WO2007023521A1 - Procédé de séparation de l'or - Google Patents

Procédé de séparation de l'or Download PDF

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Publication number
WO2007023521A1
WO2007023521A1 PCT/JP2005/015227 JP2005015227W WO2007023521A1 WO 2007023521 A1 WO2007023521 A1 WO 2007023521A1 JP 2005015227 W JP2005015227 W JP 2005015227W WO 2007023521 A1 WO2007023521 A1 WO 2007023521A1
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WO
WIPO (PCT)
Prior art keywords
gold
adsorbent
adsorption
hydrochloric acid
concentration
Prior art date
Application number
PCT/JP2005/015227
Other languages
English (en)
Japanese (ja)
Inventor
Katsutoshi Inoue
Hidetaka Kawakita
Kumiko Kajiyama
Daisuke Hirata
Original Assignee
Saga University
Muromachi Chemicals Inc.
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 Saga University, Muromachi Chemicals Inc. filed Critical Saga University
Priority to PCT/JP2005/015227 priority Critical patent/WO2007023521A1/fr
Priority to JP2007531965A priority patent/JP4827146B2/ja
Publication of WO2007023521A1 publication Critical patent/WO2007023521A1/fr

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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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • 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
    • 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
    • B01J20/3021—Milling, crushing or grinding
    • 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
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss

Definitions

  • the present invention relates to a technique for separating gold for the purpose of isolating, recovering, or purifying gold, and in particular, only gold from various metals dissolved in an aqueous hydrochloric acid solution.
  • the present invention relates to a technology for selectively and effectively separating particles as solid particles (gold particles).
  • Gold has been used in many fields in recent years as a jewelry material and electrical / electronic material in addition to jewelry. Since gold is expensive, recovery from various wastes and waste liquids has attracted attention. However, the amount of gold contained in the waste is very small, and it is easy to selectively separate and recover gold from other metals present in large excess.
  • Non-Patent Document 1 Junji Shibata, Akihiko Okuda “Precious Metal Recycling Technology” Resources and Materials, 118 ⁇ 1, p. 1 -8 (2002)
  • Non-Patent Document 2 Hideo Koshimura “Precious metals, present status of recovery technology” Chemical Technology Journal MOL, No. 4, p. 76 -81 (1986)
  • Tannin is one of the organic substances that make up plants, and has many phenol, catechol, and pyrogallol sites in its molecular structure.
  • Plant-derived natural substances rich in tannin include grapes, green tea, and red wine.
  • the amount of polyphenol contained in grapes is said to be about 200 times that of red wine.
  • Tannin is a component of plant bitterness and astringency, and what is particularly abundant in persimmon is called persimmon tannin.
  • Mature astringents at the right time for harvest contain 1-2% water-soluble tannins and immature astringents contain 5-6% persimmon tannins.
  • Non-Patent Document 3 T. Sakaguchi, A. Nakajima; separation Science and Technology, 29-2, p. 205-221 (1994)
  • non-patent documents 4 and 5 report the adsorption of metal ions by an adsorbent using mimosa tannin and watnoretannin as raw materials.
  • Non-Patent Document 4 Yamaguchi Tohiko, Iura Yoshinori, Higuchi Mitsuo, Sakata Isao; Journal of the Wood Society, 37 ⁇ 9, p. 815-820 (1991)
  • Non-patent document 5 Y. Nakano, K. Takeshita, T. Tsutsumi; Water Research, 35-2, p. 496-500 (2001)
  • these adsorbents are prepared by extracting the above tannin components from the plants containing them, and are expensive because they require the cost of extraction and recovery from those plants.
  • tannin components such as astringent peels were not used by using an adsorbent prepared by cost-effectively extracting tannin components from plants containing them. It has been found that uranium and thorium can be recovered by using as an adsorbent the plant part itself containing a large amount as a raw material. For example, Patent Document 1 has already reported it.
  • Patent Document 1 JP 2004-330005 A
  • Patent Document 1 enables efficient recovery of uranium and thorium using straw skin, but in order to prepare an insoluble adsorbent in water. It was difficult to use paraformaldehyde, which is a harmful chemical substance, in the crosslinking process. Disclosure of the invention
  • An object of the present invention is to prepare an adsorbent without using a material that is burdensome to the human body and the environment, and effectively collect gold from various wastes and waste liquids at an unprecedented low cost. It is to provide a new technology that can be separated.
  • the adsorbent obtained by treating sulfuric acid on the cocoon skin is brought into contact with an aqueous hydrochloric acid solution containing at least gold as a metal ion, whereby gold is added to the adsorbent.
  • a method for separating gold comprising a step of selectively adsorbing particles.
  • FIG. 1 is a chemical formula showing a repetitive structure of persimmon tannin that constitutes persimmon skin as a raw material of the adsorbent used in the present invention.
  • FIG. 2 Shows the relationship between adsorption percentage (A) of various metal ions and hydrochloric acid concentration ([HC1]).
  • FIG. 3 shows the relationship between the amount of gold adsorbed and the concentration of gold remaining in hydrochloric acid.
  • FIG. 4 is an X-ray diffraction pattern of the adsorbent after gold is adsorbed.
  • FIG. 5 is a digital micrograph of the adsorbent after gold adsorption.
  • the kakitannin ( ⁇ ⁇ tannin) as a raw material of the adsorbent used in the present invention is a substance in which four compounds of epicatechin 'catechin 3-gallate' epigallocatechin 'gallocatechin-3-gallate are chemically bound. It is. Their composition ratio is 1: 1: 2: 2 and has a repeating structure as shown in FIG. It is a high-molecular weight anthocyanin polymer with a molecular weight of about 15,000.
  • persimmon tannin is provided from persimmon skin, and astringent persimmon skin containing abundant persimmon tannin is particularly preferable.
  • This tannin is a water-soluble compound, and as it is, it elutes into an aqueous solution during the adsorption operation and significantly reduces the adsorption of the target substance.
  • Cross-linking treatment is necessary to prevent such elution of tannin.
  • crosslinking agents such as epichlorohydrin and norformaldehyde have been generally used for the crosslinking treatment, but these crosslinking agents are harmful and costly after use.
  • the present inventor is able to effectively absorb high-selective separation of gold by using only concentrated sulfuric acid in the cross-linking treatment of tannin without using a conventional cross-linking agent. It has been found that an agent can be obtained.
  • tannin has a large number of hydroxyl groups, so only a condensation reaction using concentrated sulfuric acid enables sufficient crosslinking, and the crosslinking reaction can be carried out between cellulose tannin molecules and also cellulose and hemisphere coexisting with tannin. It is thought to be performed between the polysaccharides of cellulose.
  • the cross-linking treatment for obtaining the adsorbent used in the present invention is carried out by pulverizing the astringent peel into a powder and then reacting it by stirring in an oil bath with concentrated sulfuric acid. After cross-linking treatment, neutralize with, for example, aqueous sodium hydrogen carbonate, wash thoroughly, for example, first with water, then with lmol / dm 3 hydrochloric acid, and finally with water again, then dry and then grind In this way, the target adsorbent is prepared.
  • the ratio of the mixture of astringent peel and concentrated sulfuric acid is 1.0 to 0.5 kg, preferably 0.7 to 0.8 kg with respect to concentrated sulfuric acid (generally 98 to 90% concentrated sulfuric acid) l dm 3 It is.
  • the temperature of the oil bath at this time is 80 to 120 ° C, preferably 90 to 1 10 ° C.
  • the reaction time is 12 to 48 hours, preferably 18 to 30 hours.
  • various forms of aqueous hydrochloric acid solutions containing various metal ions and conventional batch operations or column operations can be used. By contacting the adsorbent, gold can be selectively adsorbed and recovered.
  • Base metals such as zinc, iron, lead, copper, and cobalt and precious metals such as gold, palladium, and platinum exist as chloride complexes of anions in relatively high concentration aqueous chloride solutions.
  • anion exchange resins having primary to quaternary amino groups.
  • Dowe X 1 which is a quaternary ammonium salt type strongly basic ion exchange resin
  • Non-Patent Document 6 a very large number of metals are illustrated in Non-Patent Document 6 and the like.
  • Non-Patent Document 6 Edited by J. A. Marinsky, Ion Exchange, vol. 1, p. 317, Maec el Dekker, New York (1966)
  • the adsorbent of the present invention selectively adsorbs only gold from an aqueous chloride solution, and does not adsorb base metals as described above and noble metals other than gold at all.
  • the chloride concentration range for selectively adsorbing gold is 0.01 to 12 mol / dm 3 concentration range, preferably 0.0 to 8 mol / dm 3 when the aqueous chloride solution is hydrochloric acid. Concentration range.
  • an adsorbent derived from sulfuric acid-treated carp skin when brought into contact with an aqueous hydrochloric acid solution containing low concentrations of gold and other metal ions, only gold is selectively adsorbed.
  • the adsorbed gold is reduced and deposited as gold particles.
  • the average particle size of the gold particles is about several microns to several hundred microns, and can be easily separated from the adsorbent particles by existing methods such as sieving and gravity sorting (specific gravity difference sorting).
  • the astringent peel produced in the production of dried koji was powdered as it was, and 15 g was taken into 20 ml of 98% concentrated sulfuric acid, and the mixture was subjected to crosslinking treatment by heating and stirring at 100 ° C for 24 hours .
  • the reaction mixture was added to 500 ml of an aqueous sodium bicarbonate solution with a concentration of 100 g / dm 3 Was added to neutralize, and then washed with 1000 ml of distilled water at 50 ° C. and then with 1000 ml of distilled water at room temperature.
  • the mixture was stirred with 500 ml of hydrochloric acid having a concentration of ImolZdm 3 for 12 hours, filtered, and the filtrate was washed with distilled water until the pH became neutral. After that, it was put in a dryer at 70 ° C and dried for 24 hours. After that, it was pulverized with a ball mill, sieved, and a particle size of 150 microns or less was used as an adsorbent.
  • An aqueous hydrochloric acid solution of gold (III) having a concentration of 0.2 mmol / dm 3 was prepared by dissolving chloroauric acid in hydrochloric acid having a concentration of 0.:! To 8 mol / dm 3 . 10 ml of this aqueous solution and 10 mg of the adsorbent prepared in Example 1 were put into a triangular flask with a stopper, and adsorbed by shaking for 30 hours in a constant temperature water bath at 30 ° C. The concentration of gold in the solution before and after adsorption was measured with an AA-6650 type atomic absorption photometer manufactured by Shimadzu, and the amount of adsorption was determined. The concentration of hydrochloric acid in the solution was determined by neutralization titration. Also, the adsorption percentage (A) was obtained from the decrease in gold concentration in the solution by adsorption according to the following formula.
  • Adsorption percentage [(Gold concentration before adsorption-Gold concentration after adsorption) Gold concentration before Z adsorption) X 100
  • the base metals such as iron (III), zinc (II), copper (II), tin (IV) and the noble metals palladium (II) and Platinum (IV) was adsorbed. Some platinum adsorption was seen, but negligible compared to gold. There is very little adsorption of other metals.
  • Figure 3 shows the relationship between the gold adsorption amount (Q) and the gold concentration (Ce) in the solution after adsorption.
  • Q gold adsorption amount
  • Ce gold concentration
  • the yield of Japanese astringents is 117,900t / year, and many of them are peeled and removed, then processed into dried straw and used for food. About 9% of the skin generated when making dried straw is discarded.
  • the adsorbent used in the present invention can be prepared by applying a simple sulfuric acid treatment using such a material.
  • the present invention separates and recovers low-concentration gold in wastes and waste liquids in various industrial fields, such as anodic slime leachate produced in electrolytic ironmaking such as copper and nickel. Or, it can be refined and inexpensive and easy to handle. Can also be utilized as a gentle process.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

La présente invention concerne un procédé qui, à l'aide d'un adsorbant bon marché, permet de séparer et de récupérer sous forme de particules d'or l'or qui est présent à faible concentration dans une solution aqueuse d'acide chlorhydrique. Selon ledit procédé, un adsorbant obtenu en traitant à l'acide sulfurique des écorces de plaqueminier est mis au contact d'une solution aqueuse d'acide chlorhydrique qui contient au moins de l'or sous forme d'ions métalliques, ce qui réalise l'adsorption sélective des particules d'or sur l'adsorbant.
PCT/JP2005/015227 2005-08-22 2005-08-22 Procédé de séparation de l'or WO2007023521A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/JP2005/015227 WO2007023521A1 (fr) 2005-08-22 2005-08-22 Procédé de séparation de l'or
JP2007531965A JP4827146B2 (ja) 2005-08-22 2005-08-22 金の分離方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2005/015227 WO2007023521A1 (fr) 2005-08-22 2005-08-22 Procédé de séparation de l'or

Publications (1)

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WO2007023521A1 true WO2007023521A1 (fr) 2007-03-01

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102153160A (zh) * 2010-03-17 2011-08-17 晋城市柿宝科技发展有限公司 一种利用柿子残渣吸附清除废液中六价铬的方法
JP2012024752A (ja) * 2010-06-22 2012-02-09 Denso Corp 貴金属吸着剤及び貴金属の回収方法
CN102534211A (zh) * 2012-01-20 2012-07-04 北京科技大学 一种利用山竹渣选择性吸附提取黄金的方法
JP2012170950A (ja) * 2011-02-24 2012-09-10 Denso Corp 吸着剤及び貴金属の回収方法
CN106582553A (zh) * 2016-12-05 2017-04-26 长沙秋点兵信息科技有限公司 一种用于重金属废液处理的吸附剂的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0215128A (ja) * 1988-06-30 1990-01-18 Koji Sakaguchi 柿渋−アルデヒド−水、柿渋−酸−水から成る含水ゲル組成物を利用する貴金属などの金属元素吸着回収法
JPH0566291A (ja) * 1991-07-09 1993-03-19 Mitsubishi Nuclear Fuel Co Ltd 金属元素吸着剤の製造方法及び該吸着剤による金属元素の吸着分離方法
JPH07313870A (ja) * 1994-05-24 1995-12-05 Rengo Co Ltd 水不溶性タンニン製剤とその製造方法
JP2003226923A (ja) * 2002-02-04 2003-08-15 Mitsubishi Nuclear Fuel Co Ltd 銀の回収方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0215128A (ja) * 1988-06-30 1990-01-18 Koji Sakaguchi 柿渋−アルデヒド−水、柿渋−酸−水から成る含水ゲル組成物を利用する貴金属などの金属元素吸着回収法
JPH0566291A (ja) * 1991-07-09 1993-03-19 Mitsubishi Nuclear Fuel Co Ltd 金属元素吸着剤の製造方法及び該吸着剤による金属元素の吸着分離方法
JPH07313870A (ja) * 1994-05-24 1995-12-05 Rengo Co Ltd 水不溶性タンニン製剤とその製造方法
JP2003226923A (ja) * 2002-02-04 2003-08-15 Mitsubishi Nuclear Fuel Co Ltd 銀の回収方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102153160A (zh) * 2010-03-17 2011-08-17 晋城市柿宝科技发展有限公司 一种利用柿子残渣吸附清除废液中六价铬的方法
JP2012024752A (ja) * 2010-06-22 2012-02-09 Denso Corp 貴金属吸着剤及び貴金属の回収方法
JP2012170950A (ja) * 2011-02-24 2012-09-10 Denso Corp 吸着剤及び貴金属の回収方法
CN102534211A (zh) * 2012-01-20 2012-07-04 北京科技大学 一种利用山竹渣选择性吸附提取黄金的方法
CN106582553A (zh) * 2016-12-05 2017-04-26 长沙秋点兵信息科技有限公司 一种用于重金属废液处理的吸附剂的制备方法

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JPWO2007023521A1 (ja) 2009-02-26
JP4827146B2 (ja) 2011-11-30

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