monoxide, carbon dioxide, and mixtures thereof into a reaction zone of a reactor; and
converting the feed stream into a product stream comprising C2 to C4 hydrocarbons in the reaction zone in the presence of a hybrid catalyst, wherein the hybrid catalyst comprises:
a metal oxide catalyst component supported on zirconia, the metal oxide catalyst component comprising gallium oxide and a rare earth oxide; and
a microporous catalyst component comprising a molecular sieve having 8-MR (Member Ring) pore openings.
9. The process of claim 1, wherein a temperature within the reaction zone during the converting is from 350 °C to 480 °C.
11. The process of claim 1, wherein the metal oxide catalyst component is calcined at a temperature that is from 400 °C to 800 °C to form a calcined metal oxide catalyst component before being mixed with the microporous catalyst component.
14. The process of claim 11, wherein the calcined metal oxide catalyst component and the microporous catalyst component are mixed with a binder to form a paste, the paste is extruded to produce a hybrid catalyst,
the hybrid catalyst is dried and calcined, and
the binder is a colloidal solution, suspension, or gel of a binder precursor comprising oxides or hydroxides of aluminum, oxides or hydroxides of zirconium, or mixtures thereof.
Claims 1 and 14,16 are obvious because the combination of conflicting claims 9,11 and 14 meeting each and every limitation of claims 1, 14 and 16, therefore, claims 1, 14 and 16 are obvious.
Provisional Non-Statutory Double Patenting Rejections over Co-pending Application 19/521,956
Claims 1 and 14,16 are provisionally rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1-2 and 14 in the claim set filed on 03/23/2026 of co-pending Application No. 19/521,956 (not published yet).
The conflicting claims 1-2 respectively claims:
A process for preparing C2 to C5 hydrocarbons comprising:
introducing a feed stream comprising hydrogen gas and a carbon-containing gas selected from the group consisting of carbon monoxide, carbon dioxide, and mixtures thereof into a reaction zone of a reactor; and
converting the feed stream into a product stream comprising C2 to C5 hydrocarbons in the reaction zone in the presence of a formed hybrid catalyst, the formed hybrid catalyst comprising:
a metal oxide catalyst component comprising gallium oxide and zirconia;
a microporous catalyst component that is a molecular sieve having 8-MR (Membered Ring) pore openings; and
a binder comprising alumina, wherein the alumina binder is prepared as a colloidal solution, suspension, or gel by peptization of a binder precursor comprising oxides or hydroxides of aluminum with an organic carboxylic acid solution.
A process for preparing a formed hybrid catalyst, the process comprising:
mixing a metal oxide catalyst component and a microporous catalyst component, wherein:
the metal oxide catalyst component comprises gallium oxide and zirconia; and the microporous catalyst component comprises a molecular sieve having 8-MR (Member Ring) pore openings;
adding a binder to the metal oxide catalyst component and the microporous catalyst component to form a paste, wherein the binder is prepared as a colloidal solution, suspension, or gel by peptization of a binder precursor comprising oxides or hydroxides of aluminum, with an organic carboxylic acid solution; and
extruding the paste to produce the formed hybrid catalyst.
Claims 1 and 16 are obvious because the combination of conflicting claims 1-2 meeting each and every limitation of claims 1and 16, therefore, claims 1and 16 are obvious.
Claim 14 is obvious because the conflicting claim 14 further claims the temperature within the reaction zone during converting is 350-480ºC.
Applicant’s Argument
Applicant argues on the ground that co-pending Application No. 18/995,437, co-pending Application No. 18/995,527, co-pending Application No. 19/521,956 all has later filling date than the instant application, and the provisional rejection should be withdrawn because provisional rejection is the only rejection. Paragraph 1-3 at page 11 in the Remarks filed on 08/10/2026.
These arguments are not persuasive, while these co-pending applications all have later filling date than the instant application, they all have the same claimed subject matter, and the claimed invention is not in a condition of allowance because it is not free of the prior arts as discussed in the 103 rejection above, therefore, the provisional double patenting rejection should be made and maintained by the examiner until the rejection has been obviated or is no longer applicable. MPEP 804.B.
Terminal Disclaimer
A timely filed terminal disclaimer in compliance with 37 CFR 1.321(c) or 1.321(d) may be used to overcome an actual or provisional rejection based on nonstatutory double patenting provided the reference application or patent either is shown to be commonly owned with the examined application, or claims an invention made as a result of activities undertaken within the scope of a joint research agreement. See MPEP § 717.02 for applications subject to examination under the first inventor to file provisions of the AIA as explained in MPEP § 2159. See MPEP § 2146 et seq. for applications not subject to examination under the first inventor to file provisions of the AIA . A terminal disclaimer must be signed in compliance with 37 CFR 1.321(b).
The filing of a terminal disclaimer by itself is not a complete reply to a nonstatutory double patenting (NSDP) rejection. A complete reply requires that the terminal disclaimer be accompanied by a reply requesting reconsideration of the prior Office action. Even where the NSDP rejection is provisional the reply must be complete. See MPEP § 804, subsection I.B.1. For a reply to a non-final Office action, see 37 CFR 1.111(a). For a reply to final Office action, see 37 CFR 1.113(c). A request for reconsideration while not provided for in 37 CFR 1.113(c) may be filed after final for consideration. See MPEP §§ 706.07(e) and 714.13.
The USPTO Internet website contains terminal disclaimer forms which may be used. Please visit www.uspto.gov/patent/patents-forms. The actual filing date of the application in which the form is filed determines what form (e.g., PTO/SB/25, PTO/SB/26, PTO/AIA /25, or PTO/AIA /26) should be used. A web-based eTerminal Disclaimer may be filled out completely online using web-screens. An eTerminal Disclaimer that meets all requirements is auto-processed and approved immediately upon submission. For more information about eTerminal Disclaimers, refer to www.uspto.gov/patents/apply/applying-online/eterminal-disclaimer.
Conclusion
THIS ACTION IS MADE FINAL. 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 FRANK S. HOU whose telephone number is (571)272-1802. The examiner can normally be reached 6:30 am-2:30 pm Eastern on Monday to Friday.
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/FRANK S. HOU/Examiner, Art Unit 1692
/ALEXANDER R PAGANO/Primary Examiner, Art Unit 1692
1 Molinier has been recited in the rejection made in the previous Office action while it was not included in the rejection statement.
2 Molinier teaches that syngas is a mixture of H2, CO and CO2 Molinier at page 2, [0027], line 1-2.
3 A. Kirilin, et al, WO2020236431A1(2020)(“Kirilin”) indicates that SAPO-34 has 8-mr pore openings. See Kirilin at page 4, [0016], line 5.
Prosecution Insights