CN110184463A - Method that is a kind of while extracting golden simple substance and the second metal simple-substance - Google Patents

Method that is a kind of while extracting golden simple substance and the second metal simple-substance Download PDF

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CN110184463A
CN110184463A CN201910356411.7A CN201910356411A CN110184463A CN 110184463 A CN110184463 A CN 110184463A CN 201910356411 A CN201910356411 A CN 201910356411A CN 110184463 A CN110184463 A CN 110184463A
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substance
solution
simple substance
atrz
metal
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CN110184463B (en
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李生华
彭盼盼
庞思平
胡宝平
史庆嵘
赵超峰
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Beijing Institute of Technology BIT
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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
    • C22B11/00—Obtaining noble metals
    • C22B11/02—Obtaining noble metals by dry processes
    • C22B11/021—Recovery of noble metals from waste materials
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • 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
    • C22B47/00—Obtaining manganese
    • C22B47/0018—Treating ocean floor nodules
    • C22B47/0045—Treating ocean floor nodules by wet processes
    • C22B47/0081—Treatment or purification of solutions, e.g. obtained by leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • 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
    • C22B7/001—Dry processes
    • 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
    • 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

Abstract

The invention belongs to metal recovery technical fields, and in particular to a method of golden simple substance and the second metal simple-substance are extracted simultaneously.It is described first the waste material containing golden simple substance is smashed to pieces, grind into powder, be added in the mixed solution of concentrated nitric acid and hydrobromic acid and react to the solution of clear is obtained, alkaline solution is added dropwise to neutrality, then filters again, obtains the neutral solution of the ion containing auribromohydric acid；The solution that soluble metallic salt is added dropwise after mixing with ATRZ solution is stirred to being precipitated, and obtains intermediate product after the washing of precipitate, drying；The mixture containing elemental gold and simple substance M is obtained after intermediate product sintering；Golden simple substance is obtained after separation and M simple substance the method is easy to operate, and extraction rate is exceedingly fast.

Description

Method that is a kind of while extracting golden simple substance and the second metal simple-substance
Technical field
The invention belongs to metal recovery technical fields, and in particular to a kind of golden simple substance and the second metal simple-substance of extracting simultaneously Method.
Background technique
Gold is used as a kind of noble metal, reasonable to recycle golden resource significance since the reserves in earth's surface are lower Great, fitting has good chemical stability, electric conductivity, thermal conductivity etc., thus in instrument industry, electronics industry, electricity Plating and conductive material etc. have a wide range of applications.With the use of 21 century a large amount of electronic products, electronic component institute The waste and heavy metal ion environmental pollution of bring gold resource are the huge challenges that we face, therefore are recycled in waste material Metal be of great significance.The method that tradition extracts gold mainly uses cyaniding, Thiourea-uv Method etc., although these methods can Gold is extracted, but the above method there is a problem of being more toxic, at high cost and extraction rate is slower.
4,4 '-azos -1,2,4- triazole (ATRZ) contain multiple coordination abilities as one of azotic heterocyclic compound Stronger nitrogen-atoms, thus had a wide range of applications in field of coordinative chemistry, it is total to metal cation and auribromohydric acid ion With a kind of complex is synthesized and for recycling golden simple substance, relevant report is had not yet to see.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of method for extracting golden simple substance and the second metal simple-substance simultaneously, The method for recycling golden resource, have many advantages, such as rapidly and efficiently, it is inexpensive and environmentally protective.
To achieve the above object, technical scheme is as follows.
Method that is a kind of while extracting golden simple substance and the second metal simple-substance, the method comprises the following steps:
(1) the neutral solution preparation of the ion containing auribromohydric acid: first the waste material containing golden simple substance is smashed to pieces, grind into powder, so It is filtered after the powder to be added to in the mixed solution of concentrated nitric acid and hydrobromic acid reaction to solution clear afterwards, to resulting Alkaline solution is added dropwise in clear transparent solutions to pH=7, then filters again, obtains the neutral solution of the ion containing auribromohydric acid；
(2) ATRZ solution is obtained by ATRZ is soluble in water, the neutral solution of ATRZ solution and the ion containing auribromohydric acid is mixed, Then the solution that soluble metallic salt is added dropwise again is stirred to being precipitated, and obtains centre after gained washing of precipitate, drying after filtering Product；
(3) under inert gas shielding, intermediate product after 3~6h of heat preservation sintering, is cooled to room temperature at 400~900 DEG C, Obtain the mixture containing elemental gold and simple substance M；
(4) mixture containing elemental gold and simple substance M is separated, golden simple substance and M simple substance are obtained；
Wherein, the soluble metallic salt is mantoquita, cobalt salt or manganese salt；The water is the water of deionized water purity or more； The M simple substance is copper, cobalt or manganese；How to separate golden simple substance and M simple substance is the common knowledge of this field.
Preferably, the volume ratio of concentrated nitric acid and hydrobromic acid is 1:3 in step (1), and the reaction time is 2~5h.
Preferably, the volume ratio of concentrated nitric acid and hydrobromic acid is 1:3 in step (1), and the reaction time is 3~4h.
Preferably, solute is NaOH and NaHCO that mass ratio is 1:2 in step (1) neutral and alkali solution3Or mass ratio is 1: 2 KOH and KHCO3。
Preferably, metal ion in soluble metallic salt in step (2), auribromohydric acid ion, ATRZ molar ratio be 1:1~ 5~30min under the conditions of room temperature~50 DEG C, is stirred in 2:1~4, and obtained precipitating is washed 2~3 times, then in 50~100 DEG C of conditions 5~9h of lower drying.
Preferably, metal ion in soluble metallic salt in step (2), auribromohydric acid ion, ATRZ molar ratio be 1:1:2 ~3；Under the conditions of room temperature~50 DEG C, mixing time is 10~20min；Obtained precipitating is washed 2~3 times, in 55~70 DEG C of conditions 7~8h of lower vacuum drying.
Preferably, mantoquita described in step (2) is Cu (BF4)2、Cu(NO3)2、CuCl2、Cu(SO4)2With Cu (ClO4)2In More than one；The cobalt salt is Co (BF4)2、Co(NO3)2、CoCl2With Cu (ClO4)2One or more of；The manganese salt is Mn(NO3)2、MnCl2With Mn (ClO4)2One or more of.
Preferably, the intermediate product described in step (2) is that ATRZ@Au-M is coordinated complex, the ATRZ@ The chemical formula that Au-M is coordinated complex is [M (ATRZ)3](AuBr4)2·xH2O, wherein M is Cu, Co or Mn, when M is Cu When, x=2；When M is Co or Mn, x=6；Mn in the complex2+、Cu2+Or Co2+Centered on atom, ATRZ conduct Organic ligand forms metal cation organic backbone, AuBr4 -The hole of cationic metal organic backbone is filled in for balance anion It is intracavitary.
Preferably, sintering temperature is 500~700 DEG C in step (3), and sintering time is 4~5h.
Preferably, the mixture containing simple substance Au and M is immersed in excessive concentrated hydrochloric acid in step (4), stirring 10~ After 30min, the precipitating obtained after filtering is washed 2~3 times, obtains elemental gold after dry；The solution obtained after filtering, with active gold Belong to reduction, obtains simple substance M.
Beneficial effect
(1) under the conditions of the present invention is by existing for the coordinating metal salt, auribromohydric acid ion occurs mutual in ATRZ and solution Effect, obtains cationic metal organic backbone (MOFs).In the structural unit of the cation MOFs, ATRZ matches as organic Body, metal ions M n2+、Cu2+And Co2+It is the central atom as cationic MOFs, AuBr4 -It is filled as balance anion In the vestibule of cationic metal organic backbone, obtained intermediate product is bimetallic containing ATRZ structure and Au-M simultaneously MOFs。
(2) the method for the invention is easy to operate, it is only necessary to which normal temperature and pressure, water make solvent, can will give up under neutrallty condition Gold in material is with AuBr4 -Form extract, and extraction rate is exceedingly fast.
(3) present invention, can be at after pickling by the mixture of method two kinds of metal simple-substances of available Au and M of sintering Function removes another metal simple-substance M, this allows for the elemental gold prepared purity is high；Secondly further for clear liquid after pickling It goes to restore using active metal (such as Zn), moreover it is possible to successfully obtain another metal simple-substance M, really realize bimetallic recycling；Separately The mixed system for obtaining two kinds of metal simple-substances of Au and M outside is generally used for the use of catalyst.
Detailed description of the invention
Fig. 1 is the intermediate product that 1-3 of the embodiment of the present invention is prepared and the infrared spectrogram of ATRZ.
Fig. 2 is the crystal structure unit accumulation schematic diagram for the intermediate product that the embodiment of the present invention 1 is prepared.
Fig. 3 is the crystal structure unit accumulation schematic diagram for the intermediate product that the embodiment of the present invention 2 is prepared.
Fig. 4 is the crystal structure unit accumulation schematic diagram for the intermediate product that the embodiment of the present invention 3 is prepared.
Fig. 5 is the X-ray diffraction test result figure for the final product that the embodiment of the present invention 1 is prepared.
Fig. 6 is the X-ray energy spectrum test result figure for the final product that the embodiment of the present invention 1 is prepared.
Specific embodiment
The present invention is further described in detail below with reference to embodiment.
In following embodiment:
(1) synthesis of ATRZ is according to document " Li S H, Pang S P, Li X T, et al.Synthesis of new Tetrazene (N-N=N-N)-linked bi (1,2,4-triazole) [J] Chemistry In China flash report (English edition), 2007,18 (10): method described in 1176-1178. " is prepared.
(2) examination of infrared spectrum: the 560 type Fourier transformation of Nicolet Magna IR produced using Bruker company Infrared spectrometer, 4000~400cm of wave-length coverage of test-1, using KBr pressed disc method, resolution ratio 4cm-1.Tabletting preparation side Method are as follows: 1mg sample to be tested and 100mgKBr, tablet press machine pressure 15GPa, tabletting time 10s.
(3) X-ray diffraction is tested: diffraction data is collected on Rigaku RAXIS IP diffractometer, diffractometer condition are as follows: CCD camera, graphite monochromator, MoK α radiationRegular sample is placed into fiberglass pipe In, in 105K nitrogen atmosphere, data acquisition range: Δ ω=0.60 °；2 θ=1.73~25.01 °；Φ=0,85,170 °；χ= 54.77°；T=45s.Data integral is carried out with Saint+program package.Absorption calibration is carried out with Sadabs, is used Crystallographic software package in SHELXTL carries out structure refinement.According to above-mentioned crystallization obtained It learns message file (CIF), calculates the enterable space of solvent molecule with PLATON program.
(4) X-ray energy spectrum (EDS) is tested: using the scanning electron microscope of the model SU1510 of Hitachi, Ltd's production The X-ray energy spectrometer of the model Genensis Apollo X/XL of instrument company's production is risen with Shang Haina.It is usually electric with scanning Mirror or transmission electron microscope combination, use beam bombardment sample surfaces under vacuum chamber, and excited species emits characteristic X-ray, according to The wavelength of characteristic X-ray, qualitative and semi-quantitative analysis sample element.
Embodiment 1
Method that is a kind of while extracting golden simple substance and the second metal simple-substance, the method comprises the following steps:
(1) the neutral solution preparation of the ion containing auribromohydric acid: by AMD AthlonTMThe discarded central processing unit of 64 × 2 models (CPU), the pulverizer of the DX100 model first produced with Dongguan Ding Xiang company is crushed, further grind into powder, then Take 5g that the powder is added to (dense nitre in the configured concentrated nitric acid of 25mL (mass fraction 68%) and the mixed solution of hydrobromic acid The volume ratio 1:3 of acid and hydrobromic acid) reaction 3h, filter residue is filtered after reaction, is slowly added dropwise into the solution of clear NaOH and NaHCO3Mass ratio=1:2 alkaline solution, until pH value of solution=7, then filter again clear is molten Liquid is the neutral solution of the ion containing auribromohydric acid.
(2) auribromohydric acid ion concentration is the preparation of 10mmol/L neutral solution: emitting light using inductively coupled plasma body The initial concentration of auribromohydric acid ion, is then diluted with water in spectrometer (ICP-OES) test calibration solution, be prepared gold chloride from Sub- concentration is the neutral solution of 10mmol/L.
(3) concentration is the preparation of the ATRZ solution of 10mmol/L: the ATRZ solid of 0.0328g is placed in 20mL distilled water In, it is 70 DEG C in temperature, stirring rate stirs 20min under conditions of being 350rpm, and it is 10mmol/L's that concentration, which can be obtained, ATRZ solution.
(4) concentration is the preparation of the soluble Cu salting liquid of 10mmol/L: by the Cu (BF of 0.0237g4)2Solid is placed in In 10mL distilled water, the Cu (BF that concentration is 10mmol/L is can be obtained in ultrasonic resonance 5min dissolution4)2Solution.
(5) preparation of ATRZ@Au-Cu: to the gold chloride ion concentration of 10mL be 10mmol/L neutral solution in, first plus Then Cu (the BF of 5mL is added dropwise in the ATRZ solution of 15mL again4)2Solution, Cu (BF4)2、AuBr4 -, ATRZ molar ratio be 1:2:3, 20min is stirred at room temperature, red insoluble precipitating is obtained by filtration, distillation washing 3 times, then vacuum is dry under the conditions of 60 DEG C Dry 7h obtains intermediate product, i.e. ATRZ@Au-Cu complex.
(6) the ATRZ Au-Cu compound for taking 100mg places it in the OTF-1200X type pipe of Hefei Ke Jing company production In formula furnace, first lead to Ar2Air in emptier, it is 600 DEG C that sintering temperature, which is then arranged, continues logical Ar2Protection gas is done, is heated up Time is 2h, heat preservation sintering time 4h, then stops heating, and in Ar2Atmosphere under cooled to room temperature, later will sintering Remaining solid product, which is immersed in 30mL concentrated hydrochloric acid (mass fraction 36%), afterwards stirs 20min, filters out insoluble precipitating again, The distillation of 15mL is washed 3 times, and obtaining solid matter after dry is elemental gold.
The examination of infrared spectrum result of intermediate product is as shown in Figure 1, be 3108,1488,1371 and 1175cm in wave number-1Place There is characteristic absorption peak, wherein 3108cm-1For the C-H stretching vibration peak in triazole ring, 1488cm-1For the feature of azo bond Stretching vibration peak, 1175cm-1For the out-of-plane bending vibration peak of N-N key, show to contain ATRZ structure in final product.
Test results are shown in figure 2 for the single crystal X-ray diffraction of intermediate product, and the chemical formula of final product is [Cu (ATRZ)3] (AuBr4)2·2H2O, Cu in final product2+Centered on atom, ATRZ as organic ligand form cationic metal organic backbone (MOFs), AuBr4 -The hole for being filled in cationic metal organic backbone for balance anion is intracavitary.
Test results are shown in figure 5 for the X-ray diffraction of final powders, as the result is shown only two times of angles be 38.2 °, There is stronger diffraction maximum at 44.6 °, 64.5 ° and 78.5 °, and there is no stronger diffraction maximums in other positions, it is single by consulting There is relevant spread out when two times of angles are 38.2 °, 44.4 °, 64.6 ° and 78.5 ° in Gionee cube known to the XRD standard card of matter gold Peak is penetrated, the two result fits like a glove, and shows that final product is elemental gold.
Test results are shown in figure 6 by the EDS of final product, in the solid product obtained after step 1 vacuum-sintering as the result is shown, The only presence of Au element and C element, the result of combining powder X-ray diffraction test is it is found that Au element is with the shape of golden simple substance Existing for formula, according to constituent content as the result is shown elemental gold mass fraction be 93.45%, the purity is high of elemental gold can be calculated Up to 22.4K.
Embodiment 2
Method that is a kind of while extracting golden simple substance and the second metal simple-substance, the method comprises the following steps:
(1) the neutral solution preparation of the ion containing auribromohydric acid: by AMD AthlonTMThe discarded central processing unit of 64 × 2 models (CPU), the pulverizer of the DX100 model first produced with Dongguan Ding Xiang company is crushed, further grind into powder, then Take 5g that the powder is added to (dense nitre in the configured concentrated nitric acid of 25mL (mass fraction 68%) and the mixed solution of hydrobromic acid The volume ratio 1:3 of acid and hydrobromic acid) reaction 2h, filter residue is filtered after reaction, is slowly added dropwise into the solution of clear NaOH and NaHCO3Mass ratio=1:2 alkaline solution, until pH value of solution=7, then filter again clear is molten Liquid is the neutral solution of the ion containing auribromohydric acid.
(2) auribromohydric acid ion concentration is the preparation of 10mmol/L neutral solution: emitting light using inductively coupled plasma body The initial concentration of auribromohydric acid ion, is then diluted with water in spectrometer (ICP-OES) test calibration solution, be prepared gold chloride from Sub- concentration is the neutral solution of 10mmol/L.
(3) concentration is the preparation of the ATRZ solution of 10mmol/L: the ATRZ solid of 0.0328g is placed in 20mL distilled water In, it is 70 DEG C in temperature, stirring rate stirs 20min under conditions of being 350rpm, and it is 10mmol/L's that concentration, which can be obtained, ATRZ solution.
(4) concentration is the preparation of the soluble Co salting liquid of 10mmol/L: by the Co (NO of 0.0291g3)2·6H2O solid It is placed in 10mL distilled water, the Co (NO that concentration is 10mmol/L can be obtained in ultrasonic resonance 5min dissolution3)2Solution.
(5) preparation of ATRZ@Au-Co: to the gold chloride ion concentration of 10mL be 10mmol/L neutral solution in, first plus Then Co (the NO of 5mL is added dropwise in the ATRZ solution of 15mL again3)2Solution C o (NO3)2、AuBr4 -, ATRZ molar ratio be 1:1:2, 20min is stirred at room temperature, red insoluble precipitating is obtained by filtration, distillation washing 2 times, then vacuum is dry under the conditions of 50 DEG C Dry 9h obtains intermediate product, i.e. ATRZ@Au-Co complex.
(6) the ATRZ Au-Co compound for taking 100mg places it in the OTF-1200X type pipe of Hefei Ke Jing company production In formula furnace, first lead to Ar2Air in emptier, it is 400 DEG C that sintering temperature, which is then arranged, and heating-up time 1.5h continues to lead to Ar2Protection gas is done, then heat preservation sintering time 6h stops heating, and in Ar2Atmosphere under cooled to room temperature, later will burn Remaining solid product, which is immersed in 30mL concentrated hydrochloric acid (mass fraction 38%), after knot stirs 10min, filters out insoluble precipitating again, The distillation of 15mL is washed 3 times, and obtaining solid matter after dry is elemental gold.
The examination of infrared spectrum result of intermediate product is as shown in Figure 1, be 3108,1488,1371 and 1175cm in wave number-1Place There is characteristic absorption peak, wherein 3108cm-1For the C-H stretching vibration peak in triazole ring, 1488cm-1For the feature of azo bond Stretching vibration peak, 1175cm-1For the out-of-plane bending vibration peak of N-N key, show to contain ATRZ structure in final product.
Test results are shown in figure 3 for the single crystal X-ray diffraction of intermediate product, and the chemical formula of final product is [Co (ATRZ)3] (AuBr4)2·6H2O, Co in final product2+Centered on atom, ATRZ as organic ligand form cationic metal organic backbone, AuBr4 -The hole for being filled in cationic metal organic backbone for balance anion is intracavitary.
The X-ray diffraction test result of final powders is similar to Example 1, shows that final product is elemental gold.
Embodiment 3
Method that is a kind of while extracting golden simple substance and the second metal simple-substance, the method comprises the following steps:
(1) the neutral solution preparation of the ion containing auribromohydric acid: by AMD AthlonTMThe discarded central processing unit of 64 × 2 models (CPU), the pulverizer of the DX100 model first produced with Dongguan Ding Xiang company is crushed, further grind into powder, then Take 5g that the powder is added to (dense nitre in the configured concentrated nitric acid of 25mL (mass fraction 68%) and the mixed solution of hydrobromic acid The volume ratio 1:3 of acid and hydrobromic acid) reaction 5h, filter residue is filtered after reaction, is slowly added dropwise into the solution of clear NaOH and NaHCO3Mass ratio=1:2 alkaline solution, until pH value of solution=7, then filter again clear is molten Liquid is the neutral solution of the ion containing auribromohydric acid.
(2) auribromohydric acid ion concentration is the preparation of 10mmol/L neutral solution: emitting light using inductively coupled plasma body The initial concentration of auribromohydric acid ion, is then diluted with water in spectrometer (ICP-OES) test calibration solution, be prepared gold chloride from Sub- concentration is the neutral solution of 10mmol/L.
(3) concentration is the preparation of the ATRZ solution of 10mmol/L: the ATRZ solid of 0.0328g is placed in 20mL distilled water In, it is 70 DEG C in temperature, stirring rate stirs 20min under conditions of being 350rpm, and it is 10mmol/L's that concentration, which can be obtained, ATRZ solution.
(4) concentration is the preparation of the soluble M n salting liquid of 10mmol/L: by the MnCl of 0.0125g2Solid is placed in 10mL In distilled water, the MnCl that concentration is 10mmol/L is can be obtained in ultrasonic resonance 5min dissolution2Solution.
(5) preparation of ATRZ@Au-Mn: to the gold chloride ion concentration of 10mL be 10mmol/L neutral solution in, first plus The ATRZ solution of 15mL, is then added dropwise the MnCl of 5mL again2Solution, MnCl2、AuBr4 -, ATRZ molar ratio be 1:2:4, in room 20min is stirred under the conditions of temperature, red insoluble precipitating is obtained by filtration, then distillation washing 3 times is dried in vacuo under the conditions of 100 DEG C 5h obtains intermediate product；That is ATRZ@Au-Mn complex.
(6) the ATRZ Au-Mn compound for taking 100mg places it in the OTF-1200X type pipe of Hefei Ke Jing company production In formula furnace, first lead to Ar2Air in emptier, it is 600 DEG C, heating-up time 2h that sintering temperature, which is then arranged, continues logical Ar2 Protection gas is done, then heat preservation sintering time 4h stops heating, and in Ar2Atmosphere under cooled to room temperature, later will sintering Remaining solid product, which is immersed in 30mL concentrated hydrochloric acid solution (mass fraction 38%), afterwards stirs 20min, and it is insoluble heavy to filter out again It forms sediment, the distillation of 15mL is washed 2 times, and obtaining solid matter after dry is elemental gold.
The examination of infrared spectrum result of intermediate product is as shown in Figure 1, be 3108,1488,1371 and 1175cm in wave number-1Place There is characteristic absorption peak, wherein 3108cm-1For the C-H stretching vibration peak in triazole ring, 1488cm-1For the feature of azo bond Stretching vibration peak, 1175cm-1For the out-of-plane bending vibration peak of N-N key, show to contain ATRZ structure in final product.
Test results are shown in figure 4 for the single crystal X-ray diffraction of intermediate product, and the chemical formula of final product is [Mn (ATRZ)3] (AuBr4)2·6H2O, Mn in final product2+Centered on atom, ATRZ as organic ligand form cationic metal organic backbone, AuBr4 -The hole for being filled in cationic metal organic backbone for balance anion is intracavitary.
The X-ray diffraction test result of final powders is similar to Example 4, shows that final product is elemental gold.
From theoretical mechanism, the finally obtained product of high temperature sintering all only has tri- kinds of simple substance of C, Au and M, and H, O, Br etc. Element there is no, and it is subsequent cleaned with concentrated hydrochloric acid during, M either Cu, Co or Mn can be dissolved in dense salt Among acid, final filtration, the solid matter washed, be dried to obtain are the golden simple substance doped with minute quantity simple substance C.
Based on above theory, ATRZ@Au-Cu, ATRZ@Au-Co and ATRZ@Au-Mn are mixed two-by-two or three is mixed Close, be suitable for elemental gold of the present invention preparation, and no matter use which kind of preparation method, any dosage and match ATRZ@Au-M solid is applicable, it is not limited to which the present invention is write, and can arbitrarily be arranged in pairs or groups, all in protection model of the invention Within enclosing.
Comparative example 1
(1) operated according to step 1~3 of embodiment 1, prepare respectively concentration be 10mmol/L auribromohydric acid from Sub- solution and ATRZ solution.
(2) it is operated according to the step 4 of embodiment 1, it only need to be by the Cu (BF of 0.0237g4)20.0375g is replaced with respectively Al (NO3)3·9H2O, the Ba (NO of 0.0264g3)2With the CrCl of 0.0266g3·6H2O.
(3) it is operated according to the step 5 of embodiment 1, respectively by the Cu (BF of 5mL4)2Replace with the Al (NO of 5mL3)3、 Ba(NO3)2And CrCl3Solution stirs 20min at room temperature, and no precipitating generates, and stands after a week, is still clear Solution.It is unable to get complex, is further also not used to extract golden simple substance and the second metal simple-substance.
Comparative example 2
(1) operated according to step 1~3 of embodiment 1, prepare respectively concentration be 10mmol/L auribromohydric acid from Sub- solution and ATRZ solution.
(2) in the neutral solution for being 10mmol/L to the gold chloride ion concentration of 10mL, the ATRZ solution of 15mL is added, 20min is stirred under room temperature, and no precipitating generates, and stands after a week, is still the solution of clear.It is unable to get coordinationization Object is closed, is further also not used to extract golden simple substance and the second metal simple-substance.
Comparative example 3
By the ATRZ solution that concentration is 10mmol/L replace with 3- nitro -1,2,4- triazole that concentration is 10mmol/L, 1,2,4- triazole, 3,5- diaminostilbene, 2,4- triazole, 3- amino-1,2,4-triazol, the bromo- 1,2,4- triazole of 3,5- bis-, 5- Aminotetrazole or 1- methyl-1,2,4- triazole solution, remaining operation are generated without precipitating after reaction with embodiment 1, stand one Zhou Hou is still the solution of clear.It is unable to get complex, is further also not used to extract golden simple substance and second Metal simple-substance.
Comparative example 1-3's the result shows that, the method for the invention to reactant have certain selectivity.
The principle of the present invention mainly passes through 4,4 '-azo -1,2,4- triazoles and metal ion Cu2+、Co2+、Mn2+Etc. shapes At cation matrix, auribromohydric acid ion is coated in skeleton as balance anion using electrostatic interaction and is realized.Although 4,4 '-azos -1,2,4- triazole contain there are many complexible nitrogen-atoms (8), have stronger coordination ability, but can not A large amount of metal organic framework is quickly formed in the case where the short time not changing external condition, and the presence of auribromohydric acid ion can To promote 4,4 '-azo -1,2,4- triazoles and metal ion Cu2+、Co2+、Mn2+Cation matrix is quickly formed in a short time, The absorption to auribromohydric acid ion is realized simultaneously, this has not been reported in previous document.
The method of the invention can also be to other metal ions such as copper cobalt manganese while realizing auribromohydric acid the ion extraction Plasma, which is realized, to be extracted.Experimental result shows that simple ATRZ cannot directly extract auribromohydric acid ion, can not be short The extraction to copper cobalt and manganese is realized in time, but extraction can be realized in a short time by existing simultaneously two kinds of ions, into one Golden simple substance and the second metal simple-substance are separated to obtain after step sintering.
In conclusion invention includes but is not limited to above embodiments, it is all to be carried out under the spirit and principles in the present invention Any equivalent replacement or local improvement, all will be regarded as within protection scope of the present invention.

Claims (10)

1. a kind of method for extracting golden simple substance and the second metal simple-substance simultaneously, it is characterised in that: the method comprises the following steps:
(1) the neutral solution preparation of the ion containing auribromohydric acid: first the waste material containing golden simple substance is smashed to pieces, grind into powder, then will The powder is added in the mixed solution of concentrated nitric acid and hydrobromic acid and filters after reaction to solution clear, to resulting clarification Alkaline solution is added dropwise in clear solution to pH=7, then filters again, obtains the neutral solution of the ion containing auribromohydric acid；
(2) ATRZ solution is obtained by ATRZ is soluble in water, the neutral solution of ATRZ solution and the ion containing auribromohydric acid is mixed, then The solution that soluble metallic salt is added dropwise again is stirred to being precipitated, and obtains intermediate product after gained washing of precipitate, drying after filtering；
(3) under inert gas shielding, intermediate product after 3~6h of heat preservation sintering, is cooled to room temperature, is obtained at 400~900 DEG C Mixture containing elemental gold and simple substance M；
(4) mixture containing elemental gold and simple substance M is separated, golden simple substance and M simple substance are obtained；
Wherein, the soluble metallic salt is mantoquita, cobalt salt or manganese salt；The water is the water of deionized water purity or more；The M Simple substance is copper, cobalt or manganese.
2. a kind of method for extracting golden simple substance and the second metal simple-substance simultaneously as described in claim 1, it is characterised in that: step (1) volume ratio of concentrated nitric acid and hydrobromic acid is 1:3 in, and the reaction time is 2~5h.
3. a kind of method for extracting golden simple substance and the second metal simple-substance simultaneously as described in claim 1, it is characterised in that: step (1) volume ratio of concentrated nitric acid and hydrobromic acid is 1:3 in, and the reaction time is 3~4h.
4. a kind of method for extracting golden simple substance and the second metal simple-substance simultaneously as described in claim 1, it is characterised in that: step (1) solute is NaOH and NaHCO that mass ratio is 1:2 in neutral and alkali solution3Or mass ratio is the KOH and KHCO of 1:23。
5. a kind of method for extracting golden simple substance and the second metal simple-substance simultaneously as described in claim 1, it is characterised in that: step (2) metal ion in soluble metallic salt in, auribromohydric acid ion, ATRZ molar ratio be 1:1~2:1~4, room temperature~50 DEG C item Under part, 5~30min is stirred, obtained precipitating is washed 2~3 times, and 5~9h is then dried under the conditions of 50~100 DEG C.
6. a kind of method for extracting golden simple substance and the second metal simple-substance simultaneously as described in claim 1, it is characterised in that: step (2) metal ion in soluble metallic salt in, auribromohydric acid ion, ATRZ molar ratio be 1:1:2~3；Room temperature~50 DEG C condition Under, mixing time is 10~20min；Obtained precipitating is washed 2~3 times, and 7~8h is dried in vacuo under the conditions of 55~70 DEG C.
7. a kind of method for extracting golden simple substance and the second metal simple-substance simultaneously as described in claim 1, it is characterised in that: step (2) mantoquita described in is Cu (BF4)2、Cu(NO3)2、CuCl2、Cu(SO4)2With Cu (ClO4)2One or more of；The cobalt salt For Co (BF4)2、Co(NO3)2、CoCl2With Cu (ClO4)2One or more of；The manganese salt is Mn (NO3)2、MnCl2And Mn (ClO4)2One or more of.
8. a kind of method for extracting golden simple substance and the second metal simple-substance simultaneously as described in claim 1, it is characterised in that: step (2) intermediate product described in is that ATRZ@Au-M is coordinated complex, and the ATRZ@Au-M is coordinated complex Chemical formula be [M (ATRZ)3](AuBr4)2·xH2O, wherein M is Cu, Co or Mn, when M is Cu, x=2；When M is Co or Mn When, x=6；Mn in the complex2+、Cu2+Or Co2+Centered on atom, ATRZ as organic ligand composition metal sun Ion organic backbone, AuBr4 -The hole for being filled in cationic metal organic backbone for balance anion is intracavitary.
9. a kind of method for extracting golden simple substance and the second metal simple-substance simultaneously as described in claim 1, it is characterised in that: step (3) sintering temperature is 500~700 DEG C in, and sintering time is 4~5h.
10. a kind of method for extracting golden simple substance and the second metal simple-substance simultaneously as described in claim 1, it is characterised in that: step Suddenly the mixture containing simple substance Au and M is immersed in excessive concentrated hydrochloric acid in (4), after stirring 10~30min, is obtained after filtering Precipitating wash 2~3 times, obtain elemental gold after dry；The solution obtained after filtering, is restored with active metal, obtains simple substance M.
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