DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claim Interpretation
Claim 9, line 4, recites “subjecting the reactor filled with catalyst to reduction condition of H2/N2”. Examiner interprets this to mean “subjecting the reactor filled with catalyst to reduction condition of a gas mixture of H2 and N2”.
Claim Objections
Claim 6 objected to it because of the following informalities: Claim 6, line 2 recites preparing a mixed raw material. For consistency in terminology and clarity, please amend "a" to "the".
Claim Rejections - 35 USC § 102
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 the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
(a)(2) the claimed invention was described in a patent issued under section 151, or in an application for patent published or deemed published under section 122(b), in which the patent or application, as the case may be, names another inventor and was effectively filed before the effective filing date of the claimed invention.
Claim 1 – 3, 6 and 10 are rejected under 35 U.S.C. 102(a)(1) and (a)(2) as being anticipated by Milanov et al. US 2016/0311684 A1 (Milanov).
Regarding claim 1, Milanov discloses a method of reforming hydrocarbons, preferably methane, and carbon dioxide (i.e. a carbon dioxide reforming process) (Milanov, title, abstract).
wherein, a reactant gas (i.e. a mixed raw material) comprising hydrocarbons, preferably methane, carbon dioxide, and optionally hydrogen (Milanov, [0001]– [0004]),
wherein, the process uses a catalyst inside of a reactor (Milanov, claim 1, [0059], Figures),
wherein, an example of a reactant gas, which can be found in table 4, is 42.5% methane and 5% hydrogen, i.e. a/b = 0.12 which necessarily satisfies equation 1 (Milanov, [0118], Page 10, right column, table 4, line 11: cat. 2a_s6).
Regarding claim 2, Milanov discloses wherein the reactant gas (i.e. the mixed raw material) contacting reactant gas with precious metal catalyst and converting it to a first product gas, which is inside reactor 1 (i.e. wherein the causing the mixed raw material to contact the catalyst inside the reactor) (Milanov, claim 1, [0091]), Figure 1). Wherein, the operating temperature of the method is in the range of 500-1100° C, and especially preferably of 850-950 °C (Milanov, [0046]) (i.e. a temperature ranging from 600°C to 1000°C)
Regarding claim 3, Milanov discloses the method comprising: (i) contacting reactant gas with precious metal catalyst and converting it to a first product gas (i.e. wherein the causing the mixed raw material to contact the catalyst inside the reactor) (Milanov, claim 1). Wherein, the operating pressure of is in the range of 1-200 bar (Milanov, [0046]). Wherein, examples in table 4 were conducted at 20 bar (i.e. a pressure ranging from 0 to 20 bar(g) within the reactor) (Milanov, [0118]).
Regarding claim 6, Milanov disclose wherein a reactant gas (i.e. a mixed raw material) comprising hydrocarbons, preferably methane, CH4, carbon dioxide, CO2, and optionally hydrogen, H2, for reforming, is stored in a reactant gas reservoir. The gas, which is added to the first product gas may, for example, be gas originating from the reactant gas reservoir (i.e. preparing a mixed raw material for supplying to the reactor) (Milanov, [0001]– [0004]).
Regarding claim 10, Milanov discloses that the reactant gas for reforming may optionally contain water vapor (i.e. the mixed raw material further comprises steam) (Milanov, claim 4, [0003]). Wherein, an example of a reactant gas, which can be found in table 4, is 42.5% methane and 5% H2O, i.e. c/b = 0.12 which necessarily satisfies equation 2 (Milanov, [0118], Page 10, right column, table 4, line 11: cat. 2a_s6).
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.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claim 4 is rejected under 35 U.S.C. 103 as being unpatentable over Milanov as applied to claim 1 above, and further in view of O’Rear (GB 240663 A) (O’Rear).
Regarding claim 4, Milanov teaches wherein the reactant gas (i.e. the mixed raw material in the form of gas) enters the reactor (Milanov, [0091]).
However, Milanov does not teach, wherein a gas hourly space velocity is 250 to 3000 hr-1.
With respect to the difference, O’Rear teaches a process for producing a blended syngas from C1 alkanes, or methane (O’Rear).
As O’Rear expressly teaches space velocities can vary over a very wide range and typical range from 100 to 100,000 hr-1 and even higher depending on the particular catalyst used and the type of reactor.
O’Rear and Milanov are analogous art as they are both drawn to the production of syngas from reforming methane.
In light of the disclosure of using a gas hourly space velocity of 100 to 100,000 hr-1 as taught by O’Rear, it would have been obvious to one of ordinary skill in the art, prior to the effective filing date, to use a gas hourly space velocity of 100 to 100,000 hr-1 in the method of Milanov, depending on the particular catalysts used and type of the reactor, and obtain the predictable result of syngas production from methane. See KSR International Co. v. Teleflex Inc., 550 U.S. 398, 415-421, USPQ2d 1385, 1395 – 97 (2007) (see MPEP § 2143, A.).
As set forth in the MPEP 2144.05, in the case where claimed range “overlap or lie inside ranges disclosed by the prior art”, a prima facie case of obviousness exists, In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CPA 1976); In re Woodruff, 919 F.2D 1575, 16 USPQ2d 1934 (Fed. Cir. 1990).
Claim 5 is rejected under 35 U.S.C. 103 as being unpatentable over Milanov as applied to claim 1 above, and further in view of Mizera et al. Catalysts based on strontium titanate doped with Ni/Co/Cu for dry reforming of methane (Mizera).
Regarding claim 5, Milanov teaches a precious metal catalyst (cat 1.) comprises at least one precious metal, e.g. Ru or Rh (Milanov, [0059]), and the precious metal components are present on a catalyst support, the catalyst support material having high thermal stability. The catalyst support material preferably comprises an oxidic support material, further preferably an oxidic support material including at least one component from the group of Al, Ti, Zr, Mg, Si, Ca, La, Y, Ce. Milanov further teaches, suitable supports for the precious metal components include oxides which may comprise perovskites, scandium oxide, (Sc2O3), lanthanum, strontium oxide, (SrO) (Milanov, [0062], [0063]).
However, Milanov does not teach:
[Chemical formula 1]
Sr1-xAxTi1-yByO3-δ
A is selected from Y, Sc, and lanthanide series elements
B is Ni, Co, Fe, Mn, Cr, Mo, Ru, or Rh
x is 0 ≤ x < 1
y is 0 ≤ y < 0.2
δ is 0 ≤ δ < 1
With respect to the difference, Mizera teaches catalysts for dry reforming of methane. Mizera specifically teaches two series of strontium titanates doped with Ni, Co, or Cu with general formula of SrTi1-xMexO3 for Sr-stoichiometric and Sr0.95Ti1-xMexO3 for Sr-non-stoichiometric materials (where Me = Ni, Co or Cu and x were 0.02 and 0.06) (Mizera, abstract) This reads on chemical formula 1, i.e. where x = 0, or 0.05, where y = 0.02 or 0.06, where B is Ni, or Co, and where δ = 0.
As Mizera expressly teaches the most common materials used to catalyze the dry reforming of methane (DRM) reaction are based on nickel, nickel alloys or noble metals, such as Rh or Pt (usually 5–15 wt.%). Mizera further teaches that, in the case of noble metals, which exhibit a good resistance for coking, price and abundance are an issue. For the cheaper nickel, the aforementioned low-coking resistance and agglomeration tendency are the major problems (Mizera, Introduction, page 1-2). Mizera further teaches an additional motivation was increased (compared to Ni) resistance to coking of cobalt/copper.
Mizera is analogous art as Milanov because they are drawn to catalysts for dry reforming of methane.
In light of the motivation of using strontium titanate perovskites doped with transition metals as reforming catalysts for methane as taught by Mizera. It would have been obvious to one of ordinary skill in the art, prior to the effective filing date to substitute the precious metal catalyst (cat 1.) of Milanov for the strontium titanate perovskites doped with transition metals of Mizera, and obtain the predictable result of syngas production from methane, in order to use elements that are more abundant and cheaper than precious metals, increase coking resistance, and decrease agglomeration tendency, and thereby arrive at the current invention. See KSR International Co. v. Teleflex Inc., 550 U.S. 398, 415-421, USPQ2d 1385, 1395 – 97 (2007) (see MPEP § 2143, B.)
Claims 7 and 8 are rejected under 35 U.S.C. 103 as being unpatentable over Milanov as applied to claim 1 and 6 above, and further in view of Brunning, Making Reactions Faster: Factors Affecting Rates of Reaction (Brunning).
Regarding claim 7, Milanov teaches the carbon dioxide reforming process of claim 6, and wherein, a reactant gas (i.e. mixed raw material feed) is mixtures of hydrocarbons, preferably methane, carbon dioxide (Milanov, abstract, [0001]), and optionally hydrogen (Milanov, [0004]) Wherein the reactant gas is stored in a reactant gas reservoir, the mixture of gas is prepared when the gas is stored in a reactant gas reservoir, therefore the reactant gas reservoir reads upon a mixer (i.e. mixing the gases supplied to the mixer to produce a final mixed gas) and they must have necessarily been added sequentially or as a mixed gas (Milanov, [0002])
Milanov does not teach compressing the final mixed gas.
With respect to the difference, Brunning teaches making chemical reactions happen faster and that there are a number of different things that can be done to make a chemical reaction faster (Brunning, title, top line).
As Brunning explicitly teaches, Increasing the pressure of a reaction involving gases forces the gas particles closer together. This will increase the frequency of particle collisions and therefore increase the rate of reaction (Brunning, bottom middle section).
In light of the motivation of compressing gas streams, as taught by Brunning.
It would have been obvious to one of ordinary skill in the art, prior to the effective filing date to compress the gas mixture produced from mixing reactant gas and product gas 1 in Milanov, as taught by Brunning, in order to increase the rate of subsequent reactions, and thereby arrive at the present invention.
Regarding claim 8, Milanov, in view of Brunning teaches claim 7 above, and Milanov further teaches compressing a reactant gas (i.e. final mixed gas), wherein reactant gas is reformed to product gas 1, wherein the methane is not fully converted, therefore it necessarily comprises unreacted methane, the carbon dioxide is not fully converted, therefore it necessarily comprises carbon dioxide, and there is a H2/CO ratio, therefore it necessarily comprises hydrogen and carbon monoxide (Milanov, Table 4 examples, [0001]). Milanov further teaches, the reactant gas comprising at least hydrocarbons, preferably methane, and CO2 and optionally water vapor (i.e. adding steam to the compressed final mixed gas) (Milanov, [0019]). Milanov further teaches, wherein reactant gas in table 4 line 11 is 42.5 vol% CO2 42.5% CH4, 5% water vapor and 5% hydrogen is reformed to product gas 1, wherein the methane is not fully converted, therefore it necessarily comprises unreacted methane, the carbon dioxide is not fully converted, therefore it necessarily comprises carbon dioxide, and there is a H2/CO ratio, therefore it necessarily comprises hydrogen and carbon monoxide (Milanov, Table 4, line 11 and 12 cat. 2a/b_s6/7, [0001])
Claim 9 is rejected under 35 U.S.C. 103 as being unpatentable over Milanov as applied to claim 1 above, and further in view of Lowe, how not to do it: hydrogen gas mixtures (Lowe).
Regarding claim 9, Milanov teaches wherein the catalyst undergoes an activation and conditioning, which precedes reforming (i.e. before causing the mixed raw material to contact the catalyst inside the reactor). The activation and conditioning process comprises the thermal treatment of the catalysts in a reducing gas atmosphere comprising hydrogen (Milanov, [0048], [0049]).
However, Milanov does not teach wherein, subjecting the reactor filled with the catalyst to reduction conditions of H2/N2.
With respect to the difference, Lowe teaches the dangers of compressed gases and in particular hydrogen gas, even in anaerobic conditions, and that an 80% nitrogen and 10% hydrogen mixture lead to an explosion (Lowe, page 1, lines 6 – 12).
As Lowe expressly teaches, problem is, just about any hydrogen/air mixture will do. Anything from about 4% hydrogen in air to about 75% will ignite, and everything except the two ends of that range will go ahead and explode if given the chance (Lowe, page 2, lines 1 – 3).
Lowe and Milanov are considered analogous art as they are both drawn to handling hydrogen gas for chemical processes.
In light of the motivation of using hydrogen gas mixed with inert gas, as taught by Lowe. It would have been obvious to one of ordinary skill in the art, prior to the effective filing date, to dilute the hydrogen used in the activation and conditioning steps of Milanov with inert gas, e.g. nitrogen, as taught by Lowe, in order to lower the risk of explosions, and thereby arrive at the present invention.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to Ritchie E Hernandez whose telephone number is (571)270-1711. The examiner can normally be reached M-Th 9-4.
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/R.E.H./Examiner, Art Unit 1732
/KELING ZHANG/Primary Examiner, Art Unit 1732
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