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 .
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on October 31, 2025 has been entered.
Response to Arguments
Applicant’s arguments filed on October 31, 2025 have been fully considered.
Applicant argues that the cited references fail to disclose or teach the new limitation “wherein the coating layer has a thickness in the range 5 to 2000 μm” as recited in amended claim 1. Applicant (at page 11, fourth paragraph) notes that “… Chen (paragraph [0030]) only teaches oxide catalyst layer thicknesses of 0.5—10 nm, or 1-2 nm (i.e., approximately 0.0005—0.01 μm, or 0.001—0.002 μm), which are several orders of magnitude smaller than the claimed 5 to 2000 um coating layer.”
The argument is considered persuasive, and therefore, the rejections under 35 U.S.C. 103 as set forth in the previous Office action have been withdrawn. However, upon further consideration, a new ground(s) of rejection is made in view of the newly discovered prior art references to Nair (WO 2012/172560 A1) and Yu et al. (CN 106917163 A), detailed below.
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.
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.
Claims 1-3, 5, 6, 8, 9, 11, and 13 are rejected under 35 U.S.C. 103 as being unpatentable over Noyes ‘794 (US 2016/0016794) in view of Nair (WO 2012/172560 A1) and Yu et al. (CN 106917163 A).
The instant “system” claims are considered apparatus claims.
Regarding claim 1, Noyes ‘794 discloses a reaction system (see FIG. 2) comprising:
a reforming device comprising a reaction vessel (i.e., a methane reformer in a first reaction zone 104; see paragraph [0081]-[0082]), and a reforming catalyst (i.e., a first catalyst; see paragraph [0037]) that is provided inside the reaction vessel and able to generate carbon monoxide from a raw material gas containing hydrocarbon (i.e., methane and steam undergo reaction in the first reaction zone 104, producing a mixture containing carbon oxides and hydrogen; see paragraph [0082]);
a solid carbon capturing device comprising a reaction vessel (i.e., a Bosch reactor in a second reaction zone 110; see paragraph [0083]), and a solid carbon capturing catalyst provided inside the reaction vessel (i.e., a second catalyst; see paragraphs [0045]-[0047]); and
a flow path (i.e., an intermediate gas stream 108; see paragraph [0083]) through which a gas comprising the carbon monoxide flows from the reforming device 104 to the solid carbon capturing device 110;
wherein the solid carbon capturing catalyst comprises at least one kind of metal-containing component for accelerating the solid carbon capturing reaction and yielding a desired solid carbon product, such as carbon nanotubes (see paragraphs [0045], [0056]); and
wherein the solid carbon capturing catalyst can contain at least one kind of metal-containing component, such as a compound of iron or cobalt (see paragraphs [0045]-[0046]).
Noyes ‘794 fails to disclose that the solid carbon capturing catalyst comprises a base material and a coating layer formed on a surface of the base material; wherein the coating layer has a thickness in the range of 5 to 2,000 μm; wherein the coating layer contains at least one kind of metal-containing component selected from the group consisting of iron oxide and cobalt oxide; and wherein a ratio of the metal-containing components in the coating layer is 60 to 100 mass% on the basis of the mass of the coating layer.
Nair discloses a solid carbon capturing catalyst for producing solid carbon (i.e., carbon filaments, such as carbon nanotubes; see page 8, lines 1-3), wherein the catalyst comprises:
a base material (i.e., an inert substrate; see, e.g., page 13, first and second paragraphs; page 17, third paragraph; page 18, last paragraph); and
a coating layer formed on a surface of the base material, the coating layer containing at least one kind of metal-containing component selected from the group consisting of iron oxide and cobalt oxide (i.e., a catalytic combination of alpha form of ferrous oxide (Fe2O3) and gamma form of ferric oxide (Fe3O4) is coated onto a surface of the inert substrate; see page 10, last paragraph, to page 11, first paragraph; page 12, first paragraph; page 13, last paragraph);
wherein a ratio of the metal-containing components in the coating layer is 60 to 100 mass % on the basis of the mass of the coating layer (i.e., “The concentration of the active components i.es Iron oxide is 80%.” see page 14, fourth paragraph).
Nair also discloses that, “The thickness of the catalyst onto the inert substrate is in the range of 0.1 mm to 10 mm.” (at page 14, third paragraph). Therefore, the coating layer has a thickness in the range of 100 μm to 10,000 μm.
Yu et al. (see translation) also discloses a solid carbon capturing catalyst for producing solid carbon (i.e., a carbon fiber product), wherein the catalyst comprises:
a catalyst layer (i.e., a carbon catalyst) paved in a catalyst sample groove 5, the catalyst layer containing at least one kind of metal-containing component selected from the group consisting of iron oxide and cobalt oxide (i.e., the carbon catalyst can comprise a nano Fe2O3 catalyst or a cobalt oxide catalyst; see page 5, third paragraph);
wherein the catalyst layer has a thickness in the range of 1 mm to 10 mm (from 1,000 μm to 10,000 μm; see page 4, fifth paragraph); such as a thickness of 1 mm (1,000 μm; see Example 5, on page 8) or a thickness of 2 mm (2,000 μm; see Example 6, on page 8).
In addition, Yu et al. discloses that values outside of the stated thickness range are also applicable. However, the thickness of the catalyst layer should not be too thick, since this reduces the solid carbon yield per unit mass of the catalyst, and the thickness of the catalyst layer should not be too thin, since the catalyst dosage may not be sufficient for catalyzing the solid carbon capturing reaction. (see page 4, fifth and sixth paragraphs).
It would have been obvious for one of ordinary skill in the art before the effective filing date of the claimed invention to substitute the solid carbon capturing catalyst of Nair for the solid carbon capturing catalyst in the reaction system of Noyes ‘794 because the solid carbon capturing catalyst of Nair would allow for large scale production of the solid carbon under low temperature, with low cost, and at high yield and purity (see, e.g., paragraph bridging pages 4-5; page 7, last paragraph).
Furthermore, it would have been obvious for one of ordinary skill in the art before the effective filing date of the claimed invention to provide a thickness in the range of 5 μm to 2,000 μm for the coating layer in the reaction system of Noyes ‘794, on the basis of suitability for the intended use of forming the desired solid carbon product, because such thickness of the coating layer would have been considered suitable for catalyzing the solid carbon capturing reaction, as taught by Nair and Yu et al.
Furthermore, the specific thickness of the coating layer is not considered to confer patentability to the claim since the precise thickness would have been considered a result effective variable by one having ordinary skill in the art. Accordingly, it would have been obvious for one of ordinary skill in the art before the effective filing date of the claimed invention to routinely optimize the thickness of the coating layer in the reaction system Noyes ‘794 in order to maximize the solid carbon yield per unit mass of catalyst, while also providing a catalyst dosage that was sufficient for catalyzing the solid carbon capturing reaction, and where the general conditions of a claim are disclosed in the prior art, discovering the optimum or workable ranges involves only routine skill in the art.
Lastly, with respect to the recitation of a reaction “tube” for each of the reforming device and the solid carbon capturing device, the examiner takes Official notice that it would have been obvious for one of ordinary skill in the art before the effective filing date of the claimed invention to provide “tubes” for the reaction vessels of the reforming device 104 and the solid carbon capturing device 110 in the reaction system of Noyes ‘794 because the use of tube-shaped reaction vessels for containing catalyst and allowing for the flow of reactant gases therethrough would have been conventional in the art. This is further evidenced by Nair, which discloses that the catalyst is inserted in the path of the reactant gases which flow through a furnace or exhaust “pipe” (see page 12, second paragraph; page 14, fifth paragraph).
Regarding claim 2, Nair discloses that the base material can comprise a tubular body or a planar body (i.e., the inert substrate can have the shape of a cylinder (a tubular body) or a disc (a planar body); see page 13, first paragraph; page 19, last paragraph).
Regarding claim 3, Nair discloses that the base material can comprise a tubular body (i.e., the inert substrate can have the shape of a cylinder (a tubular body); see page 13, first paragraph; page 19, last paragraph). Nair (at page 19, last paragraph) also discloses that, “Maximum use of the flue gas is made by increasing the size of substrate and making it cylindrical. Further, the cylindrical surface is coated with the catalyst.” Therefore, as best understood, Nair discloses that the coating layer is formed on an inner wall surface of the tubular body. And, even if this were not the case, it would have been obvious for one of ordinary skill in the art before the effective filing date of the claimed invention to further form the coating layer on an inner wall surface of the tubular body in the modified reaction system of Noyes ‘794 in order to maximize the surface area available for contacting the gas with the coating layer.
Regarding claim 5, Nair discloses that the coating layer is coated onto the base material by a sputtering method (see page 13, last paragraph). During sputtering, particles are ejected onto a substrate to deposit a coating layer comprised of the particles on the substrate. The produced coating layer is inherently porous. Therefore, in the modified reaction system of Noyes ‘794, the coating layer will comprise a porous layer.
Regarding claim 6, Nair discloses that the coating layer contains Fe3O4 (i.e., the gamma form of ferric oxide (Fe3O4); see page 10, last paragraph, to page 11, first paragraph).
Regarding claim 8, Noyes ‘794 (see paragraphs [0081]-[0082]) discloses that the reforming catalyst is a steam reforming catalyst that is able to generate carbon monoxide, carbon dioxide, and hydrogen 108 from the raw material gas containing hydrocarbon and water (i.e., a process feed gas stream 102 including methane and steam).
Regarding claim 9, Noyes ‘794 discloses that the reforming catalyst comprises a base material and a catalyst activation layer formed on a surface of the base material (i.e., a Ni/MgAl2O4 catalyst available from Unicat Catalysts, which is a catalyst having nickel as a catalyst activation layer and MgAl2O4 as a base material; see paragraph [0037]).
Regarding claim 11, the same comments with respect to Noyes ‘794, Nair, and Yu et al. from the rejection of claim 1, above, apply.
Noyes ‘794 (see FIG. 2) further discloses a method for capturing solid carbon 114, comprising:
feeding the raw material gas containing hydrocarbon (i.e., a process feed gas stream 102 including methane; see paragraph [0081]) to the reaction system while heating the reforming catalyst (i.e., maintaining the methane reformer which contains the first catalyst in the first reaction zone 104 at approximately 900 °C or greater, see paragraph [0081];
using a heating mechanism coupled to the reactor to control the temperature of the reactor, see paragraph [0070], [0084]) and the solid carbon capturing catalyst (i.e., maintaining the Bosch reactor which contains the second catalyst in the second reaction zone 110 at about at least 680 °C, see paragraph [0083]; and
using a heating mechanism coupled to the reactor to control the temperature of the reactor, see paragraphs [0070], [0084]), thereby causing solid carbon (e.g., as carbon nanotubes, CNTs) to form onto the solid carbon capturing catalyst.
Nair further discloses that solid carbon is caused to precipitate on the solid carbon capturing catalyst (i.e., as carbon filaments; see page 8, first paragraph).
Regarding claim 13, the same comments with respect to Noyes ‘794, Nair, and Yu et al. from the rejection of claim 11, above, apply.
Noyes ‘794 further discloses a method for producing a gas containing hydrogen (i.e., hydrogen 112; see FIG. 2, paragraph [0083]) comprising:
capturing solid carbon 114 by the method according to claim 11; and discharging a discharge gas containing hydrogen 112 from the solid carbon capturing device 110.
Claims 4, 7, and 9 are rejected under 35 U.S.C. 103 as being unpatentable over Noyes ‘794 (US 2016/0016794) in view of Nair (WO 2012/172560 A1) and Yu et al. (CN 106917163 A), as applied to claim 1 or 3 above, and further in view of Zarabian et al. (US 2022/0089442).
Regarding claim 4, Nair discloses that the base material preferably comprises a tubular body (i.e., a cylinder; see page 13, first paragraph; page 19, last paragraph). Nair also discloses that the base material can comprise a metal (i.e., a metal substrate; see page 17, third paragraph; page 18, last paragraph). Nair, however, fails to disclose that the metal is stainless steel, such that the tubular body is a stainless steel tube.
Zarabian et al. discloses a solid carbon capturing catalyst comprising a base material (i.e., a support; see paragraph [0030]) and a coating layer formed on a surface of the base material (i.e., a catalyst layer comprising active nanoparticles for the conversion of hydrogen and carbon monoxide into carbon nanofibers and water; see paragraph [0046]-[0047]). Specifically, Zarabian et al. discloses that the base material is preferably a tubular body, with the coating layer being formed on an inner wall surface of the tubular body (i.e., a cylinder defining an empty-core cylindrical shape which allows exposure of the gas to the catalyst for reaching a high load of carbon nanofiber formation without plugging the reaction path; see paragraph [0137]), and wherein the tubular body is a stainless steel tube (i.e., a tube formed from FeCrAl alloy, which is a ferritic stainless steel; see paragraph [0053]-[0054]).
It would have been obvious for one of ordinary skill in the art before the effective filing date of the claimed invention to provide a stainless steel tube for the tubular body in the modified reaction system of Noyes ‘794 because stainless steel can be heat treated to form alumina whiskers that restrict the motion of the deposited catalyst; stainless steel can be bent (e.g., corrugated) to increase the surface area available for depositing the coating layer; and the stainless steel tube is able to conduct heat, so that heat can be distributed to prevent the formation of hot-spots; as taught by Zarabian et al. (see paragraph [0054]).
Regarding claim 7, Noyes ‘794 discloses that the reforming device 104 performs a steam reforming reaction using the reforming catalyst to generate carbon monoxide, carbon dioxide, and hydrogen 108 from a raw material gas 102 containing hydrocarbon and water (see paragraphs [0081]-[0082]). Noyes ‘794, however, fails to disclose that the reforming device 104 contains a dry reforming catalyst that is able to generate carbon monoxide and hydrogen from the raw material gas containing hydrocarbon and carbon dioxide.
Zarabian et al. discloses a reaction system (see FIG. 1) comprising:
a reforming device (i.e., a first reactor 111 for performing a reforming reaction; see paragraph [0101]) comprising a reaction vessel, and a reforming catalyst that is provided inside the reaction vessel, for generating CO (i.e., an intermediate stream 103 comprising CO and H2) from a raw material gas containing hydrocarbon (i.e., light hydrocarbons 101, e.g., C1 to C4);
a solid carbon capturing device (i.e., a second reactor 112 for converting CO and H2 to solid carbon nanofibers 106; see paragraph [0102]) comprising a reaction vessel, and a solid carbon capturing catalyst provided inside the reaction vessel; and
a flow path (i.e., a path for conveying intermediate stream 103 and 104) through which a gas flows from the reforming device 111 to the solid carbon capturing device 112;
wherein the solid capturing catalyst comprises a base material and a coating layer formed on a surface of the base material (i.e., the second reactor 112 contains a catalyst comprising a support and a coating layer including an active catalyst supported on a surface of the support, see paragraphs [0029], [0030], [0046]-[0072], [0136]-[0145]; the support may be formed as a cylinder(s) or as a sheet, see paragraph [0030]; and the support may comprise an empty-core cylindrical shape or cylindrical form, see paragraphs [0137], [0148]).
Specifically, Zarabian et al. discloses that the reforming device 111 is “configured to enable steam catalytic reforming, dry catalytic reforming, partial oxidation of the hydrocarbon or the combination thereof to produce appropriate ratio of hydrogen to carbon monoxide,” (see paragraph [0019]). In the case of dry catalytic reforming, Zarabian et al. discloses that the reforming device 111 is provided with a dry reforming catalyst that generates carbon monoxide and hydrogen 103 from a raw material gas containing hydrogen 101 and carbon dioxide 102 (see paragraphs [0100]-[0101], [0114], [0129]-[0131]).
It would have been obvious for one of ordinary skill in the art before the effective filing date of the claimed invention to configure the reforming device in the modified reaction system of Noyes ‘794 to perform a dry reforming reaction, by providing a dry reforming catalyst for the reforming catalyst and by generating CO and H2 from a raw material gas containing hydrocarbon and carbon dioxide, because steam reforming and dry reforming were considered suitable reforming reactions for generating CO (see paragraph [0019], [0127]), and it would have been obvious for one of ordinary skill in the art to select a suitable reforming reaction to obtain the appropriate ratio of hydrogen to CO, depending on the solid carbon to be formed in the solid carbon capturing device (see paragraphs [0119]-[0121]), as taught by Zarabian et al.
Regarding claim 9, Zarabian et al. further discloses that a suitable dry reforming catalyst comprises a base material (i.e., a support such as a metal oxide, see paragraph [0131]; or a support that is a substrate that facilitates bulk transport of oxygen, see paragraph [0135]) and a catalyst activation layer formed on a surface of the base material (i.e., noble and transition metals, such as Ni, Co, Rh, and Ru, see paragraph [0130]; or oxides of Ni, Zr, Rh, Ru, and Mg, see examples of catalysts for dry reforming of methane at paragraph [0133]).
Claim 12 is rejected under 35 U.S.C. 103 as being unpatentable over Noyes ‘794 (US 2016/0016794) in view of Nair (WO 2012/172560 A1) and Yu et al. (CN 106917163 A), as applied to claim 11 above, and further in view of Murdoch et al. (US 5,128,003).
Noyes ‘794 (FIG. 2) discloses that the raw material gas 102 fed to the reaction system contains a hydrocarbon comprising methane (see paragraph [0081]). Noyes ‘794 also discloses that the reaction system produces carbon dioxide (i.e., carbon oxides in a tail gas stream 138 from the second reaction zone 110; see FIG. 3; paragraph [0087]-[0088]). Noyes ‘794, however, fails to disclose that the methane is generated by a methanation reaction of CO2.
Murdoch et al. discloses a reaction system (see FIG. 1) comprising a reforming device (i.e., a reforming reactor 9; see column 3, line 60, to column 4, line 5) provided with a reforming catalyst for generating carbon monoxide (i.e., a reactor effluent stream 11 containing hydrogen and carbon monoxide) from a raw material gas (i.e., an inlet stream 6) containing hydrocarbon, wherein the hydrocarbon comprises methane. Specifically, Murdoch et al. discloses that the methane in the raw material gas 6 is generated by a methanation reaction of CO2 (i.e., carbon dioxide and hydrogen are reacted in a methanation reactor 3 in the presence of a methanation catalyst to produce the methane fed to the reforming reactor 9; see column 3, lines 10-59).
It would have been obvious for one of ordinary skill in the art before the effective filing date of the claimed invention to form the methane via a methanation reaction of CO2 in the modified method of Noyes ‘794 because the carbon dioxide from the process could be used to generate additional methane to be provided in the raw material gas, and the methane could be reformed to produce additional CO and H2, as taught by Murdoch.
Conclusion
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/JENNIFER A LEUNG/Primary Examiner, Art Unit 1774