WO2011146620A1 - Stripping agent and method of use - Google Patents

Stripping agent and method of use Download PDF

Info

Publication number
WO2011146620A1
WO2011146620A1 PCT/US2011/037002 US2011037002W WO2011146620A1 WO 2011146620 A1 WO2011146620 A1 WO 2011146620A1 US 2011037002 W US2011037002 W US 2011037002W WO 2011146620 A1 WO2011146620 A1 WO 2011146620A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
mercury
aqueous solution
acidic aqueous
carbon substrate
Prior art date
Application number
PCT/US2011/037002
Other languages
French (fr)
Inventor
Maurice C. Fuerstenau
Carl C. Nesbitt
Thomas Joseph Seal
Original Assignee
Board Of Regents Of The Nevada System Of Higher Education, On Behalf Of The University Of Nevada, Reno
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 Board Of Regents Of The Nevada System Of Higher Education, On Behalf Of The University Of Nevada, Reno filed Critical Board Of Regents Of The Nevada System Of Higher Education, On Behalf Of The University Of Nevada, Reno
Priority to US13/698,492 priority Critical patent/US20140147354A1/en
Publication of WO2011146620A1 publication Critical patent/WO2011146620A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00Obtaining noble metals
    • C22B11/04Obtaining noble metals by wet processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/34Regenerating or reactivating
    • B01J20/3416Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/34Regenerating or reactivating
    • B01J20/345Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3475Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C22B3/24Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Definitions

  • the present disclosure relates to stripping agents and their uses, including removing mercury and inorganic sealants from activated carbon used in mining or metal recovery operations.
  • Precious metal production has evolved over the past several decades, and is based principally on the ability to dissolve precious metals using a lixiviant, such as a basic aqueous cyanide solution, to form soluble metallocyanide complexes.
  • a lixiviant such as a basic aqueous cyanide solution
  • Gold and silver are most notably recovered, but often the precious metal ores contain other metallic minerals, which are also dissolved in the basic cyanide medium.
  • the processes to recover the gold and silver cyanide complexes vary with the type of ore being treated, and the quantity of other metals in the solution.
  • One of the simplest (and most widespread) techniques is to adsorb the metallocyanide complexes onto activated carbon substrates, such as an activated carbon derived from coconut shells. The carbon continues to adsorb the metallocyanide complexes until it reaches its ultimate loading, afterwards an elution process can be used to recover the precious metals in a more concentrated solution.
  • CIP carbon in pulp
  • CIL carbon in leach
  • CIC carbon in column
  • Elution (stripping) of the gold and silver cyanide complexes from the activated carbon for recovery of these precious metals may be accomplished by treating the activated carbon with a stripping agent.
  • the adsorbed mixture of precious metal cyanide complexes adsorbed on the activated carbon is treated with a sodium cyanide/sodium hydroxide stripping agent solution at elevated temperatures.
  • mercury cyanide complexes are also adsorbed, some of the mercury will be eluted with the gold and silver. However, a significant percentage of the mercury will remain affixed to the carbon after elution, reducing the effectiveness of the carbon as it is recycled to process more solution.
  • inorganic sealants include various forms of lime scale (CaCC>3, CaS0 4 ) and adsorb and blind large areas of the carbon. These inorganic sealants can remain even after the precious metals are eluted from the carbon, which is typically accomplished using a basic aqueous cyanide solution eluent. However, an acid rinse with a strong acid, such as hydrochloric acid, may be used to dissolve the inorganic sealants prior to eluting the precious metal complexes from the carbon.
  • a strong acid such as hydrochloric acid
  • Oils, greases and other volatile organic compounds are also readily adsorbed by activated carbon. But these volatile organic compounds may be removed from the carbon after the precious metals have been stripped by heating the carbon to elevated temperatures using "in-house” regeneration kilns prior to the carbon being returned to process more solution. However, any mercury that is not desorbed from the activated carbon can also become volatilized from the carbon in the high-temperature regeneration (or reactivation) process, and may be potentially emitted to the environment.
  • a method of removing mercury from an adsorbed mixture comprising mercury and gold that is adsorbed on a carbon substrate includes desorbing mercury from the carbon substrate by contacting the adsorbed mixture with an acidic aqueous solution comprising a stripping agent that is a weak acid.
  • a method of removing an inorganic sealant from an adsorbed mixture comprising the inorganic sealant, mercury, and gold that is adsorbed on an activated carbon used in a precious metal recovery process includes desorbing the inorganic sealant from the carbon substrate by contacting the adsorbed mixture with an acidic aqueous solution comprising a stripping agent that is a weak acid.
  • a method of reducing mercury emissions in precious metal mining operations includes washing an adsorbed mixture comprising mercury and gold that is adsorbed on an activated carbon substrate, with an acidic aqueous solution comprising a stripping agent that is a weak acid, wherein at least a portion of a first amount of mercury is desorbed from the activated carbon substrate.
  • the method further includes removing at least a portion of the gold from the activated carbon substrate, and regenerating the activated carbon substrate by heating, wherein a second amount of mercury remaining on the activated carbon substrate is volatilized from the activated carbon substrate, the second amount of mercury is less than the first amount of mercury.
  • FIG. 1 is a graph of the percentage of mercury stripped and Hg/Au stripping ratio versus number of stripping steps according to an embodiment of the present disclosure.
  • FIG. 2 is a graph of the amount of mercury that remained adsorbed on activated carbon (percent) versus elution temperature using sodium hydroxide and sodium cyanide over twenty-four hours of elution.
  • methods of removing mercury from an activated carbon substrate are provided.
  • the process also has the added benefit of eliminating calcium salts and other inorganic sealants that can accumulate on activated carbon used to recover precious metal cyanide complexes from leach solutions.
  • These methods which upon their application to precious metal mining, operations, advantageously also provides separating mercury from precious metals, such as gold, and also reduces atmospheric emissions of mercury, as discussed below.
  • the procedures disclosed can be substituted into the processing stream without adding unit operations or unit processing steps to the current physical plant of a mining operation.
  • the starting materials for the methods described herein can include activated carbon, such as for use in precious metal mining operations to concentrate and recover precious metal cyanide complexes from leach solutions.
  • Carbon substrates suitable for use with the described methods include those activated carbons generally used in the precious metal mining industry, and can include those carbon substrates having high porosity and superficial area of more than 1000 m 2 /g. In one example, the pores may have diameters of about 10-20 Angstroms.
  • One commonly used activated carbon substrate is available from Carbon Activated Corp. of Compton, CA (item number 004-C activated carbon, coconut shell 6x12 mesh).
  • the ores suitable for the methods described herein are not particularly limited to any specific type of precious metal-containing ore. However, gold ores found in the state of Nevada in the United States of America are exemplary of ores that also contain significant amounts of mercury.
  • an acidic aqueous solution that includes a stripping agent of a weak acid is used to desorb mercury from the adsorbed mixture of the metal cyanide complexes on the carbon substrate.
  • a weak acid is an acid that dissociates incompletely and therefore has a higher pKa than a strong acid, such as hydrochloric acid, which effectively releases substantially all of its acidic proton(s) when dissolved in water, i.e., completely dissociates.
  • weak acids include some inorganic acids, such as phosphoric acid, and organic acids, such as carboxylic acids.
  • Suitable organic acids include formic acid (HCOOH), acetic acid (CH 3 COOH), proprionic acid (CH 3 CH 2 COOH), tannic acid, oxalic acid, citric acid, and the like.
  • exemplary carboxylic acids include mono acids, such as formic acid, acetic acid, and proprionic acid.
  • the concentration of the stripping agent in the acidic aqueous solution may range from greater than 0% to about 30 percent by volume.
  • the stripping agent concentration may be about 5%, 10%, 15%, 20%, 25%, or 30% by volume.
  • the stripping agent concentration may be a dilute concentration, such as from about 0.5% by volume to about 10% by volume, from about 2% by volume to about 8% by volume, from about 3% by volume to about 7% by volume, from about 4% to about 6% by volume, or from about 4.5% to about 5.5% by volume.
  • the acidic aqueous solutions may also include one or more co-solvents such as alcohols.
  • co-solvents such as alcohols.
  • methanol, ethanol and the like may be used as a co-solvent.
  • the acidic aqueous solutions which include the stripping agent, and the adsorbed mixture may be intermixed under a variety of contacting temperatures and conditions.
  • the contacting temperature may range from about 40°C to about 120°C to affect about 75% desorption of the available mercury from the activated carbon substrate over a 24 hour period, as shown in FIG. 2.
  • the contacting temperature may be from about 50°C to about 110°C, from about 60°C to about 100°C, from about 70°C to about 100°C, or from about 80°C to about 90°C.
  • the acidic aqueous solutions and the adsorbed mixture of metal cyanide complexes and activated carbon substrate may be contacted under batch or flow conditions.
  • batch operations the combined mixture of the acidic aqueous solutions and the adsorbed mixture may be mixed or agitated by any known manner, such as stirring or shaking.
  • flow operations various parameters, such as flow rate, column dimensions, flow configuration, pressure, and the like may be optimized to affect the desired desorption results.
  • the acidic aqueous solution with its stripping agent selectively desorbs and removes mercury from the activated carbon substrate, while substantially leaving the precious metals such as gold adsorbed on the activated carbon substrate.
  • the acidic aqueous solution with its stripping agent removed about 35.4 wt% of the total adsorbed mercury on the adsorbed mixture, while only removing about 0.124 % of the total adsorbed gold from the adsorbed mixture, which provides a selectivity of
  • the Hg:Au stripped ratio is about 100 or more, about 200 or more, about 300 or more, about 400 or more, about 500 or more, or about 600 or more. In another example, the Hg:Au stripped ratio can range from about 100 to about 700.
  • Another advantage of the disclosed methods is the reduction of inorganic sealants, such as calcium carbonate and/or calcium sulfate, that can also be adsorbed onto the activated carbon substrate.
  • the acidic aqueous solution with its stripping agent can dissolve these foulants and thereby obviate or substantially reduce the amount of acid washing generally used in many reactivation procedures, as discussed below.
  • the adsorbed precious metals may be removed by any suitable method, e.g., elution with 2.5 wt% NaCN and 2.5 wt% NaOH at 130°C.
  • the carbon After the precious metals have been sufficiently desorbed and removed from the carbon substrate of the adsorbed mixture, the carbon generally needs to be reactivated, e.g., by heating at elevated temperatures in a reducing atmosphere. Therefore, the elimination or substantial reduction of mercury content remaining on the carbon substrate minimizes the amount of mercury that will be volatilized during the kilning process. As such, the methods disclosed herein allow for the reduction in mercury emissions to the environment during precious metal mining operations.
  • Gold-bearing solution was diluted with 5% HNO 3 to a selected volume so that its gold concentration was within the range of 0-2 ppm, and then analyzed with the SpectraAA-200 spectrophotometer.
  • Methanol and ethanol can be used as eluants for selective stripping of mercury cyanide from Au(CN)2 ⁇ when both cyano complexes are adsorbed on activated carbon. Results from using this method are shown in Tables 2 and 3. Conditions for the stripping were: 1.00 g carbon, loaded with 4.7 mg Au and 4.2 mg Hg; solvent volume 15 ml; these substances were placed in a 250-ml Erlenmeyer flask with a rubber stopper seal, and shaken for 5 seconds every 10 minutes for 1 hour.
  • nitric and hydrochloric acids were somewhat less effective in selectively stripping mercury cyanide from gold cyanide in the presence of 25 vol % methanol.
  • Propionic acid was also evaluated as a stripping agent.
  • Table 5 shows Hg desorption data using propionic acid. 1.00 gm carbon was loaded with 1.0 mg Hg/g C. Stripping with various total solution volumes of 10 vol% propionic acid for 6.0 hrs at 80°C.
  • Table 5 Hg desorption data using propionic acid.
  • Propionic acid functions as an effective stripping agent for mercury cyanide from activated carbon. Under the experimental conditions studied, up to 84 percent of the adsorbed Hg desorbed from the carbon after stripping with 25 ml of 10 vol % propionic acid for 6 hours.
  • Effective and selective stripping of mercury cyanide from Au(CN) 2 ⁇ can be accomplished using acetic acid when both species are adsorbed on activated carbon. In some cases, 95% or greater desorption of the mercury from the carbon can be accomplished while leaving virtually all of the gold cyanide on the carbon.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

A method of removing mercury adsorbed onto activated carbon is provided. The method includes treating an adsorbed mixture of metal cyanide complexes on a carbon substrate with an acidic solution of a stripping agent that is a weak acid. The method also eliminates inorganic sealants from the carbon substrate. In precious metal mining operations, the disclosed method reduces environmental emissions of mercury during the gold elution and carbon reactivation processes.

Description

STRIPPING AGENT AND METHOD OF USE
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Application No.
61/345,769, filed May 18, 2010; and U.S. Provisional Application No. 61/417,133, filed November 24, 2010, which are hereby incorporated by reference herein in their entirety.
GOVERNMENT LICENSE RIGHTS
[0002] This invention was made with government support under contract DE- FC26-02NT41607 awarded by the Department of Energy. The government has certain rights in the invention.
TECHNICAL FIELD
[0003] The present disclosure relates to stripping agents and their uses, including removing mercury and inorganic sealants from activated carbon used in mining or metal recovery operations.
BACKGROUND
[0004] Precious metal production has evolved over the past several decades, and is based principally on the ability to dissolve precious metals using a lixiviant, such as a basic aqueous cyanide solution, to form soluble metallocyanide complexes.
Gold and silver are most notably recovered, but often the precious metal ores contain other metallic minerals, which are also dissolved in the basic cyanide medium. The processes to recover the gold and silver cyanide complexes vary with the type of ore being treated, and the quantity of other metals in the solution. One of the simplest (and most widespread) techniques is to adsorb the metallocyanide complexes onto activated carbon substrates, such as an activated carbon derived from coconut shells. The carbon continues to adsorb the metallocyanide complexes until it reaches its ultimate loading, afterwards an elution process can be used to recover the precious metals in a more concentrated solution. There are several methods by which the carbon can be applied, such as carbon in pulp (CIP), carbon in leach (CIL) and carbon in column (CIC) operations .While this technique is quite efficient and has been used widely in the mining industry for over 50 years, it is not without its problems.
[0005] The most notable problem arises from the fact that ores often contain other substances, such as metals or sealants, which can also be adsorbed with the favored precious metal metallocyanide complexes. Specifically, cyano-complexes of mercury are also adsorbed on the activated carbon together with the gold and silver cyanide complexes. This "contaminant" is a problem from many standpoints. First, the adsorbed mercury cyanide complexes occupy space on the activated carbon, thereby reducing the space available for adsorbing the favored precious metals. Secondly, the mercury generally follows the precious metals in subsequent processes, requiring additional and expensive processing steps to remove and recover the mercury separately from the gold and silver. Thirdly, mercury is a strictly regulated "toxic substance" that must be handled with expensive processes to minimize or eliminate its release to the environment.
[0006] Elution (stripping) of the gold and silver cyanide complexes from the activated carbon for recovery of these precious metals may be accomplished by treating the activated carbon with a stripping agent. Generally, the adsorbed mixture of precious metal cyanide complexes adsorbed on the activated carbon is treated with a sodium cyanide/sodium hydroxide stripping agent solution at elevated temperatures. When mercury cyanide complexes are also adsorbed, some of the mercury will be eluted with the gold and silver. However, a significant percentage of the mercury will remain affixed to the carbon after elution, reducing the effectiveness of the carbon as it is recycled to process more solution. [0007] As stated above, metallocyanide complexes are not the only substances that are adsorbed on the carbon. In fact, inorganic and/or organic fouling is a recurring problem in gold and silver production facilities. Inorganic sealants include various forms of lime scale (CaCC>3, CaS04) and adsorb and blind large areas of the carbon. These inorganic sealants can remain even after the precious metals are eluted from the carbon, which is typically accomplished using a basic aqueous cyanide solution eluent. However, an acid rinse with a strong acid, such as hydrochloric acid, may be used to dissolve the inorganic sealants prior to eluting the precious metal complexes from the carbon.
[0008] Oils, greases and other volatile organic compounds are also readily adsorbed by activated carbon. But these volatile organic compounds may be removed from the carbon after the precious metals have been stripped by heating the carbon to elevated temperatures using "in-house" regeneration kilns prior to the carbon being returned to process more solution. However, any mercury that is not desorbed from the activated carbon can also become volatilized from the carbon in the high-temperature regeneration (or reactivation) process, and may be potentially emitted to the environment.
[0009] Accordingly, a need exists for new methods for desorbing mercury and/or inorganic sealants from an activated carbon, such as when used in mining or metal recovery operations.
SUMMARY OF THE INVENTION
[0010] Certain aspects of the present disclosure are described in the appended claims. There are additional features and advantages of the subject matter described herein. They will become apparent as this specification proceeds. In this regard, it is to be understood that the claims serve as a brief summary of varying aspects of the subject matter described herein. The various features described in the claims and below for various embodiments may be used in combination or separately. Any particular embodiment need not provide all features noted above, nor solve all problems or address all issues noted above.
[0011] According to an embodiment of the invention, a method of removing mercury from an adsorbed mixture comprising mercury and gold that is adsorbed on a carbon substrate is provided. The method includes desorbing mercury from the carbon substrate by contacting the adsorbed mixture with an acidic aqueous solution comprising a stripping agent that is a weak acid.
[0012] According to another embodiment of the invention, a method of removing an inorganic sealant from an adsorbed mixture comprising the inorganic sealant, mercury, and gold that is adsorbed on an activated carbon used in a precious metal recovery process is provided. The method includes desorbing the inorganic sealant from the carbon substrate by contacting the adsorbed mixture with an acidic aqueous solution comprising a stripping agent that is a weak acid.
[0013] According to another embodiment of the invention, a method of reducing mercury emissions in precious metal mining operations is provided. The method includes washing an adsorbed mixture comprising mercury and gold that is adsorbed on an activated carbon substrate, with an acidic aqueous solution comprising a stripping agent that is a weak acid, wherein at least a portion of a first amount of mercury is desorbed from the activated carbon substrate. The method further includes removing at least a portion of the gold from the activated carbon substrate, and regenerating the activated carbon substrate by heating, wherein a second amount of mercury remaining on the activated carbon substrate is volatilized from the activated carbon substrate, the second amount of mercury is less than the first amount of mercury. BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with a general description of the invention given above, and the detailed description of the embodiments given below, serve to explain the principles of the invention.
[0015] FIG. 1 is a graph of the percentage of mercury stripped and Hg/Au stripping ratio versus number of stripping steps according to an embodiment of the present disclosure; and
[0016] FIG. 2 is a graph of the amount of mercury that remained adsorbed on activated carbon (percent) versus elution temperature using sodium hydroxide and sodium cyanide over twenty-four hours of elution.
DETAILED DESCRIPTION OF EMBODIMENTS
[0017] Unless otherwise explained, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In case of conflict, the present specification, including explanations of terms, will control. The singular terms "a," "an," and "the" include plural referents unless context clearly indicates otherwise. Similarly, the word "or" is intended to include "and" unless the context clearly indicates otherwise. The term "comprising" means "including;" hence, "comprising A or B" means including A or B, as well as A and B together.
[0018] According to the present disclosure, methods of removing mercury from an activated carbon substrate are provided. The process also has the added benefit of eliminating calcium salts and other inorganic sealants that can accumulate on activated carbon used to recover precious metal cyanide complexes from leach solutions. These methods, which upon their application to precious metal mining, operations, advantageously also provides separating mercury from precious metals, such as gold, and also reduces atmospheric emissions of mercury, as discussed below. The procedures disclosed can be substituted into the processing stream without adding unit operations or unit processing steps to the current physical plant of a mining operation.
[0019] The starting materials for the methods described herein can include activated carbon, such as for use in precious metal mining operations to concentrate and recover precious metal cyanide complexes from leach solutions. Carbon substrates suitable for use with the described methods include those activated carbons generally used in the precious metal mining industry, and can include those carbon substrates having high porosity and superficial area of more than 1000 m2/g. In one example, the pores may have diameters of about 10-20 Angstroms. One commonly used activated carbon substrate is available from Carbon Activated Corp. of Compton, CA (item number 004-C activated carbon, coconut shell 6x12 mesh).
[0020] The ores suitable for the methods described herein are not particularly limited to any specific type of precious metal-containing ore. However, gold ores found in the state of Nevada in the United States of America are exemplary of ores that also contain significant amounts of mercury.
[0021] According to embodiments of the invention, an acidic aqueous solution that includes a stripping agent of a weak acid is used to desorb mercury from the adsorbed mixture of the metal cyanide complexes on the carbon substrate. As used herein, a weak acid is an acid that dissociates incompletely and therefore has a higher pKa than a strong acid, such as hydrochloric acid, which effectively releases substantially all of its acidic proton(s) when dissolved in water, i.e., completely dissociates. Examples of weak acids include some inorganic acids, such as phosphoric acid, and organic acids, such as carboxylic acids. Suitable organic acids include formic acid (HCOOH), acetic acid (CH3COOH), proprionic acid (CH3CH2COOH), tannic acid, oxalic acid, citric acid, and the like. Exemplary carboxylic acids include mono acids, such as formic acid, acetic acid, and proprionic acid.
[0022] The concentration of the stripping agent in the acidic aqueous solution may range from greater than 0% to about 30 percent by volume. For example, the stripping agent concentration may be about 5%, 10%, 15%, 20%, 25%, or 30% by volume. According to various embodiments, the stripping agent concentration may be a dilute concentration, such as from about 0.5% by volume to about 10% by volume, from about 2% by volume to about 8% by volume, from about 3% by volume to about 7% by volume, from about 4% to about 6% by volume, or from about 4.5% to about 5.5% by volume.
[0023] In addition to water, the acidic aqueous solutions may also include one or more co-solvents such as alcohols. For example, methanol, ethanol and the like may be used as a co-solvent.
[0024] The acidic aqueous solutions, which include the stripping agent, and the adsorbed mixture may be intermixed under a variety of contacting temperatures and conditions. According to embodiments of the invention, the contacting temperature may range from about 40°C to about 120°C to affect about 75% desorption of the available mercury from the activated carbon substrate over a 24 hour period, as shown in FIG. 2. According to certain embodiments, the contacting temperature may be from about 50°C to about 110°C, from about 60°C to about 100°C, from about 70°C to about 100°C, or from about 80°C to about 90°C.
[0025] The acidic aqueous solutions and the adsorbed mixture of metal cyanide complexes and activated carbon substrate may be contacted under batch or flow conditions. In batch operations, the combined mixture of the acidic aqueous solutions and the adsorbed mixture may be mixed or agitated by any known manner, such as stirring or shaking. In flow operations, various parameters, such as flow rate, column dimensions, flow configuration, pressure, and the like may be optimized to affect the desired desorption results.
[0026] According to embodiments of the invention, the acidic aqueous solution with its stripping agent selectively desorbs and removes mercury from the activated carbon substrate, while substantially leaving the precious metals such as gold adsorbed on the activated carbon substrate. In one example, the acidic aqueous solution with its stripping agent removed about 35.4 wt% of the total adsorbed mercury on the adsorbed mixture, while only removing about 0.124 % of the total adsorbed gold from the adsorbed mixture, which provides a selectivity of
(35.4)/(0.124) or 285 Hg:Au stripped ratio. According to one embodiment of the invention, the Hg:Au stripped ratio is about 100 or more, about 200 or more, about 300 or more, about 400 or more, about 500 or more, or about 600 or more. In another example, the Hg:Au stripped ratio can range from about 100 to about 700.
[0027] Another advantage of the disclosed methods is the reduction of inorganic sealants, such as calcium carbonate and/or calcium sulfate, that can also be adsorbed onto the activated carbon substrate. The acidic aqueous solution with its stripping agent can dissolve these foulants and thereby obviate or substantially reduce the amount of acid washing generally used in many reactivation procedures, as discussed below.
[0028] After the desired amount of mercury has been desorbed and removed from the adsorbed mixture, the adsorbed precious metals may be removed by any suitable method, e.g., elution with 2.5 wt% NaCN and 2.5 wt% NaOH at 130°C.
[0029] After the precious metals have been sufficiently desorbed and removed from the carbon substrate of the adsorbed mixture, the carbon generally needs to be reactivated, e.g., by heating at elevated temperatures in a reducing atmosphere. Therefore, the elimination or substantial reduction of mercury content remaining on the carbon substrate minimizes the amount of mercury that will be volatilized during the kilning process. As such, the methods disclosed herein allow for the reduction in mercury emissions to the environment during precious metal mining operations.
[0030] Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, suitable methods and materials are described herein. The disclosed materials, methods, and examples are illustrative only and not intended to be limiting.
[0031] General Experimental Details
[0032] Mercury Analysis: An Atomic Absorption/Mercury Cold Vapor Technique was used. To obtain metallurgical balances, the amount of mercury contained in the carbon was first established. Oxidants used were KMn04 and K2S2O8 and aqua regia was used as lixiviant. The technique developed is as follows: after filtration and water rinsing and drying, 1 , 2 or 3 grams of carbon was digested in 10 ml of aqua regia at 95 °C for 2 minutes; 2.5 ml of 5% Na2S20g was added and heated at 95 °C for 30 minutes; and then 5 ml of 5% KMn04 was added and heated at 95°C for 30 minutes. The supernatant was poured off and analyzed using a SpectraAA-200 Atomic Absorption Spectrophotometer, manufactured by Varian. This procedure represented one stage of digestion. After five stages, approximately 90% of the mercury was desorbed.
[0033] Gold Analysis: Gold-bearing solution was diluted with 5% HNO3 to a selected volume so that its gold concentration was within the range of 0-2 ppm, and then analyzed with the SpectraAA-200 spectrophotometer.
[0034] Evaluation of acetic acid as a stripping agent: The addition of acetic acid as a stripping agent selectively desorbs mercury cyanide from activated carbon leaving gold cyanide adsorbed on the carbon. Results from a method according to the present disclosure are provided in Table 1 and FIG. 1.
Table 1. Effect of concentration of acetic acid. Conditions: 2.0 g carbon loaded with 4.3 mg Au/g C and 4.5 mg Hg/g C; 37.5 ml water plus acetic acid, stripping - 1 hour at 60°C.
Cone, of Stripped (%) Stripped
Acetic Acid Hg Au Hg Au Ratio
(Vol % )
5 30.9 0.046 672
10 42.7 0.063 678
20 43.6 0.10 436
30 48.6 0.16 304
[0035] As shown in Table 1, using a 10 vol % of acetic acid stripping agent at 60°C provided that 42.7 % of the adsorbed mercury was stripped from the carbon after one hour of elution, while only 0.063% of the gold was desorbed, which gave a 678 Hg:Au stripped ratio.
[0036] Mercury stripping was also conducted with five 1 -hour stripping stages (total of five hours). Stripping conditions were: 2.0 g carbon loaded with 4.3 mg Au/g C and 4.5 mg Hg/g C. The solution volume was 37.5 ml, the temperature was 80°C, and the solution was 10 vol % acetic acid. Results are shown in FIG. 1. The stripping stages were conducted with fresh 10 vol % acetic acid in each case.
[0037] Under these conditions 51.8% of the mercury was stripped in one stage of stripping. After five stages of stripping, 85.1% of the mercury was eluted from the activated carbon.
[0038] Methanol/Ethanol
[0039] Methanol and ethanol can be used as eluants for selective stripping of mercury cyanide from Au(CN)2~ when both cyano complexes are adsorbed on activated carbon. Results from using this method are shown in Tables 2 and 3. Conditions for the stripping were: 1.00 g carbon, loaded with 4.7 mg Au and 4.2 mg Hg; solvent volume 15 ml; these substances were placed in a 250-ml Erlenmeyer flask with a rubber stopper seal, and shaken for 5 seconds every 10 minutes for 1 hour.
Table 2. Stripping of mercury cyanide and Au(CN)2~ from carbon (100% alcohol).
Temperature 23°C 52°C
Desorbed Metal Hg (%) Au (%) Hg (%) Au (%)
Methanol 41.4 39.6 69.6 38.7
Ethanol 15.7 16.3 24.8 21.7
Table 3. Stripping of mercury cyanide and Au(CN)2~ from carbon with various concentrations of methanol at 52°C.
Methanol/H20 100/0 50/50 25/75 0/100
Desorbed Metal Hg Au Hg Au Hg Au Hg Au
Desorbed Amount 69.6 39.1 31.7 28.3 18.8 17.7 2.0 0.04
(%)
[0040] These results indicated that methanol was superior to ethanol as a stripping agent. However, selective separation of mercury cyanide species and Au(CN)2~ was not observed with either of these reagents at 23°C. And while increased desorption of the metal cyano complexes was observed at higher temperatures, only modest selectivity was observed.
[0041] Effect of Various Acids
[0042] Stripping efficiency of mercury cyanide was evaluated in the presence of various acids in the presence and absence of methanol. The conditions used were 2.00 g carbon loaded with Au 4.3 mg/g and Hg 4.5 mg/g; stripping solution (methanol/H20 = 25/75 vol %); volume = 30 ml; shaken for 1 hour at 60+1 °C in a water bath. The addition of the acids into the total volume of 30 ml is given in Table 4.
Table 4. Mercury cyanide and Au(CN)2~ desorption with various acids
presence of 25 vol % methanol.
Acid Dose H Stripped % Stripped Temp.
(ml or g) Hg Au Ratio (Hg Au)
HNO3 0.36 0.74 18.7 0.22 85 60°C
HC1 0.09 1.92 4.1 0.06 68 50°C
H3PO4 0.36 1.17 35.4 0.124 285 60°C
Perchloric 0.36 1.1 40.8 0.20 204 60°C
Formic 1.5 2.2 36.7 0.107 343 60°C
Acetic 1.5 3.3 34.4 0.104 303 60°C
3.0 3.2 41.0 0.13 315 60°C
Tannic 1.5g 3.7 39.2 0.28 140 60°C
Oxalic 1.5g 1.1 35.2 0.20 176 60°C
Citric 1.5g 2.4 24.3 0.10 243 60°C
[0043] Of these acids, nitric and hydrochloric acids were somewhat less effective in selectively stripping mercury cyanide from gold cyanide in the presence of 25 vol % methanol.
[0044] Propionic acid was also evaluated as a stripping agent. Table 5 shows Hg desorption data using propionic acid. 1.00 gm carbon was loaded with 1.0 mg Hg/g C. Stripping with various total solution volumes of 10 vol% propionic acid for 6.0 hrs at 80°C.
Table 5: Hg desorption data using propionic acid.
Carbon, g Solution volume, Hg desorbed, mg Desorbed, %
ml
1.0 10 0.607 60.7
1.0 25 0.840 84.0
1.0 80 0.840 84.0
[0045] Propionic acid functions as an effective stripping agent for mercury cyanide from activated carbon. Under the experimental conditions studied, up to 84 percent of the adsorbed Hg desorbed from the carbon after stripping with 25 ml of 10 vol % propionic acid for 6 hours.
[0046] Effect of Temperature
[0047] The effects of temperature and time on mercury and gold elution from carbon with sodium cyanide and sodium hydroxide were evaluated in detail. In these methods, 3.33 g of carbon was loaded with 4.1 mg Hg/g C and 4.7 mg Au/g C. As shown in FIG. 2, optimal elution temperature ranges from 80°C to 90°C in which only about 2 wt % of the initial mercury was retained on the carbon. At the conventional elution temperature of 135°C, about 25 % of the initial mercury remains on the carbon.
[0048] Without intending to be limited by theory, the optimal temperature range might be explained on the following basis. From room temperature to about 90°C, the kinetics of desorption increases with increasing temperature. Above about 100°C, the mercury cyanide complexes become unstable, and mercuric hydroxide forms. Conditions used for this example of the method were: carbon 3.3 g; elution solution: 500 ml; (NaCN) = (NaOH) = 2.5 wt %; Au loading 4.7 mg/g; Hg loading 4.1 mg/g.
[0049] Effective and selective stripping of mercury cyanide from Au(CN)2 ~ can be accomplished using acetic acid when both species are adsorbed on activated carbon. In some cases, 95% or greater desorption of the mercury from the carbon can be accomplished while leaving virtually all of the gold cyanide on the carbon.
[0050] Acid Washing
[0051] In typical gold processing operations, activated carbons loaded
(adsorbed) with gold cyanide, are washed with dilute solutions of mineral acids, such as HC1 or HNO3, in order to remove certain inorganic sealants, such as CaC(¾. It was unexpectedly found that washing the loaded carbon with a dilute solution of an organic acid, such as acetic acid, removes inorganic sealants, and also removes mercury cyanide complexes from the substrate (carbon), without substantially removing valuable precious metal cyanide complexes, such as cyanide compounds of gold or silver, from the substrate. After washing has been carried out to a desired degree, the carbon is moved to the stripping operation. [0052] It is to be understood that the above discussion provides a detailed description of various embodiments. The above descriptions will enable those skilled in the art to make many departures from the particular examples described above to provide apparatuses constructed in accordance with the present disclosure. The embodiments are illustrative, and not intended to limit the scope of the present disclosure. The scope of the present disclosure is rather to be determined by the scope of the claims as issued and equivalents thereto.

Claims

What is claimed is:
1. A method of removing mercury from an adsorbed mixture comprising mercury and gold that is adsorbed on a carbon substrate, the method comprising: desorbing mercury from the carbon substrate by contacting the adsorbed mixture with an acidic aqueous solution comprising a stripping agent that is a weak acid.
2. The method of claim 1 , wherein prior to desorbing mercury from the carbon substrate, the method further comprises:
adsorbing mercury and gold on the carbon substrate to form the adsorbed mixture, which includes mercury and gold.
3. The method of claim 1, wherein the weak acid comprises phosphoric acid.
4. The method of claim 1 , wherein the weak acid comprises an organic acid.
5. The method of claim 1, wherein the weak acid comprises a carboxylic acid.
6. The method of claim 5, wherein the carboxylic acid is a mono acid.
7. The method of claim 6, wherein the mono acid is selected from the group consisting of formic acid, acetic acid, and propionic acid.
8. The method of claim 1, wherein the acidic solution further comprises an alcohol.
9. The method of claim 1, wherein desorbing mercury from the carbon substrate comprises contacting the adsorbed mixture with the acidic aqueous solution at a temperature from about 40°C to about 120°C.
10. The method of claim 1, wherein desorbing mercury from the carbon substrate comprises contacting the adsorbed mixture with the acidic aqueous solution at a temperature from about 60°C to about 100°C.
11. The method of claim 1 , wherein desorbing mercury from the carbon substrate comprises contacting the adsorbed mixture with the acidic aqueous solution at a temperature from about 80°C to about 90°C.
12. The method of claim 1, wherein the weak acid is present in a concentration greater than 0% and less than about 30% by volume of the acidic aqueous solution.
13. The method of claim 1, wherein the weak acid is present in a concentration from about 5% to about 20% by volume of the acidic aqueous solution.
14. The method of claim 1, wherein the weak acid is present in a concentration from about 5% to about 10% by volume of the acidic aqueous solution.
15. A method of removing an inorganic sealant from an adsorbed mixture comprising the inorganic sealant, mercury, and gold that is adsorbed on an activated carbon used in a precious metal recovery processes, the method comprising:
desorbing the inorganic sealant from the carbon substrate by contacting the adsorbed mixture with an acidic aqueous solution comprising a stripping agent that is a weak acid.
16. The method of claim 15, wherein the weak acid comprises phosphoric acid.
17. The method of claim 15, wherein the weak acid comprises an organic acid.
18. The method of claim 15, wherein the weak acid comprises a carboxylic acid.
19. The method of claim 18, wherein the carboxylic acid is a mono acid.
20. The method of claim 19, wherein the mono acid is selected from the group consisting of formic acid, acetic acid, and propionic acid.
21. The method of claim 15, wherein the acidic solution further comprises an alcohol.
22. The method of claim 15, wherein desorbing the inorganic sealant from the carbon substrate comprises contacting the adsorbed mixture with the acidic aqueous solution at a temperature from about 40°C to about 120°C.
23. The method of claim 15, wherein desorbing the inorganic sealant from the carbon substrate comprises contacting the adsorbed mixture with the acidic aqueous solution at a temperature from about 60°C to about 100°C.
24. The method of claim 15, wherein desorbing the inorganic sealant from the carbon substrate comprises contacting the adsorbed mixture with the acidic aqueous solution at a temperature from about 80°C to about 90°C.
25. The method of claim 15, wherein the weak acid is present in a concentration greater than 0% and less than about 30% by volume of the acidic aqueous solution.
26. The method of claim 15, wherein the weak acid is present in a concentration from about 5% to about 20% by volume of the acidic aqueous solution.
27. The method of claim 15, wherein the weak acid is present in a concentration from about 5% to about 10% by volume of the acidic aqueous solution.
28. The method of claim 15, wherein the inorganic sealant includes a calcium precipitate.
29. The method of claim 28, wherein the calcium precipitate is calcium carbonate.
30. The method of claim 28, wherein the calcium precipitate is calcium sulfate.
31. The method of claim 15, wherein desorbing the inorganic sealant from the carbon substrate by contacting the adsorbed mixture with the acidic aqueous solution further includes desorbing mercury from the carbon substrate.
32. A method of reducing mercury emissions in precious metal mining operations, comprising:
washing an adsorbed mixture comprising mercury and gold that is adsorbed on an activated carbon substrate with an acidic aqueous solution comprising a stripping agent that is a weak acid, wherein at least a portion of a first amount of mercury is desorbed from the activated carbon substrate;
removing at least a portion of the gold from the activated carbon substrate; and
regenerating the activated carbon substrate by heating, wherein a second amount of mercury remaining on the activated carbon substrate is volatilized from the activated carbon substrate, the second amount of mercury is less than the first amount of mercury.
33. The method of claim 32, wherein the weak acid comprises phosphoric acid.
34. The method of claim 32, wherein the weak acid comprises an organic acid.
35. The method of claim 32, wherein the weak acid comprises a carboxylic acid.
36. The method of claim 35, wherein the carboxylic acid is a mono acid.
37. The method of claim 36, wherein the mono acid is selected from the group consisting of formic acid, acetic acid, and propionic acid.
38. The method of claim 32, wherein the acidic aqueous solution further comprises an alcohol.
39. The method of claim 32, wherein the mercury is desorbed from the carbon substrate by washing the adsorbed mixture with the acidic aqueous solution at a temperature from about 40°C to about 120°C.
40. The method of claim 32, wherein the mercury is desorbed from the carbon substrate by washing the adsorbed mixture with the acidic aqueous solution at a temperature from about 60°C to about 100°C.
41. The method of claim 32, wherein the mercury is desorbed from the carbon substrate by washing the adsorbed mixture with the acidic aqueous solution at a temperature from about 80 °C to about 90 °C.
42. The method of claim 32, wherein the weak acid is present in a concentration greater than 0% and less than about 30% by volume of the acidic aqueous solution.
43. The method of claim 32, wherein the weak acid is present in a concentration from about 5% to about 20% by volume of the acidic aqueous solution.
44. The method of claim 32, wherein the weak acid is present in a concentration from about 5% to about 10% by volume of the acidic aqueous solution.
PCT/US2011/037002 2010-05-18 2011-05-18 Stripping agent and method of use WO2011146620A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US13/698,492 US20140147354A1 (en) 2010-05-18 2011-05-18 Stripping agent and method of use

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US34576910P 2010-05-18 2010-05-18
US61/345,769 2010-05-18
US41713310P 2010-11-24 2010-11-24
US61/417,133 2010-11-24

Publications (1)

Publication Number Publication Date
WO2011146620A1 true WO2011146620A1 (en) 2011-11-24

Family

ID=44992043

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2011/037002 WO2011146620A1 (en) 2010-05-18 2011-05-18 Stripping agent and method of use

Country Status (2)

Country Link
US (1) US20140147354A1 (en)
WO (1) WO2011146620A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021116274A1 (en) * 2019-12-13 2021-06-17 Siempelkamp NIS Ingenieurgesellschaft mbH Method of removing mercury

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2122527A (en) * 1936-06-02 1938-07-05 Tube Gold Extractors Proprieta Recovery of precious metals from solutions
US4474896A (en) * 1983-03-31 1984-10-02 Union Carbide Corporation Adsorbent compositions
US5078977A (en) * 1988-10-21 1992-01-07 Cyprus Minerals Company Cyanide recovery process
USRE36118E (en) * 1992-02-25 1999-03-02 Zeneca Limited Chemical process of separating metals from an organic complex
US6896808B1 (en) * 1999-11-09 2005-05-24 Oretek Limited Recovery of metal values from aqueous solutions and slurries
US20060210463A1 (en) * 2005-03-17 2006-09-21 Comrie Douglas C Reducing mercury emissions from the burning of coal

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA200006996B (en) * 1999-12-06 2001-05-29 Antonio T Robles Method for the regenaration of sorbent materials.

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2122527A (en) * 1936-06-02 1938-07-05 Tube Gold Extractors Proprieta Recovery of precious metals from solutions
US4474896A (en) * 1983-03-31 1984-10-02 Union Carbide Corporation Adsorbent compositions
US5078977A (en) * 1988-10-21 1992-01-07 Cyprus Minerals Company Cyanide recovery process
USRE36118E (en) * 1992-02-25 1999-03-02 Zeneca Limited Chemical process of separating metals from an organic complex
US6896808B1 (en) * 1999-11-09 2005-05-24 Oretek Limited Recovery of metal values from aqueous solutions and slurries
US20060210463A1 (en) * 2005-03-17 2006-09-21 Comrie Douglas C Reducing mercury emissions from the burning of coal

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021116274A1 (en) * 2019-12-13 2021-06-17 Siempelkamp NIS Ingenieurgesellschaft mbH Method of removing mercury

Also Published As

Publication number Publication date
US20140147354A1 (en) 2014-05-29

Similar Documents

Publication Publication Date Title
Roosen et al. Chemical immobilization of 8-hydroxyquinoline and 8-hydroxyquinaldine on chitosan-silica adsorbent materials for the selective recovery of gallium from Bayer liquor
JP6982318B2 (en) Thallium-containing wastewater treatment method
US3935006A (en) Process for eluting adsorbed gold and/or silver values from activated carbon
JP6083077B2 (en) Metal ion adsorbent
EP2500442B1 (en) Process for recovery of precious metal from functionalised absorption materials containing precious metals
JP2006348359A (en) Metal recovery method
CN110964910B (en) Method for recovering rhodium from rhodium catalyst waste liquid
JP2019173063A (en) Recovery method of nickel and cobalt from solution
US5176886A (en) Rapid, ambient-temperature process for stripping gold bound to activated carbon
JP2016163864A (en) Reactivation method of activated carbon and recovery method of gold
CN104651615A (en) Method for recovering silver and palladium from waste
JP2016040032A (en) Adsorbent comprising cellulose derivative and/or cross-linked chitosan derivative and adsorption method and recovery method for metal ion
US20140147354A1 (en) Stripping agent and method of use
US10301180B2 (en) Activated carbon regeneration method and gold recovery method
AU2011201892B2 (en) Method for aqueous gold thiosulfate extraction using copper-cyanide pretreated carbon adsorption
CN113481373B (en) Method for separating and recovering palladium from activating solution
CN116917058A (en) Removal of arsenic, antimony and toxic metals from contaminated substrates
JP5505604B2 (en) Method for recovering indium from oxalic acid-containing solution
Van Deventer et al. The mechanism of elution of gold cyanide from activated carbon
JP2000264902A (en) Thiourea derivative of chitosan
JP7217872B2 (en) Noble metal separation and recovery method and precious metal fine particles recovered by the method
US5028260A (en) Recovery of gold from acidic solutions
JPH05228366A (en) Algae improved in metal ion adsorptivity and filterability
KR101927405B1 (en) Humic acid-impregnated activated carbon for adsorbing mercury and the manufacturing method thereof
JP3053102B2 (en) Adsorbed substance of platinum and palladium excellent in elution characteristics and method for recovering platinum and / or palladium using the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11784171

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11784171

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 13698492

Country of ref document: US