[go: up one dir, main page]

US20190062867A1 - Methods and systems for removing polar compounds from a metal-containing solution - Google Patents

Methods and systems for removing polar compounds from a metal-containing solution Download PDF

Info

Publication number
US20190062867A1
US20190062867A1 US15/768,762 US201615768762A US2019062867A1 US 20190062867 A1 US20190062867 A1 US 20190062867A1 US 201615768762 A US201615768762 A US 201615768762A US 2019062867 A1 US2019062867 A1 US 2019062867A1
Authority
US
United States
Prior art keywords
metal
organic solution
polar
solution
organic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US15/768,762
Other languages
English (en)
Inventor
Jack Thomas Bender
Noah Oliver
Nathan Clark Emmerich
Lauren Hight
Michael Virnig
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
BASF Corp
Original Assignee
BASF SE
BASF Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE, BASF Corp filed Critical BASF SE
Priority to US15/768,762 priority Critical patent/US20190062867A1/en
Assigned to BASF CORPORATION reassignment BASF CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: Bender, Jack Thomas, OLIVER, Noah, Emmerich, Nathan Clark, HIGHT, LAUREN MICHELE, VIRNIG, MICHAEL JOSEPH
Assigned to BASF CORPORATION reassignment BASF CORPORATION CORRECTIVE ASSIGNMENT TO CORRECT THE SIGNATURE PAGE OF ASSIGNEE INSIDE THE ASSIGNMENT DOCUMENT PREVIOUSLY RECORDED AT REEL: 046319 FRAME: 0811. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT . Assignors: Bender, Jack Thomas, OLIVER, Noah, Emmerich, Nathan Clark, HIGHT, LAUREN MICHELE, VIRNIG, MICHAEL JOSEPH
Assigned to BASF SE reassignment BASF SE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BASF CORPORATION
Assigned to BASF CORPORATION reassignment BASF CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: Bender, Jack Thomas, OLIVER, Noah, Emmerich, Nathan Clark, HIGHT, LAUREN MICHELE, VIRNIG, MICHAEL JOSEPH
Publication of US20190062867A1 publication Critical patent/US20190062867A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • C22B3/0017—
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/30—Oximes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the disclosure relates to methods and systems for removing polar compounds from a metal-containing solution.
  • the disclosure relates to removing hydrolysis byproducts and other polar compounds from a metal-loaded organic solution of a solvent extraction process.
  • Metals are commonly procured by a leaching process (e.g., heap/dump leaching, vat leaching, agitation leaching, bioleaching, autoclave leaching, etc.) in combination with solvent extraction, stripping and electrowinning processes.
  • a leaching process sulfuric acid or an ammoniacal leaching solution, for example, can be applied to an ore or scrap pile such that the metal (e.g., copper and copper alloys) is dissolved into the aqueous leaching solution.
  • the resulting metal-bearing aqueous solution (a.k.a. “pregnant leach solution” or “PLS”) is transferred to a solvent extraction plant, where it undergoes mass transfer of the metal from the PLS to an organic solution via contact of the two solutions under vigorous mixing.
  • the organic solution typically contains an extractant dissolved in a kerosene-like hydrocarbon diluent.
  • the metal e.g., copper as cupric ion
  • the metal transfers from the aqueous solution into the organic solution as an ion, and subsequently, the metal-depleted aqueous solution and the metal-loaded organic solution are separated.
  • the metal-depleted aqueous solution exits the solvent extraction process as raffinate, and the metal-loaded organic solution proceeds to a stripping process, where it undergoes a mass transfer of the metal to an electrolyte aqueous strip solution.
  • the metal is transferred to an electrolyte aqueous solution and protons are transferred to the organic solution.
  • the resulting metal-depleted organic solution returns to the solvent extraction process for re-use whereas the metal-rich aqueous strip solution is transferred to an electrowinning process.
  • the metal is electro-deposited from the metal-rich aqueous strip solution to make, for example, 99.99% pure elemental copper, which can be directly turned into commercial rod or wire at a furnace operation without further refining.
  • the temperature of the PLS can range from about 10° C. to about 30° C. Consequently, the temperatures during solvent extraction typically range from about 20° C. to about 25° C., and the temperatures during stripping can range from about 30° C. to about 35° C.
  • the temperature in the electrowinning cells is typically about 45° C.
  • the rate of hydrolysis can depend on a variety of operational factors including the organic acid concentration, the concentration of contaminants, the temperature of the PLS feed and strip solutions, and the presence of impurities in the PLS and/or the organic phase, all of which can promote hydrolysis.
  • hydrolysis byproducts can build up in the organic solution until the rate of formation equals the rate of loss in entrainment. Due to their polar nature, the hydrolysis byproducts can increase the surface activity of the organic phase resulting in operational problems such as increased phase disengagement times and increased crud formation.
  • the byproducts contribute to an increase in the viscosity and density of the organic solution resulting in increased operating problems with aqueous carryover from extraction to stripping due to aqueous entrainment in the loaded organic as well as losses of expensive organic phase due to entrainment in the aqueous raffinate exiting the extraction process.
  • Increased aqueous entrainment results in carryover of undesirable metals to the metal recovery process which causes contamination or additional operating problems.
  • density and viscosity of the organic phase increases with an increase in the extractant concentration, the problems due to increased hydrolysis can be more significant for plants operating at higher reagent concentrations.
  • One trend in the industry is to treat copper sulfide concentrates via hydrometallurgical processes rather than by smelting processes.
  • Such hydrometallurgical processes produce high temperature and/or high acid concentration leach solutions.
  • other processes located upstream of the solvent extraction process can also detrimentally affect the temperature, viscosity, density, surface activity, etc. of the PLS, resulting in an increase in hydrolysis of organic components.
  • the PLS entering the solvent extraction process can range in temperature from about 35° C. to 50° C., or even higher, as compared to 10° C. to 30° C. for a standard PLS solution.
  • the amount of organic component hydrolysis can approach a level of at least 100% of the extractant concentration in the organic solution. Such degradation can cause a significant increase in the viscosity and density of the organic solution, which in turn causes slower phase disengagement and higher entrainments. Moreover, the buildup of hydrolysis byproducts can result in degradation “run-away”, which can lead to massive organic solution losses, loss of metal production, and plant shutdowns.
  • the disclosure relates to a method for removing polar compounds from a solution, comprising: contacting an organic solution comprising non-polar metal complexes and polar compounds with a polar solid and adsorbing the polar compounds onto the polar solid.
  • the method can further include contacting the organic solution with a clay prior to contacting the organic solution with the polar solid.
  • the clay can be a material such as montmorillonite, smectite, heulandite, mordenite and combinations thereof.
  • the clay can be comprised in a tank, bed or column. In certain example aspects, the clay removes aqueous components from the organic solution to a concentration of about 3000 ppm or less of the aqueous components.
  • the method can further include settling the organic solution in a tank until an organic phase separates from an aqueous phase; and removing the aqueous phase and/or coalescing the organic solution with a coalescer or an electrostatic coalescer to separate an organic phase from an aqueous phase; and removing the aqueous phase.
  • the polar solid can be comprised in a low-pressure column or a pressure column.
  • the organic solution can be partially loaded with the non-polar complexes or the organic solution can be fully loaded with the non-polar complexes.
  • the organic solution can include a water immiscible solvent and a reagent such as a ketoxime, an aldoxime or combinations thereof.
  • the water immiscible solvent can be kerosene, benzene, toluene, xylene or combinations thereof.
  • the organic solution can include a phenolic oxime.
  • the concentration of the phenolic oxime in the organic solution can be about 0.018 M to about 1.1 M.
  • the phenolic oxime can be a ketoxime or an aldoxime at a concentration of about 0.018 M to about 0.9 M.
  • the phenolic oxime can be modified or non-modified.
  • the organic solution can include 3-methyl ketoxime, 3-methyl aldoxime, 2-hydroxy-5-nonylacetophenone, 5-nonylsalicylaldoxime, 5-dodecylsalicylaldoxime, or combinations thereof.
  • the organic solution can include a 3-methyl ketoxime and a 3-methyl aldoxime in a molar ratio of about 85:15 to about 25:75.
  • the non-polar complexes can include a metal such as copper, iron, nickel, zinc, metal alloys thereof or combinations thereof.
  • the polar compounds can include phenolic oxime compounds and oxime hydrolysis byproducts.
  • the oxime hydrolysis byproducts can include ketone compounds, aldehyde compounds or combinations thereof.
  • the method can include receiving the organic solution from a solvent extraction process.
  • the polar solid can include silica, alumina, activated carbon or combinations thereof.
  • the method can include regenerating the polar solid to remove adsorbed polar compounds by contacting the polar solid with a polar solvent.
  • the disclosure relates to a method of recovering metal from a metal-containing aqueous solution, comprising: contacting an aqueous solution comprising a metal with an organic solution to extract a portion of the metal into the organic solution and forming a metal-loaded organic solution comprising polar compounds and a metal-depleted aqueous solution; separating the metal-loaded organic solution from the metal-depleted aqueous solution; removing a portion of the polar compounds from the metal-loaded organic solution by contacting the metal-loaded organic solution with a polar solid to adsorb the polar compounds onto the polar solid and forming a treated metal organic solution; recovering metal values from the treated metal organic solution.
  • the method can include contacting the metal-loaded organic solution with a clay prior to the contacting with the polar solid.
  • the clay can include montmorillonite, smectite, heulandite, mordenite or combinations thereof.
  • the clay can be comprised in a tank, bed or column.
  • the clay can remove aqueous components from the organic solution to a concentration of about 3000 ppm or less of the aqueous components.
  • the method can further include receiving the aqueous solution from a process selected from a group consisting of heap leaching, hydrometallurgical leaching, high pressure leaching, oxidative leaching, biologically assisted leaching and combinations thereof.
  • the aqueous solution can be at a temperature of about 20° C. to about 60° C.
  • the metal values can include copper, iron, nickel, zinc, metal alloys thereof or combinations thereof.
  • the organic solution can include a water immiscible solvent and a reagent selected from a group consisting of a ketoxime, an aldoxime and combinations thereof.
  • the organic solution can include a water immiscible solvent and a reagent such as a ketoxime, an aldoxime or combinations thereof.
  • the water immiscible solvent can be kerosene, benzene, toluene, xylene and combinations thereof.
  • the organic solution can include a phenolic oxime.
  • the concentration of the phenolic oxime in the organic solution can be about 0.018 M to about 1.1 M.
  • the phenolic oxime can be a ketoxime or an aldoxime at a concentration of about 0.018 M to about 0.9 M.
  • the phenolic oxime can be modified or non-modified.
  • the organic solution can include 3-methyl ketoxime, 3-methyl aldoxime, 2-hydroxy-5-nonylacetophenone, 5-nonylsalicylaldoxime, 5-dodecylsalicylaldoxime, or combinations thereof.
  • the organic solution can include a 3-methyl ketoxime and a 3-methyl aldoxime in a molar ratio of about 85:15 to about 25:75.
  • the polar compounds can include phenolic oximes and oxime hydrolysis byproducts.
  • the oxime hydrolysis byproducts can include ketone compounds, aldehyde compounds or combinations thereof.
  • the step of contacting the aqueous solution with the organic solution and separating the metal-loaded organic solution from the metal-depleted aqueous solution can be via a solvent extraction process.
  • the step of removing a portion of the polar compounds from the metal-loaded organic solution comprises, passing a bleed stream from a main stream of the metal-loaded organic solution through the polar solid and passing the treated metal organic solution to the main stream.
  • the method can further include measuring one or more parameter of the metal-loaded organic solution and of the treated metal organic solution and adjusting a flow rate through the polar solid based on the measured parameter.
  • the one or more parameter is indicative of an amount of polar compounds in the metal-loaded organic solution and the treated metal organic solution.
  • the one or more parameter can be conductivity, viscosity, density, pH, temperature, pressure and combinations thereof. Adjusting the flow rate based on the one or more parameter can include adjusting the flow rate to achieve at least one of a target conductivity and target viscosity of the treated metal organic solution.
  • the method can include measuring the one or more parameter of the aqueous solution.
  • the polar solid can be comprised in a low-pressure column or a pressure column.
  • the polar solid can include a material such as silica, alumina, activated carbon or combinations thereof.
  • the method can further include regenerating the polar solid to remove adsorbed polar compounds by contacting the polar solid with a polar solvent.
  • FIG. 1 shows a system according to various example aspects of the disclosure.
  • FIG. 2 shows a system according to various example aspects of the disclosure.
  • FIG. 3 shows a system according to various example aspects of the disclosure.
  • FIGS. 4.1 and 4.2 show results of Example 1, hydrolysis products removed vs. amount of silica gel and oxime removed.
  • FIGS. 5.1 and 5.1 show results of Example 2, hydrolysis products removed vs. contacts with silica gel and oxime removed.
  • FIGS. 6.1, 6.2 and 6.3 show results of Example 4, silica gel re-use. HNA, NSA and NP bars are left to right.
  • FIG. 7.1 shows results of Example 5, silica gel loading capacity in a flash column. HNA, NSA, NP and CU bars are left to right.
  • FIG. 8.1 shows results of Example 6, silica gel large column comparison. Starting Organic, 40 g Silica Column and 4 th Pass (40 g total) bars are left to right.
  • FIGS. 9.1, 9.2 and 9.3 show results of Example 7, alumina use as a polar solid.
  • Starting Organic, Activated Alumina Organic, Basic Alumina Organic and Silica Organic bars are left to right in FIG. 9.1 .
  • Activated Alumina, Basic Alumina and Silica bars are left to right in FIGS. 9.2 and 9.3
  • Example aspects are described herein in the context of methods and systems for removing polar compounds from a metal-containing solution. Those of ordinary skill in the art will recognize that the following description is illustrative only and is not intended to be in any way limiting. Other aspects will readily suggest themselves to those of ordinary skill in the art having the benefit of this disclosure. Reference will now be made in detail to implementations of the example aspects as illustrated in the accompanying drawings. The same reference indicators will be used to the extent possible throughout the drawings and the following description to refer to the same or like items.
  • FIG. 1 shows an example of polar compounds removal system according to various example aspects of the disclosure.
  • a stream e.g., the total stream, a bleed stream, or a bypass
  • the system of FIG. 1 can operate as a batch, semi-continuous or continuous process as would be understood by those of ordinary skill in the art.
  • the metal-loaded organic solution can be from a solvent extraction process (not shown) or any other process that produces a metal-loaded organic solution stream.
  • the metal in the metal-loaded organic solution stream is a valuable metal including, but not limited to, copper, iron, nickel, zinc, metal alloys thereof and combinations thereof.
  • the organic solution can be any suitable solution for absorbing the metal from an aqueous solution (e.g., a pregnant leach solution or “PLS”) and contains an extracting reagent (or extractant).
  • PLS pregnant leach solution
  • the metal-loaded organic solution is at least partially loaded with the non-polar metal complexes.
  • the metal-loaded organic solution is at least 80% of its maximum loading capacity, or at least 90% of its maximum loading capacity, or at least 95 to about 100% of its maximum loading capacity.
  • a fully metal-loaded organic solution is at about 100% of capacity such that there is no free phenolic oxime capacity remaining.
  • the extracting reagent is an oxime, such as a phenolic oxime, which is dissolved in a water immiscible solvent including, but not limited to, kerosene, benzene, toluene, xylene and combinations thereof to form the organic solution.
  • Phenolic oximes can be phenolic ketoximes and phenolic aldoximes and can be non-modified or modified.
  • the organic solution can include a mixture of one or more ketoximes with one or more aldoximes at a molar ratio of about 10:90 to about 90:10 of the ketoximes to the aldoximes.
  • the organic solution can include 3-methyl ketoxime and a 3-methyl aldoxime in a molar ratio of about 85:15 to about 25:75.
  • Non-modified phenolic oximes include ketoxime- or aldoxime-based reagents in a hydrocarbon diluent such as LIX 84-I (2-hydroxy-5-nonylacetophenone oxime in a hydrocarbon diluent), LIX 860N-I (5-nonylsalicylaldoxime in a hydrocarbon diluent) or LIX 860-I (5-dodecylsalicylaldoxime in a hydrocarbon diluent).
  • Non-modified reagents also include mixtures of a ketoxime with an aldoxime in varying proportions such as LIX 984N (50:50 v/v LIX 84-I and LIX 860N-I), LIX 973N (30:70 LIX 84-I and LIX 860N-I).
  • Modified reagents include a thermodynamic modifier in the formulation to improve metal (e.g., copper) stripping.
  • Modified reagents are typically a mixture of an aldoxime such as the 5-nonylsalicylaldoxime with a thermodynamic modifier.
  • thermodynamic modifiers include, but are not limited to, highly branched chain aliphatic or aliphatic-aromatic C 10 to C 30 esters or C 14 to C 30 alcohols, ⁇ -hydroxy oximes (e.g., 5,8-diethyl-7-hydroxy dodecane-6-oxime or a mixture of 1-(4′-alkylphenyl)-1,2-propanedione dioximes), 2,2,4-trimethyl-1,3-pentanediol mono-isobutyrate, 2,2,4-trimethyl-1,3-pentanediol mono-benzoate, 2,2,4-trimethyl-1,3-pentanediol di-isobutyrate, 2,2,4-trimethyl-1,3-pentanediol di-benzoate, isobutyl heptyl ketone, nonanone, 2,6,8-trimethyl-4-nonanone, diundecyl ketone, 5,8-dieth
  • any metal-free extractant that is, excess extractant that did not form a complex with the metal, can also be polar.
  • the metal-loaded organic solution can contain non-polar complexes as well as polar compounds.
  • the concentration of total active phenolic oxime extractants (i.e., free oximes plus oximes incorporated into the metal complex) plus hydrolysis byproducts can range from about 0.075 M to about 1.3 M, or from about 0.15 M to about 1.3 M, or from about 0.22 M to about 1.0 M, or from about 0.22 M to about 0.9 M in the organic solution.
  • Removal of the polar compounds from the organic solution can prevent, among other things, buildup of hydrolysis byproducts, increases in viscosity and density of the organic solution and “run-away” degradation of the extractant.
  • the system includes a polar compounds removal column for removing polar compounds, such as hydrolysis byproducts (e.g., ketones, aldehydes), and other polar compounds (e.g., metal-free oximes, humic acids derived from the leach, chemicals such as flocculants, leaching aids, filter aids used in producing the PLS and contaminants such as cleaning detergents and lubricating oils) from the metal-loaded organic solution.
  • the column includes a polar solids material capable of adsorbing the polar compounds from the metal-loaded organic solution.
  • the polar solids material can include, but is not limited to, silica, alumina, activated carbon or combinations thereof.
  • the polar solids material is activated silica or activated alumina or a combination thereof.
  • the polar solids material should be selected based on its ability to adsorb the particular polar compounds in the metal-loaded organic solution, its compatibility with the metal-loaded organic solution (e.g., pH, chemical reactivity, etc.) and its coarseness to enable high flow rates.
  • the polar solids material can be activated silica, silica gel, silica beads, silica powder, silica slurry (e.g., silica powder suspended in hexane or other organic solvent) and combinations thereof.
  • the silica polar solids material can be a coarse silica, which may be relatively inexpensive as compared to other types of silica materials (e.g., silica gel) and which would enable high flow rates through the silica polar solids material in the column.
  • the polar compounds removal column can be any suitable device for enabling the metal-loaded organic solution (or optionally the dried metal-loaded organic solution) to come into sufficient contact with the polar solids material.
  • the polar compounds removal column is a low-pressure column operating at about 2 atm or less, a pressure column operating at above 2 atm, a flash column or a packed column.
  • the polar compounds removal column could also be one or more stirred tanks where the polar solids material is mixed with the metal-loaded organic solution and then the polar solids material, hydrolysis byproducts and other polar compounds are separated from the organic phase by filtration, decantation or any other process suitable for separating such components as known to those of ordinary skill in the art. Any combination of columns, stirred tanks, pumps and filters can be used to facilitate flow of the metal-loaded organic solution through the polar compounds removal circuit.
  • the metal-loaded organic solution can also contain small amounts of entrained aqueous. Removing the aqueous with an optional drying vessel as shown in FIG. 1 can enhance the polar components removal operation.
  • the drying vessel can remove aqueous from the metal-loaded organic solution to a concentration of about 3000 ppm or less of water, or about 1000 ppm or less of water, or about 300 ppm or less of water, or about 100 ppm or less of water, or about 50 ppm or less of water.
  • the drying vessel can be any suitable open or closed batch or semi-continuous tank that includes a material for removing (e.g., drying) aqueous components from the metal-loaded organic solution.
  • the drying vessel can be a stirred tank constructed of, for example, stainless steel or a fiber reinforced plastic.
  • the material within the optional drying vessel for removing aqueous components can include, but is not limited to, activated clay in an amount of about 0.5% wt/vol to about 10% wt/vol, or about 1% wt/vol to about 4% wt/vol.
  • Any clay used in the chemical industry for decolorization of vegetable or mineral oils can be used.
  • the clay can be a montmorillonite or smectite clay.
  • the clay can be an acid-activated montmorillonite clay such as, a Super Filtrol Grade 1 acid treated clay, Filtrol Grade 25 acid treated clay, Engelhard F20 clay, a heulandite clay, a mordenite clay and combinations thereof.
  • the clay material can have a layered silicate structure.
  • Montmorillonite and smectite clays carry negative surface charges (e.g., SiO 4 tetrahedra with lattice substitution) balanced by interlayer cations (e.g., Ca 2+ ).
  • the interlayer spacing can be about 10 ⁇ to about 15.5 ⁇ .
  • the interlayer spaces of these clays can be penetrated by cations, water and layers of polar organic liquids. Acid activation of the clay leaches out certain elements in the clay lattice, creating a large surface area of about 250 m 2 /g.
  • the system of FIG. 1 can optionally include two or more drying vessels such that one can maintain operation while the other vessels are serviced.
  • the material within the drying vessel can be replaced or regenerated from time to time as it begins to lose efficacy for removing aqueous components.
  • the system of FIG. 1 can optionally include two or more polar components removal columns so that while one is in operation, the other(s) can be serviced or regenerated.
  • the spent adsorbent in the polar components removal column(s) can be stripped of the hydrolysis byproducts by passing a polar organic solvent through the column and/or washing the recovered solids. The cleaned column and adsorbent is then ready for use.
  • a variety of instruments can be used to monitor the organic solution exiting the polar components removal vessel to determine if servicing or regeneration is required.
  • gas chromatography, thin layer chromatography, liquid chromatography and infrared spectroscopy can be used to monitor the organic solution exiting the polar components removal column for breakthrough of polar compounds.
  • the metal-loaded organic solution flows through a main line to, for example, a stripping and/or electrowinning process.
  • a bleed line can be used to divert a portion of the main line through the polar compounds removal system.
  • the entire main line (not just a bleed line) can be directed through the polar compounds removal system (not shown).
  • the metal-loaded organic solution can flow into an optional drying tank to remove water from (or dry) the metal-loaded organic solution. Removing the aqueous components from the metal-loaded organic solution can be desirable, particularly if such components have a tendency to degrade and/or affect the performance of the polar solids material in the polar compounds removal column.
  • the metal-loaded organic solution (or optionally the dried metal-loaded organic solution) flows into the polar compounds removal column where the polar compounds are adsorbed onto the polar solids material.
  • the treated metal-loaded organic solution exiting the column is depleted in polar compounds.
  • the metal-loaded organic solution entering the bleed line can contain polar compounds at an amount that is about 50% to about 100% higher than the amount of polar compounds in the treated metal organic solution exiting the polar compounds removal column.
  • a control system can be used to achieve a target polar compounds concentration in the treated metal organic solution.
  • the treated metal organic solution is then returned to the solvent extraction circuit.
  • the drying material e.g., clay
  • the metal-loaded organic solution can be mixed with the metal-loaded organic solution and then agitated for a period of time (e.g., about 1 min to about 24 hours, or about 1 min to about 12 hours, or about 1 min to about 6 hours, or about 1 min to about 3 hours, or about 1 min to about 90 min, or about 1 min to about 45 min).
  • a period of time e.g., about 1 min to about 24 hours, or about 1 min to about 12 hours, or about 1 min to about 6 hours, or about 1 min to about 3 hours, or about 1 min to about 90 min, or about 1 min to about 45 min.
  • short contact times e.g., about 3 hours or less, or about 1 hour or less, or about 30 min or less
  • the oximes begin to adsorb onto the clay and displace the surfactants lessening the effect of clay treatment.
  • the clay can be subsequently separated from the dried metal-loaded organic solution by sedimentation or pressure filtration.
  • the mixer can be turned off after about 5 minutes. Thereafter, the clay is allowed to settle and the dried organic solution is decanted out of the vessel. Finally, the wetted clay is drained out of the vessel.
  • the organic solution can be mixed for the entire filtration cycle of about 30 minutes to about 60 minutes in order to provide a mixed feed for the filter. According to various example aspects, the phase disengagement and extraction kinetics of the organic solution before and after clay treatment can be measured.
  • FIG. 2 shows a system according to various example aspects of the disclosure.
  • the system of FIG. 2 can include ore leaching, solvent extraction, stripping and electrowinning operations together with a polar compounds removal system.
  • the leaching operation can be of any type known to those of ordinary skill in the art including heap leaching, hydrometallurgical leaching, high pressure leaching, oxidative leaching, biologically assisted leaching and combinations thereof.
  • the leaching operation results in an aqueous pregnant leaching solution having a temperature of about 20° C. to about 60° C., or about 25° C. to about 55° C., or about 35° C. to about 50° C. and/or having a pH of about 0 to about 7, or about 0 to about 6, or about 0 to about 5.
  • the solvent extraction operation can be any suitable system known to those of ordinary skill in the art.
  • the stripping and electrowinning operations can be any suitable operations known to those of ordinary skill in the art.
  • a closed loop circuit can consist of extraction stages followed by stripping stages and, in some cases, secondary stages for washing and/or treating the organic solution.
  • the extractant species in the organic solution is typically selected based on the metal or metals in the PLS and can consist of various compounds from tertiary-amines to hydroxyl-oximes. However, in the context of copper recovery, the extractant can be a phenolic-oxime. According to various example aspects of the disclosure, the system as shown in FIG. 2 can be used for a variety of valuable metals (discussed above), and below are general chemical structures of extractants for copper.
  • the extraction and stripping equilibrium in copper solvent extraction is driven by copper concentration in extraction and acid concentration in stripping.
  • the phenolic hydroxyl proton is donated to the aqueous phase and copper(II) ion binds, non-covalently, to the hydroxyl oxygen in a 2:1 stoichiometry (two extractant molecules to one copper(II)).
  • the copper ion is stripped off by re-protonation of the phenolic hydroxyl group by the high acid concentration in the strip electrolyte solution. Such reactions are listed below.
  • a drawback in the implementation of heap-leaching/SX/EW is the low solubility of copper sulfide ores in acidic or basic aqueous solutions, making this technology historically applicable only to the harvesting of oxide ores.
  • the oxime functionality (—CR ⁇ N—OH) of the reactant undergoes acid catalyzed hydrolysis to produce the phenolic aldehyde/ketone (—CR ⁇ O). This is the primary route of chemical degradation of the active extraction reagent in copper SX operation.
  • the contact of the organic stream with the stripping electrolyte was the main contributor to hydrolysis because of the temperature (about 30° C. to about 40° C.) and acid concentration (about 150 g/L to about 200 g/L H 2 SO 4 ) in such electrolyte liquors.
  • the leach solution introduced into a copper SX plant can be an additional, if not major, contributor to hydrolysis in the copper SX circuit.
  • these hydrolysis products build up in the organic phase and have no extractive capacity. This is a major problem for these operations because this hydrolysis build up will increase the viscosity of the organic phase, which in turn leads to much higher entrainment losses and generation of solid-stabilized-emulsions (“CRUD”).
  • CRUD solid-stabilized-emulsions
  • Selective removal of these hydrolysis byproducts in, for example, a copper SX operation can be accomplished by solid phase extraction using a polar stationary phase (i.e., a polar solids material).
  • a polar stationary phase i.e., a polar solids material
  • unbound (i.e., stripped of metal or metal-free) oxime is polar enough to bind to the polar solids material, while the metal (e.g., copper) complex (e.g., oxime2-Cu) is non-polar.
  • the metal-loaded organic solution can be diverted from the SX process and into a polar compounds removal system as described above with respect to FIG. 1 .
  • the metal-loaded organic solution can be optionally passed through a drying vessel and then through the polar components removal column leaving behind the polar compounds, including any unloaded oxime and any hydrolysis product.
  • This polar solid bed can then be stripped with a polar solvent and the hydrolysis byproducts, plus any unloaded oxime bound to the polar solid, can be collected.
  • This mixture can then be regenerated back into the oxime by distilling away the solvent used to strip off the hydrolysis byproducts followed by oximation, and then reintroduced into the SX plant as fresh oxime extraction reagent.
  • a control system can be used to control the removal rate of polar compounds from the system as shown in FIG. 3 .
  • a controller for example, a programmable logic controller (“PLC”), can be connected to one or more sensors for measuring parameters of the fluid in the system and can also be connected to a device for controlling flow rate through the polar components removal system.
  • the one or more sensors can measure conductivity, viscosity, density, pH, flow rate, temperature and any other parameter suitable for controlling the removal rate of polar compounds from the metal-loaded organic solution (or the dried metal-loaded organic solution).
  • the device for controlling flow rate can be any suitable device known to those of ordinary skill in the art.
  • the device can be a positive displacement pump, a centrifugal pump, a peristaltic pump, a rotameter among others.
  • a method for removing polar compounds from a solution comprising contacting an organic solution comprising non-polar metal complexes and polar compounds with a polar solid and adsorbing the polar compounds onto the polar solid.
  • the clay comprises a material selected from a group consisting of montmorillonite, smectite, heulandite, mordenite and combinations thereof.
  • the method of embodiments 2 or 3 wherein the clay is comprised in a tank, bed or column.
  • the organic solution comprises a phenolic oxime.
  • the organic solution comprises a phenolic oxime in the organic solution is about 0.018 M to about 1.1 M.
  • the organic solution comprises a ketoxime or an aldoxime at a concentration of about 0.018 M to about 0.9 M.
  • E16 The method of any of the preceding embodiments, wherein the organic solution comprises a modified or non-modified phenolic oxime. E17.
  • the organic solution comprises 3-methyl ketoxime, 3-methyl aldoxime, 2-hydroxy-5-nonylacetophenone, 5-nonylsalicylaldoxime, 5-dodecylsalicylaldoxime, or combinations thereof.
  • the organic solution comprises a 3-methyl ketoxime and a 3-methyl aldoxime in a molar ratio of about 85:15 to about 25:75.
  • the non-polar complexes comprise a metal selected from a group consisting of copper, iron, nickel, zinc, metal alloys thereof and combinations thereof.
  • the organic solution comprises polar compounds comprising phenolic oxime compounds and oxime hydrolysis byproducts.
  • the organic solution comprises oxime hydrolysis byproducts comprising ketone compounds, aldehyde compounds or combinations thereof.
  • the polar solid comprises a material selected from the group consisting of silica, alumina, activated carbon and combinations thereof.
  • the polar solid comprises silica.
  • a method of recovering metal from a metal-containing aqueous solution comprising: contacting an aqueous solution comprising a metal with an organic solution to extract a portion of the metal into the organic solution and forming a metal-loaded organic solution comprising polar compounds and a metal-depleted aqueous solution; separating the metal-loaded organic solution from the metal-depleted aqueous solution; removing a portion of the polar compounds from the metal-loaded organic solution by contacting the metal-loaded organic solution with a polar solid to adsorb the polar compounds onto the polar solid and forming a treated metal organic solution; recovering metal values from the treated metal organic solution.
  • removing further comprises: contacting the metal-loaded organic solution with a clay prior to the contacting with the polar solid.
  • the clay comprises a material selected from a group consisting of montmorillonite, smectite, heulandite, mordenite and combinations thereof.
  • the method of any of the preceding embodiments further comprising: receiving the aqueous solution from a process selected from a group consisting of heap leaching, hydrometallurgical leaching, high pressure leaching, oxidative leaching, biologically assisted leaching and combinations thereof.
  • a process selected from a group consisting of heap leaching, hydrometallurgical leaching, high pressure leaching, oxidative leaching, biologically assisted leaching and combinations thereof.
  • the aqueous solution is at a temperature of about 20° C. to about 60° C.
  • the metal values are selected from a group consisting of copper, iron, nickel, zinc, metal alloys thereof and combinations thereof.
  • the organic solution comprises a water immiscible solvent and a reagent selected from a group consisting of a ketoxime, an aldoxime and combinations thereof.
  • the water immiscible solvent is selected from a group consisting of kerosene, benzene, toluene, xylene and combinations thereof.
  • the organic solution comprises a phenolic oxime.
  • the organic solution comprises a phenolic oxime at a concentration from about 0.018 M to about 1.1 M. E13.
  • the organic solution comprises a phenolic ketoxime or an aldoxime at a concentration of about 0.018 M to about 0.9 M.
  • the organic solution comprises a phenolic oxime which is modified or non-modified.
  • the organic solution comprises 3-methyl ketoxime, 3-methyl aldoxime, 2-hydroxy-5-nonylacetophenone, 5-nonylsalicylaldoxime, 5-dodecylsalicylaldoxime, or combinations thereof.
  • the organic solution comprises a 3-methyl ketoxime and a 3-methyl aldoxime in a molar ratio of about 85:15 to about 25:75.
  • the polar compounds comprise phenolic oximes and oxime hydrolysis byproducts.
  • the polar compounds comprise oxime hydrolysis byproducts comprising ketone compounds, aldehyde compounds and combinations thereof.
  • contacting the aqueous solution with the organic solution and separating the metal-loaded organic solution from the metal-depleted aqueous solution comprises a solvent extraction process.
  • removing a portion of the polar compounds from the metal-loaded organic solution comprises passing a bleed stream from a main stream of the metal-loaded organic solution through the polar solid and passing the treated metal organic solution to the main stream.
  • removing a portion of the polar compounds from the metal-loaded organic solution comprises passing a bleed stream from a main stream of the metal-loaded organic solution through the polar solid and passing the treated metal organic solution to the main stream.
  • E21. The method of any of the preceding embodiments, further comprising: measuring one or more parameters of the metal-loaded organic solution and of the treated metal organic solution and adjusting a flow rate through the polar solid based on the measured parameter.
  • the one or more parameters are indicative of an amount of polar compounds in the metal-loaded organic solution and the treated metal organic solution.
  • the polar solid comprises a material selected from a group consisting of silica, alumina, activated carbon and combinations thereof.
  • the polar solid comprises silica.
  • E29. The method of any of the preceding embodiments, further comprising: regenerating the polar solid to remove adsorbed polar compounds by contacting the polar solid with a polar solvent.
  • a synthetic organic solution of about 0.15 mol/L (M) C 9 ketoxime (Ket) and 0.18 M C 9 aldoxime (Ald) was prepared and used for all three experiments.
  • M C 9 ketoxime
  • Ald 0.18 M C 9 aldoxime
  • HNA 0.2 M C 9 ketone
  • NSA 0.2 M C 9 aldehyde
  • the solution was made up in a 2 ⁇ 2 L volumetric flasks and diluted in Shellsol D-70 kerosene diluent. The total 4 liters was mixed together. 800 ml of the solution was removed and set aside while the rest of the solution was max loaded with copper according to standard BASF quality control procedures.
  • FIG. 4.1 shows that increased amounts of hydrolysis products are removed from the organic, with increased amounts of silica gel.
  • FIG. 4.2 shows a loss of oxime with 40% silica gel that may suggest the slight loss of components other than unloaded oxime.
  • Table 1.1 it can be seen that there is a significant removal of nonyl phenol (NP) from the organic (about 76% loss).
  • NP nonyl phenol
  • the organic was then contacted again with fresh 5% w/v silica gel and filtered again (organic volume was reduced due to loss in filtering after each contact, thus the amount of silica gel was adjusted accordingly to maintain 5% w/v). This was done a total of nine (9) times. After each contact a sample of organic was collected and analyzed for components. After each filtering, the recovered silica gel was washed with 100 ml of kerosene diluent and stripped with 50:50 hexane:ethylacetate. The stripped material was dried, weighed, and analyzed by GC for relative amounts of components. Results are found in Table 2.1 and FIGS. 5.1 and 5.2 .
  • Example 1 As in Example 1, it can be seen that hydrolysis products are removed (about 50%). Oxime is removed to roughly the same degree as in Example 1 (about 30% loss of ketoxime to remove about 50% hydrolysis product). Note the drop in contact #5 in FIG. 5.2 is most likely due to a compromised sample). The loss of NP is also large (85%).
  • a flash column was set up using pressure glassware.
  • a pressure manifold was made using a valve, an adjustable pressure relief valve and a pressure gauge.
  • a 250 mL pressure equalizing addition funnel was attached to a small column with about 30 mL volume.
  • the manifold was attached to the compressed air source then to the top of the flash column assembly using flexible tubing. The entire assembly was supported in a hood and the column ran pressurized at 5 psi.
  • the column was packed with glass wool, a weighed amount of polar solid and glass wool.
  • the organic used was 0.075 mol/L (M) C 9 ketoxime (Ket) and 0.09 M C 9 aldoxime (Ald) in Shellsol D70 max loaded with copper according to standard BASF quality control procedures.
  • the organic was spiked with 0.1 M C 9 ketone (HNA) and 0.1 M C 9 aldehyde (NSA). Each test passed 500 ml of the organic through the column collecting fractions at approximately 100 mL. After the column had run dry and the solution had stopped dripping out of the column 100 mL of hexane was passed through the column.
  • Example 2 The purpose of this experiment was to test the effectiveness of stripping the silica gel and any subsequent reduction in the silica gel's loading capacity.
  • This experiment followed Example 2 exactly, using the same method and starting organic. This time the organic was re-passed through the same silica gel column after stripping the column without replacing the silica gel. This was repeated so that the organic was passed through the column for a total of three times. After stripping the column, using the same silica gel, a fresh batch of organic was passed through the column, the same batch of organic was used up, so for this pass a new batch of organic was made up which had very similar levels of degradation. Results are found in Table 4.1 and FIGS. 6.1, 6.2 and 6.3 .
  • a flash column was set up and loaded with 10 g of silica gel. Then fresh organic (500 ml) was passed through the column. The silica gel was subsequently replaced with another 10 g of silica gel and the same organic was passed through the column again. This was repeated for eight passes through the column with fresh silica gel but the same 500 ml of organic each time. Samples of the organic were taken after each pass and analyzed by GC. Results are found in FIG. 7.1 .
  • Example 7 Allumina Use as a Polar Solid
  • the results include the silica gel results from Example 3 for comparison. It can be seen that using the same weights of activated (heat) alumina and basic alumina that both behaved similarly. Basic alumina removed slightly more HNA and NSA, but less NP in the organic. The activated alumina passed more degrandants into the hexane especially NP. The acetone wash was similar for both. Silica gel removed the degradants at a much higher rate specifically with NP which was removed at a higher concentration and stripped with the acetone.
  • Each column using various polar solids can be compared by looking at how much degradant is removed from each organic based on the starting weight of each degradant in the 500 ml portion put through the column and how much remains in the organic after being passed through the column. From this, a total weigh of degradants removed can be calculated and then the capacity of the polar solid can be determined.
  • silica gel has by far the highest ability to load degradants and then be stripped by acetone. Additionally, silica gel had the lowest amount of lost degradants.
  • Table 8.4 shows that the oxime loss was 8.2% when the reagent was loaded only 80% of the max load. The losses drop to 3.6% when the reagent is loaded completely. When a wash of the silica gel was used before stripping only 0.3% of the oxime was lost.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Manufacture And Refinement Of Metals (AREA)
US15/768,762 2015-10-19 2016-10-18 Methods and systems for removing polar compounds from a metal-containing solution Abandoned US20190062867A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/768,762 US20190062867A1 (en) 2015-10-19 2016-10-18 Methods and systems for removing polar compounds from a metal-containing solution

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201562243474P 2015-10-19 2015-10-19
PCT/US2016/057506 WO2017070102A1 (en) 2015-10-19 2016-10-18 Methods and systems for removing polar compounds from a metal-containing solution
US15/768,762 US20190062867A1 (en) 2015-10-19 2016-10-18 Methods and systems for removing polar compounds from a metal-containing solution

Publications (1)

Publication Number Publication Date
US20190062867A1 true US20190062867A1 (en) 2019-02-28

Family

ID=57219031

Family Applications (1)

Application Number Title Priority Date Filing Date
US15/768,762 Abandoned US20190062867A1 (en) 2015-10-19 2016-10-18 Methods and systems for removing polar compounds from a metal-containing solution

Country Status (11)

Country Link
US (1) US20190062867A1 (ru)
EP (1) EP3365471A1 (ru)
CN (1) CN108463566A (ru)
AU (1) AU2016341136A1 (ru)
BR (1) BR112018007715A2 (ru)
CA (1) CA3002534A1 (ru)
CL (1) CL2018001012A1 (ru)
MX (1) MX2018004865A (ru)
PE (1) PE20181150A1 (ru)
RU (1) RU2018118338A (ru)
WO (1) WO2017070102A1 (ru)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020077028A1 (en) * 2018-10-12 2020-04-16 Basf Se Leaching aids and methods of using leaching aids

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020077026A1 (en) * 2018-10-12 2020-04-16 Basf Se Reagent compositions for metal solvent extraction and methods of preparation and use thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AUPS074902A0 (en) * 2002-02-25 2002-03-21 Umatilla Resources Pty. Ltd. Device and process for solvent extraction

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020077028A1 (en) * 2018-10-12 2020-04-16 Basf Se Leaching aids and methods of using leaching aids

Also Published As

Publication number Publication date
PE20181150A1 (es) 2018-07-17
EP3365471A1 (en) 2018-08-29
BR112018007715A2 (pt) 2019-01-15
WO2017070102A8 (en) 2018-05-03
RU2018118338A (ru) 2019-11-22
WO2017070102A1 (en) 2017-04-27
CL2018001012A1 (es) 2018-09-04
CA3002534A1 (en) 2017-04-27
CN108463566A (zh) 2018-08-28
AU2016341136A1 (en) 2018-05-10
MX2018004865A (es) 2018-08-01

Similar Documents

Publication Publication Date Title
US20210187492A1 (en) Composite Extractant-Enhanced Polymer Resin, Method of Making the Same, and Its Usage for Extraction of Valuable Metal(s)
Artzer et al. Removal of Antimony and Bismuth from Copper Electrorefining Electrolyte: Part I—A Review: Artzer, Moats, and Bender
WO2001029276A1 (en) Resin-in-pulp method for recovery of nickel and cobalt from oxidic ore leach slurry
JP6852599B2 (ja) スカンジウムの精製方法
WO2018217083A1 (en) Process for metal recovery by ammonia leaching and solvent extraction with gas desorption and absorption
FI97395B (fi) Nikkelin uutosprosessi
CA2400673A1 (en) Process for recovery of metals from metal-containing ores
CN116445750A (zh) 从酸性浆料或酸性溶液中选择性回收稀土金属
JP5375631B2 (ja) 有機相からの金属元素の除去方法
US20190062867A1 (en) Methods and systems for removing polar compounds from a metal-containing solution
JP6922478B2 (ja) スカンジウムの精製方法
WO2013086606A1 (en) Separation of iron from value metals in leaching of laterite ores
RU2339713C1 (ru) Способ экстракции меди из сернокислых растворов
WO2001023063A1 (en) Process for extracting copper values from copper-containing ores
JP7419514B2 (ja) 亜鉛保有原料から亜鉛を回収するための改良された方法
CN107923055B (zh) 从精炼厂电解质溶液中减少杂质金属的方法和系统
JP6988435B2 (ja) 有機相に含まれる水相の液滴を除去する方法
WO2013146472A1 (ja) 希土類元素回収方法
CN106068336A (zh) 用于控制冶金过程期间的杂质金属浓度的方法和系统
CN114959299B (zh) 一种从含钴氧化铜矿萃铜余液中回收钴的方法
EP4092147A1 (en) Separation of arsenic from antimony and bismuth in an eluate
JP7127388B2 (ja) 低Ｎｉ濃度塩化コバルト水溶液の製造方法
Artzer Removal of antimony and bismuth from copper electrorefining electrolyte by two proprietary solvent extraction extractants
AU2012314172A1 (en) Process for treating an effluent that contains metals
WO2016081976A1 (en) Method for improving the recovery of uranium and base metals from heap leach pregnant liquor

Legal Events

Date Code Title Description
AS Assignment

Owner name: BASF CORPORATION, NEW JERSEY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BENDER, JACK THOMAS;OLIVER, NOAH;VIRNIG, MICHAEL JOSEPH;AND OTHERS;SIGNING DATES FROM 20180614 TO 20180630;REEL/FRAME:046319/0811

AS Assignment

Owner name: BASF CORPORATION, NEW JERSEY

Free format text: CORRECTIVE ASSIGNMENT TO CORRECT THE SIGNATURE PAGE OF ASSIGNEE INSIDE THE ASSIGNMENT DOCUMENT PREVIOUSLY RECORDED AT REEL: 046319 FRAME: 0811. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT;ASSIGNORS:BENDER, JACK THOMAS;OLIVER, NOAH;VIRNIG, MICHAEL JOSEPH;AND OTHERS;SIGNING DATES FROM 20180614 TO 20180630;REEL/FRAME:046596/0409

AS Assignment

Owner name: BASF SE, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BASF CORPORATION;REEL/FRAME:046439/0060

Effective date: 20180612

AS Assignment

Owner name: BASF CORPORATION, NEW JERSEY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BENDER, JACK THOMAS;OLIVER, NOAH;VIRNIG, MICHAEL JOSEPH;AND OTHERS;SIGNING DATES FROM 20180614 TO 20180630;REEL/FRAME:046532/0870

STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION