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WO2013035301A1 - Agent d'absorption de métaux nobles, procédé de récupération de métaux nobles - Google Patents

Agent d'absorption de métaux nobles, procédé de récupération de métaux nobles Download PDF

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Publication number
WO2013035301A1
WO2013035301A1 PCT/JP2012/005580 JP2012005580W WO2013035301A1 WO 2013035301 A1 WO2013035301 A1 WO 2013035301A1 JP 2012005580 W JP2012005580 W JP 2012005580W WO 2013035301 A1 WO2013035301 A1 WO 2013035301A1
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Prior art keywords
noble metal
metal adsorbent
adsorbent
palladium
platinum
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English (en)
Japanese (ja)
Inventor
倉田　稔
欣也 渥美
福田　裕章
勝利 井上
啓介 大渡
英孝 川喜田
カンジャナ クナタイ
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Saga University NUC
Denso Corp
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Saga University NUC
Denso Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
    • 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
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • 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
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B01J20/3251—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such comprising at least two different types of heteroatoms selected from nitrogen, oxygen or sulphur
    • 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
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/3272—Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/12—Unicellular algae; Culture media therefor
    • 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
    • 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
    • B01J2220/4843—Algae, aquatic plants or sea vegetals, e.g. seeweeds, eelgrass
    • 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 disclosure relates to a noble metal adsorbent that can be used for recovering noble metals (for example, palladium and platinum) and a method for recovering noble metals.
  • noble metals for example, palladium and platinum
  • the extraction solvent used in the method (2) is soluble in water and requires cost for wastewater treatment.
  • This disclosure aims to provide a noble metal adsorbent that can separate and recover a specific type of noble metal from other noble metals and base metals, and a method for recovering the noble metal.
  • the noble metal adsorbent is an algae, a residue of the algae, a strong acid-treated product of the algae, which is chemically modified with a functional group containing at least one of an N atom and an S atom. It is comprised from one of the strong acid processed materials of a residue.
  • a specific kind of precious metal for example, platinum, palladium
  • the method for recovering the noble metal includes dissolving the noble metal in a solution and adsorbing the noble metal on the noble metal adsorbent according to the first aspect of the present disclosure.
  • a specific type of precious metal for example, platinum, palladium
  • FIG. 1 is an explanatory diagram showing a process of chemically modifying algae residue with dithiooxamide
  • FIG. 2 is a graph showing the measurement results of the adsorption percentage when the noble metal adsorbent 2A is used.
  • FIG. 3 is a graph showing the measurement results of the adsorption percentage when the noble metal adsorbent 3A is used.
  • FIG. 4 is a graph showing the measurement results of the adsorption percentage when the residue QA is used,
  • FIG. 5 is a graph showing the relationship between the shaking time and the amount of palladium adsorbed when the noble metal adsorbent 2A is used, FIG.
  • FIG. 6 is a graph showing the relationship between the shaking time and the platinum adsorption amount when the noble metal adsorbent 2A is used
  • FIG. 7 is a graph showing the relationship between the palladium concentration after adsorption and the amount of palladium adsorbed when the noble metal adsorbent 2A is used
  • FIG. 8 is a graph showing the relationship between the platinum concentration after adsorption and the adsorption amount of platinum when the noble metal adsorbent 2A is used
  • FIG. 9 is a graph showing the relationship between the bed volume when adsorption is performed using a column filled with adsorbent 2A and the relative concentration of each metal at the column outlet;
  • FIG. 10 is a graph showing the relationship between the bed volume and the relative concentration of each metal at the column outlet during elution
  • FIG. 11 is a graph showing the functional group evaluation results of the noble metal adsorbent 2A and the residue QA by FTIR
  • FIG. 12A is a scanning electron micrograph of 200 times magnification representing the surface of the noble metal adsorbent 2A.
  • FIG. 12B is a diagram of the photograph of FIG.
  • FIG. 12C is a scanning electron micrograph of the magnification of 1000 times representing the surface of the noble metal adsorbent 2A.
  • FIG. 12D is a diagram of the photograph of FIG.
  • FIG. 13 is an explanatory diagram showing a process of chemically modifying algae residue with polyethyleneimine
  • FIG. 14 is an explanatory diagram showing the chemical structure of polyethyleneimine
  • FIG. 15 is a graph showing the measurement results of the adsorption percentage when the noble metal adsorbent 5A is used
  • FIG. 16 is a graph showing the relationship between the shaking time and the amount of adsorption of the noble metal when the noble metal adsorbent 5A is used
  • FIG. 17 is a graph showing the relationship between the precious metal concentration after adsorption and the amount of precious metal adsorbed when the precious metal adsorbent 5A is used
  • FIG. 18 is a graph showing the functional group evaluation results of the noble metal adsorbent 5A and the residue QA by FTIR
  • FIG. 15 is a graph showing the measurement results of the adsorption percentage when the noble metal adsorbent 5A is used
  • FIG. 16 is a graph showing the relationship between the shaking time and the amount of adsorption of the noble metal when the noble metal adsorbent 5A is used
  • FIG. 17 is a graph
  • FIG. 19A is a scanning electron micrograph of 200 times magnification representing the surface of the noble metal adsorbent 5A.
  • FIG. 19B is a diagram of the photograph of FIG. 19A;
  • FIG. 19C is a scanning electron micrograph at a magnification of 750 times representing the surface of the noble metal adsorbent 5A.
  • FIG. 19D is a diagram of the photograph of FIG. 19C;
  • FIG. 20 is a diagram showing the contents of the noble metal adsorbents 1A to 5B.
  • FIG. 21 is a diagram showing saturated adsorption amounts of palladium ions and platinum ions with respect to the adsorbent 2A at each temperature.
  • FIG. 22 is a diagram showing the results of elemental analysis of the residue QA and the noble metal adsorbent 2A.
  • FIG. 23 is a diagram showing the results of elemental analysis of the residue QA and the noble metal adsorbent 5A.
  • FERM BP-10484 Genus pseudochoricystis Species: ellipsoidea Stock: MBIC11204
  • the microalgae were collected by centrifugation. In addition, you may collect
  • the flocculant include aluminum sulfate-based flocculants, cationic polymer flocculants, and amphoteric polymer flocculants.
  • the collected microalgae were dried and then pulverized in a mortar until the particle size became about 100 ⁇ m.
  • the pulverized microalgae was designated as a pulverized product PA.
  • the functional group of dithiooxamide was introduced and fixed (chemical modification) to the pulverized product PA as follows.
  • ⁇ First stage reaction> First, 5 g of the dried pulverized product PA and 200 mL of pyridine were placed in a 500 mL three-necked flask and kept in an ice bath. Next, 30 mL of thionyl chloride was dropped in a nitrogen gas atmosphere, and then reacted at 70 ° C. for 5 hours. In this reaction, the raw material (pulverized product PA) is chlorinated to produce an intermediate product.
  • the above-described reaction for introducing and immobilizing the functional group of dithiooxamide can be expressed as shown in FIG. That is, in the first stage reaction, the hydroxyl group of the raw material (algae, its residue, or their strong acid treated product) is chlorinated with thionyl chloride or the like to produce an intermediate product, and in the second stage reaction, By reacting the intermediate product and dithiooxamide in a basic atmosphere such as a mixed solution of sodium carbonate and N, N-dimethylformamide, the functional group of dithiooxamide is introduced into the raw material and immobilized.
  • a basic atmosphere such as a mixed solution of sodium carbonate and N, N-dimethylformamide
  • a functional group of dithiooxamide was introduced and fixed to the residue QA to obtain a noble metal adsorbent 2A.
  • the method for introducing and immobilizing the functional group of dithiooxamide was the same as in the case of the noble metal adsorbent 1A.
  • (1-4) Noble metal adsorbent 2B The pulverized product PB was immersed in an organic solvent (a mixture of chloroform and methanol at a ratio of 2: 1), and the oil component in the microalgae was dissolved in the organic solvent. Thereafter, the organic solvent was evaporated and the oil component was recovered. The residue of the microalgae remaining after removing the oil was designated as residue QB.
  • the functional group of dithiooxamide was introduce
  • the method for introducing and immobilizing the functional group of dithiooxamide was the same as in the case of the noble metal adsorbent 1A.
  • Noble metal adsorbent 3A The residue QA was immersed in concentrated sulfuric acid at 100 ° C. for 24 hours. At this time, in the residue QA, it is considered that crosslinking occurs due to the condensation reaction of a pair of hydroxyl groups. Then, it neutralized with sodium hydrogencarbonate (bicarbonate), filtered and dried. The substance obtained by this step was designated as concentrated sulfuric acid treated product RA.
  • a functional group of dithiooxamide was introduced and fixed to the concentrated sulfuric acid treated product RA to obtain a noble metal adsorbent 3A.
  • the method for introducing and immobilizing the functional group of dithiooxamide was the same as in the case of the noble metal adsorbent 1A.
  • Noble metal adsorbent 3B The residue QB was immersed in concentrated sulfuric acid at 100 ° C. for 24 hours. At this time, in the residue QB, it is considered that crosslinking occurs due to the condensation reaction of a pair of hydroxyl groups. Then, it neutralized with sodium hydrogencarbonate (bicarbonate), filtered and dried. The substance obtained by this step was designated as concentrated sulfuric acid treated product RB.
  • a functional group of dithiooxamide was introduced and fixed to the concentrated sulfuric acid treated product RB to obtain a noble metal adsorbent 3B.
  • the method for introducing and immobilizing the functional group of dithiooxamide was the same as in the case of the noble metal adsorbent 1A.
  • FIG. 20 also shows the contents of the noble metal adsorbents 4A to 5B produced in Example 2 described later.
  • a in the column of “type of algae” in FIG. 20 is an algae used for manufacturing the precious metal adsorbent 1A
  • B is an algae used for manufacturing the precious metal adsorbent 1B.
  • X ((Ci-C) / Ci) X100 (X: percentage of adsorption, Ci: concentration of metal ions in hydrochloric acid before adsorption, C: concentration of metal ions in hydrochloric acid after adsorption)
  • X percentage of adsorption
  • Ci concentration of metal ions in hydrochloric acid before adsorption
  • C concentration of metal ions in hydrochloric acid after adsorption
  • platinum ions, palladium ions, copper ions, zinc ions, nickel ions, and iron ions were used as metal ions.
  • the adsorption percentage was measured individually for each metal ion.
  • Each metal ion is a special grade reagent such as platinum chloride (IV) acid, palladium (II) chloride, copper (II) hydrochloride, zinc (II) hydrochloride, nickel (II) ⁇ hydrochloride, and It is formed by dissolving iron (III) hydrochloride in hydrochloric acid. Further, the adsorption percentage was measured at each of a plurality of hydrochloric acid concentrations.
  • the measurement results when the noble metal adsorbent 2A is used are shown in FIG. 2, the measurement results when the noble metal adsorbent 3A is used are shown in FIG. 3, and the measurement results when the residue QA is used are shown in FIG.
  • the noble metal adsorbent 2A and the noble metal adsorbent 3A selectively adsorbed platinum and palladium, and hardly adsorbed zinc, copper, nickel and iron.
  • the noble metal adsorbent 2A adsorbed platinum and palladium more remarkably. Therefore, if these noble metal adsorbents are used, palladium and platinum can be separated and recovered from base metals such as iron and zinc.
  • the noble metal adsorbents 1A, 1B, 2B, 3B were used, almost the same results were obtained.
  • the residues QA and QB were used, the amount of adsorption of platinum and palladium was small.
  • the concentration of hydrochloric acid in the aqueous hydrochloric acid solution was 0.1 mol / dm 3 .
  • the amount of adsorption was measured at several different shaking times. Moreover, the measurement was performed individually for each of the case where the hydrochloric acid aqueous solution contained palladium ions and the case where the hydrochloric acid aqueous solution contained platinum ions. Moreover, the measurement was performed in each of cases where the initial concentration of noble metal ions (palladium ions, platinum ions) in the aqueous hydrochloric acid solution was 1 mM, 2.1 mM, and 3.2 mM.
  • FIG. 5 shows the measurement results when palladium ion is contained in the hydrochloric acid aqueous solution. Moreover, the measurement result in the case of containing platinum ion in hydrochloric acid aqueous solution is shown in FIG. 5 and 6, the horizontal axis represents the shaking time, and the vertical axis represents the adsorption amount of noble metal ions (palladium ions or platinum ions). In both FIG. 5 and FIG. 6, the noble metal was adsorbed on the noble metal adsorbent 2A in a short shaking time.
  • the concentration of hydrochloric acid in the aqueous hydrochloric acid solution was 0.1 mol / dm 3 .
  • the amount of adsorption was measured when the temperature at the time of shaking was 298K, 303K, 313K, and 323K. Further, various initial concentrations of noble metal ions (palladium ions, platinum ions) were set, and measurement was performed in each case.
  • the measurement result when palladium ion is contained in the hydrochloric acid aqueous solution is shown in FIG. Moreover, the measurement result when platinum ion is contained in hydrochloric acid aqueous solution is shown in FIG. 7 and 8, the horizontal axis represents the concentration of the noble metal (palladium ion, platinum ion) in the aqueous solution after adsorption, and the vertical axis represents the amount of adsorption of the noble metal.
  • FIG. 9 shows the relationship between the bed volume (horizontal axis) and the relative concentration (vertical axis) of each metal.
  • the bed volume is a value obtained by dividing the total volume of the aqueous solution passed through the column by the volume of the noble metal adsorbent packed in the column.
  • FIG. 10 shows the relationship between the relative concentration of each metal (outlet concentration / inlet concentration) in the effluent mixed aqueous solution and the bed volume of the mixed aqueous solution during elution. All of the adsorbed palladium (II) and platinum (IV) were eluted and flowed out. Further, copper (II) was not detected during the elution.
  • the upper spectrum in FIG. 11 is that of the residue QA, and the lower spectrum is that of the noble metal adsorbent 2A.
  • the new absorption seen at 2364 cm ⁇ 1 in the lower spectrum is that of ⁇ NH
  • the new absorption seen at 770 cm ⁇ 1 is due to stretching vibrations of C ⁇ S or CN bonds.
  • the new absorption observed at 617 cm ⁇ 1 is due to the stretching vibration of the C—S bond. From such a spectrum, it can be confirmed that the functional group of dithiooxamide is immobilized on the metal adsorbent 2A.
  • FIG. 22 shows the results of elemental analysis of the residue QA and the noble metal adsorbent 2A.
  • the noble metal adsorbent 2A has increased nitrogen and sulfur contents, which indicates that the dithiooxamide functional group is introduced and immobilized in the noble metal adsorbent 2A.
  • FIG. 12A to 12D show scanning electron micrographs of the noble metal adsorbent 2A.
  • FIG. 12A is a photograph at a magnification of 200 times
  • FIG. 12B is a diagram thereof
  • FIG. 12C is a photograph at a magnification of 1000 times
  • FIG. 12D is a diagram thereof.
  • This final product is designated as a noble metal adsorbent 4A.
  • a functional group of polyethyleneimine is introduced.
  • the above-described reaction for introducing and immobilizing a functional group of polyethyleneimine can be expressed as shown in FIG. That is, in the first stage reaction, the hydroxyl group of the raw material (algae, its residue, or their strong acid treated product) is chlorinated with thionyl chloride or the like to produce an intermediate product, and in the second stage reaction, Then, by reacting the intermediate product and polyethyleneimine in a basic atmosphere such as a mixed solution of sodium carbonate and N, N-dimethylformamide, the functional group of polyethyleneimine is introduced and immobilized in the raw material. .
  • a basic atmosphere such as a mixed solution of sodium carbonate and N, N-dimethylformamide
  • the polyethyleneimine used for the production of the precious metal adsorbent 4A is a polymer having the chemical structure shown in FIG. 14 and an average molecular weight of about 75000, and can be purchased from MP Biomedicals LLC.
  • This polyethyleneimine has various amino groups as shown in FIG. 14, and the content thereof is as follows.
  • the method for introducing and fixing the functional group of polyethyleneimine was the same as that for the noble metal adsorbent 4A.
  • Noble metal adsorbent 5B A functional group of polyethyleneimine was introduced and fixed to the residue QB obtained in the same manner as in Example 1 to obtain a noble metal adsorbent 5B.
  • the method for introducing and fixing the functional group of polyethyleneimine was the same as that for the noble metal adsorbent 4A.
  • X ((Ci-C) / Ci) X100 (X: percentage of adsorption, Ci: concentration of metal ions in hydrochloric acid before adsorption, C: concentration of metal ions in hydrochloric acid after adsorption)
  • X percentage of adsorption
  • Ci concentration of metal ions in hydrochloric acid before adsorption
  • C concentration of metal ions in hydrochloric acid after adsorption
  • metal ions platinum ions, palladium ions, copper ions, zinc ions, nickel ions, and iron ions were used as metal ions.
  • the adsorption percentage was measured individually for each metal ion.
  • Each metal ion is a special grade reagent such as platinum chloride (IV) acid, palladium chloride (II), copper (II) hydrochloride, zinc (II) hydrochloride, nickel (II) hydrochloride, and It is formed by dissolving iron (III) hydrochloride in hydrochloric acid.
  • the initial concentration of metal ions in hydrochloric acid is 0.2 mmol / dm 3 for palladium (II) and platinum (IV), and 1.0 mmol / dm 3 for other metal ions.
  • the adsorption percentage was measured at each of a plurality of hydrochloric acid concentrations.
  • FIG. 15 shows the measurement results when the noble metal adsorbent 5A is used.
  • the precious metal adsorbent 5A selectively adsorbed platinum and palladium, and hardly adsorbed zinc, copper, nickel and iron.
  • platinum and palladium were more significantly adsorbed in a low concentration region where the hydrochloric acid concentration was about 0.1 mmol / dm 3 . Therefore, if this noble metal adsorbent is used, palladium and platinum can be separated and recovered from base metals such as iron and zinc.
  • the noble metal adsorbents 4A, 4B, and 5B were used, almost the same results were obtained.
  • the concentration of hydrochloric acid in the aqueous hydrochloric acid solution was 0.1 mol / dm 3 .
  • the amount of adsorption was measured at several different shaking times.
  • the initial concentration of palladium ions in the aqueous hydrochloric acid solution and the initial concentration of platinum ions in the aqueous hydrochloric acid solution were 2 mmol / dm 3 , respectively.
  • the measurement results are shown in FIG.
  • the horizontal axis in FIG. 16 is the shaking time, and the vertical axis is the amount of adsorption of noble metal ions (palladium ions or platinum ions). Both palladium ions and platinum ions were adsorbed on the precious metal adsorbent 5A with a short shaking time.
  • (2-3) Measurement of adsorption isotherm 10 mg of the noble metal adsorbent 5A and 10 ml of hydrochloric acid aqueous solution containing palladium ions or platinum ions are shaken at 30 ° C. for 48 hours, to the noble metal adsorbent 5A of metal ions. The adsorption amount of was measured.
  • the concentration of hydrochloric acid in the aqueous hydrochloric acid solution was 0.1 mol / dm 3 . Further, various initial concentrations of noble metal ions (palladium ions, platinum ions) were set, and measurement was performed in each case.
  • the measurement results are shown in FIG.
  • the horizontal axis in FIG. 17 is the concentration of the noble metal (palladium ion, platinum ion) in the aqueous solution after adsorption, and the vertical axis is the amount of adsorption of the noble metal.
  • FIG. 23 shows the results of elemental analysis of the residue QA and the noble metal adsorbent 5A.
  • the noble metal adsorbent 5A shows an increase in the nitrogen content, so that it can be seen that in the noble metal adsorbent 5A, the functional group of polyethyleneimine is introduced and immobilized.
  • FIG. 19A to 19D show scanning electron micrographs of the noble metal adsorbent 5A.
  • FIG. 19A is a photograph at 200 ⁇ magnification
  • FIG. 19B is a diagram thereof
  • FIG. 19C is a photograph at a magnification of 750 times
  • FIG. 19D is a diagram thereof.
  • this indication is not limited to the said Example at all, and it cannot be overemphasized that it can implement in a various aspect in the range which does not deviate from this indication.
  • the solution containing the noble metal may not be an aqueous hydrochloric acid solution, but an aqueous solution acidified with another acid (for example, sulfuric acid).
  • another acid for example, sulfuric acid
  • functional groups used for chemical modification of algae, algae residues, or their strong acid-treated products are functional groups containing N and / or S atoms other than dithiooxamide and polyethyleneimine (for example, amino groups, thiol groups). Etc.) may be selected as appropriate.
  • Example 2 instead of the polyethyleneimine used in Example 2, another polyethyleneimine (having different molecular weights, or different ratios of primary amino group, secondary amino group, and tertiary amino group) was used. Also good.
  • the above disclosure includes the following aspects.
  • the noble metal adsorbent is an algae, a residue of the algae, a strong acid-treated product of the algae, which is chemically modified with a functional group containing at least one of an N atom and an S atom. It is comprised from one of the strong acid processed materials of a residue.
  • a specific kind of precious metal for example, platinum, palladium
  • Examples of the functional group containing N atom and / or S atom include dithiooxamide (1,2-diaminoethane-1,2-dithione, C 2 H 4 N 2 S 2 ), polyethyleneimine, amino group, and thiol group. Etc.
  • the functional group is dithiooxamide or polyethyleneimine, the effect of separating and recovering a specific kind of noble metal (for example, platinum or palladium) from other noble metals or base metals becomes more remarkable.
  • the noble metal adsorbent of the present invention can be used, for example, by adsorbing and recovering platinum or palladium.
  • Examples of the residue include a residue after oil is extracted from algae by a solvent extraction method using an organic solvent.
  • the strong acid-treated product is obtained by, for example, subjecting algae or a residue thereof to a treatment (for example, mixing) with a strong acid (eg, concentrated sulfuric acid, concentrated hydrochloric acid, etc.).
  • a strong acid eg, concentrated sulfuric acid, concentrated hydrochloric acid, etc.
  • the treatment with a strong acid may be performed at room temperature or while heating. Heating requires less processing time.
  • the treatment time with a strong acid is preferably 1 second or longer.
  • the temperature of the strong acid used is preferably 80 ° C. or higher.
  • the hydroxyl group in the algae or its residue is dehydrated and condensed to form an ether bond. By having an absorption site showing an ether bond, the effect of selecting and recovering a noble metal is even higher.
  • the algae are preferably microalgae.
  • This microalgae means a unicellular algae.
  • the size of the microalgae is preferably in the range of several ⁇ m or less, for example.
  • Examples of the algae include unicellular algae belonging to green algae, red algae, cyanobacteria, brown algae, dinoflagellates and the like.
  • the dosage form of the noble metal adsorbent can be, for example, a powder.
  • the particle size of the powder is preferably in the range of 10 to 150 ⁇ m, more preferably in the range of 50 to 120 ⁇ m, considering the clogging of the apparatus and the adsorption surface area.
  • Examples of the method for making the precious metal adsorbent dosage form include a method of pulverizing with a mortar. By changing the time and strength of pulverization in a mortar, the particle size of the powder can be adjusted as appropriate.
  • the method for recovering the noble metal includes dissolving the noble metal in a solution and adsorbing the noble metal on the noble metal adsorbent according to the first aspect of the present disclosure.
  • a specific type of precious metal for example, platinum, palladium
  • a specific type of precious metal for example, platinum, palladium
  • the liquid temperature during stirring is preferably 30 ° C or higher, and more preferably 50 ° C or higher.
  • the adsorption rate of the noble metal to the noble metal adsorbent is improved.
  • the adsorption capacity of the noble metal with respect to the noble metal adsorbent is improved.

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Abstract

L'agent d'absorption de métaux nobles de l'invention se compose d'au moins un des matériaux suivants : une algue, un résidu de ladite algue, une substance de ladite algue traitée avec un acide fort, ou une substance du résidu de ladite algue traitée avec un acide fort, chimiquement modifiées par un groupe fonctionnel contenant au moins un atome N ou S. À l'aide de cet agent d'absorption de métaux nobles, il est possible de séparer pour les récupérer des variétés spécifiques de métaux nobles, telles que le platine ou le palladium d'autres métaux nobles ou de métaux communs.
PCT/JP2012/005580 2011-09-07 2012-09-04 Agent d'absorption de métaux nobles, procédé de récupération de métaux nobles Ceased WO2013035301A1 (fr)

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JP2011195263A JP5792565B2 (ja) 2011-09-07 2011-09-07 貴金属吸着剤及び貴金属の回収方法
JP2011-195263 2011-09-07

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CN105777993A (zh) * 2016-03-15 2016-07-20 青岛聚大洋藻业集团有限公司 利用脱胶海藻渣制备农用保水剂的方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016011456A (ja) * 2013-10-24 2016-01-21 東ソー株式会社 白金族金属分離剤及び白金族金属イオンの分離方法
WO2023032815A1 (fr) * 2021-08-31 2023-03-09 株式会社Ihi Matériau de récupération de métal, et procédé de récupération de métal à partir d'une solution contenant des ions métalliques ou des ions de complexe métallique

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JPS58174235A (ja) * 1982-02-02 1983-10-13 イエ−リンノヴアシヨ−ン・ハンデルスアクチエボラグ 金属イオン吸着剤
JPS6415133A (en) * 1987-07-09 1989-01-19 Lion Corp Adsorbent for noble metal or the like
JPH05228366A (ja) * 1992-02-17 1993-09-07 Takao Kuwabara 金属イオン吸着性と濾過性を改善した藻類
JP2011225521A (ja) * 2010-03-30 2011-11-10 Sony Corp 殺菌剤、光触媒複合材料、吸着剤及び浄化剤
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

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JPS62500931A (ja) * 1984-12-03 1987-04-16 リサ−チ・コ−ポレイション 金および他の金属の回収法
EP2434006A3 (fr) * 2005-04-12 2012-04-04 Denso Corporation Nouvelles micro-algues et procédé de production d'hydrocarbures
JP4740050B2 (ja) * 2006-06-30 2011-08-03 国立大学法人北海道大学 重金属捕捉剤

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JPS58174235A (ja) * 1982-02-02 1983-10-13 イエ−リンノヴアシヨ−ン・ハンデルスアクチエボラグ 金属イオン吸着剤
JPS6415133A (en) * 1987-07-09 1989-01-19 Lion Corp Adsorbent for noble metal or the like
JPH05228366A (ja) * 1992-02-17 1993-09-07 Takao Kuwabara 金属イオン吸着性と濾過性を改善した藻類
JP2011225521A (ja) * 2010-03-30 2011-11-10 Sony Corp 殺菌剤、光触媒複合材料、吸着剤及び浄化剤
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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105777993A (zh) * 2016-03-15 2016-07-20 青岛聚大洋藻业集团有限公司 利用脱胶海藻渣制备农用保水剂的方法

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