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 .
Information Disclosure Statement
The information disclosure statement (IDS) submitted on 09/17/2025 is being considered by the examiner.
Response to Amendments/ Status of Claims
An amendment, filed 08/29/2025, is acknowledged.
Claims 1-17 are currently pending.
Claim 1 has been amended, amendment finds supports in the paragraphs [0056] and [0081] of the instant specification.
Claim 17 are added, finds supports in the paragraphs [0062] of the instant specification.
Therefore, claims 1-1 are currently under consideration for this office action.
Status of Previous Rejections
The previous 35 USC § 102 rejections of the claims 1-5, 7, 10, 12-15, and 35 USC § 103 rejections of the claims 6, 11 and 16 have been withdrawn, due to amendment of claim 1.
The previous 35 USC § 102 rejections of the claims 8 and 9 have been maintained.
The previous alternative 35 USC § 103 rejections of the claims 1 and 8-9 have been maintained.
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.
Claims 8-9 are rejected under 35 U.S.C. 102(a)(1) and (a)(2) as anticipated by Hiroshi Takenouchi, et.al. [US20210180154A1] (PCT filed on Nov. 28, 2018, provided in the IDS).
Regarding claims 8, Takenouchi discloses a method for recovering a valuable metal from a waste lithium-ion battery, the method comprising obtaining a leachate by leaching a sulfide comprising copper and nickel and/or cobalt with an acid, the sulfide being generated by sulfurizing a molten body obtained by reducing, heating, and melting the waste lithium-ion battery (a method, wherein first, a material containing copper, nickel, and cobalt is sulfurized to obtain a sulfide, specifically, a waste lithium ion battery is regarded as a treatment target, by subjecting the waste lithium ion battery to a dry treatment in which heating and melting, and reducing are performed, an alloy containing copper, nickel, and cobalt is obtained, this alloy is sulfurized using a sulfurizing agent, and thus a sulfide containing copper, nickel, and cobalt can be obtained) [Section 0047-49, claim 1, 5], wherein the sulfide is subjected to a pulverizing treatment so as to have a particle size of 800 µm or less (an atomization method (equivalent to pulverizing) is applied to the molten metal of the sulfide obtained by sulfurization, and thus a powder sulfide can also be obtained) [Section 0055] and (a sulfide into a powder shape, the particle diameter of the sulfide is preferably approximately 300 µm or less. By using a powder-shaped sulfide having a particle diameter of 300 µm or less, the sulfide is easily treated in the next contact with an acid solution, which is preferable) [Section 0056].
Takenouchi’s disclosed particle size is within the as recited in the instant claim.
Therefore, it is either anticipatory when the prior art is within a claimed range and/or teaches overlapping the claimed range [See MPEP § 2131.03]. [Section 0055-0056].
Takenouchi further discloses the pulverized sulfide is subjected to a leaching treatment with an acid under a condition in which a sulfurizing agent is present (the sulfide obtained as described above is brought into contact with an acid solution. Since copper remains as a sulfide ( copper sulfide), while the sulfide is brought into contact with the acid solution and subjected to a reaction, and thus copper is directly separated as a copper sulfide and separated from the original sulfide by being precipitated, etc. on the bath bottom of a reaction bath due to a difference in specific gravity, nickel and cobalt are selected and leached by a sulfuric acid on the basis of the following Reaction Formulas (1) and (2) so as to exist as ions in the leachate. Note that, even if some of nickel and cobalt are in the form of a sulfide, due to the presence of an acid, the sulfides of nickel and cobalt are decomposed on the basis of the following reaction Formulas (1)' and (2’) so as to exist in a state of ions in the leachate [Section 0058-059]. According to Takenouchi’s Formulas (1)' and (2’) H2S is present in the leachate and H2S (hydrogen sulfide) is a sulfurizing agent as taught in the [Section 0053] of Takenouchi. Therefore, Takenouchi anticipates the limitation of “a condition in which a sulfurizing agent is present”.
Regarding claims 9, Takenouchi discloses a method for recovering a valuable metal from a waste lithium-ion battery, the method comprising a pyrometallurgical treatment, in which the waste lithium-ion battery is reduced, heated, and melted to obtain a molten body, and sulfurizing the molten body to obtain a sulfide containing copper and nickel and/or cobalt (a method, wherein first, a material containing copper, nickel, and cobalt is sulfurized to obtain a sulfide, specifically, a waste lithium ion battery is regarded as a treatment target, by subjecting the waste lithium ion battery to a dry treatment in which heating and melting, and reducing are performed, an alloy containing copper, nickel, and cobalt is obtained, this alloy is sulfurized using a sulfurizing agent, and thus a sulfide containing copper, nickel, and cobalt can be obtained) [Section 0047-49, claim 1, 5]. Takenouchi’s dry treatment anticipates the limitation of a pyrometallurgical treatment as in both the waste lithium-ion battery is reduced, heated, and melted to obtain a molten body.
Takenouchi then discloses a hydrometallurgical treatment, in which the sulfide is leached with an acid, wherein, in the hydrometallurgical treatment, the sulfide is pulverized so as to have a particle size of 800 µm or less (an atomization method (equivalent to pulverizing) is applied to the molten metal of the sulfide obtained by sulfurization, and thus a powder sulfide can also be obtained) [Section 0055] and (a sulfide into a powder shape, the particle diameter of the sulfide is preferably approximately 300 µm or less. By using a powder-shaped sulfide having a particle diameter of 300 µm or less, the sulfide is easily treated in the next contact with an acid solution, which is preferable) [Section 0056].
Takenouchi’s disclosed particle size is within the as recited in the instant claim.
Therefore, it is either anticipatory when the prior art is within a claimed range and/or teaches overlapping the claimed range [See MPEP § 2131.03]. [Section 0055-0056].
Takenouchi further discloses the pulverized sulfide is subjected to a leaching treatment with an acid under a condition in which a sulfurizing agent is present (the sulfide obtained as described above is brought into contact with an acid solution. Since copper remains as a sulfide ( copper sulfide), while the sulfide is brought into contact with the acid solution and subjected to a reaction, and thus copper is directly separated as a copper sulfide and separated from the original sulfide by being precipitated, etc. on the bath bottom of a reaction bath due to a difference in specific gravity, nickel and cobalt are selected and leached by a sulfuric acid on the basis of the following Reaction Formulas (1) and (2) so as to exist as ions in the leachate. Note that, even if some of nickel and cobalt are in the form of a sulfide, due to the presence of an acid, the sulfides of nickel and cobalt are decomposed on the basis of the following reaction Formulas (1)' and (2’) so as to exist in a state of ions in the leachate [Section 0058-059]. According to Takenouchi’s Formulas (1)' and (2’) H2S is present in the leachate and H2S (hydrogen sulfide) is a sulfurizing agent as taught in the [Section 0053] of Takenouchi. Therefore, Takenouchi anticipates the limitation of “a condition in which a sulfurizing agent is present”.
Claim Rejections - 35 USC § 103
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 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 1-2, 7, 12 and 17 are rejected under 35 U.S.C. 103 as being unpatentable over Hiroshi Takenouchi, et.al. [US20210180154A1] (PCT filed on Nov. 28, 2018, provided in the IDS) and further in view of Tatsuya Higaki, et.al. [US20200216929A1].
Regarding claims 1, Takenouchi discloses a method for treating a sulfide comprising copper and nickel and/or cobalt (a separating method, wherein first, a material containing copper, nickel, and cobalt is sulfurized to obtain a sulfide and a sulfide containing a copper sulfide as a main component and containing a nickel metal and a cobalt metal is produced) [Section 0047, 0050], the method comprising:
pulverizing the sulfide by subjecting the sulfide to a pulverizing treatment to obtain a pulverized sulfide (an atomization method (equivalent to pulverizing) is applied to the molten metal of the sulfide obtained by sulfurization, and thus a powder sulfide can also be obtained) [Section 0055] having a particle size of 800 µm or less (a sulfide into a powder shape, the particle diameter of the sulfide is preferably approximately 300 µm or less. By using a powder-shaped sulfide having a particle diameter of 300 µm or less, the sulfide is easily treated in the next contact with an acid solution, which is preferable) [Section 0056].
Takenouchi’s disclosed particle size is within the as recited in the instant claim.
Therefore, it would have been obvious to one of ordinary skill in the art, before the effective filling date of the present invention, to have selected and produced a pulverized sulfide from the teachings of Takenouchi that falls within the instantly-claimed ranges, because “In the case where the claimed ranges "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 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990)” [See MPEP § 2144.05.I].
Takenouchi then discloses leaching the pulverized sulfide and subjecting the pulverized sulfide to a leaching treatment with an acid under a condition in which a sulfurizing agent is present, to obtain a leachate (the sulfide obtained as described above is brought into contact with an acid solution. Since copper remains as a sulfide ( copper sulfide), while the sulfide is brought into contact with the acid solution and subjected to a reaction, and thus copper is directly separated as a copper sulfide and separated from the original sulfide by being precipitated, etc. on the bath bottom of a reaction bath due to a difference in specific gravity, nickel and cobalt are selected and leached by a sulfuric acid on the basis of the following Reaction Formulas (1) and (2) so as to exist as ions in the leachate. Note that, even if some of nickel and cobalt are in the form of a sulfide, due to the presence of an acid, the sulfides of nickel and cobalt are decomposed on the basis of the following reaction Formulas (1)' and (2’) so as to exist in a state of ions in the leachate [Section 0058-059]. According to Takenouchi’s Formulas (1)' and (2’) H2S is present in the leachate and H2S (hydrogen sulfide) is a sulfurizing agent as taught in the [Section 0053].
Takenouchi further teaches some of copper is leached from the sulfide and copper remains in the leachate. In a case where some of copper remains in the leachate and the copper is directly discharged from a leaching facility or the like, a load to a treatment of separating nickel and cobalt is increased. Therefore, it is desirable that the remaining copper is separated and removed from the leachate in advance [Section 0070], using a sulfurizing treatment of sulfurizing copper by adding a sulfurizing agent [Section 0072, Claim 7].
Takenouchi differs from the instant claim that Takenouchi’s treatment of removing copper remaining in the leachate is performed after the solid containing copper and the leachate containing nickel and cobalt are separated.
However, with respect to meet that difference, Higaki’s teaches an alloy obtained by subjecting the lithium ion battery to the dry treatment is a sparingly soluble and anticorrosive copper alloy and it is conventionally difficult to efficiently and selectively separate copper, nickel, and cobalt from this alloy [Section 0051]. In order to solve this problem, Higaki teaches in order to bring the sulfurization agent into contact with the alloy, a means for containing or applying a solid sulfurization agent into the alloy in the dry treatment is used [Section 0062]. Higaki then discloses examples of a waste lithium ion battery (waste LIB) is provided to a dry treatment of heat-melting and reducing the waste LIB to obtain a molten metal of the alloy containing copper, nickel and cobalt, and thereby obtaining an atomized powder [Section 0069]. Next, 1.0 g of this alloy powder is mixed with an addition of 0.35 g of elemental sulfur (a solid of sulfur) that becomes equivalent forming a copper sulfide represented by the above Formula (1), the alloy powder is prepared [Section 0054 0070].
Higaki discloses leaching of the pulverized sulfide (alloy powder containing sulfide) by subjecting the pulverized sulfide to a leaching treatment with an acid under a condition in which a sulfurizing agent is present adding a sulfurizing agent to the pulverized sulfide to create conditions where the pulverized sulfide and the sulfurizing agent coexist, and subjecting the pulverized sulfide to a leaching treatment with an acid under the conditions, to obtain a leachate (the alloy is brought into contact with an acid in the coexistence of a sulfurization agent. Copper leached from the alloy is precipitated as a copper sulfide, thereby obtaining a solid containing copper, while leached nickel and cobalt remain in the leachate, and therefore, copper, nickel and cobalt can be efficiently and selectively separated. Since copper is precipitated as a sulfide, most of copper does not exist in the leachate and nickel and cobalt exist at a very high ratio in an acidic solution (leachate). Therefore, selectivity is very high and copper, nickel and cobalt can be separated from each other) [Section 0053]. Higaki teaches the sulfurization agent can be elemental sulfur, or a liquid or gaseous sulfurization agent such as sodium hydrogen sulfide (hydrogenated sodium sulfide), sodium sulfide, or hydrogen sulfide gas etc. [Section 0055]. Higaki’s example teaches a leaching solution is obtained by hydrochloric acid with respect to the total amount of nickel and cobalt contained in the alloy powder and each of 1.0 g of the alloy powder, each of 0.35 g of the sulfur are respectively added at the same time and stirred [Section 0071-0072]. Higaki further teaches the leaching rate of copper was suppressed to 2.2% or less, and depending on the reaction temperature, the hydrochloric acid amount, and the reaction time, the leaching rate of copper was suppressed to less than 1 %. On the other hand, the leaching rates of nickel, cobalt, and iron were considerably higher than the leaching rate of copper in each Example, and depending on the reaction temperature, the hydrochloric acid amount, and the reaction time, 90% or more thereof was leached. Bringing an alloy containing copper, nickel and cobalt into contact with hydrochloric acid in the coexistence of a sulfurization agent, copper is precipitated as a copper sulfide, nickel and cobalt are selectively leached in the leachate, and thus copper, nickel and cobalt can be efficiently and selectively separated from the alloy [Section 0073].
HIgaki is analogous to claim 1 as well as Takenouchi as all are in the related field of treating a pulverized sulfide alloy obtained from the waste of lithium ion battery.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filling date of the present invention, to have Higaki’s teaching of adding a sulfurizing agent to a leaching treatment to modify Takenouchi, to bring the pulverized sulfide into contact with hydrochloric acid in the coexistence of a sulfurization agent, for efficient and selective separation of copper, nickel and cobalt from the pulverized sulfide alloy.
Regarding claims 2, all the above discussions regarding claim 1 are applicable to claim 2, in addition, Takenouchi discloses in the leaching step, a leaching treatment is performed with at least one or more types selected from sulfuric acid, hydrochloric acid, and nitric acid to obtain a leachate (the acid solution, a solution containing any one type of hydrochloric acid, nitric acid, and sulfuric acid or a solution obtained by mixing two or more types thereof can be used) [Section 0060]. Takenouchi further discloses from the viewpoint of so-called "battery-to-battery" that nickel and cobalt are recovered from the inside of the waste lithium ion battery and a lithium ion battery is reproduced, it is desirable that sulfuric acid is used as an acid solution and nickel is obtained as a sulfate that is in the form of a raw material for a positive electrode material of a lithium ion battery [Section 0060].
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filling date of the present invention to have Takenouchi’s teachings for selecting an acid for leaching solution based on the further intended use of the recovered material.
Regarding claims 7, all the above discussions regarding claim 1 are applicable to claim 7, in addition, Takenouchi discloses the sulfide is generated by adding a sulfurizing agent to a molten body obtained by reducing, heating, and melting a waste lithium-ion battery (a waste lithium ion battery is subjected to a dry treatment in which heating and melting, and reducing are performed, an alloy containing copper, nickel, and cobalt is obtained, this alloy is sulfurized using a sulfurizing agent, and thus a sulfide containing copper, nickel, and cobalt can be obtained) [Section 0047].
Takenouchi then discloses a waste lithium ion battery is introduced into a roasting furnace and roasted the roasted material (roasted product) thus obtained is introduced into a melting furnace, the alloy obtained in this way becomes a material containing copper, nickel, and cobalt that is a target to be sulfurized [Section 0048]. Takenouchi discloses upon sulfurizing the material containing copper, nickel, and cobalt, sulfurizing conditions are not particularly limited, but at least a copper component may be contained in the form of a copper sulfide [Section 0049]. In order to produce a sulfide in which only copper becomes a sulfide and nickel and cobalt exist as metal, Takenouchi teaches controlling the addition amount of the sulfurizing agent or the pressure conditions to adjust the degree of sulfurization, a partial sulfurization reaction in which only copper is sulfurized is caused. A sulfide containing a copper sulfide as a main component and containing a nickel metal and a cobalt metal is a so-called partial sulfide, a difference in degree of solubility of copper, nickel, and cobalt contained in the sulfide is generated, leaching is performed with an acid by the next treatment, and thus it is considered that copper becomes a residue as a copper sulfide and nickel and cobalt can be selectively leached [Section 0051-52].
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filling date of the present invention to have Takenouchi’s teachings for treating a waste lithium ion battery using heating, melting, reducing and sulfurizing for performing leaching with an acid having a residue of copper sulfide and to promote selective leaching of nickel and cobalt.
Regarding claims 12, all the above discussions regarding claim 1 and 2 are applicable to claim 12, in addition, Takenouchi discloses the sulfide is generated by adding a sulfurizing agent to a molten body obtained by reducing, heating, and melting a waste lithium-ion battery (a waste lithium ion battery is subjected to a dry treatment in which heating and melting, and reducing are performed, an alloy containing copper, nickel, and cobalt is obtained, this alloy is sulfurized using a sulfurizing agent, and thus a sulfide containing copper, nickel, and cobalt can be obtained) [Section 0047].
Takenouchi then discloses a waste lithium ion battery is introduced into a roasting furnace and roasted the roasted material (roasted product) thus obtained is introduced into a melting furnace, the alloy obtained in this way becomes a material containing copper, nickel, and cobalt that is a target to be sulfurized [Section 0048]. Takenouchi discloses upon sulfurizing the material containing copper, nickel, and cobalt, sulfurizing conditions are not particularly limited, but regarding a sulfide to be produced, at least a copper component may be contained in the form of a copper sulfide [Section 0049]. In order to produce a sulfide in which only copper becomes a sulfide and nickel and cobalt exist as metal, by controlling the addition amount of the sulfurizing agent or the pressure conditions to adjust the degree of sulfurization, a partial sulfurization reaction in which only copper is sulfurized is caused. A sulfide containing a copper sulfide as a main component and containing a nickel metal and a cobalt metal is a so-called partial sulfide, a difference in degree of solubility of copper, nickel, and cobalt contained in the sulfide is generated, leaching is performed with an acid by the next treatment, and thus it is considered that copper becomes a residue as a copper sulfide and nickel and cobalt can be selectively leached [Section 0051-52].
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filling date of the present invention to have Takenouchi’s teachings for treating a waste lithium ion battery using heating, melting, reducing and sulfurizing for performing leaching with an acid having a residue of copper sulfide and to promote selective leaching of nickel and cobalt.
Regarding claims 17, all the above discussions regarding claim 1 are applicable to claim 17, in addition, Takenouchi teaches it is preferable that the leaching state is determined by measuring an oxidation-reduction potential (ORP, reference electrode: silver/silver chloride electrode) of a leachate obtained by bringing the sulfide into contact with the acid solution, and the addition amount of the sulfide or the addition amount of the acid solution is adjusted such that the ORP is maintained in a range of 150 mV or less. Note that, it is preferable that, at the end of the leaching, the leaching is finished such that the ORP is in a negative region [Section 0064]. The addition amount of the acid solution is preferably adjusted depending on the leaching state based on the ORP of the leachate [Section 0064].
Takenouchi’s disclosed oxidation-reduction potential (ORP) is within the as recited in the instant claim.
Therefore, it would have been obvious to one of ordinary skill in the art, before the effective filling date of the present invention, to have selected and produced an oxidation-reduction potential from the teachings of Takenouchi that falls within the instantly-claimed ranges, because “In the case where the claimed ranges "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 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990)” [See MPEP § 2144.05.I].
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filling date of the present invention to have Takenouchi’s teachings for treating a waste lithium ion battery by adjusting the addition amount of the sulfide or the addition amount of the acid solution depending on the leaching state based on the ORP of the leachate.
Claim 3-6, 10-11 and 13-16 are rejected under 35 U.S.C. 103 as being unpatentable over Hiroshi Takenouchi, et.al. [US20210180154A1] (PCT filed on Nov. 28, 2018, provided in the IDS) and in view of Tatsuya Higaki, et.al. US[20200216929A1] as applied to claim 1, and further in view of Dominique Morin, et.al.[US20210376399A1] (PCT filed on Sep. 27, 2018). An evidentiary reference Daniel C. Harris [A book of “Quantitative Chemical Analysis”, Seventh Edition, Printed on 2007] (Harris hereafter) is presented.
Regarding claims 3, all the above discussions regarding claim 1 are applicable to claim 3, but both Takenouchi and Higashi are silent about the reducing the leachate by using a metal that has a lower standard reduction potential than copper.
However, Morin teaches materials used for the manufacturing of lithium-ion batteries, are projected to be at risk in the near feature and demand for alternative source of those materials in an affordable cost for lithium-ion batteries. Recycling is also necessary to obtain a positive environmental impact as the raw materials exploitation of the battery components have a large environmental burden [Section 0002]. Morin then teaches a pyrometallurgical processes are used to separate the different elements of a spent lithium-ion battery. By heating at high temperature and metals such as cobalt, copper and nickel are melted into an alloy, and the other elements end up in a slag, [Section 0004] and a hydrometallurgical processes are used after mechanical treatment to separate and purify the different metals [Section 0005].
Morin disclosed process comprising pulverizing battery waste to a particle size between 0.1 to 2 millimeters [Section 0058], and the fine particles subjected to a hydrometallurgical process, fine particles are mixed with sulfuric acid [Section 0061]. Morin teaches to remove the left over ionic copper in solution, coming from the leached metallic copper, the copper impurities is precipitated by binding with sulfide ions (S-). The source of sulfide ions can be any sulfide ionic compound such as, but not limited to, sodium sulfide (Na2S) or bubbling hydrogen sulfide (H2S). The sulfide will selectively bind to copper to form copper sulfide (CuS) which is insoluble [Section 0065]. Morin further discloses a reduction agent is added to the reaction tank to help leach transition metals, such as, but not limited to, aluminum powder (Al). The transition metals in the slurry (Co, Ni) are reduced, at which they are more readily leachable. Leaching of the metal oxides slurry produces a leachate of metal sulfate which is filtered from solid non-leachable materials [Section 0062]. Morin further discloses the efficiency of the leaching operation is improved by optimizing its parameters, like reducing agents, such as aluminum (foil) [Section 0096, Example III]. As presented in the evidentiary reference of Harris, the standard reduction potential value of Al is -1.677 V, which is lower than the standard reduction potential of copper 0.34 V, i.e. Morin’s reducing the leachate by using Al foil has a lower standard reduction potential than copper.
Morin is analogous to the claim as well as Takenouchi and Higaki as all are in the related field of treating a pulverized sulfide alloy obtained from the waste of lithium ion battery.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filling date of the present invention to have Morin’s teaching to modify Takenouchi for increasing the efficiency of the leaching operation using a metal reducing agent to promote leaching of transition metals (Co, Ni).
Regarding claims 4, all the above discussions regarding claim 1 and 3 are applicable to claim 4, Takenouchi discloses method for treating a sulfide further comprising oxidizing a solution obtained by adding an oxidant and a neutralizing agent to the solution obtained in the reduction step, to obtain a solution containing nickel and/or cobalt (when a sulfide is brought into contact with an acid solution, an oxidizing agent such as oxygen, air, or hydrogen peroxide is added. According to this, leaching of nickel and cobalt is accelerated, which is preferable) [Section 0062, 0072].
In addition, Morin discloses further comprising oxidizing and neutralizing a solution obtained in the reduction step by adding an oxidant and a neutralizing agent to the solution obtained in the reduction step, to obtain a solution containing nickel and/or cobalt (hydrogen peroxide (H2O2), manganese oxide (MnO2), or aluminum powder (Al) are added to the leaching solution. The transition metals in the slurry (Co, Ni, Mn) are reduced, or oxidized to a divalent (2+) oxidation state, at which they are more readily leachable. Leaching of the metal oxides slurry produces a leachate of metal sulfate which is filtered from solid non-leachable materials) [Section 0062]. Morin then discloses the efficiency of the leaching operation is improved by optimizing its parameters, like using Reducing agents, such as aluminum (foil) or manganese dioxide, are used to substitute partially or entirely the hydrogen peroxide [Section 0096, Example III]. Morin further discloses the leachate is then neutralized to a pH between 3.5 and 5.0 with the addition of sodium hydroxide (NaOH) to precipitate the remaining iron and aluminum, which will form hydroxides (Al(OH)3, Fe(OH)3) that are insoluble [Section 0066] and solution containing Co and/or Ni [Section 0067, Fig. 3].
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filling date of the present invention to have Morin’s teaching to modify Takenouchi for increasing the efficiency of the leaching operation using an oxidant to promote leaching of transition metals (Co, Ni, Mn) and neutralizing agent for separating the remaining iron and aluminum from the leachate.
Regarding claims 5, all the above discussions regarding claim 1, and 3-4 are applicable to claim 5, wherein Morin already discloses the oxidant is one or more types selected from hydrogen peroxide and hypochlorous acid (the efficiency of the leaching operation is improved by optimizing its parameters, like using Reducing agents, such as aluminum (foil) or manganese dioxide are used to substitute partially or entirely the hydrogen peroxide. Adding H2O2 and MnO2 seemed lo he the most efficient) [Section 0096, Example III]. Hydrogen peroxide (H2O2) and MnO2 are oxidants.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filling date of the present invention to have Morin’s teaching to modify Takenouchi for increasing the efficiency of the leaching operation using an oxidant to promote leaching of transition metals (Co, Ni, Mn).
Regarding claims 6, all the above discussions regarding claim 1 and 3-4 are applicable to claim 6, wherein Morin already discloses the neutralizing agent is one or more types selected from sodium hydroxide (the leachate is then neutralized to a pH between 3.5 and 5.0 with the addition of sodium hydroxide (NaOH) to precipitate the remaining iron and aluminum, which will form hydroxides (Al(OH)3, Fe(OH)3) that are insoluble in water) [Section 0066].
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filling date of the present invention to have Morin’s teaching to modify Takenouchi using neutralizing agent for separating the remaining iron and aluminum from the leachate.
Regarding claims 10, all the above discussions regarding claim 1 and 2 are applicable to claim 10, but Takenouchi is silent about the reducing the leachate by using a metal that has a lower standard reduction potential than copper.
However, Morin discloses the reducing the leachate by using a metal that has a lower standard reduction potential than copper (a reduction agent is added to the reaction tank to help leach transition metals, such as, but not limited to aluminum powder (Al). The transition metals in the slurry (Co, Ni) are reduced, at which they are more readily leachable. Leaching of the metal oxides slurry produces a leachate of metal sulfate which is filtered from solid non-leachable materials) [Section 0062]. Morin further discloses the efficiency of the leaching operation is improved by optimizing its parameters, like using Reducing agents. such as aluminum (foil) [Section 0096, Example III]. As presented in the evidentiary reference of Harris, the standard reduction potential of Al is -1.677 V, which is lower than the standard reduction potential of copper 0.34 V.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filling date of the present invention to have Morin’s teaching to modify Takenouchi for increasing the efficiency of the leaching operation using a reducing agent to promote leaching of transition metals (Co, Ni, Mn).
Regarding claims 11, all the above discussions regarding claim 1 and 3-5 are applicable to claim 11, wherein Morin already discloses the neutralizing agent is one or more types selected from sodium hydroxide (the leachate is then neutralized to a pH between 3.5 and 5.0 with the addition of sodium hydroxide (NaOH) to precipitate the remaining iron and aluminum, which will form hydroxides (Al(OH)3, Fe(OH)3) that are insoluble in water) [Section 0066].
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filling date of the present invention to have Morin’s teaching to modify Takenouchi for increasing the efficiency of the leaching operation using an oxidant to promote leaching of transition metals (Co, Ni) and using neutralizing agent for separating the remaining iron and aluminum from the leachate containing Co and Ni.
Regarding claims 13, all the above discussions regarding claim 1 and 3 are applicable to claim 13, in addition, Takenouchi discloses the sulfide is generated by adding a sulfurizing agent to a molten body obtained by reducing, heating, and melting a waste lithium-ion battery (a waste lithium ion battery is subjected to a dry treatment in which heating and melting, and reducing are performed, an alloy containing copper, nickel, and cobalt is obtained, this alloy is sulfurized using a sulfurizing agent, and thus a sulfide containing copper, nickel, and cobalt can be obtained) [Section 0047].
Takenouchi then discloses a waste lithium ion battery is introduced into a roasting furnace and roasted the roasted material (roasted product) thus obtained is introduced into a melting furnace, the alloy obtained in this way becomes a material containing copper, nickel, and cobalt that is a target to be sulfurized [Section 0048]. Takenouchi discloses upon sulfurizing the material containing copper, nickel, and cobalt, sulfurizing conditions are not particularly limited, but regarding a sulfide to be produced, at least a copper component may be contained in the form of a copper sulfide [Section 0049]. In order to produce a sulfide in which only copper becomes a sulfide and nickel and cobalt exist as metal, by controlling the addition amount of the sulfurizing agent or the pressure conditions to adjust the degree of sulfurization, a partial sulfurization reaction in which only copper is sulfurized is caused. A sulfide containing a copper sulfide as a main component and containing a nickel metal and a cobalt metal is a so-called partial sulfide, a difference in degree of solubility of copper, nickel, and cobalt contained in the sulfide is generated, leaching is performed with an acid by the next treatment, and thus it is considered that copper becomes a residue as a copper sulfide and nickel and cobalt can be selectively leached [Section 0051-52].
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filling date of the present invention to have Takenouchi’ teachings for treating a waste lithium ion battery using heating, melting, reducing and sulfurizing for performing leaching with an acid having a residue of copper sulfide and to promote selective leaching of nickel and cobalt.
Regarding claims 14, all the above discussions regarding claim 1 and 4 are applicable to claim 14, in addition, Takenouchi discloses the sulfide is generated by adding a sulfurizing agent to a molten body obtained by reducing, heating, and melting a waste lithium-ion battery (a waste lithium ion battery is subjected to a dry treatment in which heating and melting, and reducing are performed, an alloy containing copper, nickel, and cobalt is obtained, this alloy is sulfurized using a sulfurizing agent, and thus a sulfide containing copper, nickel, and cobalt can be obtained) [Section 0047].
Takenouchi then discloses a waste lithium ion battery is introduced into a roasting furnace and roasted the roasted material (roasted product) thus obtained is introduced into a melting furnace, the alloy obtained in this way becomes a material containing copper, nickel, and cobalt that is a target to be sulfurized [Section 0048]. Takenouchi discloses upon sulfurizing the material containing copper, nickel, and cobalt, sulfurizing conditions are not particularly limited, but regarding a sulfide to be produced, at least a copper component may be contained in the form of a copper sulfide [Section 0049]. In order to produce a sulfide in which only copper becomes a sulfide and nickel and cobalt exist as metal, by controlling the addition amount of the sulfurizing agent or the pressure conditions to adjust the degree of sulfurization, a partial sulfurization reaction in which only copper is sulfurized is caused. A sulfide containing a copper sulfide as a main component and containing a nickel metal and a cobalt metal is a so-called partial sulfide, a difference in degree of solubility of copper, nickel, and cobalt contained in the sulfide is generated, leaching is performed with an acid by the next treatment, and thus it is considered that copper becomes a residue as a copper sulfide and nickel and cobalt can be selectively leached [Section 0051-52].
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filling date of the present invention to have Takenouchi’ teachings for treating a waste lithium ion battery using heating, melting, reducing and sulfurizing for performing leaching with an acid having a residue of copper sulfide and to promote selective leaching of nickel and cobalt.
Regarding claims 15, all the above discussions regarding claim 1 and 5 are applicable to claim 15, in addition, Takenouchi discloses the sulfide is generated by adding a sulfurizing agent to a molten body obtained by reducing, heating, and melting a waste lithium-ion battery (a waste lithium ion battery is subjected to a dry treatment in which heating and melting, and reducing are performed, an alloy containing copper, nickel, and cobalt is obtained, this alloy is sulfurized using a sulfurizing agent, and thus a sulfide containing copper, nickel, and cobalt can be obtained) [Section 0047].
Takenouchi then discloses a waste lithium ion battery is introduced into a roasting furnace and roasted the roasted material (roasted product) thus obtained is introduced into a melting furnace, the alloy obtained in this way becomes a material containing copper, nickel, and cobalt that is a target to be sulfurized [Section 0048]. Takenouchi discloses upon sulfurizing the material containing copper, nickel, and cobalt, sulfurizing conditions are not particularly limited, but regarding a sulfide to be produced, at least a copper component may be contained in the form of a copper sulfide [Section 0049]. In order to produce a sulfide in which only copper becomes a sulfide and nickel and cobalt exist as metal, by controlling the addition amount of the sulfurizing agent or the pressure conditions to adjust the degree of sulfurization, a partial sulfurization reaction in which only copper is sulfurized is caused. A sulfide containing a copper sulfide as a main component and containing a nickel metal and a cobalt metal is a so-called partial sulfide, a difference in degree of solubility of copper, nickel, and cobalt contained in the sulfide is generated, leaching is performed with an acid by the next treatment, and thus it is considered that copper becomes a residue as a copper sulfide and nickel and cobalt can be selectively leached [Section 0051-52].
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filling date of the present invention to have Takenouchi’ teachings for treating a waste lithium ion battery using heating, melting, reducing and sulfurizing for performing leaching with an acid having a residue of copper sulfide and to promote selective leaching of nickel and cobalt.
Regarding claims 16, all the above discussions regarding claim 1 and 6 are applicable to claim 16, in addition, Takenouchi discloses the sulfide is generated by adding a sulfurizing agent to a molten body obtained by reducing, heating, and melting a waste lithium-ion battery (a waste lithium ion battery is subjected to a dry treatment in which heating and melting, and reducing are performed, an alloy containing copper, nickel, and cobalt is obtained, this alloy is sulfurized using a sulfurizing agent, and thus a sulfide containing copper, nickel, and cobalt can be obtained) [Section 0047].
Takenouchi then discloses a waste lithium ion battery is introduced into a roasting furnace and roasted the roasted material (roasted product) thus obtained is introduced into a melting furnace, the alloy obtained in this way becomes a material containing copper, nickel, and cobalt that is a target to be sulfurized [Section 0048]. Takenouchi discloses upon sulfurizing the material containing copper, nickel, and cobalt, sulfurizing conditions are not particularly limited, but regarding a sulfide to be produced, at least a copper component may be contained in the form of a copper sulfide [Section 0049]. In order to produce a sulfide in which only copper becomes a sulfide and nickel and cobalt exist as metal, by controlling the addition amount of the sulfurizing agent or the pressure conditions to adjust the degree of sulfurization, a partial sulfurization reaction in which only copper is sulfurized is caused. A sulfide containing a copper sulfide as a main component and containing a nickel metal and a cobalt metal is a so-called partial sulfide, a difference in degree of solubility of copper, nickel, and cobalt contained in the sulfide is generated, leaching is performed with an acid by the next treatment, and thus it is considered that copper becomes a residue as a copper sulfide and nickel and cobalt can be selectively leached [Section 0051-52].
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filling date of the present invention to have Takenouchi’ teachings for treating a waste lithium ion battery using heating, melting, reducing and sulfurizing for performing leaching with an acid having a residue of copper sulfide and to promote selective leaching of nickel and cobalt.
Claim(s) 1, 8 and 9 are alternatively rejected under 35 U.S.C. 103 as being unpatentable over Tatsuya Higaki, et.al. US[20200216929A1].
Regarding claims 1, 8 and 9, Higaki discloses a method for treating a sulfide comprising copper and nickel and/or cobalt, the method comprising, pulverizing the sulfide by subjecting the sulfide to a pulverizing treatment (teaches a material which is obtained by heat-melting and reducing the waste battery, a powdery material such as alloy powder obtained by applying an atomization method to the molten metal of the alloy obtained by heat-melting and reducing the waste battery. [Section 0048-0049]. An alloy obtained by subjecting the lithium ion battery to the dry treatment is a sparingly soluble and anticorrosive copper alloy and it is conventionally difficult to efficiently and selectively separate copper, nickel, and cobalt from this alloy it is possible to efficiently and selectively separate copper, nickel, and cobalt [Section 0051]. In order to solve this problem, Higaki teaches in order to bring the sulfurization agent into contact with the alloy, a means for containing or applying a solid sulfurization agent into the alloy in the dry treatment is used [Section 0062].
Higaki’s disclosed particle size is 300 µm or less [Section 0050] which is within the as recited in the instant claim.
Therefore, it would have been obvious to one of ordinary skill in the art, before the effective filling date of the present invention, to have selected and produced a pulverized sulfide from the teachings of Higaki that falls within the instantly-claimed ranges, because “In the case where the claimed ranges "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 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990)” [See MPEP § 2144.05.I].
Higaki discloses leaching the pulverized sulfide (alloy powder containing sulfide) by subjecting the pulverized sulfide to a leaching treatment with an acid under a condition in which a sulfurizing agent is present adding a sulfurizing agent to the pulverized sulfide to create conditions where the pulverized sulfide and the sulfurizing agent coexist, and subjecting the pulverized sulfide to a leaching treatment with an acid under the conditions, to obtain a leachate (an alloy is brought into contact with an acid in the coexistence of a sulfurization agent. Copper leached from the alloy is precipitated as a copper sulfide, thereby obtaining a solid containing copper, while leached nickel and cobalt remain in the leachate, and therefore, copper, nickel and cobalt can be efficiently and selectively separated. Since copper is precipitated as a sulfide, most of copper does not exist in the leachate and nickel and cobalt exist at a very high ratio in an acidic solution (leachate). Therefore, selectivity is very high and copper, nickel and cobalt can be separated from each other [Section 0053]. Higaki teaches the sulfurization agent can be elemental sulfur, or a liquid or gaseous sulfurization agent such as sodium hydrogen sulfide (hydrogenated sodium sulfide), sodium sulfide, or hydrogen sulfide gas etc. [Section 0055].
Higaki then discloses an example of a waste lithium ion battery (waste LIB) is provided to a dry treatment of heat-melting and reducing the waste LIB to obtain a molten metal of the alloy containing copper, nickel and cobalt, and thereby obtaining an atomized powder [Section 0069]. Next, 1.0 g of this alloy powder is mixed with an addition of 0.35 g of elemental sulfur (a solid of sulfur) that becomes equivalent forming a copper sulfide represented by the above Formula (1), the alloy powder is pre