Method for extracting gold using super-fan

Abstract

The present invention provides a method for extracting gold using super-branched gold ions. A specific super-branched gold ion molecule is used to adsorb a material containing gold ions in a solution system to obtain a solid material adsorbed with the gold element. The super-branched gold ion molecule can selectively extract, adsorb, and reduce gold ions in a solution system containing multi-component cations and anions, electronic wastewater, and gold mines under the extremely simple conditions of immersion and stirring at room temperature. The method has the advantages of fast adsorption rate, high adsorption capacity, high selectivity, easy recovery, simple operation, and relatively low cost. The method can be used for large-scale industrial extraction and recovery of gold.

Description

Technical Field

[0001] The present invention belongs to the technical field of resource recovery, and in particular, relates to a method for extracting gold using superoxide. Background Art

[0002] Gold, a precious metal, has a long history in human civilization, possessing not only cultural and sentimental value but also financial value. Besides being used as jewelry, currency, and an investment, gold possesses excellent physical properties such as high conductivity, thermal stability, plasticity, and ductility, making it widely used in various electronics industries, such as nanodevices and electronic devices. However, while the world's gold reserves are limited, the rapid development of the electronics manufacturing industry has increased demand for gold, necessitating the recovery of gold from secondary products. Approximately 10% of annual gold production is allocated to the electronics manufacturing industry, primarily for use in printed circuit boards (PCBs) or CPUs for mobile phones and computers. The rapid advancement of technology, particularly mobile phones and computers, leads to rapid replacement and short lifespans, resulting in the generation of vast quantities of electronic waste (e-waste). Discarded e-waste reportedly contains more gold than all existing gold-bearing ore, with one ton of ore containing as much gold as 40 mobile phones. This makes discarded mobile phone PCBs or CPUs a promising source of gold for recycling.

[0003] Currently, the most common method for extracting gold from gold mines in industry is cyanide extraction. This method is simple to operate and widely used. However, the waste often contains large amounts of cyanide, which poses a threat to the personal safety of workers and poses a significant challenge in subsequent waste disposal.

[0004] According to statistics, the world's industrial production of electronic waste reaches 45 million tons annually (2016), yet the recycling rate is very low (only 20%). Therefore, developing methods for selectively recovering gold from discarded electronic products is of great significance. Currently, the most common methods for recovering gold from electronic waste in industry are reportedly cyanide extraction and organic phase extraction. While these two methods are both affordable and widely used, the former uses large amounts of cyanide during the processing process, which is highly toxic and poses significant environmental and worker health risks. The latter, on the other hand, requires large amounts of organic solvents during the extraction process, resulting in cumbersome and energy-intensive post-processing, which contradicts the current national energy conservation and emission reduction initiatives. Furthermore, electronic waste often contains significant amounts of copper, nickel, and iron, as well as smaller amounts of other transition metals, which can significantly interfere with gold extraction. Therefore, developing novel gold recovery systems is of great significance. In recent years, the research group of Professor J. Fraser Stoddart, Nobel Prize winner in Chemistry, at Northwestern University, reported a series of methods for selectively separating gold ions by coprecipitation using cyclodextrin as the main component. After years of optimization, the recovery rate of this method has increased from an initial 78.3% to 99.8%. In April 2019, the research group of Tang Benzhong at South China University of Technology developed a class of polyselenourea polymer materials for the selective enrichment and recovery of gold ions from aqueous solutions (Application No.: 201910309311.9). This material exhibits excellent selectivity and adsorption capacity. However, the synthesis of this material is complex and the material itself has certain limitations. In the same year, the research group of Xu Huaping at Tsinghua University developed a method for extracting and enriching gold using selenide ethers (Application No.: 201911049189.2). This method has a high removal rate, but the adsorption time is long and the adsorption capacity is low. High-temperature calcination is required for effective recovery of elemental gold, which has certain limitations in practical application.

[0005] Therefore, it is of great significance to develop a green, environmentally friendly, highly efficient, highly selective and widely applicable method for gold enrichment and recovery. Summary of the Invention

[0006] In order to solve the above technical problems, the present invention provides a method for extracting gold using superoxide.

[0007] To achieve the above objectives, the present invention proposes the following solutions:

[0008] A method for extracting gold using super-fan, wherein super-fan is used to adsorb a material containing gold ions in a solution system to obtain a solid material adsorbed with gold elements;

[0009] The molecular formula of the superfan is:

[0010] .

[0011] Preferably, the method comprises immersing the superfan in a solution containing gold ions or adding a solid containing gold ions into an organic solution of the superfan, stirring until the gold element is completely adsorbed, and performing solid-liquid separation to obtain a solid material adsorbed with the gold element.

[0012] Preferably, the method further comprises: immersing the solid material adsorbed with gold element into a mixed solution of thiourea and one or more selected from potassium carbonate, potassium bicarbonate, sodium carbonate and sodium bicarbonate, and heating and stirring the solution to regenerate the super gold.

[0013] Preferably, the solution containing gold ions or the solid containing gold ions further contains halogen anions; for example, Cl - Br - wait.

[0014] Preferably, the solution containing gold ions is at least one of catalytic waste liquid, electronic waste liquid, gold mine leachate, gold concentrate leachate and a solution with competing cations; the electronic waste liquid includes but is not limited to CPU leachate and mobile phone PCB leachate.

[0015] Preferably, in the organic solution of superfan, the solvent is one or more of chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane and dimethyl sulfoxide.

[0016] Preferably, the competing cation is selected from Cu 2+ 、 Ni 2+ 、Fe 3+ Mg 2+ 、Al 3+ 、Cd 2+ , Pb 2+ Cr 3+ 、Co 2+ 、Zn 2+ and Hg 2+ One or more of; the concentration of each competing cation is 1-1000ppm, more preferably 10-100ppm.

[0017] Preferably, the pH value of the solution containing gold ions is 1-11 or the hydrogen ion concentration in the solution is below 2 mol / L.

[0018] Preferably, the stirring speed is 500-1000 rpm.

[0019] Preferably, the heat preservation temperature of the heating and stirring is 25-40° C.; and the heating and stirring time is 1-4 h.

[0020] Preferably, the concentration of thiourea in the mixed solution is 1-10 wt %; the total concentration of potassium carbonate, potassium bicarbonate, sodium carbonate and sodium bicarbonate in the mixed solution is 1-5 mmol / L.

[0021] Preferably, the molar ratio of the super alumina to gold ions is 1:10-300:1.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] The super-aluminum molecules of the present invention can selectively extract, adsorb, and reduce gold ions in solution systems containing multi-component cations and anions, electronic wastewater, catalytic waste liquid, gold mines, and other materials under the extremely simple conditions of room temperature immersion and stirring. They have the advantages of fast adsorption rate, high adsorption capacity, high selectivity, easy recovery, simple operation, and relatively low cost. The ability to recover low-concentration gold through simple operation surpasses the recovery and enrichment efficiency of current traditional processes for gold. Furthermore, the post-processing process does not require the introduction of highly toxic cyanide, making it environmentally friendly and highly industrially valuable. Furthermore, the super-aluminum molecules exhibit no significant changes in adsorption performance after repeated recycling, demonstrating good recyclability. The super-aluminum structure exhibits excellent selective adsorption performance, a simple adsorption process, convenient recovery, and relatively low cost, making it suitable for large-scale industrial extraction and recovery of gold. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0025] Figure 1 For the super-bronze and AuBr2 in Example 1 + Crystal structure diagram, where (a) is the top view, (b) is the front view, and (c) is the crystal stacking diagram.

[0026] Figure 2 These are the solid test results of the samples taken for adsorption at different time periods in Example 2, where (a) is the XRD pattern; (b) is the XPS fine spectrum of Au4f; (c) is the XPS fine spectrum of Cl 2p; and (d) is the XPS fine spectrum of N 1s.

[0027] Figure 3 This is a diagram of the ICP-MS analysis results in Example 18.

[0028] Figure 4 This is a diagram of the ICP-MS analysis results in Example 29.

[0029] Figure 5 These are the ICP-MS analysis results of Examples 31-36, where (a) corresponds to Example 31; (b) corresponds to Example 32, (c) corresponds to Example 33, (d) corresponds to Example 34; (e) corresponds to Example 35, and (f) corresponds to Example 36.

[0030] Figure 6 37, wherein (a) is a diagram showing the adsorption and desorption efficiency at different numbers of cycles, and (b) is a NMR comparison diagram of the recovered superfan after 31 cycles and the uncycled superfan.

[0031] Figure 7 The following are pictures of gold recovered from different liquids by Chaofan, where (a) is the gold recovered in Example 38; (b) is the gold recovered in Example 39. DETAILED DESCRIPTION

[0032] After extensive research, the present applicant has found that the supermolecule having a secondary amine and amide structure and a chemical formula as shown in Formula 1 below can effectively inhibit the oxidation of Au in many gold ion-containing solutions. 3+ It has a good extraction and enrichment effect on gold in solids. After research, it was found that the amide and protonated secondary amine in the super-acid structure have good anion recognition ability (multiple hydrogen bond donors), and have the ability to selectively extract Au from complex cationic and strongly acidic systems. 3+ With anions (preferably halogen anions, such as Cl - Or Br - ) The potential of the coordinated cationic salt to be extracted or adsorbed, during the adsorption and extraction process, AuY4 - Will gradually remove the halogen to form AuY3 and AuY2 + , thus stabilizing between molecular cages, and the secondary amine has good reducing properties, which can effectively release the gradually released Au 3+ Reduced to gold, thus exposing the binding sites to continue binding AuCl2 + or AuBr2 +. This extraction method can achieve green and environmentally friendly and highly selective adsorption and reduction of trivalent gold elements in solutions with different pH environments and containing various competitive cations (such as cationic salts of Mg, Cu, Al, Si, Ca, Ti, Cr, Mn, V, Fe, Co, Ni, Zn, As, Sr, Y, Zr, Mo, Rh, Pd, Cd, In, Sb, Sn, Cs, Ba, W, Tl, Pb, Bi, and Ag), gold-containing catalytic waste liquids, electronic wastewater, and gold ore leachate, overcoming the defects and limitations of existing methods for extracting gold from electronic waste (electronic waste such as computer CPUs and mobile phone PCB boards), gold-containing catalysts, and gold ores and gold concentrates. Unlike traditional supramolecular extraction (recognition and extraction both utilize the inner cavity of the main molecule), this system mainly extracts gold from Au. 3+ The adsorption and extraction of Au is mainly carried out by using the outer cavity of the super-branched molecular cage to identify the halogen-coordinated cation Au in a two-sphere model. 3+ For adsorption and stabilization, the inner cavity is mainly encapsulated with gold salt (AuY4 - ) gradually removes the halogen anion (Cl - Or Br - ) plays a synergistic adsorption role, using the cavity between the molecular cages for extraction and adsorption, and in the process of gold recovery, it mainly targets AuY3 and AuY2 + extraction and adsorption,

[0033]

[0034] Formula 1.

[0035] This functional molecule can achieve selective extraction, adsorption and reduction of gold ions in the presence of multi-component cations, electronic wastewater and gold mines under the extremely simple conditions of immersion and stirring at room temperature. It has the advantages of fast adsorption rate, high adsorption capacity, high selectivity and easy recovery.

[0036] Based on the above research results, the present invention provides a method for extracting gold using super-fan of formula 1, wherein super-fan is used to adsorb materials containing gold ions in a solution system to obtain a solid material adsorbed with gold elements.

[0037] In some preferred embodiments, the method comprises immersing the super-porous substance in a solution containing gold ions or adding a solid containing gold ions into an organic solution of the super-porous substance, stirring until the gold element is completely adsorbed, and performing solid-liquid separation to obtain a solid material adsorbed with the gold element.

[0038] In some preferred embodiments, the solution containing gold ions or the solid containing gold ions further contains halogen anions; for example, Cl - Br -The presence of halogen ions can promote the extraction and enrichment of gold by super-fan.

[0039] In some preferred embodiments, the stirring speed is 500-1000 rpm, such as 600, 700, 800, 900 rpm, etc.

[0040] Some preferred embodiments further include immersing the solid material adsorbed with gold in a mixed solution of thiourea and one or more of potassium carbonate, potassium bicarbonate, sodium carbonate, and sodium bicarbonate, and heating and stirring to regenerate the super-gold. The mixed solution may be, for example, an aqueous solution, or other solvents may be used in place of water, as long as the super-gold can be regenerated.

[0041] In some preferred embodiments, the solution containing gold ions is at least one of catalytic waste liquid, electronic waste liquid, gold mine leachate, gold concentrate leachate and a solution with competitive cations; the electronic waste liquid includes but is not limited to CPU leachate and mobile phone PCB leachate; in the solution with competitive cations, the competitive cation is selected from Cu 2+ 、Ni 2+ 、Fe 3 + 、 Mg 2+ 、Al 3+ 、Cd 2+ , Pb 2+ Cr 3+ 、Co 2+ 、Zn 2+ and Hg 2+ one or more of; the concentration of each competing cation is 1-1000 ppm, further preferably 10-100 ppm, for example 20, 30, 40, 50, 60, 70, 80, 90 ppm and the like.

[0042] In some preferred embodiments, the solvent in the organic solution of superfan is one or more of chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane and dimethyl sulfoxide.

[0043] In some preferred embodiments, the pH value of the solution containing gold ions is 1-11 or the hydrogen ion concentration in the solution containing gold ions is 2 mol / L or less; the solution containing gold ions can be prepared using a mixed acid solution of HCl or HBr and HNO3, and the pH can be adjusted using an alkali such as NaOH, KOH, etc.

[0044] In some preferred embodiments, the heating and holding temperature is 25-40° C.; and the heating and stirring time is 1-4 h.

[0045] In some preferred embodiments, the concentration of thiourea in the mixed solution is 1-10 wt %; and the total concentration of potassium carbonate, potassium bicarbonate, sodium carbonate and sodium bicarbonate in the mixed solution is 1-5 mmol / L.

[0046] In some preferred embodiments, the molar ratio of the super amorphous metal to the gold ion is 1:10-300:1, for example, including 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1, 85:1, 90:1, 95:1, 100:1, 125:1, 150:1, 175:1, 200:1, 225:1, 250:1, 275:1, 300:1 and the like.

[0047] To facilitate understanding of the present invention, the present invention will be described in more comprehensive and detailed form below in conjunction with the accompanying drawings and preferred embodiments. However, the scope of protection of the present invention is not limited to the following specific embodiments.

[0048] Unless otherwise defined, all technical terms used hereinafter have the same meanings as those generally understood by those skilled in the art. The technical terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0049] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods. The compounds of formula 1 are used in the following examples.

[0050] Extraction of gold based on super-solid-liquid extraction method:

[0051] Example 1

[0052] A 3mM super-brominated chloroform solution was prepared, and a solid containing NaAuBr4 was placed in the super-brominated chloroform solution. After 12 hours, a large amount of black precipitate was found. The black precipitate was filtered and dissolved in deuterated DMSO. It was found that the NMR spectrum was consistent with that of the mixture of NaAuBr4 and super-brominated dissolved in deuterated DMSO, indicating that super-brominated can extract gold salt into chloroform in the form of solid-liquid extraction.

[0053] In addition, the chloroform solution of the super-magnesium was placed in a solid gold-containing vial and allowed to stand for 24 hours to obtain a gold-containing single crystal. The gold-containing single crystal was tested by an X-ray single crystal diffractometer, and the structure was analyzed and refined by olex2 to export pictures from different perspectives, such as Figure 1 As shown, the super-bronze and AuBr2 +The crystal structure diagram includes (a) top view; (b) front view and (c) crystal stacking diagram.

[0054] From the crystal structure, we can see that the super cavity is encapsulated by Br - And AuBr2 exists outside the cavity + , mainly through the two-sphere model acting on the halogen (Br) of the coordination center gold to form a hydrogen bond framework network structure.

[0055] Example 2

[0056] Weigh 6 groups of 20 mg of super molecular cages and place them in 10 mL of 1600 ppm Au solution. 3+ The solution, in which the anion is chloride ion, was stirred at 1000 rpm at room temperature, and the stirring was stopped at 1 min, 5 min, 0.5 h, 2 h, 12 h and 24 h, and the solution was filtered and dried. The solid was subjected to XRD and XPS tests, and the test results are shown in the figure. Figure 2 As shown, Figure 2 (a) is the XRD pattern of the solid obtained after Chaofan adsorbed gold at different times. Figure 2 (b) is the XPS fine spectrum of solid Au 4f obtained after super-fan adsorbed gold at different times. Figure 2 (c) is the XPS fine spectrum of Cl 2p; Figure 2 (d) is the XPS fine spectrum of N 1s of the solid test sampled at different adsorption periods, where Fresh 2 is the untreated super-branch molecular cage.

[0057] From the XRD spectrum, it can be seen that with the increase of adsorption time, the peaks of Au (111), (200), (220) and (311) which are characteristic peaks of gold appear. From (b), (c) and (d), it can be seen that with the increase of time, Au3 + Gradually reduced to Au + and elemental Au, and the fine spectrum of Cl 2p showed the peaks of Au-Cl, the peaks of Au-Cl and N interaction, and the peaks of Cl wrapped in the cage. N 1s showed that the site was NH and NH2 after protonation. + , indicating that the adsorption process is indeed the same as the single crystal process, with the gradual dissociation and the encapsulation of anions by the super-porous cavity, as well as the Au 3+ It is gradually reduced to Au element, and the stable sites for gold after reduction are NH and protonated NH2 + .

[0058] Extraction of gold based on super liquid-liquid extraction method:

[0059] Example 3

[0060] 2 mL of 1 mM Au 3+ Aqueous solution (solution pH = 1, the anion is Cl - ) and 3 mL of chloroform solution with a concentration of 1.5 mM superoxide, extracted at 1000 rpm for 10 seconds, and then sampled and tested the remaining Au content in the water by ICP-MS. The results showed that the Au content in the aqueous solution 3+ The removal rate is 98%.

[0061] Example 4

[0062] 2 mL of 1 mM Au 3+ Aqueous solution (solution pH = 3, the anion is Cl - ) and 3 mL of chloroform solution with a concentration of 1.5 mM superoxide, extracted at 1000 rpm for 10 seconds, and then sampled and tested the remaining Au content in the water by ICP-MS. The results showed that the Au content in the aqueous solution 3+ The removal rate is 99%.

[0063] Example 5

[0064] 2 mL of 1 mM Au 3+ Aqueous solution (solution pH = 5, the anion is Cl - ) and 3 mL of chloroform solution with a concentration of 1.5 mM superoxide, extracted at 1000 rpm for 10 seconds, and then sampled and tested the remaining Au content in the water by ICP-MS. The results showed that the Au content in the aqueous solution 3+ The removal rate is 99%.

[0065] Example 6

[0066] 2 mL of 1 mM Au 3+ Aqueous solution (solution pH = 7, the anion is Cl - ) and 3 mL of chloroform solution with a concentration of 1.5 mM superoxide, extracted at 1000 rpm for 10 seconds, and then sampled and tested the remaining Au content in the water by ICP-MS. The results showed that the Au content in the aqueous solution 3+ The removal rate is 98%.

[0067] Example 7

[0068] 2 mL of 1 mM Au 3+ Aqueous solution (pH = 9, the anion is Cl - ) and 3 mL of chloroform solution with a concentration of 1.5 mM superoxide, extracted at 1000 rpm for 10 seconds, and then sampled and tested the remaining Au content in the water by ICP-MS. The results showed that the Au content in the aqueous solution 3+ The removal rate is 98%.

[0069] Example 8

[0070] 2 mL of 1 mM Au 3+ Aqueous solution (pH = 11, the anion is Cl - ) and 3 mL of chloroform solution with a concentration of 1.5 mM superoxide, extracted at 1000 rpm for 10 seconds, and then sampled and tested the remaining Au content in the water by ICP-MS. The results showed that the Au content in the aqueous solution 3+ The removal rate is 99%.

[0071] Example 9

[0072] 2 mL of 1 mM Au 3+ Aqueous solution (pH = 14, the anion is Cl - ) and 3 mL of chloroform solution with a concentration of 1.5 mM superoxide, extracted at 1000 rpm for 10 seconds, and then sampled and tested the remaining Au content in the water by ICP-MS. The results showed that the Au content in the aqueous solution 3+ The removal rate is 51%.

[0073] Example 10

[0074] 2 mL of 1 mM Au 3+ Aqueous solution (aqueous solution pH = 1, the anion is Cl - ) and 3 mL of 0.067 mM superbion chloroform solution (superbion: Au molar ratio is 0.1:1), extracted at 1000 rpm for 10 s, and then sampled for ICP-MS test. 3+ The extraction efficiency is 85%.

[0075] Example 11

[0076] 2 mL of 1 mM Au 3+ Aqueous solution (pH = 1, the anion is Cl - ) and 3 mL of chloroform solution of 0.334 mM superbion (superbion: Au molar ratio is 0.5:1), extracted at 1000 rpm for 10 seconds, and then sampled for ICP-MS test. 3+ The extraction efficiency is 90%.

[0077] Example 12

[0078] 2 mL of 1 mM Au 3+ Aqueous solution (pH = 1, the anion is Cl - ) and 3 mL of chloroform solution of 0.667 mM superbion (superbion: Au molar ratio is 1:1), extracted at 1000 rpm for 10 seconds, and then sampled for ICP-MS test. 3+The extraction efficiency is 99%.

[0079] Example 13

[0080] 2 mL of 1 mM Au 3+ Aqueous solution (pH = 1, the anion is Cl - ) and 3 mL of chloroform solution of superbion with a concentration of 1.334 mM (superbion: Au molar ratio is 2:1), extracted at 1000 rpm for 10 seconds, and then sampled for ICP-MS test. It was found that the 3+ The extraction efficiency is 99%.

[0081] Example 14

[0082] 2 mL of 1 mM Au 3+ Aqueous solution (pH = 1, the anion is Cl - ) and 3 mL of chloroform solution of 2 mM superbion (superbion: Au molar ratio is 3:1), extracted at 1000 rpm for 10 seconds, and then sampled for ICP-MS test. 3+ The extraction efficiency is 99%.

[0083] Example 15

[0084] 3 mL of 10 ppm Au 3+ aqueous solution (where other counter cations Cu 2+ 、Ni 2+ 、Fe 3+ Mg 2+ 、Al 3+ 、Cd 2+ , Pb 2+ Cr 3+ 、Co 2+ 、Zn 2+ and Hg 2+ The concentration is 10 ppm, and the negative ion is Cl - , solution pH = 1) and 2mL of chloroform solution with a concentration of 1.5mM superfan were mixed and extracted at 1000rpm. Samples were taken at different time points for ICP-MS test. Finally, it was found that after 30s of extraction, the Au 3+ The extraction efficiency is 99%.

[0085] Example 16

[0086] 3 mL of 10 ppm Au 3+ Aqueous solution (where the counter cation Cu 2+ 、Ni 2+ 、Fe 3+ Mg 2+ 、Al 3+、Cd 2+ , Pb 2+ Cr 3+ 、Co 2+ 、Zn 2+ and Hg 2+ The concentration is 100 ppm, and the anion is Cl - , solution pH = 1) and 2mL of 1.5mM super molecular cage solution were mixed, extracted at 1000rpm for 30s, and then sampled for ICP-MS test. 3+ The extraction efficiency is 99%.

[0087] Example 17

[0088] 3 mL of 10 ppm Au 3+ Aqueous solution (where the counter cation Cu 2+ 、Ni 2+ 、Fe 3+ Mg 2+ 、Al 3+ 、Cd 2+ , Pb 2+ Cr 3+ 、Co 2+ 、Zn 2+ and Hg 2+ The concentration is 1000 ppm, and the negative ion is Cl - , solution pH = 1) and 2mL of 1.5mM super molecular cage solution were mixed, extracted at 1000rpm for 30s, and then sampled for ICP-MS test. 3+ The extraction efficiency is 99%.

[0089] Example 18

[0090] 3 mL of 5 ppm Au 3+ solution (where the counter cation Cu 2+ 、Ni 2+ 、Fe 3+ Mg 2+ 、Al 3+ 、Cd 2+ , Pb 2+ Cr 3+ 、Co 2+ 、Zn 2+ and Hg 2+ The concentration is 1000 ppm, and the negative ion is Cl - , solution pH = 1) and 2mL of 1.5mM super-branch molecular cage solution were mixed, extracted at 1000rpm for 30s, and then sampled for ICP-MS test. The test results are as follows Figure 3 As shown in the figure, it can be seen that 3+The extraction efficiency is 99%, indicating that the super molecular cage can selectively remove Au in the presence of ultra-high competitive cations. 3+ .

[0091] Based on the super-fluorescence of Au in aqueous solution 3+ Adsorption:

[0092] Example 19

[0093] 3mg of super-branched molecular cage and 3mL of 20ppm Au 3+ Solution (solution pH = 1, counter anion is Br - ) were mixed and stirred at 1000 rpm at room temperature for adsorption experiment. After stirring for 1 min, samples were taken for ICP-MS test. 3+ The adsorption rate is 99%.

[0094] Example 20

[0095] 3mg of super-branched molecular cage and 3mL of 20ppm Au 3+ Solution (pH = 3, counter anion is Br - ) were mixed and stirred at 1000 rpm at room temperature for adsorption experiment. After stirring for 1 min, samples were taken for ICP-MS test. 3+ The adsorption rate is 99%.

[0096] Example 21

[0097] 3mg of super-branched molecular cage and 3mL of 20ppm Au 3+ Solution (pH = 5, anion is Br - ) were mixed and stirred at 1000 rpm at room temperature for adsorption experiment. After stirring for 1 min, samples were taken for ICP-MS test. 3+ The adsorption rate is 99%.

[0098] Example 22

[0099] 3mg of super-branched molecular cage and 3mL of 20ppm Au 3+ Solution (pH = 7, counter anion is Br - ) were mixed and stirred at 1000 rpm at room temperature for adsorption experiment. After stirring for 1 min, samples were taken for ICP-MS test. 3+ The adsorption rate is 99%.

[0100] Example 23

[0101] 3mg of super-branched molecular cage and 3mL of 20ppm Au 3+Solution (pH = 9, counter anion is Br - ) were mixed and stirred at 1000 rpm at room temperature for adsorption experiment. After stirring for 1 min, samples were taken for ICP-MS test. 3+ The adsorption rate is 99%.

[0102] Example 24

[0103] 3mg of super-branched molecular cage and 3mL of 20ppm Au 3+ Solution (pH = 11, counter anion is Br - ) were mixed and stirred at 1000 rpm at room temperature for adsorption experiment. After stirring for 1 min, samples were taken for ICP-MS test. 3+ The adsorption rate is 99%.

[0104] Example 25

[0105] 3mg of super-branched molecular cage and 3mL of 20ppm Au 3+ Solution (pH = 14, counter anion is Br - ) were mixed and stirred at 1000 rpm at room temperature for adsorption experiment. After stirring for 1 min, samples were taken for ICP-MS test. 3+ The adsorption rate is 78%.

[0106] Example 26

[0107] 3 mg of super-branched molecular cage and 3 mL of 10 ppm Au 3+ aqueous solution (where the competitive cation Cu 2+ 、Ni 2+ 、Fe 3+ 、 Mg 2+ 、Al 3+ 、Cd 2+ , Pb 2+ Cr 3+ 、Co 2+ 、Zn 2+ and Hg 2+ The concentrations were 10 ppm, and the counter anion was Cl - , the solution pH was 1) and stirred at 1000 rpm for 2 min at room temperature. ICP-MS analysis was performed. 3+ The removal rate of ions is 99%, and the adsorption rate of other ions is less than 15%.

[0108] Example 27

[0109] 3 mg of super-branched molecular cage and 3 mL of 10 ppm Au 3+aqueous solution (where the competitive cation Cu 2+ 、 Ni 2 + 、Fe 3+ 、 Mg 2+ 、 Al 3+ 、 Cd 2+ 、 Pb 2+ Cr 3+ 、Co 2+ 、Zn 2+ and Hg 2+ The concentrations were 100 ppm, and the counter anion was Cl - , solution pH = 1) were mixed and stirred at 1000 rpm for 2 min at room temperature. ICP-MS analysis was performed. 3+ The removal rate of ions is 97%, and the adsorption rates of other ions are below 12%.

[0110] Example 28

[0111] 3mg super molecular cage and 3mL Au with a concentration of 10ppm 3+ Aqueous solution (wherein the competitive cation Cu 2+ 、 Ni 2+ 、Fe 3+ 、 Mg 2+ 、Al 3+ 、Cd 2+ , Pb 2+ Cr 3+ 、Co 2+ 、Zn 2+ and Hg 2+ The concentrations were 1000 ppm, and the counter anion was Cl - , solution pH = 1) were mixed and stirred at 1000 rpm for 2 min at room temperature. ICP-MS analysis was performed. 3+ The removal rate of ions is 94%, and the adsorption rate of other ions is less than 4%.

[0112] Example 29

[0113] 3 mg of super-branched molecular cage and 3 mL of 5 ppm Au 3+ Aqueous solution (competitive cation ion Cu 2+ 、 Ni 2 + 、Fe 3+ 、 Mg 2+ 、Al 3+ 、Cd 2+ , Pb 2+ Cr 3+ 、Co 2+ 、Zn2+ and Hg 2+ The concentrations were 1000 ppm, and the counter anion was Cl - , solution pH = 1) were mixed and stirred at 1000 rpm for 2 min at room temperature. ICP-MS analysis was performed. 3+ The removal rate of ions is 99%, and the adsorption rate of other ions is less than 3%.

[0114] Example 30

[0115] 3 mg of super-branched molecular cage and 3 mL of 10 ppm Au 3+ Aqueous solution (competitive cation Cu 2+ 、Ni 2+ 、Fe 3+ Mg 2+ 、 Al 3+ 、Cd 2+ , Pb 2+ Cr 3+ 、Co 2+ 、Zn 2+ and Hg 2+ The concentrations were 1000 ppm, and the counter anion was Cl - The solution was mixed with a hydrogen ion concentration of 2 mol / L and a ratio of 100:1 (ppm:ppm). The mixture was stirred at 1000 rpm for 2 min at room temperature and analyzed by ICP-MS. The results were as follows: Figure 4 As shown, for Au 3+ The removal rate of Au was 99%, and the adsorption rate of other ions was below 3.4%, indicating that the super molecular cage can selectively remove Au in the presence of ultra-high competitive cations. 3+ .

[0116] Based on Chaofan's adsorption of gold in actual systems:

[0117] Example 31

[0118] The top cover of a locally purchased discarded CPU (AMD) was removed and treated with a 10M NaOH solution overnight to remove organic matter such as resin. The CPU was then washed with abundant pure water until neutral. The solution was then placed in 50 mL of aqua regia solution and stirred at room temperature for 24 hours. The insoluble matter was filtered out, and the pH was adjusted to 1 with 4M NaOH solution and ultrapure water. The volume was then fixed to 100 mL. Three mL of the CPU waste solution was mixed with 6 mg of the super-branched cage at room temperature, stirred at 1000 rpm for 5 minutes, filtered, and subjected to ICP-MS analysis. The results were as follows: Figure 5 (a) shows that the 3+The clearance rate was 99.01%, and the competitive cation species and concentrations contained were Cu: 1522 ppm, Ni: 93 ppm, Sn: 0.25 ppm, Ag: 0.02ppm, of which the concentration of Au was 3.59 ppm.

[0119] Example 32

[0120] The top cover of a discarded CPU (Inter) purchased locally was removed and treated with a 10M NaOH solution overnight to remove organic matter such as resin. The CPU was then washed with a large amount of pure water until neutral. The CPU was placed in 50 mL of aqua regia solution and stirred at room temperature for 24 hours. The insoluble matter was filtered out, and the pH was adjusted to 1 with 4M NaOH solution and ultrapure water. The volume was then fixed to 100 mL. Three mL of the CPU waste solution was mixed with 6 mg of the super-branched molecular cage at room temperature, stirred at 1000 rpm for 5 minutes, filtered, and subjected to ICP-MS analysis. The results were as follows: Figure 5 (b) shows that the 3+ The removal rate was 99.30 %, and the competitive cation species and concentrations included were Mg: 158.03 ppm, Cu: 2920.07 ppm, Ni: 157.99 ppm, Sn: 5.17 ppm, Ag: 1.71ppm, Al: 195.80 ppm, Si: 35.49 ppm, Ca: 51.26 ppm, Ti: 0.05 ppm, Cr: 6.33 ppm, Mn:3.48 ppm, Fe: 408.01 ppm, Co: 0.43 ppm, Zn: 218.44 ppm, Sr: 0.07 ppm, Y: 0.01 ppm, Zr: 0.13 ppm, Mo: 0.78 ppm, Cd: 1.37 ppm, In: 0.03 ppm, Sb: ppm, Ba: 0.65 ppm, Pb:19.83 ppm and Bi: 0.03ppm, of which the concentration of Au is 1.28 ppm.

[0121] Example 33

[0122] Five discarded mobile phone PCBs purchased locally were placed in a 10M NaOH solution overnight to remove organic matter such as resin. They were then washed with abundant pure water until neutral and placed in 250 mL of aqua regia solution. After stirring at room temperature for 24 hours, the insoluble matter was filtered out. 4M NaOH solution and ultrapure water were added to adjust the pH to 1, and the volume was fixed to 500 mL. Three mL of the PCB waste solution was mixed with 6 mg of the super-branched cage at room temperature, stirred at 1000 rpm for 5 minutes, filtered, and subjected to ICP-MS analysis. The results were as follows: Figure 5 (c) shows that the 3+ The removal rate was 99.51%, and the competitive cation species and concentrations included were Mg:170.02 ppm, Cu: 11162.88 ppm, Al: 212.40 ppm, Si: 19.07 ppm, Ca: 53.75 ppm, Cr:15.84 ppm, Mn: 166.87 ppm, Fe: 386.16 ppm, Co: 3.33 ppm, Ni: 861.97 ppm, Zn:371.39ppm, Sr: 29.61 ppm, Y: 0.60 ppm, Rh: 0.07 ppm, Pd: 1.09 ppm, Cd: 1.36 ppm, In: 0.15ppm, Sn: 0.12 ppm, Sb: 0.38 ppm, Ba: 42.05 ppm, Pb: 553.64 ppm, Bi: 5.24 ppm and Ag: 237.19 ppm, with an initial gold concentration of 2.52 ppm.

[0123] Example 34

[0124] Take 10 mL of aqua regia waste liquid containing gold catalyst, adjust the pH to 1 with 4M NaOH solution and ultrapure water and dilute to 25 mL for later use. Take 3 mL of catalytic waste liquid and 3 mg of super-branch molecular cage and mix them at room temperature. Stir at 1000 rpm for 5 minutes, filter and perform ICP-MS test. The results are as follows: Figure 5 (d) shows that the 3+ The removal rate was 99.33%, and the types and concentrations of competitive cations contained were Cu: 102.31 ppm, Al: 31.94 ppm, Ti: 5.21 ppm, Mn:10.34 ppm, Co: 25.74 ppm, Ba: 2.36 ppm and Ag: 56.32 ppm, and the initial concentration of gold was 121.41 ppm.

[0125] Example 35

[0126] Dissolve 100 g of gold ore sand 1 in 80 mL of freshly prepared aqua regia and stir for 24 h. Filter and adjust the pH to 1 with 4 M NaOH solution and distilled water. Dose the mixture to a 250 mL volumetric flask. Mix 4 mL of the gold ore solution and 8 mg of the cage and stir for 5 min. Filter and perform ICP-MS analysis. The results are as follows: Figure 5 (e) shows that the 3+The removal rate was 91.7 %, and the competitive cation species and concentrations included were Mg: 338.31 ppm, Cu: 935.27 ppm, Al: 865.73 ppm, Si: 29.86 ppm, Ca: 24.95 ppm, Cr: 12.32 ppm, Mn: 58.93 ppm, Fe: 14065.93 ppm, Co:15.37 ppm, Ni: 18.80 ppm, Zn: 2793.19 ppm, Sr: 0.06 ppm, Y: 0.58 ppm, Rh: 0.05ppm, Pd: 0.02 ppm, Cd: 22.36 ppm, In: 1.17 ppm, Sb: 2.82 ppm, Ba: 0.38 ppm, Pb:52.41 ppm, Bi: 51.03 ppm, Sn: 1.08 ppm and Ag: 52.43 ppm, and the initial concentration of gold is 1.58 ppm.

[0127] Example 36

[0128] Dissolve 100 g of gold ore sand 2 in 80 mL of freshly prepared aqua regia and stir for 24 h. Filter and adjust the pH to 1 with 4 M NaOH solution and distilled water. Dose the mixture to a 250 mL volumetric flask. Mix 4 mL of the gold ore solution with 8 mg of cage and stir for 5 min. Filter and perform ICP-MS analysis. The results are as follows: Figure 5 (f) shows that the 3+ The clearance rate was above 89.6%, and the competitive cation types and concentrations contained were Mg: 374.36 ppm, Cu: 559.17 ppm, Al: 572.37 ppm, Si: 30.48 ppm, Ca: 20.02 ppm, Cr: 50.35 ppm, V: 1.55 ppm, Fe: 10791.53 ppm, Co: 6.39 ppm, Ni: 23.40 ppm, Zn: 940.13 ppm, As: 1.12 ppm, Sr: 0.29 ppm, Y: 0.56ppm, Zr: 0.33 ppm, Mo: 1.35 ppm, Rh: 0.05 ppm, Pd: 0.01 ppm, Cd: 7.14 ppm, In:0.39 ppm, Sn: 0.77 ppm, Cs: 0.39 ppm, Ba: 0.46 ppm, W: 1.42 ppm, Tl: 0.02 ppm, Pb:189.16 ppm, Bi: 24.78 ppm and Ag: 72.76 ppm, with an initial gold concentration of 1.35 ppm.

[0129] from Figure 5 It can be seen that Chaofan has the ability to efficiently and selectively recover gold in actual systems.

[0130] Based on Chaofan's recovery, release and recycling of gold elements, as well as scale-up experiments:

[0131] Example 37

[0132] Take 10 mL of gold-containing catalyst waste liquid, adjust the pH to 1 with 4 mL of NaOH solution and ultrapure water and dilute to 25 mL for use, take 10 mL of catalytic waste liquid and 300 mg of super-branched molecular cages and mix them at room temperature, stir at 1000 rpm for 5 minutes, filter, place the solid in 10 wt% thiourea and 2.5 M K2CO3 solution, stir at 40 ° C for four hours, filter, and obtain the super-branched molecular cages after desorption of gold. The gold removal rate is above 94%. The process is repeated 31 times. The adsorption and desorption efficiencies in different cycle numbers are as follows: Figure 6 As shown in (a), it can be seen from the figure that the cleaning effect has not changed significantly. The superfan recovered after 31 cycles and the superfan without cycling (i.e., the newly prepared superfan) were subjected to NMR testing. The NMR comparison spectra are shown as follows: Figure 6 As shown in (b), the figure shows that after 31 cycles, the super-fan molecules have not undergone obvious changes, indicating that super-fan has the potential for reuse.

[0133] Example 38

[0134] 40 mobile phone PCBs were placed in a 10M NaOH solution overnight to remove organic matter such as resin. They were then washed with a large amount of pure water until neutral and placed in 500 mL of aqua regia solution. After soaking at room temperature for 24 hours, the insoluble matter was filtered out. 4M NaOH solution and ultrapure water were added to adjust the pH to 1 and the volume was fixed to 1L. 1L of PCB waste liquid was mixed with 1g of super-branched cages at room temperature, stirred at 1000rpm for 24 hours, filtered, and the filtrate was tested by ICP-MS. 3+The clearance rate was 92.6%, and the competitive cations contained were Mg: 1.65ppm, Cu: 389.40 ppm, Al: 19.828 ppm, Si:20.12 ppm, Ca: 67.68 ppm, Sc: 8.78ppm, Ti: 15.51ppm, V: 8.56ppm, Cr: 110.46ppm, Mn: 5.83 ppm, Fe: 28.01ppm, Co: 0.14ppm, Ni: 15.98 ppm, Zn: 5.83 ppm, Sr:22.91ppm, Zr: 1.48ppm, Mo: 1.36ppm, Y: 3.37ppm, Rh: 0.84 ppm, Pd: 3.80 ppm, In:18.81 ppm, Sn: 4557.30ppm. ppm, Sb: 12.15 ppm, Ba: 110.92 ppm, W: 1.15ppm, Pb: 8.08ppm, Bi: 9.55 ppm, Ag: 101.64ppm, the initial concentration of gold is Au: 123.58 ppm, the filtered solid is placed in a muffle furnace and calcined at 1000℃ for 5h to obtain the recovered elemental gold, such as Figure 7 As shown in (a), its purity is 21.9K.

[0135] Example 39

[0136] Add 4M NaOH solution and ultrapure water to the gold-containing catalytic waste liquid (from the gold-containing catalyst in the laboratory), adjust the pH to 1, and make the volume to 600 mL. 600 mL of pH-adjusted catalytic waste liquid and 600 mg of super-branched molecular cages were mixed at room temperature, stirred at 1000 rpm for 24 h, filtered, and the filtrate was tested by ICP-MS. The removal rate was above 95.7%. The competitive cations contained in the filtrate were Mg: 1.50 ppm, Cu: 1.15 ppm, Al: 3.47 ppm, Si: 8.61 ppm, Ca: 10.69 ppm, Cr: 0.12 ppm, Mn: 0.44 ppm, Zr: 1.88 ppm, Fe: 23.86 ppm, Co: 0.13 ppm, Sc: 7.33 ppm, Ti: 0.69 ppm, Mo: 128.94, Ag: 2.55 ppm, and the initial gold concentration was Au: 210.98 ppm. The filtered solid was placed in a muffle furnace and calcined at 1000℃ for 5h to obtain the recovered elemental gold. Figure 7 As shown in (b), its purity is 23.5K.

[0137] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for extracting gold using super-aluminum, characterized in that: The method comprises the following steps: using a super absorbent to adsorb a material containing gold ions in a solution system to obtain a solid material adsorbed with gold elements; the material containing gold ions is a solution containing gold ions or a solid containing gold ions; the solution containing gold ions or the solid containing gold ions contains halogen anions; The molecular formula of the superfan is shown in Formula 1: Formula 1.

2. The method for extracting gold using super-aluminum as claimed in claim 1, wherein: Immerse the Chaofan in a solution containing gold ions or add a solid containing gold ions into the organic solution of Chaofan and stir until the gold element is completely adsorbed. After solid-liquid separation, a solid material adsorbed with gold elements is obtained.

3. The method for extracting gold using super-aluminum as claimed in claim 1, wherein: Also includes: The solid material adsorbed with gold element is immersed in a mixed solution of thiourea and one or more selected from potassium carbonate, potassium bicarbonate, sodium carbonate and sodium bicarbonate, and heated and stirred to regenerate the super gold.

4. The method for extracting gold using super-aluminum as claimed in claim 2, wherein: The solution containing gold ions is at least one of catalytic waste liquid, electronic waste liquid, gold ore leaching liquid, and gold concentrate leaching liquid; the electronic waste liquid includes CPU leaching liquid and mobile phone PCB leaching liquid; In the organic solution of the super-brominated chlorinated hydrocarbon, the solvent is one or more of chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane and dimethyl sulfoxide.

5. The method for extracting gold using super-aluminum as claimed in claim 2, wherein: The solution containing gold ions is a solution having competing cations.

6. The method for extracting gold using super-aluminum as claimed in claim 5, characterized in that: The competing cation is selected from Cu 2+ 、Ni 2+ 、Fe 3+ Mg 2+ 、Al 3+ 、Cd 2+ , Pb 2+ Cr 3+ 、Co 2+ 、Zn 2+ and Hg 2+ One or more of; the concentration of each competing cation is 1-1000ppm.

7. The method for extracting gold using super-aluminum as claimed in claim 6, wherein: The concentration of each competing cation was 10-100 ppm.

8. The method for extracting gold using super-aluminum according to any one of claims 4 to 7, wherein: The pH value of the solution containing gold ions is 1-11 or the hydrogen ion concentration in the solution is below 2 mol / L.

9. The method for extracting gold using super-aluminum as claimed in claim 2, wherein: The stirring speed is 500-1000 rpm.

10. The method for extracting gold using super-aluminum as claimed in claim 3, characterized in that: The heat preservation temperature of the heating and stirring is 25-40° C.; the heating and stirring time is 1-4 hours.

11. The method for extracting gold using super-aluminum as claimed in claim 3, characterized in that: The concentration of thiourea in the mixed solution is 1-10 wt %; the total concentration of potassium carbonate, potassium bicarbonate, sodium carbonate and sodium bicarbonate in the mixed solution is 1-5 mmol / L.

12. The method for extracting gold using super-aluminum as claimed in claim 1, wherein: The molar ratio of the super alumina to gold ions is 1:10-300:1.

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