CN113999972B

CN113999972B - Resource utilization production process of waste metal composite material

Info

Publication number: CN113999972B
Application number: CN202111182153.9A
Authority: CN
Inventors: 辛丰; 董仕宏
Original assignee: Suzhou Shijing Technology Co ltd
Current assignee: Suzhou Shijing Technology Co ltd
Priority date: 2021-10-11
Filing date: 2021-10-11
Publication date: 2023-09-08
Anticipated expiration: 2041-10-11
Also published as: CN113999972A

Abstract

The invention discloses a resource utilization production process of a waste metal composite material, and relates to the technical field of metal composite materials. The process realizes the resource utilization of the waste metal composite material by a metal separation system, an extraction ion exchange, a back extraction system, electrodialysis-ultrasound and a copper carbonate crystallization technology, and obtains products such as copper crystals, fine metal powder, zinc salts, copper carbonate crystals and the like. The production process is carried out under a full-automatic production line in a closed environment, and all the generated waste gas and waste liquid are recycled after being treated by corresponding environment-friendly equipment, so that zero emission is achieved, and no environmental pollution is generated. The solid waste mainly comes from a waste filter element generated in the filtering process, and is entrusted with the disposal of qualification units. The generation process does not have any potential safety hazards such as high-temperature high-pressure dust and the like.

Description

Resource utilization production process of waste metal composite material

Technical Field

The invention relates to the technical field of metal composite materials, in particular to a resource utilization production process of a waste metal composite material.

Background

The metal layered composite material is changed into a material which is essential for functional application from the original simple replacement in the fields of military industry and civil application, such as electric power and electric communication, aerospace, building decoration, electric heating kitchen ware, new energy batteries and the like. With the rapid development of metal composite materials, the amount of metal composite material waste is increasing, and the waste material sources of the composite materials mainly adopt waste generated in the manufacturing process and products which are retired after use, and the metal composite materials have high strength, good corrosion resistance and inherent heterogeneous property, so that the waste materials are difficult to treat and utilize, and therefore, the waste materials are not properly recycled. The method has no good resource utilization technology for the military and civil waste metal composite material at present, and most of the waste metal composite material is used as dangerous waste or solid waste to be directly treated, so that environmental pollution and resource waste are caused. The pollution of the metal composite material waste to the environment has attracted extensive attention worldwide, and is also a technical bottleneck for preventing the development of the metal composite material industry in China. Therefore, the technology of disposing and utilizing the metal composite material waste to realize the recycling of the waste has become one of the international research hotspots.

Aiming at the military civil waste metal composite material, no available recycling way is reported at present, namely, high outsourcing expense (more than 5000 yuan/ton) is mainly used for outsourcing as dangerous waste treatment, a dangerous waste treatment factory usually adopts strong acid for dissolution, and a large amount of copper-containing sludge and zinc-containing sludge is finally obtained, so that a large amount of heavy metal copper and zinc resources are wasted, and simultaneously, a large amount of generated copper-containing sludge and zinc-containing sludge need to be buried, and a large amount of land is occupied, so that secondary environmental pollution is caused.

Disclosure of Invention

In order to solve the technical problems, the invention provides a resource utilization production process of a waste metal composite material.

The invention aims to provide a resource utilization production process of waste metal composite material, which comprises the following steps,

s1, crushing the waste copper-zinc metal composite material into fragments, then adding etching solution, and separating and extracting to obtain valuable metal solution and copper crystals; the valuable metals are copper ions and zinc ions;

s2, carrying out back extraction on the valuable metal solution obtained in the step S1 to obtain a copper ion-containing solution and a zinc ion-containing solution;

s3, centrifuging and drying the zinc ion solution obtained in the step S2 to obtain zinc salt;

electrodialysis-ultrasound is carried out on the copper ion-containing solution in the step S2, so that crude copper metal powder and low-concentration copper ion-containing solution are obtained;

s4, ball-milling the crude copper metal powder obtained in the step S3 to obtain fine copper metal powder;

and (3) adding an oxidant into the low-concentration copper ion-containing solution in the step (S3), and crystallizing to obtain copper salt.

Further, after the waste metal composite material (copper 90% and zinc 10%) passes through the metal separation system, 80-85% of copper in the composite material can be separated out and then used for producing copper metal substrates.

Further, in the step S1, the particle size of the chips is 50-100mm.

Further, in step S1, the etching liquid is composed of sulfuric acid and hydrogen peroxide. An etching system with sulfuric acid (98 percent) -hydrogen peroxide (30 percent) as etching liquid is adopted, the etching speed is 40-80mL/min, the copper dissolving capacity is 100-150g/L, and the etching coefficient is 2.5-3.5. Compared with other types of etching solutions, the sulfuric acid/hydrogen peroxide etching solution is most environment-friendly, does not introduce new impurities such as copper ions, iron ions, ammonium ions and the like, and does not conflict with a back extractant (sulfuric acid) at the back.

Further, in step S1, the extracting agent for extraction is dioctyl phosphate. The method adopts dioctyl phosphate and high flash point kerosene as a mixture of hydrocarbon diluents as an extracting agent to carry out continuous multistage extraction ion exchange and metal separation system to purify copper, wherein the copper extraction rate is more than 88 percent.

Further, in the step S2, the stripping agent for stripping is sulfuric acid, so that a zinc sulfate recycling product can be obtained. The 9.0 to 9.2 percent of zinc can be back extracted by the sulfuric acid back extractant, the back extraction rate can reach 94.7 to 96.8 percent, and the corresponding zinc metal solution obtained after back extraction is subjected to centrifugal dryer to obtain zinc metal salt products (mainly zinc sulfate). Copper metal ion solution (copper content 13.5-18%, zinc content 0.3-0.5%) remained after back extraction system. The copper-containing metal ion solution is subjected to closed electrodialysis ultrasonic electric device to vibrate and disperse the metal transferred and deposited on the surface of the positive film to obtain crude copper metal powder.

Further, in the step S3, the electrodialysis-ultrasound is an electrodialysis ultrasound electric device, and under the action of an externally applied direct current electric field, the permeability of the ion exchange membrane is utilized, that is, the cation membrane only allows the cation to permeate, and the anion membrane only allows the anion to permeate, so that the copper ions are deposited on the cation membrane. Then the crude copper metal powder is obtained by adopting a metal vibration dispersion technology, and the sulfuric acid stripping agent can be recovered to enter a stripping system. The copper ion removal rate is 97.5-98.8%, and the copper content in the obtained low-concentration copper-containing metal solution is 0.21-0.33%, and the zinc content is about 0.1-0.3%.

Further, in the steps S3 and S4, the low concentration is a concentration of less than 5000mg/L.

Further, in the steps S3 and S4, the particle diameter of the crude copper metal powder is 200 to 300nm

Further, in step S4, the oxidizing agent is hypochlorous acid. The oxidant is a novel molecular hypochlorous acid water oxidant which has strong oxidizing property and pH value of 6-7, and is decomposed into H after participating in oxidation and vein breaking ₂ O and Cl ^- Is an environment-friendly strong oxidant, and does not cause secondary pollution.

Further, in step S4, the crystallization is a copper carbonate crystallization technique: and adding sodium hydroxide and sodium carbonate to react to obtain copper carbonate crystals. The copper carbonate crystallization technology can treat low-concentration copper-containing wastewater to generate copper carbonate crystals, the water content of the crystals is 15-20%, and compared with copper-containing sludge generated by a traditional precipitation method, the copper carbonate crystallization technology has low water content and higher resource utilization value.

Further, in the step S4, the mass concentration ratio of the sodium hydroxide to the sodium carbonate is 1.6-2:1.

the copper crystal can be used for producing copper metal substrates, the metal substrate is a metal circuit board material, belongs to an electronic general component, consists of a heat conduction insulating layer, a metal plate and a metal foil, and has the characteristics of special magnetic conductivity, excellent heat dissipation, high mechanical strength, good processability and the like. Among them, the copper substrate is the most expensive one of the metal substrates, and the heat conduction effect is many times better than that of both the aluminum substrate and the iron substrate.

The superfine metal powder provided by the invention is taken as a main powder material for 3D printing, and is high-end powder in various industries such as 3D printing metal products, powder metallurgy products for aerospace, high-purity powder metallurgy targets, metal injection molding, diamond synthesis, tools, medical implants and the like.

The zinc salt meets the agricultural-grade requirements, can be applied to industries such as chemical industry, feed and the like, and can also be directly supplied to related zinc sulfate production enterprises for reprocessing and purifying to be applied to the battery industry;

the copper carbonate crystal is a chemical raw material with wide application, can be used as an analysis reagent, and is used for preparing various copper compounds in the inorganic salt industry. Therefore, the project is a scientific and technological resource recycling project which accords with national relevant resource recycling and energy conservation and emission reduction industry policies.

Compared with the prior art, the technical scheme of the invention has the following advantages:

(1) The electrodialysis-ultrasonic technology adopted by the technology is a novel electrodialysis technology, and compared with the traditional electrodialysis technology, the technology is a selective electrodialysis technology capable of utilizing membrane characteristics to conduct ion selective separation, and the technology also utilizes a pulse electric field to control membrane interface concentration polarization phenomenon. The traditional electrodialysis has high separation efficiency of anions and cations of 97 percent, but has low separation efficiency of ions with the same charge and different valence states. The introduction of ion exchange membranes having monovalent and multivalent ion separation properties into an electrodialysis device will greatly increase the separation efficiency of homogeneous charge ions of different valence states. Electrodialysis ultrasound technology enhances cation flux by introducing ion channels composed of aromatic frameworks and ionic side chains into a membrane framework, introduces polyquaternary ammonium salts of amphoteric structures into the membrane structure, induces hydrophobicity of the membrane by various alkyl chains and nitrogen-centered functional groups on the polymer backbone, and simultaneously improves selectivity and copper ion flux of the membrane and reduces membrane swelling.

(2) The process realizes the resource utilization of the waste metal composite material by a metal separation system, an extraction ion exchange system, a back extraction system, electrodialysis-ultrasound and a copper carbonate crystallization technology. The production process is carried out under a full-automatic production line in a closed environment, and all the generated waste gas and waste liquid are recycled after being treated by corresponding environment-friendly equipment, so that zero emission is achieved, and no environmental pollution is generated. The solid waste mainly comes from a waste filter element generated in the filtering process, and is entrusted with the disposal of qualification units. The generation process does not have any potential safety hazards such as high-temperature high-pressure dust and the like.

Drawings

In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:

FIG. 1 is a process scheme employed in the present invention.

Detailed Description

The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.

Example 1

A waste metal composite material resource utilization production process is shown in figure 1, and comprises the following steps:

s1, mechanically recycling, firstly cutting the waste copper-zinc metal composite material (90% of copper and 10% of zinc) to be recycled into fragments of 50-100mm at low speed, then separating copper crystals in an etching solution leaching tank, and purifying valuable metal solution through continuous multistage extraction ion exchange. Wherein, an etching system of sulfuric acid (98 percent) -hydrogen peroxide (30 percent) is adopted as etching liquid, the etching speed is about 60mL/min, the copper dissolving capacity reaches 120g/L, and the etching coefficient is 3. The experimental result shows that 85% of copper in the waste metal composite material can be purified, only 0.4% of zinc is extracted, and then the purified copper is used for producing copper metal substrates.

S2, back-extracting the residual solution in the previous step by a sulfuric acid (98%) back-extracting agent, wherein 9.2% zinc can be back-extracted, the back-extraction rate can reach 96.8%, and the corresponding zinc metal solution obtained after back-extraction is subjected to centrifugal drying to obtain a zinc metal salt product (mainly zinc sulfate).

S3, vibrating the metal transferred and deposited on the surface of the positive film by a closed electrodialysis ultrasonic electric device to obtain crude copper metal powder, wherein the copper ion removal rate is about 98.8%, and the copper content in the obtained low-concentration copper-containing metal solution is about 0.33% and the zinc content is about 0.3%. Among them, the electrodialysis ultrasonic electric device is under the action of an externally applied direct current electric field.

S4, the corresponding low-content copper metal solution (the copper content in the solution is 0.33 percent and the zinc content is about 0.3 percent) is subjected to the process of breaking the collaterals by an oxidant and then is treated by the copper carbonate crystallization technology (by adding NaOH and Na into a fluidized state reactor ₂ CO ₃ Controlling the adding mass concentration ratio of the two to 1.6:1 (mg/L) to obtain copper carbonate crystals with 15% water content. ) Then the waste water is recycled after selective oxidation adsorption treatment. Wherein the oxidant is a novel molecular hypochlorous acid water oxidant which has strong oxidizing property and pH value of about 6, and is decomposed into H after participating in oxidation and vein breaking ₂ O and Cl ^- . Wherein, the copper carbonate crystallization technology can treat low-concentration copper-containing wastewater to generate copper carbonate crystals, and the water content of the crystals is 15 percent.

And S5, finally, carrying out superfine grinding on the coarse-particle metal powder by a high-performance ball mill to obtain superfine metal powder, wherein the powder purity is more than 99.99%, and the average particle size of the spherical metal powder is 90nm.

Example 2

s1, mechanically recycling, firstly cutting the waste copper-zinc metal composite material (90% of copper and 10% of zinc) to be recycled into fragments of 50-100mm at low speed, then separating copper crystals in an etching solution leaching tank, and purifying valuable metal solution through continuous multistage extraction ion exchange. Wherein, an etching system of sulfuric acid (98 percent) -hydrogen peroxide (30 percent) is adopted as etching liquid, the etching speed is about 60mL/min, the copper dissolving capacity reaches 120g/L, and the etching coefficient is 3. The experimental result shows that 80% of copper in the waste metal composite material can be purified, only 0.3% of zinc is extracted, and then the purified copper is used for producing copper metal substrates.

S2, back-extracting the residual solution in the previous step by a sulfuric acid (98%) back-extracting agent, wherein 9.0% zinc can be back-extracted, the back-extraction rate can reach 94.7%, and the corresponding zinc metal solution obtained after back-extraction is subjected to centrifugal drying to obtain a zinc metal salt product (mainly zinc sulfate).

S3, vibrating the metal transferred and deposited on the surface of the positive film by a closed electrodialysis ultrasonic electric device to obtain crude copper metal powder, wherein the copper ion removal rate is about 97.5%, and the copper content and the zinc content of the obtained low-concentration copper-containing metal solution are about 0.21% and 0.1%, respectively. Among them, the electrodialysis ultrasonic electric device is under the action of an externally applied direct current electric field.

S4, the corresponding low-content copper metal solution (the copper content in the solution is about 0.21 percent and the zinc content is about 0.1 percent) is subjected to the process of breaking the collaterals by an oxidant and then is treated by the copper carbonate crystallization technology (by adding NaOH and Na into a fluidized state reactor ₂ CO ₃ Controlling the mass concentration ratio of the two additives to 2:1 (mg/L) to obtain copper carbonate crystals with the water content of 19 percent. ) Then the waste water is recycled after selective oxidation adsorption treatment. Wherein the oxidant is a novel molecular hypochlorous acid water oxidant which has strong oxidizing property and pH value of about 6, and is decomposed into H after participating in oxidation and vein breaking ₂ O and Cl ^- . Wherein, the copper carbonate crystallization technology can treat low-concentration copper-containing wastewater to generate copper carbonate crystals, and the water content of the crystals is 16%.

Comparative example 1

Basically the same as in example 1, except that S4 is directly treated by crystallization technology without breaking the collaterals by an oxidizing agent, the specific steps are as follows: :

S3, vibrating the metal transferred and deposited on the surface of the positive film by a copper metal ion solution (copper content is 18% and zinc content is 0.5%) remained after the back extraction system through a closed electrodialysis ultrasonic electric device to obtain crude copper metal powder, wherein the copper ion removal rate in the step is about 98.8%, and the obtained low-concentration copper-containing metal solution has copper content of 0.33% and zinc content of about 0.3%. Among them, the electrodialysis ultrasonic electric device is under the action of an externally applied direct current electric field.

S4, the corresponding low-content copper metal solution (the copper content in the solution is 0.33 percent and the zinc content is about 0.3 percent) is directly treated by the copper carbonate crystallization technology without being broken by an oxidant (by adding NaOH and Na into a fluidized state reactor) ₂ CO ₃ Controlling the adding mass concentration ratio of the two to 1.6:1 (mg/L)), the experimental result shows that after treatment, the copper content of the effluent is 2020mg/L (0.202%), the copper removal rate is only 45.7%, and the effluent cannot be reused after selective adsorption oxidation treatment because the copper content of the effluent is too high, and the wastewater cannot reach the discharge standard.

Comparative example 2

S4, after the corresponding low-content copper metal solution (the copper content in the solution is 0.33 percent and the zinc content is about 0.3 percent) is subjected to the network breaking by the oxidant, the fluidized reactor is not adopted for reaction, but a traditional reactor is adopted, naOH solution is added into the fluidized reactor to generate copper-containing sludge, the copper-containing sludge has a water content of 85 percent, the sludge content is large, the sludge is required to be treated outside a solid waste commission, and the recycling utilization cannot be realized.

Comparative example 3

S1, mechanically recycling, firstly cutting the waste copper-zinc metal composite material (90% of copper and 10% of zinc) to be recycled into fragments of 50-100mm at low speed, then separating copper crystals in an etching solution leaching tank, and purifying valuable metal solution through continuous multistage extraction ion exchange. Wherein, an etching system of sulfuric acid (98 percent) -hydrogen peroxide (30 percent) is adopted as etching liquid, the etching speed is about 30mL/min, the copper dissolving capacity reaches 60g/L, and the etching coefficient is 1.5. The experimental result shows that the copper purification rate in the waste metal composite material is only 55%, and the copper purification rate is very low, because the etching system is possibly set with low etching speed, low copper dissolution capacity and small etching coefficient, only a small part of copper ions can be purified.

S2, the residual solution in the previous step is back-extracted by sulfuric acid (98%) back-extraction agent, only 3.5% of zinc can be back-extracted, and the back-extraction rate is very low, because the residual solution possibly contains a large amount of copper ions, and the back-extraction effect of the zinc ions is affected.

S3, vibrating the metal transferred and deposited on the surface of the positive film by a copper metal ion solution (copper content is 30% and zinc content is 6%) remained after the copper metal ion solution passes through a back extraction system through a closed electrodialysis ultrasonic electric device to obtain crude copper metal powder, wherein the analysis shows that the crude copper metal powder obtained in the step has 81.2% of copper content, 18.8% of zinc content and too high zinc impurity content, so that the crude copper metal powder cannot be used as a recycling product. Meanwhile, the copper content in the obtained residual copper-containing metal solution is about 16.2%, the copper content in the solution is too high to be treated by a copper carbonate crystallization technology after the use of an oxidant for breaking the collaterals, and the subsequent experimental steps are cancelled.

Comparative example 4

S1, mechanically recycling, firstly cutting the waste copper-zinc metal composite material (90% of copper and 10% of zinc) to be recycled into fragments of 50-100mm at low speed, then separating copper crystals in an etching solution leaching tank, and purifying valuable metal solution through continuous multistage extraction ion exchange. Wherein, an etching system of sulfuric acid (98 percent) -hydrogen peroxide (30 percent) is adopted as etching liquid, the etching speed is about 60mL/min, the copper dissolving capacity reaches 120g/L, and the etching coefficient is 3. The experimental result shows that only 80% of copper in the waste metal composite material can be purified out, and the extracted solution also contains 6.6% of zinc, so that the tributyl phosphate is used as the extractant, the copper extraction rate is about 87%, the zinc extraction rate is about 66%, and copper and zinc cannot be effectively separated, so that the purity of a copper metal substrate prepared subsequently is influenced, and the recycling can not be realized. Copper and zinc cannot be effectively separated, and subsequent experimental steps are canceled.

The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.

Claims

1. A resource utilization production process of waste metal composite material is characterized by comprising the following steps,

s1, crushing the waste copper-zinc metal composite material into fragments, then adding etching solution, and separating and extracting to obtain valuable metal solution and copper crystals; the valuable metals are copper ions and zinc ions; the etching solution is an etching system of 98% sulfuric acid and 30% hydrogen peroxide; the extracting agent for extraction is dioctyl phosphate;

s2, carrying out back extraction on the valuable metal solution obtained in the step S1 to obtain a copper ion-containing solution and a zinc ion-containing solution; the back extraction agent of the back extraction is 98% sulfuric acid;

adding an oxidant into the low-concentration copper ion-containing solution in the step S3, and crystallizing to obtain copper salt; the oxidant is hypochlorous acid.

2. The process for recycling waste metal composite material according to claim 1, wherein in the step S1, the particle size of the chips is 50-100mm.

3. The process for recycling waste metal composite material according to claim 1, wherein in the steps S3 and S4, the low concentration is less than 5000mg/L.

4. The process for recycling waste metal composite material according to claim 1, wherein the crude copper metal powder has a particle size of 200-300nm in steps S3 and S4.

5. The process for recycling waste metal composite material according to claim 1, wherein in step S4, the crystallization is a copper carbonate crystallization technique: and adding sodium hydroxide and sodium carbonate to react to obtain copper carbonate crystals.

6. The process for recycling waste metal composite material according to claim 5, wherein in step S4, the NaOH and Na are contained in the waste metal composite material ₂ CO ₃ The mass concentration ratio is 1.6-2:1.