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 .
Drawings
The drawing is objected to because the labeled box for "nickel precipitation" contains a typographic error. Corrected drawing sheets in compliance with 37 CFR 1.121(d) are required in reply to the Office action to avoid abandonment of the application. Any amended replacement drawing sheet should include all of the figures appearing on the immediate prior version of the sheet, even if only one figure is being amended. The figure or figure number of an amended drawing should not be labeled as “amended.” If a drawing figure is to be canceled, the appropriate figure must be removed from the replacement sheet, and where necessary, the remaining figures must be renumbered and appropriate changes made to the brief description of the several views of the drawings for consistency. Additional replacement sheets may be necessary to show the renumbering of the remaining figures. Each drawing sheet submitted after the filing date of an application must be labeled in the top margin as either “Replacement Sheet” or “New Sheet” pursuant to 37 CFR 1.121(d). If the changes are not accepted by the examiner, the applicant will be notified and informed of any required corrective action in the next Office action. The objection to the drawings will not be held in abeyance.
Claim Rejections - 35 USC § 103
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claims 1-10 are rejected under 35 U.S.C. 103 as being unpatentable over Zhu 2021 (CN 109182732 B), in view of Dong 2020 (CN 111994925 A), Bi 2020 (CN 111600013 A), and Welsh 1960 (US 2956860 A), and non-patent literature Williams 2013, Hydrometallurgy, Volume 138, June 2013, Pages 84-92. English translations of Zhu, Dong, and Bi, as provided with this office action, are cited herein.
Regarding claim 1, Zhu teaches the following:
A method for separating and recovering valuable metals from waste ternary lithium batteries (method for extraction and recycling of valuable metal elements in waste ternary lithium batteries, 0008), comprising:
Adding a reducing agent and first acid to a waste ternary lithium battery powder for oxidative acid leaching (0015) to obtain a first filtrate, then adding alkali solution to adjust the pH (0016), wherein the alkali solution is sodium or potassium hydroxide (0065)
Adding sodium persulfate to the filtrate rich in lithium, nickel, cobalt, and manganese ions to perform a redox reaction (0018)
Conducting solid-liquid separation to obtain a leaching liquor and a leaching residue (second filtrate and MnO2 precipitate, 0018)
Adding extractant and diluent to the leaching liquor to obtain an organic phase and inorganic phase (0019); adjusting the pH of the inorganic phase to 13-14 and filtering to obtain Ni(OH)2 and a third filtrate (0021)
Adding a carbonate to the third filtrate and conducting solid-liquid separation to obtain lithium carbonate (0022)
Adding a second acid to the organic phase mixture and conducting back-extraction to obtain a cobalt solution (0020)
See a translated copy of Figure 1 of CN 109182732 B below.
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The instant claim additionally requires, which Zhu does not teach, the following:
Adding a persulfate along with the first acid to the waste ternary battery powder before the first alkali addition (step 1)
Adding an alkali to the leaching liquor after solid-liquid separation (step 2)
Adding a sulfide salt to allow a second precipitation reaction (step 2) and conducting solid-liquid separation to obtain a second liquid phase (step 2)
Subjecting the leaching residue obtained in step (1) to calcination, then adding a chlorate, heating a resulting mixture, and conducting solid-liquid separation to obtain a solid phase and a liquid phase, wherein the solid phase is manganese dioxide and the liquid phase is a cobalt solution (step 4)
However, regarding limitations I and II, it has been held that differences in the order of performing process steps is obvious in the absence of new or unexpected results (see MPEP 2114.04.IV.C.). It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to perform the method as suggested by Zhu where the addition of sodium persulfate (0018) is conducted in any order of the taught process including before and after the first adjustment of pH by using alkali (0016) for the purpose of carrying out a redox reaction, as Zhu teaches (0018). Similarly, it would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to perform the method as suggested by Zhu where the addition of an alkali (0016) is conducted in any order of the taught process including before and after the addition of persulfate and filtration to obtain a leaching liquor (0018) for the purpose of removing impurities in the mixed slurry, as Zhu teaches (0064). Furthermore, one of ordinary skill in the art would have reasonable expectation of obtaining a predictable outcome by adding alkali solution to adjust the pH after the addition of persulfate, given that Zhu teaches that extractant and diluent are added to the leaching liquor to perform a saponification reaction (0027, 0079). The addition of an alkali solution, which provides alkali and hydroxide ions, to the saponification reaction would reasonably be expected to perform predictably and successfully as saponification to one skilled in the art.
Regarding limitation III, Dong teaches a method for the comprehensive utilization of valuable resources in waste lithium batteries (0002) wherein a mixed solution containing cobalt, nickel, manganese, and lithium is obtained (0012), analogous to the leaching liquor obtained by Zhu, and a sulfide salt, sodium sulfide, is added after aluminum and iron removal in order to perform a copper removal step (0014). It would be obvious to one skilled in the art before the effective filing date of the invention to modify the invention taught by Zhu with the addition of sodium sulfide as taught by Dong; one would be motivated to do so in order to remove/precipitate copper from the solution containing the Co, Mn, Ni, Li ions, as both Dong (0014) and Zhu (0064) teach.
Regarding limitation IV, Bi teaches a method for preparing a manganese source precursor for a manganese-based lithium battery cathode material (0011), wherein MnO2 is calcined and then leached with H2SO4 (0012, 0013) with heating (hot sulfuric acid, temperature of 50-100 degrees Celsius, 0014) to achieve the disproportionation of manganese, where the result is subjected to solid-liquid separation (filtration, 0013) to obtain active MnO2. It would be obvious to one skilled in the art to modify the invention taught by Zhu with the steps taught by Bi; one would be motivated to do so in order to obtain active MnO2 for use as a high-valence manganese source grain precursor for synthesizing manganese-based lithium battery cathode materials, as Bi teaches (0028).
Zhu modified by Bi does not teach the addition of a chlorate. However, Welsh teaches that disproportionation of manganese can also be achieved with sodium chlorate (Experiments I and II, C2/L40-52). Welsh therefore discloses that chlorate is a known equivalent useful for conducting the disproportionation treatment of manganese. It would be obvious to one skilled in the art to modify the invention of Zhu, modified with the steps taught by Bi, by adding sodium chlorate, and arrive at the claimed steps of adding a chlorate to a second acid and heating the resulting mixture. One would be motivated to do so because Bi teaches that the disproportionation reaction generates MnSO4 and MnO2 (0037), and Welsh teaches the disproportionation of manganese to obtain MnO2 from MnSO4 + MnO2 (Experiments I and II, C2/L40-52), and Welsh teaches that the reaction rate can be favorably optimized by the use of catalytically active MnO2 (C2/L29-34). It is prima facie obvious to combine two compositions known for the same purpose each of which is taught by the prior art to be useful for the same purpose to form a third composition to be used for the very same purpose. See MPEP 2144.06.I. It therefore would have been obvious to one of ordinary skill in the art at the time of filing of the invention to perform the method taught by Zhu by subjecting the leaching residue to a second acid and a chlorate as disclosed by Bi and Welsh as the mere combination of equivalents known for the same purpose.
Zhu modified by Bi and Welsh does not teach that the liquid phase is a cobalt solution. However, Williams teaches the selective leaching of nickel from mixed nickel cobalt hydroxide precipitate (title) wherein sodium persulfate (Na2S2O8) is added to oxidize manganese and cobalt (p. 86 column 1). Williams discloses that the selection of a suitable oxidant and oxidant addition rate can allow one skilled in the art to selectively stabilize Co and Mn in the solid phase while leaving Ni in solution (p. 85 column 2). It would be obvious to one skilled in the art to modify the invention of Zhu modified by Bi and Welsh with the reaction conditions of the persulfate addition step taught by Williams, thus arriving at a residue containing both manganese and cobalt ions that are subjected to the calcination, acid+chlorate leaching, heating, and separation as taught by Bi and Welsh, which would yield a manganese dioxide product while obtaining a cobalt solution (Zhu teaches that the extraction of cobalt with sulfate yields cobalt sulfate in solution, 0020). One would be motivated to do so because Williams teaches that the extraction of cobalt is often incomplete and loads with nickel, reducing nickel purity (p. 85 column 1). One of ordinary skill in the art would therefore arrive at the presently claimed invention with reasonable predictability.
Regarding claim 2, Zhu modified by Williams, Williams teaches conducting the oxidizing leaching at 80 ℃ at a pH of 4.6 (Table 2). This lies within the claimed range of temperatures of 80-120 ℃, while falling outside the claimed range of pH of 0.5-1.0. However, Williams discloses the effect of pH on metal deportment (2.3.1, p. 86 column 2). As the metal deportment is a variable that can be modified, among others, by adjusting the pH, with metal recovery being influenced as the pH is increased/decreased, the precise pH would have been considered a result effective variable by one having ordinary skill in the art before the effective filing date of the invention. As such, without showing unexpected results, the claimed range of pH cannot be considered critical. Accordingly, one of ordinary skill in the art before the effective filing date of the invention would have optimized, by routine experimentation, the pH in the method taught by Zhu and modified by Williams to obtain the desired effects as taught by Williams (In re Boesch, 617 F.2d. 272, 205 USPQ 215 (CCPA 1980)), since it has been held that where the general conditions of the claim are disclosed in the prior art, discovering the optimum or workable ranges involves only routine skill in the art. (In re Aller, 105 USPQ 223). “[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation.” See In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955). The discovery of an optimum value of a known result effective variable, without producing any new or unexpected results, is within the ambit of a person of ordinary skill in the art. See In re Boesch, 205 USPQ 215 (CCPA 1980) (see MPEP § 2144.05, II.).
Regarding claim 3, Zhu teaches the use of sodium persulfate (0018).
Regarding claim 4, Zhu teaches that the alkali solution is at least one of sodium hydroxide solution and potassium hydroxide solution (0032).
Regarding claim 5, Zhu modified by Dong, Dong teaches sodium sulfide (0014).
Regarding claim 6, Zhu teaches adjusting the pH to 13-14. This falls outside the claimed range of 9.5-10.0. However, it would be obvious to one skilled in the art before the effective filing date of the claimed invention to adjust the pH within a workable optimum range to obtain a desired amount of precipitated nickel hydroxide, as Zhu teaches (0033, 0084). One of ordinary skill in the art would therefore arrive at the claimed invention predictably through routine optimization; see MPEP 2144.05.II.
Regarding claim 7, Zhu teaches sodium carbonate (0022).
Regarding claim 8, Zhu modified by Bi, Welsh, and Williams, Zhu teaches a first acid of sulfuric acid (0057, 0097), and the second acid is taught by Bi, Welsh, and Williams; Bi teaches hot sulfuric acid (0013), Welsh teaches sulfuric acid heated to 85℃ (C2/L41), and Williams teaches sulfuric acid (sulphuric acid, 2.3 p. 86 column 1).
Regarding claim 9, Zhu modified by Welsh, Welsh teaches sodium chlorate (NaClO3, C2/L42).
Regarding claim 10, Zhu modified by Williams, Williams teaches the use of the cobalt containing solution to prepare CoOOH(s) (Equation 2, p. 86 column 2). It would be obvious to one skilled in the art to use the obtained cobalt solution from the invention of modified Zhu to prepare cobalt hydroxide, including CoOOH. One would be motivated to do so in order to efficiently further recycle cobalt from waste ternary lithium batteries, as Zhu teaches (0083).
Conclusion
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/Eileen Moudou/ Examiner, Art Unit 1738
/MICHAEL FORREST/ Primary Examiner, Art Unit 1738