CN114870815A - Preparation method and application of polyimide dioxime film for gold recovery - Google Patents
Preparation method and application of polyimide dioxime film for gold recovery Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a polyimide dioxime film for gold recovery. The method comprises the following steps: preparing a polyimide dioxime precursor solution; heating and stirring, and centrifuging to obtain a polyimide dioxime supernatant which is completely oximated; and (3) at room temperature, dropwise adding the polyimide dioxime solution into deionized water at a constant speed by using an automatic sample injector to obtain the regular circular polyimide dioxime film at once. The polyimide dioxime film prepared by the method is applied to recycling gold in electronic waste. The invention uses low-cost polyacrylonitrile as a main body, uses complete oximation and innovatively utilizes the hydrophobicity of the polyacrylonitrile, can instantly obtain a circular membrane by simply dripping at room temperature, and has the advantages of quick and simple preparation and easy mass production. In addition, the membrane can efficiently, quickly and selectively recover gold in the electronic waste, and a new idea is provided for the design and preparation of the subsequent related practical electronic waste adsorbent.
Description
Technical Field
The invention relates to the field of gold adsorption recovery in electronic waste, in particular to a preparation method and application of a polyimide dioxime film for gold recovery.
Background
With the rapid development of modern science and technology, electronic equipment is more widely and closely applied to human production and life, and more electronic wastes follow the electronic equipment, and because no scientific and reasonable treatment method is available, most of the electronic equipment is regarded as garbage landfill, so that scarce resources are wasted, other heavy metals in the electronic wastes are harmful to the environment, and the efficient extraction, recovery and reutilization of precious metals in the electronic wastes becomes urgent. The current method is (1) high temperature metallurgy, and the metal is extracted by high temperature melting. However, this method not only consumes a lot of energy and lacks selectivity, but also produces harmful waste. (2) The hydrometallurgical process dissolves and leaches precious metals from electronic waste by using aqua regia thiourea or cyanide. The method is low in cost, simple to operate and has certain selectivity, but needs excellent adsorbent to solve the problem of slower leaching adsorption kinetics. (3) The biological metallurgy process has higher selectivity and sustainability, but the mechanism analysis is still unclear and is still in the starting stage, so that the industrial application is difficult. Therefore, the method for efficiently extracting the noble metal from the electronic waste mixed solution by adopting the technologies of adsorption, cementation, extraction, ion exchange and the like is an ideal method which can be easily operated at low cost and has industrial application potential. Among them, the adsorption method is considered as the most promising recovery method because of its simple operation and high adsorption rate.
In terms of specific binding to noble metals, some adsorbents containing special functional groups were developed due to the high affinity of the functional groups N and S to noble metals. For example, PAF-1 is obtained by modifying thiourea on a porous aromatic skeleton, and is a fiber obtained by modifying imidazole on mesoporous silica and then covalently bonding N, N-dimethylaminoethyl methacrylate. In addition to polymers, nitrogen-containing metal-organic frameworks, such as iron-based metal frameworks/polydopamine and amino-modified zirconium-based metal framework materials, are also used for precious metal recovery. Although the above adsorbent has selectivity, the adsorption efficiency is lowered by lowering the ratio of the effective functional groups after loading and modification. In addition to selectivity, the adsorption rate of noble metals is also considered, and most reports start from the microstructure of the adsorbent, and polymers with a porous structure containing chelating functional groups provide more excellent adsorption performance and faster adsorption kinetics due to more active sites and ultra-fast transmission channels, but most of the adsorbents are in a powder form and are not beneficial to recycling. Therefore, the design of the three-dimensional layered porous polymer membrane adsorbent containing the multifunctional adsorption group has important practical significance for recycling the noble metal.
Polyacrylonitrile is widely used as a polymer membrane matrix because of its hydrophobicity and ease of electrostatic spinning. Because the nitrile group in polyacrylonitrile is rich in electrons, for example, the electrospun polyacrylonitrile nanofiber membrane can quickly recover noble metals. Has higher nitrogen content and excellent multidentate ligand structure. Such as polyimide dioxime nanofibers, and the like. But its treatment of noble metals is blank. Moreover, in order to combine the polyimide dioxime modification into a usable form, the main functional amidoxime group effective binding site is reduced, and the compactness causes that heavy metal ions are difficult to permeate to cause slow adsorption kinetics, so that the polyimide dioxime modification has larger obstruction and lower efficiency in practical application. And the preparation conditions are complicated, such as the use of expensive equipment and complicated operation procedures in the electrostatic spinning and the irradiation grafting.
The method for simply, rapidly and massively preparing the three-dimensional layered porous polyimide dioxime membrane is provided for the first time, and the obtained polyimide dioxime membrane is used for extracting and recovering the precious metals in the electronic waste for the first time. The relative hydrophobicity of the amidoxime group functionalized polymer is skillfully utilized, and the regular round film can be immediately obtained by dripping the polyimide dioxime solution into water by using an automatic sampler. The three-dimensional porous structure is obtained after water washing, the flexibility and the strength are well maintained, the denaturation accompanying with amino oximation treatment is avoided, repeated utilization of multiple times of elution is facilitated, meanwhile, reaction sites are added to the special three-dimensional porous layered structure, the adsorption efficiency is greatly improved, and the adsorption kinetics is remarkably improved through the thin film structure. The method has excellent recovery effect on precious metals such as gold, platinum, palladium and the like in the actual electronic waste, wherein the recovery efficiency of gold is highest.
Disclosure of Invention
In view of the problems and proposed feasible methods, the invention provides a preparation method and application of a polyimide dioxime film for gold recovery. The method overcomes the defects of low selectivity and adsorption performance of the traditional adsorbent for noble metals, can be quickly prepared at room temperature, simplifies the steps of the method, saves energy, is ecological and environment-friendly, can be used for batch industrial production, and achieves the aims of efficiently, quickly and highly selectively removing and recycling the gold in the electronic waste for many times.
A preparation method of a polyimide dioxime film comprises the steps of firstly preparing a polyimide dioxime precursor solution, heating and stirring the solution, and centrifuging the solution to obtain a completely oximated polyimide dioxime supernatant; and (3) at room temperature, dropwise adding the polyimide dioxime solution into deionized water at a constant speed by using an automatic sample injector to obtain a circular and uniform polyimide dioxime film at once.
The invention is realized by the following technical scheme:
a preparation method of a polyimide dioxime film for gold recovery comprises the following steps:
(1) preparing a polyimide dioxime precursor solution;
(2) heating and stirring the polyimide dioxime precursor solution prepared in the step (1), and centrifuging to obtain polyimide dioxime supernatant;
(3) and dropwise adding the polyimide dioxime supernatant into deionized water at a constant speed through an automatic sample injector, and reacting at room temperature to obtain the polyimide dioxime film.
Further, the polyimide dioxime supernatant is completely oximated polyimide dioxime supernatant.
Further, the step (1) includes: adding hydroxylamine hydrochloride and sodium hydroxide into N, N-dimethylformamide, stirring, adding polyacrylonitrile after 0.5-1 h, and continuously stirring for 0.5-1 h to obtain the polyimide dioxime precursor solution.
Further, in the step (1), hydroxylamine hydrochloride: sodium hydroxide: polyacrylonitrile: the ratio of the N, N-dimethylformamide solution is 10-20 g: 5-15 g: 5-15 g: 80-120 mL.
Further, in the step (1), hydroxylamine hydrochloride: sodium hydroxide: polyacrylonitrile: the ratio of the N, N-dimethylformamide solution was 15 g: 10 g: 10 g: 100 mL.
Further, in the step (2), the heating temperature is 70-100 ℃, the stirring speed is 900-1200 rpm, and the time is 10-14 hours.
Further, in the step (2), two times of centrifugal operation are carried out in the centrifugal step, the centrifugal rotating speed is 7000-9000 rpm, and the time is 5-8 min.
Further, in the step (3), the sample injection operation is performed at room temperature, the volume of the sample injection container is 5-10 mL, and the sample injection rate is 2-5 mL/min.
The invention provides application of a polyimide dioxime film prepared according to any one of the methods in adsorption recovery of gold in electronic waste.
Furthermore, the usage amount of the polyimide dioxime film in a water body is 0.04-0.06 g/L.
Furthermore, the adsorption treatment time of the adsorbent in the water body is 22-26 h, and the pH value of the water body is adjusted to 1.0-3.0.
Further, the adsorption treatment time of the adsorbent in the electronic waste leaching solution is 22-26 hours, and the pH value of the electronic waste leaching solution is adjusted to 1.0-3.0.
Specifically, the preparation method of the polyimide dioxime film comprises the following steps:
(1) adding 15g of hydroxylamine hydrochloride and 10g of sodium hydroxide into 100mL of N, N-dimethylformamide solution, adding 10g of polyacrylonitrile after 0.5h, and stirring for 0.5h to obtain polyimide dioxime precursor solution;
(2) stirring the polyimide dioxime precursor solution at 80 ℃ for 12h, and centrifuging to ensure the complete oximation of polyacrylonitrile and obtain polyimide dioxime supernatant;
(3) and dropwise adding the polyimide dioxime solution into deionized water at a constant speed through an automatic sampler, and reacting at room temperature to obtain a round and uniform polyimide dioxime film at once.
Specifically, in the step (1), hydroxylamine hydrochloride and sodium hydroxide are added while stirring.
Specifically, in the step (1), the stirring speed is 1000 rpm.
Specifically, in the step (2), the usage amount of the polyimide dioxime precursor solution is 100 mL.
Specifically, in the step (2), the centrifugation speed is 8000rpm, and the time is 5 min.
Specifically, in the step (3), the sample injection rate is 3 mL/min.
Specifically, in the above steps (1) and (3), the reaction temperature is room temperature.
The invention also provides application of the polyimide dioxime membrane in adsorbing and recovering gold from actual electronic waste, wherein the usage amount of the polyimide dioxime membrane in a water body is 0.05g/L, the adsorption treatment time is 24h, the pH value of the adsorbed water body is adjusted to be 2, and the pH value of the electronic waste leachate is adjusted to be 2.
According to the technical scheme, the invention has the beneficial effects that:
(1) the polyimide dioxime membrane provided by the invention is a hierarchical porous polyimide dioxime membrane obtained by self-crosslinking and hydrophobic action of a polyimide dioxime long chain under a room-temperature water phase synthesis strategy which is efficient and rapid in synthesis, simple to operate and easy to prepare in batches. Due to the layered hierarchical porous structure, rich functional groups, larger surface area and sufficient active sites, the membrane can be used as an adsorbent for gold in electronic waste, so that the aims of efficiently, quickly and selectively adsorbing and recovering gold which is a scarce metal resource in waste are fulfilled, and meanwhile, the membrane has excellent environmental adaptability, can be used in a wider pH range, can be used for removing gold in the electronic waste for multiple times, and has good cycle stability and excellent selectivity.
(2) The saturated adsorption capacity of the polyimide dioxime film prepared by the method on gold can reach 9250 mg/g; the 0.05g/L adsorbent can remove 99% of 1ppm gold within 4min, and the balance is basically achieved within 8 min; can remove gold repeatedly, and has a separation coefficient of 2.5 × 10 5 mL/g, indicating ultrahigh selectivity to gold.
Drawings
In order to more conveniently and clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a scanning electron micrograph and a real image photograph of a polyimide dioxime film produced in example 1 of the present invention;
FIG. 2 is a Fourier transform infrared spectrum of a polyimide dioxime film produced in example 1 of the present invention;
FIG. 3 is a schematic diagram showing the adsorption effect of the polyimide dioxime film prepared in example 1 of the present invention on gold and the fitting result;
FIG. 4 is a schematic diagram of adsorption kinetics of a polyimide dioxime film prepared in example 1 of the present invention at different time points for gold, and a fitting result;
fig. 5 is a schematic view of the gold adsorption effect of the polyimide dioxime film prepared in example 1 of the present invention in a cycle experiment.
Fig. 6 is a schematic diagram of gold adsorption selectivity of the polyimide dioxime film prepared in example 1 of the present invention in an actual leaching adsorption experiment of electronic waste CPU.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The preparation method and performance of the polyimide dioxime film for gold recovery according to the present invention will be described in detail below. Details which are not described in detail in the embodiments of the invention belong to the prior art which is known to the person skilled in the art.
Example 1
A preparation method of a polyimide dioxime film comprises the steps of firstly preparing a polyimide dioxime precursor solution, heating and violently stirring the solution, and centrifuging the solution to obtain a completely oximated polyimide dioxime supernatant; at room temperature, the polyimide dioxime solution is dripped into deionized water at a constant speed through an automatic sample injector to immediately obtain a circular and uniform polyimide dioxime film, and the preparation method comprises the following steps:
(1) adding 15g of hydroxylamine hydrochloride and 10g of sodium hydroxide into 100mL of N, N-dimethylformamide solution, reacting at room temperature for 0.5h, adding 10g of polyacrylonitrile (M.w.150000), and magnetically stirring at 1000rpm for 0.5h to obtain polyimide dioxime precursor solution;
(2) stirring 100mL of the obtained polyimide dioxime precursor solution at 80 ℃ for 12h at the stirring speed of 1000rpm, and finally centrifuging at 8000rpm for 5min to obtain 10g/mL of completely oximated polyimide dioxime supernatant;
(3) 5mL of polyimide dioxime supernatant was added dropwise to 1L of deionized water at a constant rate of 3mL/min by an autosampler, and reacted at room temperature to immediately obtain a round and uniform ultrathin polyimide dioxime film (thickness 2 μm).
Further, a polyimide dioxime film produced according to the above production method.
Further, the embodiment also provides that the polyimide dioxime film is directly used as an adsorbent for adsorbing gold, the dosage of the adsorbent in the water body is 0.05g/L, and when the adsorbent is subjected to adsorption treatment in the water body, the pH value of the water body is controlled to be 2, and the time of the adsorption treatment is controlled to be 24 h. In practical application, the adsorption performance of the adsorbent provided by the invention on water gold can be tested by adopting the following scheme: preparing a gold solution with a certain concentration, adjusting the temperature and the pH value of the solution, adding the adsorbent provided by the invention, continuously stirring, and measuring the gold content by using ICP (inductively coupled plasma), thereby obtaining the adsorption capacity of the adsorbent on gold; preparing a 1ppm gold solution, adding the adsorbent provided by the invention when the pH value and the temperature of the mixed solution reach the optimum, taking out a certain amount of liquid at regular intervals, and measuring the content of gold by ICP (inductively coupled plasma), namely the adsorption effect of the polyimide dioxime film on gold at different adsorption times. The polyimide dioxime film adsorbed with gold was washed repeatedly about 5 times with 100mL of an eluent obtained by mixing 50mL of a ferric nitrate solution (0.3g/L) and 50mL of a thiourea solution (0.4g/L), and washed with deionized water several times to regenerate the adsorbent. Then 10ppm of gold solution is prepared, the polyimide dioxime film prepared in the embodiment of the invention is added, after continuous stirring, ICP-OES is used for respectively detecting the gold concentration, thereby detecting the cycle performance of the adsorbent; in an actual electronic waste adsorption recovery experiment, firstly, removing a plastic part on a waste CPU, washing, leaching for 24 hours by using aqua regia, separating and recovering a leaching solution, adjusting the pH value of the leaching solution to 2.0 by using KOH, performing an adsorption experiment, controlling the adsorption treatment time to be 24 hours, and then measuring the gold content by using ICP (inductively coupled plasma), thus obtaining the adsorption recovery performance of the adsorbent on gold in the actual waste CPU.
And (4) analyzing results:
the polyimide dioxime film prepared by the embodiment of the invention is subjected to microstructure observation, component analysis and performance detection, so that the following experimental results are obtained:
(1) the polyimide dioxime film prepared in the embodiment of the present invention was observed and photographed using a scanning electron microscope (SU8020, Hitachi) and a camera, so that a real photograph of the polyimide dioxime film prepared in the embodiment as shown in fig. 1 was obtained, which shows batch preparation and regular uniformity characteristics of the polyimide dioxime film. The inset clearly shows that the membrane has a hierarchical pore effect.
(2) The polyimide dioxime film obtained in the example of the present invention was subjected to composition analysis using a Fourier transform infrared spectrometer (NEXUS, Thermo Nicolet), thereby obtaining a Fourier transform film as shown in FIG. 2Infrared spectroscopy. As can be seen from fig. 2: the polyimide dioxime film has a polyimide dioxime characteristic peak (1638 cm) -1 、1381cm -1 And 933cm -1 ). The position of the infrared peak of the finally prepared product of the embodiment of the invention can correspond to the characteristic peak of the polyimide dioxime functional group. Indicating the successful synthesis of the polyimide dioxime film.
(3) An adsorption isotherm test of gold was performed using the polyimide dioxime film obtained in example 1 of the present invention as an adsorbent. Specifically, the method comprises the following steps: preparing 30mL of gold solutions of 1ppm, 5ppm, 10ppm, 20ppm, 50ppm, 100ppm, 500ppm, 1000ppm, 1500ppm and 2000ppm respectively, adjusting the pH value to 2, then respectively adding 1.5mg of polyimide dioxime membranes prepared by the embodiment of the invention into each solution as an adsorbent, continuously stirring for 24h at 25 ℃, using a 0.22 mu m filter membrane to remove part of liquid, collecting the filtrate and marking, and respectively detecting the concentrations of gold, thereby obtaining a schematic diagram of the adsorption effect on water under different gold concentration conditions as shown in FIG. 3. As can be seen from fig. 3: when the concentration of gold is low, the adsorption capacity of the polyimide dioxime film provided by the embodiment 1 of the invention is continuously increased along with the increase of the concentration of gold; after the initial gold concentration exceeds 1000ppm, the change of the adsorption quantity is small along with the increase of gold, and finally, the balance is achieved; the Langmuir fitting results show that: the process of gold adsorption belongs to monomolecular layer chemical adsorption; according to the calculation of a Langmuir adsorption model, the maximum removal amount of gold in a water body by the polyimide dioxime film provided by the embodiment 1 of the invention can reach 9250mg/g, which is far more than that of the currently reported adsorbent.
(4) The polyimide dioxime film prepared by the embodiment of the invention is used as an adsorbent to perform an adsorption kinetics test on gold, and ICP is used for detecting the gold content, so that the removal rate of the adsorbent on gold is obtained. Specifically, the method comprises the following steps: preparing 2L of gold adsorption test solution with the concentration of 1 ppm; adjusting the pH value of the adsorption test solution to 2 by using 0.01M hydrochloric acid or potassium hydroxide; then adding 1g of the polyimide dioxime film prepared in the embodiment 1 of the invention into the gold adsorption test solution respectively and timing; continuously stirring at 25 ℃, respectively transferring partial liquid from the solution at the time points of 30s, 1min, 2min, 5min, 8min, 10min, 15min, 20min, 25min, 30min and 40min by using a filter membrane of 0.22 mu m, collecting the filtrate, marking, and finally detecting the concentration of gold in the filtrate at different time points by using ICP (inductively coupled plasma), thereby obtaining a schematic diagram of the adsorption effect on gold at different adsorption time points as shown in figure 4; wherein, FIG. 4a is a graph showing the adsorption kinetics of gold by the polyimide dioxime film prepared in example 1 of the present invention; figure 4b is a schematic after fitting using a quasi-secondary adsorption kinetic model. As can be seen from fig. 4: the polyimide dioxime film prepared in the embodiment 1 of the invention has good gold adsorption performance and high removal efficiency, and the polyimide dioxime film prepared in the embodiment 1 of the invention can achieve adsorption balance within 8min of gold adsorption, and shows high adsorption efficiency.
(5) The polyimide dioxime film prepared by the embodiment of the invention is used as an adsorbent to carry out a cyclic adsorption test, and ICP is used for detecting the gold content, so that the adsorption capacity and the cyclic performance of the adsorbent to gold are obtained. Specifically, the method comprises the following steps: the gold-adsorbed polyimide dioxime film was washed repeatedly about 5 times with 100mL of an eluent prepared by mixing 50mL of a ferric nitrate solution (0.3g/L) and 50mL of a thiourea solution (0.4g/L), and washed with deionized water several times. Then 30mL of 10ppm gold solution is prepared, 1.5mg of the polyimide dioxime film prepared by the embodiment of the invention is added, and the concentration of gold in the solution is measured after 24h, so that a schematic diagram of the adsorption effect of the polyimide dioxime film on gold in a water body in a circulation experiment shown in figure 5 is obtained. As can be seen from fig. 5: the polyimide dioxime film prepared by the embodiment of the invention still has good adsorption performance in multiple cycle use.
(6) The polyimide dioxime film prepared by the embodiment of the invention is used as an adsorbent, an adsorption selectivity experiment of precious metal gold in the CPU leachate of the actual electronic waste is carried out, and the content of gold is detected by ICP (inductively coupled plasma), so that the adsorption selectivity of the adsorbent to gold is obtained. Specifically, the method comprises the following steps:
20g of CPU is put into 500mL of deionized water and cleaned at the rotating speed of 1000rpm, surface plastic is removed after cleaning, 8.5g of circuit board is left and is soaked in 200mL of aqua regia (the volume ratio of hydrochloric acid to nitric acid is 3: 1) to be stirredStirring at the stirring speed of 1000 rpm; the maceration extract was aspirated using a 5mL syringe and filtered through a 0.22 μm filter, and 192mL of CPU extract containing 1556, 234, 8.84, 1.24, 1.03, 0.58 and 23.5ppm of metal ions such as copper, nickel, iron, cobalt, lead, chromium and gold was collected. Adjusting the pH of the leachate to 2 by 0.01M potassium hydroxide; adding 0.5g of the polyimide dioxime membrane prepared in the embodiment 1 of the invention into an adsorption test solution, transferring part of the solution from the solution by using a filter membrane of 0.22 mu m after adsorbing for 24h, collecting the filtrate, marking, and finally detecting the concentrations of different metal ions in the filtrate by using ICP (inductively coupled plasma), thereby obtaining a schematic diagram of competitive adsorption effect shown in figure 6; the removal rate of gold by the adsorbent reaches 99 percent, which is far higher than that of other metals in the CPU. Calculated gold separation coefficient of 2.5X 10 5 mL/g is higher than other metal elements by 4-5 orders of magnitude, which shows that the polyimide dioxime film prepared by the embodiment of the invention can selectively adsorb and recycle gold in the actual waste CPU, and has important economic value and practicability.
In conclusion, the embodiment of the invention designs a simple and rapid strategy for preparing a novel polyimide dioxime membrane with a hierarchical pore structure for recovering gold on a large scale, and the membrane can effectively, spontaneously and rapidly recover precious metals, particularly gold, at room temperature. Because of the higher binding site content and the chelating structure, the saturated adsorption capacity to gold far exceeds the highest level reported in history, the production cost is low, the gold is easy to expand, and the like, and the precious metal gold in the electronic waste can be efficiently, highly selectively, quickly and circularly removed for many times.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (13)
1. A preparation method of a polyimide dioxime film for gold recovery is characterized by comprising the following steps:
(1) preparing a polyimide dioxime precursor solution;
(2) heating and stirring the polyimide dioxime precursor solution prepared in the step (1), and centrifuging to obtain polyimide dioxime supernatant;
(3) and (3) dropwise adding the polyimide dioxime supernatant prepared in the step (2) into deionized water at a constant speed by an automatic sampler at room temperature to obtain the polyimide dioxime film.
2. The method of claim 1, wherein step (1) comprises: adding hydroxylamine hydrochloride and sodium hydroxide into N, N-dimethylformamide, stirring, adding polyacrylonitrile after 0.5-1 h, and continuously stirring for 0.5-1 h to obtain the polyimide dioxime precursor solution.
3. The method according to claim 1, wherein in step (1), the ratio of hydroxylamine hydrochloride: sodium hydroxide: the ratio of the N, N-dimethylformamide solution is 10-20 g: 5-15 g: 80-120 mL; preferably, in step (1), hydroxylamine hydrochloride: sodium hydroxide: the ratio of the N, N-dimethylformamide solution was 15 g: 10 g: 100 mL.
4. The method according to claim 1, wherein in the step (1), the ratio of polyacrylonitrile to the N, N-dimethylformamide solution is 5-15 g: 80-120 mL; preferably, the ratio of polyacrylonitrile to N, N-dimethylformamide solution is 10 g: 100 mL.
5. The method according to claim 1, wherein in step (1), the ratio of hydroxylamine hydrochloride: sodium hydroxide: polyacrylonitrile: the ratio of the N, N-dimethylformamide solution is 10-20 g: 5-15 g: 5-15 g: 80-120 mL; preferably, the ratio of hydroxylamine hydrochloride: sodium hydroxide: polyacrylonitrile: the ratio of the N, N-dimethylformamide solution was 15 g: 10 g: 10 g: 100 mL.
6. The method according to claim 1, wherein in the step (2), the heating temperature is 70-100 ℃, the stirring speed is 900-1200 rpm, and the time is 10-14 h.
7. The method according to claim 1, wherein in the step (2), the centrifugation is performed at 7000-9000 rpm for 5-10 min.
8. The method according to claim 1, wherein in the step (3), the sample injection operation is performed at room temperature, the volume of the sample injection container is 5-10 mL, and the sample injection rate is 2-5 mL/min.
9. Use of a polyimide dioxime film produced by the method of any one of claims 1 to 8 for the adsorptive recovery of gold from electronic waste.
10. The use according to claim 9, wherein the polyimide dioxime film is used in an amount of 0.04 to 0.06g/L in a water body.
11. The use of claim 9, wherein the adsorbent is adsorbed in the gold aqueous solution for 22-26 h, and the pH of the water is adjusted to 1.0-3.0.
12. The application of claim 9, wherein the pH of the leaching solution of the electronic waste is adjusted to 1.0-3.0.
13. The application of the gold-adsorbent leaching solution for the electronic waste as claimed in claim 9, wherein the concentration ratio of gold to the adsorbent in the leaching solution for the electronic waste is 1-2000 mg/L: 0.01-0.1 mg/L.
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