Method for recovering metal from acid leaching residues

Abstract

The invention relates to the technical field of resource recycling, and discloses a method for recovering metal from acid leaching residue, which comprises the following preparation steps: placing neutral leaching residue in a crusher for crushing, sieving, placing in hydrochloric acid for acid leaching, adding a surfactant, stirring, adding a composite adsorption material, and after adsorption is completed, filtering and collecting filtrate A and filter residue A; sieving the filter residue A to obtain a filter residue B and a composite adsorption material rich in valuable metals; completely desorbing the adsorbing material rich in valuable metals by using sulfuric acid, and filtering and collecting filtrate C and a composite adsorbing material; mixing the filtrate A and the filtrate C, adding a sodium hydroxide solution, stirring for reaction, centrifugally collecting precipitate, and sintering the precipitate to obtain the metal oxide. And the recovery rate of valuable metal cations in the neutral leaching residues can be obviously improved.

Description

Technical Field

[0001] The present invention relates to the technical field of resource recycling, and particularly to a method for recovering metals from acid leaching residues. Background Art

[0002] Intermediate leaching residues (leaching residues) refer to the solid materials remaining after the valuable components in ores, concentrates, roasted ores or other solid materials are leached with leaching agents. The composition of intermediate leaching residues depends on the composition of the leached materials and the leaching method. Intermediate leaching residues contain a large amount of valuable metals, and the intermediate leaching residues should be comprehensively utilized as much as possible to reduce their environmental pollution. Otherwise, the storage and discharge of intermediate leaching residues will become an important factor restricting the development of hydrometallurgy.

[0003] When the intermediate leaching residues are acid-leached, the valuable metal ions in the intermediate leaching residues can be effectively dissolved and released, improving the recovery rate. However, a large number of anionic groups such as hydroxide, sulfate, chloride ions, etc. will remain in the acid solution of the intermediate leaching residues, which are easy to combine with the dissolved valuable metals to form complexes or precipitates, resulting in a reduction in the recovery rate of valuable metal ions in the intermediate leaching residues. Summary of the Invention

[0004] The present invention provides a method for recovering metals from acid leaching residues, which solves the problem of low recovery rate of valuable metal ions in intermediate leaching residues.

[0005] The technical solution of the present invention is as follows:

[0006] A method for recovering metals from acid leaching residues includes the following preparation steps:

[0007] S1. Place the intermediate leaching residues in a crusher for crushing. After sieving, place them in hydrochloric acid for acid leaching, add a surfactant, stir for 20 - 30 min, then add a composite adsorption material. After adsorption, filter to collect filtrate A and filter residue A;

[0008] S2. Sieve filter residue A to obtain filter residue B and a composite adsorption material rich in valuable metals;

[0009] S3. After completely desorbing the adsorption material rich in valuable metals with sulfuric acid, filter to collect filtrate C and the composite adsorption material;

[0010] S4. Mix filtrate A and filtrate C, add sodium hydroxide solution, stir and react for 1 - 2 h, centrifuge to collect the precipitate, and sinter the precipitate at 850 - 950 °C for 1 - 2 h to obtain metal oxides.

[0011] Further, in step S1, the acid leaching conditions are: liquid-solid ratio (5 - 7):1, temperature 80 - 90 °C, reaction time 4 - 6 h, hydrochloric acid concentration 8 - 10 g / L, stirring speed 300 - 500 r / min.

[0012] Further, in step S1, the surfactant is a cationic surfactant, and the cationic surfactant is selected from any one of cetyltrimethylammonium bromide, dodecyltrimethylammonium bromide, ethylene bis(dodecyldimethylammonium bromide), and methyltrioctylammonium chloride.

[0013] Further, in step S1, the addition amount of the surfactant is 13-15%; the addition amount of the composite adsorbent material is 15-17%.

[0014] Further, in steps S1 and S2, the mesh aperture of the sieve is 200-300 mesh.

[0015] Further, in step S3, the mass ratio of the adsorbent material rich in valuable metals to sulfuric acid is 1:(8-10).

[0016] Further, in step S3, the concentration of sulfuric acid is 4-6 mol / L.

[0017] Further, in step S4, the mass fraction of the sodium hydroxide solution is 10-20%, and the addition amount of the sodium hydroxide solution is 20-30%.

[0018] Further, the composite adsorbent material is obtained by mixing the monomer formed by the reaction of citric acid and ethylenediaminetetraacetic acid with zeolite loaded with porous carbon.

[0019] Further, the composite adsorbent material is specifically prepared by the following steps:

[0020] A1. Add citric acid into deionized water, stir until the citric acid is completely dissolved, add ethylenediaminetetraacetic acid, heat up to 60-70 °C, stir evenly, add hydrochloric acid, continue stirring and reacting for 15-20 min, cool to room temperature, filter to remove impurities, and obtain a monomer solution;

[0021] A2. Add zeolite, rice husk powder, and oxalic acid into ethanol, stir evenly, add hydrochloric acid, after stirring and reacting, filter, wash, dry, place in a tubular furnace, add potassium hydroxide solution for activation, then introduce nitrogen, carry out high-temperature carbonization at 800-900 °C for 3-5 h, cool to room temperature, take out, wash, and dry to obtain zeolite loaded with porous carbon;

[0022] A3. Add the zeolite loaded with porous carbon into the monomer solution, stir at 100-105 °C for 3-5 min, filter, and dry until the water evaporates to obtain the composite adsorbent material.

[0023] Further, in the above A1 reaction process, citric acid is dissolved in deionized water, and under the action of the catalyst hydrochloric acid, the hydroxyl group in citric acid reacts with the carboxyl group of ethylenediaminetetraacetic acid, so that ethylenediaminetetraacetic acid is grafted onto citric acid to obtain a monomer solution.

[0024] Furthermore, during the above A2 reaction process, oxalic acid is used as a linker, which can chemically bond with the hydroxyl groups on the zeolite surface and the oxygen-containing functional groups in the rice husk powder, enabling the rice husk powder to be coated on the zeolite surface. Potassium hydroxide is used as an activator. After high-temperature carbonization, the carbon precursor decomposes by heat to form a dense carbon layer, and the activator potassium hydroxide molecules decompose to form pores on the surface of the dense carbon layer, realizing the synthesis of porous carbon on the zeolite surface and obtaining zeolite loaded with porous carbon.

[0025] Furthermore, during the above A3 reaction process, the zeolite loaded with porous carbon has excellent adsorption performance, enabling the monomer solution to penetrate into the pores of the zeolite loaded with porous carbon. After drying, the water evaporates, causing the monomer to adhere to the pore walls of the zeolite loaded with porous carbon, obtaining an adsorption material.

[0026] Furthermore, in step A1, the mass ratio of citric acid, deionized water, ethylenediaminetetraacetic acid, and hydrochloric acid is (3.6 - 3.8):(65 - 75):(2 - 2.5):(1 - 2).

[0027] Furthermore, in step A2, the mass ratio of zeolite, rice husk powder, oxalic acid, ethanol, hydrochloric acid, and potassium hydroxide solution is (6.5 - 6.9):(5.3 - 5.7):(0.3 - 0.5):(75 - 85):(0.4 - 0.6):(4 - 6).

[0028] Furthermore, in step A3, the volume ratio of the zeolite loaded with porous carbon to the monomer solution is (5 - 6):(75 - 85).

[0029] The present invention has the following beneficial effects:

[0030] (1) In the technical solution of the present invention, after the middle leaching residue is acid-leached, valuable metal cations can be dissolved and released. By compounding a cationic surfactant, the positively charged groups carried by the cationic surfactant can electrostatically adsorb with the anionic groups carried on the surface of the acid-leached middle leaching residue, enabling the cationic surfactant to adsorb on the surface of the acid-leached middle leaching residue, forming a positive charge barrier to repel the valuable metal cations dissolved in the acid solution, and preventing a large amount of anionic groups such as hydroxide, sulfate, and chloride ions from remaining in the acid solution on the middle leaching residue, which are likely to combine with the dissolved valuable metal ions to form complexes or precipitates, affecting the recovery rate of valuable metal ions.

[0031] (2) In the technical solution of the present invention, porous carbon is synthesized on the surface of zeolite. On the one hand, the synthesized porous carbon has a high adsorption capacity, improving the adsorption and recovery performance of valuable metal cations dissolved in the acid solution. Moreover, the combined use of porous carbon and zeolite provides sufficient adsorption capacity for valuable metal cations. On the other hand, porous carbon has good acid resistance, which can protect the zeolite framework from collapsing easily in the acid leaching solution, maintaining good adsorption performance of valuable metal cations. And the zeolite loaded with porous carbon can be simply desorbed with an acid solution, which is beneficial to the recovery of valuable metal cations.

[0032] (3) In the technical solution of the present invention, ethylenediaminetetraacetic acid is grafted onto citric acid, increasing the binding sites of valuable metal cations dissolved in the acid solution, improving the adsorption and recovery efficiency of valuable metal cations, and avoiding the low metal ion removal efficiency caused by the easy saturation of citric acid in adsorbing metal ions.

[0033] (4) In the technical solution of the present invention, the zeolite loaded with porous carbon is mixed with the monomer solution. On the one hand, the monomer penetrates into the pores of the porous carbon and zeolite, making the porous carbon and zeolite more tightly combined through the monomer, improving the binding force between the porous carbon and zeolite, and avoiding the easy separation of the porous carbon and zeolite in the acidic solution, which affects the adsorption and recovery effect. On the other hand, the monomer contains citric acid and ethylenediaminetetraacetic acid. As a metal ion complexing agent, the functional groups carried can complex with valuable metal cations, improving the recovery efficiency. Detailed implementation mode

[0034] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0035] The raw materials used in the embodiments of the present invention are as follows, and all the reagents used are of analytical grade.

[0036] Among them, the cationic surfactant is selected from cetyltrimethylammonium bromide.

[0037] The particle size of the zeolite is 30 mesh;

[0038] Component content of the intermediate leaching residue

[0039] Component Lead Zinc Copper Iron Chromium Calcium Indium Content / % 7.02 5.86 0.06 6.08 6.51 10.23 0.02

[0040] Example 1

[0041] A method for recovering metals from acid leaching residue includes the following preparation steps:

[0042] S1. Place the intermediate leaching residue in a pulverizer, pulverize it, pass through a 200-mesh sieve, then place it in hydrochloric acid for acid leaching. After that, add cetyltrimethylammonium bromide, stir for 20 min, then add the composite adsorbent material. After adsorption is completed, filter to collect filtrate A and residue A;

[0043] Among them, the acid leaching conditions are: liquid-solid ratio 5:1, temperature 80 °C, reaction time 4 h, hydrochloric acid concentration 8 g / L, stirring speed 300 r / min;

[0044] The addition amount of cetyltrimethylammonium bromide is 13%; the addition amount of the composite adsorbent material is 15%;

[0045] S2. Pass residue A through a 200-mesh sieve to obtain residue B and the composite adsorbent material rich in valuable metals;

[0046] S3. After completely desorbing the adsorbent material rich in valuable metals with sulfuric acid, filter to collect filtrate C and the composite adsorbent material;

[0047] Among them, the mass ratio of the adsorbent material rich in valuable metals to sulfuric acid is 1:8; the sulfuric acid concentration is 4 mol / L;

[0048] S4. Mix filtrate A and filtrate C, add sodium hydroxide solution, stir and react for 1 h, centrifuge to collect the precipitate, and sinter the precipitate at 850 °C for 1 h to obtain metal oxides.

[0049] Among them, the mass fraction of the sodium hydroxide solution is 10%, and the addition amount of the sodium hydroxide solution is 20%.

[0050] The composite adsorbent material is specifically prepared by the following steps:

[0051] A1. Add citric acid to deionized water, stir until the citric acid is completely dissolved, add ethylenediaminetetraacetic acid, heat up to 60 °C, stir evenly, add hydrochloric acid with a mass fraction of 36%, continue to stir and react for 15 min, cool to room temperature, and filter to remove impurities to obtain the monomer solution; the mass ratio of citric acid, deionized water, ethylenediaminetetraacetic acid, and hydrochloric acid is 3.6:65:2:1;

[0052] A2. Add zeolite, rice husk powder and oxalic acid to ethanol, stir evenly, add hydrochloric acid with a mass fraction of 36%, stir and react at 70 °C for 30 min after completion, filter, wash with deionized water 3 times, dry in an oven at 70 °C for 10 min, place in a tubular furnace, add potassium hydroxide solution with a mass fraction of 25% for activation, then introduce nitrogen, carry out high-temperature carbonization at 800 °C for 3 h, cool to room temperature, take out, wash with deionized water 3 times, dry in an oven at 70 °C for 10 min to obtain zeolite loaded with porous carbon; the mass ratio of zeolite, rice husk powder, oxalic acid, ethanol, hydrochloric acid and potassium hydroxide solution is 6.5:5.3:0.3:75:0.4:4;

[0053] A3. Add the zeolite loaded with porous carbon to the monomer solution, stir at 100 °C for 3 min, filter, and place in an oven at 80 °C to dry until the water evaporates to obtain the composite adsorbent material; the ratio of the zeolite loaded with porous carbon to the monomer solution is 5:75.

[0054] Example 2

[0055] A method for recovering metals from acid leaching residues, comprising the following preparation steps:

[0056] S1. Place the medium leaching residue in a pulverizer to pulverize it. After passing through a 250-mesh sieve, place it in hydrochloric acid for acid leaching, add cetyltrimethylammonium bromide, stir for 25 min, then add the composite adsorbent material. After adsorption is completed, filter to collect filtrate A and filter residue A;

[0057] Among them, the acid leaching conditions are: liquid-solid ratio of 6:1, temperature of 85 °C, reaction time of 5 h, hydrochloric acid concentration of 9 g / L, and stirring speed of 400 r / min;

[0058] The addition amount of cetyltrimethylammonium bromide is 13-15%; the addition amount of the composite adsorbent material is 15-17%;

[0059] S2. Pass filter residue A through a 250-mesh sieve to obtain filter residue B and a composite adsorbent material rich in valuable metals;

[0060] S3. After completely desorbing the adsorbent material rich in valuable metals with sulfuric acid, filter to collect filtrate C and the composite adsorbent material;

[0061] Among them, the mass ratio of the adsorbent material rich in valuable metals to sulfuric acid is 1:9; the sulfuric acid concentration is 5 mol / L;

[0062] S4. Mix filtrate A and filtrate C, add sodium hydroxide solution, stir and react for 1.5 h, centrifuge to collect the precipitate, and sinter the precipitate at 900 °C for 1.5 h to obtain metal oxides.

[0063] Among them, the mass fraction of the sodium hydroxide solution is 15%, and the addition amount of the sodium hydroxide solution is 25%.

[0064] The composite adsorbent material is specifically prepared by the following steps:

[0065] A1. Add citric acid to deionized water, stir until the citric acid is completely dissolved, add ethylenediaminetetraacetic acid, heat to 65 °C, stir evenly, add hydrochloric acid with a mass fraction of 36%, continue to stir and react for 18 min, cool to room temperature, filter to remove impurities, and obtain a monomer solution; the mass ratio of citric acid, deionized water, ethylenediaminetetraacetic acid and hydrochloric acid is 3.7:70:2.3:1.5;

[0066] A2. Add zeolite, rice husk powder and oxalic acid to ethanol, stir evenly, add hydrochloric acid with a mass fraction of 36%, after stirring and reacting at 70 °C for 30 min, filter, wash with deionized water 3 times, dry in an oven at 70 °C for 10 min, place in a tubular furnace, add potassium hydroxide solution with a mass fraction of 25% for activation, then introduce nitrogen, carry out high-temperature carbonization at 850 °C for 4 h, cool to room temperature, take out, wash with deionized water 3 times, dry in an oven at 70 °C for 10 min, and obtain zeolite loaded with porous carbon; the mass ratio of zeolite, rice husk powder, oxalic acid, ethanol, hydrochloric acid and potassium hydroxide solution is 6.7:5.5:0.4:80:0.5:5;

[0067] A3. Add the zeolite loaded with porous carbon to the monomer solution, stir at 103 °C for 4 min, filter, and place in an oven at 80 °C to dry until the water evaporates, obtaining the composite adsorbent material; the ratio of the zeolite loaded with porous carbon to the monomer solution is 5.5:80.

[0068] Example 3

[0069] A method for recovering metals from acid leaching residues includes the following preparation steps:

[0070] S1. Place the medium leaching residue in a pulverizer to pulverize it. After passing through a 300-mesh sieve, place it in hydrochloric acid for acid leaching, add cetyltrimethylammonium bromide, stir for 30 min, then add the composite adsorbent material. After adsorption, filter to collect filtrate A and filter residue A;

[0071] Among them, the acid leaching conditions are: liquid-solid ratio 7:1, temperature 90 °C, reaction time 6 h, hydrochloric acid concentration 10 g / L, stirring speed 500 r / mi;

[0072] The addition amount of cetyltrimethylammonium bromide is 15%; the addition amount of the composite adsorbent material is 17%;

[0073] S2. Pass the filter residue A through a 300-mesh sieve to obtain filter residue B and a composite adsorbent material rich in valuable metals;

[0074] S3. After the adsorption material rich in valuable metals is completely desorbed with sulfuric acid, filter to collect the filtrate C and the composite adsorption material;

[0075] Among them, the mass ratio of the adsorption material rich in valuable metals to sulfuric acid is 1:10; the sulfuric acid concentration is 6 mol / L;

[0076] S4. Mix the filtrate A and the filtrate C, add sodium hydroxide solution, stir and react for 2 h, centrifuge to collect the precipitate, and sinter the precipitate at 950 °C for 2 h to obtain metal oxide.

[0077] Among them, the mass fraction of the sodium hydroxide solution is 20%, and the addition amount of the sodium hydroxide solution is 30%.

[0078] The composite adsorption material is specifically prepared by the following steps:

[0079] A1. Add citric acid to deionized water, stir until the citric acid is completely dissolved, add ethylenediaminetetraacetic acid, heat up to 70 °C, stir evenly, add hydrochloric acid with a mass fraction of 36%, continue to stir and react for 20 min, cool to room temperature, filter to remove impurities to obtain a monomer solution; the mass ratio of citric acid, deionized water, ethylenediaminetetraacetic acid and hydrochloric acid is 3.8:75:2.5:2;

[0080] A2. Add zeolite, rice husk powder and oxalic acid to ethanol, stir evenly, add hydrochloric acid with a mass fraction of 36%, after stirring and reacting at 70 °C for 30 min, filter, wash with deionized water 3 times, dry in an oven at 70 °C for 10 min, place in a tubular furnace, add potassium hydroxide solution with a mass fraction of 25% for activation, then introduce nitrogen, carry out high-temperature carbonization at 900 °C for 5 h, cool to room temperature, take out, wash with deionized water 3 times, dry in an oven at 70 °C for 10 min to obtain zeolite loaded with porous carbon; the mass ratio of zeolite, rice husk powder, oxalic acid, ethanol, hydrochloric acid and potassium hydroxide solution is 6.9:5.7:0.5:85:0.6:6;

[0081] A3. Add the zeolite loaded with porous carbon to the monomer solution, stir at 105 °C for 5 min, filter, and dry in an oven at 80 °C until the water evaporates to obtain the composite adsorption material; the ratio of the zeolite loaded with porous carbon to the monomer solution is 6:85.

[0082] Comparative Example 1

[0083] A method for recovering metals from acid leaching residues includes the following preparation steps:

[0084] S1. Place the medium leaching residue in a pulverizer to pulverize it, pass it through a 300-mesh sieve, then place it in hydrochloric acid for acid leaching, add the composite adsorption material, after adsorption is completed, filter to collect the filtrate A and the filter residue A;

[0085] Among them, the acid leaching conditions are as follows: liquid-solid ratio of 7:1, temperature of 90 °C, reaction time of 6 h, hydrochloric acid concentration of 10 g / L, and stirring speed of 500 r / mi;

[0086] The addition amount of the composite adsorbent material is 17%;

[0087] S2. Filter residue A is sieved through a 300-mesh sieve to obtain filter residue B and a composite adsorbent material rich in valuable metals;

[0088] S3. After the adsorbent material rich in valuable metals is completely desorbed with sulfuric acid, the filtrate C and the composite adsorbent material are collected by filtration;

[0089] Among them, the mass ratio of the adsorbent material rich in valuable metals to sulfuric acid is 1:10; the sulfuric acid concentration is 6 mol / L;

[0090] S4. Mix filtrate A and filtrate C, add sodium hydroxide solution, stir and react for 2 h, centrifuge to collect the precipitate, and sinter the precipitate at 950 °C for 2 h to obtain metal oxide.

[0091] Among them, the mass fraction of the sodium hydroxide solution is 20%, and the addition amount of the sodium hydroxide solution is 30%.

[0092] The composite adsorbent material is specifically prepared by the following steps:

[0093] A1. Add citric acid to deionized water, stir until the citric acid is completely dissolved, add ethylenediaminetetraacetic acid, heat up to 70 °C, stir evenly, add hydrochloric acid with a mass fraction of 36%, continue to stir and react for 20 min, cool to room temperature, filter to remove impurities to obtain a monomer solution; the mass ratio of citric acid, deionized water, ethylenediaminetetraacetic acid and hydrochloric acid is 3.8:75:2.5:2;

[0094] A2. Add zeolite, rice husk powder and oxalic acid to ethanol, stir evenly, add hydrochloric acid with a mass fraction of 36%, after stirring and reacting at 70 °C for 30 min, filter, wash with deionized water 3 times, dry in an oven at 70 °C for 10 min, place in a tubular furnace, add potassium hydroxide solution with a mass fraction of 25% for activation, then introduce nitrogen, carry out high-temperature carbonization at 900 °C for 5 h, cool to room temperature, take out, wash with deionized water 3 times, dry in an oven at July 2023 10 min to obtain zeolite loaded with porous carbon; the mass ratio of zeolite, rice husk powder, oxalic acid, ethanol, hydrochloric acid and potassium hydroxide solution is 6.9:5.7:0.5:85:0.6:6;

[0095] A3. Add the zeolite loaded with porous carbon to the monomer solution, stir at 105 °C for 5 min, filter, and dry in an oven at 80 °C until the water evaporates to obtain the composite adsorbent material; the volume ratio of the zeolite loaded with porous carbon to the monomer solution is 6:85.

[0096] Comparative Example 2

[0097] A method for recovering metals from acid leaching residues, comprising the following preparation steps:

[0098] S1. Place the intermediate leaching residue in a pulverizer, pulverize it, pass it through a 300-mesh sieve, then place it in hydrochloric acid for acid leaching, add cetyltrimethylammonium bromide, stir for 30 min, then add a composite adsorbent material. After adsorption is completed, filter to collect filtrate A and filter residue A;

[0099] Among them, the acid leaching conditions are: liquid-solid ratio 7:1, temperature 90 °C, reaction time 6 h, hydrochloric acid concentration 10 g / L, stirring speed 500 r / mi;

[0100] The addition amount of cetyltrimethylammonium bromide is 15%; the addition amount of the composite adsorbent material is 17%;

[0101] S2. Pass filter residue A through a 300-mesh sieve to obtain filter residue B and a composite adsorbent material rich in valuable metals;

[0102] S3. After completely desorbing the adsorbent material rich in valuable metals with sulfuric acid, filter to collect filtrate C and the composite adsorbent material;

[0103] Among them, the mass ratio of the adsorbent material rich in valuable metals to sulfuric acid is 1:10; the sulfuric acid concentration is 6 mol / L;

[0104] S4. Mix filtrate A and filtrate C, add sodium hydroxide solution, stir and react for 2 h, centrifuge to collect the precipitate, and sinter the precipitate at 950 °C for 2 h to obtain metal oxides.

[0105] Among them, the mass fraction of the sodium hydroxide solution is 20%, and the addition amount of the sodium hydroxide solution is 30%.

[0106] The composite adsorbent material is specifically prepared by the following steps:

[0107] A1. Add citric acid to deionized water and stir until the citric acid is completely dissolved to obtain a monomer solution; the mass ratio of citric acid, deionized water, ethylenediaminetetraacetic acid and hydrochloric acid is 3.8:75;

[0108] A2. Add zeolite, rice husk powder and oxalic acid to ethanol, stir evenly, add hydrochloric acid with a mass fraction of 36%, stir and react for 30 min after completion at 70 °C. After filtration, wash with deionized water three times, dry in an oven at 70 °C for 10 min, place in a tubular furnace, add potassium hydroxide solution with a mass fraction of 25% for activation, then introduce nitrogen, carry out high-temperature carbonization at 900 °C for 5 h, cool to room temperature, take out, wash with deionized water three times, dry in an oven at 70 °C for 10 min to obtain zeolite supported with porous carbon; the mass ratio of zeolite, rice husk powder, oxalic acid, ethanol, hydrochloric acid and potassium hydroxide solution is 6.9:5.7:0.5:85:0.6:6;

[0109] A3. Add the zeolite supported with porous carbon to the monomer solution, stir at 105 °C for 5 min, filter, and dry in an oven at 80 °C until the water evaporates to obtain the composite adsorbent material; the volume ratio of the zeolite supported with porous carbon to the monomer solution is 6:85.

[0110] Comparative Example 3

[0111] A method for recovering metals from acid leaching residues, comprising the following preparation steps:

[0112] S1. Place the medium leaching residue in a pulverizer to pulverize it. After passing through a 300-mesh sieve, place it in hydrochloric acid for acid leaching, add cetyltrimethylammonium bromide, stir for 30 min, then add the composite adsorbent material. After adsorption, filter to collect filtrate A and filter residue A;

[0113] Among them, the acid leaching conditions are: liquid-solid ratio of 7:1, temperature of 90 °C, reaction time of 6 h, hydrochloric acid concentration of 10 g / L, stirring speed of 500 r / mi;

[0114] The addition amount of cetyltrimethylammonium bromide is 15%; the addition amount of the composite adsorbent material is 17%;

[0115] S2. Pass filter residue A through a 300-mesh sieve to obtain filter residue B and the composite adsorbent material rich in valuable metals;

[0116] S3. After completely desorbing the adsorbent material rich in valuable metals with sulfuric acid, filter to collect filtrate C and the composite adsorbent material;

[0117] Among them, the mass ratio of the adsorbent material rich in valuable metals to sulfuric acid is 1:10; the sulfuric acid concentration is 6 mol / L;

[0118] S4. Mix filtrate A and filtrate C, add sodium hydroxide solution, stir and react for 2 h, centrifuge to collect the precipitate, and sinter the precipitate at 950 °C for 2 h to obtain metal oxides.

[0119] Among them, the mass fraction of the sodium hydroxide solution is 20%, and the addition amount of the sodium hydroxide solution is 30%.

[0120] The composite adsorbent material is specifically prepared by the following steps:

[0121] A1. Mix deionized water and ethylenediaminetetraacetic acid, heat to 70 °C, and stir evenly to obtain a monomer solution; the mass ratio of deionized water to ethylenediaminetetraacetic acid is 75:2.5;

[0122] A2. Add zeolite, rice husk powder and oxalic acid to ethanol, stir evenly, add hydrochloric acid with a mass fraction of 36%, stir and react at 70 °C for 30 min after completion, filter, wash 3 times with deionized water, dry in an oven at 70 °C for 10 min, place in a tubular furnace, add potassium hydroxide solution with a mass fraction of 25% for activation, then introduce nitrogen, carry out high-temperature carbonization at 900 °C for 5 h, cool to room temperature, take out, wash 3 times with deionized water, and dry in an oven at 70 °C for 10 min to obtain zeolite loaded with porous carbon; the mass ratio of zeolite, rice husk powder, oxalic acid, ethanol, hydrochloric acid and potassium hydroxide solution is 6.9:5.7:0.5:85:0.6:6;

[0123] A3. Add the zeolite loaded with porous carbon to the monomer solution, stir at 105 °C for 5 min, filter, and place in an oven at 80 °C to dry until the water evaporates to obtain the composite adsorbent material; the volume ratio of the zeolite loaded with porous carbon to the monomer solution is 6:85.

[0124] Comparative Example 4

[0125] A method for recovering metals from acid leaching residues, including the following preparation steps:

[0126] S1. Place the intermediate leaching residue in a pulverizer, pulverize it, pass through a 300-mesh sieve, then place it in hydrochloric acid for acid leaching, add cetyltrimethylammonium bromide, stir for 30 min, then add the composite adsorbent material. After adsorption, filter to collect filtrate A and filter residue A;

[0127] Among them, the acid leaching conditions are: liquid-solid ratio 7:1, temperature 90 °C, reaction time 6 h, hydrochloric acid concentration 10 g / L, stirring speed 500 r / mi;

[0128] The addition amount of cetyltrimethylammonium bromide is 15%; the addition amount of the composite adsorbent material is 17%;

[0129] S2. Pass filter residue A through a 300-mesh sieve to obtain filter residue B and a composite adsorbent material rich in valuable metals;

[0130] S3. After completely desorbing the adsorbent material rich in valuable metals with sulfuric acid, filter to collect filtrate C and the composite adsorbent material;

[0131] Among them, the mass ratio of the adsorbent material rich in valuable metals to sulfuric acid is 1:10; the sulfuric acid concentration is 6 mol / L;

[0132] S4. Mix filtrate A and filtrate C, add sodium hydroxide solution, stir and react for 2 h, centrifuge to collect the precipitate, and sinter the precipitate at 950 °C for 2 h to obtain metal oxide.

[0133] Among them, the mass fraction of the sodium hydroxide solution is 20%, and the addition amount of the sodium hydroxide solution is 30%.

[0134] The composite adsorbent material is specifically prepared by the following steps:

[0135] A1. Add citric acid to deionized water, stir until the citric acid is completely dissolved, add ethylenediaminetetraacetic acid, heat up to 70 °C, stir evenly, add hydrochloric acid with a mass fraction of 36%, continue to stir and react for 20 min, cool to room temperature, filter to remove impurities to obtain a monomer solution; the mass ratio of citric acid, deionized water, ethylenediaminetetraacetic acid and hydrochloric acid is 3.8:75:2.5:2;

[0136] A2. Add zeolite to the monomer solution, stir at 105 °C for 5 min, filter, and place it in an 80 °C oven to dry until the water evaporates to obtain a composite adsorbent material; the volume ratio of zeolite to the monomer solution is 6:85.

[0137] Now, perform performance tests on the pig feed additive compositions prepared in Examples 1-3 and Comparative Examples 1-5.

[0138] The test results are shown in Table 1 below.

[0139] Determine the recovery rate of valuable metal cations in the leaching residue during the determination:

[0140] Specific method: Place the filter residue B in a 250 mL glass reactor, add deionized water, stir evenly, the mass ratio of the filter residue B to the deionized water is 5:7, adjust the pH with sodium hydroxide, continuously shake on a shaker at 150 rpm and 23 °C for 3 d, and measure the metal ion concentration in it by inductively coupled plasma atomic emission spectrometry and record it as M1. The metal ion concentration in the middle leaching residue without acid leaching adsorption recovery is recorded as M0, and the recovery rate = (M0 - M1) / M0;

[0141] The test results are shown in Table 1 below.

[0142] Table 1

[0143]

[0144] It can be seen from the data in Table 1 that the method for recovering metals from acid leaching residue in Examples 1-3 can significantly improve the adsorption and recovery performance of valuable metal cations in the middle leaching residue.

[0145] In Comparative Example 1, cetyltrimethylammonium bromide was not added, and metals were recovered from the acid-leached residue. The recovery rate of valuable metal cations in the leached residue decreased, which proved that the cationic surfactant adsorbed on the surface of the intermediate leached residue after acid leaching, forming a positive charge barrier to repel the valuable metal cations dissolved in the acid solution, and avoiding a large amount of anionic groups such as hydroxide, sulfate, and chloride ions remaining in the intermediate leached residue in the acid solution, which were likely to combine with the dissolved valuable metal ions to form complexes or precipitates, affecting the recovery rate of valuable metal ions.

[0146] In Comparative Example 2, the composite adsorbent material prepared without adding ethylenediaminetetraacetic acid was used to recover metals from the acid-leached residue, and its [recovery rate] decreased, which proved that ethylenediaminetetraacetic acid was grafted onto citric acid, increasing the binding sites for valuable metal cations dissolved in the acid solution, improving the adsorption and recovery efficiency of valuable metal cations, and avoiding the low removal efficiency of metal ions caused by the easy saturation of citric acid in adsorbing metal ions.

[0147] In Comparative Example 3, the composite adsorbent material prepared without adding citric acid was used to recover metals from the acid-leached residue, and its [recovery rate] decreased, which proved that citric acid, as a metal ion complexing agent, carried functional groups that could complex with valuable metal cations, improving the recovery efficiency, and the monomer formed by citric acid and ethylenediaminetetraacetic acid could improve the binding force between porous carbon and zeolite, improving the recovery efficiency.

[0148] In Comparative Example 4, the composite adsorbent material prepared by replacing the zeolite loaded with porous carbon with zeolite was used to recover metals from the acid-leached residue, and its [recovery rate] decreased, which proved that synthesizing porous carbon on the surface of zeolite provided sufficient adsorption capacity for valuable metal cations, and porous carbon had good acid resistance, which could protect the zeolite framework from collapsing easily in the acid leaching solution and maintain good adsorption performance for valuable metal cations.

[0149] In the description of the specification, the description referring to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0150] The above content is only an example and illustration of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar methods to replace them. As long as they do not deviate from the invention or exceed the scope defined by the claims of this patent, they should fall within the protection scope of the present invention. Note: In the translation of ID=4, ID=7, and ID=10, the word "recovery rate" is added in square brackets because the original text seems to be incomplete in terms of clearly stating what is decreasing. This is to make the translation more complete and understandable. If there is more context available, a more accurate translation can be provided.

Claims

1. A method for recovering metals from acid leaching residues, characterized in that It includes the following steps: S1. Place the medium leaching residue in a crusher for crushing. After sieving, place it in hydrochloric acid for acid leaching. Then add a surfactant and stir for 20 - 30 min. Next, add a composite adsorbent material. After adsorption, filter to collect filtrate A and filter residue A; S2. Sieve filter residue A to obtain filter residue B and a composite adsorbent material rich in valuable metals; S3. After completely desorbing the adsorbent material rich in valuable metals with sulfuric acid, filter to collect filtrate C and the composite adsorbent material; S4. Mix filtrate A and filtrate C, add sodium hydroxide solution, stir and react for 1 - 2 h, centrifuge to collect the precipitate, and sinter the precipitate at 850 - 950 °C for 1 - 2 h to obtain metal oxides.

2. The method for recovering metals from acid leaching residues according to claim 1, characterized in that, In step S1, the acid leaching conditions are: liquid - solid ratio (5 - 7):1, temperature 80 - 90 °C, reaction time 4 - 6 h, hydrochloric acid concentration 8 - 10 g / L, stirring speed 300 - 500 r / min.

3. The method for recovering metals from acid leaching residues according to claim 1, characterized in that, In step S1, the surfactant is a cationic surfactant, and the cationic surfactant is selected from any one of cetyltrimethylammonium bromide, dodecyltrimethylammonium bromide, ethylene bis(dodecyldimethylammonium bromide), and methyltrioctylammonium chloride; The addition amount of the surfactant is 13 - 15%; the addition amount of the composite adsorbent material is 15 - 17%.

4. The method for recovering metals from acid leaching residues according to claim 1, wherein In steps S1 and S2, the mesh aperture of the sieve is 200 - 300 mesh.

5. The method for recovering metals from acid leaching residues according to claim 1, characterized in that, In step S3, the mass ratio of the adsorbent material rich in valuable metals to sulfuric acid is 1:(8 - 10); The concentration of the sulfuric acid is 4 - 6 mol / L.

6. The method for recovering metals from acid leaching residues according to claim 1, characterized in that, In step S4, the mass fraction of the sodium hydroxide solution is 10 - 20%, and the addition amount of the sodium hydroxide solution is 20 - 30%.

7. The method for recovering metals from acid leaching residues according to claim 1, characterized in that, The composite adsorbent material is specifically prepared by the following steps: A1. Add citric acid to deionized water, stir until the citric acid is completely dissolved, add ethylenediaminetetraacetic acid, heat up to 60 - 70 °C, stir evenly, add hydrochloric acid, continue to stir and react for 15 - 20 min, cool to room temperature, filter to remove impurities to obtain a monomer solution; A2. Add zeolite, rice husk powder, and oxalic acid to ethanol, stir evenly, add hydrochloric acid, after stirring and reacting, filter, wash, dry, place it in a tubular furnace, add potassium hydroxide solution for activation, then introduce nitrogen, carry out high - temperature carbonization at 800 - 900 °C for 3 - 5 h, cool to room temperature, take out, wash, and dry to obtain zeolite loaded with porous carbon; A3. Add the zeolite loaded with porous carbon to the monomer solution, stir at 100 - 105 °C for 3 - 5 min, filter, and dry until the water evaporates to obtain the composite adsorbent material.

8. A method for recovering metals from acid leaching residues according to claim 7, characterized in that, In step A1, the mass ratio of citric acid, deionized water, ethylenediaminetetraacetic acid, and hydrochloric acid is (3.6 - 3.8):(65 - 75):(2 - 2.5):(1 - 2).

9. The method for recovering metals from acid leaching residues according to claim 7, characterized in that, In step A2, the mass ratio of zeolite, rice husk powder, oxalic acid, ethanol, hydrochloric acid, and potassium hydroxide solution is (6.5 - 6.9):(5.3 - 5.7):(0.3 - 0.5):(75 - 85):(0.4 - 0.6):(4 - 6).

10. A method for recovering metals from acid leaching residues according to claim 7, characterized in that, In step A3, the amount ratio of the zeolite loaded with porous carbon to the monomer solution is (5-6):(75-85).

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