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 statements (IDS) submitted on December 12, 2023, March 31, 2025, and December 12, 2025 are in compliance with the provisions of 37 CFR 1.97. Accordingly, the information disclosure statements are being considered by the examiner.
The information disclosure statement submitted on December 12, 2023 contains the following reference under Non Patent Literature Documents: Yuanchao Li et al., "New Developments in the High-Energy-Density Solid-Liquid Storage Technology for Redox Flow Batteries," ECS Fall 3033 Meeting, Symposium A01, Presentation # A01-0043; pp.: 1- 13. The year in the provided citation is listed as 3033, which has not happened yet. The presentation provided by the applicant provides the year 2022 (Slide 1). Therefore, the examiner interpreted 3033 as 2022 and considered this reference during examination.
Drawings
The drawings are objected to as failing to comply with 37 CFR 1.84(p)(5) because they include the following reference character(s) not mentioned in the description:
B5 from Fig. 2
Corrected drawing sheets in compliance with 37 CFR 1.121(d), or amendment to the specification to add the reference character(s) in the description in compliance with 37 CFR 1.121(b) 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. 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.
Specification
The disclosure is objected to because of the following informalities:
Page 11, paragraph [0059], “while15.5 M” should read as “while 15.5 M”
Page 12, paragraph [0064], in the row labeled as V(V), “VO2+ in the solution” should read as “VO2+ in solution”
Appropriate correction is required.
Claim Interpretation
The specification provides a table with a list of symbols and terms, including V(III), V(IV), and V(V) (see Table 2, [0064]). Therefore, V(III) cations will be broadly interpreted as V3+, V(IV) cations as V4+ or VO2+, and V(V) cations as V5+ or VO2+.
Claim 1, line 5 uses the phrase “free of vanadium cations.” The specification defines the phrase “free of vanadium cations” as the concentration of vanadium cations in solution is no more than 5%, no more than 4%, no more than 3%, no more than 2%, or no more than 1% wherein all of the percentage values refer to percentage by mass ([0005] defines the phrase “free of vanadium cations” in regards to the draw solution). The examiner will interpret the phrase “free of vanadium cations” as the concentration of vanadium cations in solution is no more than 5% by mass.
Claim 14, line 3 uses the term “densification level.” The specification defines densification level as the parameter used to describe the amount of water removed, which can be calculated using the formula shown below ([0074]). The examiner will interpret the term using the definition disclosed in the specification.
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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.
Claims 1-3 are rejected under 35 U.S.C. 103 as being unpatentable over Arias-Paic, et. al. 2020, US 2020/0398221 A1, referred to as Arias-Paic from herein, in view of Sun, et. al. 2015, CN 204905353 U, referred to as Sun from herein.
Regarding claim 1, Arias-Paic teaches a process for concentrating ions in an ionic solution (Abstract) comprising of:
(a) delivering a draw solution (described as a regenerant solution, [0007]) to a draw chamber of a forward osmosis module (Fig. 4 shows a forward osmosis module where the concentrated regeneration solution is being delivered to the draw chamber, 600) the draw solution comprising of water and a solute (composition of regenerant solution is described in [0007], where the solute is described as the regenerant solute in [0007] and water is not explicitly stated until mentioned as a solvent in [0008]);
(b) delivering a feed solution (described as elution solution, [0007]) to a feed chamber of the forward osmosis modules (Fig. 4 shows a forward osmosis module with a membrane, 590, separating the draw chamber, 600, and the feed chamber, 575); the feed solution comprising of water, ions, and the same solute (elution solution is described in [0007] where the regeneration solute displaces resin-phase ions when the regenerant solution passes through the contactor);
wherein water passes across the membrane from the feed solution to the draw solution, thereby providing a concentrated solution (Fig. 4, concentrated elution solution 620) as the feed chamber output and a diluted solution (Fig. 4, diluted regeneration solution, 730) as the draw chamber output.
While Arias-Paic does not use vanadium nor sulfuric acid in their examples, Arias-Paic provides a list of resin-phase ions, including vanadium ([0006]), and a list of regenerant solutes, including sulfuric acid ([0007]), which can be used with the process disclosed in the prior art. Arias-Paic does not give further indication as to which of the resin-phase ion, regenerant solute, or combination thereof would likely be successful.
Additionally, while Arias-Paic teaches of a process for concentrating ions in an ionic solution where the ions may be vanadium cations and the solution may contain sulfuric acid, Arias-Paic does not teach why one would want to increase the concentration of a vanadium electrolyte solution.
Sun teaches the importance of concentrating low concentration vanadium solutions and the relationship between vanadium concentration and battery performance ([0006]). Sun further teaches low concentrations of vanadium cations in vanadium electrolyte solutions lead to decreases in battery capacity and battery degradation ([0006]). The process disclosed in Sun specifically concentrates spent vanadium electrolyte solutions from used batteries in order to reduce costs associated with vanadium battery systems ([0005] – [0006] describes high costs associated with vanadium electrolytes solutions).
Arias-Paic and Sun are both considered to be analogous to the present invention because Arias-Paic is in the same field of increasing the concentration of ions in aqueous solutions using forward osmosis, like the present invention, while Sun is analogous to the present invention because it is in the same field of concentrating vanadium electrolytic solutions using circular techniques, like the present invention. It would be reasonable for one of ordinary skill in the art before the effective filing date to perform the forward osmosis process disclosed in Arias-Paic using vanadium as the resin phase-ion and sulfuric acid as the regenerant solute and to modify this process with a low concentration vanadium electrolyte from a used battery as the feed solution, as taught in Sun, to reduce costs in manufacturing new vanadium electrolyte solutions and to obtain higher concentrated vanadium electrolyte solutions that may lead to improved battery capacity.
Regarding claim 2, Arias-Paic in view of Sun teaches a process for concentrating a vanadium electrolyte solution according to claim 1, and Arias-Paic further teaches combining the diluted acid solution (described as the diluted regeneration solution in [0037]; Fig. 6) and a source of vanadium to provide the feed solution ([0037] describes recycling the diluted regenerant solute and producing a new elution solution; Fig. 6). It would be obvious to one of ordinary skill in the art before the effective filing date to implement the process with the alternative embodiment disclosed in Arias-Paic to avoid performing additional recovery steps that may be resource intensive ([0014] - [0015])
Regarding claim 3, Arias-Paic in view of Sun teaches a process for concentrating a vanadium electrolyte solution according to claim 1, and Arias-Paic further teaches the draw solution (described as the regenerant solution, [0007]) consisting of water and sulfuric acid (where sulfuric acid is provided in the list of regenerant solutes, [0007]). Arias-Paic discloses that the regeneration solution is prepared by mixing a regeneration solvent with a regeneration solute ([0007]) where the regeneration solvent is water as implied in [0008] (“a limitation, however, is that the solvent (e.g., water) cannot be recovered for future use”) and in Examples 1 and 2 ([0041] – [0051]). Therefore, one of ordinary skill in the art before the effective filing date would reasonably conclude that the regenerant solution, or the draw solution, consists of the solvent, which is water, and a regenerant solute, which may be sulfuric acid.
Claims 4-6 are rejected under 35 U.S.C 103 as being unpatentable over Arias-Paic in view of Sun, as applied in claim 1, in view of Cath, et. al. 2006, “Forward Osmosis: Principles, Applications, and Recent Developments” Journal of Membrane Science 281 (2006) 70-87, referred to as Cath from herein, and in view of Robertson, et. al. 1964, “The State of the Proton in Aqueous Sulfuric Acid” Journal of the American Chemical Society 86 (1964) 5080-5089, referred to as Robertson from herein.
Regarding claim 4, Arias-Paic in view of Sun teaches a process for concentrating a vanadium electrolyte solution according to claim 1, and Cath teaches the importance of concentration when preparing draw solutions. Cath teaches that forward osmosis is dictated by the differential osmotic pressure, i.e. the difference in osmotic pressure between the draw and feed solutions (Section 2 titled “Osmotic Processes” on Pages 71-73). Cath further teaches that it is necessary for draw solutions to have a higher osmotic pressure (describes having high osmotic pressure is the main criterion for selecting draw solutions in Section 2.1 titled “Draw Solutions” on Page 72), which is proportional to concentration according to the formula shown below (where Π is osmotic pressure, i is the van’t Hoff factor, M is concentration, R is the ideal gas constant, and T is temperature; while this equation represents ideal solutions and supersaturated solutions are not considered ideal, proportionality of variables still holds).
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However, Cath does not teach sulfuric acid as a draw solution nor explicit concentration ranges. Robertson teaches the solubility of sulfuric acid in aqueous solutions where the total of concentration of solute ions, i.e. H+, SO42-, HSO4- and undissociated H2SO4, peaks at around 15 M (adding columns 5, 7-9 of Table 1 on Page 5082; a plot using the values in Table 1 is recreated below), which is similar to the applicant’s finding (Fig. 5, description of which species are considered in calculating the total solute concentration is in [0061]).
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Cath and Robertson are analogous to the present invention because Cath teaches applications of forward osmosis, like the present invention, while Robertson investigates the solubility of sulfuric acid in aqueous solutions, which influences the desired concentration for the draw solution in the present invention. It would be obvious to one of ordinary skill of the art before the effective filing date to modify Arias-Paic in view of Cath with the teachings from Robertson to maximize the concentration of sulfuric acid in the draw solution to induce forward osmosis. Since Robertson teaches that all of the species of sulfuric acid saturates at around 15 M, it would be reasonable for one of ordinary skill in the art before the effective filing date to prepare a draw solution using 15 M sulfuric acid.
Regarding claim 5, Arias-Paic in view of Sun teaches a process for concentrating a vanadium electrolyte solution according to claim 1, and Arias-Paic in view of Sun, in view of Cath and in view of Robertson teaches the draw solution concentration is in a range of 13 M to 18.4 M according to claim 4. Arias-Paic in view of Sun, in view of Cath and in view of Robertson further teaches the draw solution concentration is in a range of 14.5 M to 17.5 M due to similar reasonings as claim 4.
Regarding claim 6, Arias-Paic in view of Sun teaches a process for concentrating a vanadium electrolyte solution according to claim 1, and Arias-Paic in view of Sun, in view of Cath and in view of Robertson teaches the draw solution concentration is in a range of 13 M to 18.4 M according to claim 4. Arias-Paic in view of Sun, in view of Cath and in view of Robertson further teaches the draw solution concentration is in a range of 15 M to 15.5 M due to similar reasonings as claim 4.
Claim 7 is rejected under 35 U.S.C. 103 as being unpatentable over Arias-Paic in view of Sun.
Regarding claim 7, Arias-Paic in view of Sun teaches a process for concentrating a vanadium electrolyte solution according to claim 1, and Sun further teaches of a vanadium electrolyte solution with a low vanadium cation concentration between 1 – 1.2 M (Example 1 uses a low concentration vanadium cation electrolyte solution with a vanadium concentration of 1 M and Example 2 uses a low concentration vanadium electrolyte solution with a vanadium cation concentration of 1.2 M, see [0031] – [0033]; the low concentration vanadium electrolyte solutions will be concentrated using the disclosed process).
It would be reasonable for one of ordinary skill in the art before the effective filing date to prepare a feed solution with a low concentration of vanadium cations between 1 – 1.2 M, as taught by Sun, to further concentrate in order to obtain vanadium electrolyte solutions that will lead to higher battery capacity.
Claim 8 is rejected under 35 U.S.C. 103 as being unpatentable over Arias-Paic in view of Sun, as applied in claim 1 and in claim 7, and in view of Miyabayashi, et. al. 1997, EP 0790658 A2, referred to as Miyabayashi from herein.
Regarding claim 8, Arias-Paic in view of Sun teaches a process for concentrating a vanadium electrolyte solution in claim 1 and Arias-Paic in view of Sun teaches the vanadium cation concentration according to claim 7. Miyabayashi teaches of preferable sulfuric acid concentrations for preparing vanadium electrolyte solutions. More specifically, Miyabayashi teaches using a sulfuric acid concentration between 0.5 – 9 M, most preferably between 1.5 – 6 M (Page 8, lines 2 – 5 describes preferrable ranges of sulfuric acid concentrations, most preferably 1.5 – 6 M).
Miyabayashi is analogous to the present invention because it is in the same field of optimizing vanadium electrolytic solutions like the present invention. It would be reasonable for one of ordinary skill in the art before the effective filing date modify the process of Arias-Paic in view of Sun with the teachings of suitable vanadium electrolyte concentrations as taught by Miyabayashi and prepare the feed solution with an acid concentration of 1.5 – 6 M.
The range recommended by Miyabayashi is broader than in the present invention. It is noted that the courts have stated where the claimed ranges “overlap or lie inside the ranges disclosed by the prior art” a prima facie case of obviousness exists (see 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); Titanium Metals Corp. of America v. Banner, 778 F2d 775. 227 USPQ 773 (Fed. Cir. 1985) (see MPEP 2144.05.01). Therefore, the claimed value of 4 M merely represents an obvious variant and/or routine optimization of the values of the cited prior art.
Claims 9 and 10 are rejected under 35 U.S.C. 103 as being unpatentable over Arias-Paic in view of Sun, as applied in claim 1, in view of Skyllas-Kazacos, et. al. 2016, “Vanadium Electrolyte Studies for the Vanadium Redox Battery – A Review” ChemSusChem 9 (2016) 1521 – 1543, referred to as Skyllas-Kazacos from herein.
Regarding claim 9, Arias-Paic in view of Sun teaches a process for concentrating a vanadium electrolyte solution according to claim 1, and Skyllas-Kazacos teaches the vanadium cations in the aqueous sulfuric acid solutions are V(V) cations, V(IV) cations, V(III) cations, V(II) cations, or combinations thereof (Page 1524, Section 2 titled “Chemistry of Vanadium in Aqueous Systems”). Skyllas-Kazacos teaches that only vanadium with oxidation states of +2, +3, +4, and +5 exist in aqueous solutions (Page 1524, Section 2 titled “Chemistry of Vanadium in Aqueous Systems”).
Skyllas-Kazacos is considered to be analogous to the claimed invention as both are in the field of vanadium redox flow batteries, including the preparation of vanadium electrolytes. It would be reasonable for one of ordinary skill in the art before the effective filing date to perform the process according to Arias-Paic in view of Sun where the feed solution contains V(V) cations, V(IV) cations, V(III) cations, V(II) cations, or combinations thereof as these are the only possible vanadium cations that can exist in aqueous sulfuric acid solutions as taught by Skyllas-Kazacos.
Regarding claim 10, Arias-Paic in view of Sun teaches a process for concentrating a vanadium electrolyte solution in claim 1, and Skyllas-Kazacos teaches the vanadium cations in the feed solution selected from V(V) cations, V(IV) cations, V(III) cations and combinations thereof (Page 1524, Section 2 titled “Chemistry of Vanadium in Aqueous Systems”) due to a similar reasoning as claim 9.
Claim 11 is rejected under 35 U.S.C. 103 as being unpatentable over Arias-Paic in view of Sun, as applied in claim 1.
Regarding claim 11, Arias-Paic in view of Sun teaches a process for concentrating a vanadium electrolyte solution according to claim 1 and Arias-Paic further teaches 60% by volume of the feed solution is removed as water drawn from the feed solution to the draw solution. Arias-Paic teaches of an example using nitrate as the resin-phase ion (i.e. feed solution ion) and sodium chloride as the regenerant solute (i.e. draw solution) with a 66±2% volume reduction (Example 2, see Table 5 and [0050]).
While Arias-Paic does not have an example with vanadium and sulfuric acid nor teaches the optimal percentage of volume removed, they do disclose that the forward osmosis process is stopped to minimize the deterioration of the membrane (Example 1, [0042]) or the amount of precipitate formed (Example 2, [0050]). Therefore, it would be obvious to one of ordinary skill in the art before the effective filing date to optimize the duration of the forward osmosis process, and therefore the volume reduction, to avoid deterioration of the membrane or unwanted precipitate formation. The courts have found that “where 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.” In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955). See MPEP 2144.05 II. Therefore, the claimed percentage of volume of the feed solution removed merely represents an obvious variant and/or routine optimization of the process taught by Arias-Paic.
Claim 12 is rejected under 35 U.S.C. 103 as being unpatentable over Arias-Paic in view of Sun, and in view of Miyabayashi.
Regarding claim 12, Arias-Paic in view of Sun teaches a process for concentrating a vanadium electrolyte solution according to claim 1, and Miyabayashi teaches of a concentrated vanadium electrolyte solution with a total vanadium cation concentration of 3.5 M (Page 7, line 58 – Page 8, line 1 discloses that the concentration of vanadium should be between 0.5 – 8 M to ensure there is high enough battery energy but to avoid having highly viscous electrolytic solutions that decrease the battery efficiency) and a sulfuric acid concentration of 7 M (Page 8, lines 2 – 5 describes preferrable ranges of sulfuric acid concentrations, more preferably 1 – 8 M).
While Miyabayashi does not teach of forward osmosis, Miyabayashi teaches of desirable concentrations for vanadium electrolytic solution concentration as well as how they may influence battery performance (Page 7, line 55 – Page 8, line 5). Therefore, it would be reasonable for one of ordinary skill in the art before the effective filing date to run the forward osmosis module until the resultant feed solution has a vanadium cation concentration of 3.5 M and a sulfuric acid concentration of 7 M so that the resultant vanadium electrolyte solution will lead to a reasonable battery energy without being too viscous.
The ranges disclosed in Miyabayashi are broader than in the present invention. It is noted that the courts have stated where the claimed ranges “overlap or lie inside the ranges disclosed by the prior art” a prima facie case of obviousness exists (see 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); Titanium Metals Corp. of America v. Banner, 778 F2d 775. 227 USPQ 773 (Fed. Cir. 1985) (see MPEP 2144.05.01). Therefore, the claimed values of 3.5 M for the vanadium cation concentration and 7 M for the sulfuric acid concentration merely represent obvious variants and/or routine optimization of the values of the cited prior art.
Claims 13 and 14 are rejected under U.S.C. 103 as being unpatentable over Arias-Paic in view of Sun as applied in claim 1, in view of Liu, et. al. 2018, CN 106395900 B, referred to as Liu from herein, and in view of Mullin, 2001, “Nucleation” in Crystallization, 4th ed. Butterworth-Heinemann (2001) 181-215, referred to as Mullin from herein.
Regarding claim 13, Arias-Paic in view of Sun teaches a process for concentrating a vanadium electrolyte solution according claim 1, and Liu teaches of subjecting a concentrated vanadium electrolyte to a solidification process (crystallization, [0032]) comprising of adding a nucleation material (vanadium oxysulfate, see Example 1 [0036] – [0037]) to a concentrated vanadium electrolyte solution (describes a vanadium supersaturated solution in [0032]). Liu discloses a process to remove impurities from the nucleation material, or the seed crystal. Therefore, it would be reasonable for one of ordinary skill in the art before the effective filing date to modify the process in Arias-Paic in view of Sun with the teachings of Liu to remove any impurities or contaminants.
However, Liu does not disclose mixing for a period of time during nucleation.
Mullin teaches that agitation, such as mixing, is frequently used to induce crystallization and is generally considered to improve nucleation (Page 190 says that agitation is frequently used to induce crystallization). Liu and Mullin are analogous to the present invention because both are in the field of nucleation similar to the solidification process in the present invention. It would be obvious for one of ordinary skill in the art before the effective filing date incorporate the teachings of Mullin with the process of Arias-Paic in view of Sun, in view of Liu and mix the solution in order to enhance nucleation.
Regarding claim 14, Arias-Paic in view of Sun teaches a process for concentrating a vanadium electrolyte solution according to claim 1, and Arias-Paic in view of Sun, in view of Liu and in view of Mullin teaches of subjecting a concentrated vanadium electrolyte to a solidification process in claim 13. Arias-Paic in view of Sun, in view of Liu and in view of Mullin further teaches the nucleation material is VOSO4 (Liu teaches vanadium oxysulfate, [0032]) added in amount of no more than 20 mg/mL (Liu describes 8 – 10 g/L of the seed crystal is added, where 8 – 10 g/L is equivalent to 8 – 10 mg/mL in [0032]), the concentrated vanadium electrolyte solution has a densification level of no more than 60% (see Example 2, Table 5 and [0050] in Arias-Paic; also see claim 11) and mixing for a period of time (Mullin, Page 190).
While Mullin does not teach how long to mix, Mullin teaches that the time between supersaturating the solution and the appearance of crystals (the period of time is described as the induction period, Page 206), the time before desupersaturation (described as the latent period, Page 207; see Fig. 5.12), and the desupersaturation rate depend on a variety of variables, including agitation (Pages 206 – 207; Fig. 5.12). Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to optimize the period of time mixing the solution to obtain the desired amount of precipitate, as taught by Mullin, thereby arriving at the instantly claimed invention. The courts have found that “where 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.” In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955). See MPEP 2144.05 II. Therefore, the claimed time of 2 hours of mixing merely represent an obvious variant and/or routine optimization of agitation in nucleation processes taught by Mullin.
Claim 15 is rejected under 35 U.S.C. 103 as being unpatentable over Arias-Paic in view of Sun.
Regarding claim 15, Arias-Paic in view of Sun teaches a process for concentrating ions in an ionic solution (Abstract) comprising of:
(a) delivering a draw solution (described as a regenerant solution, [0007]) to a draw chamber of a forward osmosis module (Fig. 4 shows a forward osmosis module where the concentrated regeneration solution is being delivered to the draw chamber, 600) the draw solution consisting of water and a solute (composition of regenerant solution is described in [0007], where the solute is described as the regenerant solute in [0007] and water is not explicitly stated until mentioned as a solvent in [0008]);
(b) delivering a feed solution (described as elution solution, [0007]) to a feed chamber of the forward osmosis modules (Fig. 4 shows a forward osmosis module with a membrane, 590, separating the draw chamber, 600, and the feed chamber, 575); the feed solution comprising of water, ions, and the same solute (elution solution is described in [0007] where the regeneration solute displaces resin-phase ions when the regenerant solution passes through the contactor);
wherein water passes across the membrane from the feed solution to the draw solution, thereby providing a concentrated solution (Fig. 4, concentrated elution solution 620) as the feed chamber output and a diluted solution (Fig. 4, diluted regeneration solution, 730) as the draw chamber output.
(c) combining the diluted acid solution (described as the diluted regeneration solution in [0037]; Fig. 6) and a source of vanadium to provide the feed solution ([0037] describes recycling the diluted regenerant solute and producing a new elution solution; Fig. 6).
While Arias-Paic does not use vanadium nor sulfuric acid in their examples, Arias-Paic provides a list of resin-phase ions, including vanadium ([0006]), and a list of regenerant solutes, including sulfuric acid ([0007]), which can be used with the process disclosed in the prior art. Arias-Paic does not give further indication as to which of the resin-phase ion, regenerant solute, or combination thereof would likely be successful.
Additionally, while Arias-Paic teaches of a process for concentrating ions in an ionic solution where the ions may be vanadium cations and the solution may contain sulfuric acid, Arias-Paic does not teach why one would want to increase the concentration of a vanadium electrolyte solution.
Sun teaches the importance of concentrating low concentration vanadium solutions and the relationship between vanadium concentration and battery performance ([0006]). Sun further teaches low concentrations of vanadium cations in vanadium electrolyte solutions lead to decreases in battery capacity and battery degradation ([0006]). The process disclosed in Sun specifically concentrates spent vanadium electrolyte solutions from used batteries in order to reduce costs associated with vanadium battery systems ([0005] – [0006] describes high costs associated with vanadium electrolytes solutions).
It would be reasonable for one of ordinary skill in the art before the effective filing date to perform the forward osmosis process disclosed in Arias-Paic using vanadium as the resin phase-ion and sulfuric acid as the regenerant solute and to modify this process with a low concentration vanadium electrolyte from a used battery as the feed solution, as taught in Sun, to reduce costs in manufacturing new vanadium electrolyte solutions and to obtain higher concentrated vanadium electrolyte solutions that may lead to improved battery capacity.
Claim 16 is rejected under 35 U.S.C 103 as being unpatentable over Arias-Paic in view of Sun, as applied in claim 15, in view of Cath and in view of Robertson.
Regarding claim 16, Arias-Paic in view of Sun teaches a process for concentrating a vanadium electrolyte solution according to claim 15, and Cath teaches the importance of concentration when preparing draw solutions. Cath teaches that forward osmosis is dictated by the differential osmotic pressure, i.e. the difference in osmotic pressure between the draw and feed solutions (Section 2 titled “Osmotic Processes” on Pages 71-73). Cath further teaches that it is necessary for draw solutions to have higher osmotic pressure (describes having high osmotic pressure is the main criterion for selecting draw solutions in Section 2.1 titled “Draw Solutions” on Page 72), which is proportional to concentration according to the equation shown in claim 4.
However, Cath does not teach sulfuric acid as a draw solution nor explicit concentration ranges. Robertson teaches the solubility of sulfuric acid in aqueous solutions where the total of concentration of solute ions, i.e. H+, SO42-, HSO4- and undissociated H2SO4, peaks at around 15 M (adding columns 5, 7-9 of Table 1 on Page 5082; see plot using the values in Table 1 in claim 4), which is similar to the applicant’s finding (Fig. 5, description of which species are considered in calculating the total solute concentration is in [0061]).
It would be obvious to one of ordinary skill of the art before the effective filing date to modify Arias-Paic in view of Cath with the teachings from Robertson to maximize the concentration of sulfuric acid in the draw solution to induce forward osmosis. Since Robertson teaches that all of the species of sulfuric acid saturates at around 15 M, it would be reasonable for one of ordinary skill in the art before the effective filing date to prepare a draw solution using 15 M sulfuric acid.
Claim 17 is rejected under 35 U.S.C. 103 as being unpatentable over Arias-Paic in view of Sun.
Regarding claim 17, Arias-Paic in view of Sun teaches a process for concentrating a vanadium electrolyte solution according to claim 15, and Sun further teaches of a vanadium electrolyte solution with a low vanadium cation concentration between 1 – 1.2 M (Example 1 uses a low concentration vanadium cation electrolyte solution with a vanadium concentration of 1 M and Example 2 uses a low concentration vanadium electrolyte solution with a vanadium cation concentration of 1.2 M, see [0031] – [0033]; the low concentration vanadium electrolyte solutions will be concentrated using the disclosed process).
It would be reasonable for one of ordinary skill in the art before the effective filing date to prepare a feed solution with a low concentration of vanadium cations between 1 – 1.2 M, as taught by Sun, to further concentrate in order to obtain vanadium electrolyte solutions that will lead to higher battery capacity.
Claim 18 is rejected under 35 U.S.C. 103 as being unpatentable over Arias-Paic in view of Sun, as applied in claim 15, in view of Skyllas-Kazacos.
Regarding claim 18, Arias-Paic in view of Sun teaches a process for concentrating a vanadium electrolyte solution according to claim 15, and Skyllas-Kazacos teaches the vanadium cations in the aqueous sulfuric acid solutions are V(V) cations, V(IV) cations, V(III) cations, V(II) cations, or combinations thereof (Page 1524, Section 2 titled “Chemistry of Vanadium in Aqueous Systems”). Skyllas-Kazacos teaches that only vanadium with oxidation states of +2, +3, +4, and +5 exist in aqueous solutions (Page 1524, Section 2 titled “Chemistry of Vanadium in Aqueous Systems”). Therefore, it would be reasonable for one of ordinary skill in the art before the effective filing date to perform the process according to Arias-Paic in view of Sun where the feed solution contains V(V) cations, V(IV) cations, V(III) cations, V(II) cations, or combinations thereof as these are the possible vanadium cations that can exist in aqueous sulfuric acid solutions as taught by Skyllas-Kazacos.
Claim 19 is rejected under 35 U.S.C. 103 as being unpatentable over Arias-Paic in view of Sun, as applied in claim 15.
Regarding claim 19, Arias Paic in view of Sun teaches a process for concentrating a vanadium electrolyte solution according to claim 15, and Arias-Paic further teaches 60% by volume of the feed solution is removed as water drawn from the feed solution to the draw solution. Arias-Paic teaches of an example using nitrate as the resin-phase ion (i.e. feed solution ion) and sodium chloride as the regenerant solute (i.e. draw solution) with a 66±2% volume reduction (Example 2, see Table 5 and [0050]).
While Arias-Paic does not have an example with vanadium and sulfuric acid nor teaches the optimal percentage of volume removed, they do disclose that the forward osmosis process is stopped to minimize the deterioration of the membrane (Example 1, [0042]) or the amount of precipitate formed (Example 2, [0050]). Therefore, it would be obvious to one of ordinary skill in the art before the effective filing date to optimize the duration of the forward osmosis process, and therefore the volume reduction, to avoid deterioration of the membrane or unwanted precipitate formation. The courts have found that “where 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.” In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955). See MPEP 2144.05 II. Therefore, the claimed percentage of volume of the feed solution removed merely represents an obvious variant and/or routine optimization of the process taught by Arias-Paic.
Claim 20 is rejected under 35 U.S.C. 103 as being unpatentable over Arias-Paic in view of Sun, as applied in claim 15, in view of Miyabayashi.
Regarding claim 20, Arias-Paic in view of Sun teaches a process for concentrating a vanadium electrolyte solution according to claim 15, and Miyabayashi teaches of a concentrated vanadium electrolyte solution with a total vanadium cation concentration of 3.5 M (Page 7, line 58 – Page 8, line 1 discloses that the concentration of vanadium should be between 0.5 – 8 M to ensure there is high enough battery energy but to avoid having highly viscous electrolytic solutions that decrease the battery efficiency) and a sulfuric acid concentration of 7 M (Page 8, lines 2 – 5 describes preferrable ranges of sulfuric acid concentrations, more preferably 1 – 8 M).
While Miyabayashi does not teach of forward osmosis, Miyabayashi teaches of desirable concentrations for vanadium electrolytic solution concentration as well as how they may influence battery performance (Page 7, line 55 – Page 8, line 5). Therefore, it would be reasonable for one of ordinary skill in the art before the effective filing date to run the forward osmosis module until the resultant feed solution has a vanadium cation concentration of 3.5 M and a sulfuric acid concentration of 7 M so that the resultant vanadium electrolyte solution will lead to a reasonable battery energy without being too viscous.
The ranges disclosed in Miyabayashi are broader than in the present invention. It is noted that the courts have stated where the claimed ranges “overlap or lie inside the ranges disclosed by the prior art” a prima facie case of obviousness exists (see 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); Titanium Metals Corp. of America v. Banner, 778 F2d 775. 227 USPQ 773 (Fed. Cir. 1985) (see MPEP 2144.05.01). Therefore, the claimed values of 3.5 M for the vanadium cation concentration and 7 M for the sulfuric acid concentration merely represent obvious variants and/or routine optimization of the values of the cited prior art.
Conclusion
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/VIVIAN F CRUM/Examiner, Art Unit 1738 /MICHAEL FORREST/Primary Examiner, Art Unit 1738
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