Detailed Action
This is a Non-Final Office action based on application 18/562,214 filed on 17 November 2023. The application is a 371 of PCT/ JP2023/ 000069 with priority to JP 2022-004700 filed 14 January 2022.
Claims 1-7 are pending and have been fully considered.
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 .
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.
Claims 1-7 are 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 applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Claim 1, at step (C), recites the limitation “the separated solid content”. However, at this point in the claim, no separated solid content has yet been recited. Therefore there is insufficient antecedent basis for this limitation in the claim. For the sake of treating the claim against the art in this action, Examiner interprets the antecedent of “the separated solid content” at claim 1 step (C) is the liquid hydroxide crystal separated in step (C).
Claim 3 contains references to the process step (G), which is recited in claim 2. However, claim 3 depends from claim 1, not from claim 2. Therefore there is insufficient antecedent basis in claim 3 for the limitation “said step (G)”.
Claim 4 contains references to the process step (G), which is recited in claim 2, and to the process step (H), which is recited in claim 3. However, claim 4 depends from claim 1, not from claim 2 or 3. Therefore there is insufficient antecedent basis in claim 4 for the limitations “said step (G)” and “the above step (H)”.
Claim 5, which depends from claim 1, recites the limitation “the washing step according to the claim 4”. There is insufficient antecedent basis for this limitation in the claim.
For the sake of treating the claims against the art in this action, Examiner interprets that claim 3 depends from claim 2, claim 4 depends from claim 3, and claim 5 depends from claim 4.
Claim 2 recites that process step (G) produces “a lithium-containing solid content” and “a liquid content” via a solid-liquid separation step. However, claim 2 also incorporates the limitations of claim 1, which recites, at process step (D), the production of “a lithium-containing solid content” and “a liquid content” via a solid-liquid separation step. Claim 2 subsequently recites that “the obtained solid content in the said solid-liquid separation step” is fed to step (E). Claim 2 is indefinite because there are multiple different solid contents obtained in multiple different solid-liquid separation steps, and it is not clear whether “the obtained solid content in the said solid-liquid separation step” is referring to the crystal of step (C), the solid content of step (D), or the solid content of step (G).
Along similar lines:
Claim 3 is indefinite because it recites “the obtained slurry” and does not clearly indicate whether this phrase refers to the slurry produced in step (D), the slurry produced in step (G), or the slurry produced in step (H)
Claim 3 is indefinite because it recites “the liquid content obtained by said solid-liquid separation process” and does not clearly indicate whether this phrase refers to the liquid content produced at step (D), at step (G), or at step (H).
Claim 7 is indefinite because it recites a “washing step of cleaning the said solid content”, and does not clearly indicate whether the “said solid content” is the solid content from step (C), from step (D), or the crystals of step (K).
To bring the claim language into conformance with §112(b), the claim language should be amended in such a way that each claimed element has a unique name that allows it be distinctly identified. One way this could be accomplished is by naming elements according to the process step in which they are produced, e.g. “the solid content obtained in step (D)”, “the solid content obtained in step (G)”, etc.
Since claim 1 is indefinite, claims 2-7 are also indefinite because they depend from claim 1.
Claim Rejections - 35 USC § 102
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 1-3 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Zbranek et al (US 8,431,005 B1).
Regarding claim 1, Zbranek teaches a process (figures 5 and 6) for producing lithium hydroxide from lithium sulfate as a starting material containing at least one of sodium and potassium as impurities, which process comprises the following steps of (A) to (F):
(A) a production step of an aqueous lithium hydroxide solution and sulfuric acid by an electrochemical membrane separation method using lithium sulfate as a raw material (figure 5-6, membrane electrolysis device 513/613 takes a Li2SO4 solution feed, and produces a lithium hydroxide solution from its negative chamber and a Li2SO4 / H2SO4 solution from its positive chamber; col 19 ln 29-31; col 20 ln 7-9);
(B) a crystallization step producing a lithium hydroxide crystal by crystallization using the obtained aqueous lithium hydroxide solution in the above electrochemical membrane separation step as a raw material (figure 5-6, lithium hydroxide solution from the membrane electrolysis cathode stream is directed to evaporator 514 / 614, then to cooling crystallization process 515 / 615; col 19 ln 30-34; col 20 ln 9-12; col 23 ln 10-19);
(C) a solid-liquid separation step in which a portion of slurry in the above crystallization step is discharged and is subjected to solid-liquid separation to separate a lithium hydroxide crystal and crystallization mother liquor (figure 5-6, slurry from crystallizer 515/615 is passed to centrifuge 516, and mother liquor is drawn off (“LiOH M.L.”)), and thereafter a washing step to clean the separated solid content (figure 5-6, water is passed into the centrifuge, wash liquid (“Wash Liq.”) is drawn off and returned to the evaporator 514/614, and the remaining solids pass to dryer 517/617 which outputs LiOH·H2O product; col 23 ln 10-19);
(D) a carbonation step obtaining a slurry comprising a lithium-containing carbonate compound as a solid content by discharging a portion of crystallization mother liquor in said crystallization step and reacting said discharged crystallization mother liquor with carbon dioxide gas (figure 5-6, carbonation step 518/618 takes in the crystallization mother liquor “LiOH M.L.” from centrifuge 516/616, and CO2 from reactor 512/612, forming a slurry of lithium carbonate compound) , and a solid-liquid separation step separating said slurry into a lithium-containing solid content and a liquid content (figure 5-6, filtration step 519 separates the carbonation slurry into a lithium-containing solid (“Li2CO3 Cake”) and a liquid content (“Alkali Carb. Solution Recycle”); col 19 ln 35-42, col 20 ln 13-20) ;
(E) an acid dissolution step producing a lithium sulfate aqueous solution by reacting said lithium-containing solid content with sulfuric acid (col 19 ln 41-42, “The solid lithium carbonate can be recycled back to reactor 512 for a further pass through the conversion circuit”; figure 5-6, the lithium containing solid (“Li2CO3 Cake”) passes to reactor 512 / 612 where it is combined with water and a sulfuric acid stream (“Li2SO4 / H2SO4 Solution” from the anode of the electrolysis device), producing a Li2SO4 solution; col 19 ln 25-30, col 20 ln 5-7);
(F) a mixing step reusing the lithium sulfate aqueous solution obtained by said acid dissolution step as the raw material of said step of (A) (figure 5-6, the Li2SO4 thus produced at reactor 512 / 612 is the raw material passed into membrane electrolysis device 513 / 613; col 19 ln 29-30, col 20 ln 7-9).
Regarding claim 2, Zbranek teaches the process of claim 1, further comprising:
(G) a carbonate concentration-crystallization step obtaining a slurry by subjecting said liquid content obtained from said carbonation step and from said solid-liquid separation step in said step (D) to concentration-crystallization (col 19 ln 35-42, “The mother liquor from centrifuge 516 ... carbonated with carbon dioxide ... filtered out in filter 519, leaving solid lithium carbonate and an alkali carbonate recycle stream for insertion at the lithium carbonate precipitator 502”; col 19 ln 1-9, “Lithium carbonate is precipitated in precipitator 502 by adding sodium carbonate to the concentrated pregnant leach solution. Precipitator 502 produces lithium carbonate crystals and a lithium-barren mother liquor. The lithium carbonate crystals are dried in dryer 511 to form lithium carbonate product.”)
and a solid-liquid separation step separating the obtained slurry into a lithium-containing solid content and a liquid content (col 19 ln 4-13, “Precipitator 502 produces lithium carbonate crystals and a lithium-barren mother liquor. The lithium carbonate crystals are dried in dryer 511 to form lithium carbonate product ... The mother liquor is acidified in acidification process 503 and conveyed to precipitator 504”)
wherein an operation so as to feed the obtained solid content in the said solid-liquid separation step to the above step (E) is further included (col 19 ln 7-9, “the lithium carbonate crystals may be introduced into reactor 512”).
Regarding claim 3, Zbranek teaches the process of claim 2, further comprising the following step (H) comprising:
- an aqueous sulfate solution production step by adding sulfuric acid to the liquid content obtained by the carbonate concentration-crystallization step and solid-liquid separation step in said step (G) (col 19 ln 4-24, the lithium-barren mother liquor remaining from the carbonation and lithium carbonate separation step (G) is combined with acid in acidification process 503; per figure 7, the acid added to the lithium-barren liquor at the acidification is anolyte from the electrolysis process, which comprises sulfuric acid),
- a sulfate concentration-crystallization step by concentration-crystallization of the obtained sulfate solution to obtain a slurry (col 19 ln 4-24 and figure 5 steps 503-506, the acidified mother liquor is subjected to a crystallization process producing a slurry of glaserite (K2Na6(SO4)4) crystals), and
- a solid-liquid separation step to separate the obtained slurry to a solid content and liquid content (col 19 ln 4-24, glaserite crystals are separated at 506, and the remaining mother liquor is subject to a second crystallization and solid-liquid separation 510, producing crystals of Glauber’s salt (Na2SO4·10 H2O)),
wherein an operation of feeding the liquid content obtained by the said solid-liquid separation process to the above step (E) or step (F) is further included (col 19 ln ln 17-18, “The mother liquor from this process is recycled to evaporator 501”; col 19 ln 1-9 and 25-29, the liquid content fed to evaporator 501 is concentrated and precipitated to yield lithium carbonate which is fed to step (E)).
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 4-7 are rejected under 35 U.S.C. 103 as being unpatentable over Zbranek as applied to claims 1-3 above, and further in view of Dai et al (US 2020/0385280 A1).
Regarding claim 4, Zbranek teaches the method of claims 1-3, teaching that the lithium carbonate solids obtained at step (D) are purified by filtering (col 19 ln 38-41), the lithium carbonate solids at step (G) are separated from their mother liquor by solid-liquid separation and are dried (col 19 ln 4-7), and the sulfate solids obtained in the sulfate concentration crystallization step (H) are separated from their respective mother liquor by solid-liquid separation (col 19 ln 10-24). Zbranek does not teach that any of the solids obtained at any of these three steps is subjected to a washing step after solid-liquid separation.
Dai is similarly directed to a process for producing lithium hydroxide (abstract; figures 1-3), comprising steps of :
(A) a production step of an aqueous lithium hydroxide solution by bipolar electrodialysis of an aqueous lithium salt solution (para [0093]-[0103], figure 2, “Composite electrodialysis” block);
(B) a crystallization step producing a lithium hydroxide crystal by crystallization using the obtained aqueous lithium hydroxide solution in the above electrochemical membrane separation step as a raw material (figure 2, lithium hydroxide solution output from the composite electrodialysis step is subjected to concentration and crystallization; para [0104]-[0108]);
(C) a solid-liquid separation step in which a portion of slurry in the above crystallization step is discharged and is subjected to solid-liquid separation to separate a lithium hydroxide crystal and crystallization mother liquor (figure 2, after concentration and crystallization, the lithium hydroxide magma is directed to solid-liquid separation, yielding “Wet fine lithium hydroxide” (a lithium hydroxide crystal) and “base solution” (crystallization mother liquor); para [0105]-[0108]), and thereafter a washing step to clean the separated solid content (para [0108], “to be filtered, washed and dried”);
(D) a carbonation step obtaining a slurry comprising a lithium-containing carbonate compound as a solid content by discharging a portion of crystallization mother liquor in said crystallization step and reacting said discharged crystallization mother liquor with carbon dioxide gas (figure 2, the mother liquor (“Base solution” retrieved from solid liquid separation of lithium hydroxide) is directed to a carbonization step where it is combined with carbon dioxide), and a solid-liquid separation step separating said slurry into a lithium-containing solid content and a liquid content (figure 2, after carbonization, said slurry is subjected to solid-liquid separation, producing battery grade lithium carbonate (a lithium-containing solid content) and carbonized mother liquor (a liquid content); para [0120]);
(G) a carbonate concentration-crystallization step obtaining a slurry by subjecting said liquid content obtained from said carbonation step and from said solid-liquid separation step in said step (D) to concentration-crystallization and a solid-liquid separation step separating the obtained slurry into a lithium-containing solid content and a liquid content (figure 2, the carbonized mother liquor is recycled to “Impurity removal and refining” followed by “Precipitation reaction” and “Solid-liquid separation”, yielding “Wet fine lithium carbonate” (a lithium containing solid content) and “Lithium precipitation mother liquor” (a liquid content); para [0122]-[0124]),
(E) an acid dissolution step producing a lithium salt aqueous solution by reacting said lithium-containing solid content with acid (figure 2, “Wet fine lithium carbonate” is treated with acid at “Acidolysis” step, yielding a lithium salt aqueous solution; para [0134]);
(F) a mixing step reusing the lithium sulfate aqueous solution obtained by said acid dissolution step as the raw material of said step of (A) (figure 2, lithium salt aqueous solution produced at step (E) is refined and then passed into the “Composite electrodialysis” step).
Dai further teaches the lithium containing solids produced at step (D) are washed (para [0121], “The wet battery grade lithium carbonate is washed, dried, crushed, deferrized and otherwise post-treated”) and the lithium-containing solids produced at step (G) are washed (para [0124], “The wet fine lithium carbonate is washed”).
Dai teaches that washing the lithium carbonate after solid-liquid separation improves the lithium carbonate’s purity (para [0081], [0082], “solid-liquid separation and washing are facilitated to be conducive to the purity of obtained wet fine lithium carbonate”)
It would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to modify Zbranek by including steps of washing the lithium carbonate solids obtained at step (D) and/or at step (G), in order to improve the purity of the lithium feed stream that is fed into the electrochemical cell, based on Dai’s teaching that, in a similar electrochemical method of lithium hydroxide preparation, that similarly comprises carbonating the lithium hydroxide crystallization mother liquor, crystallizing lithium carbonate solids therefrom, and re-dissolving the obtained lithium carbonate solids into the electrolyte solution that is fed into the electrochemical device, the lithium carbonate solids are washed (para [0121], [0124]), and the washing of the lithium carbonate improves its purity (para [0081], [0082]).
Furthermore, the claimed limitations are obvious because all the claimed elements were known in the prior art and one skilled in the art could have combined the elements as claimed by known methods with no change in their respective functions, and the combination yielded nothing more than predictable results [MPEP 2143(A)].
Regarding claim 5, Zbranek in view of Dai renders the method of claim 4 obvious. Dai further teaches that the washing filtrate obtained in the washing step according to claim 4 can be used to prepare a sodium carbonate solution (para [0084], [0123]), and said sodium carbonate solution is fed back into the process stream ahead of step (E) (figure 2, sodium carbonate solution is added to the process stream at step (G) (the second precipitation reaction of the carbonized mother liquor), which is immediately upstream of step (E)). Therefore, at least a part of the washing filtrate is being fed into step (E).
Regarding claim 6, Zbranek teaches the process of claim 1, but describes their electrochemical membrane separation method process as “membrane electrolyzer 513” (col 19 ln 25-31; figure 5) and does not disclose that the process is an electrodialysis process.
Dai, similarly directed to a lithium hydroxide production process, comprising a step (A) of treating an aqueous lithium salt solution to an electrochemical membrane separation process to yield a lithium hydroxide solution, teaches that a suitable electrochemical membrane separation process is an electrodialysis process (para [0092]-[0103]).
It would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to modify the process of Zbranek by using, as the electrochemical membrane separation process, an electrodialysis process as disclosed in Dai, because Zbranek is directed to using the electrochemical membrane separation process to produce a solution of lithium hydroxide, and Dai teaches that electrodialysis is a suitable process for producing a lithium hydroxide solution (para [0092]-[0103]).
Furthermore, the claimed limitations are obvious because all the claimed elements were known in the prior art and one skilled in the art could have combined the elements as claimed by known methods with no change in their respective functions, and the combination yielded nothing more than predictable results [MPEP 2143(A)].
Regarding claim 7, Zbranek teaches the process of claim 1. Zbranek does not teach steps (I), (J), and (K) of re-dissolving and re-crystallizing the lithium hydroxide crystals from step (B), and supplying the recrystallization mother liquor from step (K) to one of steps (B), (D), or (J).
Dai is similarly directed to a process for producing lithium hydroxide (abstract; figures 1-3), comprising steps of:
(A) a production step of an aqueous lithium hydroxide solution by bipolar electrodialysis of an aqueous lithium salt solution (para [0093]-[0103], figure 2, “Composite electrodialysis” block);
(B) a crystallization step producing a lithium hydroxide crystal by crystallization using the obtained aqueous lithium hydroxide solution in the above electrochemical membrane separation step as a raw material (figure 2, lithium hydroxide solution output from the composite electrodialysis step is subjected to concentration and crystallization; para [0104]-[0108]);
(C) a solid-liquid separation step in which a portion of slurry in the above crystallization step is discharged and is subjected to solid-liquid separation to separate a lithium hydroxide crystal and crystallization mother liquor (figure 2, after concentration and crystallization, the lithium hydroxide magma is directed to solid-liquid separation, yielding “Wet fine lithium hydroxide” (a lithium hydroxide crystal) and “base solution” (crystallization mother liquor); para [0105]-[0108]), and thereafter a washing step to clean the separated solid content (para [0108], “to be filtered, washed and dried”);
(D) a carbonation step obtaining a slurry comprising a lithium-containing carbonate compound as a solid content by discharging a portion of crystallization mother liquor in said crystallization step and reacting said discharged crystallization mother liquor with carbon dioxide gas (figure 2, the mother liquor (“Base solution” retrieved from solid liquid separation of lithium hydroxide) is directed to a carbonization step where it is combined with carbon dioxide), and a solid-liquid separation step separating said slurry into a lithium-containing solid content and a liquid content (figure 2, after carbonization, said slurry is subjected to solid-liquid separation, producing battery grade lithium carbonate (a lithium-containing solid content) and carbonized mother liquor (a liquid content); para [0120]);
(E) an acid dissolution step producing a lithium salt aqueous solution by reacting said lithium-containing solid content with acid (figure 2, “Wet fine lithium carbonate” is treated with acid at “Acidolysis” step, yielding a lithium salt aqueous solution; para [0134]);
(F) a mixing step reusing the lithium sulfate aqueous solution obtained by said acid dissolution step as the raw material of said step of (A) (figure 2, lithium salt aqueous solution produced at step (E) is refined and then passed into the “Composite electrodialysis” step).
Dai further teaches the process comprises steps of:
(I) a re-dissolving step of re-dissolving the lithium hydroxide crystals in the crystallization step (B) in an aqueous medium (para [0110]; figure 2, the lithium hydroxide crystals from step (B) (“Wet fine lithium hydroxide”) are passed to a step of “Dissolution”)
(J) a re-crystallization step producing lithium hydroxide crystals by further crystallization a second lithium hydroxide crystallization step (para [0112]; figure 2, following the “Dissolution” of step (I) are Filtration and Recrystallization), and
(K) a re-solid-liquid separation step of separating the slurry obtained in the re- crystallization step into lithium hydroxide crystals and a crystallization mother liquor, and washing step of cleaning the said solid content (figure 2, following the iltration and recrystallization of step (J) is a step of solid-liquid separation and washing, yielding wet high purity grade lithium hydroxide);
further comprising an operation supplying the crystallization mother liquor obtained in the re-solid-liquid separation to the crystallization step (B) and/or to the carbonation step (D) and the re-crystallization step (J) (figure 2, the solid-liquid separation & washing of step (K) yields a solid stream (“Wet high purity grade lithium hydroxide”) and a second stream (unlabeled) which is understood to include the crystallization mother liquor. This second stream is recycled to the “Concentration and crystallization” block of step (B)).
Dai teaches that by treating the battery-grade lithium hydroxide obtained from step (B) to dissolution, recrystallization, and re-separation steps (I), (J), and (K), a high-purity lithium hydroxide product with a purity of at least 99.99% can be obtained (para [0112]-[0113]).
It would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to add, to Zbranek’s process, the steps of re-dissolving, re-crystallizing, and re-separating the lithium hydroxide crystals, and recycling the recrystallization mother liquor back into the lithium production process, based on Dai’s teaching that these additional steps can improve the lithium hydroxide purity to a purity of at least 99.99%. All the claimed elements were known in the prior art and one skilled in the art could have combined the elements as claimed by known methods with no change in their respective functions, and the combination yielded nothing more than predictable results. The incorporation of a predictable improvement into a known base invention, based on a finding that the prior art contained a comparable device that has been improved in the same way, is prima facie obvious as being part of the ordinary capabilities of one skilled in the art (MPEP 2143(C)).
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
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/ANDREW KOLTONOW/Examiner, Art Unit 1795 /ALEXANDER W KEELING/Primary Examiner, Art Unit 1795
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