CN112374678A - Treatment method of chemical nickel plating waste liquid - Google Patents

Treatment method of chemical nickel plating waste liquid Download PDF

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Publication number
CN112374678A
CN112374678A CN202011165937.6A CN202011165937A CN112374678A CN 112374678 A CN112374678 A CN 112374678A CN 202011165937 A CN202011165937 A CN 202011165937A CN 112374678 A CN112374678 A CN 112374678A
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waste liquid
nickel plating
plating waste
chemical nickel
nickel
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郭学军
冷思文
马娜
张翔垣
郑子杰
孙悦
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Beijing Normal University
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Beijing Normal University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/105—Phosphorus compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/02—Temperature
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH

Abstract

The invention relates to a method for treating waste liquid, in particular to a method for treating chemical nickel plating waste liquid. The processing method comprises the following steps: firstly removing nickel from the chemical nickel plating waste liquid to be treated to obtain a first treatment liquid; and concentrating the first treatment solution until the solid content is more than 20%, and carrying out high-temperature oxidation at the oxygen concentration of 20-100% and the temperature of 300-1200 ℃. The treatment method provided by the invention can completely oxidize low-valence phosphorus (namely monovalent hypophosphite and trivalent phosphite) in the chemical nickel plating waste liquid into pentavalent phosphate with biological effectiveness so as to obtain resource recovery; meanwhile, the nickel in the chemical nickel plating waste liquid can be efficiently removed so as to realize resource utilization of the nickel in the waste liquid; wherein the removal rate of nickel is as high as 99.99%.

Description

Treatment method of chemical nickel plating waste liquid
Technical Field
The invention relates to a method for treating waste liquid, in particular to a method for treating chemical nickel plating waste liquid.
Background
In recent years, the electroplating industry is rapidly developed; among them, electroless nickel plating is a novel metal surface treatment technique, and is increasingly concerned by researchers due to the advantages of simple and convenient process, energy saving, environmental protection and the like. The nickel deposition is a surface treatment process widely applied in the circuit board industry, and the process is mainly to plate a layer of nickel on the copper surface of the circuit board. However, the chemical nickel plating waste liquid contains up to 2000-. Nickel has carcinogenic and sensitizing effects, and can cause skin cancer, lung cancer, nasal cavity cancer, etc.; at present, heavy metal nickel and compounds thereof are listed as pollutants for preferential control, and the surface water environment emission concentration cannot be higher than 0.1 mg/L. Phosphorus is one of the main pollution factors causing water eutrophication, and the water eutrophication can be caused when the concentration of the total phosphorus in the water environment reaches 0.03 mg/L. On the other hand, nickel and phosphorus are valuable resources.
It is not easy to efficiently recover nickel and phosphorus from the chemical nickel plating waste liquid (i.e. the waste water generated in the chemical nickel plating production process); the reason is that: the chemical nickel plating waste liquid contains a large amount of strong complex compounds, and nickel ions are strongly complexed by a complexing agent; ② the chemical nickel plating waste liquid contains high-concentration phosphorus with various complex forms, such as sodium hypophosphite with +1 valence, sodium phosphite with +3 valence, sodium phosphate with +5 valence and various phosphorus-containing compounds; the chemical nickel plating treatment difficulty is high due to the reasons, and the treatment can hardly reach the standard. Based on this, the electroless nickel plating waste liquid is considered as a liquid hazardous waste which is difficult to treat.
In summary, it is an urgent technical problem to be solved by the skilled person in the art to provide a simple and efficient method for treating the chemical nickel plating waste liquid to efficiently recover and recycle nickel and phosphorus.
Disclosure of Invention
The invention provides a brand-new treatment method of chemical nickel plating waste liquid, which can separate nickel and phosphorus and efficiently recycle the nickel and the phosphorus so as to realize resource utilization.
Specifically, the method for treating the chemical nickel plating waste liquid comprises the following steps: firstly removing nickel from the chemical nickel plating waste liquid to be treated to obtain a first treatment liquid; and concentrating the first treatment solution until the solid content is more than 20%, and carrying out high-temperature oxidation at the oxygen concentration of 20-100% and the temperature of 300-1200 ℃.
In the prior art, after low-valent phosphate is oxidized into high-valent phosphate by adopting an oxidant, calcium salt, iron salt or aluminum salt is applied to precipitate phosphorus in the chemical nickel plating waste liquid, and then the phosphorus in the waste liquid is removed. However, the removal of phosphorus by the above method requires the addition of a large amount of oxidizing agent and flocculant, which is extremely high in cost and low in efficiency, and the generated calcium phosphate, iron phosphate or aluminum phosphate precipitate is not highly bioavailable, thereby affecting the resource recycling of phosphorus.
Based on the problems, the invention continuously researches the technical means for converting low-valence phosphorus into pentavalent phosphate, and accidentally finds that the nickel in the chemical nickel plating waste liquid is completely removed, then the chemical nickel plating waste liquid is concentrated until the solid content is more than 20 percent, and finally the chemical nickel plating waste liquid is subjected to high-temperature oxidation; the method can oxidize low-valence phosphorus into pentavalent phosphate, is expected to solve the problems of low phosphorus removal efficiency and high cost, generates the pentavalent phosphate without containing toxic nickel, has biological effectiveness, and is favorable for resource utilization.
In order to completely oxidize the low-valence phosphorus, the invention optimizes the high-temperature oxidation conditions, and concretely comprises the following steps:
preferably, when the solid content is 50-90%, the temperature of the high-temperature oxidation is 500-1000 ℃; concentrating the first treatment solution until the solid content is 50-90%, and carrying out high-temperature oxidation at the oxygen concentration of 20-100% and the temperature of 500-1000 ℃. The high-temperature oxidation is carried out under the conditions, so that the low-valence phosphorus is completely oxidized into pentavalent phosphate.
Preferably, the nickel content in the chemical nickel plating waste liquid to be treated is 500-10000 mg/L, and the phosphorus content is 10000-80000 mg/L; further, the pH value of the chemical nickel plating waste liquid to be treated is 1-5. The waste liquid treatment method provided by the invention is particularly suitable for the chemical nickel plating waste liquid.
Preferably, the content of nickel in the chemical nickel plating waste liquid to be treated is 3000-5000 mg/L, and the content of phosphorus is 50000-57000 mg/L. The waste liquid treatment method provided by the invention is particularly suitable for the chemical nickel plating waste liquid.
Preferably, the step of removing nickel comprises:
step (1): adjusting the pH value of the chemical nickel plating waste liquid to be treated to 4-9;
step (2): and (2) adding at least one of sulfide, dithiocarbamate and xanthate into the chemical nickel plating waste liquid obtained in the step (1).
In the technical scheme, the nickel sediments obtained in the step (2) are dewatered through centrifugation or plate-and-frame filter pressing to realize resource recovery after solid-liquid separation, and the residual liquid is subjected to subsequent phosphorus removal.
In order to further improve the removal rate of nickel, the method optimizes the step of removing nickel, and specifically comprises the following steps:
preferably, in the step (1), the pH value of the chemical nickel plating waste liquid to be treated is adjusted to 7-8; the precipitation efficiency of nickel can be remarkably improved by adjusting the pH value of the chemical nickel plating waste liquid to the above range in advance.
Preferably, in the step (2), sulfide is added into the chemical nickel plating waste liquid obtained in the step (1); or, firstly adding sulfide into the chemical nickel plating waste liquid obtained in the step (1), and then adding at least one of dithiocarbamate substances and xanthate substances.
Preferably, the sulfide is added into the chemical nickel plating waste liquid obtained in the step (1), and at least one of dithiocarbamate and xanthate is added until the concentration of the residual nickel in the solution is reduced to below 2 ppm.
Further, sulfide is added into the chemical nickel plating waste liquid obtained in the step (1), so that most of nickel ions can be precipitated as nickel sulfide, preferably, the sulfide is at least one of sodium sulfide, sodium hydrosulfide and hydrogen sulfide, and the sulfide isS in sulfide2-And Ni in the chemical nickel plating waste liquid2+The molar ratio of (A) to (B) is 0.5-1.2: 1; and adding at least one of dithiocarbamate and xanthate until the concentration of residual nickel in the solution is reduced to below 2 ppm.
In the technical scheme, sulfide is added in the first step to enable most of nickel ions in the waste liquid to be precipitated as nickel sulfide, then first solid-liquid separation is immediately carried out, at least one of dithiocarbamate substances and xanthate substances is added, and when the concentration of residual nickel in the solution is reduced to be below 2ppm, second nickel precipitation and second solid-liquid separation are carried out.
In the step of precipitating nickel, a Polyacrylamide (PAM) coagulant aid can be used to assist flocculation precipitation so as to ensure complete precipitation of nickel.
Preferably, one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and slaked lime is/are used as the pH regulator.
As a better technical scheme of the invention, the treatment method of the chemical nickel plating waste liquid comprises the following steps:
step (1): adjusting the pH value of the chemical nickel plating waste liquid to be treated to 7-8;
step (2): firstly, adding sulfide into the chemical nickel plating waste liquid with the pH value regulated in the step (1), wherein S in the sulfide2-And Ni in the chemical nickel plating waste liquid2+The molar ratio of (a) to (b) is 0.5 to 1.2: 1; adding at least one of dithiocarbamate and xanthate until the concentration of residual nickel in the solution is reduced to below 2 ppm; carrying out solid-liquid separation to obtain a first treatment liquid with high phosphorus content and nickel-rich slag;
and (3): concentrating the first treatment solution until the solid content is 50-90% to obtain a second treatment solution;
and (4): and carrying out high-temperature oxidation on the second treatment liquid at the oxygen concentration of 20-100% and the temperature of 500-1000 ℃.
In the above-mentioned embodiment, the concentration in the step (3) is preferably an evaporation concentration, more preferably an evaporation concentration under normal pressure or reduced pressure, and still more preferably a concentration under reduced pressure (vacuum). The type of equipment for evaporation is not limited, and may be a single effect type or a multiple effect type, preferably a multiple effect type. The evaporator is not limited in structure and can be a standard evaporator, a suspended frame evaporator, a Levenu evaporator, a coil evaporator, an external heating evaporator, a crystallization evaporator, a forced circulation evaporator, a rising film or falling film evaporator, or a thin film evaporator.
In the above technical solution, the type of the equipment used in the high temperature oxidation in step (4) is not limited, and may be a blast furnace, an electric furnace, an open hearth furnace, a flash furnace, a reverberatory furnace, a rotary furnace (kiln), a multi-hearth furnace, a fluidized bed furnace, or the like. The proper temperature range is 500-1000 ℃, and the concentration range of oxygen conveyed into the furnace is 20-100% so as to ensure that hypophosphite and phosphite in the materials are fully oxidized and converted into pentavalent phosphate. In addition, the chemical nickel waste liquid contains various organic complexes and has a certain fuel value, so that the addition of auxiliary fuel in the high-temperature phosphorus oxidation process can be reduced.
In a specific embodiment, the high-temperature oxidation process in step (4) may be incorporated into the production of a calcium-magnesium-phosphate fertilizer, that is, the above-mentioned high-phosphorus-content organic mixture is added to production ingredients such as fuel, phosphate ore, and melting aid required for the production of the calcium-magnesium-phosphate fertilizer, and is melted together with other materials in a high-temperature furnace, and finally recycled in the form of the calcium-magnesium-phosphate fertilizer.
The invention has the beneficial effects that:
(1) the treatment method provided by the invention can completely oxidize low-valence phosphorus (namely monovalent hypophosphite and trivalent phosphite) in the chemical nickel plating waste liquid into pentavalent phosphate with biological effectiveness, and further obtain resource recovery.
(2) The treatment method provided by the invention can efficiently remove nickel in the chemical nickel plating waste liquid so as to realize resource utilization of nickel in the waste liquid; wherein the removal rate of nickel is as high as 99.99%.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
Respectively taking 250 ml of chemical nickel plating waste liquidThe measured content of Ni element in the waste liquid is 3600mg/L, the content of P element is 56400mg/L, and the pH value is 1.2. Adding 50% sodium hydroxide, and adjusting the pH values of the chemical nickel plating waste liquid to 2, 4, 6, 7, 8 and 9 respectively. According to S2-/Ni2+In a molar ratio of 0.8:1, adding sodium hydrosulfide to precipitate nickel for the first time and accelerating the coagulation with an appropriate amount of PAM, and measuring the residual nickel concentration in the solution after the nickel precipitate is subjected to centrifugal solid-liquid separation, the results are shown in table 1.
TABLE 1 residual nickel concentration after nickel precipitation from sodium hydrosulfide at different pH' s
pH 2 4 6 7 8 9
Residual nickel concentration mg/L 2970 1620 1180 797 708 555
Removal rate% 17.5 55.0 67.2 77.86 80.3 84.58
As can be seen from Table 1, when the pH of the electroless nickel plating waste liquid is adjusted to 7-9, the removal rate is relatively ideal; however, when the pH of the electroless nickel plating waste liquid is adjusted to 9, although the removal rate is optimal, unnecessary cost is increased in the actual operation process, and the effect is optimal when the pH of the electroless nickel plating waste liquid is adjusted to 7-8.
Example 2
250 ml of chemical nickel plating waste liquid is respectively taken, and the element Ni in the waste liquid is 3600mg/L, the element P is 56400mg/L and the pH value is 1.2. Adding 50% sodium hydroxide, and adjusting the pH value of the chemical nickel plating waste liquid to 7. According to S2-/Ni2+The molar ratios of (1) to (2) were 0.42:1, 0.56:1, 0.73:1, 0.80:1, 0.88:1, 0.96:1, 1.05:1, 1.12:1 and 1.22:1, respectively, sodium hydrosulfide was added to precipitate nickel for the first time and an appropriate amount of PAM was used to accelerate coagulation, and the concentration of nickel remaining in the solution was measured after centrifugal solid-liquid separation of the nickel sludge, and the results are shown in table 2.
TABLE 2 relationship between sodium hydrosulfide addition and residual nickel concentration at pH 7
Figure BDA0002745778060000061
Example 3
250 ml of chemical nickel plating waste liquid is respectively taken, and the determination shows that the element Ni in the waste liquid is 5000mg/L, the element P is 50000mg/L and the pH value is 4.0. Adding 50% sodium hydroxide, and adjusting the pH value of the chemical nickel plating waste liquid to 7.0. According to S2-/Ni2+The molar ratio of the nickel to the nickel is 1:1, adding sodium hydrosulfide to precipitate nickel for the first time, accelerating the coagulation by using a proper amount of PAM, and measuring the concentration of the residual nickel in the solution after the nickel sediment is subjected to centrifugal solid-liquid separation. Adding proper amount of ethyl sulfur nitrogen to make the solution colorless, and making second-step nickel precipitation and second solid-liquid separation. High phosphorus content after nickel removalThe organic acid solution was evaporated in vacuo and concentrated to 50% solids. 2.0g of the concentrated high phosphorus organic mixture is put into a tube furnace, oxygen is introduced into the tube furnace, the temperature is kept constant at 900 ℃ for 2 hours, and then the heating is stopped.
The results of the pilot scale show that the product is S2-/Ni2+Was added with sodium hydrosulfide to precipitate nickel primarily, and the residual nickel concentration in the solution was determined to be 2.2 mg/L. Adding proper amount of ethidium and azote, and performing the second step of nickel precipitation and solid-liquid separation to obtain colorless solution with residual nickel concentration of 0.53 mg/L. The recovery rate of nickel can reach 99.99% after two steps of nickel precipitation and solid-liquid separation; the nickel concentration in the recovered nickel slag is as high as 29.5 percent, and the method has great resource recycling value. XPS analysis of the sample after high-temperature oxidation shows that the monovalent hypophosphite and the trivalent phosphite are all oxidized into pentavalent phosphate with biological effectiveness to be recycled.
Example 4
250 ml of chemical nickel plating waste liquid is respectively taken, and the determination shows that the element Ni in the waste liquid is 5000mg/L, the element P is 50000mg/L and the pH value is 4.0. Adding 50% sodium hydroxide, and adjusting the pH value of the chemical nickel plating waste liquid to 7.0. According to S2-/Ni2+The molar ratio of (1) to (2) is 0.9:1, adding sodium hydrosulfide to make nickel precipitate for the first time, accelerating coagulation by using a proper amount of PAM, and measuring the residual nickel concentration in the solution after the nickel precipitate is subjected to centrifugal solid-liquid separation. Adding proper amount of ethyl sulfur nitrogen to make the solution colorless, and making second-step nickel precipitation and second solid-liquid separation. And (3) carrying out vacuum evaporation on the high-phosphorus-content organic acid solution after nickel removal and concentrating until the solid content is 50%. 2.0g of the concentrated high phosphorus organic mixture is put into a tube furnace, oxygen is introduced into the tube furnace, the temperature is kept constant at 900 ℃ for 2 hours, and then the heating is stopped.
The results of the pilot scale show that the product is S2-/Ni2+Was added to the solution at a molar ratio of 0.9:1 to precipitate nickel primarily, and the residual nickel concentration in the solution was determined to be 300 mg/L. Adding proper amount of ethidium and azote, and performing the second step of nickel precipitation and solid-liquid separation to obtain colorless solution with residual nickel concentration of 1.2 mg/L. The recovery rate of nickel can reach 99.99% after two steps of nickel precipitation and solid-liquid separation; go back toThe nickel concentration in the collected nickel slag is as high as 30 percent, and the method has great resource recycling value. XPS analysis of the sample after high-temperature oxidation shows that the monovalent hypophosphite and the trivalent phosphite are all oxidized into pentavalent phosphate with biological effectiveness to be recycled.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A treatment method of chemical nickel plating waste liquid is characterized by comprising the following steps: firstly removing nickel from the chemical nickel plating waste liquid to be treated to obtain a first treatment liquid; and concentrating the first treatment solution until the solid content is more than 20%, and carrying out high-temperature oxidation at the oxygen concentration of 20-100% and the temperature of 300-1200 ℃.
2. The method for treating an electroless nickel plating waste liquid according to claim 1, wherein the temperature of the high temperature oxidation is 500 to 1000 ℃ when the solid content is 50 to 90%.
3. The method for treating the chemical nickel plating waste liquid as claimed in claim 1 or 2, wherein the content of nickel in the chemical nickel plating waste liquid to be treated is 500-10000 mg/L, and the content of phosphorus in the chemical nickel plating waste liquid to be treated is 10000-80000 mg/L.
4. The method for treating the chemical nickel plating waste liquid as claimed in claim 3, wherein the pH of the chemical nickel plating waste liquid to be treated is 1-5.
5. The method for treating an electroless nickel plating waste liquid according to claim 1, wherein the step of removing nickel comprises:
step (1): adjusting the pH value of the chemical nickel plating waste liquid to be treated to 4-9;
step (2): and (2) adding at least one of sulfide, dithiocarbamate and xanthate into the chemical nickel plating waste liquid obtained in the step (1).
6. The method for treating the chemical nickel plating waste liquid as claimed in claim 5, wherein in the step (1), the pH of the chemical nickel plating waste liquid to be treated is adjusted to 7-8.
7. A method for treating waste electroless nickel plating solution according to claim 5, wherein in the step (2), sulfide is added to the waste electroless nickel plating solution obtained in the step (1); or, firstly adding sulfide into the chemical nickel plating waste liquid obtained in the step (1), and then adding at least one of dithiocarbamate substances and xanthate substances.
8. A method for treating waste electroless nickel plating solution according to claim 7, characterized in that sulfide is added to the waste electroless nickel plating solution obtained in step (1), and at least one of dithiocarbamate and xanthate is added until the concentration of residual nickel in the solution is reduced to 2ppm or less.
9. The method for treating an electroless nickel plating waste liquid according to claim 7 or 8, characterized in that the sulfide is at least one of sodium sulfide, sodium hydrosulfide and hydrogen sulfide; s in the sulfide2-And Ni in the chemical nickel plating waste liquid2+The molar ratio of (A) to (B) is 0.5-1.2: 1.
10. The method for treating chemical nickel plating waste liquid according to claim 1, characterized by comprising the following steps:
step (1): adjusting the pH value of the chemical nickel plating waste liquid to be treated to 7-8;
step (2): firstly, adding sulfide into the chemical nickel plating waste liquid with the pH value regulated in the step (1), wherein S in the sulfide2-And Ni in the chemical nickel plating waste liquid2+Is 0.5-1.2: 1; adding at least one of dithiocarbamate and xanthate until the concentration of residual nickel in the solution is reduced to below 2 ppm; carrying out solid-liquid separation to obtain a first treatment liquid with high phosphorus content and nickel-rich slag;
and (3): concentrating the first treatment solution until the solid content is 50-90% to obtain a second treatment solution;
and (4): and carrying out high-temperature oxidation on the second treatment liquid at the oxygen concentration of 20-100% and the temperature of 500-1000 ℃.
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CN113562877A (en) * 2021-07-26 2021-10-29 中南大学 Treatment method of EDTA-Ni-containing wastewater

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