DETAILED ACTION
Examiner’s Comments
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
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 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.
Column and line (or Paragraph Number) citations have been provided as a convenience for Applicants, but the entirety of each reference should be duly considered. Any recitation of a Figure element, e.g. “Figure 1, element 1” should be construed as inherently also reciting “and relevant disclosure thereto”.
Claim Objections
Claims 77 – 80 are objected to as being dependent upon a rejected base claim, but would be allowable if rewritten in independent form including all of the limitations of the base claim and any intervening claims.
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 1 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 pre-AIA the applicant regards as the invention.
Claim 1 recites the limitation "said Li Brine" in 3rd from the last line (“… extracting said Li Brine …”). There is insufficient antecedent basis for this limitation in the claim. This rejection can be overcome by amending this clause to recite “extracting [said] a Li Brine …”, which is how the claim has been interpreted when considering the prior art.
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 of this title, 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.
Claims 1, 62, 66 – 73, 81 and 82 are rejected under 35 U.S.C. 103(a) as being unpatentable over WO 2020/092157 to Albemarle Corporation (hereinafter, “Albemarle") in view of JP 4631818 to Sumitomo Metal Mining Co. Ltd. (hereinafter, "Sumitomo").
The Examiner notes that this is the same general rejection as set forth in the Written Opinion/ISR.
Regarding claims 1 and 66, Albemarle disclose a method (Albemarle, Abstract, Processes for extracting metals from lithium-ion batteries) comprising the steps: - depositing a first quantity of black mass derived from processed lithium-ion batteries in an acid-reduction reactor (Albemarle, Para. [0041] processes for extracting one or more metals from spent lithium ion batteries (LIBS). The LIBs may be processed so as to form a black mass; Paras. [0043}; [0044] preparing a combination comprising the one or more metals, a liquid, an acid, and one or more other components ... As illustrated in FIG. 1, the combination may be prepared by contacting the black mass with an acid and a liquid soivent, for example, an aqueous acid solution comprising the acid and water ... the combination is contacted with a reducing agent so as to form an acid leachate); - reductive-acid leaching said black mass through the introduction of an acid solution (Albemarle, Paras. (0043); [0044] preparing a combination comprising the one or more metals, a liquid, an acid, and one or more other components ... As illustrated in FIG. 1, the combination may be prepared by contacting the black mass with an acid and a liquid solvent, for example, an aqueous acid solution comprising the acid and water ... the combination is contacted with a reducing agent so as to form an acid leachate) causing the production of: - a mother leachate containing a mixture of solubilized metals (Albemarle, Para. [0044] Fig. 1 the one or more metals of the CAM (e.g., lithium, cobalt, nickel, and/or manganese) are released into the acid leachate along with any iton and/or aluminum, i.e. solubilized metals); - a quantity of bulk solid material (Albemarle, Para. [0044] copper and phosphorous remain in their solid forms, i.e. bulk solid); - increasing the pH of the mother leachate causing said solubilized metals to form metal hydroxides and further precipitating said metal hydroxides from the leachate (Albemarle, Paras. [0054]; [0056] The process also comprises contacting the acid leachate with a base adapted to adjust the pH of the acid leachate ... the acid leachate may be contacted with a base solution comprising lithium hydroxide (LiOH) under conditions sufficient so as to form a precipitate comprising aluminum hydroxide (Al(OH)3) ... The base comprises one or more selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, and any combination of two or more; Paras. [0055] In an aspect, the pH of the acid leachate is a value ranging from about 2 to about 8; Para. [0059] After the pH adjustment step, the process may comprise separating solids from the acid leachate. For example, following the pH adjustment step, solid waste may be separated from the acid leachate by filtration. The solid/liquid separation results in removal of solids from the acid leachate thereby resulting in the acid leachate being a Li/Co-rich solution. The solids may comprise aluminum hydroxide (Al (OH)3) and iron(Ill) hydroxide (Fe(OH)3), i.e. as shown in Fig. 1 solid A(OH)3 and Fe(OH)3 precipitates separated from acid leachate);- oxidizing aqueous manganese (Mn) present in the leachate forming insoluble manganese dioxide (MnO2) and precipitating said MnO2 from the leachate (Albemarle, Para. [0044] Fig. 1 the one or more metals of the CAM (e.g., lithium, cobalt, nickel, and/or manganese) are released into the acid leachate along with any iron and/or aluminum; Para. [0061] Accordingly, Fe(Il) and Mn(Il) can be selectively oxidized, precipitated and removed from the acid leachate, i.e. as shown in Fig. 1, MnO2 is removed from aqueous leachate); - increasing the pH of the leachate precipitating cobalt, nickel and other trace metals remaining in the leachate as hydroxides (Albemarle, Para. [0071] contacting the acid leachate with a solvent adapted to extract cobalt from the acid leachate so as to form an organic/aqueous mixture ... an alkaline base, such as a alkaline solution comprising LiOH and/or NaOH, is added to the organic/aqueous mixture continuously to maintain pH in the range of about 5 to about 5.5; Para. [0078] Following the solvent extraction, two aqueous streams are typically generated: (1) a purified Co-rich solution, and (2) a Ni/Li/Na solution; Para. [0079] The Co-rich solution ... can be precipitated as various salts such as Co(OH)2, i.e. cobalt hydroxide precipitate; Para. [0080] Nickel may be separated from the Ni/Li/Na solution to generate a Li/Na solution. One approach is to increase the pH of the Ni/Li/Na solution so that is in the range of from about 10 to about 11, where substantially all Ni can be precipitated from the Ni/Li/Na solution as nickel hydroxide (Ni(OH)2, i.e. Nicke! hydroxide precipitate; Para. [0072] Once these impurities (i.e., Cu, Al, Fe and/or P) are removed from or reduced in the acid leachate, the separation of Co and Ni from the acid leachate is generally fairly straightforward; Para. [0066] a base solution, such as LiOH or NaOH, may be used to increase the pH to about 3.5 to about 4 to help ensure that substantially all Fe(ill) is precipitated from the acid leachate along with MnO2, i.e. iron hydroxide precipitate, wherein iron is present as a trace impurity); - generating a Lithium (Li) bleed stream (Albemarle, Para. [0078)} Following the solvent extraction, two aqueous streams are typically generated: (1) a purified Co-rich solution, and (2) a Ni/Li/Na solution; Para. [0080] Nickel may be separated from the Ni/Li/Na solution to generate a Li/Na solution, i.e. as shown in Fig. 1 a Li/Na bleed stream comprising the Li brine is generated); and - extracting said Li Brine from the bleed stream, or recycling said Li Brine back into said acid-reduction reactor with an additional quantity of black mass (Albemarle, Para. [0080] The thus generated Li/Na solution can then be processed to make one or more lithium containing compounds, i.e. as shown in Fig. 1 a Li/Na bleed stream comprising the Li brine can be extracted).
Albemarle fails to explicitly disclose electrowinning the leachate to form a quantity of cobalt/nickel alloy and extracting the cobalt/nickel alloy.
However, Sumitomo is in the field of hydrometallurgical processes for recovering metals (Sumitomo, Abstract), and teaches electrowinning a leachate to form a quantity of cobalt/nickel alloy and extracting the cobalt/nickel alloy (Sumitomo, Abstract, “leachate is fed to an electrolytic cell, and is subjected to electrowinning, so as to produce a nickel and cobalt-containing alloy"; Para. [0042] The electrocollection/electrowinning step is a step of supplying the leachate obtained in the solid-liquid separation step to an electrolytic tank and subjecting the leachate to electrocollection/electrowinning to produce an alloy containing nickel and cobalt. As a result, the nickel and cobalt are metalized and separated from a poor solution containing other impurity elements, and the nickel and cobalt are concentrated as electrodeposits; i.e. electrowinning step for extracting cobalt/nickel alloy).
It would have been obvious to one of ordinary skill in the art at the time of the invention to modify Albemarle to include electrowinning the leachate to form a quantity of cobalt/nickel alloy and extracting the cobalt/nickel alloy as taught by Sumitomo. The motivation would have been to provide a purified product having a high degree of concentration of nickel and cobalt and tow moisture adhesion (Sumitomo, Para. [0012)).
Regarding claim 62, Albemarle and Sumitomo are relied upon as described above. Albemarle further discloses wherein said acid solution is introduced into said acid-reduction reactor until a pH of between 1-4 is achieved causing the metals in said black mass to be solubilized (Albemarle, Paras. [0043); (0044] Fig. 1 combination may be prepared by contacting the black mass with an acid and a liquid solvent, for example, an aqueous acid solution comprising the acid and water ... the combination is contacted with a reducing agent so as to form an acid leachate; Para. [0055] the pH of the acid leachate is a value ranging from about 2 to about 8). In addition, Albemarle further discloses wherein said quantity of bulk solid material comprises a quantity of graphite (Albemarle, Para. (0044] copper and phosphorous remain in their solid forms, i.e. bulk solid; Para. [0059] The solids may comprise one or more selected from the group consisting of graphite).
Regarding claims 67 and 70, Albemarle further discloses wherein said acid solution comprises a solution of sulfur dioxide (SO2) and/or a solution sulfuric acid (H2SO4), and/or an acid solution generated by said electrowinning step (Albemarle, Paras. [0043]; {0044] the combination may be prepared by contacting the black mass with an acid and a liquid solvent, for example, an aqueous acid solution comprising the acid and water; Para. [0045] The acid comprises one or more selected from the group consisting of sulfuric acid). The Examiner notes that either the amount of SO2 could have been optimized to the claimed up to 2 moles by a person of ordinary skill in the art, or the teaching above renders obvious using 0 moles and instead using sulfuric acid or acid solution generated by the electrowinning step, as discussed above.
Regarding claims 68 and 69, these limitations are met for the reasons cited above.
Regarding claims 71 – 73, Albemarle further discloses wherein said acid solution is introduced into said acid-reduction reactor until a pH of between 1-4 is achieved causing the metals in said black mass to be solubilized (Albemarle, Paras. [0043); (0044] Fig. 1 combination may be prepared by contacting the black mass with an acid and a liquid solvent, for example, an aqueous acid solution comprising the acid and water ... the combination is contacted with a reducing agent so as to form an acid leachate; Para. [0055] the pH of the acid leachate is a value ranging from about 2 to about 8). Albemarle further discloses wherein said step of increasing the pH of the mother leachate compromises introducing one or more of the following to the mother leachate: - recycling downstream produced metal hydroxides to increase the pH in the leachate; and introducing a base compound to increase the pH in the leachate (Albemarle, Para. [0054] The process also comprises contacting the acid leachate with a base adapted to adjust the pH of the acid leachate; Para. [0056] The base comprises one or more selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, and any combination of two or more of the foregoing). In addition, Albemarle further discloses wherein said step of increasing the pH of the mother leachate compromises increasing the pH of the leachate to between 4 and 7 (Albemarle, Para. [0054] The process also comprises contacting the acid leachate with a base adapted to adjust the pH of the acid leachate; Para. [0055] In an aspect, the pH of the acid leachate is a value ranging from about 2 to about 8).
Regarding Claim 81, Albemarle further discloses wherein said quantity of bulk solid material comprises a quantity of graphite (Albemarle, Para. (0044] copper and phosphorous remain in their solid forms, i.e. bulk solid; Para. [0059] The solids may comprise one or more selected from the group consisting of graphite). The Examiner notes that silicon is also conventionally used in lithium ion batteries and it would have been obvious for the bulk solid to include silicon, though the ‘and/or’ language does not require silicon to be present in the claim coverage.
Regarding Claim 82, Albemarle further discloses further comprising the step of purifying said quantity of graphite (Albemarle, Para. [0059] Fig. 1 After the pH adjustment step, the process may comprise separating solids from the acid leachate ... The solids may comprise one or more selected from the group consisting of graphite, i.e. as shown in Fig. 1 the solid waste comprising graphite is washed and further separated).
Claims 74 – 76 are rejected under 35 U.S.C. 103(a) as being unpatentable over Albemarle in view of Sumitomo as applied above, and further in view of WO 2003/054238 to Congo Mineral Developments Ltd et al. (hereinafter, "Congo").
The Examiner notes that this is the same general rejection as set forth in the Written Opinion/ISR.
Albemarle and Sumitomo are relied upon as described above.
Regarding claims 74 and 76, neither Albemarle nor Sumitomo explicitly disclose wherein said step of oxidizing aqueous Mn comprises the step of contacting said leachate with SO2 and oxygen (O2) forming insoluble MnO2.
However, Congo is in the field of removing manganese values from a leach solution (Congo, Abstract; Pg. 5, Paras. 1 & 3) and teaches wherein said step of oxidizing aqueous Mn comprises the step of contacting said leachate with SO2 and oxygen (O2) forming insoluble MnO2 (Congo, Pg. 5, Paras. 1 & 3 method of removing manganese values from a solution containing manganese values by introducing into the solution a gas mixture of sulphur dioxide and air or oxygen so as in a single step to oxidize the manganese values from the manganous to the manganic state and then to precipitate the manganese values as manganic oxide ... The solution may be for example a leach solution; Pg. 6 Para. 1 manganese values are removed from the solution by oxidation and precipitation utilizing a sulphur dioxide gas in oxygen or in air; Pg. 6 2nd to last line, "Manganese Oxidation and Precipitation" Reaction [8]; Pg. 7 Para. 3 Manganese is oxidized, by the gas mixture, from the mangenous to the manganic state, and thereafter the manganic manganese are precipitated as oxides reaction [8}).
It would have been obvious to one of ordinary skill in the art at the time of the invention to modify Albemarle to include wherein said step of oxidizing aqueous Mn comprises the step of contacting said leachate with SO2 and oxygen (02) forming insoluble MnO2 as taught by Congo. The motivation would have been to provide a process for removing manganese impurities from a solution (Congo, Pg. 1 Para. 1).
Regarding Claim 75, neither Albemarle nor Sumitomo explicitly disclose wherein the Mn remaining in said leachate after oxidation is less than 2 g/l but not less than 0.5 g/l. However, Congo is in the field of removing manganese values from a leach solution (Congo, Abstract; Pg. 5, Paras. 1 & 3) and teaches wherein the Mn remaining in said leachate after oxidation is less than 2 g/l but not less than 0.5 g/l (Congo, Pg. 5, Paras. 1 & 3 method of removing manganese values from a solution containing manganese values by introducing into the solution a gas mixture of sulphur dioxide and air or oxygen so as in a single step to oxidize the manganese values from the manganous to the manganic state and then to precipitate the manganese values as manganic oxide ... The solution may be for example a leach solution; Pg. 14 Last Para. through Pg. 15 first table, a leach solution described in table 2 is treated as described in "Steps (1) and (2) Iron/Manganese/Aluminum Removal’ ... as shown in the first solution analyses table on Pg. 15, the Mn remaining in the "Iron/Manganese/Aluminum Free Solution" is 80 mgj/l, i.e. 0.8/1). It would have been obvious to one of ordinary skill in the art at the time of the invention to modify Albemarle to include wherein the Mn remaining in said leachate after oxidation is less than 2 g/t but not less than 0.5 g/t as taught by Congo. The motivation would have been to provide a process for removing manganese impurities from a solution (Congo, Pg. 1 Para. 1).
Regarding claim 76, neither Albemarle nor Sumitomo explicitly disclose wherein said step of oxidizing aqueous Mn occurs prior to the step of precipitating said metal hydroxides from the leachate. However, it would have been obvious to one of ordinary skill in the art at the time the invention was made to modify Albemarle to include wherein said step of oxidizing aqueous Mn occurs prior to the step of precipitating said metal hydroxides from the leachate, since selection of any order of process steps which did not result in a new or unexpected result would involve only routine skill in the art. The motivation for doing so would have been to provide an improved LIB recycling method that is less prone to carry impurities along with the metals of interest (Albemarle, Para. [0005)).
Allowable Subject Matter
The following is a statement of reasons for the indication of allowable subject matter: claims 77 – 80 are deemed allowable over the prior art because the prior art fails to teach the specifics of the process in the independent claim, nor the added limitations in any of these dependent claims for the same reasoning as set forth in the Written Opinion/ISR filed on the January 3, 2023 IDS (see comments directed to at least international claims 19, 20, 22, 25 and 44).
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
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/KEVIN M BERNATZ/Primary Examiner, Art Unit 1785
August 19, 2025