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 .
Response to Arguments
Applicant's arguments filed 14 August 2026 have been fully considered but they are not persuasive. Applicant has argued that Staker fails to teach the solid phase reaction product isolated in the isolating step included a copper product comprising Cu0 (i.e. metallic copper).
In response, the Office disagrees for two reasons.
First, Staker teaches (see col. 2, lines 2-7) that the solid phase reaction product (“residue”) “may contain copper, copper sulfide, precious metals, silicious gangue and unreacted concentrate, the exact types and amounts of products depending on the specific chalcopyrite ore or concentrate, transition metal ion and reaction conditions employed”. The presence of both “copper” and “copper sulfide” indicates that the first refers to metallic copper, Cu0.
Second, the evidence currently of record supports that conclusion that the process of Staker inherently produces at least some metallic copper in the residue. Here, the Office points to reaction (4) of Staker (col. 2, lines 36-37) which is identical to reaction (3) in paragraph [0050] of the instant specification. This is evidence that the residue of Staker included Cu2S. Reaction (4) in paragraph [0050] of the instant specification would have been expected by one of ordinary skill in the art to have inherently occurred in the process of Staker since the residue contained Cu2S and the solution contained protons/acid (H+) and vanadium (ii) cations (V+2).
Further, the Office does acknowledge that Staker performs an assay on the solid residue (see Examples 1 and 2 in cols. 2-3) wherein the residue contained amounts of Cu, Fe, and S. Note that Staker shows, in example 5 in col. 4, an assay wherein metallic copper was present, that metallic copper was reported differently than copper bound in a compound, so the solid residue discussed in examples 1 and 2 is not considered to include measurable amounts of metallic copper. However, the assay of Staker was performed only after filtering, washing and drying the residue. The instant specification teaches (see paragraph [0079]) that during an air-drying step, metallic copper in the copper product can react with atmospheric oxygen and chemical residue on the surface of the metallic copper to oxidize the metallic copper according to reaction (9). Thus, since Staker only performs the assay after a drying step, a reaction similar to reaction (9) would have been expected to take place (noting that Staker used HCl instead of H2SO4, so the expected product would be CuCl2) resulting in the absence of metallic copper in the fully dried product. This does not exclude the presence of metallic copper in the not yet dried copper product.
In the absence of some additional evidence and/or claimed reaction conditions (e.g. concentrations, temperature, duration, etc.) that are shown to be required to produce metallic copper, the rejection grounds using Staker are maintained.
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.
Claims 1, 2, 9, and 10 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Staker (US 3,958,983 A).
Staker teaches (see abstract, cols. 1 and 2) a process for producing a copper product (e.g. copper, copper sulfide) from a copper concentrate (chalcopyrite concentrate) comprising providing the copper concentrate (chalcopyrite concentrate), contacting the composition with an aqueous solution including a chemical reducing agent (vanadium, chromium or titanium ions), reacting the copper concentrate with the chemical reducing agent to reduce copper within the copper concentrate (reaction (1) and formation of copper metal noted at col. 2, lines 2-7) and isolating (liquid-solid separation techniques) the solid phase reaction product that included a copper product.
With respect to the claim limitation that the copper product comprises Cu0, it is noted that Staker mentions that the recovered solids may include copper (i.e. metallic copper) (see col. 2, lines 2-7). Further, Staker teaches applying the same chemical reducing agent (V+2 ions) to the same reactant (copper concentrate comprising chalcopyrite), and thus one of ordinary skill in the art would have expected the process of Staker to have inherently performed the same method as that disclosed in the instant application, including production of at least some Cu0 in the solid residue. See MPEP § 2112. When the prior art teaches each of the claimed steps except for failure to recognize a feature, Applicant bears the burden of providing evidence that the feature does not inherently occur in the process of the prior art.
Regarding claim 2, Staker teaches the copper concentrate being chalcopyrite.
Regarding claim 9, Staker teaches using compounds including vanadium (II) ions as the chemical reducing agent.
Regarding claim 10, in equation (1), col. 2, lines 30-31, Staker teaches the chemical reducing agent being chromium (ii) chloride.
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.
Claims 3-5 are rejected under 35 U.S.C. 103 as being unpatentable over Staker (US 3,958,983 A) in view of Blanco et al (US 4,093,526 A).
Regarding claims 3-5, Staker teach (see col. 2, lines 19-26) that the solid phase reaction product may be leached with copper chloride with subsequent electrowinning to isolate the copper product.
Staker fails to teach the copper chloride leachant being acidic or the electrowinning step regenerating the acid.
Blanco et al teach (see fig. 1, abstract, col. 7, lines 11-31) a process for the recovery of copper metal from a copper bearing material, comprising leaching the copper-bearing material with sulfuric acid followed by electrowinning of the pregnant solution which recovered pure copper metal and regenerated the sulfuric acid which is recycled to the leaching step.
Therefore, it would have been obvious to one of ordinary skill in the art to have applied the sulfuric acid leaching step taught by Blanco et al in place of the copper chloride leaching step of Staker by simple substitution according to known techniques because the leaching and electrowinning steps of Blanco et al recovered copper as pure metal while also regenerating the leachant, thereby reducing waste.
Claims 6-8 are rejected under 35 U.S.C. 103 as being unpatentable over Staker (US 3,958,983 A) in view of Heimala et al (US 2010/0180727 A1).
Regarding claims 6 and 7, Staker discloses isolating the liquid phase reaction product (“residue and solution are separated by conventional liquid-solid separation techniques”). The oxidized chemical reducing agent, e.g. vanadium or chromium ions having an oxidation state higher than +2, e.g. +3, +4, +5, +6, was inherently present in the liquid phase reaction product since the vanadium or chromium ions were not recovered in the solid residue.
Staker does not teach treatment of the liquid phase in an electrochemical reactor.
Heimala et al teach (see abstract, fig. 1, paragraphs [0026], [0027], and [0036]) a process wherein a liquid phase reaction product from a leaching step of a copper bearing material with a solution containing vanadium or chromium ions is fed to an electrochemical device where the oxidized (higher oxidation state) vanadium or chromium ions were reduced (lower oxidation state) at the anode of the electrochemical device and the now reduced oxidized chemical reducing agent is returned to the leaching step.
Therefore, it would have been obvious to one of ordinary skill in the art to have added an electrochemical device as taught by Heimala et al to the process of Staker for the purpose of regenerating the vanadium or chromium chemical reducing agent from its oxidized state for the purpose of reducing the amount of waste generated by the process of Staker by regenerating the low oxidation state vanadium or chromium ion chemical reducing agent.
Regarding claim 8, Heimala et al teach (see fig. 1, paragraph [0033]) that a copper product was isolated from the liquid phase reaction product.
Therefore, it would have been obvious to one of ordinary skill in the art to have performed the copper recovery step of Heimala et al on the liquid phase reaction product of Staker to recover additional copper that had become solubilized into the liquid phase reaction product.
Claim 11 is rejected under 35 U.S.C. 103 as being unpatentable over Staker (US 3,958,983 A) in view of Heimala et al (US 2010/0180727 A1) as applied to claim 6 above, and further in view of Deberry et al (US 5,705,135 A and Souentie et al (“Temperature, charging current and state of charge effects on iron-vanadium flow batteries operation”).
Staker teaches (see col. 2, lines 13-18) that the iron liberated from the chalcopyrite is recovered as ferrous (iron (ii)) ions. Staker additionally teaches (see col. 1, lines 64-67) isolation (collection) of the gaseous hydrogen sulfide product and potentially converting it to elemental sulfur by means of conventional processes.
Heimala et al teach (see paragraph [0036]) that within the electrochemical cell oxidation of metal ions occurs at the anode and reduction of metal ions occurs at the cathode. Heimala et al also teach that additional oxidation of the anolyte may be performed by feeding oxygen-containing gas into the anolyte and/or that additional reduction of the catholyte may be performed by performing an additional reduction.
Staker and Heimala et al fail to teach the conversion of the hydrogen sulfide product to elemental sulfur being done by reaction with a stream of ferric iron and sending the resulting ferrous iron stream to the electrochemical cell.
Deberry et al teach (see abstract, figs. 2 and 3) a process for converting hydrogen sulfide to elemental sulfur comprising reacting the hydrogen sulfide with a stream of ferric iron (Fe+3) which results in the formation of elemental sulfur and ferrous iron (Fe+2). The ferrous iron is then sent to an electrochemical cell (20) where the ferrous iron is oxidized at the anode to form ferric iron. Note that Deberry et al required a voltage of 5.5 V to drive the regeneration of the ferric ions.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of filing to have applied the process for converting hydrogen sulfide to elemental sulfur taught by Deberry et al to the process of Staker because Staker teaches using conventional methods for converting hydrogen sulfide to elemental sulfur and Deberry et al teach that the process operated (see col. 2, lines 52-67) in an ecologically prudent manner with no release of sulfur, no generation of solid waste, while also using a regenerable absorbent with minimal equipment footprint.
From Staker, Heimala et al and Deberry et al, there was no recognition that the electrochemical cell of Heimala et al and the electrochemical cell of Deberry et al were the same electrochemical cell as required by the recitation in claim 11 of “the electrochemical device” (emphasis added).
In the field of electrochemical cells, iron-vanadium flow batteries are known. See Souentie et al at abstract, fig. 1. During charging of the flow battery, the opposite of reactions (7)-(9) (see section 3.1) occurs. These charging reactions include oxidation of ferrous (Fe+2) iron ions to ferric (Fe+3) iron ions and reduction of vanadium (III) ions to vanadium (II) ions. The overall voltage necessary to drive the reactions was 1.029 V.
One of ordinary skill in the art would have recognized that (1) the reaction required by the electrochemical cell of Heimala et al in the context of the process of Staker was reduction of the vanadium (III) ions to vanadium (II) ions and (2) the reaction required by the electrochemical cell of Deberry et al was oxidation of ferrous ions to ferric ions. The charging cycle of the iron-vanadium flow battery performs these same reactions at a voltage of just over 1 V, which is significantly lower than the voltage required by the electrochemical cell of Deberry et al. Therefore, it would have been obvious to one of ordinary skill in the art at the time of filing to have applied the reaction scheme of charging an iron-vanadium flow battery to the system of Staker as modified by Heimala et al and Deberry et al by using a single electrochemical cell to perform the regeneration of the vanadium (II) ions and the ferric ions at a lower voltage than that required by the electrochemical cell of Deberry et al.
Claims 19 and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Staker (US 3,958,983 A) in view of Heimala et al (US 2010/0180727 A1), Deberry et al (US 5,705,135 A), Souentie et al (“Temperature, charging current and state of charge effects on iron-vanadium flow batteries operation”) and Blanco et al (US 4,093,526 A).
Staker teaches (see abstract, cols. 1 and 2) a process for producing a copper product (e.g. copper, copper sulfide) from a chalcopyrite concentrate comprising providing the chalcopyrite concentrate, contacting the composition with an aqueous solution including a chemical reducing agent (vanadium (II) , chromium (II) or titanium (II) ions), reacting the chalcopyrite concentrate with the chemical reducing agent to reduce copper within the chalcopyrite concentrate (reaction (1) and formation of copper metal noted at col. 2, lines 2-7) and separating a solids reaction product stream and a liquid reaction product (liquid-solid separation techniques) and also separating a gaseous reaction product stream (collection of hydrogen sulfide). The solid phase reaction product that included a copper product, the liquid product included oxidized reducing agent (inherently present since the vanadium, chromium or titanium ions were not recovered in the solid phase), and the gaseous product was hydrogen sulfide.
With respect to the claim limitation that the solids reaction product stream includes Cu0, it is noted that Staker mentions that the recovered solids may include copper (i.e. metallic copper) (see col. 2, lines 2-7). Further, Staker teaches applying the same chemical reducing agent (e.g. V+2 ions) to the same reactant (copper concentrate comprising chalcopyrite), and thus one of ordinary skill in the art would have expected the process of Staker to have inherently performed the same method as that disclosed in the instant application, including production of at least some Cu0 in the solid residue. See MPEP § 2112. When the prior art teaches each of the claimed steps except for failure to recognize a feature, Applicant bears the burden of providing evidence that the feature does not inherently occur in the process of the prior art.
Staker fails to teach the “providing”, “reducing”, “contacting”, “treating”, “recycling”, “contacting”, and “electrowinning” steps as set forth at the end of claim 19.
Regarding the “providing”, “reducing”, and “contacting” steps, the oxidized chemical reducing agent, e.g. vanadium or chromium ions having an oxidation state higher than +2, e.g. +3, +4, +5, +6, was inherently present in the liquid phase reaction product of Staker since the vanadium or chromium ions were not recovered in the solid residue.
Staker does not teach treatment of the liquid phase in an electrochemical reactor.
Heimala et al teach (see abstract, fig. 1, paragraphs [0026], [0027], and [0036]) a process wherein a liquid phase reaction product from a leaching step of a copper bearing material with a solution containing vanadium or chromium ions is provided to an electrochemical device where the oxidized (higher oxidation state) vanadium or chromium ions were reduced (lower oxidation state) at the anode of the electrochemical device and the now reduced oxidized chemical reducing agent is returned to the leaching step for contacting fresh copper bearing material.
Therefore, it would have been obvious to one of ordinary skill in the art to have added the “providing”, “reducing”, and “contacting” steps using an electrochemical device as taught by Heimala et al to the process of Staker for the purpose of regenerating the vanadium or chromium chemical reducing agent from its oxidized state for the purpose of reducing the amount of waste generated by the process of Staker by regenerating the low oxidation state vanadium or chromium ion chemical reducing agent.
Regarding the “treating” step, Staker and Heimala et al fail to teach the conversion of the hydrogen sulfide product to elemental sulfur being done by reaction with a stream of ferric iron and sending the resulting ferrous iron stream to the electrochemical cell.
Deberry et al teach (see abstract, figs. 2 and 3) a process for converting hydrogen sulfide to elemental sulfur comprising reacting the hydrogen sulfide with a stream of ferric iron (Fe+3) which results in the formation of elemental sulfur and ferrous iron (Fe+2). The ferrous iron is then sent to an electrochemical cell (20) where the ferrous iron is oxidized at the anode to form ferric iron which is used for conversion of additional hydrogen sulfide. Note that Deberry et al required a voltage of 5.5 V to drive the regeneration of the ferric ions.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of filing to have applied the process for converting hydrogen sulfide to elemental sulfur taught by Deberry et al to the process of Staker because Staker teaches using conventional methods for converting hydrogen sulfide to elemental sulfur and Deberry et al teach that the process operated (see col. 2, lines 52-67) in an ecologically prudent manner with no release of sulfur, no generation of solid waste, while also using a regenerable absorbent with minimal equipment footprint.
Regarding the “recycling” step, from Staker, Heimala et al and Deberry et al, there was no recognition that the electrochemical cell of Heimala et al and the electrochemical cell of Deberry et al were the same electrochemical cell as required by the recitation in the “recycling” step of claim 19 (“the electrochemical device” (emphasis added)).
In the field of electrochemical cells, iron-vanadium flow batteries are known. See Souentie et al at abstract, fig. 1. During charging of the flow battery, the opposite of reactions (7)-(9) (see section 3.1) occurs. These charging reactions include oxidation of ferrous (Fe+2) iron ions to ferric (Fe+3) iron ions and reduction of vanadium (III) ions to vanadium (II) ions. The overall voltage necessary to drive the reactions was 1.029 V.
One of ordinary skill in the art would have recognized that (1) the reaction required by the electrochemical cell of Heimala et al in the context of the process of Staker was reduction of the vanadium (III) ions to vanadium (II) ions and (2) the reaction required by the electrochemical cell of Deberry et al was oxidation of ferrous ions to ferric ions. The charging cycle of the iron-vanadium flow battery performs these reactions at a voltage of just over 1 V, which is significantly lower than the voltage required by the electrochemical cell of Deberry et al. Therefore, it would have been obvious to one of ordinary skill in the art at the time of filing to have applied the reaction scheme of charging an iron-vanadium flow battery to the system of Staker as modified by Heimala et al and Deberry et al by using a single electrochemical cell to perform the regeneration of the vanadium (II) ions and the ferric ions at a lower voltage than that required by the electrochemical cell of Deberry et al.
Regarding the “contacting” and “electrowinning” steps, Staker teach (see col. 2, lines 19-26) that the solid phase reaction product may be leached with copper chloride with subsequent electrowinning to isolate the copper product.
Staker fails to teach the copper chloride leachant being acidic or the electrowinning step regenerating the acid.
Blanco et al teach (see fig. 1, abstract, col. 7, lines 11-31) a process for the recovery of copper metal from a copper bearing material, comprising leaching the copper-bearing material with sulfuric acid followed by electrowinning of the pregnant solution which recovered pure copper metal and regeneration of the sulfuric acid which is recycled to the leaching step.
Therefore, it would have been obvious to one of ordinary skill in the art to have applied the sulfuric acid leaching step taught by Blanco et al in place of the copper chloride leaching step of Staker by simple substitution according to known techniques because the leaching and electrowinning steps of Blanco et al recovered copper as pure metal while also regenerating the leachant, thereby reducing waste.
Regarding claim 20, although not expressed as a molar concentration, the examples of Staker utilized the reducing agent at amounts that fall within the claimed concentration range. For example, Example 2 of Staker included 46 g of VOCl2 in 200 mL of solution. This is about 1/3 of a mole of VOCl2 in 200 mL, or about 0.166 M.
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to HARRY D WILKINS III whose telephone number is (571)272-1251. The examiner can normally be reached M-F 9:30am -6:00pm.
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/HARRY D WILKINS III/Primary Examiner, Art Unit 1794
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