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
Applicant’s arguments, see Remarks, filed 6/24/2026, with respect to the rejection(s) of claim(s) 1 under 35 USC 102 have been fully considered and are persuasive. Therefore, the rejection has been withdrawn. However, upon further consideration, a new ground(s) of rejection is made in view of Varadan et al (Synthesis of carbon nanocoils by microwave CVD, Smart Mater. Struct. 11 (2002) 728-734 hereinafter cited as Varadan).
Applicant persuasively argues that Grigorevich does not teach or suggest, “applying microwave radiation to a feedstock comprising the acetylene in the presence of a catalyst comprising metal atoms wherein the radiation directly heats the catalyst to decompose the acetylene of the feedstock into hydrogen and at least one solid carbon product.”. Varadan is cited for teaches a process comprising applying microwave radiation to directly heat the catalyst to decompose the acetylene of the feedstock. Grigorevich is cited here as prior art showing that decomposing acetylene to deposit solid carbon produces hydrogen and that separation of hydrogen would be obvious as a valuable product.
Claim Objections
Claim 1 is objected to because of the following informalities: “causes” in line 5 should be struck for grammar. Appropriate correction is required.
Claim Rejections - 35 USC § 103
The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
Claim(s) 1, 7-9, and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Varadan et al (Synthesis of carbon nanocoils by microwave CVD, Smart Mater. Struct. 11 (2002) 728-734 hereinafter cited as Varadan) and in further view of Grigorevich et al (RU-2522636 where citations are from the machine translation provided by the Office).
Varadan teaches a method for microwave CVD synthesis of carbon nanotubes, the method comprising:
Applying microwave radiation to a feedstock comprising acetylene in the presence of a catalyst comprising nickel particles, wherein the microwave directly heats the catalyst to decompose the acetylene of the feedstock to decompose into carbon nanotubes;
Exhausting the gas from a gas outlet;
Separating the carbon nanotubes from the substrate (see Experimental Details and Figure 1).
Varadan does not specifically teach that the catalytic CVD using microwaves produces hydrogen gas and does not teach separating the hydrogen.
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:
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 (see Page 4 Middle and Page 5, ¶3).
Grigorevich therefore teaches that carbon and hydrogen are valuable products for which demand is high (see Bottom of Page 1 and Top of Page 2).
First regarding the acetylene decomposing into hydrogen, one of ordinary skill in the art would recognize that the CVD process as taught by Varadan produces hydrogen as a primary by product gas since like Grigorevich, Varadan-2 also teaches a deposition of carbon on a catalyst surface from acetylene (C2H2) by the reaction C2H2 [Wingdings font/0xE0] 2 C (solid) + H2 (gas).
Second regarding separating the hydrogen, it would have been obvious to one of ordinary skill in the art at the time of filing of the invention to perform the process as taught by Varadan-2.
Regarding claim 7, Varadan discloses catalyst comprising nickel particles dispersed on a substrate with a spatula (i.e. an unsupported catalyst since the catalyst is not embedded in the substrate).
Regarding claim 8, as applied above Varadan teaches a nickel catalyst.
Regarding claim 9, as applied above Varadan teaches a monometallic catalyst.
Regarding claim 20, Varadan-2 teaches a process for producing carbon material and hydrogen from hydrocarbons using microwave plasma and a catalyst. “[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 Varadan 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 Varadan-2. See Ex parte Gray, 10 USPQ2d 1922.
Claim(s) 2-5, 10-12, 14, and 17-19 are rejected under 35 U.S.C. 103 as being unpatentable over Varadan and Grigorevich 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, Varadan and Grigorevich teaches a process comprising applying microwave radiation to a feedstock comprising acetylene in the presence of a metal catalyst (nickel) to decompose the acetylene into hydrogen and a solid carbon product and separating the hydrogen and the solid carbon product.
Regarding claim 2, Varadan and Grigorevich do 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 Varadan and 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 claim 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 Varadan and Grigorevich and in further view of Hu et al (US 20190084832 hereinafter Hu-2).
As applied to claim 1, Varadan and 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, Varadan and Grigorevich do 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 Varadan and 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]).
Claim(s) 16 is/are rejected under 35 U.S.C. 103 as being unpatentable over Varadan, Grigorevich and Hu-2, as applied to claim 15 and in further view of Hu-1.
As applied to claim 15, Varadan, Grigorevich and Hu-2 teaches a process comprising applying microwave radiation to acetylene in the presence of a metal catalyst to decompose the acetylene into hydrogen and a solid carbon product and separating the hydrogen and the solid carbon product where the catalyst comprises a Pd doped Ni catalyst and the support comprises Al2O3.
Regarding claim 16, Varadan, Grigorevich and Hu-2 do not teach where the catalyst comprises a ratio of Ni:Pd:support from about 8:1:91 to about 12:1:87.
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 Varadan and 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 Varadan, 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, Varadan, Grigorevich and Hu-1 teaches a process comprising applying microwave radiation to acetylene in the presence of a nickel metal catalyst to decompose the acetylene into hydrogen and a solid carbon product and separating the hydrogen and the solid carbon product where the catalyst comprises a Pd doped Ni catalyst.
Regarding claim 13, Varadan, 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 Varadan, 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.
Citation of Pertinent Art
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
Varadan et al (US 2004/0265212 hereinafter referred to as Varadan-2) teaches a method for microwave CVD synthesis of carbon nanotubes, the method comprising: Applying microwave radiation to a feedstock comprising a hydrocarbon in the presence of a supported catalyst comprising metal particles, wherein the microwave field directly heats the catalyst to decompose the acetylene of the feedstock to decompose into carbon nanotubes; Exhausting the gas from a gas outlet; Separating the carbon nanotubes from the substrate (See [0017]). Varadan-2 further teaches where source gas is acetylene (see claim 35). Varadan-2 teaches a process where the catalyst support contains pores to give rise to the growth of coiled carbon nanotubes (see [0021]).
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). 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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/MICHAEL FORREST/Primary Examiner, Art Unit 1738
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