Notice of Pre-AIA or AIA Status
The present application is being examined under the pre-AIA first to invent provisions.
Election/Restrictions
Applicant’s election without traverse of Group I, claims 7-15 and 22, in the reply filed on 04/17/2026 is acknowledged.
Priority
Acknowledgment is made of applicant’s claim for foreign priority under 35 U.S.C. 119 (a)-(d). The certified copies have been filed in parent Application No. 13133583, filed on 06/08/2011.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 7-15 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Regarding claim 7, line 6, the term “comprising” in the phrase “the promoter P1 comprising one or more element(s) selected from the group of…” is indefinite. The use of the word “comprising” is not appropriate here as it is open ended language such that it is unclear what other things are included in the group. See MPEP 2173.05(h).
Claims 8-15 all depend from claim 7 and thus, are also rendered indefinite.
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 pre-AIA 35 U.S.C. 103(a) which forms the basis for all obviousness rejections set forth in this Office action:
(a) A patent may not be obtained though the invention is not identically disclosed or described as set forth in section 102, if the differences between the subject matter sought to be patented and the prior art are such that the subject matter as a whole would have been obvious at the time the invention was made to a person having ordinary skill in the art to which said subject matter 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 pre-AIA 35 U.S.C. 103(a) 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.
Claims 7, 9-10, and 13-15 are rejected under pre-AIA 35 U.S.C. 103(a) as being unpatentable over Espinoza et al. (US20040122115A1; cited in IDS dated 08/08/2023).
Regarding claim 7, Espinoza teaches a process for preparing an iron-based Fischer-Tropsch catalyst that displays high activity in hydrocarbon production (Abstract). Espinoza teaches the catalyst is prepared by precipitating at least one iron compound to provide a precipitate, preparing a slurry of the precipitated iron compound and adding a first promoter and optionally a second promoter, followed by drying the precursor slurry and calcining the catalyst precursor particles to prepare the catalyst ([0018]).
Espinoza teaches the first promoter can consist of the alkali metals sodium, lithium, potassium, rubidium, cesium and any combination thereof while the at least one second promoter is selected from the group of calcium, magnesium, boron, aluminum and any combination thereof ([0023]). Espinoza further teaches the designations “first and second promoters do not imply any sort of order of addition or priority of importance. The current designations are intended only to differentiate one class of promoter from the next” ([0023]). Accordingly, the teachings of Espinoza, when put in the context of the present invention, teach the first promoter P1 being one or more elements selected from the group of boron, germanium, nitrogen, phosphorus, arsenic, antimony, sulphur, selenium, and tellurium, with a second promoter P2 selected from alkali metals and/or alkaline earth metals, added at any time.
Espinoza further teaches the second promoter of at least one of calcium, magnesium, boron, aluminum and any combination thereof (equivalent to P1) is present from about 0.001 wt.% to about 4 wt.% of metal based on the total weight of the catalyst and that the catalyst contains from about 50 to about 95 wt.% of iron based on the total weight of the catalyst ([0021]; [0024]). Converting the wt.% of Espinoza to a value of promoter P1 value from 0.02 to 1.0 g/100 g Fe in the catalyst as required by the claims, Espinoza provides a taught range of 0.00001 g promoter/100 g Fe to 0.08 g promoter/100 g Fe. In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. MPEP 2144.05 (I). In the instant case, the range taught by Espinoza (0.00001 g promoter/100 g Fe to 0.08 g promoter/100 g Fe) overlaps with the claimed range (at least 0.02 g/100 g Fe). Therefore, the range in Espinoza renders obvious the claimed range.
Calculations:
Wt.% = g/100; 4 wt.% = 4 g promoter
To convert wt.% iron to 100 g iron:
Example, 50 wt.% = 50 g iron; 50 g iron x 2 = 100 g iron
High end = 4 g promoter / 50 g iron = 10 g promoter / 100 g iron
Low end = 0.001 g promoter /95 g iron = 0.0525 g promoter / 100 g iron
Regarding claim 9, Espinoza teaches the process of claim 7 and Espinoza further teaches the solvent is aqueous solution ([0035]).
Regarding claim 10, Espinoza teaches the process of claim 7 and Espinoza further teaches the calcination is performed between about 200 and about 500 °C, while teaching examples of a calcination of 300 °C ([0046]; [0067]-[0074])
Regarding claim 13, Espinoza teaches the process of claim 7 and Espinoza further teaches the promoter can be selected from boron (Claim 1; [0053]). Espinoza explicitly states “that the designations “first” and "second” promoters do not imply any sort of order of addition or priority of importance” and that “the current designations are intended only to differentiate one
class of promoter from the next.” [0023]. Accordingly, the explicit disclosure of boron meets the claimed limitation for P1.
Regarding claim 14, Espinoza teaches the process of claim 7 and Espinoza further teaches the alkali promoter is present from about 0.05 wt.% to about 5 wt.% of metal based on the total weight of the catalyst and that the catalyst contains from about 50 to about 95 wt.% of iron based on the total weight of the catalyst ([0021]; [0024]). Converting the wt.% of Espinoza to a value of alkali metal and/or alkaline earth metal from 0.02 to 1.0 g/100 g Fe in the catalyst as required by the claims provides a taught range in Espinoza of 0.0525 g alkali metal/100 g Fe to 10 g alkali metal/100 g Fe. In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. MPEP 2144.05 (I). In the instant case, the range taught by Espinoza (0.0525-10 g alkali metal/100 g iron) overlaps with the claimed range (0.02 to 1.0 g alkali metal and/or alkaline earth metal / 100 g iron). Therefore, the range in Espinoza renders obvious the claimed range.
Calculations:
Wt.% = g/100; 5 wt.% = 5 g alkali metal
To convert wt.% iron to 100 g iron:
Example, 50 wt.% = 50 g iron; 50 g iron x 2 = 100 g iron
High end = 5 g alkali metal / 50 g iron = 10 g alkali metal / 100 g iron
Low end = 0.05 g alkali metal /95 g iron = 0.0525 g alkali metal / 100 g iron
Regarding claim 15, Espinoza teaches the process of claim 7 and Espinoza further teaches an alkali metal can be added as a basic solution which is added as sodium carbonate or sodium bicarbonate ([0036]). Espinoza further teaches when adding lithium as a promoter, lithium carbonate can be used ([0039]). The claim does not list lithium as a promoter P2, however a skilled artisan could readily selected sodium, potassium, and/or cesium carbonates as the promoter precursor given the explicit teaching of Espinoza establishing the suitability of these metals as promoters and inventive examples utilizing potassium. ([0020]; [0025]).
The teachings of Espinoza support the conclusion that a skilled artisan would expect substitution of potassium for lithium as promoter to serve the same purpose. See MPEP 2144.06.II.
Claim 8 is rejected under pre-AIA 35 U.S.C. 103(a) as being unpatentable over Espinoza et al. (US20040122115A1; cited in IDS dated 08/08/2023) in view of Bromfield et al. (Studies in Surf. Sci. Cat. 2000, 130, 1133-1138).
Regarding claim 8, Espinoza teaches the process of claim 7 and Espinoza further teaches the method includes providing a suitable solution of at least one iron compound and adding suitable solutions that provide a precipitate, where the promoters can be added at any time ([0023]; [0035]).
The claim further requires “in step (a) a solution of iron in a solvent is provided in which a precursor of a promoter P1 is present, and then a suspension is obtained by forming a precipitate containing iron and the precursor of promoter P1 from the solution before step (b) is carried out.” Espinoza does not explicitly teach adding a solution of the promoter P1 to a solution of iron, despite suggesting the promoter addition can occur at any time.
Bromfield teaches a method of preparing a precipitated iron Fischer-Tropsch catalyst that first prepares a solution of iron and sodium and adds a solution of sulfide ions to the reactant solutions that produces a precipitate (Pg. 1133, 2. Experimental).
Advantageously, adding sulfide ions during the precipitation reaction provides an enhancement of catalytic activity to the catalyst (Pg. 1133, 1. Introduction).
Thus, prior to the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to add sulfide ions during the precipitation reaction in the method of Espinoza in order to provide a catalyst with enhanced catalytic activity, as taught by Bromfield.
Claims 11-12 are rejected under pre-AIA 35 U.S.C. 103(a) as being unpatentable over Espinoza et al. (US20040122115A1) in view of Espinoza et al. (US20030162850A1; cited in IDS dated 08/08/2023). Note, hereafter, Espinoza et al. (US20030162850A1) is cited as Espinoza ‘850.
Regarding claim 11, Espinoza teaches the method of claim 7 and the claim further requires “the product of step (b) has a surface area of 50 to 500 m2/g” to which Espinoza is silent.
Espinoza ‘850 teaches a method of preparing a hydrocarbon synthesis catalysts comprising a precipitated iron product and a catalyst promoter where the surface area of the catalyst prior to performing reductive heat treatment is above 100 m2/g (Abstract; [0032]; [0063]-[0066]). Espinoza ‘850 further teaches the surface area of the non-reduced catalyst, i.e. prior to reductive heat treatment and after performing a non-reductive heat treatment, is from 10 to 80 m2/g and is reduced by about 20% from the surface area prior to performing heat treatment ([0067]). Accordingly, Espinoza ‘850 teaches the surface area of the catalyst prior to heat treatment ranges from about 12 to 96 m2/g (i.e. 20% increase of the range 10-80 m2/g). In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. MPEP 2144.05 (I). In the instant case, the range taught by Espinoza ‘850 (12 to 96 m2/g prior to heat treatment) overlaps with the claimed range (50 to 500 m2/g after step (b)). Therefore, the range in Espinoza ‘850 renders obvious the claimed range.
Advantageously, the process of Espinoza ‘850, including the targeted surface areas throughout synthesis, provides a catalyst with enhanced performance in fluidized bed processes by withstanding turbulent dynamics without negatively affecting performance ([0014]).
Thus, prior to the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to provide a surface area between about 12 to 96 m2/g after removing solvent but prior to heat treatment in the method of Espinoza in order to provide a catalyst with enhanced performance in fluidized bed processes, as taught by Espinoza ‘850.
Regarding claim 12, Espinoza teaches the method of claim 7 and the claim further requires “the product of step (c) has a surface area of 10 to 80 m2/g” to which Espinoza is silent.
Espinoza ‘850 teaches a method of preparing a hydrocarbon synthesis catalysts comprising a precipitated iron product and a catalyst promoter where the surface area of the catalyst after performing a non-reductive heat treatment is from 10 to 80 m2/g (Abstract; [0067]). In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. MPEP 2144.05 (I). In the instant case, the range taught by Espinoza ‘850 (10 to 80 m2/g after heat treatment) overlaps with the claimed range (10 to 80 m2/g after step (c)). Therefore, the range in Espinoza ‘850 renders obvious the claimed range.
Advantageously, the process of Espinoza ‘850, including the targeted surface areas throughout synthesis, provides a catalyst with enhanced performance in fluidized bed processes by withstanding turbulent dynamics without negatively affecting performance ([0014]).
Thus, prior to the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to provide a surface area between about 10 to 80 m2/g after heat treatment in the method of Espinoza in order to provide a catalyst with enhanced performance in fluidized bed processes, as taught by Espinoza ‘850.
Claim 22 is rejected under pre-AIA 35 U.S.C. 103(a) as being unpatentable over Bromfield et al. (App. Cat. A. General 1999, 186, 297-307; cited in IDS dated 08/08/2023) in view of Davis et al. (US2717260; cited in IDS dated 08/08/2023), Espinoza et al. (US20040122115A1; cited in IDS dated 08/08/2023), and Espinoza ‘850 et al. (US20030162850A1; cited in IDS dated 08/08/2023). Note, Bromfield et al. (App. Cat. A. General 1999, 186, 297-307) is hereafter cited as Bromfield ’99. The copy of Bromfield et al. (Studies in Surf. Sci. Cat. 2000, 130, 1133-1138) provided by Applicant is incomplete and is missing multiple pages (at least Pg. 298 and 300). Citations below are from a full copy provided by Examiner.
Regarding claim 22, Bromfield ’99 teaches a method of preparing an iron precipitated catalyst for Fischer-Tropsch catalysis where solutions of Fe(NO3)3•9 H20, Na2CO3, and Na2S are combined in aqueous solution to produce a precipitate that is dried prior to performing calcination (Pg. 1133, 2. Experimental).
Bromfield ’99 further teaches the catalyst contains FeS (i.e. iron sulfide) sites where sulfide ions are bound to iron from the iron oxide precipitate, where the presence of FeS sites leads to improved product crystallinity (Pg. 302, left col.). Bromfield ’99 teaches the iron sulfate sites become iron sulfide ones after performing a reduction treatment (Pg. 303, right col.). Iron sulfide is a compound comprising Fe and S atoms bound together, which is equivalent to the claimed “chemical bond” between metal and the second promoter.
The claim further requires “the calcined catalyst comprising an amount of sulfur of at least 0.12 g/100 g Fe” to which Bromfield ‘99 does not explicitly teach.
Davis teaches a catalyst for performing hydrocarbon synthesis where the catalyst is comprised of Fe3O4 with the remainder being up to 0.5 weight % sulfur (col. 2, lines 20-45). Davis teaches the catalyst is comprised of taconite ore (col. 3, lines 4-20). Converting the values taught in Davis to a value of sulfur / 100 g Fe as required by the claim provides a 0.69 g S / 100 g Fe (see calculations below). In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. MPEP 2144.05 (I). In the instant case, the range taught by Davis (0.69 g S/100 g iron) overlaps with the claimed range (at least 0.12 g sulfur / 100 g iron). Therefore, the range in Davis renders obvious the claimed range.
Calculations:
Fe3O4 = 231. 533 g/mol; Fe = 55.845 g/mol.
3 mol Fe in 1 mol Fe3O4; 3 x 55.845 g/mol =167.535 g/mol / 231.533 g/mol = 0.72% Fe
Wt.% = g/100; Converting 0.72% Fe to 100 % Fe = 0.72 x 1.39 (operator required to arrive at 1 total Fe) = 1
Sulfur 0.5 wt.% * 1.39 = 0.69 g sulfur per 100 g Fe
Advantageously, Davis teaches the sulfur concentration is quite important, as excessive addition of sulfur will destroy the catalyst activity while arriving within the range taught by Davis increases catalyst activity (col. 2, lines 20-45).
Thus, prior to the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to include about 0.69 g sulfur per 100 g Fe in the method of Bromfield ’99 in order to provide a catalyst with enhanced activity that does not destroy catalyst activity, as taught by Davis.
The claim further “providing a precursor of a second promoter to the calcined catalyst, the second precursor comprising an alkali metal and/or an alkaline-earth metal, the second precursor provided to the calcined catalyst by at least one: adding the second precursor to the precipitation mixture and retaining the metal of the second precursor while removing the solvent from the precipitation mixture; adding the second precursor to the precipitation mixture after the solvent has been removed; and adding the second precursor to the calcined catalyst, wherein the precursor of the second promoter is provided in amount sufficient to provide in the calcined catalyst a ratio of the metal of the second precursor to the combined amount of the metalloid and/or the non-metal of the first precursor of 0.8:1 to 20:1,” to which Bromfield ’99 and Davis are silent.
Espinoza teaches a Fischer-Tropsch catalyst comprising precipitated iron and a first and second promoter, where the second promoter can be added to a slurry of the precipitated iron mixture containing the first promoter prior to removing solvent from the mixture ([0020]; [0031]-[0034]). For clarity, this is equivalent to “adding the second precursor to the precipitation mixture and retaining the metal of the second precursor while removing the solvent from the precipitation mixture.”
Espinoza further teaches the second promoter is present from about 0.001 wt.% to about 4 wt.% element to total weight of the catalyst while the first promoter is present in an amount preferably between about 0.001 wt. % and about 5 wt. % of metal to total weight of catalyst ([0022]; [0026]). Converting the wt.% ranges to a ratio as required by the claim provides a taught ratio of second promoter to first promoter of between 0.0002 to 4000 (i.e. 4/0.001; 0.001/5). In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. MPEP 2144.05 (I). In the instant case, the range taught by Espinoza (second promoter to first promoter ratio of 0.0002 to 4000) overlaps with the claimed range (a ratio of the metal of the second precursor to the combined amount of the metalloid and/or the non-metal of the first precursor of 0.8:1 to 20:1). Therefore, the range in Espinoza renders obvious the claimed range.
Advantageously, the catalyst prepared by the method of Espinoza provides a catalyst with low water-gas shift activity and high selectivity and productivity towards producing hydrocarbon wax ([0017]).
Thus, prior to the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to provide a second promoter to a precipitated iron slurry comprising a first promoter prior to removing solvent, where the ratio of second promoter to first promoter is between 0.0002 to 4000 in the method of Bromfield ’99 in order to provide a catalyst with low water-gas shift activity and high selectivity and productivity towards producing hydrocarbon wax, as taught by Espinoza.
The claim further requires “reducing the calcined catalyst comprising the precursor of the second promoter… and wherein at least 75 wt.% of the Fe is in the zero oxidation state,” to which Bromfield ’99 teaches reducing the catalyst, but is silent regarding a separate calcination and the valence of the Fe. Davis and Espinoza are silent regarding this limitation.
Espinoza ‘850 teaches a method of preparing a hydrocarbon synthesis catalysts comprising a precipitated iron product and a catalyst promoter where a heat treatment can be carried out, equivalent to calcination, followed by a reducing heat treatment process that serves to reduce iron oxide to metallic iron, where the catalyst contains at least 70% metallic iron (Abstract; [0053]-[0059]). Metallic iron is equivalent to Fe in the zero oxidation state (I.e. Fe0). In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. MPEP 2144.05 (I). In the instant case, the range taught by Espinoza ‘850 (at least 70% metallic iron in reduced catalyst) overlaps with the claimed range (at least 75 wt.% Fe in the zero oxidation state). Therefore, the range in Espinoza ‘850 renders obvious the claimed range.
Advantageously, the catalyst of Espinoza ‘850 may exhibit a prolonged useful lifetime due to an unusually low rate of carbon deposition when compared to conventional fluidized Fischer-Tropsch Synthesis processes and correspondingly, there occurs less expansion of the fluidized bed ([0062]).
Thus, prior to the effective filing date of the claimed invention, it would have been obvious to one of ordinary skill in the art to provide a reducing heat treatment to the precipitated iron catalyst comprising a second promoter, where the reduced catalyst has at least 70% metallic iron, in the method of Bromfield ’99 in order to provide a catalyst with prolonged useful lifetimes that introduce less expansion of the fluidized bed, as taught by Espinoza ‘850.
Conclusion
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/JORDAN W TAYLOR/Examiner, Art Unit 1738
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