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 Statement filed 11 September 2023 has been considered.
Claim Objections
Claims 13, 14, 18, and 20 are objected to because of the following informalities:
Claim 13, line 6, “SO3” should read “SO3”.
Claim 14, line 3, "minutes,; the" should read "minutes; the".
Claim 14, line 4, “fractionand” should read “fraction and”.
Claim 18, line 3, “to obtain the precipitation” should read “to precipitate”
Claim 18, line 4, “acid flow (21)” should read “acid flow”.
Claim 20, line 5, “1/30 s/l10” should read “1/30 s/l”.
Appropriate correction is required.
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 13-22 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 13 recites the limitation "the treatment of jarosite" in line 1. There is insufficient antecedent basis for this limitation in the claim. This limitation is interpreted as requiring a method for treating jarosite.
Claim 13 recites the limitation "the zinc and lead production industry" in lines 1-2. There is insufficient antecedent basis for this limitation in the claim. This limitation is interpreted as requiring treating jarosite and other residues of a zinc and lead production industry.
Claim 13, line 3, recites “thermal treatment of the residues”. It is unclear if “the residues” includes jarosite. This limitation is interpreted as requiring thermal treatment of the jarosite and other residues.
Claim 13 recites the limitation "the evaporation of the imbibition water" in lines 4-5. There is insufficient antecedent basis for this limitation in the claim. This limitation is interpreted as requiring thermal treatment…to evaporate imbibition water.
Claim 13 recites the limitation "the demolition of the jarosite molecule" in 5. There is insufficient antecedent basis for this limitation in the claim. This limitation is interpreted as requiring thermal treatment…to demolish the jarosite.
Claim 13 recites the limitation "the dev" in lines 5-6. There is insufficient antecedent basis for this limitation in the claim. This limitation is interpreted as requiring demolishing the jarosite, resulting in SO3 development.
Claim 13 recites the limitation "the removal of OH" in line 6. There is insufficient antecedent basis for this limitation in the claim. This limitation is interpreted as requiring demolishing the jarosite, resulting in OH- group removal.
Claim 13 recites the limitation "the obtainment" in line 7. There is insufficient antecedent basis for this limitation in the claim.
Claim 13 recites the limitation "the recondensation" in line 7. There is insufficient antecedent basis for this limitation in the claim. This limitation is interpreted as requiring recondensation.
Claim 13, line 7, recites “recondensation of these components”. It is unclear what “these components” are. This limitation is interpreted as requiring recondensation of the water and the SO3.
Claim 13 recites the limitation "the simultaneous formation" in line 8. There is insufficient antecedent basis for this limitation in the claim.
Claim 13, line 9, recites “zinc, lead, silver, copper sulphates”. It is unclear if the zinc, lead, and silver are in the form of a metal sulphate. This limitation is interpreted as requiring a solid fraction composed of…zinc sulphate, lead sulphate, silver sulphate, copper sulphate.
Claim 13, lines 11-12, recite “zinc, copper and silver sulphates”. It is unclear if zinc and copper are in the form of a metal sulphate. It is further unclear if these sulphates are the sulphates obtained in claim 1, line 9. This limitation is interpreted as requiring a solution of the zinc sulphate, the copper sulphate, and the silver sulphate.
Claim 13, lines 12-13, recite “a solid fraction enriched in iron oxides, lead sulphate and silver sulphate”. It is unclear if the iron oxide, lead sulphate, and silver sulphate are the iron(III) oxide, silver sulphate, and copper sulphate of claim 1, line 9. This limitation is interpreted as requiring a solid fraction enriched in the iron(III) oxide, the lead sulphate and the silver sulphate.
Claim 13, line 15, recites “a saline solution containing lead and silver”. It is unclear if the lead and silver are the lead and silver from the lead sulphate and the silver sulphate of claim 1, lines 12-13. This limitation is interpreted as requiring a saline solution containing the lead and the silver. This interpretation further applies to the saline solution of claim 1, line 17.
Claim 13, lines 15-16, recite “a solid fraction enriched in iron(III) oxide”. It is unclear if the iron(III) oxide is the iron(III) oxide claim 1, line 12. This limitation is interpreted as requiring a solid fraction enriched in the iron(III) oxide. This limitation further applies to the solid fraction of claim 1, line 19.
Claim 13, line 19, recites “purification of the silica of the solid fraction…by using an acid solution” without any active, positive steps delimiting how this use is actually practiced. See MPEP 2173.05(q). This limitation is interpreted as requiring purification of silica of the solid fraction…by washing the solid fraction with an acid solution per the bottom of pg. 16 of the Specification of the present application.
Claim 13, lines 19-24, recite:
purification of the silica of the solid fraction…to obtain
solubilization of iron(III);
separation of the solubilized iron(III) from the silica…; and
precipitation of iron(III) to obtain iron oxide pigment.
It is unclear if the purification of the silica by washing the solid fraction with an acid solution results in solubilization of iron, separation of the solubilized iron, and precipitation of iron, due to the bullet points following the phase “to obtain”.
It is further unclear if the iron(III) in line 24 is the solubilized iron(III) of claim 1, line 22.
This limitation is interpreted as requiring:
purification of the silica of the solid fraction…by washing the solid fraction with an acid solution to obtain solubilization of the iron (III), and separating the solubilized iron(III) from the silica…; and
precipitation of the solubilized iron(III) to obtain iron oxide pigment.
Claim 16, lines 1-2, recite “said acid leaching solution is reintegrated using the diluted sulfuric acid solution”. It is unclear what reintegration of said acid leaching solution requires. This limitation is interpreted as requiring recycling of the diluted sulfuric acid solution such that said acid leaching solution comprises the diluted sulfuric acid solution (per Fig. 1 and pg. 8 of the Specification of the present application).
Claim 16 recites the limitation "the recondensation of the vapours produced during the thermal pre-treatment step at 700°C" in lines 2-3. There is insufficient antecedent basis for this limitation in the claim. There is sufficient antecedent basis for “the diluted sulfuric acid solution” (claim 1, line 8) such that the phrase “obtained from the recondensation of the vapours produced during the thermal pre-treatment step” is redundant. The limitation “the recondensation of vapours” is interpreted to be recondensation of the water and the SO3. The limitation “the thermal-pretreatment step” is interpreted to be the thermal treatment step. This limitation is interpreted as requiring recycling the diluted sulfuric acid solution such that said acid leaching solution comprises the diluted sulfuric acid solution, and the maximum temperature of the thermal treatment step is 700°C.
Claim 21 recites the limitation "said acid purification solution" in line 1. There is insufficient antecedent basis for this limitation in the claim. This limitation is interpreted as requiring said acid solution from said purification step.
Claim 22, lines 2-3, recite “said refinement treatment step of the saline solution containing lead and silver obtained from said saline leaching step is obtained by adding sodium sulphide”. It is unclear what is being obtained, as the claim appears to recite “said refinement treatment step…is obtained”. This limitation is interpreted as requiring said refinement treatment step of the saline solution containing lead and silver obtained from said saline leaching step comprises adding sodium sulphide to the saline solution to form insoluble PbS and AgS”.
Claim 22 recites the limitation "the saline leaching cycle" in line 5. There is insufficient antecedent basis for this limitation in the claim. This limitation is interpreted as requiring the saline solution is reused in the saline leaching step.
Claims 14-15 and 17-20 are indefinite as they depend from an indefinite base and fail to cure the deficiencies of the base claim.
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 13, 15-16, and 19-22 are rejected under 35 U.S.C. 103 as being unpatentable over Swain ("Recycling of Jarosite For Recovery of Valuable Metals and its Utilisation") in view of Imerito (WO 2022003747) and Rastas (US 4,355,005) and Starliper (US 3,676,107) and Antonescu (RO 113478) and Wilson (US 3,273,997).
Regarding Claim 13, Swain discloses a method for the treatment of jarosite by acid leaching jarosite with nitric acid and malic acid, adding sulfuric acid to the jarosite and placing in a furnace preheated to a required temperature, and roasting at 200-750°C (roasting meets the limitation of thermal treatment; pg. 38)). Swain further discloses jarosite samples were collected from the dump yard outside a zinc production plant (pg. 37), such that Swain meets the broad limitation of treating jarosite and other residues of the zinc production industry. Swain further discloses decomposition of the sulphates (jarosite) in the roasting step (decomposition of jarosite meets the limitation of demolition of the jarosite), producing ZnSO4, PbSO4, and Fe2(SO4)3 and water (pg. 41), wherein the Fe2(SO4)3 decomposes to Fe2O3 and SO3 at temperatures of 600-750°C, and obtaining a jarosite residue (residue meets the limitation of a solid fraction) comprising the sulfates and Fe2O3 (pg. 42). At a roasting temperature of 200-750°C, the evaporation of the imbibition water and the removal of OH- groups to give additional water in the gaseous phase is necessarily present in Swain. Swain further discloses jarosite contains silver, copper, aluminum, etc. (pg. 38-39, Table 4.1), such that the formation of silver and copper sulphates and other minor elements would be necessarily present in Swain after thermal treatment of the jarosite.
Regarding the roasting temperature in claim 13, it appears that roasting at 200-750°C taught by Swain overlaps the claimed range of a minimum of 250°C up to a maximum between 500°C and 700°C between such that the range taught by Swain obviates the claimed range. See MPEP 2144.05 (I).
Swain is silent to treating jarosite and other residues of the lead production industry.
Imerito discloses treatment of various types of residues generated by the zinc and lead production industry (pg. 1, lines 10-12). Imerito further discloses these residues still contain valuable elements (jarosite, goethite, KSS slag, Waelz slag, residues from thermal fuming of jarosite, goethite or KSS slag) (pg. 1, lines 13-19).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Imerito to treat residues from the zinc and lead production industries, because jarosite as well as other residues of the zinc and lead production industries contain valuable elements, as recognized by Imerito (pg. 1, lines 13-19).
Swain is further silent to roasting at an increasing temperature.
Swain, however, discloses iron sulfate decomposes to iron oxide at 600-750°C (pg. 42).
Rastas discloses a method for treatment of a jarosite by drying and heating (heating meets the limitation of thermal treatment at an increasing temperature) to so high a temperature that the zinc is converted to zinc sulfate and iron to hematite, and further treating the solid phase slurried in water in order to leach the sulfates and separate them from hematite (Abstract). Rastas further discloses the dried solid phase jarosite is directed to thermal treatment, comprising the thermal decomposition of jarosite in a temperature range of 400-500°C (400-500°C meets the limitation of a minimum of 250°C) and the sulfating reaction of zinc ferrite within a temperature range of 600-680°C, forming iron oxide (600-680°C meets the limitation of a maximum between 500°C and 700°C; Col. 7, lines 22-30).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Rastas to thermally treat the residues at an increasing temperature from a minimum of 250°C up to a maximum between 500°C and 700°C in order to decompose jarosite and form iron oxide, absent a showing of unexpected results or criticality, as both Swain and Rastas teach forming iron oxide at temperatures of 600°C and up to 680-750°C, such that the desired result of producing iron oxide occurs when the temperature is fixed and when the temperature is increasing, as long as the temperature reaches 600°C.
Swain is further silent to obtaining an aqueous solution of diluted sulfuric acid due to condensation of gaseous SO3 and H2O.
Starliper discloses a method for the treatment of iron-bearing wastes using sulphuric acid to form sulfates of iron, copper, lead, manganese and zinc followed by roasting at 550-700°C to convert iron sulphate to iron oxide and leaching with water to remove soluble copper, zinc, and manganese sulfates (Abstract). Starliper discloses SO3 is formed during roasting when iron sulfate is converted to iron oxide (Col. 2, lines 38-44). Starliper further discloses the SO3 is collected and combined with water to form dilute sulfuric acid which may be used to leach copper, zinc, and manganese sulfates (Col. 2, lines 45-47).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Starliper to obtain an aqueous solution of diluted sulfuric acid due to condensation of gaseous SO3 and H2O in order to leach copper, zinc, and manganese sulfates from the residue, as recognized by Starliper (Col. 2, lines 45-47).
Swain further discloses leaching the roasted jarosite residue with water to recover water soluble zinc as ZnSO4 in solution, and PbSO4 and Fe2O3 remain in the residue (pg. 42). Swain discloses jarosite contains silver and copper (pg. 38-39, Table 4.1), such that the presence of silver and copper sulphates in the solution and the presence of silver sulphate in the solid fraction would be necessarily present in Swain after leaching the jarosite residue with water.
Swain is silent to acid leaching after thermal treatment.
However, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain perform acid leaching after thermal treatment instead of acid leaching and adding H2SO4 before thermal treatment followed by leaching with water, because both produce a solid fraction comprising iron oxides and lead sulphate as well as a solution of zinc sulphate, and selection of any order of performing process steps is prima facie obvious in the absence of new or unexpected results (MPEP 2144.04 IV C).
Swain further discloses after water leaching, the jarosite residue was subjected to chloride leaching using NaCl (chloride leaching with NaCl meets the limitation of saline leaching), producing a leach liquor and a leach residue (pg. 38). Swain further discloses insoluble lead sulphate is converted to soluble lead chloride (pg. 43), such that a saline solution containing lead is obtained. Swain discloses jarosite contains silver (pg. 38-39, Table 4.1), such that the presence of silver in the saline solution would be necessarily present in Swain after leaching the jarosite residue with NaCl. Swain further discloses SiO2 (silica) present in the jarosite residue with Fe2O3 after brine (NaCl) leaching, and the Fe2O3 can find market as pigment (pg. 46).
Swain is silent to refining treatment of the saline solution containing lead and silver obtained from said saline leaching step.
Antonescu discloses a process for recovering lead from residues containing lead sulphate resulting in hydrometallurgical processes such as zinc hydrometallurgy by treating residues with a solution of NaCl, solubilizing the lead in the form of a complex ion solution, a solution which, after thickening and filtration, is separated and then Na2S (sodium sulphide) is added in solid form, after filtration and drying, resulting in PbS as a concentrate (reacting a saline solution of lead sulphate with sodium sulphide to form lead sulphide meets the limitation of refining treatment of the saline solution; pg. 1, "Description", par. 1-pg. 2, par. 1). The process of Antonescu is an economic and non-polluting process for the recovery of lead from PbSO4 residues (pg. 1, "Description, par. 5) and requires moderate consumption of energy, fuel, and reagents; the temperatures used are moderate, no pressure is used, and the flow is simple and short; and the flow can be completely automated (pg. 2, par. 2-4).
Similarly, regarding the silver in the residue, Imerito discloses the residual solid from leaching of the Waelz slag was leached with sodium chloride salt solution to obtain a saline solution containing silver, and adding sodium sulphide to the saline solution containing silver to recover silver as silver sulphide (reacting a saline solution of silver sulphate with sodium sulphide to form silver sulphide meets the limitation of refining treatment of the saline solution; pg. 14, lines 11-20).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Antonescu and Imerito to perform a refining treatment on the saline solution containing lead and silver obtained from said saline leaching step, because the process of Antonescu is an economic and non-polluting process for the recovery of lead from PbSO4 residues (pg. 1, "Description, par. 5) and requires moderate consumption of energy, fuel, and reagents; the temperatures used are moderate, no pressure is used, and the flow is simple and short; and the flow can be completely automated (pg. 2, par. 2-4).
Swain is further silent to purification of the silica of the solid fraction enriched in iron(III) oxide and containing silica obtained from said saline leaching step, by using an acid solution, to obtain solubilization of iron(III); separation of the solubilized iron(III) from the silica, which remains insolubilized; and precipitation of iron(III) to obtain iron oxide pigment.
Swain, however, discloses the Fe2O3 can be marketed as a pigment (pg. 46).
Wilson discloses a method for the treatment of waste slag wherein no external heat is required to effect maximum dissolution of metals, metal oxides, and metal silicates (Col. 1, line 69-Col. 2, line 7). Wilson further discloses ferric oxide and silica are separated by conversion of ferric oxide into an acid-soluble salt and conversion of silica into an acid-insoluble compound (Col. 1, lines 51-62), wherein the acid is sulfuric acid and the soluble iron is mechanically separated from the insoluble silica (Col. 2, lines 24-35). Wilson further discloses the silica-free solution may be treated to form ferric oxide (Col. 2, lines 38-47). Wilson further discloses selective separation, isolation, and recovery of ferric oxide in waste slag (Col. 3, lines 6-19).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Wilson to purify the silica of the solid fraction by washing the solid fraction with an acid solution to obtain solubilization of the iron (III), and separating the solubilized iron(III) from the silica; and precipitate the solubilized iron(III) to obtain iron oxide pigment in order to selectively separate, isolate, and recover ferric oxide in waste slag, as recognized by Wilson (Col. 3, lines 6-19), thereby obtaining a high purity iron oxide pigment.
Regarding Claim 15, Swain is silent to the acid leaching solution being a sulfuric acid solution at a concentration between 0.005 mol/L and 0.1 mol/L.
Imerito discloses a method for treatment of residues of the non-ferrous metallurgical industry, in particular Waelz slag and residues deriving from thermal fuming processes of jarosite, goethite, or KSS slag comprising thermal pre-treatment by the addition of ammonium sulphate and/or sulphuric acid and gradually increasing temperature from ambient temperature to a final temperature in the range of 200°C to 600°C, and adding water and mixing and correction of acidity up to a pH of 2-8 to obtain a precipitation of iron and separating the precipitate from the solution and purifying to product pigments based on iron oxide (Abstract). Imerito further discloses the solid resulting the heat treatment (pg. 7, lines 29-32) is subjected to acid leaching with 0.1 M (mol/L) sulfuric acid (pg. 14, lines 13-14).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Imerito to acid leach with a sulfuric acid solution at a concentration between 0.005 mol/L and 0.1 mol/L, because using sulfuric acid at a concentration in the claimed range is a process parameter well-known in the art of acid leaching residues of the zinc and lead production industry which have just been subjected to thermal treatment, as recognized by Imerito.
Regarding Claim 16, Swain discloses roasting at 200-750°C (pg. 38).
Regarding the thermal treatment temperature in claim 16, it appears that 200-750°C taught by Swain overlaps the claimed value of 700°C such that the range taught by Swain obviates the claimed value. See MPEP 2144.05 (I).
Swain is silent to forming and recycling diluted sulfuric acid solution such that said acid leaching solution comprises the diluted sulfuric acid solution.
Starliper discloses a method for the treatment of iron-bearing wastes using sulphuric acid to form sulfates of iron, copper, lead, manganese and zinc followed by roasting at 550-700°C to convert iron sulphate to iron oxide and leaching with water to remove soluble copper, zinc, and manganese sulfates (Abstract). Starliper discloses SO3 is formed during roasting when iron sulfate is converted to iron oxide (Col. 2, lines 38-44). Starliper further discloses the SO3 is collected and combined with water to form dilute sulfuric acid which may be used to leach copper, zinc, and manganese sulfates (Col. 2, lines 45-47), which meets the limitation of forming and recycling diluted sulfuric acid solution such that said acid leaching solution comprises the diluted sulfuric acid solution.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Starliper to forming and recycling diluted sulfuric acid solution such that said acid leaching solution comprises the diluted sulfuric acid solution in order to leach copper, zinc, and manganese sulfates from the residue, as recognized by Starliper (Col. 2, lines 45-47).
Regarding Claim 19, Swain discloses leaching the roasted jarosite residue with water. Swain further discloses after water leaching, the jarosite residue was subjected to chloride leaching to recover lead using NaCl, producing a leach liquor and a leach residue (pg. 38), such that Swain meets the limitation of, before being subjected to the saline leaching step, the solid fraction obtained from said acid leaching step is subjected to washing with water.
Regarding Claim 20, Swain discloses saline leaching with 220 g/L NaCl (220 g/L NaCl meets the limitation of between 20 g/L and 350 g/L) at 80°C for 60 min (60 min meets the limitation of between 10 and 120 minutes; pg. 38).
Swain is silent to the ratio between the amount of solid fraction to be leached and the NaCl solution being between 1/5 s/I and 1/30 s/l.
Antonescu discloses treating residues with NaCl at a concentration of 300 g/l, a solid/liquid weight ratio of 1/5 for 1 hour (solid/liquid weight ratio of 1/5 meets the limitation of between 1/5 s/l and 1/30 s/l; pg. 1, "Description", par. 6). Antonescu further discloses no pressure is used (pg. 2, par. 3), such that Antonescu meets the limitation of at atmospheric pressure.
Swain is further silent to saline leaching at a temperature ranging from 15°C and 60°C.
Imerito discloses saline leaching at 25-50°C (25-50°C meets the limitation of from 15°C to 60°C; pg. 9, lines 21-26).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Antonescu and Imerito to perform the saline leaching at a temperature ranging from 15°C and 60°C, at atmospheric pressure, for a time ranging between 10 and 120 minutes, with a concentration between 20 g/L and 350 g/L, the ratio between the amount of solid fraction to be leached and the NaCl solution being between 1/5 s/I and 1/30 s/1, because the claimed ranges are process-parameters well-known in the art of saline leaching jarosite residues to recover lead, as recognized by Antonescu and Imerito.
Regarding Claim 21, Swain is silent to purification of the silica of the solid fraction enriched in iron oxide and containing silica, wherein the acid is hydrochloric acid, sulfuric acid, nitric acid or mixtures thereof.
Wilson discloses a method for the treatment of waste slag wherein no external heat is required to effect maximum dissolution of metals, metal oxides, and metal silicates (Col. 1, line 69-Col. 2, line 7). Wilson further discloses ferric oxide and silica are separated by conversion of ferric oxide into an acid-soluble salt and conversion of silica into an acid-insoluble compound (Col. 1, lines 51-62), wherein the acid is sulfuric acid and the soluble iron is mechanically separated from the insoluble silica (Col. 2, lines 24-35). Wilson further discloses the silica-free solution may be treated to form ferric oxide (Col. 2, lines 38-47). Wilson further discloses selective separation, isolation, and recovery of ferric oxide in waste slag (Col. 3, lines 6-19).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Wilson to purify the silica of the solid fraction by washing the solid fraction with an acid solution of sulfuric acid to obtain solubilization of the iron (III), and separating the solubilized iron(III) from the silica; and precipitate the solubilized iron(III) to obtain iron oxide pigment in order to selectively separate, isolate, and recover ferric oxide in waste slag, as recognized by Wilson (Col. 3, lines 6-19), thereby obtaining a high purity iron oxide pigment.
Regarding Claim 22, Swain is silent to a refining treatment of the saline solution.
Antonescu discloses a process for recovering lead from residues containing lead sulphate resulting in hydrometallurgical processes such as zinc hydrometallurgy by treating residues with a solution of NaCl, solubilizing the lead in the form of a complex ion solution, a solution which, after thickening and filtration, is separated and then Na2S (sodium sulphide) is added in solid form, after filtration and drying, resulting in PbS as a concentrate (pg. 1, "Description", par. 1-pg. 2, par. 1). Antonescu further discloses after thickening and filtration, the separate NaCl solution is recycled in the process (NaCl solution is recycled in the process meets the limitation of the concentration of the saline solution is reused in the saline leaching cycle; pg. 2, par. 7). The process of Antonescu is an economic and non-polluting process for the recovery of lead from PbSO4 residues (pg. 1, "Description, par. 5) and requires moderate consumption of energy, fuel, and reagents; the temperatures used are moderate, no pressure is used, and the flow is simple and short; and the flow can be completely automated (pg. 2, par. 2-4).
Similarly, regarding the silver in the residue, Imerito discloses the residual solid from leaching of the Waelz slag was leached with sodium chloride salt solution to obtain a saline solution containing silver, and adding sodium sulphide to the saline solution containing silver to recover silver as silver sulphide (pg. 14, lines 11-20).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Antonescu and Imerito to perform a refining treatment on the saline solution containing lead and silver obtained from said saline leaching step, because the process of Antonescu is an economic and non-polluting process for the recovery of lead from PbSO4 residues (pg. 1, "Description, par. 5) and requires moderate consumption of energy, fuel, and reagents; the temperatures used are moderate, no pressure is used, and the flow is simple and short; and the flow can be completely automated (pg. 2, par. 2-4).
Claim 14 is rejected under 35 U.S.C. 103 as being unpatentable over Swain ("Recycling of Jarosite For Recovery of Valuable Metals and its Utilisation") in view of Imerito (WO 2022003747) and Rastas (US 4,355,005) and Starliper (US 3,676,107) and Antonescu (RO 113478) and Wilson (US 3,273,997) and Clevenger (US 3,524,802).
Regarding Claim 14, Swain, Imerito, Rastas, Starliper, Antonescu, and Wilson teach the elements as described above with regards to claim 13.
Swain discloses leaching with HNO3 and malic acid at 70°C for 4 hours, and leaching with tap water at 40°C for 60 min (pg. 38).
Swain is silent to acid leaching at a temperature between 15°C and 60°C, at atmospheric pressure, for a time ranging from 10 minutes to 120 minutes; the ratio between the amount of solid fraction and acid leaching solution ranging from 1/3 s/l to 1/30 s/l.
Imerito discloses acid leaching at 45°C (45°C meets the limitation of between 15°C and 60°C) for 1 hour (1 hour meets the limitation of 10 minutes to 120 minutes) at a liquid/solid ratio of 10 (pg. 14, lines 13-14), which is equivalent to 1/10 s/l (1/10 s/l meets the limitation of 1/3 s/l to 1/30 s/l), wherein a stirred reactor at atmospheric pressure is used for leaching (pg. 13, lines 6-7).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Imerito to perform acid leaching at a temperature between 15°C and 60°C, at atmospheric pressure, for a time ranging from 10 minutes to 120 minutes; the ratio between the amount of solid fraction and acid leaching solution ranging from 1/3 s/l to 1/30 s/l, because acid leaching within the claimed ranges is well-known in the art of treating various types of residues generated by the zinc and lead production industry, as recognized by Imerito.
Swain and Imerito are silent to acid leaching in a pH range between pH 1.5 and pH 3.5.
Clevenger discloses calcining ore to form ferric iron oxide followed by leaching the calcined concentrate with sulfuric acid at pH 2-4 to produce copper sulfate solution while precipitating the ferric salts of iron (Abstract). Clevenger further discloses an increase in pH greater than 4 would tend to precipitate the copper (Col. 1, line 69-Col. 2, line 3).
Regarding the pH in claim 14, it appears that 2-4 taught by Clevenger overlaps the claimed range of 1.5 to 3.5 such that the range taught by Clevenger obviates the claimed range. See MPEP 2144.05 (I).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Clevenger to acid leach in a pH range between pH 1.5 and pH 3.5, because an increase in pH greater than 4 would tend to precipitate the copper, as recognized by Clevenger (Col. 1, line 69-Col. 2, line 3), and Swain aims to precipitate only the iron oxide, iron sulphate, and lead sulphate while keeping other metal sulphate is in the solution (pg. 42). Additionally, acid leaching at a pH of 1.5 to 3.5 is well-known in the art of leaching iron oxide containing residues, as recognized by Clevenger.
Claim 17 is rejected under 35 U.S.C. 103 as being unpatentable over Swain ("Recycling of Jarosite For Recovery of Valuable Metals and its Utilisation") in view of Imerito (WO 2022003747) and Rastas (US 4,355,005) and Starliper (US 3,676,107) and Antonescu (RO 113478) and Wilson (US 3,273,997) and Dyvik (US 4,710,277).
Regarding Claim 17, Swain, Imerito, Rastas, Starliper, Antonescu, and Wilson teach the elements as described above with regards to claim 13.
Swain is silent to the acid flow obtained from said acid leaching step is returned to the zinc and lead production plant from which the residues come.
Dyvik discloses a method for manufacturing zinc from zinc-containing starting materials comprising leaching stages, purifying stages, and electrowinning stages for recovering metallic zinc from the leaching solution (Abstract), wherein the acid can be recycled to the leaching phase (Col. 4, lines 22-24) in order to leach out/extract the zinc present in the material (Col. 1, lines 16-18).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Dyvik to return the acid flow obtained from said acid leaching step to the zinc and lead production plant from which the residues come, because recycled acid solutions are useful in leaching/extracting zinc out of starting materials in the zinc production industry, as recognized by Dyvik (Col. 1, lines 16-18).
Claim 18 is rejected under 35 U.S.C. 103 as being unpatentable over Swain ("Recycling of Jarosite For Recovery of Valuable Metals and its Utilisation") in view of Imerito (WO 2022003747) and Rastas (US 4,355,005) and Starliper (US 3,676,107) and Antonescu (RO 113478) and Wilson (US 3,273,997) and Herbert (US 1,555,567) and Ke (CN 109971964).
Regarding Claim 18, Swain, Imerito, Rastas, Starliper, Antonescu, and Wilson teach the elements as described above with regards to claim 13.
Swain is silent to said acid flow obtained from said acid leaching step is treated with chlorides, at a temperature between 15°C and 60°C, at atmospheric pressure, for a time ranging from 5 to 60 minutes, to obtain the precipitation of the silver present in the acid flow.
Herbert discloses a method for treatment of concentrates, tailings, slimes, other metallurgical products, crude ores to recover zinc by roasting and leaching (pg. 1, lines 23-39). Herbert further discloses the sulphate of iron is converted to ferric oxide (pg. 3, lines 11-13). Herbert further discloses in the furnacing operation of the residues mixed with sulphuric acid, a certain amount of silver is rendered soluble and this silver is precipitated by chlorides contained in the leaching solution and if insufficient chlorides are present soluble chlorides will be added (pg. 3, lines 122-129).
Ke discloses a method for precipitating silver by adding sodium chloride (sodium chloride meets the limitation of treatment with chlorides) to a silver containing copper removal solution [0017] at atmospheric pressure, a temperature of 30-85°C, for 0.5-1.5 hours [0024].
Regarding the temperature in claim 18, it appears that 30-85°C taught by Ke overlaps the claimed range of between 15°C and 60°C such that the range taught by Ke obviates the claimed range. See MPEP 2144.05 (I).
Regarding the reaction time in claim 18, it appears that 0.5-1.5 hours taught by Ke overlaps the claimed range of 5 to 60 minutes such that the range taught by Ke obviates the claimed range. See MPEP 2144.05 (I).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Herbert and Ke to treat the acid flow obtained from said acid leaching step with chlorides, at a temperature between 15°C and 60°C, at atmospheric pressure, for a time ranging from 5 to 60 minutes, to obtain the precipitation of the silver present in the acid flow, and reacting at the claimed temperature, pressure, and time are process parameters well-known in the art of reacting silver sulphates in solution with silver chlorides in order to precipitate silver, as recognized by Ke.
Claims 13, 15-16, and 19-22 are rejected under 35 U.S.C. 103 as being unpatentable over Swain ("Recycling of Jarosite For Recovery of Valuable Metals and its Utilisation") in view of Kukurugya (US 2021/0292869; US PG Pub of IDS doc EP 3587599) and Imerito (WO 2022003747) and Rastas (US 4,355,005) and Starliper (US 3,676,107) and Antonescu (RO 113478) and Wilson (US 3,273,997).
An alternative rejection of claim 13 is provided in case Swain does not meet the limitation of treating other residues.
Alternatively, regarding Claim 13, Swain discloses a method for the treatment of jarosite by acid leaching jarosite with nitric acid and malic acid, adding sulfuric acid to the jarosite and placing in a furnace preheated to a required temperature, and roasting at 200-750°C (roasting meets the limitation of thermal treatment; pg. 38)). Swain further discloses jarosite samples were collected from the dump yard outside a zinc production plant (pg. 37) such that Swain meets the limitation of treating jarosite of the zinc production industry. Swain further discloses decomposition of the sulphates (jarosite) in the roasting step (decomposition of jarosite meets the limitation of demolition of the jarosite), producing ZnSO4, PbSO4, and Fe2(SO4)3 and water (pg. 41), wherein the Fe2(SO4)3 decomposes to Fe2O3 and SO3 at temperatures of 600-750°C, and obtaining a jarosite residue (residue meets the limitation of a solid fraction) comprising the sulfates and Fe2O3 (pg. 42). At a roasting temperature of 200-750°C, the evaporation of the imbibition water and the removal of OH- groups to give additional water in the gaseous phase is necessarily present in Swain. Swain further discloses jarosite contains silver, copper, aluminum, etc. (pg. 38-39, Table 4.1), such that the formation of silver and copper sulphates and other minor elements would be necessarily present in Swain after thermal treatment of the jarosite.
Regarding the roasting temperature in claim 13, it appears that roasting at 200-750°C taught by Swain overlaps the claimed range of a minimum of 250°C up to a maximum between 500°C and 700°C between such that the range taught by Swain obviates the claimed range. See MPEP 2144.05 (I).
Swain is silent to treating other residues of the zinc and lead production industry.
Kukurugya discloses mixing goethite and jarosite followed by roasting at 700°C, leaching, and saline leaching (Fig. 3) Kukurugya further discloses an enormous amount of jarosite and goethite waste is produced every year, making jarosite and goethite residues one of the biggest environmental problems in the zinc production industry [0002].
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Kukurugya to treat jarosite and other residues of the zinc production industry, because both jarosite and goethite residues are the biggest environmental problems in the zinc production industry, are recognized by Kukurugya [0002].
Imerito discloses treatment of various types of residues generated by the zinc and lead production industry (pg. 1, lines 10-12). Imerito further discloses these residues still contain valuable elements (jarosite, goethite, KSS slag, Waelz slag, residues from thermal fuming of jarosite, goethite or KSS slag) (pg. 1, lines 13-19).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Imerito to treat residues from the zinc and lead production industries, because jarosite as well as other residues of the zinc and lead production industries contain valuable elements, as recognized by Imerito (pg. 1, lines 13-19).
Swain is further silent to roasting at an increasing temperature.
Swain, however, discloses iron sulfate decomposes to iron oxide at 600-750°C (pg. 42).
Rastas discloses a method for treatment of a jarosite by drying and heating (heating meets the limitation of thermal treatment at an increasing temperature) to so high a temperature that the zinc is converted to zinc sulfate and iron to hematite, and further treating the solid phase slurried in water in order to leach the sulfates and separate them from hematite (Abstract). Rastas further discloses the dried solid phase jarosite is directed to thermal treatment, comprising the thermal decomposition of jarosite in a temperature range of 400-500°C (400-500°C meets the limitation of a minimum of 250°C) and the sulfating reaction of zinc ferrite within a temperature range of 600-680°C, forming iron oxide (600-680°C meets the limitation of a maximum between 500°C and 700°C; Col. 7, lines 22-30).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Rastas to thermally treat the residues at an increasing temperature from a minimum of 250°C up to a maximum between 500°C and 700°C in order to decompose jarosite and form iron oxide, absent a showing of unexpected results or criticality, as both Swain and Rastas teach forming iron oxide at temperatures of 600°C and up to 680-750°C, such that the desired result of producing iron oxide occurs when the temperature is fixed and when the temperature is increasing, as long as the temperature reaches 600°C.
Swain is further silent to obtaining an aqueous solution of diluted sulfuric acid due to condensation of gaseous SO3 and H2O.
Starliper discloses a method for the treatment of iron-bearing wastes using sulphuric acid to form sulfates of iron, copper, lead, manganese and zinc followed by roasting at 550-700°C to convert iron sulphate to iron oxide and leaching with water to remove soluble copper, zinc, and manganese sulfates (Abstract). Starliper discloses SO3 is formed during roasting when iron sulfate is converted to iron oxide (Col. 2, lines 38-44). Starliper further discloses the SO3 is collected and combined with water to form dilute sulfuric acid which may be used to leach copper, zinc, and manganese sulfates (Col. 2, lines 45-47).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Starliper to obtain an aqueous solution of diluted sulfuric acid due to condensation of gaseous SO3 and H2O in order to leach copper, zinc, and manganese sulfates from the residue, as recognized by Starliper (Col. 2, lines 45-47).
Swain further discloses leaching the roasted jarosite residue with water to recover water soluble zinc as ZnSO4 in solution, and PbSO4 and Fe2O3 remain in the residue (pg. 42). Swain discloses jarosite contains silver and copper (pg. 38-39, Table 4.1), such that the presence of silver and copper sulphates in the solution and the presence of silver sulphate in the solid fraction would be necessarily present in Swain after leaching the jarosite residue with water.
Swain is silent to acid leaching after thermal treatment.
However, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain perform acid leaching after thermal treatment instead of acid leaching and adding H2SO4 before thermal treatment followed by leaching with water, because both produce a solid fraction comprising iron oxides and lead sulphate as well as a solution of zinc sulphate, and selection of any order of performing process steps is prima facie obvious in the absence of new or unexpected results (MPEP 2144.04 IV C).
Swain further discloses after water leaching, the jarosite residue was subjected to chloride leaching using NaCl (chloride leaching with NaCl meets the limitation of saline leaching), producing a leach liquor and a leach residue (pg. 38). Swain further discloses insoluble lead sulphate is converted to soluble lead chloride (pg. 43), such that a saline solution containing lead is obtained. Swain discloses jarosite contains silver (pg. 38-39, Table 4.1), such that the presence of silver in the saline solution would be necessarily present in Swain after leaching the jarosite residue with NaCl. Swain further discloses SiO2 (silica) present in the jarosite residue with Fe2O3 after brine (NaCl) leaching, and the Fe2O3 can find market as pigment (pg. 46).
Swain is silent to refining treatment of the saline solution containing lead and silver obtained from said saline leaching step.
Antonescu discloses a process for recovering lead from residues containing lead sulphate resulting in hydrometallurgical processes such as zinc hydrometallurgy by treating residues with a solution of NaCl, solubilizing the lead in the form of a complex ion solution, a solution which, after thickening and filtration, is separated and then Na2S (sodium sulphide) is added in solid form, after filtration and drying, resulting in PbS as a concentrate (reacting a saline solution of lead sulphate with sodium sulphide to form lead sulphide meets the limitation of refining treatment of the saline solution; pg. 1, "Description", par. 1-pg. 2, par. 1). The process of Antonescu is an economic and non-polluting process for the recovery of lead from PbSO4 residues (pg. 1, "Description, par. 5) and requires moderate consumption of energy, fuel, and reagents; the temperatures used are moderate, no pressure is used, and the flow is simple and short; and the flow can be completely automated (pg. 2, par. 2-4).
Similarly, regarding the silver in the residue, Imerito discloses the residual solid from leaching of the Waelz slag was leached with sodium chloride salt solution to obtain a saline solution containing silver, and adding sodium sulphide to the saline solution containing silver to recover silver as silver sulphide (reacting a saline solution of silver sulphate with sodium sulphide to form silver sulphide meets the limitation of refining treatment of the saline solution; pg. 14, lines 11-20).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Antonescu and Imerito to perform a refining treatment on the saline solution containing lead and silver obtained from said saline leaching step, because the process of Antonescu is an economic and non-polluting process for the recovery of lead from PbSO4 residues (pg. 1, "Description, par. 5) and requires moderate consumption of energy, fuel, and reagents; the temperatures used are moderate, no pressure is used, and the flow is simple and short; and the flow can be completely automated (pg. 2, par. 2-4).
Swain is further silent to purification of the silica of the solid fraction enriched in iron(III) oxide and containing silica obtained from said saline leaching step, by using an acid solution, to obtain solubilization of iron(III); separation of the solubilized iron(III) from the silica, which remains insolubilized; and precipitation of iron(III) to obtain iron oxide pigment.
Swain, however, discloses the Fe2O3 can be marketed as a pigment (pg. 46).
Wilson discloses a method for the treatment of waste slag wherein no external heat is required to effect maximum dissolution of metals, metal oxides, and metal silicates (Col. 1, line 69-Col. 2, line 7). Wilson further discloses ferric oxide and silica are separated by conversion of ferric oxide into an acid-soluble salt and conversion of silica into an acid-insoluble compound (Col. 1, lines 51-62), wherein the acid is sulfuric acid and the soluble iron is mechanically separated from the insoluble silica (Col. 2, lines 24-35). Wilson further discloses the silica-free solution may be treated to form ferric oxide (Col. 2, lines 38-47). Wilson further discloses selective separation, isolation, and recovery of ferric oxide in waste slag (Col. 3, lines 6-19).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Wilson to purify the silica of the solid fraction by washing the solid fraction with an acid solution to obtain solubilization of the iron (III), and separating the solubilized iron(III) from the silica; and precipitate the solubilized iron(III) to obtain iron oxide pigment in order to selectively separate, isolate, and recover ferric oxide in waste slag, as recognized by Wilson (Col. 3, lines 6-19), thereby obtaining a high purity iron oxide pigment.
Regarding Claim 15, Swain is silent to the acid leaching solution being a sulfuric acid solution at a concentration between 0.005 mol/L and 0.1 mol/L.
Imerito discloses a method for treatment of residues of the non-ferrous metallurgical industry, in particular Waelz slag and residues deriving from thermal fuming processes of jarosite, goethite, or KSS slag comprising thermal pre-treatment by the addition of ammonium sulphate and/or sulphuric acid and gradually increasing temperature from ambient temperature to a final temperature in the range of 200°C to 600°C, and adding water and mixing and correction of acidity up to a pH of 2-8 to obtain a precipitation of iron and separating the precipitate from the solution and purifying to product pigments based on iron oxide (Abstract). Imerito further discloses the solid resulting the heat treatment (pg. 7, lines 29-32) is subjected to acid leaching with 0.1 M (mol/L) sulfuric acid (pg. 14, lines 13-14).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Imerito to acid leach with a sulfuric acid solution at a concentration between 0.005 mol/L and 0.1 mol/L, because using sulfuric acid at a concentration in the claimed range is a process parameter well-known in the art of acid leaching residues of the zinc and lead production industry which have just been subjected to thermal treatment, as recognized by Imerito.
Regarding Claim 16, Swain discloses roasting at 200-750°C (pg. 38).
Regarding the thermal treatment temperature in claim 16, it appears that 200-750°C taught by Swain overlaps the claimed value of 700°C such that the range taught by Swain obviates the claimed value. See MPEP 2144.05 (I).
Swain is silent to forming and recycling diluted sulfuric acid solution such that said acid leaching solution comprises the diluted sulfuric acid solution.
Starliper discloses a method for the treatment of iron-bearing wastes using sulphuric acid to form sulfates of iron, copper, lead, manganese and zinc followed by roasting at 550-700°C to convert iron sulphate to iron oxide and leaching with water to remove soluble copper, zinc, and manganese sulfates (Abstract). Starliper discloses SO3 is formed during roasting when iron sulfate is converted to iron oxide (Col. 2, lines 38-44). Starliper further discloses the SO3 is collected and combined with water to form dilute sulfuric acid which may be used to leach copper, zinc, and manganese sulfates (Col. 2, lines 45-47), which meets the limitation of forming and recycling diluted sulfuric acid solution such that said acid leaching solution comprises the diluted sulfuric acid solution.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Starliper to forming and recycling diluted sulfuric acid solution such that said acid leaching solution comprises the diluted sulfuric acid solution in order to leach copper, zinc, and manganese sulfates from the residue, as recognized by Starliper (Col. 2, lines 45-47).
Regarding Claim 19, Swain discloses leaching the roasted jarosite residue with water. Swain further discloses after water leaching, the jarosite residue was subjected to chloride leaching to recover lead using NaCl, producing a leach liquor and a leach residue (pg. 38), such that Swain meets the limitation of, before being subjected to the saline leaching step, the solid fraction obtained from said acid leaching step is subjected to washing with water.
Regarding Claim 20, Swain discloses saline leaching with 220 g/L NaCl (220 g/L NaCl meets the limitation of between 20 g/L and 350 g/L) at 80°C for 60 min (60 min meets the limitation of between 10 and 120 minutes; pg. 38).
Swain is silent to the ratio between the amount of solid fraction to be leached and the NaCl solution being between 1/5 s/I and 1/30 s/l.
Antonescu discloses treating residues with NaCl at a concentration of 300 g/l, a solid/liquid weight ratio of 1/5 for 1 hour (solid/liquid weight ratio of 1/5 meets the limitation of between 1/5 s/l and 1/30 s/l; pg. 1, "Description", par. 6). Antonescu further discloses no pressure is used (pg. 2, par. 3), such that Antonescu meets the limitation of at atmospheric pressure.
Swain is further silent to saline leaching at a temperature ranging from 15°C and 60°C.
Imerito discloses saline leaching at 25-50°C (25-50°C meets the limitation of from 15°C to 60°C; pg. 9, lines 21-26).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Antonescu and Imerito to perform the saline leaching at a temperature ranging from 15°C and 60°C, at atmospheric pressure, for a time ranging between 10 and 120 minutes, with a concentration between 20 g/L and 350 g/L, the ratio between the amount of solid fraction to be leached and the NaCl solution being between 1/5 s/I and 1/30 s/1, because the claimed ranges are process-parameters well-known in the art of saline leaching jarosite residues to recover lead, as recognized by Antonescu and Imerito.
Regarding Claim 21, Swain is silent to purification of the silica of the solid fraction enriched in iron oxide and containing silica, wherein the acid is hydrochloric acid, sulfuric acid, nitric acid or mixtures thereof.
Wilson discloses a method for the treatment of waste slag wherein no external heat is required to effect maximum dissolution of metals, metal oxides, and metal silicates (Col. 1, line 69-Col. 2, line 7). Wilson further discloses ferric oxide and silica are separated by conversion of ferric oxide into an acid-soluble salt and conversion of silica into an acid-insoluble compound (Col. 1, lines 51-62), wherein the acid is sulfuric acid and the soluble iron is mechanically separated from the insoluble silica (Col. 2, lines 24-35). Wilson further discloses the silica-free solution may be treated to form ferric oxide (Col. 2, lines 38-47). Wilson further discloses selective separation, isolation, and recovery of ferric oxide in waste slag (Col. 3, lines 6-19).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Wilson to purify the silica of the solid fraction by washing the solid fraction with an acid solution of sulfuric acid to obtain solubilization of the iron (III), and separating the solubilized iron(III) from the silica; and precipitate the solubilized iron(III) to obtain iron oxide pigment in order to selectively separate, isolate, and recover ferric oxide in waste slag, as recognized by Wilson (Col. 3, lines 6-19), thereby obtaining a high purity iron oxide pigment.
Regarding Claim 22, Swain is silent to a refining treatment of the saline solution.
Antonescu discloses a process for recovering lead from residues containing lead sulphate resulting in hydrometallurgical processes such as zinc hydrometallurgy by treating residues with a solution of NaCl, solubilizing the lead in the form of a complex ion solution, a solution which, after thickening and filtration, is separated and then Na2S (sodium sulphide) is added in solid form, after filtration and drying, resulting in PbS as a concentrate (pg. 1, "Description", par. 1-pg. 2, par. 1). Antonescu further discloses after thickening and filtration, the separate NaCl solution is recycled in the process (NaCl solution is recycled in the process meets the limitation of the concentration of the saline solution is reused in the saline leaching cycle; pg. 2, par. 7). The process of Antonescu is an economic and non-polluting process for the recovery of lead from PbSO4 residues (pg. 1, "Description, par. 5) and requires moderate consumption of energy, fuel, and reagents; the temperatures used are moderate, no pressure is used, and the flow is simple and short; and the flow can be completely automated (pg. 2, par. 2-4).
Similarly, regarding the silver in the residue, Imerito discloses the residual solid from leaching of the Waelz slag was leached with sodium chloride salt solution to obtain a saline solution containing silver, and adding sodium sulphide to the saline solution containing silver to recover silver as silver sulphide (pg. 14, lines 11-20).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Antonescu and Imerito to perform a refining treatment on the saline solution containing lead and silver obtained from said saline leaching step, because the process of Antonescu is an economic and non-polluting process for the recovery of lead from PbSO4 residues (pg. 1, "Description, par. 5) and requires moderate consumption of energy, fuel, and reagents; the temperatures used are moderate, no pressure is used, and the flow is simple and short; and the flow can be completely automated (pg. 2, par. 2-4).
Claim 14 is rejected under 35 U.S.C. 103 as being unpatentable over Swain ("Recycling of Jarosite For Recovery of Valuable Metals and its Utilisation") in view of Kukurugya (US 2021/0292869; US PG Pub of IDS doc EP 3587599) and Imerito (WO 2022003747) and Rastas (US 4,355,005) and Starliper (US 3,676,107) and Antonescu (RO 113478) and Wilson (US 3,273,997) and Clevenger (US 3,524,802).
Regarding Claim 14, Swain, Kukurugya, Imerito, Rastas, Starliper, Antonescu, and Wilson teach the elements as described above with regards to claim 13.
Swain discloses leaching with HNO3 and malic acid at 70°C for 4 hours, and leaching with tap water at 40°C for 60 min (pg. 38).
Swain is silent to acid leaching at a temperature between 15°C and 60°C, at atmospheric pressure, for a time ranging from 10 minutes to 120 minutes; the ratio between the amount of solid fraction and acid leaching solution ranging from 1/3 s/l to 1/30 s/l.
Imerito discloses acid leaching at 45°C (45°C meets the limitation of between 15°C and 60°C) for 1 hour (1 hour meets the limitation of 10 minutes to 120 minutes) at a liquid/solid ratio of 10 (pg. 14, lines 13-14), which is equivalent to 1/10 s/l (1/10 s/l meets the limitation of 1/3 s/l to 1/30 s/l), wherein a stirred reactor at atmospheric pressure is used for leaching (pg. 13, lines 6-7).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Imerito to perform acid leaching at a temperature between 15°C and 60°C, at atmospheric pressure, for a time ranging from 10 minutes to 120 minutes; the ratio between the amount of solid fraction and acid leaching solution ranging from 1/3 s/l to 1/30 s/l, because acid leaching within the claimed ranges is well-known in the art of treating various types of residues generated by the zinc and lead production industry, as recognized by Imerito.
Swain and Imerito are silent to acid leaching in a pH range between pH 1.5 and pH 3.5.
Clevenger discloses calcining ore to form ferric iron oxide followed by leaching the calcined concentrate with sulfuric acid at pH 2-4 to produce copper sulfate solution while precipitating the ferric salts of iron (Abstract). Clevenger further discloses an increase in pH greater than 4 would tend to precipitate the copper (Col. 1, line 69-Col. 2, line 3).
Regarding the pH in claim 14, it appears that 2-4 taught by Clevenger overlaps the claimed range of 1.5 to 3.5 such that the range taught by Clevenger obviates the claimed range. See MPEP 2144.05 (I).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Clevenger to acid leach in a pH range between pH 1.5 and pH 3.5, because an increase in pH greater than 4 would tend to precipitate the copper, as recognized by Clevenger (Col. 1, line 69-Col. 2, line 3), and Swain aims to precipitate only the iron oxide, iron sulphate, and lead sulphate while keeping other metal sulphate is in the solution (pg. 42). Additionally, acid leaching at a pH of 1.5 to 3.5 is well-known in the art of leaching iron oxide containing residues, as recognized by Clevenger.
Claim 17 is rejected under 35 U.S.C. 103 as being unpatentable over Swain ("Recycling of Jarosite For Recovery of Valuable Metals and its Utilisation") in view of Kukurugya (US 2021/0292869; US PG Pub of IDS doc EP 3587599) and Imerito (WO 2022003747) and Rastas (US 4,355,005) and Starliper (US 3,676,107) and Antonescu (RO 113478) and Wilson (US 3,273,997) and Dyvik (US 4,710,277).
Regarding Claim 17, Swain, Kukurugya, Imerito, Rastas, Starliper, Antonescu, and Wilson teach the elements as described above with regards to claim 13.
Swain is silent to the acid flow obtained from said acid leaching step is returned to the zinc and lead production plant from which the residues come.
Dyvik discloses a method for manufacturing zinc from zinc-containing starting materials comprising leaching stages, purifying stages, and electrowinning stages for recovering metallic zinc from the leaching solution (Abstract), wherein the acid can be recycled to the leaching phase (Col. 4, lines 22-24) in order to leach out/extract the zinc present in the material (Col. 1, lines 16-18).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Dyvik to return the acid flow obtained from said acid leaching step to the zinc and lead production plant from which the residues come, because recycled acid solutions are useful in leaching/extracting zinc out of starting materials in the zinc production industry, as recognized by Dyvik (Col. 1, lines 16-18).
Claim 18 is rejected under 35 U.S.C. 103 as being unpatentable over Swain ("Recycling of Jarosite For Recovery of Valuable Metals and its Utilisation") in view of Kukurugya (US 2021/0292869; US PG Pub of IDS doc EP 3587599) and Imerito (WO 2022003747) and Rastas (US 4,355,005) and Starliper (US 3,676,107) and Antonescu (RO 113478) and Wilson (US 3,273,997) and Herbert (US 1,555,567) and Ke (CN 109971964).
Regarding Claim 18, Swain, Kukurugya, Imerito, Rastas, Starliper, Antonescu, and Wilson teach the elements as described above with regards to claim 13.
Swain is silent to said acid flow obtained from said acid leaching step is treated with chlorides, at a temperature between 15°C and 60°C, at atmospheric pressure, for a time ranging from 5 to 60 minutes, to obtain the precipitation of the silver present in the acid flow.
Herbert discloses a method for treatment of concentrates, tailings, slimes, other metallurgical products, crude ores to recover zinc by roasting and leaching (pg. 1, lines 23-39). Herbert further discloses the sulphate of iron is converted to ferric oxide (pg. 3, lines 11-13). Herbert further discloses in the furnacing operation of the residues mixed with sulphuric acid, a certain amount of silver is rendered soluble and this silver is precipitated by chlorides contained in the leaching solution and if insufficient chlorides are present soluble chlorides will be added (pg. 3, lines 122-129).
Ke discloses a method for precipitating silver by adding sodium chloride (sodium chloride meets the limitation of treatment with chlorides) to a silver containing copper removal solution [0017] at atmospheric pressure, a temperature of 30-85°C, for 0.5-1.5 hours [0024].
Regarding the temperature in claim 18, it appears that 30-85°C taught by Ke overlaps the claimed range of between 15°C and 60°C such that the range taught by Ke obviates the claimed range. See MPEP 2144.05 (I).
Regarding the reaction time in claim 18, it appears that 0.5-1.5 hours taught by Ke overlaps the claimed range of 5 to 60 minutes such that the range taught by Ke obviates the claimed range. See MPEP 2144.05 (I).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Swain to incorporate the teachings of Herbert and Ke to treat the acid flow obtained from said acid leaching step with chlorides, at a temperature between 15°C and 60°C, at atmospheric pressure, for a time ranging from 5 to 60 minutes, to obtain the precipitation of the silver present in the acid flow, and reacting at the claimed temperature, pressure, and time are process parameters well-known in the art of reacting silver sulphates in solution with silver chlorides in order to precipitate silver, as recognized by Ke.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to SLONE ELZABETH SIMKINS whose telephone number is (571)272-3214. The examiner can normally be reached Monday - Friday 8:30AM-4:30PM.
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/S.E.S./Examiner, Art Unit 1735
/PAUL A WARTALOWICZ/Primary Examiner, Art Unit 1735