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CN119859006B - Method for recycling nickel and phosphorus resources in chemical nickel plating waste liquid - Google Patents

Method for recycling nickel and phosphorus resources in chemical nickel plating waste liquid Download PDF

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Publication number
CN119859006B
CN119859006B CN202510356756.8A CN202510356756A CN119859006B CN 119859006 B CN119859006 B CN 119859006B CN 202510356756 A CN202510356756 A CN 202510356756A CN 119859006 B CN119859006 B CN 119859006B
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waste liquid
stirring
nickel plating
plating waste
ferroferric oxide
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CN119859006A (en
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王凌云
王小培
殷康健
王六平
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Huaihua J&c New Materials Technology Co ltd
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Huaihua J&c New Materials Technology Co ltd
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
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    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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Abstract

本发明提出了一种化学镀镍废液中镍、磷资源回收利用方法，属于废液处理技术领域。包括：（1）调节化学镀镍废液的pH值，向化学镀镍废液中加入氯化钙，搅拌反应沉淀，离心，收集沉淀，沉淀为含有磷酸钙和亚磷酸钙的物质；（2）向上清液中调节pH值，离心，分离固体，上清液中加入水合肼，搅拌反应，沉淀，离心，收集沉淀，为含有金属镍的物质；（3）通入二氧化碳，沉淀，加入吸附净化剂，搅拌吸附，分离吸附净化剂，滤液检测达标后排放。采用简单环保的方法有效分离化学镀镍废液中的镍、磷，得到相对较高纯度的磷、镍副产物，进行资源化利用，提高了其经济价值，进一步吸附纯化后，可以直接排放，更加节约成本，绿色环保，具有广阔的应用前景。The present invention proposes a method for recycling nickel and phosphorus resources in chemical nickel plating waste liquid, which belongs to the technical field of waste liquid treatment. The method comprises: (1) adjusting the pH value of chemical nickel plating waste liquid, adding calcium chloride to the chemical nickel plating waste liquid, stirring reaction precipitation, centrifuging, collecting precipitation, and precipitating into a substance containing calcium phosphate and calcium phosphite; (2) adjusting the pH value of the supernatant, centrifuging, separating solids, adding hydrazine hydrate to the supernatant, stirring reaction, precipitation, centrifuging, collecting precipitation, and obtaining a substance containing metallic nickel; (3) introducing carbon dioxide, precipitation, adding an adsorption purifier, stirring adsorption, separating the adsorption purifier, and discharging the filtrate after the filtrate meets the standard. A simple and environmentally friendly method is used to effectively separate nickel and phosphorus in chemical nickel plating waste liquid, obtain relatively high-purity phosphorus and nickel byproducts, and utilize them as resources, thereby improving their economic value. After further adsorption and purification, they can be directly discharged, which is more cost-saving, green and environmentally friendly, and has broad application prospects.

Description

Method for recycling nickel and phosphorus resources in chemical nickel plating waste liquid
Technical Field
The invention relates to the technical field of waste liquid treatment, in particular to a method for recycling nickel and phosphorus resources in chemical nickel plating waste liquid.
Background
Electroplating is a common procedure in the national processing and manufacturing industry, and has wide application in the fields of machinery, electronics, aerospace and the like. Electroless nickel plating is an important branch in the electroplating industry, and the plating layer has wide application in the world due to the advantages of excellent corrosion resistance, wear resistance, weldability, uniform thickness of the plating layer and the like.
The chemical nickel plating waste liquid contains 2-8g/L nickel ions, about 100-200g/L phosphite, sodium sulfate >80g/L, ammonia nitrogen 10-20g/L, chemical Oxygen Demand (COD) >200g/L, trace other metal impurities and the like. On the one hand, the waste plating solution contains available resources such as nickel, phosphorus, nitrogen and the like, and on the other hand, nickel and the like are also important pollution sources, and the direct discharge generates pollution to the environment. Therefore, the chemical nickel plating process is to be applied to industrial production, and the waste liquid treatment is a urgent need to be solved.
Nickel is a scarce and expensive metal resource. In recent years, a large number of scholars are studying how to extract increasingly valuable phosphorus resources from sludge produced in domestic sewage treatment plants. If nickel and phosphorus in the electroless nickel plating waste liquid are not recycled and are discharged at will, the waste of such scarce precious resources is liable to be caused.
Meanwhile, in recent years, a large number of scholars are researching how to extract increasingly valuable phosphorus resources from sludge produced in domestic sewage treatment plants. If the phosphorus in the electroless nickel plating waste liquid is not recycled and is discharged at will, the waste of such scarce precious resources is liable to be caused.
At present, the main treatment methods of the chemical nickel plating waste liquid include a chemical precipitation method, a Fenton method and the like, a large amount of sewage treatment agents are needed to be added in the methods, the cost is high, meanwhile, the phosphorus resources in the waste liquid are difficult to recover, the resource waste is caused, a large amount of sludge is generated, and secondary pollution is easy to cause.
Disclosure of Invention
The invention aims to provide a method for recycling nickel and phosphorus resources in chemical nickel plating waste liquid, which adopts a simple and environment-friendly method to effectively separate nickel and phosphorus in the chemical nickel plating waste liquid, can obtain phosphorus and nickel byproducts with relatively high purity, further carries out resource utilization, improves the economic value of the chemical nickel plating waste liquid, can be directly discharged after further adsorption and purification, saves more cost, is environment-friendly, and has wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a method for recycling nickel and phosphorus resources in chemical nickel plating waste liquid, which comprises the following steps:
(1) Regulating the pH value of the chemical nickel plating waste liquid, adding calcium chloride into the chemical nickel plating waste liquid, stirring, reacting, precipitating, centrifuging, collecting precipitate, and precipitating to obtain a substance containing calcium phosphate and calcium phosphite;
(2) Adding sodium hydroxide into the supernatant in the step (1) to adjust the pH value, centrifuging, separating solids, adding hydrazine hydrate into the supernatant, stirring for reaction, stopping adding the hydrazine hydrate after no bubbles are generated in the reaction liquid, continuing stirring for reaction, standing for precipitation, centrifuging, and collecting the precipitate as a metal nickel-containing substance;
(3) Introducing carbon dioxide into the supernatant in the step (2), precipitating, adding an adsorption purifying agent into the filtrate, stirring for adsorption, separating the adsorption purifying agent by a magnet, detecting the filtrate to reach the standard, and discharging;
the adsorption purifying agent is prepared by taking magnetic ferroferric oxide as a core, loading TiO 2/ZnO, then carrying out hydrogenation treatment, depositing carbon nano tubes on the surface, modifying polydopamine, and reacting with zirconium tetrachloride and 2-amino terephthalic acid.
As a further improvement of the invention, the adding amount of the calcium chloride in the electroless nickel plating waste liquid in the step (1) is that 12-15g of the calcium chloride is added into every 100mL of the electroless nickel plating waste liquid, the stirring reaction and precipitation time is 1-2h, and the pH value of the electroless nickel plating waste liquid is regulated to be 6.9-7.1.
As a further improvement of the invention, in the step (2), the pH value is adjusted to be 10-11, the stirring reaction time is 0.5-1h, and the stirring reaction continuing time is 0.5-1h.
As a further improvement of the invention, the adding amount of the adsorption purifying agent in the step (3) is 3-5wt%, the stirring adsorption time is 10-20min, the ventilation amount of the carbon dioxide is 10-100mL/min, and the preparation method of the adsorption purifying agent is as follows:
S1, under the protection of inert gas, adding ferric chloride and ferrous chloride into water, dropwise adding ammonia water to adjust the pH value of the solution, heating and stirring for reaction, centrifuging, washing, ball milling, drying and calcining to obtain the magnetic ferroferric oxide;
S2, preparing a doped TiO 2/ZnO@magnetic ferroferric oxide compound, namely dissolving zinc acetate and copper chloride in water, adding diethylene glycol, stirring to form a solution A, uniformly mixing tetrabutyl titanate, thiourea, acetic acid and ethanol to obtain a solution B, mixing the solution A and the solution B, adding magnetic ferroferric oxide, heating, stirring for reaction, centrifuging, washing, ball milling, drying and calcining to obtain the doped TiO 2/ZnO@magnetic ferroferric oxide compound;
S3, hydrotreating, namely introducing inert gas into the TiO 2/ZnO@magnetic ferroferric oxide composite to replace air, then introducing hydrogen, heating, stopping introducing hydrogen, and cooling to room temperature to obtain the black doped TiO 2/ZnO@magnetic ferroferric oxide composite;
S4, depositing a carbon nano tube, namely dissolving ferrocene in dimethylbenzene to obtain a solution, introducing inert gas into the black doped TiO 2/ZnO@magnetic ferroferric oxide composite to replace air, closing the inert gas, introducing hydrogen, heating, dropwise adding the solution, stopping heating and introducing hydrogen, and cooling to room temperature to obtain the carbon nano tube deposited black doped TiO 2/ZnO@magnetic ferroferric oxide composite;
S5, polydopamine modification, namely adding the prepared black doped TiO 2/ZnO@magnetic ferroferric oxide compound deposited on the carbon nano tube into water, adding dopamine hydrochloride and a catalyst, heating and stirring for reaction, separating by a magnet, washing and drying to obtain a modified substance;
S6, preparing an adsorption purifying agent, namely adding the modified substance, zirconium tetrachloride and 2-amino terephthalic acid into N, N-dimethylformamide, stirring and mixing uniformly, dropwise adding acetic acid, carrying out hydrothermal reaction, carrying out magnet separation, washing and drying to obtain the adsorption purifying agent.
As a further improvement of the invention, the mass ratio of the ferric chloride to the ferrous chloride in the step S1 is 3.24:1.26, the pH value of the regulating solution is 10-11, the temperature of the heating and stirring reaction is 75-85 ℃ for 4-6 hours, the temperature of the calcination is 400-600 ℃ for 1-3 hours.
As a further improvement of the invention, in the step S2, the mass ratio of the zinc acetate, the copper chloride, the diethylene glycol, the tetrabutyl titanate, the thiourea, the acetic acid and the magnetic ferroferric oxide is 7-10:0.2-0.4:3-5:12-15:1-2:4-6:6-8, the temperature of the heating and stirring reaction is 65-75 ℃ for 1-2h, the temperature of the calcination is 500-600 ℃ for 1-3h.
As a further improvement of the invention, the hydrogen gas is introduced in the step S3 until the hydrogen pressure is 20-30bar, the temperature of the heating treatment is 180-220 ℃ and the time is 4-6d.
As a further improvement of the invention, the mass ratio of the ferrocene to the dimethylbenzene in the step S4 is 1-2:100, the ventilation of the hydrogen is 50-100mL/min, and the heating temperature is 800-900 ℃.
As a further improvement of the invention, in the step S5, the carbon nano tube is deposited with a Tris-HCl solution with the pH value of the catalyst being 8.5-9.5, wherein the mass ratio of the black doped TiO 2/ZnO@magnetic ferroferric oxide compound to the dopamine hydrochloride to the catalyst is 10:3-5:0.5-1, the temperature of the heating and stirring reaction is 45-55 ℃ and the time is 3-5h.
As a further improvement of the invention, the mass ratio of the modifier, zirconium tetrachloride, 2-amino terephthalic acid and acetic acid in the step S6 is 10:4-5:3-4:2-4, and the temperature of the hydrothermal reaction is 120-140 ℃ and the time is 20-24 hours.
The invention has the following beneficial effects:
In the invention, soluble calcium salt-calcium chloride is adopted as a precipitator, and reacts with redundant phosphate radical and phosphite radical in waste liquid to form precipitate, in order to prevent calcium hydroxide precipitate from being generated due to overhigh pH value, the experiment of dissolving the generated precipitate to influence the removal effect of phosphorus in the waste liquid is firstly carried out under the condition of about 7, and excessive calcium salt-calcium chloride is added to ensure that the phosphorus can be fully precipitated, the obtained substance containing calcium phosphate and calcium phosphite can be further recycled after being further purified, the utilization rate of the waste liquid is greatly improved, the economic value of the waste liquid is improved, and meanwhile, the participation of phosphorus in the subsequent hydrazine hydrate reaction process is avoided.
Subsequently, the invention uses hydrazine hydrate as a reducing agent, and the chemical equation is as follows:
2Ni2+ + N2H4 + 4OH- = 2Ni↓ + N2↑ + 4H2O
The method comprises the steps of adopting hydrazine hydrate to reduce excessive Ni 2+ in waste liquid, adopting hydrazine hydrate to reduce nickel salt in water phase to obtain nickel nano particles, enabling the particle size to be uniform, enabling products to be nitrogen and water, introducing other impurities into the waste liquid, and purifying obtained substances containing metallic nickel to obtain Ni metal with higher purity.
After the main pollutants of phosphorus and nickel are separated, carbon dioxide is introduced to remove redundant calcium ions and other large amounts of metal ions, and an adsorption purifying agent is further added to further treat the waste liquid, so that other small amounts of impurity heavy metal ions, organic matters, ammonia nitrogen impurities and the like can be adsorbed, and the waste water can reach the standard capable of being discharged, thereby being beneficial to environmental protection.
The adsorption purifying agent prepared by the invention takes the magnetic ferroferric oxide as a core, which is favorable for the magnet separation of the adsorption purifying agent, so that the adsorption purifying agent is easy to operate, and the operation steps are simplified. The TiO 2/ZnO compound is deposited on the surface of the magnetic ferroferric oxide, and metal copper, nonmetal sulfur and nitrogen are used as dopants, so that the band gap structure of titanium dioxide and zinc oxide can be adjusted, the band gap structure is more sensitive to visible light, the response capability of the titanium dioxide and zinc oxide to the visible light is improved, a new energy level is introduced, the band gap is reduced, and the visible light absorption capability is improved, and therefore, the adsorption purifying agent can effectively utilize the visible light to carry out photocatalytic degradation on organic impurities in water, and has a purifying effect.
The prepared TiO 2/ZnO@magnetic ferroferric oxide compound is subjected to hydrogenation treatment, so that the compound is converted into black, the band gap is obviously reduced, visible light, infrared light and ultraviolet light can be absorbed, and a large number of oxygen vacancies and Ti 3+ self-doping defects are introduced into the surface, so that the separation efficiency of photo-generated charges is enhanced, the photocatalytic performance is improved, and the pollutant purifying capacity is improved.
The prepared black doped TiO 2/ZnO@magnetic ferroferric oxide compound is further deposited with carbon nano tubes on the surface, a heterostructure is constructed, the recombination of photon-generated carriers can be effectively inhibited, the photocatalysis efficiency is improved, meanwhile, the specific surface area of the compound is greatly improved, and the adsorption and fixation of pollutants are facilitated.
The prepared carbon nano tube is deposited with black doped TiO 2/ZnO@magnetic ferroferric oxide compound, and the surface of the prepared modified substance is modified by polydopamine, so that on one hand, the modified substance contains rich amino and other active groups, metal ions are fixed by forming a complex bond, organic matters and the like are fixed by forming a hydrogen bond, zirconium ions can be adsorbed, a UiO-66-NH 2 structure is generated on the surface of the modified substance, the fixation of heavy metal ions and organic matters is enhanced by amino straw, and the adsorption effect on pollutants is greatly improved by a large specific surface area.
The method for recycling the nickel and phosphorus resources in the chemical nickel plating waste liquid effectively separates the nickel and phosphorus in the chemical nickel plating waste liquid by adopting a simple and environment-friendly method, can obtain phosphorus and nickel byproducts with relatively high purity, further carries out resource utilization, improves the economic value of the chemical nickel plating waste liquid, can be directly discharged after further adsorption and purification, saves more cost, is environment-friendly, and has wide application prospect.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Preparation example 1 preparation of adsorption purification agent
The method comprises the following steps:
S1, under the protection of nitrogen, adding 3.24g of ferric chloride and 1.26g of ferrous chloride into 150mL of water, dropwise adding ammonia water to adjust the pH value of the solution to 10, heating to 75 ℃, stirring and reacting for 4 hours, centrifuging, washing, ball-milling for 1 hour, drying, and calcining at 400 ℃ for 1 hour to prepare the magnetic ferroferric oxide;
S2, preparing a doped TiO 2/ZnO@magnetic ferroferric oxide compound, namely dissolving 7g of zinc acetate and 0.2g of copper chloride in 200mL of water, adding 3g of diethylene glycol, stirring to form a solution A, stirring and mixing 12g of tetrabutyl titanate, 1g of thiourea, 4g of acetic acid and 100mL of ethanol for 10min to obtain a solution B, mixing the solution A and the solution B, adding 6g of magnetic ferroferric oxide, heating to 65 ℃, stirring and reacting for 1h, centrifuging, washing, ball-milling for 1h, drying and calcining at 500 ℃ for 1h to obtain the doped TiO 2/ZnO@magnetic ferroferric oxide compound;
S3, hydrotreating, namely introducing nitrogen into the TiO 2/ZnO@magnetic ferroferric oxide composite to replace air, then introducing hydrogen until the hydrogen pressure is 20bar, heating to 180 ℃, treating for 4d, stopping introducing hydrogen, and cooling to room temperature to obtain the black TiO 2/ZnO@magnetic ferroferric oxide composite;
s4, depositing a carbon nano tube, namely dissolving 0.05g of ferrocene into 5g of dimethylbenzene to obtain a solution, introducing nitrogen into the black doped TiO 2/ZnO@magnetic ferroferric oxide composite to replace air, closing the nitrogen, introducing hydrogen, heating to 800 ℃ with the ventilation of 50mL/min, dropwise adding the solution, maintaining for 30min, stopping heating and introducing hydrogen, and cooling to room temperature to obtain the carbon nano tube deposited black doped TiO 2/ZnO@magnetic ferroferric oxide composite;
S5, polydopamine modification, namely adding 10g of carbon nano tube deposited black doped TiO 2/ZnO@magnetic ferroferric oxide compound into 150mL of water, adding 3g of dopamine hydrochloride and 0.5g of catalyst, heating to 45 ℃, stirring and reacting for 3h, separating magnets, washing and drying to obtain a modified substance;
Tris-HCl solution of ph=8.5 of the catalyst;
s6, preparing an adsorption purifying agent, namely adding 10g of modified substance, 4g of zirconium tetrachloride and 3g of 2-amino terephthalic acid into 500mL of N, N-dimethylformamide, stirring and mixing for 15min, dropwise adding 2g of acetic acid, carrying out hydrothermal reaction at 120 ℃ for 20h, separating by a magnet, washing and drying to obtain the adsorption purifying agent.
Preparation example 2 preparation of adsorbent purification agent
The method comprises the following steps:
S1, under the protection of nitrogen, adding 3.24g of ferric chloride and 1.26g of ferrous chloride into 150mL of water, dropwise adding ammonia water to adjust the pH value of the solution to 11, heating to 85 ℃, stirring and reacting for 6 hours, centrifuging, washing, ball-milling for 1 hour, drying, and calcining at 600 ℃ for 3 hours to obtain the magnetic ferroferric oxide;
S2, preparing a doped TiO 2/ZnO@magnetic ferroferric oxide compound, namely dissolving 10g of zinc acetate and 0.4g of copper chloride in 200mL of water, adding 5g of diethylene glycol, stirring to form a solution A, stirring and mixing 15g of tetrabutyl titanate, 2g of thiourea, 6g of acetic acid and 100mL of ethanol for 10min to obtain a solution B, mixing the solution A and the solution B, adding 8g of magnetic ferroferric oxide, heating to 75 ℃, stirring and reacting for 2h, centrifuging, washing, ball-milling for 1h, drying and calcining at 600 ℃ for 3h to obtain the doped TiO 2/ZnO@magnetic ferroferric oxide compound;
S3, hydrotreating, namely introducing nitrogen into the TiO 2/ZnO@magnetic ferroferric oxide composite to replace air, then introducing hydrogen until the hydrogen pressure is 30bar, heating to 220 ℃, treating for 6d, stopping introducing hydrogen, and cooling to room temperature to obtain the black TiO 2/ZnO@magnetic ferroferric oxide composite;
S4, depositing a carbon nano tube, namely dissolving 0.1g of ferrocene into 5g of dimethylbenzene to obtain a solution, introducing nitrogen into the black doped TiO 2/ZnO@magnetic ferroferric oxide composite to replace air, closing the nitrogen, introducing hydrogen, heating to 900 ℃ with the ventilation volume of 100mL/min, dropwise adding the solution, maintaining for 40min, stopping heating and introducing hydrogen, and cooling to room temperature to obtain the carbon nano tube deposited black doped TiO 2/ZnO@magnetic ferroferric oxide composite;
S5, modifying polydopamine, namely adding 10g of carbon nano tube deposited black doped TiO 2/ZnO@magnetic ferroferric oxide compound into 150mL of water, adding 5g of dopamine hydrochloride and 1g of catalyst, heating to 55 ℃, stirring and reacting for 5 hours, separating by using a magnet, washing and drying to obtain a modified substance;
Tris-HCl solution of ph=9.5 of the catalyst;
s6, preparing an adsorption purifying agent, namely adding 10g of modified substance, 5g of zirconium tetrachloride and 4g of 2-amino terephthalic acid into 500mL of N, N-dimethylformamide, stirring and mixing for 15min, dropwise adding 4g of acetic acid, performing hydrothermal reaction at 140 ℃ for 24h, separating by a magnet, washing and drying to obtain the adsorption purifying agent.
Preparation example 3 preparation of adsorption purification agent
The method comprises the following steps:
S1, under the protection of nitrogen, adding 3.24g of ferric chloride and 1.26g of ferrous chloride into 150mL of water, dropwise adding ammonia water to adjust the pH value of the solution to 10.5, heating to 80 ℃, stirring and reacting for 5 hours, centrifuging, washing, ball-milling for 1 hour, drying, and calcining at 500 ℃ for 2 hours to obtain the magnetic ferroferric oxide;
S2, preparing a doped TiO 2/ZnO@magnetic ferroferric oxide compound, namely dissolving 8.5g of zinc acetate and 0.3g of copper chloride in 200mL of water, adding 4g of diethylene glycol, stirring to form a solution A, stirring and mixing 13.5g of tetrabutyl titanate, 1.5g of thiourea, 5g of acetic acid and 100mL of ethanol for 10min to obtain a solution B, mixing the solution A and the solution B, adding 7g of magnetic ferroferric oxide, heating to 70 ℃, stirring and reacting for 1.5h, centrifuging, washing, ball-milling for 1h, drying, and calcining at 550 ℃ for 2h to obtain the doped TiO 2/ZnO@magnetic ferroferric oxide compound;
S3, hydrotreating, namely introducing nitrogen into the TiO 2/ZnO@magnetic ferroferric oxide composite to replace air, then introducing hydrogen until the hydrogen pressure is 25bar, heating to 200 ℃, treating for 5d, stopping introducing hydrogen, and cooling to room temperature to obtain the black TiO 2/ZnO@magnetic ferroferric oxide composite;
S4, depositing a carbon nano tube, namely dissolving 0.07g of ferrocene into 5g of dimethylbenzene to obtain a solution, introducing nitrogen into the black doped TiO 2/ZnO@magnetic ferroferric oxide composite to replace air, closing the nitrogen, introducing hydrogen, heating to 850 ℃ with the ventilation of 70mL/min, dropwise adding the solution, maintaining for 35min, stopping heating and introducing hydrogen, and cooling to room temperature to obtain the carbon nano tube deposited black doped TiO 2/ZnO@magnetic ferroferric oxide composite;
S5, polydopamine modification, namely adding 10g of carbon nano tube deposited black doped TiO 2/ZnO@magnetic ferroferric oxide compound into 150mL of water, adding 4g of dopamine hydrochloride and 0.7g of catalyst, heating to 50 ℃, stirring and reacting for 4 hours, separating magnets, washing and drying to obtain a modified substance;
Tris-HCl solution of ph=9 of the catalyst;
s6, preparing an adsorption purifying agent, namely adding 10g of modified substance, 4.5g of zirconium tetrachloride and 3.5g of 2-amino terephthalic acid into 500mL of N, N-dimethylformamide, stirring and mixing for 15min, dropwise adding 3g of acetic acid, performing hydrothermal reaction at 130 ℃ for 22h, separating by using a magnet, washing and drying to prepare the adsorption purifying agent.
Comparative preparation example 1
The difference from preparation example 3 is that copper chloride is not added in step S2.
The method comprises the following steps:
S2, preparing a doped TiO 2/ZnO@magnetic ferroferric oxide compound, namely dissolving 8.5g of zinc acetate in 200mL of water, adding 4g of diethylene glycol, stirring to form a solution A, stirring and mixing 13.5g of tetrabutyl titanate, 1.8g of thiourea, 5g of acetic acid and 100mL of ethanol for 10min to obtain a solution B, mixing the solution A and the solution B, adding 7g of magnetic ferroferric oxide, heating to 70 ℃, stirring and reacting for 1.5h, centrifuging, washing, ball-milling for 1h, drying and calcining at 550 ℃ for 2h to obtain the doped TiO 2/ZnO@magnetic ferroferric oxide compound.
Comparative preparation example 2
In comparison with preparation example 3, the difference is that no thiourea was added in step S2.
The method comprises the following steps:
S2, preparing a doped TiO 2/ZnO@magnetic ferroferric oxide compound, namely dissolving 8.5g of zinc acetate and 1.8g of copper chloride in 200mL of water, adding 4g of diethylene glycol, stirring to form a solution A, stirring and mixing 13.5g of tetrabutyl titanate, 5g of acetic acid and 100mL of ethanol for 10min to obtain a solution B, mixing the solution A and the solution B, adding 7g of magnetic ferroferric oxide, heating to 70 ℃, stirring and reacting for 1.5h, centrifuging, washing, ball-milling for 1h, drying and calcining at 550 ℃ for 2h to obtain the doped TiO 2/ZnO@magnetic ferroferric oxide compound.
Comparative preparation example 3
In comparison with preparation example 3, the difference is that copper chloride and thiourea are not added in step S2.
The method comprises the following steps:
S2, preparing the TiO 2/ZnO@magnetic ferroferric oxide compound, namely dissolving 8.5g of zinc acetate in 200mL of water, adding 4g of diethylene glycol, stirring to form a solution A, stirring and mixing 13.5g of tetrabutyl titanate, 5g of acetic acid and 100mL of ethanol for 10min to obtain a solution B, mixing the solution A and the solution B, adding 7g of magnetic ferroferric oxide, heating to 70 ℃, stirring and reacting for 1.5h, centrifuging, washing, ball-milling for 1h, drying, and calcining at 550 ℃ for 2h to obtain the TiO 2/ZnO@magnetic ferroferric oxide compound.
Comparative preparation example 4
In comparison with preparation example 3, the difference is that step S3 is not performed.
The method comprises the following steps:
S1, under the protection of nitrogen, adding 3.24g of ferric chloride and 1.26g of ferrous chloride into 150mL of water, dropwise adding ammonia water to adjust the pH value of the solution to 10.5, heating to 80 ℃, stirring and reacting for 5 hours, centrifuging, washing, ball-milling for 1 hour, drying, and calcining at 500 ℃ for 2 hours to obtain the magnetic ferroferric oxide;
S2, preparing a doped TiO 2/ZnO@magnetic ferroferric oxide compound, namely dissolving 8.5g of zinc acetate and 0.3g of copper chloride in 200mL of water, adding 4g of diethylene glycol, stirring to form a solution A, stirring and mixing 13.5g of tetrabutyl titanate, 1.5g of thiourea, 5g of acetic acid and 100mL of ethanol for 10min to obtain a solution B, mixing the solution A and the solution B, adding 7g of magnetic ferroferric oxide, heating to 70 ℃, stirring and reacting for 1.5h, centrifuging, washing, ball-milling for 1h, drying, and calcining at 550 ℃ for 2h to obtain the doped TiO 2/ZnO@magnetic ferroferric oxide compound;
S3, depositing a carbon nano tube, namely dissolving 0.07g of ferrocene into 5g of dimethylbenzene to obtain a solution, introducing nitrogen into the TiO 2/ZnO@magnetic ferroferric oxide composite to replace air, closing the nitrogen, introducing hydrogen, heating to 850 ℃ with the ventilation volume of 70mL/min, dropwise adding the solution, maintaining for 35min, stopping heating and introducing hydrogen, and cooling to room temperature to obtain the carbon nano tube deposited TiO 2/ZnO@magnetic ferroferric oxide composite;
S4, modifying polydopamine, namely adding 10g of carbon nano tube deposition doped TiO 2/ZnO@magnetic ferroferric oxide compound into 150mL of water, adding 4g of dopamine hydrochloride and 0.7g of catalyst, heating to 50 ℃, stirring and reacting for 4 hours, separating by using a magnet, washing and drying to obtain a modified substance;
Tris-HCl solution of ph=9 of the catalyst;
S5, preparing an adsorption purifying agent, namely adding 10g of modified substance, 4.5g of zirconium tetrachloride and 3.5g of 2-amino terephthalic acid into 500mL of N, N-dimethylformamide, stirring and mixing for 15min, dropwise adding 3g of acetic acid, performing hydrothermal reaction at 130 ℃ for 22h, separating by using a magnet, washing and drying to prepare the adsorption purifying agent.
Comparative preparation example 5
In comparison with preparation example 3, the difference is that step S4 is not performed.
The method comprises the following steps:
S1, under the protection of nitrogen, adding 3.24g of ferric chloride and 1.26g of ferrous chloride into 150mL of water, dropwise adding ammonia water to adjust the pH value of the solution to 10.5, heating to 80 ℃, stirring and reacting for 5 hours, centrifuging, washing, ball-milling for 1 hour, drying, and calcining at 500 ℃ for 2 hours to obtain the magnetic ferroferric oxide;
S2, preparing a doped TiO 2/ZnO@magnetic ferroferric oxide compound, namely dissolving 8.5g of zinc acetate and 0.3g of copper chloride in 200mL of water, adding 4g of diethylene glycol, stirring to form a solution A, stirring and mixing 13.5g of tetrabutyl titanate, 1.5g of thiourea, 5g of acetic acid and 100mL of ethanol for 10min to obtain a solution B, mixing the solution A and the solution B, adding 7g of magnetic ferroferric oxide, heating to 70 ℃, stirring and reacting for 1.5h, centrifuging, washing, ball-milling for 1h, drying, and calcining at 550 ℃ for 2h to obtain the doped TiO 2/ZnO@magnetic ferroferric oxide compound;
S3, hydrotreating, namely introducing nitrogen into the TiO 2/ZnO@magnetic ferroferric oxide composite to replace air, then introducing hydrogen until the hydrogen pressure is 25bar, heating to 200 ℃, treating for 5d, stopping introducing hydrogen, and cooling to room temperature to obtain the black TiO 2/ZnO@magnetic ferroferric oxide composite;
S4, modifying polydopamine, namely adding 10g of black doped TiO 2/ZnO@magnetic ferroferric oxide compound into 150mL of water, adding 4g of dopamine hydrochloride and 0.7g of catalyst, heating to 50 ℃, stirring and reacting for 4 hours, separating by using a magnet, washing and drying to obtain a modified substance;
Tris-HCl solution of ph=9 of the catalyst;
S5, preparing an adsorption purifying agent, namely adding 10g of modified substance, 4.5g of zirconium tetrachloride and 3.5g of 2-amino terephthalic acid into 500mL of N, N-dimethylformamide, stirring and mixing for 15min, dropwise adding 3g of acetic acid, performing hydrothermal reaction at 130 ℃ for 22h, separating by using a magnet, washing and drying to prepare the adsorption purifying agent.
Comparative preparation example 6
In comparison with preparation example 3, the difference is that step S6 is not performed.
The method comprises the following steps:
S1, under the protection of nitrogen, adding 3.24g of ferric chloride and 1.26g of ferrous chloride into 150mL of water, dropwise adding ammonia water to adjust the pH value of the solution to 10.5, heating to 80 ℃, stirring and reacting for 5 hours, centrifuging, washing, ball-milling for 1 hour, drying, and calcining at 500 ℃ for 2 hours to obtain the magnetic ferroferric oxide;
S2, preparing a doped TiO 2/ZnO@magnetic ferroferric oxide compound, namely dissolving 8.5g of zinc acetate and 0.3g of copper chloride in 200mL of water, adding 4g of diethylene glycol, stirring to form a solution A, stirring and mixing 13.5g of tetrabutyl titanate, 1.5g of thiourea, 5g of acetic acid and 100mL of ethanol for 10min to obtain a solution B, mixing the solution A and the solution B, adding 7g of magnetic ferroferric oxide, heating to 70 ℃, stirring and reacting for 1.5h, centrifuging, washing, ball-milling for 1h, drying, and calcining at 550 ℃ for 2h to obtain the doped TiO 2/ZnO@magnetic ferroferric oxide compound;
S3, hydrotreating, namely introducing nitrogen into the TiO 2/ZnO@magnetic ferroferric oxide composite to replace air, then introducing hydrogen until the hydrogen pressure is 25bar, heating to 200 ℃, treating for 5d, stopping introducing hydrogen, and cooling to room temperature to obtain the black TiO 2/ZnO@magnetic ferroferric oxide composite;
S4, depositing a carbon nano tube, namely dissolving 0.07g of ferrocene into 5g of dimethylbenzene to obtain a solution, introducing nitrogen into the black doped TiO 2/ZnO@magnetic ferroferric oxide composite to replace air, closing the nitrogen, introducing hydrogen, heating to 850 ℃ with the ventilation of 70mL/min, dropwise adding the solution, maintaining for 35min, stopping heating and introducing hydrogen, and cooling to room temperature to obtain the carbon nano tube deposited black doped TiO 2/ZnO@magnetic ferroferric oxide composite;
S5, modifying polydopamine, namely adding 10g of carbon nano tube deposited black doped TiO 2/ZnO@magnetic ferroferric oxide compound into 150mL of water, adding 4g of dopamine hydrochloride and 0.7g of catalyst, heating to 50 ℃, stirring and reacting for 4 hours, separating magnets, washing and drying to obtain a modified substance, namely an adsorption purifying agent;
Tris-HCl solution of ph=9 for the catalyst.
Comparative preparation example 7
In comparison with preparation example 3, the difference is that steps S5 and S6 are not carried out.
The method comprises the following steps:
S1, under the protection of nitrogen, adding 3.24g of ferric chloride and 1.26g of ferrous chloride into 150mL of water, dropwise adding ammonia water to adjust the pH value of the solution to 10.5, heating to 80 ℃, stirring and reacting for 5 hours, centrifuging, washing, ball-milling for 1 hour, drying, and calcining at 500 ℃ for 2 hours to obtain the magnetic ferroferric oxide;
S2, preparing a doped TiO 2/ZnO@magnetic ferroferric oxide compound, namely dissolving 8.5g of zinc acetate and 0.3g of copper chloride in 200mL of water, adding 4g of diethylene glycol, stirring to form a solution A, stirring and mixing 13.5g of tetrabutyl titanate, 1.5g of thiourea, 5g of acetic acid and 100mL of ethanol for 10min to obtain a solution B, mixing the solution A and the solution B, adding 7g of magnetic ferroferric oxide, heating to 70 ℃, stirring and reacting for 1.5h, centrifuging, washing, ball-milling for 1h, drying, and calcining at 550 ℃ for 2h to obtain the doped TiO 2/ZnO@magnetic ferroferric oxide compound;
S3, hydrotreating, namely introducing nitrogen into the TiO 2/ZnO@magnetic ferroferric oxide composite to replace air, then introducing hydrogen until the hydrogen pressure is 25bar, heating to 200 ℃, treating for 5d, stopping introducing hydrogen, and cooling to room temperature to obtain the black TiO 2/ZnO@magnetic ferroferric oxide composite;
S4, depositing a carbon nano tube, namely dissolving 0.07g of ferrocene into 5g of dimethylbenzene to obtain a solution, introducing nitrogen into the black doped TiO 2/ZnO@magnetic ferroferric oxide composite to replace air, closing the nitrogen, introducing hydrogen, heating to 850 ℃ with the ventilation of 70mL/min, dropwise adding the solution, maintaining for 35min, stopping heating and introducing hydrogen, and cooling to room temperature to obtain the carbon nano tube deposited black doped TiO 2/ZnO@magnetic ferroferric oxide composite, namely the adsorption purifying agent.
Test example 1 measurement of specific surface area
The specific surface areas of the adsorption purifiers prepared in preparation examples 1 to 3 and comparative preparation examples 1 to 7 were measured using a 3-FLEX 3500 multi-station high flux gas adsorbent apparatus. The results are shown in Table 1.
TABLE 1
As is clear from the above table, the adsorbent purifying agents prepared in preparation examples 1 to 3 of the present invention have a large specific surface area.
Test example 2
10 -4 Mol/L of cefalexin solution is prepared as antibiotic polluted sewage, 0.1mol/L of hydrochloric acid and 0.01mol/L of sodium hydroxide are used for adjusting the pH value of the sewage to be 7, 100ml of the cefalexin solution is taken, 5mg of the adsorption purifying agents prepared in preparation examples 1-3 and comparative preparation examples 1-7 are respectively added, and the adsorption purifying agents are stirred for 10 minutes at 500r/min under irradiation of visible light and separated by a magnet. Collecting the clear liquid, centrifuging at 10000rpm for 10min, collecting the supernatant, detecting the absorption peak of the solution at 262nm by using an ultraviolet-visible light spectrophotometer, and calculating the cleaning effect of the adsorption purifying agent on cephalexin, wherein the result is shown in Table 2.
TABLE 2
As shown in the table above, the adsorption purifying agent prepared in the preparation examples 1-3 has better visible light catalytic degradation effect on the antibiotic organic.
Example 1
The embodiment provides a method for recycling nickel and phosphorus resources in chemical nickel plating waste liquid, which comprises the following steps:
(1) Regulating the pH value of the chemical nickel plating waste liquid to be 6.9, then adding calcium chloride into the chemical nickel plating waste liquid, wherein the addition amount of the calcium chloride is that 12g of calcium chloride is added into every 100mL of chemical nickel plating waste liquid, stirring, reacting and precipitating for 1h, centrifuging, collecting precipitate, and precipitating to obtain a substance containing calcium phosphate and calcium phosphite;
(2) Adding sodium hydroxide into the supernatant in the step (1) to adjust the pH value to 10, centrifuging, separating solids, adding hydrazine hydrate into the supernatant, stirring and reacting for 0.5h, stopping adding the hydrazine hydrate after no bubbles are generated in the reaction liquid, continuously stirring and reacting for 0.5h, standing and precipitating, centrifuging, and collecting the precipitate as a substance containing metallic nickel;
(3) Introducing carbon dioxide into the supernatant in the step (2), introducing the carbon dioxide into the supernatant for 1h, precipitating for 1h, adding the adsorption purifying agent prepared in the preparation example 1 into the filtrate, stirring and adsorbing for 10min, separating the adsorption purifying agent by a magnet, and discharging after the filtrate reaches the standard after detection.
Example 2
The embodiment provides a method for recycling nickel and phosphorus resources in chemical nickel plating waste liquid, which comprises the following steps:
(1) Regulating the pH value of the chemical nickel plating waste liquid to 7.1, then adding calcium chloride into the chemical nickel plating waste liquid, wherein the addition amount of the calcium chloride is 15g of calcium chloride added into every 100mL of chemical nickel plating waste liquid, stirring, reacting and precipitating for 2 hours, centrifuging, collecting precipitate, and precipitating to obtain a substance containing calcium phosphate and calcium phosphite;
(2) Adding sodium hydroxide into the supernatant in the step (1) to adjust the pH value to 11, centrifuging, separating solids, adding hydrazine hydrate into the supernatant, stirring and reacting for 1h, stopping adding the hydrazine hydrate after no bubbles are generated in the reaction liquid, continuously stirring and reacting for 1h, standing for precipitation, centrifuging, and collecting the precipitate as a substance containing metallic nickel;
(3) Introducing carbon dioxide into the supernatant in the step (2), introducing the carbon dioxide into the supernatant for 1h, precipitating for 1h, adding the adsorption purifying agent prepared in the preparation example 2 into the filtrate, stirring and adsorbing for 20min, separating the adsorption purifying agent by a magnet, and discharging after the filtrate reaches the standard after detection.
Example 3
The embodiment provides a method for recycling nickel and phosphorus resources in chemical nickel plating waste liquid, which comprises the following steps:
(1) Regulating the pH value of the chemical nickel plating waste liquid to 7, then adding calcium chloride into the chemical nickel plating waste liquid, wherein the adding amount of the calcium chloride is 13g of calcium chloride added into every 100mL of chemical nickel plating waste liquid, stirring, reacting and precipitating for 1.5h, centrifuging, collecting precipitate, and precipitating to obtain a substance containing calcium phosphate and calcium phosphite;
(2) Adding sodium hydroxide into the supernatant in the step (1) to adjust the pH value to 10.5, centrifuging, separating solids, adding hydrazine hydrate into the supernatant, stirring and reacting for 1h, stopping adding the hydrazine hydrate after no bubbles are generated in the reaction liquid, continuously stirring and reacting for 1h, standing and precipitating, centrifuging, and collecting the precipitate as a substance containing metallic nickel;
(3) Introducing carbon dioxide into the supernatant in the step (2), introducing the carbon dioxide with the ventilation capacity of 75mL/min, introducing the carbon dioxide for 1h, precipitating for 1h, adding the adsorption purifying agent prepared in the preparation example 3 into the filtrate, stirring and adsorbing for 15min, separating the adsorption purifying agent by a magnet, and discharging after the filtrate reaches the standard after detection.
Comparative example 1
The difference compared to example 3 is that an adsorption purifier was prepared from comparative preparation 1.
Comparative example 2
The difference compared to example 3 is that an adsorption purifier was prepared from comparative preparation 1.
Comparative example 3
The difference compared to example 3 is that an adsorption purifier was prepared from comparative preparation 1.
Comparative example 4
The difference compared to example 3 is that an adsorption purifier was prepared from comparative preparation 1.
Comparative example 5
The difference compared to example 3 is that an adsorption purifier was prepared from comparative preparation 1.
Comparative example 6
In comparison with example 3, the difference is that the adsorption purification agent is prepared from comparative preparation 1
Comparative example 7
The difference compared to example 3 is that an adsorption purifier was prepared from comparative preparation 1.
Comparative example 8
In comparison with example 3, the difference is that step (1) is not performed.
The method comprises the following steps:
(1) Adding sodium hydroxide into the chemical nickel plating waste liquid to adjust the pH value to 10.5, centrifuging, separating solids, adding hydrazine hydrate into supernatant, stirring and reacting for 1h, stopping adding the hydrazine hydrate after no bubbles are generated in the reaction liquid, continuing stirring and reacting for 1h, standing and precipitating, centrifuging, and collecting the precipitate as a substance containing metallic nickel;
(2) Introducing carbon dioxide into the supernatant in the step (1), introducing the carbon dioxide into the supernatant for 1h, precipitating for 1h, adding the adsorption purifying agent prepared in the preparation example 3 into the filtrate, stirring and adsorbing for 15min, separating the adsorption purifying agent by a magnet, and discharging after the filtrate reaches the standard after detection.
Comparative example 9
In comparison with example 3, the difference is that step (2) was not performed.
The method comprises the following steps:
(1) Regulating the pH value of the chemical nickel plating waste liquid to 7, then adding calcium chloride into the chemical nickel plating waste liquid, wherein the adding amount of the calcium chloride is 13g of calcium chloride added into every 100mL of chemical nickel plating waste liquid, stirring, reacting and precipitating for 1.5h, centrifuging, collecting precipitate, and precipitating to obtain a substance containing calcium phosphate and calcium phosphite;
(2) Introducing carbon dioxide into the supernatant in the step (1), introducing the carbon dioxide into the supernatant for 1h, precipitating for 1h, adding the adsorption purifying agent prepared in the preparation example 3 into the filtrate, stirring and adsorbing for 15min, separating the adsorption purifying agent by a magnet, and discharging after the filtrate reaches the standard after detection.
Test example 3
The liquids and stock solutions discharged in examples 1 to 3 and comparative examples 1 to 9 were examined, and the results are shown in Table 3.
TABLE 3 Table 3
As can be seen from the above table, the discharged liquid can meet the standard requirements and the nickel recovery rate is high after the treatment method in the embodiments 1-3 of the invention.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (10)

1. The method for recycling the nickel and phosphorus resources in the chemical nickel plating waste liquid is characterized by comprising the following steps of:
(1) Regulating the pH value of the chemical nickel plating waste liquid, adding calcium chloride into the chemical nickel plating waste liquid, stirring, reacting, precipitating, centrifuging, collecting precipitate, and precipitating to obtain a substance containing calcium phosphate and calcium phosphite;
(2) Adding sodium hydroxide into the supernatant in the step (1) to adjust the pH value, centrifuging, separating solids, adding hydrazine hydrate into the supernatant, stirring for reaction, stopping adding the hydrazine hydrate after no bubbles are generated in the reaction liquid, continuing stirring for reaction, standing for precipitation, centrifuging, and collecting the precipitate as a metal nickel-containing substance;
(3) Introducing carbon dioxide into the supernatant in the step (2), precipitating, adding an adsorption purifying agent into the filtrate, stirring for adsorption, separating the adsorption purifying agent by a magnet, detecting the filtrate to reach the standard, and discharging;
the adsorption purifying agent is prepared by taking magnetic ferroferric oxide as a core, loading TiO 2/ZnO, then carrying out hydrogenation treatment, depositing carbon nano tubes on the surface, modifying polydopamine, and reacting with zirconium tetrachloride and 2-amino terephthalic acid.
2. The method for recycling nickel and phosphorus resources in the electroless nickel plating waste liquid according to claim 1, wherein the adding amount of calcium chloride in the electroless nickel plating waste liquid in the step (1) is 12-15g of calcium chloride added into every 100mL of electroless nickel plating waste liquid, the stirring reaction and precipitation time is 1-2h, and the pH value of the electroless nickel plating waste liquid is adjusted to be 6.9-7.1.
3. The method for recycling nickel and phosphorus resources in the electroless nickel plating waste liquid according to claim 1, wherein in the step (2), the pH value is adjusted to 10-11, the stirring reaction time is 0.5-1h, and the stirring reaction continuing time is 0.5-1h.
4. The method for recycling nickel and phosphorus resources in electroless nickel plating waste liquid according to claim 1, wherein the adding amount of the adsorption purifying agent in the step (3) is 3-5wt%, the stirring and adsorbing time is 10-20min, the ventilation amount of carbon dioxide is 10-100mL/min, and the preparation method of the adsorption purifying agent is as follows:
S1, under the protection of inert gas, adding ferric chloride and ferrous chloride into water, dropwise adding ammonia water to adjust the pH value of the solution, heating and stirring for reaction, centrifuging, washing, ball milling, drying and calcining to obtain the magnetic ferroferric oxide;
S2, preparing a doped TiO 2/ZnO@magnetic ferroferric oxide compound, namely dissolving zinc acetate and copper chloride in water, adding diethylene glycol, stirring to form a solution A, uniformly mixing tetrabutyl titanate, thiourea, acetic acid and ethanol to obtain a solution B, mixing the solution A and the solution B, adding magnetic ferroferric oxide, heating, stirring for reaction, centrifuging, washing, ball milling, drying and calcining to obtain the doped TiO 2/ZnO@magnetic ferroferric oxide compound;
S3, hydrotreating, namely introducing inert gas into the TiO 2/ZnO@magnetic ferroferric oxide composite to replace air, then introducing hydrogen, heating, stopping introducing hydrogen, and cooling to room temperature to obtain the black doped TiO 2/ZnO@magnetic ferroferric oxide composite;
S4, depositing a carbon nano tube, namely dissolving ferrocene in dimethylbenzene to obtain a solution, introducing inert gas into the black doped TiO 2/ZnO@magnetic ferroferric oxide composite to replace air, closing the inert gas, introducing hydrogen, heating, dropwise adding the solution, stopping heating and introducing hydrogen, and cooling to room temperature to obtain the carbon nano tube deposited black doped TiO 2/ZnO@magnetic ferroferric oxide composite;
S5, polydopamine modification, namely adding the prepared black doped TiO 2/ZnO@magnetic ferroferric oxide compound deposited on the carbon nano tube into water, adding dopamine hydrochloride and a catalyst, heating and stirring for reaction, separating by a magnet, washing and drying to obtain a modified substance;
S6, preparing an adsorption purifying agent, namely adding the modified substance, zirconium tetrachloride and 2-amino terephthalic acid into N, N-dimethylformamide, stirring and mixing uniformly, dropwise adding acetic acid, carrying out hydrothermal reaction, carrying out magnet separation, washing and drying to obtain the adsorption purifying agent.
5. The method for recycling nickel and phosphorus resources in electroless nickel plating waste liquid according to claim 4, wherein in the step S1, the mass ratio of ferric chloride to ferrous chloride is 3.24:1.26, the pH value of the solution is adjusted to be 10-11, the temperature of the heating and stirring reaction is 75-85 ℃ for 4-6 hours, the temperature of the calcination is 400-600 ℃ for 1-3 hours.
6. The method for recycling nickel and phosphorus resources in the electroless nickel plating waste liquid according to claim 4, wherein in the step S2, the mass ratio of zinc acetate, copper chloride, diethylene glycol, tetrabutyl titanate, thiourea, acetic acid and magnetic ferroferric oxide is 7-10:0.2-0.4:3-5:12-15:1-2:4-6:6-8, the temperature of the heating and stirring reaction is 65-75 ℃, the time is 1-2h, the calcination temperature is 500-600 ℃ and the time is 1-3h.
7. The method for recycling nickel and phosphorus resources in electroless nickel plating waste liquid according to claim 4, wherein the hydrogen gas is introduced to a hydrogen pressure of 20-30bar in the step S3, the temperature of the heating treatment is 180-220 ℃ and the time is 4-6d.
8. The method for recycling nickel and phosphorus resources in electroless nickel plating waste liquid according to claim 4, wherein the mass ratio of ferrocene to xylene in the step S4 is 1-2:100, the ventilation amount of hydrogen is 50-100mL/min, and the heating temperature is 800-900 ℃.
9. The method for recycling nickel and phosphorus resources in electroless nickel plating waste liquid according to claim 4, wherein in the step S5, the carbon nano tube is deposited with a mass ratio of black doped TiO 2/ZnO@magnetic ferroferric oxide compound, dopamine hydrochloride and a catalyst of 10:3-5:0.5-1, the pH=8.5-9.5 of Tris-HCl solution of the catalyst, the temperature of the heating stirring reaction is 45-55 ℃ and the time is 3-5h.
10. The method for recycling nickel and phosphorus resources in electroless nickel plating waste liquid according to claim 4, wherein in the step S6, the mass ratio of the modifier to zirconium tetrachloride to 2-amino terephthalic acid to acetic acid is 10:4-5:3-4:2-4, the temperature of the hydrothermal reaction is 120-140 ℃ and the time is 20-24h.
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CN119191618A (en) * 2024-10-23 2024-12-27 乐清力川环保科技有限公司 A method for recycling iron phosphate from chemical nickel plating waste liquid

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JP3981318B2 (en) * 2002-10-09 2007-09-26 日本化学産業株式会社 Treatment method of electroless nickel plating aging solution
JP4405281B2 (en) * 2004-02-18 2010-01-27 株式会社アステック入江 Recycling method of electroless nickel plating waste liquid
US20090324467A1 (en) * 2006-08-25 2009-12-31 National University Corporation Nagoya University Magnetic chemical absorbent, production process for the same and recycling method for the same, as well as waste-liquid treating method
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CN115739064A (en) * 2022-11-22 2023-03-07 杭州中科沐森环保科技有限公司 Nano material for ultraviolet light catalytic degradation and preparation method thereof
CN119191618A (en) * 2024-10-23 2024-12-27 乐清力川环保科技有限公司 A method for recycling iron phosphate from chemical nickel plating waste liquid

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