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 .
Response to Arguments
With respect to the rejection of Claims 17-18, 25 and 36 under 35 U.S.C. 103 as being unpatentable over Bittencourt et al. in view of Choudhary et al., as understood the traversal relies on arguments. Applicant argues “As an initial matter, the Examiner characterizes 0.05% w/w platinum as an "intermediate" value between 0 and 0.1 wt.% Pt. However, Choudhary only discloses discrete platinum concentrations of 0.1 wt.%, 0.5 wt.%, and 2.5 wt.%. Choudhary does not identify or suggest that values below 0.1 wt.% Pt constitute an operable range or that such values would yield meaningful catalytic performance. In fact, Choudhary provides no data or guidance regarding Pt concentrations below 0.1 wt.% whatsoever.” [Remarks, Page 8, Paragraph 1]. This is unpersuasive. In the Applicants’ analysis they fail to consider that Choudhary et al. discloses a catalyst with 0 wt.% Pt as an effective catalyst. It is thus inaccurate to state “Choudhary does not identify or suggest that values below 0.1 wt.% platinum constitute an operable range or that such values would yield meaningful catalytic performance.” As can be seen from Table 1 of Choudhary (reproduced by Applicant on page 9) the catalyst with 0% Pt is able to achieve 84.0% conversion, very similar to the 0.1 wt.% catalyst at 84.8%.
Applicant further argues “the Examiner has failed to articulate why a person of ordinary skill in the art would have had a reasonable expectation of success to formulate the claimed "platinum in a concentration of 0.05% w/w, calculated as a metallic element in a final catalyst," as claimed in the independent claims. In addition, Choudhary fails to provide such an expectation.” [Remarks, Page 8, Paragraph 3]. This is unpersuasive. The reasonable expectation of success is that as it is known from the prior art that a catalyst with 0 wt.% Pt and 0.1 wt.% Pt have useful catalytic properties, it would not be reasonable to expect a catalyst with an intermediate amount of Pt to have no useful catalytic properties.
Applicant further argues “As shown in Choudhary's Table 1 reproduced below, Choudhary teaches that increasing platinum concentration from 0.1 wt.% to 0.5 wt.% to 2.5 wt.% improves catalytic performance, including lowering reaction start temperature and increasing methane conversion” [Remarks, Page 8, Paragraph 4]. This is unpersuasive. It is conceded that Choudhary teaches that increasing Pt concentration improves catalytic performance, including lowering reaction start T and increasing methane conversion, however, as described in the previous Office Action, one of ordinary skill in the art would know that Pt is a particularly expensive metal. Adding 2 wt.% Pt to a catalyst with 0.5 wt.% Pt therefore results in 400% more cost associated with purchasing platinum for only a 0.8% increase in conversion. In other words it is not obvious to seek the maximal conversion when it may make the overall process significantly less profitable.
Applicant further argues “Cost considerations do not provide a reasonable expectation that such reduction in platinum concentration would retain the desired catalytic functionality.” [Remarks, Page 9, Paragraph 2]. This is unpersuasive. The Examiner agrees that cost considerations alone do not make the reduction in Pt loading obvious, however the Applicants’ arguments are moot in light of explicit teaching from Choudhary et al. that reduction in Pt concentration would retain the desired catalytic functionality (see above).
Applicant further argues “a person of ordinary skill in the art would not be motivated to combine Bittencourt and Choudhary to teach a steam pre-reforming catalyst having "platinum in a concentration of 0.05% w/w." As explained in greater detail below, Bittencourt and Choudhary are directed to entirely different processes occurring under different conditions … Bittencourt discloses a process for pre-reforming hydrocarbons in the presence of steam and absence of oxygen and a catalyst for use therein … the catalyst disclosed in Choudhary is used with oxygen in order to convert methane to syngas” [Remarks, Page 10, Paragraph 1-2]. This is unpersuasive. The first line of Choudhary et al. reads “Ni/Al2O-3 in its reduced (i.e. Ni0) form is an active catalyst commonly used in the steam reforming and oxidative conversion of methane to syngas” [emphasis added]. Therefore the motivation to combine derives from the explicit disclosure of Choudhary et al. that the catalyst is useful for the same process as disclosed by Bittencourt.
Applicant further argues “A person of ordinary skill in the art would thus have no motivation to modify Bittencourt's catalyst based on the teachings of Choudhary because doing so would not further Bittencourt's objective of improving resistance to coke deposition. Choudhary is silent on any benefits that its catalyst composition provides with respect to coking resistance or the processing of olefin-containing streams, as Choudhary concerns a fundamentally different reaction system and performance objective.” [Remarks, Page 11, Paragraph 2]. This is unpersuasive. The motivation to combine references was not based on Choudhary et al. teaching that the combination would reduce coke formation and therefore the arguments do not traverse the rejection that was presented. The rejections are 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.
Claims 17-18, 25 and 36 are rejected under 35 U.S.C. 103 as being unpatentable over US 9637381 B2 Bittencourt et al. in view of NPL - "Beneficial effects of Noble Metal Addition to Ni/Al-2-O3 Catalyst Oxidative Methane-to-Syngas Conversion " Choudhary et al. Claim 17 requires ” A steam pre-reforming catalyst, comprising: a) an inorganic oxide support selected from alumina, magnesium aluminate, or mixture thereof”. Bittencourt et al. is directed at a nickel catalyst for steam pre-reforming hydrocarbons [Abstract]. Bittencourt et al. discloses “an inorganic oxide support, preferably comprised of alumina, magnesium aluminate, calcium aluminate, or a mixture thereof” [Column 5, lines 24-26].
Claim 17 further requires “b) a mixture of nickel, lanthanum, and cerium oxides, with the total content of nickel expressed as nickel oxide (NiO), from 6 to 15:1 (w/w) between NiO and La2O3, and 2 to 4:1 (w/w) between Ce2O3 and La2O3, and a total NiO content within the catalyst is between 5 to 50% w/w”. Bittencourt et al. discloses “oxides of Ni, La, and Ce in a proportion of 6:1 (w/w) to 15:1 (w/w) of NiO:La2O3 and Ce2O3:La2O3 in proportion of 2:1 (w/w) to 4:1 (w/w) and a total content of NiO between 4% w/w and 50% w/w”. [Column 5, lines 27-30].
Claim 17 further requires “and c) platinum in a concentration of 0.05% w/w, calculated as a metallic element in a final catalyst”. Bittencourt et al. does not teach platinum as part of the nickel-based catalyst.
Claim 17 further requires “the steam pre-reforming catalyst converts hydrocarbons to hydrogen and/or syngas in a steam reforming process with a steam/carbon ratio between 0.8 to 3.0 mol/mol”. Bittencourt et al. discloses “The steam/carbon ratio at the entrance to the reactor containing the catalyst is between 0.1 mol/mol and 5 mol/mol” [Col. 6, Lines 50-52] which has significant overlap with the claimed range.
Claim 17 further requires “wherein the steam pre-reforming catalyst converts hydrocarbons to hydrogen and/or syngas … at temperatures of 330-500°C”. Bittencourt et al. discloses “Catalysts prepared in this way may be used to produce a gas rich in methane and hydrogen, free of other hydrocarbons, at pressures between 1 kgf/cm and 50 kgf/cm and temperatures between 300 °C. and 650 °C”. [Column 6, Lines 64-67].
Claim 17 further requires “wherein the steam pre-reforming catalyst converts hydrocarbons to hydrogen and/or syngas … at a H2/load ratio between 0.1 to 0.3 Nm3 of H2/kg of load”. The term “load” is interpreted to mean the hydrocarbon to be reformed. Bittencourt et al. discloses “H2/hydrocarbon content being 0.05 mol/mol to 0.4 mol/mol.” [Col. 11, Line 26] in the claims. It is understood that the hydrocarbons in Bittencourt et al. are mostly methane (CH4) with small amounts of olefins such as ethylene (see Example 4-7). For the following calculation it is assumed that the average molar mass of hydrocarbons is the same as the molar mass of methane for simplicity, therefore it should be understood that the following calculation is an approximation. Converting the endpoints of the range of Bittencourt et al. from H2/hydrocarbon in mol/mol to H2/load in Nm3/kg yields the following: 0.05 mol H2 at STP occupies a volume of 1.12 L (0.05 mol * 22.4 L/mol) which is equivalent to 0.00112 m3. 1 mol of methane weighs 16 grams, or 0.016 kg, so the lower end of the range is 0.07 Nm3/kg (0.00112/0.016). The upper end of the range is given by 0.4 mol of H2 at STP occupies a volume of 8.96 L (0.4 mol * 22.4 L/mol) which is equivalent to 0.00896 m3, the methane is the same 0.016 kg. The upper end of the range is therefore 0.56 Nm3/kg (0.00896/0.016). Therefore it is understood that Bittencourt et al. discloses a H2/load ratio between about 0.07 to about 0.56 Nm3 of H2/kg of load which significantly overlaps with the range claimed.
Claim 17 further requires “wherein the steam pre-reforming catalyst converts hydrocarbons to hydrogen and/or syngas … at a space velocity between 1,200 to 2,000 h-1 based on hydrocarbon flow.”. Bittencourt et al. discloses 18,000 h-1 GHSV [Col. 10, Table 1] which is higher than the range claimed. However, it is noted that Claim 17 does not require a space velocity between 1,200 to 2,000 h-1, only a catalyst that can convert some amount of hydrocarbon at those space velocities. Nothing in the disclosure of Bittencourt et al. teaches or suggests that high space velocities are required, or that low space velocities are wholly ineffective. It is therefore understood that the catalyst suggested by the combination of Bittencourt et al. and Choudhary et al., having the same physical composition as what is claimed would have the same physical properties, including an effective range of space velocities, see MPEP 2112.01.II.
Regarding the limitation not taught by Bittencourt, namely the platinum concentration, Choudhary et al. discloses a steam reforming catalyst, Pt-Ni/Al2O3, with 0, 0.1, and 0.5 wt.% platinum [Page 753, Table 1]. Choudhary teaches “The as-prepared/calcined form of the catalyst contains a catalytically inactive NiAl2O4 phase, which is difficult to reduce … However, the reaction on calcined Ni/MgO, Ni/CaO, and Ni/rare earth oxide [La2O3 and Ce2O3] catalysts is found to start at much lower temperatures because of their ease of reduction during the initial reaction period” [page 752, Column 1, Paragraph 1]. Choudhary concludes “the addition of noble metal (Pt, Pd, or Ru) to Ni/Al2O3 catalyst results in a large decrease in the reaction start temperature in the oxidative conversion of methane to syngas over the unreduced catalyst and also causes an improvement in the catalytic activity/selectivity” [Page 754, last paragraph of column 1 through the top of column 2].
It is noted that the limitation of 0.05% Pt (w/w) is not explicitly disclosed by Choudhary et al., however Choudhary et al. clearly identified Pt concentration as a results effective variable (see MPEP 2144.05.II), that is by varying the amount of Pt on the catalyst a predictable trend of lower activation temperature and higher methane conversion was observed. This makes the selection of an intermediate value between 0% and 0.1% Pt, such as 0.05% Pt, obvious to try to see if the disclosed benefits could be realized with a lower Pt loading, thus saving start-up cost of an operation.
It would have been obvious for one of ordinary skill in the art to have combined the catalyst of Bittencourt et al. with the teaching to use platinum of Choudhary et al. because these catalysts have the same active species (Ni0) and perform the same reaction (conversion of hydrocarbons and steam into syngas mixtures). Furthermore, although Choudhary et al. does not specifically study nickel catalyst supported on rare earth oxides they do teach that such catalysts are useful because they are more easily reduced than the nickel catalysts supported on Al2O3 alone. The motivation to combine these catalysts is given in Choudhary et al. when they teach that the addition of platinum results in a decrease in the reaction start temperature and an improvement in the catalytic activity/selectivity. Having a lower start temperature in the first stage is useful because that means less energy cost has to be spent to start the reaction. An improvement in catalytic activity/selectivity is obviously beneficial. Therefore it would have been obvious to one of ordinary skill in the art to combine the support of Bittencourt et al. with the platinum doping of Choudhary et al. to have arrived at the invention as claimed. Furthermore Choudhary et al. teaches that platinum concentration and reaction temperature have a result effective variable relationship [Page 753, Table 1] and therefore it would have been obvious to try to optimize the concentration of platinum in order to balance the initial upfront cost savings of using less platinum with the running costs savings expected from a catalyst with more platinum that lowered reaction temperatures.
Regarding Claim 18, Bittencourt et al. and Choudhary et al. together teach all of the limitations of Claim 17. Claim 18 further requires “a total content of NiO within the catalyst is between 7 and 30% w/w”. Bittencourt et al. discloses “a total content of NiO between 4% w/w and 50% w/w, preferably between 7% w/w and 30% w/w” [Column 5, lines 30-31].
Claim 25 requires “A steam pre-reforming catalyst, comprising: a) nickel oxide (NiO)”. Bittencourt et al. discloses “oxides of Ni, La, and Ce in a proportion of 6:1 (w/w) to 15:1 (w/w) of NiO:La2O3 and Ce2O3:La2O3 in proportion of 2:1 (w/w) to 4:1 (w/w) and a total content of NiO between 4% w/w and 50% w/w” [Column 6, lines 34-37].
Claim 25 further requires “and b) platinum in a concentration of 0.05% w/w, calculated as a metallic element in the final catalyst.”. Bittencourt et al. does not disclose the final catalyst comprises platinum.
Choudhary et al. discloses platinum containing catalysts with 0, 0.1, and 0.5 wt.% platinum [Table 1, Page 753] and identifies Pt loading as a results-effective variable (see Claim 17). This renders a Pt loading of 0.05% obvious to try to one of ordinary skill in the art.
Claim 25 further requires “the steam pre-reforming catalyst converts hydrocarbons to hydrogen and/or syngas with a steam/carbon ratio between 0.8 to 3.0 mol/mol, at temperatures of 330-500 °C, at a H2/load ratio between 0.1 to 0.3 Nm3 of H2/kg of load, and at a space velocity between 1,200 to 2,000 h-1 based on hydrocarbon flow”. These limitations are identical to those found in Claim 17 and therefore support for them can be found above. It would have been obvious for one of ordinary skill in the art to have combined the catalyst of Bittencourt et al. with the teaching to use platinum of Choudhary et al. because these catalysts have the same active species (Ni0) and perform the same reaction (conversion of hydrocarbons and steam into syngas mixtures). Furthermore, although Choudhary et al. does not specifically study nickel catalyst supported on rare earth oxides they do teach that such catalysts are useful because they are more easily reduced than the nickel catalysts supported on Al2O3 alone. The motivation to combine these catalysts is given in Choudhary et al. when they teach that the addition of platinum results in a decrease in the reaction start temperature and an improvement in the catalytic activity/selectivity. Having a lower start temperature in the first stage is useful because that means less energy cost has to be given to start the reaction. An improvement in catalytic activity/selectivity is obviously beneficial. Therefore it would have been obvious to one of ordinary skill in the art to combine the support of Bittencourt et al. with the platinum doping of Choudhary et al. to have arrived at the invention as claimed. Furthermore Choudhary et al. teaches that platinum concentration and reaction temperature have a result effective variable relationship [Page 753, Table 1] and therefore it would have been obvious to try and optimize the concentration of platinum in order to balance the initial upfront cost savings by using less platinum with the running costs savings expected from a catalyst with more platinum that required lower temperatures to be effective.
Regarding Claim 36, Bittencourt et al. and Choudhary et al. together teach all of the limitations of Claim 17. Claim 36 further requires “the steam pre-reforming catalyst is effective for a steam pre-reforming process of converting hydrocarbons to hydrogen and/or syngas at a pressure between 2 to 40 kgf/cm2.”. Bittencourt et al. discloses “Catalysts prepared in this way may be used to produce a gas rich in methane and hydrogen, free of other hydrocarbons, at pressures between 1 kgf/cm and 50 kgf/cm” [Column 6, Lines 64-66]. Although the units of the present invention and Bittencourt et al. differ (kgf/cm2 vs. kgf/cm) this is understood to be due to an obvious typo, as kgf/cm is not a unit of pressure (Force/Area) and one of ordinary skill in the art would recognize that the intended pressure of Bittencourt et al. was between 1 kgf/cm2 and 50 kgf/cm2.
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.
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/JOSHUA MAXWELL SPEER/
Examiner
Art Unit 1736
/DANIEL BERNS/Primary Examiner, Art Unit 1736
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