WO2013129017A1 - 活性炭に吸着された金の回収方法及びそれを用いた金の製造方法 - Google Patents
活性炭に吸着された金の回収方法及びそれを用いた金の製造方法 Download PDFInfo
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- WO2013129017A1 WO2013129017A1 PCT/JP2013/052101 JP2013052101W WO2013129017A1 WO 2013129017 A1 WO2013129017 A1 WO 2013129017A1 JP 2013052101 W JP2013052101 W JP 2013052101W WO 2013129017 A1 WO2013129017 A1 WO 2013129017A1
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- Prior art keywords
- gold
- activated carbon
- thiosulfate
- elution
- eluent
- Prior art date
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- 239000010931 gold Substances 0.000 title claims abstract description 123
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 121
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 119
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000010828 elution Methods 0.000 claims abstract description 43
- 239000003480 eluent Substances 0.000 claims abstract description 30
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical class OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000002378 acidificating effect Effects 0.000 claims abstract description 15
- 238000011084 recovery Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 16
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 9
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 claims description 3
- 239000011260 aqueous acid Substances 0.000 abstract 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 20
- 238000002386 leaching Methods 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000003463 adsorbent Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000012141 concentrate Substances 0.000 description 8
- 229920001021 polysulfide Polymers 0.000 description 8
- 239000005077 polysulfide Substances 0.000 description 8
- 150000008117 polysulfides Polymers 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- -1 halide ion Chemical class 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229940006280 thiosulfate ion Drugs 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052951 chalcopyrite Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052976 metal sulfide Inorganic materials 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- XEIPQVVAVOUIOP-UHFFFAOYSA-N [Au]=S Chemical compound [Au]=S XEIPQVVAVOUIOP-UHFFFAOYSA-N 0.000 description 2
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- 239000011028 pyrite Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 230000036962 time dependent Effects 0.000 description 2
- 210000003462 vein Anatomy 0.000 description 2
- 241000416536 Euproctis pseudoconspersa Species 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052947 chalcocite Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3416—Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
-
- 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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/046—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper or baths
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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 present invention relates to a method for recovering gold adsorbed on activated carbon and a method for producing gold using the same.
- Gold is one of the most valuable metals and exists as simple particles in natural veins. Gold is often contained in small amounts as an accompaniment of pyrite, chalcopyrite, and other sulfide metal ores, not gold veins, and gold is separated when smelting its main component and separately smelted into metal gold There are many cases.
- gold When processing gold produced accompanying metal sulfide ore, such as chalcopyrite, gold is generally transferred to the anode in the dry copper smelting process, and then concentrated in the electrolytic slime in the electrolytic purification process. Gold in the electrolytic slime is recovered as metallic gold by a wet smelting method (Patent Documents 1 and 2) or a dry smelting method.
- Patent Document 3 A method of leaching gold with a strong acid having been proposed (Patent Document 3).
- the solution containing gold dissolved in acid in this manner is often adsorbed on an adsorbent and concentrated.
- Activated carbon, functional resin, etc. are known as gold adsorbents, but the most general and versatile are known.
- a high adsorbent is activated carbon.
- Patent Document 3 As a method of recovering gold after adsorbing gold on activated carbon, there is a method of burning activated carbon after adsorption or eluting with a cyanide solution, and electrolytically collecting or chemically reducing the eluent (Patent Document 3).
- the inventors of the present invention have made extensive studies to solve the above-mentioned problems.
- an eluent obtained by adding sodium thiosulfate to an acidic aqueous solution can be used to efficiently and efficiently produce gold. It was found that it can be recovered.
- the present invention completed on the background of the above knowledge is, in one aspect, eluting gold adsorbed on activated carbon with an eluent prepared by adding thiosulfate to an acidic aqueous solution to form an acidic concentrated gold solution.
- a method for recovering gold comprising a step of obtaining.
- the acidic aqueous solution has a pH of 4-7.
- the thiosulfate is a reducing agent containing at least one selected from sodium thiosulfate, thiosulfuric acid, and potassium thiosulfate.
- the concentration of thiosulfate in the eluent is 0.01 mol / L or more.
- the concentration of thiosulfate in the eluent is 0.01 to 1.0 mol / L or more.
- the elution is performed using a batch reactor at an elution temperature of 20 to 100 ° C.
- the elution temperature is set to 60 to 85 ° C.
- a gold manufacturing method in which single gold is produced by reduction from a concentrated gold solution obtained by the gold recovery method of the present invention.
- gold adsorbed on activated carbon can be efficiently recovered at low cost.
- Gold is often contained in trace amounts as a simple substance in sulfide metal ores such as chalcocite, chalcopyrite, copper indigo, chalcopyrite, pyrite, arsenite, arsenite. For this reason, in order to collect this, it is preferable to first concentrate the metal sulfide ore by crushing and then concentrating it by a flotation method. In addition, it is possible to further concentrate gold to the leaching residue by solid-liquid separation after leaching 80% or more of copper or iron as a main component metal from this concentrate using an acidic leaching solution. It becomes good.
- cyan leaching is a technique that can be avoided because its use is not limited by the high toxicity of cyan.
- a strong oxidizing acid is known as a mixed acid such as aqua regia, hydrogen peroxide + hydrochloric acid, etc., but it can also be dissolved in a mixed acid of a halide ion that stabilizes a Lewis acid and a gold ion.
- a ligand that stabilizes gold ions is important, and halide ions and cyan are generally known.
- the gold adsorbed on the activated carbon is efficiently recovered at low cost. That is, in the present invention, first, gold is dissolved with a strong oxidizing leach solution, and gold is adsorbed on activated carbon.
- activated carbon such as coconut shell activated carbon and coke activated carbon, those derived from any raw material may be used.
- the method for adsorbing gold may be a batch method in which activated carbon is added or a solution in which activated carbon is filled in an adsorption tower and gold is leached may be continuously passed.
- the activated carbon that has sufficiently adsorbed gold is recovered, and gold is eluted using an eluent containing thiosulfate ions prepared by adding thiosulfate to an acidic aqueous solution.
- the concentration of thiosulfate is preferably 0.01 mol / L or more.
- the thiosulfate concentration is 0.01 to 1.0 mol / L from the viewpoint of cost. Is more preferable.
- the amount of thiosulfuric acid required varies depending on the amount of gold adsorbed on the activated carbon, but gold is not lost even if the elution is insufficient as described above.
- the thiosulfate includes at least one selected from sodium thiosulfate, thiosulfate, and potassium thiosulfate.
- the acidic aqueous solution used for the eluent is preferably pH 4-7.
- weak acid thiosulfate is gradually decomposed into sulfurous acid (which is converted into sulfuric acid by air oxidation) and polysulfide. Therefore, by using such a weakly acidic eluent, the thiosulfate is satisfactorily decomposed to generate a polysulfide that promotes gold elution as described below. Further, since the eluent is weakly acidic as described above, handling safety and cost are improved.
- the elution step is preferably performed using a batch reactor at an elution temperature of 20 to 100 ° C.
- the elution temperature is more preferably 60 to 85 ° C.
- the elution rate increases.
- the elution temperature reaches 25 ° C.
- the elution rate decreases significantly.
- activated carbon is repeatedly used after the elution operation, even if the elution of gold is incomplete, it is not lost. Considering the energy cost and the efficiency of temperature increase, 60 to 85 ° C. is appropriate.
- the thiosulfate ion is unstable under acidic conditions and decomposes as shown in (Formula 1) to produce sulfur and sulfurous acid, and finally only sulfuric acid becomes sulfuric acid.
- (Formula 1) When a continuous liquid flow method using an adsorption tower is employed for elution, there is a risk of clogging due to the generated sulfur, so it is preferable to perform elution in a batch reactor.
- S 2 O 3 2- ⁇ S + SO 3 2- ⁇ oxidation, hydrolysis ⁇ H 2 SO 4 (Formula 1)
- polysulfide which is a reaction intermediate produced when decomposing into sulfur and sulfurous acid in (Formula 1), elutes gold. It is thought to promote.
- Polysulfide ions have a great influence on the dissolution and leaching of gold. Specifically, first, when gold contained in the sulfide metal ore is leached by the method of the present invention, the gold in the solution exists as a polysulfide type complex. Even if this complex is adsorbed on activated carbon, it is not reduced to an inactive simple substance.
- the form in which the gold polysulfide complex is adsorbed on the activated carbon is considered to be gold sulfide or the following form.
- Non-patent Document 1 Seiji Takagi, Qualitative Analytical Chemistry Volume 1, Ion Reaction, Nanedo
- concentrated gold solution can be obtained by elution from activated carbon.
- concentrated gold solution refers to a solution containing 50 to 5000 mg / L of gold.
- reduction with sodium oxalate, chemical reduction with sulfur dioxide, or solvent extraction-electrolytic collection method is known. Obtainable.
- the activated carbon which is an adsorbent, can be used repeatedly to adsorb gold, which is advantageous in terms of cost.
- Example 1 Metal sulfide concentrate containing gold (Cu: 17% by mass, Fe: 27% by mass, S: 25% by mass, Au: 90 ppm) was weighed so as to be 35 g / L with respect to the leachate.
- the leachate contained Cl: 180 g / L, Br: 20 g / L, Cu: 18 g / L, Fe: 2 g / L, and the pH was 1.5.
- the leachate was heated to 85 ° C. and stirred while blowing air of 0.1 L per minute.
- the leachate having a gold concentration of 2 mg / L or more thus obtained was passed through a column packed with coconut shell-derived activated carbon (coconut MC manufactured by Taihei Chemical Sangyo Co., Ltd.) to adsorb gold onto the activated carbon.
- coconut shell-derived activated carbon coconut MC manufactured by Taihei Chemical Sangyo Co., Ltd.
- the activated carbon was taken out and the gold concentration was quantified to be about 9000 g / ton.
- the gold concentration was concentrated by ash blowing, dissolved in aqua regia, and quantified by ICP-AES.
- An eluent was prepared by adding sodium thiosulfate to an aqueous solution adjusted to pH 4, 8, 12 with hydrochloric acid and sodium hydroxide so that the concentration of sodium thiosulfate was 0.5 mol / L (56 g / L as thiosulfate ion).
- the activated carbon adsorbed with gold was immersed in an eluent at a rate of 20 g / L, and stirred at 80 ° C. for elution.
- the gold concentration was adjusted to 100 mL by adding 2 mL of hydrogen peroxide and further diluted with hydrochloric acid, and the supernatant was quantified by ICP-AES.
- Example 1 Using activated carbon prepared in the same manner as in Example 1, dilute sulfuric acid having a pH of 4 was used as an eluent, and activated carbon was immersed in the eluent at a rate of 20 g / L and stirred at 80 ° C. for elution.
- FIG. 1 shows the change over time in the gold concentration in the eluent when elution was performed in Example 1 and Comparative Example 1. It can be seen that when thiosulfuric acid is added, elution of gold is clearly and efficiently achieved, and a weakly acidic pH 4 is most effective. The elution in the strong alkaline region of pH 12 is more efficient than the neutral pH of 8, but the activated carbon prepared by this method is leached even in the strong alkali, which reflects the influence of alkali more strongly than the effect of adding thiosulfuric acid. .
- Example 2 Using an activated carbon prepared in the same manner as in Example 1, an eluent was prepared by adding sodium thiosulfate to 0.1 mol / L (11.2 g / L as thiosulfate ion). The pH of the eluent was 4. The activated carbon adsorbed with gold was immersed in an eluent at a rate of 20 g / L, and stirred at 80 ° C. for elution. FIG. 2 shows the change over time in the elution rate converted from the gold concentration in the eluent.
- Example 3 Using an activated carbon prepared in the same manner as in Example 1, an eluent was prepared by adding sodium thiosulfate to 0.1 mol / L (11.2 g / L as thiosulfate ion). The pH of the eluent was 4. The activated carbon adsorbed with gold was immersed in an eluent at a rate of 20 g / L, and stirred at 25 ° C. for elution. FIG. 2 shows the change over time of the gold concentration in the eluent.
- a polysulfide ion is generally a divalent anion having about 2 to 6 sulfur atoms, and even when two molecules are coordinated to gold, thiosulfuric acid is at most 12 mole times, so even if it is about 10 mole times, the effect can be obtained. Presumed to appear.
- the elution effect is almost the same when the concentration of thiosulfate is 0.1 to 0.5 mol / L. That is, the elution effect is saturated at a thiosulfate concentration of 0.1 mol / L (100 mol times gold).
- the amount of thiosulfuric acid required varies depending on the amount of gold adsorbed on the activated carbon, but gold is not lost even if the elution is insufficient as described above.
- Example 4 19 mL of activated carbon (produced by Taihei Chemical Industrial Co., Ltd .: CC-202) adsorbing 9800 g / t of gold was packed in a glass column with a cock having an inner diameter of 11 mm and a height of 200 mm. The activated carbon was previously washed with HCl. Next, sodium thiosulfate is added to pure water so that the concentration is 0.01 mol / L, 0.1 mol / L, 0.5 mol / L, or 1.0 mol / L, and the pH is adjusted to 5 with sulfuric acid. This was used as an eluent.
- the eluent was supplied to the column packed with activated carbon at 4.1 mL / min, and after passing through the solution, the solution was fractionated and collected every 5 to 7 mL.
- the column internal temperature was 70 ° C.
- SV of column liquid flow The space velocity was 13 (1 / h), LV: linear velocity was 2.6 (m / h), and BV: liquid flow rate was 156 (mL).
- the gold concentration in the fraction was measured by ICP-AES, and the quality of gold contained in the activated carbon was calculated.
- Table 1 the relationship between the obtained liquid flow rate and the gold quality in the activated carbon is shown in Table 2, and the graph is shown in FIG.
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Abstract
Description
S2O3 2- ⇔ S+SO3 2- → 酸化、加水分解 → H2SO4 (式1)
Au(HSnH)mX
(Xはハロゲン、mは1~4の整数、nは1~9の整数)
前者の形態(硫化金)の場合はS2-と反応して溶解することで溶離される(非特許文献1)。後者の形態の場合、NaOHと配位しているポリ硫化水素のHが反応して錯体が負電荷を帯びることで溶離される。
(非特許文献1)高木誠司、定性分析化学中巻、イオン反応編、南江堂
金を含む硫化金属精鉱(Cu:17質量%、Fe:27質量%、S:25質量%、Au:90ppm)を、浸出液に対し35g/Lとなるよう秤量した。浸出液は、Cl:180g/L、Br:20g/L、Cu:18g/L、Fe:2g/Lを含有し、pHは1.5とした。浸出液を85℃に加温し、空気を1分当たり0.1L吹き込みながら攪拌した。こうして得た金濃度が2mg/L以上の浸出液をヤシ殻由来活性炭(太平化学産業社製ヤシコールMC)を充填したカラムに通し、金を活性炭に吸着させた。適当に金を吸着させたところで活性炭を取り出し、金濃度を定量したところ9000g/ton程度であった。金の濃度は灰吹き法で濃縮した後に王水に溶解し、ICP-AESにより定量した。
塩酸と水酸化ナトリウムでpHを4、8、12に調整した水溶液にチオ硫酸ナトリウムを0.5mol/L(チオ硫酸イオンとして56g/L)となるように添加した溶離液を調製した。この金を吸着した活性炭を20g/Lの割合で溶離液に浸漬して80℃で攪拌して溶離を行った。金の濃度は過酸化水素を2mL添加し、さらに塩酸で希釈して100mLに規正した後に上澄みをICP-AESにより定量した。
実施例1と同様にして調整した活性炭を用いてpH4の希硫酸を溶離液とし、活性炭を20g/Lの割合で溶離液に浸漬して80℃で攪拌して溶離を行った。
実施例1と同様にして調整した活性炭を用いてチオ硫酸ナトリウムを0.1mol/L(チオ硫酸イオンとして11.2g/L)となるように添加した溶離液を調製した。溶離液のpHは4とした。この金を吸着した活性炭を20g/Lの割合で溶離液に浸漬して80℃で攪拌して溶離を行った。溶離液中の金濃度から換算した溶離率の経時変化を図2に示す。
実施例1と同様にして調整した活性炭を用いてチオ硫酸ナトリウムを0.1mol/L(チオ硫酸イオンとして11.2g/L)となるように添加した溶離液を調製した。溶離液のpHは4とした。この金を吸着した活性炭を20g/Lの割合で溶離液に浸漬して25℃で攪拌して溶離を行った。溶離液中の金濃度の経時変化を図2に示す。
金を9800g/t吸着した活性炭(太平化学産業社製:CC-202)19mLを内径11mm、高さ200mmのコックつきガラスカラムに充填した。活性炭はあらかじめHClにより洗浄しておいた。次に、純水に濃度:0.01mol/L、0.1mol/L、0.5mol/L、又は、1.0mol/Lとなるようチオ硫酸ナトリウムを添加し、pHを硫酸で5に調整し、これを溶離液とした。続いて、活性炭を充填したカラムに溶離液を4.1mL/分で供給して通液後液を5~7mLごとに分画して採取した。カラム内部温度は70℃とした。カラム通液のSV:空間速度は13(1/h)とし、LV:線速度は2.6(m/h)とし、BV:通液量は156(mL)とした。次に、分画液中の金濃度をICP-AESで測定し、活性炭に含まれる金の品位を算出した。上記試験条件を表1に示し、得られた通液量と活性炭中の金品位との関係を表2に示し、そのグラフを図3に示す。
Claims (8)
- 活性炭に吸着された金を、酸性水溶液にチオ硫酸塩を添加して調製された溶離液で溶離して、酸性の濃厚金溶液を得る工程を備えた金の回収方法。
- 前記酸性水溶液はpH4~7である請求項1に記載の金の回収方法。
- 前記チオ硫酸塩はチオ硫酸ナトリウム、チオ硫酸、及び、チオ硫酸カリウムから選択された少なくとも一種を含む還元剤である請求項1又は2に記載の金の回収方法。
- 前記溶離液中のチオ硫酸塩の濃度が0.01mol/L以上である請求項1~3のいずれかに記載の金の回収方法。
- 前記溶離液中のチオ硫酸塩の濃度が0.01~1.0mol/L以上である請求項4に記載の金の回収方法。
- 前記溶離を、溶離温度を20~100℃として回分式反応器を用いて行う請求項1~5のいずれかに記載の金の回収方法。
- 前記溶離温度を60~85℃とする請求項1~6のいずれかに記載の金の回収方法。
- 請求項1~7のいずれかに記載の金の回収方法で得られた濃厚金溶液から還元によって単体の金を作製する金の製造方法。
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CA2865721A CA2865721C (en) | 2012-03-01 | 2013-01-30 | Method of recovering gold adsorbed on activated carbon and method of manufacturing gold using the same |
AU2013200947A AU2013200947B2 (en) | 2012-03-01 | 2013-01-30 | Method of recovering gold absorbed on activated carbon and method of manufacturing gold using the same |
EP13754888.9A EP2821513A4 (en) | 2012-03-01 | 2013-01-30 | METHOD FOR OBTAINING ACTIVE CARBON ABSORBED GOLD AND GOLD MANUFACTURING METHOD THEREWITH |
JP2014502081A JP5840761B2 (ja) | 2012-03-01 | 2013-01-30 | 活性炭に吸着された金の回収方法及びそれを用いた金の製造方法 |
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Cited By (4)
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CN104928487A (zh) * | 2015-06-06 | 2015-09-23 | 长春黄金研究院 | 一种炭浆提金工艺中粉炭的处理方法 |
US10597752B2 (en) | 2013-05-29 | 2020-03-24 | Barrick Gold Corporation | Method for pre-treatment of gold-bearing oxide ores |
CN115385413A (zh) * | 2021-11-03 | 2022-11-25 | 董河贵 | 一种含金废水的处理组合物及其使用方法 |
US11639540B2 (en) | 2019-01-21 | 2023-05-02 | Barrick Gold Corporation | Method for carbon-catalysed thiosulfate leaching of gold-bearing materials |
Families Citing this family (2)
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WO2016104113A1 (ja) | 2014-12-26 | 2016-06-30 | Jx金属株式会社 | 活性炭からの金の回収方法 |
CN107400778B (zh) * | 2017-08-08 | 2019-01-18 | 中南大学 | 一种从强碱性阴离子交换树脂上解吸金硫代硫酸根配离子的方法 |
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Cited By (5)
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US10597752B2 (en) | 2013-05-29 | 2020-03-24 | Barrick Gold Corporation | Method for pre-treatment of gold-bearing oxide ores |
US11401580B2 (en) | 2013-05-29 | 2022-08-02 | Barrick Gold Corporation | Method for pre-treatment of gold-bearing oxide ores |
CN104928487A (zh) * | 2015-06-06 | 2015-09-23 | 长春黄金研究院 | 一种炭浆提金工艺中粉炭的处理方法 |
US11639540B2 (en) | 2019-01-21 | 2023-05-02 | Barrick Gold Corporation | Method for carbon-catalysed thiosulfate leaching of gold-bearing materials |
CN115385413A (zh) * | 2021-11-03 | 2022-11-25 | 董河贵 | 一种含金废水的处理组合物及其使用方法 |
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AU2013200947B2 (en) | 2013-12-12 |
AU2013200947A1 (en) | 2013-09-19 |
PE20190559A1 (es) | 2019-04-17 |
CA2865721A1 (en) | 2013-09-06 |
PE20142107A1 (es) | 2014-12-13 |
CL2014002292A1 (es) | 2014-11-21 |
JPWO2013129017A1 (ja) | 2015-07-30 |
JP5840761B2 (ja) | 2016-01-06 |
CA2865721C (en) | 2017-08-01 |
EP2821513A1 (en) | 2015-01-07 |
EP2821513A4 (en) | 2015-12-09 |
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