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 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.
Claim 17 is 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.
Claim 1 recites the limitation “separating the hydrogen and the at least one solid carbon product”. The claim is indefinite because the scope of “separating” is unclear. More specifically, based on the disclosure, an artisan of ordinary skill in the art would be unclear on which elements are to be separated since it can be interpreted as separating the hydrogen from the at least one solid carbon product as Figure 1B can be interpreted or separating the hydrogen and the at least one solid carbon product from the catalyst or process as in Figure 1A. Therefore an artisan is not reasonably made aware of what constitutes infringement based on the claim language. For purposes of compact prosecution, the claim is interpreted as in either way.
Claim 17 recites the limitation "the supporting solid carbon product" in Line 1-2. There is insufficient antecedent basis for this limitation in the claim.
Claim 19 recites the limitation “the method of claim 25” in Line 1. There is insufficient antecedent basis for this limitation in the claim. For purposes of compact prosecution this is interpreted as depending on the method of claim 3.
Claim Rejections - 35 USC § 102
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.
Claim(s) 1, 7, and 20 is/are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Grigorevich (RU2522636 with citations from the machine translation provided by the Office).
Regarding claim 1, Grigorevich teaches a process for producing carbon nanotubes and hydrogen from hydrocarbons using microwave plasma and a catalyst (see Abstract). Grigorevich further discloses a process wherein
a catalyst and methane is heated leading to the formation of unsaturated hydrocarbons (ethylene, acetylene), as well as active particles (ion radicals, excited molecules) that contribute to the decomposition of hydrocarbons in chain reactions;
Converted and remaining gases, hydrocarbon products are carried into the zone of the concentrator of the microwave electromagnetic field where the plasma of the microwave gas discharge decomposes the unsaturated hydrocarbons into carbon and hydrogen.
The catalyst participates in the chemical reaction resulting in crystalline carbon nanotube on the catalyst surface;
Carbon and hydrogen are carried out by the gas stream from the plasma-chemical reaction zone;
where the catalyst is for example iron filings (see Page 4 Middle and Page 5, ¶3).
Grigorevich therefore discloses a process comprising applying microwave radiation to acetylene in the presence of a metal catalyst (iron filings) to decompose the acetylene into hydrogen and a solid carbon product (carbon nanotubes) and separating the hydrogen and the solid carbon product.
Regarding claim 7, Regarding claim 7, Grigorevich discloses catalyst comprising iron filings (i.e., unsupported metal).
Regarding claim 20, Grigorevich teaches a process for producing carbon nanotubes and hydrogen from hydrocarbons using microwave plasma and a catalyst (see Abstract). Grigorevich further discloses a process wherein a catalyst and methane is heated leading to the formation of unsaturated hydrocarbons (ethylene, acetylene), as well as active particles (ion radicals, excited molecules) that contribute to the decomposition of hydrocarbons in chain reactions. Converted and remaining gases, hydrocarbon products are carried into the zone of the concentrator of the microwave electromagnetic field where the plasma of the microwave gas discharge decomposes the unsaturated hydrocarbons into carbon and hydrogen. The catalyst participates in the chemical reaction resulting in crystalline carbon nanotube on the catalyst surface (see Page 5, ¶3). Grigorevich further discloses a process where the catalyst is for example iron filings (see Page 4, Middle).
“[E]ven though product-by-process claims are limited by and defined by the process, determination of patentability is based on the product itself. The patentability of a product does not depend on its method of production. If the product in the product-by-process claim is the same as or obvious from a product of the prior art, the claim is unpatentable even though the prior product was made by a different process.” In re Thorpe, 777 F.2d 695, 698, 227 USPQ 964, 966 (Fed. Cir. 1985).
As a practical matter, the Patent Office is not equipped to manufacture products by the myriad of processes put before it and then obtain prior art products and make physical comparisons therewith. A lesser burden of proof is required to make out a case of prima facie obviousness for product-by-process claims because of their particular nature than when a product is claimed in the conventional fashion. In re Brown, 59 CCPA 1063, 173 USPQ 685 (1972); In re Fessmann, 180 USPQ 324 (CCPA 1974).
Here, the prior art Grigorevich discloses a composition comprising hydrogen and carbon nanotubes produced by applying microwave radiation to acetylene in the presence of a metal catalyst. The instant claim implies the identical structure of a product comprising carbon nanomaterial and hydrogen. One of ordinary skill in the art would also reasonably expect that any differences the processes would not impart structural differences to the end product carbon nanomaterial and hydrogen since the raw material acetylene which is C2H2 contains only carbon and hydrogen. In the event any slight differences can be shown between the two carbon nanotube and hydrogen products, the burden is on Applicant to provide concrete evidence that the difference exhibits unexpected properties compared to the prior art Grigorevich. See Ex parte Gray, 10 USPQ2d 1922.
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(s) 2-5, 8-12, 14, and 17-19 are rejected under 35 U.S.C. 103 as being unpatentable over Grigorevich et al (RU-2522636 where citations are from the machine translation provided by the Office) and in further view of Hu et al (WO-2021087408 which has a publication date of 5/6/2021 hereinafter referred to as Hu-1).
As applied to claim 1, Grigorevich teaches a process comprising applying microwave radiation to acetylene in the presence of a metal catalyst (iron filings) to decompose the acetylene into hydrogen and a solid carbon product (carbon nanotubes) and separating the hydrogen and the solid carbon product.
Regarding claim 2, Grigorevich does not disclose contacting the catalyst and the at least one solid carbon product with an acid composition causing the metal atoms to separate from the solid carbon product; removing the metal atoms form the acid composition; and removing the at least one solid carbon product from the acid composition.
Hu-1 discloses a process for co-producing hydrogen and solid forms of carbon via methane decomposition, the method comprising:
using a catalyst supported on a first solid carbon product to decompose methane into a second solid carbon product and hydrogen for a second time;
collecting hydrogen;
contacting the first solid carbon product, the second solid carbon product and the catalyst supported on the first solid carbon product with an acid composition, wherein the acid composition causes the metal ions or atoms of the catalyst to separate from the first solid carbon product and the second solid carbon product;
removing the metal ions or atoms of the catalyst from the acid composition;
removing the first solid carbon product and the second solid carbon product from the acid composition;
using a portion of the first solid carbon product and the second solid carbon product to restart the method from step (a) (see Page 12).
Hu-1 discloses that the method is environmentally friendly, inexpensive, and enables easier catalyst recycling while maintaining performance over many catalytic cycles and an improvement over catalysts that deactivate over time (see [0069]).
It would have been obvious to one of ordinary skill in the art at the time of filing of the invention to perform the method as taught by Grigorevich where the catalyst comprises a metal catalyst on carbon product and where the process comprises steps for contacting the first solid carbon product, the second solid carbon product and the catalyst supported on the first solid carbon product with an acid composition, wherein the acid composition causes the metal ions or atoms of the catalyst to separate from the first solid carbon product and the second solid carbon product; removing the metal ions or atoms of the catalyst from the acid composition; removing the first solid carbon product and the second solid carbon product from the acid composition; and using a portion of the first solid carbon product and the second solid carbon product to restart the method from step (a) as disclosed by Hu-1 so that the process is environmentally friendly, inexpensive, and to make the catalyst easier to recycle.
Regarding claim 3, as applied above Hu-1 discloses using a portion of the first solid carbon product and the second solid carbon product to restart the method from step (a).
Regarding claim 4, as applied above Hu-1 discloses catalysts comprising a support.
Regarding claim 5, as applied above Hu-1 discloses catalysts comprising solid carbon product as a supporting carbon product.
Regarding claims 8-10, Hu-1 discloses catalysts comprising monometallic Ni/CNT or bimetallic Ni-Pd/CNT (see [0085]).
Regarding claim 11, Hu-1 discloses catalysts comprising low amounts of Pd distributed in larger amounts of Ni (i.e., where Pd is a dopant) (see [0077]).
Regarding claim 12, Hu-1 discloses a catalyst comprising a Pd dopant (i.e., a transition metal dopant).
Regarding claim 14, Hu-1 discloses a catalyst comprising Ni-Pd on carbon nanotubes (See [0085]).
Regarding claim 17, Hu-1 discloses a method where the solid carbon product and the supporting solid carbon product independently comprise nanoparticles, fullerenes, carbon filaments, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers or combinations thereof (see [0127] and [0133]).
Regarding claim 18, Hu-1 discloses a method where the single-walled carbon nanotubes, multi-walled carbon nanotubes, or carbon nanofibers have a length from 20 nm to 50 µm (see [0131]).
Regarding claim 19, Hu-1 discloses a method wherein about 5 wt% to about 95 wt% of the product carbon are used to restart the method at step (a) (see [0108]).
Claim(s) 4-6 and 15-16 is/are rejected under 35 U.S.C. 103 as being unpatentable over Grigorevich et al (RU-2522636 where citations are from the machine translation provided by the Office) and in further view of Hu et al (US 20190084832 hereinafter Hu-2).
As applied to claim 1, Grigorevich teaches a process comprising applying microwave radiation to acetylene in the presence of a metal catalyst (iron filings) to decompose the acetylene into hydrogen and a solid carbon product (carbon nanotubes) and separating the hydrogen and the solid carbon product.
Regarding claim 4, Grigorevich does not teach a catalyst comprising a support.
Hu-2 discloses a method for the simultaneous production of carbon nanotubes and hydrogen gas from lower hydrocarbon including but not limited to C1-C4 alkanes and including methane (see [0107] and [0108]) comprising:
thermal decomposition on a heated catalyst comprising a 3d transition metal and a support material where the 3d transition metal is selected from Ni, Fe, Co, Mn, Cr, Mo and combinations thereof; wherein the support material is selected from a silica, an alumina, a zeolite, a titanium dioxide or mixtures there (see [0021]);
separating carbon nanotubes from the catalyst by acid reflux wherein acid treatment effectively removes metal and support residue of spent catalyst from CNT and maintained the crystalline nature of the CNTs (See [0502]).
Hu-2 discloses that the carbon nanotubes base grown on his metal supported catalysts produces grown carbon nanotubes that are easily harvested and the catalyst can be regenerated without being consumed during the extraction process (see [0005]). It would have been obvious to one of ordinary skill in the art at the time of filing of the invention to perform a process for co-producing hydrogen and carbon nanotubes by catalytic decomposition of hydrocarbon as disclosed by Grigorevich where the catalyst comprises a metal supported catalyst as disclosed by Hu-2 so that the catalyst is regenerable and the carbon nanotubes are easily harvestable.
Regarding claim 5, Hu-2 discloses Al2O3 support (see [0089]).
Regarding claim 6, Hu-2 discloses an alumina aerogel support (see [0096-0098] and [0518]).
Regarding claim 15, Hu-2 discloses a Ni catalyst supported on Al2O3 aerogel (see [0518]).
Regarding claim 16, Hu-1 discloses a catalyst where the catalyst comprises Ni-Pd and wherein the ratio of Ni:Pd:support is 10 wt% Ni : 1 wt% Pd :89 wt% CNT (see [0203]). It would have been obvious to one of ordinary skill in the art at the time of filing of the invention to perform a method as suggested by Grigorevich, Hu-1, and Hu-2 where the ratio of Ni:Pd:support is 10:1:89 as disclosed by Hu-1 since Hu-1 suggests that it is a ratio suitable for forming carbon and hydrogen from hydrocarbon.
Claim(s) 13 is/are rejected under 35 U.S.C. 103 as being unpatentable over Grigorevich and Hu-1, as applied to claim 12 and in further view of Musamali (Decomposition of Methane into Carbon and Hydrogen over Ni-Li/CaO catalysts, (Doctoral Dissertation) (2018), pp. 1-115).
As applied to claim 12, Grigorevich and Hu-1 teaches a process comprising applying microwave radiation to acetylene in the presence of a metal catalyst (iron filings) to decompose the acetylene into hydrogen and a solid carbon product (carbon nanotubes) and separating the hydrogen and the solid carbon product where the catalyst comprises a Pd doped Ni catalyst.
Regarding claim 13, Grigorevich and Hu-1 do not disclose a catalyst doped with Li, Na, K, Cs or a combination thereof.
Musamali teaches a Ni-Li/CaO catalyst for decomposition of methane into carbon and hydrogen where introduction of lithium to Ni/CaO catalyst improved its performance tremendously attributed to providing more catalyst active sites and a molten environment for proper dispersion of the nickel metal (see Abstract and Page 83, Conclusion). Musamali also teaches the life of the supported catalyst was extended due to less pronounced coking (see Page 83, Conclusions). It would have been obvious to one of ordinary skill in the art at the time of filing of the invention to perform a method as taught by Grigorevich and Hu-1 where the doped Ni supported catalyst is doped with Li as taught by Musamali in order to increase catalytic activity and improve the life of the catalyst.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to MICHAEL FORREST whose telephone number is (571)270-5833. The examiner can normally be reached Monday-Friday (10AM-6PM).
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/MICHAEL FORREST/Primary Examiner, Art Unit 1738