CN112960844A - Reactor for separating and recovering precious metals and application thereof - Google Patents

Abstract

The invention provides a reactor for separating and recovering precious metals and heavy metals and application thereof, belonging to the technical field of precious metal and heavy metal recovery. The reactor comprises: the anode comprises an anode cylinder, wherein a porous anode outer cover is arranged outside the anode cylinder, the bottom end of the porous anode outer cover is communicated with a water inlet pipe through a reducer, and a modified polymer adsorbent is arranged between the anode cylinder and the porous anode outer cover; the cathode cylinder is arranged on the outer side of the porous anode outer cover, and a cathode starting polar plate is arranged on the inner wall of the cathode cylinder; the outer frame is arranged outside the cathode cylinder, a water outlet pipe is arranged at the upper part of the outer frame and connected with a precious metal online analyzer, and the precious metal online analyzer is connected with a water outlet tank and a water inlet tank. The reactor provided by the invention is mainly used for separating and recovering the noble metal and the heavy metal in the acid solution, and has good adsorption and separation effects.

Description

A kind of reactor for separation and recovery of precious metals and its application

technical field

The invention belongs to the technical field of precious and heavy metal recovery, and in particular relates to a reactor for separation and recovery of precious metals and its application.

Background technique

Precious and heavy metals are often used in catalysis, electronic equipment and other fields. The main sources of precious and heavy metal recovery are non-ferrous metallurgy and secondary resources. Among them, the content of heavy metals such as copper, zinc, nickel and iron is 0.1-10g/L, of which precious metals content cannot be ignored. For example, the content of precious metals such as gold in non-ferrous metallurgical wastewater is 0-10mg/L; e-waste in secondary resources is called "sleeping minerals", for example, a ton of discarded mobile phones contains more than 270g of gold.

For precious metals, conventional recovery methods include solvent extraction, adsorption, ion exchange, etc. Among them, the adsorption method to recover precious metals has the advantages of simple operation, fast speed and high adsorption capacity.

For heavy metals, conventional recovery methods include chemical precipitation, ion exchange, adsorption, and electrodeposition. Since the specificity of metal redox ability is more significant than other physical and chemical properties, electrodeposition can be used to adjust the voltage or Electric current and other parameters realize the separation and efficient recovery of metals.

The conventional electrodeposition recovery equipment for precious and heavy metals is mainly a swirling electrodeposition tank. Its working principle is to use the high-speed water flow pumped by the lift pump to form a swirling flow in the electrodeposition tank, which reduces the concentration polarization in the cathode area. By adjusting the power parameters, the efficient separation and recovery of heavy metals can be achieved. However, in acidic solutions, noble metals often exist in the form of complex ions with anions in the solution, such as AuCl ₄ ^- , PtCl ₄ ^- and so on. These complex anions are difficult to migrate to the cathode surface due to their opposite charge characteristics to generate the corresponding noble metals. deposition, resulting in extremely serious loss of precious metals.

SUMMARY OF THE INVENTION

The present invention proposes a reactor that combines selective adsorption and deposition technology to achieve efficient separation and recovery of precious and heavy metals, utilizes the difference in the occurrence forms of precious and heavy metals in acidic solution, combines the adsorption technology of selective adsorption of precious metal ions in the anode region and the cathode Electrodeposition technology for reducing heavy metals realizes the separation and efficient recovery of metal resources in multi-element precious and heavy metal solutions.

The present invention proposes a reactor for separation and recovery of precious metals, the reactor comprising:

Anode cylinder, the anode cylinder is provided with a porous anode cover, the bottom end of the porous anode cover is connected with the water inlet pipe through a reducer, and a modified polymer adsorption is arranged between the anode cylinder and the porous anode cover agent;

The cathode cylinder is arranged on the outer side of the porous anode cover, and the inner wall of the cathode cylinder is provided with a cathode starting plate;

The outer frame is arranged outside the cathode cylinder, and the upper part of the outer frame is provided with a water outlet pipe, and the water outlet pipe is connected with the precious metal online analyzer, and the precious metal online analyzer is connected with the water outlet tank and the water inlet tank.

Further, the device is equipped with a DC power supply, and the anode cylinder is connected to the positive pole of the DC power supply,

The cathode cylinder is connected to the negative pole of the DC power supply.

Further, the anode cylinder is a titanium mesh cylinder supporting precious metals, and the precious metals are ruthenium and iridium;

The porous anode cover is a titanium cylinder; the bottom of the porous anode cover is a mesh structure; the openings on the porous anode cover are circular or square.

Further, the cathode cylinder is a titanium cylinder or a stainless steel cylinder;

The cathode starting plate is a copper plate, a titanium plate or a stainless steel plate.

Further, a lift pump is arranged between the water inlet pipe and the water inlet tank.

Further, the preparation method of the modified polymer adsorbent comprises the following steps:

(1) mixing elemental sulfur, polyvalent amine-based compound, polyvalent carbonyl compound, and loading substrate, adding an organic solvent to obtain a solid-liquid mixed solution;

(2) under a protective gas atmosphere, the above-mentioned solid-liquid mixed solution is heated and reacted to obtain a modified polymer mixed solution;

(3) cooling the above-mentioned modified polymer mixed solution to room temperature, washing, centrifuging, and drying to obtain a modified polymer adsorbent;

Wherein, the supporting substrate is a large-particle porous adsorbent material, and the particle size of the large-particle porous adsorbent material is between 1 cm-5 cm.

Further, in step (1), the ratio of the number of moles of carbonyl groups in the polyvalent carbonyl compound: the number of moles of amine groups in the polyvalent amine compound: the number of moles of sulfur atoms in the elemental sulfur is (1～6):1:(1～6) ;

In step (1), the mass ratio of the loaded substrate to the elemental sulfur is (0.5-10):1.

Further, in step (1), the elemental sulfur is sublimation sulfur;

In step (1), the polyamine-based compound contains a primary amino group or a secondary amino group;

In step (1), the polyvalent carbonyl compound contains an aldehyde group or a carboxyl group;

In step (1), the large-particle porous adsorption material includes at least one of columnar activated carbon, carbon nanotubes, carbon felt, activated carbon fibers and carbon-based composite materials.

Further, in step (2), the temperature of the heating reaction is 60°C-120°C; the time of the heating reaction is 4-24h.

In step (3), the rotating speed of the centrifugation is 5000-13000rpm; the time of the centrifugation is 5-10 minutes;

In step (3), the temperature of described drying is 20 ℃-50 ℃;

In step (3), the drying adopts vacuum drying for more than 12 hours.

The present invention also proposes the application of any of the above reactors in separating and recovering precious metals and heavy metals in an acidic solution, where the pH value of the acidic solution is less than or equal to 4.

The present invention has the following advantages:

The reactor for the separation and recovery of precious metals proposed by the present invention adopts a specific modified polymer adsorbent, combined with selective adsorption and deposition technology to achieve efficient separation and recovery of precious and heavy metals, and utilizes the physicochemical properties of precious and heavy metals in acidic solution. Finally, the precious metals are recovered by the specific adsorption particles in the vicinity of the anode, and the heavy metals undergo electrodeposition in the cathode region, thereby realizing the effective separation and recovery of precious metals and heavy metals.

Description of drawings

The accompanying drawings constituting a part of the present invention are used to provide further understanding of the present invention, and the exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the attached image:

Fig. 1 is the reactor structure schematic diagram proposed by the present invention; wherein,

1-anode cylinder; 1a-porous anode cover; 1b-reducer;

2- cathode cylinder; 2a- cathode starting plate; 2b- modified polymer adsorbent;

3-outer frame; 4-DC power supply; 5-precious metal online analyzer; 6-water outlet; 7-water inlet; 8-water inlet pipe; 9-water outlet pipe.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Embodiments of the invention and features of the embodiments may be combined with each other without conflict.

As shown in FIG. 1, an embodiment of the present invention provides a reactor for separation and recovery of precious metals, the reactor includes:

Anode cylinder 1, the anode cylinder 1 is provided with a porous anode cover 1a, the bottom end of the porous anode cover 1a is communicated with the water inlet pipe 8 through a reducer 1b, the anode cylinder 1 and the porous anode cover A modified polymer adsorbent 2b is arranged between 1a;

The cathode cylinder 2 is arranged on the outer side of the porous anode cover 1a, and the inner wall of the cathode cylinder 2 is provided with a cathode starting plate 2a;

The outer frame 3 is arranged outside the cathode cylinder 2, and the upper part of the outer frame 3 is provided with a water outlet pipe 9, the water outlet pipe 9 is connected with the precious metal online analyzer 5, and the precious metal online analyzer 5 is connected with the water outlet tank 6 Connected to the water inlet tank 7.

The reactor for the separation and recovery of precious metals proposed in the embodiment of the present invention adopts a specific modified polymer adsorbent, combined with selective adsorption and deposition technology to achieve efficient separation and recovery of precious and heavy metals, and utilizes the precious and heavy metals in acidic solution. The difference in physical and chemical properties realizes the opposite migration effect under the action of the electric field. The noble metal complex anions are selectively adsorbed by the modified polymer adsorbent at the anode, while the heavy metal cations can migrate to the cathode through the openings on the porous anode cover, where deposition occurs. Finally, precious metals are recovered by specific adsorption particles near the anode at the anode, while the heavy metals undergo electrodeposition in the cathode region, thereby realizing the effective separation of precious metals and heavy metals.

It should be pointed out that the precious metals mentioned herein include precious metals and heavy metals. The precious metal includes at least one of gold, platinum, rhodium, and iridium. The heavy metals include at least one of copper, nickel, zinc, and iron.

Further, the device is equipped with a DC power source 4 , the anode cylinder 1 is connected to the positive electrode of the DC power source 4 , and the cathode cylinder 2 is connected to the negative electrode of the DC power source 4 .

Preferably, the voltage provided by the DC power supply 4 is 1-10V. More preferably, the voltage provided by the DC power supply 4 is 3-6V. By adjusting different voltages, different kinds of heavy metals can be recovered.

Specifically, the anode cylinder 1 is a columnar anode cylinder. The anode cylinder is a titanium mesh cylinder supporting noble metal, and the noble metal is ruthenium, iridium and the like.

The porous anode housing 1a is a titanium cylinder.

The bottom of the porous anode housing 1a is a mesh structure. The arrangement of the mesh structure, on the one hand, is used to load the modified polymer adsorbent 2b, and on the other hand, it is convenient for the waste liquid to enter the porous anode housing from the bottom, so that the waste liquid can fully interact with the modified polymer adsorbent 2b.

The openings in the porous anode housing can be circular or square. When the opening is circular, its diameter may be 0.3-1 cm. The pore size of the openings on the porous anode housing is smaller than the particle size of the large-particle porous adsorbent material.

Specifically, the cathode cylinder 2 is a columnar cathode cylinder. The cathode cylinder is a titanium cylinder or a stainless steel cylinder. The cathode starting plate is a copper plate, a titanium plate or a stainless steel plate.

As shown in FIG. 1 , the bottom end of the porous anode housing 1a is communicated with the water inlet pipe 9a through the bottom of the cathode cylinder 2 through the reducer 1b.

A lift pump is provided between the water inlet pipe 8 and the water inlet tank 7 . It is used to quickly transfer the waste liquid to be treated in the water inlet tank 7 to between the porous anode housing 1a and the anode cylinder 1 through the water inlet pipe through the action of the lift pump for treatment.

The on-line analyzer 5 for precious metals is respectively connected with the outlet tank 6 and the inlet tank 7 of the reactor through a three-way valve. The water samples analyzed by the precious metal online analyzer 5 are respectively distributed to the water outlet tank 6 and the water inlet tank 7 through the three-way valve. Among them, if the detection reaches the standard, it will be directly delivered to the water outlet 6. If the detection fails to meet the standard, re-enter the water inlet tank 7 for recycling and separation.

In an embodiment of the present invention, the preparation method of the modified polymer adsorbent comprises the following steps:

(1) mixing elemental sulfur, polyvalent amine-based compound, polyvalent carbonyl compound, and loading substrate, adding an organic solvent to obtain a solid-liquid mixed solution;

(2) under a protective gas atmosphere, the above-mentioned solid-liquid mixed solution is heated and reacted to obtain a modified polymer mixed solution;

(3) cooling the above-mentioned modified polymer mixed solution to room temperature, washing, centrifuging, and drying to obtain a modified polymer adsorbent;

Wherein, the supporting substrate is a large-particle porous adsorbent material, and the particle size of the large-particle porous adsorbent material is between 1 cm-5 cm.

The modified polymer adsorbent proposed by the present invention is used to add large particles of porous adsorbent material as a loading substrate, and the sulfur element, polyamine-based compound and polyvalent carbonyl compound are in-situ polymerized on the surface of the loaded substrate. As a loading substrate, the material can significantly improve the adsorption rate and adsorption capacity, so that the obtained adsorbent has the excellent properties of strong load stability, fast adsorption rate, strong selectivity and large adsorption capacity, thereby effectively improving the adsorption effect.

In an embodiment of the present invention, in step (1), the ratio of the moles of carbonyl groups in the polyvalent carbonyl compound: the moles of amine groups in the polyvalent amine compound: the moles of sulfur atoms in the elemental sulfur is (1-6):1:( 1 to 6).

In step (1), the mass ratio of the loaded substrate to the elemental sulfur is (0.5-10):1.

In an embodiment of the present invention, in step (1), the elemental sulfur is sublimed sulfur;

In step (1), the polyamine-based compound contains a primary amino group or a secondary amino group;

In step (1), the polyvalent carbonyl compound contains an aldehyde group or a carboxyl group.

In an embodiment of the present invention, in step (1), the polyamine-based compound contains a primary amino group or a secondary amino group;

Preferably, the polyamine-based compound includes hexamethylenediamine, piperazine, p-phenylenediamine, ethylenediamine, 1,4-cyclohexanediamine, dimethylpropylenediamine, N N'-diethyl ethylene diamine Diamine, 1,8-diamino-3,6-dioxoctane, 4,4'-diaminodiphenyl ether, N N'-diethylethylenediamine, N N'-diethylethyl At least one of diamine, p-xylylenediamine, 1,3-bis(4-piperidinyl)propane, and o-phenylenediamine;

In step (1), the polyvalent carbonyl compound contains an aldehyde group or a carboxyl group;

Preferably, the polyvalent carbonyl compound includes polyurethane, terephthalaldehyde, p-toluenesulfonic acid, isophthalic acid, 2,5-thiophenedicarbaldehyde, 1H-pyrrole-2,5-dicarbaldehyde, phthalic acid At least one of formaldehyde, pyridine-2,6-dicarbaldehyde, and 1,4-diacetophenone.

In an embodiment of the present invention, in step (1), the large-particle porous adsorbent material includes at least one of columnar activated carbon, carbon nanotubes, carbon felt, activated carbon fiber, and carbon-based composite materials.

In an embodiment of the present invention, in step (2), the temperature of the heating reaction is 60°C-120°C; the time of the heating reaction is 4-24h.

In an embodiment of the present invention, in step (3), the washing times are 4-6 times.

The rotating speed of the centrifugation is 5000-13000rpm; the time of the centrifugation is 5-10 minutes.

The drying temperature is 20°C-50°C.

The drying adopts vacuum drying for more than 12 hours.

An embodiment of the present invention also proposes the application of any of the above reactors in separating and recovering precious metals and heavy metals in an acidic solution. Preferably, the pH value of the acidic solution is less than or equal to 4.

Further, the precious metal includes at least one of gold, platinum, rhodium, and iridium; and the heavy metal includes at least one of copper, nickel, zinc, and iron. In addition, the reactor proposed by the present invention can also be used to reduce the metal arsenic in the acidic solution to pentavalent arsenic at the anode, thereby reducing the toxicity of the wastewater.

An embodiment of the present invention also proposes a method for separating and recovering precious metals and heavy metals in an acidic solution by utilizing the above-mentioned reactor, including the following steps:

The waste water containing precious metals in the water inlet tank 7 enters between the porous anode housing 1a and the cathode cylinder 2 through the lift pump. Driven by the high-speed water flow, the modified polymer adsorbent 2b moves in the form of a fluidized bed to make the modified polymer The adsorbent 2b is in full contact with the precious and heavy metals in the wastewater, and the heavy metals flow to the cathode cylinder 2 along with the openings of the porous anode housing 1a and deposit on the cathode starting plate 2a.

The present invention will be described in detail below in conjunction with the embodiments.

Embodiment 1 A kind of preparation method of modified polymer adsorbent, comprises the steps:

(1) Weigh 48.1 mg of elemental sulfur, 145.6 mg of terephthalic acid, 58.1 mg of hexamethylene diamine and 24 mg of columnar activated carbon (5 mm in diameter) into a 20 mL pressure-resistant tube, add 2 mL of N,N-dimethylacetamide, Add the magnetic rotor and stir for 12 minutes, put it into the ultrasonic instrument for 12 minutes, and obtain a solid-liquid mixture;

(2) vacuuming the solid-liquid mixture obtained in step (1) to no bubbles, filling with nitrogen, heating to 100° C. for reaction for 15 hours, to obtain a modified polymer mixture;

(3) Add 4 mL of N,N-dimethylformamide to the modified polymer mixture obtained in step (2), stir for 10 minutes, slowly drop it into 100 mL of methanol, centrifuge for 5 minutes, remove the supernatant and collect Precipitate; then wash the precipitate with methanol, centrifuge again for 5 minutes after washing, remove the supernatant, and repeat for 5 times. Finally, the centrifuged precipitate is placed in a vacuum drying box and dried at 40 ° C for 12 hours , that is, a modified polymer adsorbent for selective adsorption and recovery of precious metal ions is obtained.

Test Example 1 A method for wastewater treatment (gold, copper, nickel, zinc) using modified polymer adsorbents, including the following steps:

Selected reactor: the cathode starting plate is a titanium plate, the anode is a titanium mesh cylinder plated with ruthenium, the aperture of the porous anode outer cover is 5mm, and the modified polymer adsorbent 1 (the gained of Example 1) is loaded into the inside of the porous anode outer cover, The columnar modified polymer adsorbent 1 accounted for 50% of the total volume of the anode housing.

Reactor operation: put 1L of acidic multicomponent heavy and precious metal solution (pH of 3) in the water storage tank, the precious metal in the solution is gold ion (concentration is 0.1g/L), and the heavy metal has copper ion (concentration is 10g/L) , nickel ions (concentration of 0.5g/L), zinc ions (concentration of 1g/L), and metalloid arsenic (concentration of 0.1g/L).

Adjust the pumping flow of the lift pump to 0.4L/h, turn on the DC power supply, and set the voltage to 1.5-3V. After circulating for 90 minutes, the recovery rate of gold ions is 99.6% and the recovery rate of copper ions is 90%.

After the copper sheet deposited at the cathode is recovered, cut off an area of 0.4cm×0.4cm, put it into concentrated nitric acid for digestion, and test the contents of gold, copper, nickel and zinc ions. After testing, the contents of gold, nickel and zinc ions are less than 3%, 5%, 5% (mass concentration). In addition, the adjustment voltage is 2.8-4V, and the deposition of copper and nickel can be deposited on the cathode. The adjustment voltage is 5-6V, and both copper, zinc and nickel can be deposited on the cathode.

The gold sorbent recovered at the anode was calcined at 1000°C for 2 hours, and the purity of the gold particles reached more than 90%, indicating that the reactor can achieve the purpose of efficient separation and recovery of precious and heavy metals. At the same time, the metalloid arsenic in the wastewater is reduced to pentavalent arsenic at the anode, the toxicity of the wastewater is reduced, and the effluent is further treated to remove the metalloid arsenic.

Embodiment 2 A kind of preparation method of modified polymer adsorbent, comprises the steps:

(1) Weigh 481mg of sulfur element, 1750mg of piperazine, 1660mg of terephthalaldehyde and 200mg of polyurethane (a cube of 1cm*1cm*1cm) into a pressure-resistant tube, add 20mL of N,N-dimethylacetamide, Add the magnetic rotor and stir for 12 minutes, put it into the ultrasonic instrument for 12 minutes, and obtain a solid-liquid mixture;

(2) vacuuming the solid-liquid mixture obtained in step (1) to no bubbles, filling with nitrogen, heating to 100° C. for reaction for 15 hours, to obtain a modified polymer mixture;

(3) The modified polymer mixture obtained in step (2) was slowly added dropwise to 200 mL of methanol, centrifuged for 5 minutes, and the supernatant was removed to collect the precipitate; then the precipitate was washed with methanol, and centrifuged again after washing. Treat for 5 minutes, remove the supernatant, repeat this for 5 times, and finally place the centrifuged precipitate in a vacuum drying box, and dry it at 50 ° C for 12 hours to obtain a modified polymer for selective adsorption and recovery of precious metal ions adsorbent.

Test example 2 utilizes the modified polymer adsorbent to carry out the method for waste water treatment (platinum, zinc), comprises the following steps:

Put 1L of acidic multicomponent heavy and precious metal solution (pH of 4) in the water storage tank, the precious metal in the solution is platinum ion, the concentration is 0.05g/L, the heavy metal is zinc ion, the concentration is 10g/L.

The cathode starting plate of the reactor is a titanium plate, the anode is a titanium mesh cylinder plated with ruthenium, and the modified polymer adsorbent 2 is loaded into the porous anode housing, and the modified polymer adsorbent 2 (obtained in Example 2) accounts for the total volume of the anode housing. 50%. Adjust the pumping flow of the pump to 0.2L/min, turn on the DC power supply, set the voltage to 5-6V, and after circulating for 120min, the recovery rate of platinum ions is 99.5%, and the recovery rate of zinc ions is 90%.

After the zinc deposited at the cathode is recovered, the area of 0.4cm×0.4cm is cut off, put into concentrated nitric acid for digestion, and the content of platinum and zinc ions is tested. After testing, the content of platinum ions is less than 3% (mass concentration).

After the sorbent for recovering platinum at the anode was calcined at 1000℃ for 4 hours, the purity of the particle platinum reached more than 90%, indicating that the reactor can achieve the purpose of efficient separation and recovery of precious and heavy metals.

Embodiment 3 A kind of preparation method of modified polymer adsorbent, comprises the steps:

(1) Weigh 240mg of sulfur element, 581mg of hexamethylenediamine, 830mg of terephthalaldehyde and 200mg of carbon felt (0.5cm*2cm*1cm small cuboid) into a pressure-resistant tube, add 30mL of p-toluenesulfonic acid , add the magnetic rotor and stir for 12 minutes, put it into the ultrasonic instrument for 12 minutes, and obtain a solid-liquid mixture;

(2) vacuuming the solid-liquid mixture obtained in step (1) to no bubbles, filling with nitrogen, heating to 100° C. for reaction for 15 hours, to obtain a modified polymer mixture;

(3) The modified polymer mixture obtained in step (2) was slowly added dropwise to 250 mL of methanol, centrifuged for 5 minutes, and the supernatant was removed to collect the precipitate; then the precipitate was washed with methanol, and centrifuged again after washing. Treat for 5 minutes, remove the supernatant, repeat this for 5 times, and finally place the centrifuged precipitate in a vacuum drying box, and dry it at 50 ° C for 12 hours to obtain a modified polymer for selective adsorption and recovery of precious metal ions adsorbent.

Test example 3 utilizes modified polymer adsorbent to carry out the method for waste water treatment (gold, zinc, copper), comprises the following steps:

Put 1L of acidic multicomponent heavy and precious metal solution (pH is 4) in the water storage tank. The precious metal in the solution is gold ion with a concentration of 0.2g/L, and the heavy metal is copper and zinc ion with a concentration of 10g/L.

The cathode starting plate of the reactor is a titanium plate, the anode is a titanium mesh cylinder plated with ruthenium, and the modified polymer adsorbent 3 is loaded into the porous anode housing, and the modified polymer adsorbent 3 (obtained in Example 3) accounts for the total volume of the anode housing. 50%. Adjust the pumping flow of the pump to 0.4L/h, the DC power supply voltage to 2V, and after the solution circulates for 120min, take out the deposited copper sheet. Replace the titanium plate, adjust the pumping flow of the pump to 0.2L/h, set the DC voltage to 6V, and take out the deposited zinc flakes after the solution circulates for 120min. The adsorbent for recovering gold was calcined at 1000° C. for 2 hours to obtain particle gold. After treatment, the concentration of the solution was detected, and the recovery rate of gold was 99%, and the recovery rate of copper and zinc was 90%.

Cut a 0.4cm×0.4cm recovered sheet, and test the concentrations of its copper, zinc and gold after being digested by concentrated nitric acid. It is found that the contents of gold and zinc in the recovered copper sheet are less than 3% and 5% (mass concentration), and the zinc is recovered. The content of gold and copper in the sheet is less than 3% and 1% (mass concentration). The purity of the recovered particle gold is more than 90%, indicating that the reactor can achieve the purpose of efficient separation and recovery of precious and heavy metals.

The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention. within.

Claims (10)

1. A reactor for the separation and recovery of precious metals, characterized in that it comprises:

the device comprises an anode cylinder (1), wherein a porous anode cover (1a) is arranged outside the anode cylinder (1), the bottom end of the porous anode cover (1a) is communicated with a water inlet pipe (8) through a reducing pipe (1b), and a modified polymer adsorbent (2b) is arranged between the anode cylinder (1) and the porous anode cover (1 a);

the cathode cylinder (2) is arranged on the outer side of the porous anode outer cover (1a), and a cathode starting polar plate (2a) is arranged on the inner wall of the cathode cylinder (2);

the outer frame (3) is arranged outside the cathode cylinder (2), a water outlet pipe (9) is arranged at the upper part of the outer frame (3), the water outlet pipe (9) is connected with the precious metal online analyzer (5), and the precious metal online analyzer (5) is connected with a water outlet groove (6) and a water inlet groove (7).

2. The reactor of claim 1, wherein:

the device is provided with a direct current power supply (4), the anode cylinder (1) is connected with the anode of the direct current power supply (4), and the cathode cylinder (2) is connected with the cathode of the direct current power supply (4).

3. The reactor of claim 1, wherein:

the anode cylinder (1) is a titanium mesh cylinder loaded with noble metals, and the noble metals are ruthenium and iridium;

the porous anode outer cover (1a) is a titanium cylinder; the bottom of the porous anode outer cover (1a) is of a net structure; the opening on the porous anode outer cover is round or square.

4. The reactor of claim 1, wherein:

the cathode cylinder (2) is a titanium cylinder or a stainless steel cylinder;

the cathode starting plate (2a) is a copper plate, a titanium plate or a stainless steel plate.

5. The reactor of claim 1, wherein:

and a lifting pump is arranged between the water inlet pipe (8) and the water inlet tank (7).

6. The reactor of claim 1, wherein:

the preparation method of the modified polymer adsorbent comprises the following steps:

(1) mixing elemental sulfur, a multi-amino compound, a multi-carbonyl compound and a load substrate, and adding an organic solvent to obtain a solid-liquid mixed solution;

(2) heating the solid-liquid mixed solution to react under the atmosphere of protective gas to obtain a modified polymer mixed solution;

(3) cooling the modified polymer mixed solution to room temperature, washing, centrifuging and drying to obtain a modified polymer adsorbent;

wherein the loading substrate is a large-particle porous adsorption material, and the particle size of the large-particle porous adsorption material is between 1cm and 5 cm.

7. The reactor of claim 6, wherein:

in the step (1), the molar number of carbonyl groups in the polybasic carbonyl compound is as follows: the molar number of amine groups in the polyamine compound is as follows: the molar ratio of sulfur atoms in the elemental sulfur is (1-6) to 1 (1-6);

in the step (1), the mass ratio of the load substrate to the elemental sulfur is (0.5-10): 1.

8. The reactor of claim 6, wherein:

in the step (1), the elemental sulfur is sublimed sulfur;

in the step (1), the polyamine-based compound contains primary amine groups or secondary amine groups;

in the step (1), the polybasic carbonyl compound contains aldehyde group or carboxyl;

in the step (1), the large-particle porous adsorption material comprises at least one of columnar activated carbon, carbon nanotubes, a carbon felt, activated carbon fibers and a carbon-based composite material.

9. The reactor of claim 6, wherein:

in the step (2), the temperature of the heating reaction is 60-120 ℃; the heating reaction time is 4-24 h.

In the step (3), the rotation speed of the centrifugation is 5000-13000 rpm; the centrifugation time is 5-10 minutes;

in the step (3), the drying temperature is 20-50 ℃;

in the step (3), the drying is carried out for more than 12 hours in vacuum.

10. Use of a reactor according to any one of claims 1 to 9 for separating and recovering precious and heavy metals from an acidic solution, wherein the acidic solution has a pH of 4 or less.

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