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 .
Priority
Receipt is acknowledged of certified copies of papers required by 37 CFR 1.55.
Information Disclosure Statement
The information disclosure statement (IDS) submitted on 07/20/2023 is in compliance with the provisions of 37 CFR 1.97. Accordingly, the information disclosure statement is being considered by the examiner.
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 1-13 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 recites “the dilute sulfuric acid has a mass percentage of less than or equal to 25%;” this language is unclear as to whether the claim requires that the total mass of solids and liquids present in the leaching by heating step should be included in this mass percentage, or whether the mass percentage is required of the sulfuric acid priori to it being included in the leaching step. This renders claim 1 indefinite in scope. It is reasonable to broadly interpret this language as being inclusive of any other potentially present solids and liquids in the leaching step, and this interpretation is used to proceed with further examination.
Claims 2-13 are dependent upon claim 1 and do not rectify the issues of indefiniteness, and are therefore similarly rejected.
Claim 10 additionally recites “washing the waste vanadium catalyst wet slag after raffinate collection with water” which is indefinite because it obfuscates the relationship of the raffinate collection step and the purpose of the water. Here the language used does not clarify if the limitation “with water” applies to the washing or to the raffinate collection. The scope of the claim is therefore indefinite. To proceed with further examination, the interpretation of the phrasing “washing the waste vanadium catalyst wet slag with water after raffinate collection” will be used.
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 1-9 and 11 are rejected under 35 U.S.C. 103 as being unpatentable over Wei et al. (CN 101552346 A) in view of Shi et al. (CN 111876604 A) and in further view of Zhang et al. (CN 112542603 A), referred to herein as Wei, Shi, and Zhang, respectively. English translations of all documents, as provided with this office action, are cited herein.
Regarding claim 1, Wei teaches a method for preparing a vanadium battery electrolyte (0002) by dissolving a waste vanadium-containing coal ore (0011) with sulfuric acid (0012) comprising the following steps: immersing the coal containing V2O5 in dilute sulfuric acid, and conducting leaching by heating to obtain a vanadium leaching masterbatch (leaching agents—a mixture of sulfuric acid, hydrofluoric acid, and sodium hypochlorite—are used… the leaching temperature is ≥85℃, 0013); wherein the leaching by heating is conducted for less than or equal to 2 h (two hours, Ex 1, 0027); and the vanadium leaching masterbatch comprises tetravalent vanadium ions and pentavalent vanadium ions (most of the vanadium in the leachate exists in the form of VOSO4, and a small amount of vanadium exists in the form of (VO2)2SO4, 0017; the oxidation state of vanadium in either compound is IV and V, respectively); and mixing the vanadium leaching masterbatch with a reducing agent (0012), and subjecting an obtained reduced masterbatch to solid-liquid separation to obtain the vanadium battery electrolyte (“After phase separation, a vanadium oxysulfate solution with a concentration of 1.20 mol/L was obtained”, Ex 1, 0027) wherein the vanadium battery electrolyte is a vanadyl sulfate solution. It is noted that vanadium oxysulfate is represented by the formula VOSO4, which is equivalent to vanadyl sulfate, meeting the requirements of the instant claim.
Wei does not teach that the process can dissolve waste vanadium catalyst, and does not teach that the dilute sulfuric acid has a mass percentage of less than or equal to 25%. However, Shi discloses an analogous process for the disposal and utilization of waste vanadium-silicon based sulfuric acid production catalysts (0002) in which the sulfuric acid used in the acid leaching step is 8-12 wt% (0020), where wt% is a mass percentage.
It would be obvious to one of ordinary skill in the art before the effective filing date of the invention to apply the invention taught by Wei for the disposal and utilization of waste vanadium catalyst, as taught by Shi, and to further use the concentration of sulfuric acid taught in Shi to modify the invention taught by Wei. One would be motivated to apply the method towards waste vanadium catalysts in order to avoid environmental pollution and turn the waste into valuable products such as calcium vanadate, as taught by Shi (0009). One would be motivated to use the concentration of sulfuric acid taught by Shi in order to determine the purity of the final product and the resource utilization rate, motivation taught by Shi (0065).
Wei modified by Shi does not teach mixing the vanadium leaching masterbatch with an oxalic acid solution, conducting reduction by heating. However, Zhang teaches a method for preparing an energy storage vanadium electrolyte using low-purity vanadium pentoxide (n0001) in which oxalic acid is added to V2O5 and heated over 2.5-3 hours to obtain tetravalent vanadium electrolyte (0013).
It would be obvious to one of ordinary skill in the art before the effective filing date of the invention to substitute the reducing agent taught by Wei (the reducing agent added in the impurity removal process is sodium thiosulfate; 0012) with the heating and oxalic acid taught by Zhang. One of ordinary skill in the art would be motivated to do so because Zhang teaches the use of oxalic acid as a known reducing agent in the art to obtain reduced vanadium (n0002), and teaches heating at 80-90℃ to obtain the tetravalent vanadium (0013). One of ordinary skill in the art would additionally be motivated to use the heating and oxalic acid because of the low cost of the materials used and the effectiveness for use on low-purity vanadium pentoxide, as taught by Zhang (n0004). This would be obvious because the starting material of the method taught by modified Wei is a low-purity source of vanadium pentoxide (≥0.5% w of vanadium pentoxide, 0016). Therefore one of ordinary skill in the art would be motivated to replace the reductant of sodium thiosulfate with the reductant of oxalic acid by adding it at a heated temperature, and have a reasonable expectation of success, thus arriving at the claimed invention.
Regarding claim 2, modified Wei does not teach the mass percentage of dilute sulfuric acid being 15% to 25%. However, as the purity of the final product and the resource utilization rate are variables that can be modified, among others, by adjusting the mass percentage of sulfuric acid, with the purity of the final product and the resource utilization rate both increasing/decreasing as the mass percentage is increased/decreased, the precise mass percentage 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 mass percentage 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 mass percentage in modified Wei to obtain the desired balance between the purity of the final product/the resource utilization rate and mass percentage/concentration as taught by Shi (0065) (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 claims 3 and 6, modified Wei teaches the leaching by heating being conducted for two hours (0027).
Regarding claim 4, modified Wei teaches that the leaching temperature is ≥85°C, 0013.
Regarding claim 5, modified Wei teaches that the leaching temperature is ≥85°C, 0013.
Regarding claim 7, Zhang teaches that the oxalic acid is added at 0.65-0.7 times the weight of the low-purity V2O5 added (0012), which is 170-174 g (0009). In 1000 mL solution, this results in a molar concentration of 110.5-121.8 g/90 g mol-1 ≈ 1.23-1.35 mol L-1 oxalic acid. Zhang teaches that the 170-174 g of low-purity V2O5 is added to 1 L of solution, with 0.05 L of hydrogen peroxide and 60-70 g of ammonium sulfate (0010). Zhang teaches that the content of pentavalent vanadium in the low-purity V2O5 is 97% (n0007). With 97% of 170-174 g = 164.9-168.8 g V2O5 = 0.91-0.93 mol V2O5 = 1.82-1.85 mol V(V), this results in a molar concentration of 164.9-168.8 g/(1000 mL + 50 mL + (70 to 60 g ammonium sulfate/1.77 g mL-1) ) = (0.91-0.93 mol V2O5)/(1.09 to 1.08 L total solution) = 0.835-0.855 M V2O5 ≈ 1.7-1.7 mol L-1 V(V).
Regarding claim 8, Zhang teaches that the reducing agent is added at 80-90°C (0013). Wei and Zhang do not disclose that the reduction is conducted for 1 h.
However, Shi teaches that the leaching step where the reducing agent is added (Step 4) occurs over 0.5-1 h before being filtered.
It would be obvious to one of ordinary skill in the art before the effective filing date of the invention to use the reaction time disclosed by Shi in the reduction for the method disclosed by Wei and modified by Zhang. One would be motivated to do so in order to determine the purity of the final product and the resource utilization rate, motivation taught by Shi (0065). One skilled in the art would therefore arrive at the presently claimed invention with reasonable expectation of success.
Regarding claim 9, Shi teaches that the leaching step where the reducing agent is added (Step 4) occurs over 0.5-1 h before being filtered. It would be obvious to one of ordinary skill in the art before the effective filing date of the invention to use the reaction time disclosed by Shi in the reduction for the method disclosed by Wei and modified by Zhang. One would be motivated to do so in order to determine the purity of the final product and the resource utilization rate, motivation taught by Shi (0065). One skilled in the art would therefore arrive at the presently claimed invention with reasonable expectation of success.
Regarding claim 11, modified Wei teaches that a second extraction and back-extraction are necessary to meet the vanadium concentration requirements of the electrolyte for a battery (0021) and that the method obtains a concentration of VOSO4 at 1-5 mol/L (0021, please note that the English translation reads “VO<sub>3</sub> solution” where the original text reads “VOSO4” on page 4). It would have been obvious to one of ordinary skill in the art at the time of filing of the invention to perform the method as taught by Wei and modified by Shi and Zhang where the concentration is tuned to any workable or optimum range including the claimed range since Wei teaches that the final concentration of V(IV) is controlled by the extent of extraction steps (0021).
Claims 10, 12, and 13 are rejected under 35 U.S.C. 103 as being unpatentable over Wei in view of Shi and in further view of Zhang, as applied to claim 1 above, and in further view of Xu et al. (CN 108878944 A), referred to herein as Xu. An English translation of Xu, as provided with this office action, is cited herein.
Regarding claim 10, modified Wei teaches the method as applied to claim 1 above. Modified Wei does not teach the post-treatment steps after the solid-liquid separation step.
However, Xu teaches an analogous method for preparing vanadium battery electrolyte using waste vanadium catalyst (0002), in which step (B) teaches cleaning the soaked catalyst with water which can be used for the next soaking (0029). The motivation for the invention disclosed by Xu is to avoid generating environmentally polluting waste (0020). It would therefore be obvious to one skilled in the art to further modify the invention taught by Wei and modified by Shi and Zhang with the steps of the invention taught by Xu that include collecting the residual electrolyte on a surface of the waste slag (0029), combining the residual electrolyte with the vanadium battery electrolyte (the vanadium recovery rate can reach 97-99%, 0029), and washing the waste vanadium catalyst wet slag after raffinate collection with water (0029), and using the obtained washed solution as a dilution solvent of the dilute sulfuric acid (solvent used for soaking in step A, 0029), in order to modify the method towards avoiding generating environmentally polluting waste, as taught by Xu (0020). Thus one of ordinary skill in the art would arrive at the claimed invention with reasonable expectation of success.
Regarding claim 12, modified Wei teaches the method as applied to claim 1 above. Modified Wei does not teach that the vanadium battery electrolytic concentrate has a stack discharge efficiency of 75% to 85%. However, Xu teaches that the stack discharge efficiency of vanadium electrolyte is 75-85% when the vanadium ion concentration in the vanadium electrolyte is 1.5-2.2 mol/L (0031). Since one skilled in the art would recognize that the stack discharge efficiency is a property of the electrolyte affected by concentration, it would be obvious to one skilled in the art before the effective filing date of the invention to modify the concentration as a result-effective variable to obtain a stack discharge efficiency of 75% to 85% as required by the instant claim, and thus obtain the claimed invention. 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 13, modified Wei teaches the method as applied to claim 1 above. Modified Wei does not teach that after the solid-liquid separation is completed, the method further comprises conducting concentration on the vanadium battery electrolyte to dryness to obtain a crystalline vanadyl sulfate solid product.
However, Xu teaches an analogous method for preparing vanadium battery electrolyte using waste vanadium catalyst (0002) wherein filtration is taught (0031) and after filtration, the vanadium electrolyte is used to concentrate and crystallize solid vanadium oxysulfate (0031).
It would be obvious to one skilled in the art before the effective filing date of the invention to further modify the invention taught by Wei and modified by Shi and Zhang to further concentrate the obtained electrolyte to dryness to obtain a solid product. One would be motivated to do so in order to make solid vanadium batteries, as taught by Xu (0031).
Conclusion
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/Eileen Moudou/Examiner, Art Unit 1738
/MICHAEL FORREST/Primary Examiner, Art Unit 1738