CN109183117B

CN109183117B - Method and system for utilizing coloring recovery coloring agent and reclaimed water in nickel-tin salt coloring

Info

Publication number: CN109183117B
Application number: CN201810841772.6A
Authority: CN
Inventors: 熊映明
Original assignee: Foshan Sanshui Xiongying Innovation Center For Aluminum Surface Technnologies Co ltd
Current assignee: Foshan Sanshui Xiongying Innovation Center For Aluminum Surface Technnologies Co ltd
Priority date: 2018-07-27
Filing date: 2018-07-27
Publication date: 2021-01-15
Anticipated expiration: 2038-07-27
Also published as: CN109183117A

Abstract

The utilization method of the nickel-tin salt coloring recovered colorant and the reclaimed water and the system thereof comprise the following steps: nickel-tin wastewater treatment operation, nickel phosphate recovery operation and N-P compound fertilizer recovery operation; the system comprises: a nickel-tin wastewater collection system, a nickel-tin separation system, a nickel phosphate recovery system and an N-P compound fertilizer recovery system; the invention utilizes an on-line classification recovery method, and by means of the designed system, water for coloring and cleaning is intercepted and collected, and a nickel-tin solid mixture is recovered and converted into a nickel-tin salt coloring agent; the treated reclaimed water is recycled and converted into N-P compound liquid fertilizer, the pollution of the nickel-tin-containing wastewater to a wastewater treatment center is blocked, the discharge of industrial hazardous waste is reduced, and the resource recycling of toxic waste is realized.

Description

Method and system for utilizing coloring recovery coloring agent and reclaimed water in nickel-tin salt coloring

Technical Field

The invention relates to the technical field of aluminum material processing, in particular to a method and a system for utilizing coloring recovery coloring agent and reclaimed water of nickel-tin salt.

Background

The aluminum alloy has the advantages of excellent processing performance, good corrosion resistance, beautiful surface, high recovery rate and the like, and is widely applied to the industries of buildings, transportation, machinery, electric power and the like. In recent years, the trend of replacing copper, wood and steel with aluminum and expanding the application range of aluminum is more obvious. The aluminum processing industry is not only a traditional industry, but also a sunrise industry full of bobby vitality. According to statistics, people in developed countries in Europe and America consume more than 32kg of aluminum alloy every year, while people in China only have about 13kg and only one third of developed countries, and the consumption of the aluminum alloy in China has huge growth space. However, in the new economic normality, the common problems of high energy consumption, large total pollution discharge amount and low resource recycling rate in the aluminum processing industry are obviously bottlenecks and obstacles for restricting the development of the industry.

The production in the aluminum industry comprises the working procedures of electrolysis, casting, pressure processing, surface treatment and the like, and waste gas, waste water and waste residue with different degrees are generated in each working procedure during production. A large amount of aluminum ash is generated during electrolysis and casting, a die-cooking alkaline waste liquid is generated in the extrusion process, and various waste water and waste residues containing acid, alkali, treatment agents, chromium, nickel heavy metal ions and other complex components are generated in the surface treatment process.

Source of waste residue in aluminium industry

1. The electrolytic casting of aluminum ash is generated in the processes of electrolysis, smelting and casting of aluminum and aluminum alloy, and the total loss of aluminum caused by the aluminum ash is 1-12%. About 20-40kg of aluminum ash is generated when one ton of raw aluminum is processed, the amount of aluminum liquid generated during direct casting is less, the amount of aluminum ingot is more during remelting, and about 100-250kg of aluminum ash is generated during regeneration of one ton of waste aluminum.

The aluminum ash can be divided into two types: one is primary aluminum ash, which is scum and skimming produced in the processes of electrolyzing raw aluminum, casting and the like without adding salt flux, and the like, and mainly comprises metal aluminum and aluminum oxide, wherein the content of aluminum can reach 15-70 percent, and the color is white; the other is secondary aluminum ash, which is the waste after the primary aluminum ash is subjected to aluminum extraction and recovery, and the aluminum content is lower than that of the primary aluminum ash, and the secondary aluminum ash is generally gray black. The secondary aluminum ash has complex components and contains toxic and harmful components such as metallic aluminum (5-30%), aluminum oxide (30-70%), silicon dioxide and ferric oxide (5-15%), potassium, sodium, calcium and magnesium chloride (10-30%) and nitrogen, fluorine, arsenic and the like. The aluminum ash is referred to as secondary aluminum ash.

The national electrolytic aluminum yield is 3250 ten thousand tons in 2016, the aluminum product yield of extrusion and calendering exceeds 2000 ten thousand tons, the conservative estimation of the aluminum ash amount in the whole country every year is more than 200 ten thousand tons, and the total amount of the aluminum ash is considered to be 850 ten thousand tons in 600 days. The aluminum ash is a renewable resource and has higher comprehensive recycling value, but the aluminum ash is not paid enough attention all the time, so that huge resource waste is caused. Meanwhile, the aluminum ash contains toxic and harmful substances such as fluoride, ammonia nitrogen, arsenic and the like, and is classified as dangerous waste, the waste category of the aluminum ash in 'national dangerous waste record' of 2016 edition is HW48, and the dangerous characteristic T (danger) -toxic dangerous waste. Along with the development of economy, the accumulation amount of the waste aluminum ash is greatly increased year by year, and if an economical, effective and harmless method is not found for treatment, the serious threat to the environment is more and more highlighted. At present, the recovery of the aluminum ash in China is still in a starting stage, a recovery method which is mature, reliable and good in economical efficiency is lacked, the aluminum ash treatment recovery rate is low, the energy consumption and the waste are large, and the utilization approaches are few. Even if the treated aluminum ash still contains a large amount of harmful substances, the aluminum ash can be only stockpiled or buried in a yard, so that the method has great environmental hazard and simultaneously a manufacturer bears great illegal risks. In 2018, the environmental protection tax Law of the people's republic of China, which is applied from 1 month and 1 day, stipulates that an aluminum ash emission enterprise will pay an environmental protection tax of 1000 yuan/ton.

2. Extrusion surface treatment of waste water and waste residue

The production of aluminum products consumes a large amount of water, at least 15 tons of water are consumed for producing 1 ton of aluminum materials, 2000 ten thousand tons of extruded materials are produced in the whole industry year, about 2.25 hundred million tons of waste water is discharged, about 150 ten thousand tons of waste residues are produced after the waste water is treated, and the quantity is extremely remarkable.

2.1 extruding the waste liquid, waste water and waste residue of the pot mold

After the aluminum profile extrusion die is used, the aluminum profile extrusion die is put into high-concentration alkali liquor to be die-stewed, and aluminum in a die cavity is corroded. The concentration of sodium hydroxide in the mold-boiling liquid reaches 200-300g/L, the content of aluminum ions is continuously increased along with the reaction, and when the concentration reaches above 60-70g/L and the reaction speed is obviously reduced, the mold-boiling liquid needs to be discharged. The discharged waste liquid contains a large amount of aluminum ions and sodium hydroxide, and the potential economic value is very high. The treatment of the waste liquid of the die pot generally adopts a mode of treating waste by waste, and the waste liquid is directly discharged into the center of waste water to be neutralized with waste acid generated in an oxidation process. The waste residue produced by the treatment method is very large, and the die-cooking waste residue can account for about 28% of the total slag of an enterprise; meanwhile, a large amount of sodium ions enter the wastewater center to pollute reclaimed water, and the possibility of reclaimed water reuse is completely cut off. The rough treatment mode of the mold boiling liquid not only does not utilize the economic value of the mold boiling liquid, but also increases the cost, and the treatment of waste water and waste residue becomes a heavy burden for environmental protection.

2.2 surface treatment of waste Water and slag

Aluminum materials are subjected to surface treatment in order to enhance corrosion resistance and decorative properties. Common surface treatment methods include anodic oxidation coloring, electrocoating, powder spraying, fluorocarbon paint spraying, and the like. The surface treatment process produces large amounts of wastewater of complex composition.

The waste water and waste residue produced by the anodic oxidation process (figure 2) are divided according to the process: the alkaline waste water and waste residue generated by the alkaline etching solution account for 18 percent of the total residue; acid waste water and waste residue generated by the oxidizing liquid account for 25% of the total residue, and nickel-containing waste residue generated by the coloring and hole sealing liquid accounts for 9% of the total residue; the acid waste water and waste residue produced by the spraying process account for 18 percent of the total residue. The aluminum slag source of the wastewater center of the aluminum processing enterprise is subdivided into: the mold-stewing liquid caustic sludge accounts for 28 percent of the total slag, the caustic etching liquid caustic sludge accounts for 18 percent of the total slag, the oxidizing liquid acid sludge accounts for 25 percent of the total slag, and the coloring and hole-sealing liquid nickel slag accounts for 9 percent of the total slag; the spraying acid waste residue accounts for 18 percent of the total residue. In addition, some enterprises produce polished aluminum materials, which generate a large amount of polishing waste.

Wastewater collected in wastewater center, containing Al³⁺、Na⁺、NH₄ ⁺、Ni²⁺、Sn²⁺、Cr⁶⁺Iso cation, SO₄ ^2-、F^-、NO₃ ^-、NO₂ ^-、S^2-、Cl^-Anions such as tartrate, gluconate, and acetate, and organic substances such as organic phenols, surfactants, and acrylic resins. The acidic waste water and the alkaline waste water are usually treated by mixing and neutralization, while the chromium-containing waste water and the nickel-containing waste water must be treated separately. In recent years, the proportion of the oxidation electrophoresis material is reduced, but most aluminum material factories still have more acidic wastewater than alkaline wastewater, acid and alkali water are all mixed together for treatment, the wastewater is acidic after being mixed, a large amount of caustic soda flakes, lime, PAC and PAM are required to be added, and a large amount of waste residues are generated. A large amount of useful resources such as metallic aluminum, acid, alkali and the like in the waste residue are not utilized, and huge resource waste is caused. The waste residue belongs to hazardous waste, contains various toxic and harmful substances such as aluminum hydroxide, fluoride, sulfide, nickel salt, phenol, nitrate, nitrite and the like, has great environmental hazard, can not be buried, and has great environmental hazard. After the central treatment and solid-liquid separation of the waste water, the reclaimed water contains sodium ions, ammonium ions, sulfate radicals, nitrate radicals and nitriteAcid radical, acetate radical, tartrate radical, thiosulfate radical, chloride ion, sulfide ion, fluoride ion and the like, and can not be recycled. The current environment-friendly situation forces enterprises to change and develop towards the direction of energy conservation, emission reduction and resource recycling, but the enterprises are lack of mature and reliable technologies. Realizes the complete reuse of reclaimed water, zero output of waste residue and maximized resource utilization value, and has great environmental benefit, social benefit and economic benefit.

Reduction and resource direction of aluminum ash and aluminum slag in aluminum industry

1. The principle followed is: the reduction control, the harmless treatment and the resource utilization can be actively developed only by combining three forces of government promotion, enterprise dominance and third party market allocation resources;

2. source control, namely classification interception, on-line conversion and resource utilization of each medicament tank, and reduction of the discharge amount of waste water and waste residue;

3. the surface treatment agent formula is improved, and the traditional Na-containing chemical component is replaced by a non-toxic, low-toxicity, easily-recycled and easily-cleaned chemical component⁺、NH₄ ⁺、Ni²⁺、Sn²⁺、Cr⁶⁺、NO₂ ^-、NO₃ ^-、Cl^-、F^-、CH₃COO^-Gluconate, tartrate, S₂O₃ ^2-And the like, and the technical threshold of waste water recycling, solid waste harmless and resource utilization is reduced from the source;

4. and the production and research combination is strengthened, the thought and the field of comprehensive utilization of waste residues are expanded, and the maximum comprehensive utilization value is realized.

Disclosure of Invention

The invention aims to provide a nickel-tin salt coloring recovered coloring agent and a method for utilizing reclaimed water, which is used for recovering coloring cleaning water and converting the coloring cleaning water into a nickel-tin salt coloring agent.

The invention also provides a nickel tin salt coloring recycled colorant and a water system for recycling coloring washing water to be converted into a nickel tin salt colorant.

In order to achieve the purpose, the invention adopts the following technical scheme:

the method for utilizing the coloring recovered coloring agent and the reclaimed water of the nickel-tin salt comprises the following steps: nickel-tin wastewater treatment operation, nickel phosphate recovery operation and N-P compound fertilizer recovery operation;

(1) the nickel-tin wastewater treatment operation comprises the following steps: opening a valve 1, starting a pump 1, and pumping the nickel-tin wastewater discharged from a water outlet at the bottom of the No. 14 flowing water washing tank into a coloring hole-sealing nickel-tin wastewater collecting tank for later use; opening the valve 2 and the valve 3, closing the valve 4, starting the pump 2, and pumping the nickel-tin wastewater into a nickel-tin solid recovery tank as a reaction solution; opening the valve 4 and the valve 6, starting the pump 3 and the No. 1 electric stirring, and circulating the reaction liquid; slowly opening the valve 5, sucking liquid ammonia in the liquid ammonia tank into the pump 3, and fully mixing the reaction liquid by utilizing the high-speed rotation of the pump 3; adding liquid ammonia, detecting the pH value of the reaction solution, closing the valve 5 when the pH value reaches 8.5-9.0, stopping adding the liquid ammonia, and continuously circularly stirring for 1 hour; opening the No. 1 filter press, opening the valve 7, closing the valve 6 and the valve 8, and carrying out solid-liquid separation on nickel-tin solids and primary filtrate; repeatedly spraying and rinsing the nickel-tin solid for 10 minutes, recovering the nickel-tin solid, and enabling primary filtrate to flow into a nickel phosphate recovery tank;

(2) the nickel phosphate recovery operation comprises: closing the valve 9 and the valve 11, opening the valve 8 and the valve 10, starting the

pumps

4 and 2# to electrically stir, and circulating the reaction liquid; slowly opening the valve 9, sucking phosphoric acid in the phosphoric acid tank into the pump 4, and fully mixing the reaction liquid by utilizing the high-speed rotation of the pump 4; adding phosphoric acid, detecting the pH value of the reaction solution, closing the valve 9 when the pH value reaches 6.5-7.5, stopping adding the chemicals, and continuously and circularly stirring for 1 hour; opening the No. 2 filter press, opening the valve 11, closing the valve 10, and performing solid-liquid separation on the nickel phosphate and the secondary filtrate; repeatedly spraying and rinsing the nickel phosphate solid for 10 minutes, recovering a nickel phosphate product, and enabling secondary filtrate to flow into a compound fertilizer recovery tank;

(3) the N-P compound fertilizer recovery operation comprises the following steps: and opening the valve 12 and the valve 13, starting the pump 5, filtering the secondary filtrate by using a filter, conveying the secondary filtrate to a greening land to be used as an N-P compound fertilizer containing nitrogen and phosphorus, wherein filter residues of the filter are nickel phosphate, and remaining in a nickel phosphate recovery tank for waiting for next recovery.

Further, in 14# running water wash tank, pH was controlled to pH > 3.0.

In the nickel-tin wastewater treatment operation, the nickel-tin solid contains tin hydroxide, stannous hydroxide and nickel hydroxide solid, and pure water, tin powder and sulfuric acid are added into the recovered nickel-tin solid to be converted into stannous sulfate and nickel sulfate; adding proper excess sulfuric acid, wherein the reaction end point is that the pH value reaches 0.8-1.0; under the condition that (pure water weight/solid mixture weight) is 3 and tin powder is in proper excess, precipitating and filtering reaction liquid to obtain an unsaturated solution and filter residue which are mixed by stannous sulfate and nickel sulfate; the pH value of the unsaturated solution is 0.8-1.0, the content is lower than the saturation point, and the liquid nickel-tin salt colorant can be prepared; and the filter residue is tin powder and is retained in the reactor to wait for the next reaction.

In the nickel-tin wastewater treatment operation, the liquid nickel-tin salt colorant is prepared by using stannous sulfate and nickel sulfate, the content of the stannous sulfate and nickel sulfate mixed unsaturated solution is firstly titrated, and then the medicament ratio is adjusted according to the (nickel sulfate concentration/stannous sulfate concentration) of 2.5 and the (nickel sulfate concentration/tartaric acid concentration) of 25/8, so that the stannous sulfate and nickel sulfate mixed unsaturated solution is converted into the liquid nickel-tin salt colorant.

Further, when the recovered nickel-tin solid is converted into a mixed solution of stannous sulfate and nickel sulfate, the recovered nickel-tin solid is directly reacted with sulfuric acid after rinsing, adding tin powder and pure water.

Furthermore, after the liquid nickel-tin salt colorant is prepared by using the mixed solution of stannous sulfate and nickel sulfate, the liquid nickel-tin salt colorant is directly used for slotting and adding a 13# nickel-tin salt coloring tank without concentration and crystallization.

A system for the utilization of recycled colorants and reclaimed water for tinsalt coloration, comprising: a nickel-tin wastewater collection system, a nickel-tin separation system, a nickel phosphate recovery system and an N-P compound fertilizer recovery system;

the nickel-tin wastewater collection system is used for collecting nickel-tin wastewater and sending the nickel-tin wastewater to the nickel-tin separation system;

the nickel-tin separation system is used for treating nickel-tin wastewater of the nickel-tin wastewater collection system, and adding liquid ammonia to react to generate a nickel-tin solid mixture; the nickel-tin separation system is provided with a first separation device, and the first separation device is used for separating nickel-tin solid and primary filtrate after processing a nickel-tin solid mixture; the nickel-tin separation system is also used for sending the separated primary filtrate to the nickel phosphate recovery system;

the nickel phosphate recovery system is used for treating primary filtrate of the nickel-tin separation system, and phosphoric acid is added to react to generate a nickel phosphate mixture; the nickel phosphate recovery system is also provided with a second separation device, and the second separation device is used for separating nickel phosphate solid and secondary filtrate after processing a nickel phosphate mixture; the nickel phosphate recovery system is also used for sending the separated secondary filtrate to the N-P compound fertilizer recovery system;

and the N-P compound fertilizer recovery system is used for collecting secondary filtrate, and collecting the collected secondary filtrate into the greening fertilizer after filtering operation.

Still further, the nickel-tin wastewater collection system comprises: a No. 14 flowing water washing tank, a pump 1, a coloring nickel tin wastewater collecting tank and a pump 2; the 14# flowing rinsing bath, the pump 1, the coloring nickel-tin wastewater collecting tank and the pump 2 are adjacently and sequentially connected; the No. 14 flowing water washing tank is filled with nickel-tin wastewater;

the coloring nickel-tin wastewater collection tank is connected to the nickel-tin separation system through the pump 2; the pump 2 is used for pumping the nickel-tin wastewater collected by the coloring nickel-tin wastewater collecting tank to the nickel-tin solid recovery tank;

the nickel tin separation system includes: a nickel-tin solid recovery tank, a pump 3, a liquid ammonia tank and a No. 1 filter press; the liquid ammonia tank is filled with liquid ammonia;

the pump 2 is connected to the nickel-tin solid recovery tank; the bottom of the nickel-tin solid recovery tank, the pump 3 and the No. 1 filter press are adjacently and sequentially connected; the liquid ammonia tank is provided with a pipeline and is connected to a connecting pipeline between the nickel-tin solid recovery tank and the pump 3; the pump 3 is also provided with a pipeline connected to the top of the nickel-tin solid recovery tank;

the nickel phosphate recovery system includes: a nickel phosphate recovery tank, a pump 4, a phosphoric acid tank and a No. 2 filter press; the liquid ammonia tank is filled with phosphoric acid;

the No. 1 filter press is connected with the nickel phosphate recovery tank; the bottom of the nickel phosphate recovery tank, the pump 4 and the No. 2 filter press are adjacently and sequentially connected; the phosphoric acid tank is provided with a connecting pipeline connected with the nickel phosphate recovery tank and the pump 4; the pump 4 is also provided with a pipeline connected to the top of the nickel phosphate recovery tank;

the 2# filter press is used for separating nickel phosphate solid and secondary filtrate from primary filtrate after reaction with phosphoric acid, and sending the secondary filtrate to the N-P compound fertilizer recovery system;

the N-P compound fertilizer recovery system comprises: a compound fertilizer recovery tank, a filter, a pump 5 and a green fertilizer collector;

the 2# filter press, the compound fertilizer recovery tank, the filter, the pump 5 and the greening fertilizer collector are adjacently and sequentially connected;

the compound fertilizer recovery tank is used for collecting secondary filtrate of the 2# filter press and sending the secondary filtrate to the filter; the pump 5 is used for collecting the secondary filtrate after the filter treatment to the greening fertilizer collector.

Furthermore, the nickel-tin solid recovery tank is internally provided with a No. 1 electric stirrer, and the nickel phosphate recovery tank is internally provided with a No. 2 electric stirrer.

The invention has the beneficial effects that:

the invention utilizes an on-line classification recovery method, and by means of the designed system, water for coloring and cleaning is intercepted and collected, and a nickel-tin solid mixture is recovered and converted into a nickel-tin salt coloring agent; the treated reclaimed water is recycled and converted into N-P compound liquid fertilizer, the pollution of the nickel-tin-containing wastewater to a wastewater treatment center is blocked, the discharge of industrial hazardous waste is reduced, and the resource recycling of toxic waste is realized.

Drawings

FIG. 1 is a nickel tin salt tinting recycle colorant and mid water system;

FIG. 2 is a diagram of a conventional oxidation coloring hole sealing process and slot layout according to an embodiment of the present invention.

Detailed Description

The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.

The invention relates to a large source of toxic waste residues generated in the aluminum processing industry, namely toxic waste residues containing nickel and tin generated by oxidation and coloring, wherein the waste residues account for 7 percent of the total amount of the waste residues for surface treatment of aluminum processing enterprises, about 7.5 ten thousand tons, and about 2400 ten thousand tons of water containing nickel and tin, belonging to the field of aluminum processing.

The oxidation coloring process flow is shown in figure 2, the 1#, 4#, 7#, 10#, 13# and 16# tanks are working tanks, each working tank is provided with two flowing water washing tanks, 18 tank positions are needed for oxidation treatment, wherein 13# is a nickel-tin salt coloring tank containing stannous sulfate and nickel sulfate, and the subsequent 14# and 15# flowing water washing tanks bring nickel-tin-containing wastewater into a wastewater treatment center, so that 2.25 million tons of water in the whole industry are polluted, and 150 million tons of mixed toxic waste residues containing nickel and tin are generated. The invention relates to a No. 13-15 tank, which intercepts and collects 2400 ten thousand tons of coloring and cleaning water containing nickel and tin, independently recovers nickel and tin containing waste residues, converts the nickel and tin containing waste residues into a nickel and tin salt coloring agent, and realizes zero discharge of the nickel and tin containing waste water and waste residues. The function of # 13-15 is as follows:

13# Nickel tin salt coloring tank (also called 13# tank)

The electrolytic coloring of nickel-tin salt can be carried out by coloring with bronze, imitation stainless steel color, champagne color and pure black color. The electrolytic coloring liquid of nickel-tin salt has good coloring dispersibility, and the formed colored film has uniform color, elegance and luxury, good sun resistance, corrosion resistance and wear resistance, and the coloring liquid has strong anti-fouling capability. The control parameters suitable for large-scale production are as follows:

6-12g/L stannous sulfate; nickel sulfate 20-30g/L (containing 6 crystal water); 15-20g/L of sulfuric acid;

tartaric acid 8-10 g/L; pH is 0.8-1.0; the temperature is 20-25 ℃; the time is 30s-15 min; the voltage is 14-16V;

(1) formula (II)

The coloring by the nickel-tin salt electrolyte not only has low cost and long service time, but also can obtain the color and quality which cannot be obtained by the single nickel salt or tin salt, thereby being deeply favored by the majority of aluminum manufacturers. However, like the monostannate coloration, stannous ions in nickel tin salt electrolytic coloring systems are extremely unstable. Even in an acidic solution having a pH of 1.0, oxygen electrolytically released from the air or from hydroxyl ions is easily oxidized to high-valent tin ions, and further hydrolyzed to form white stannic acid precipitates, which slightly affect the quality of the colored film and, if so, completely deactivate the coloring liquid. Therefore, the control is mainly focused on ensuring the stability of stannous ions and controlling the color tone.

The nickel-tin salt is colored, the tin salt is the main, and the coloring speed and uniformity are improved due to competitive reduction when the nickel-tin salt and the tin salt coexist. The nickel tin salt is less in dosage and more stable than the single tin salt, and the color tone of the nickel tin salt is yellow and transparent red. The nickel salt is preferably 20-30g/L, too high color is dark, but the pure black color is preferably raised to 45 g/L. In general, 6-8g/L of stannous salt is suitable. The lower limit is taken in summer, the upper limit is used in winter, and the pure black color is required to be increased to 10-12 g/L. The additive plays the roles of improving the uniformity, preventing the stannous from hydrolysis and the like, but the complexing ability of the current coloring tank is not enough, and the stannous can be oxidized and hydrolyzed as usual, so tartaric acid is added to complex stannous ions. The sulfuric acid has double functions of preventing hydrolysis of tin salt and raising electric conductivity, and free sulfuric acid is controlled in 15-20g/L preferably. Sulfuric acid is less glossy, the coloring speed and gloss of sulfuric acid are reduced too much, and the coloring speed is increased to 25g/L only when the coloring speed is too high, so that hydroxide is prevented from being generated on the surface. Some nickel tin salt coloring liquid is added with boric acid which has a buffering effect in holes, is beneficial to nickel electrodeposition, improves uniformity and improves color impression, preferably 20-25g/L, and has dark color when being too high.

Sn²⁺The ions are easily oxidized by all oxidants and then hydrolyzed into colloidal Sn (OH)₂And Sn (OH)₄Either settled on the bottom of the tank or suspended in the solution. During the coloring process, Sn is precipitated in several cases²⁺Oxidation and hydrolysis:

1. oxidation by agitation of the bath

In order to make the temperature and concentration of the bath solution uniform, the coloring bath solution should be stirred during production, and although a circulating pump is adopted to avoid direct stirring by air, the opportunity that the bath solution is contacted with air is increased, and the reaction that bivalent tin is oxidized into tetravalent tin occurs in the contact with air

SnSO₄+H₂SO₄+O＝H₂O+Sn(SO₄)₂↓ (2) type

2. Oxidation and hydrolysis occurring at electrode reaction

When the electrode is at the anode half-cycle, the reaction of losing electrons from hydroxyl to generate oxygen occurs:

4OH^--4e^-＝2O+2H₂o (3) formula

In the coloring process, Sn²⁺The oxygen generated in the reaction of the formula (3) is easily reacted with the oxygen in the electrode reaction to generate oxidation, and a turbid substance is generated according to the formula (2). In addition, the aluminum alloy is used as a cathode, and the hydrogen evolution reaction can cause the local pH value to rise, thereby promoting the Sn in the tank²⁺And Sn⁴ ⁺Ionic hydrolysis reaction

Sn²⁺+2OH^-＝Sn(OH)²↓ (4) type

Sn⁴⁺+4OH^-＝Sn(OH)⁴↓ (5) type

Due to the presence of the above reaction and Sn²⁺The longer the using period of the bath solution, the more serious the suspension turbidity. Good additives should have a certain combination of ability to protect against Sn²⁺The hydrolysis of ion precipitation also has the functions of accelerating ionization and improving dispersion capability. Otherwise, the coordination of complexing and ionization dynamic equilibrium is not good in the coloring process, Sn²⁺Poor deposition conditions in the pores affect the coloring efficiency and coloring tone.

The surface can be uniformly colored by adding additives such as magnesium sulfate, aluminum sulfate, ammonium thiosulfate and the like into the coloring liquid. The electrolytic coloring liquid mainly containing tin salt has the main problems of preventing or slowing down the oxidation of bivalent tin, improving the stability of the electrolytic coloring liquid and prolonging the service life of the electrolytic coloring liquid. In addition to additives such as tartaric acid, phenol, sulfuric acid, boric acid, etc., oxidation inhibitors such as ascorbic acid, biphenyl, hydroquinone, etc. may be added. Wherein the sulfuric acid can acidify the solution and reduce the pH value; the boric acid has buffering and complexing functions, and the tartaric acid, the citric acid and the ammonium tartrate can complex stannous ions and also have a buffering function on the pH value. The addition of thiourea or hydrazine sulfate can reduce tetravalent tin ions. Adding an agent which is oxidized instead of the stannous ion, such as ferrous ion, when the stannous ion and the ferrous ion coexistThe oxidation reaction of ferrous ions occurs before the oxidation reaction of stannous ions to tetravalent tin ions, thereby controlling the conversion of stannous ions to tetravalent tin ions. The additives added in the method are substances with buffering effect, complexing effect and antioxidation effect and can complex Sn²⁺Ions, or capable of being preferentially oxidized by dissolved oxygen in solution to prevent Sn²⁺The ions are oxidized to Sn by air⁴⁺Further, Sn (OH) is generated₄White precipitates affect the coloration.

By comprehensively considering the factors, the formula design of the coloring stabilizer must meet four requirements: 1. the uniformity of the coloring is improved; 2. preventing white spots and cracks from being generated; 3. stabilizing the stannous salt; 4. the conductivity of the electrolyte is improved.

In order to obtain the color uniformity of the stainless steel champagne color series aluminum profile, the technological parameters of the anodic oxidation tank need to be strictly controlled, the thickness of the oxidation film is required to be consistent, the smaller the deviation is, the better the deviation is, and the better the deviation is, the control is 12 μm. The anodizing time is determined according to the process parameter conditions of the anodizing bath. Furthermore, the coloration parameters must also be controlled:

(1) time and temperature

Experiments prove that the time of electrolytic coloring is accurate to the time calculated by seconds, and is determined according to the conditions of various process parameters of the electrolytic coloring tank. The difference of one second of coloring time has obvious influence on the color of champagne electrophoretic painting aluminum profiles, the coloring time is prolonged, the Sn content in the oxide film is increased, and the color of the oxide film is gradually deepened. The Sn content of the oxide film linearly increases with time, and the relation is that W is 4.4+2.5t (1 ≦ t ≦ 5).

The bath temperature of the electrolytic coloring bath can be regulated to be 20-25 ℃. When the temperature of the coloring bath solution rises, the conductivity of the coloring solution increases, and Sn²⁺The precipitation reaction speed is accelerated, and the coloring speed is accelerated. In addition, the increase of the coloring liquid temperature is not favorable for Sn²⁺The stability of (2). Sn (tin)²⁺The oxidation reaction speed of (2) increases as the temperature of the coloring liquid increases. Therefore, in order to ensure the color consistency of champagne electrophoretic painting aluminum profile, the temperature of the coloring bath solution is controlled well, and the smaller the fluctuation range is, the moreGood results are obtained.

(2) pH value

When the pH value of the coloring bath solution is about 1.0, the coloring speed is basically unchanged. When the pH is more than 1.1, the coloring speed is high and is difficult to control; if the pH is too small, the corrosion resistance of the colored film is adversely affected. Therefore, pH values of 0.8 to 1.0 are important factors for generating a uniform color of champagne-colored aluminum profiles.

(3) Voltage of

The voltage of the coloring liquid is controlled to be 14-16V (stainless steel color is 10-13V), and the current density is 0.6-0.8A/dm²And keeping the zero voltage for 1-1.5 min. Boost control is important, boosting the voltage by 1V approximately every 3 s. The coloring speed is greatly affected when the voltage is less than 14V or more than 16V.

(4) Washing with water

The anode is not accurately placed in the first washing tank after being oxidized, and the anode is colored when the anode is placed in the second washing tank for not more than 2min, so that the adverse effect of sulfuric acid in the washing tank on an oxidation film is avoided. The pH value of the second rinsing bath is required to be more than or equal to 3. After the coloring timing is finished, the cloth is lifted to be transferred to a next rinsing bath immediately and then is subjected to color matching, the cloth cannot stay in the coloring bath, and the lifting transfer time in the air is strictly controlled. The pH value of the colored rinsing bath is required to be more than or equal to 3. During the water washing process, the coloring metal salt in the pores of the film is easily attacked by acidic substances in water, resulting in discoloration.

From the coloring effect, the color of the nickel-tin salt is more beautiful than the color of the nickel salt or the tin salt which is singly used, and the heat resistance and the light resistance of the nickel-tin salt meet the requirements. When the stannous sulfate is less than 2g/L, the coloring speed is relatively slow, and when the stannous sulfate is increased to more than 5g/L, the coloring speed is obviously accelerated; the concentration range of nickel sulfate is wide.

14# running water wash tank and 15# running water wash tank (also called 14# tank and 15# tank)

The two rinsing tanks are provided for cleaning the residual coloring liquid carried out from the coloring tank. Tap water enters from the No. 15 tank and exits from the No. 14 tank and is connected in series in a reverse direction, the water consumption is about 2.0 to 3.0 tons per ton of wood, the water consumption is too large, and the discharged nickel-tin-containing wastewater increases the environmental protection treatment pressure. The control parameters suitable for large-scale production are as follows: no. 14 flowing water wash tank pH > 3.0; no. 15 flowing water wash tank pH > 5.5; (6) formula (II)

16# hole sealing groove

The purpose of the groove is to seal the micropores of the oxide film and ensure the corrosion resistance. The well-sealing tank can also be replaced by an electrophoresis tank. The hole sealing method is divided into high-temperature, medium-temperature and normal-temperature hole sealing according to the working temperature. The high-temperature hole sealing is to treat the aluminum material in pure water at 95-100 ℃, has good hole sealing quality, but has high energy consumption, large water evaporation capacity, easy ash hanging and easy impurity ion poisoning, and needs to frequently replace bath solution; the medium-temperature hole sealing is generally carried out by adopting a method of adding an additive into nickel acetate, the treatment is carried out at 55-65 ℃, the hole sealing speed is high, less ash is attached, the film is not cracked, but the hole sealing contains nickel and tin, and the environment is not protected; the normal temperature hole sealing adopts a method of adding additive into nickel fluoride, the hole sealing is processed at 25-35 ℃, the hole sealing speed is fast, less ash is attached, the energy consumption is low, and the use is convenient. But the film is easy to crack, and the fluorine and the nickel are not beneficial to environmental protection. At present, the medium-temperature hole sealing is taken as a main treatment method in China.

The indexes controlled by the medium-temperature hole sealing in the design are as follows:

quantitative and qualitative analysis for coloring recovery coloring agent of nickel-tin salt and utilization of reclaimed water

1) The 1L of recovery liquid of getting coloring nickel tin waste water collection tank contains stannous sulfate, nickel sulfate, tartaric acid and sulphuric acid, and the detection reagent concentration of this design is:

stannous sulfate 0.2g/L

Nickel sulfate 0.5g/L (containing 6 crystal water)

Tartaric acid 0.16g/L (8) formula

pH 3.15

Slowly adding liquid ammonia while stirring, and gradually increasing the pH value to change as follows:

when the pH value is lower than 7.0, the bath solution is turbid, the precipitation is increased, and stannous hydroxide and stannic hydroxide are separated out according to the formulas (4) and (5); at a pH between 7.0 and 7.5, the bath is more turbid and the precipitate contains green crystalline nickel hydroxide:

when the pH value is between 7.5 and 8.0, the bath solution is turbid, and the nickel hydroxide of the green crystal precipitate is increased;

when the pH is between 8.0 and 8.5, the bath solution is turbid, and the nickel hydroxide of the green crystal precipitate is increased;

when the pH value is between 8.5 and 9.0, the bath solution is turbid, and the nickel hydroxide of the green crystal precipitate is not increased any more;

when the pH value is between 9.0 and 10.0, the bath solution is turbid, and the nickel hydroxide of the green crystal precipitate is not increased any more.

According to the experimental result, the first reaction end point pH5.5-6.0 can be taken, solid-liquid separation is carried out, the tin hydroxide and the stannous hydroxide are recovered, and the filtrate contains nickel sulfate; adding liquid ammonia into the filtrate, taking the second reaction end point pH value to be 8.5-9.0, and recovering nickel hydroxide. Considering the range of the pH value of 3.0-6.0 in the first reaction stage, when liquid ammonia is added, the local pH value of the reaction liquid may exceed 7.5, so that the risk of generating nickel hydroxide is high, and nickel hydroxide may be mixed in the recovered tin hydroxide and stannous hydroxide, so that the separation is not good; in addition, the recovered tin hydroxide and stannous hydroxide need to be rinsed, the water consumption is too large, and an over-high threshold is preset for subsequent reclaimed water recycling, so that the method adopts one-step reaction, takes the pH value of 8.5-9.0 as a reaction end point, and directly recovers a solid mixture of the tin hydroxide, the stannous hydroxide and the nickel hydroxide for later use;

2) ammonium sulfate and ammonium tartrate did not precipitate and remained in the liquid. According to the formula (9), with the addition of liquid ammonia, the pH value is continuously raised, tin hydroxide, stannous hydroxide and nickel hydroxide are continuously separated out, but ammonium sulfate and ammonium tartrate are not decomposed and precipitated and are remained in the liquid;

3) and (4) carrying out solid-liquid separation, filtering out ammonium sulfate and ammonium tartrate along with the filtrate, and recovering a solid mixture of tin hydroxide, stannous hydroxide and nickel hydroxide. According to the formula (9), the reaction product is subjected to solid-liquid separation. The ammonium sulfate and the ammonium tartrate flow out along with the filtrate to obtain a solid mixture of the stannic hydroxide, the stannous hydroxide and the nickel hydroxide; rinsing and drying to obtain a mixture solid; the solubility of nickel hydroxide in the filtrate is 130mg/L, which is far higher than the discharge standard of 0.5mg/L, and secondary treatment is needed, so that the nickel hydroxide can reach the standard and be recycled;

4) and adding sulfuric acid (the concentration is 98 percent), converting a solid mixture of tin hydroxide, stannous hydroxide and nickel hydroxide, and reacting to generate a mixed solution of stannous sulfate and nickel sulfate. Weighing 100g of solid mixture of tin hydroxide, stannous hydroxide and nickel hydroxide obtained after rinsing and drying (only drying in a laboratory for metering and rinsing clean in mass production without drying, thereby saving the production cost), wherein according to the concentration of the medicament provided by the formula (8), about 44g of stannous hydroxide, 55g of nickel hydroxide and 1g of tin hydroxide are contained in 100g of mixed solid, and about 63g of stannous sulfate and about 156g of nickel sulfate (containing 6 crystal water) are generated through reaction. The reaction solution is designed according to the solubility of stannous sulfate of 330g/L and the solubility of nickel sulfate (containing 6 crystal water) of 625 g/L. 1g of tin powder and 300g of pure water are added, the mixture is uniformly mixed, sulfuric acid (with the concentration of 98%) is slowly added, and the reaction is as follows (tetravalent tin is reduced by the tin powder):

Sn(OH)₂+H₂SO₄＝SnSO₄+2H₂O

Ni(OH)₂+H₂SO₄＝NiSO₄+2H₂O (10)

Sn+Sn(OH)₄+2H₂SO₄＝2SnSO₄+4H₂O

taking excessive sulfuric acid, adding while detecting, and determining the reaction end point when the pH value of the reaction solution is 0.8-1.0. Filtering the reaction liquid, wherein the filter residue is residual tin powder, remaining in the reactor, and waiting for the next reaction; the filtrate is a mixed solution of stannous sulfate and nickel sulfate and is stored for later use;

5) and preparing the nickel-tin salt coloring liquid. Taking the stannous sulfate and nickel sulfate mixed solution produced in the formula (10), and controlling indexes of the nickel-tin salt coloring tank according to the formula (1), wherein the modification method comprises the following steps:

nickel sulfate concentration/stannous sulfate concentration 25/10(g/L)

Nickel sulfate/tartaric acid concentration 25/8(g/L) (11)

The concentration of nickel sulfate and stannous sulfate is titrated, the concentration of stannous sulfate is about 200g/L, the concentration of nickel sulfate is about 500g/L, and the concentration is lower than a saturation point, so that crystallization is avoided; adding corresponding agents according to the formula (11), adjusting the components of the agents, and preparing the nickel-tin salt coloring liquid. The chemical agent recovered from the 14# tank is compatible with the 13# nickel-tin salt coloring tank, so that the nickel-tin salt coloring liquid produced according to the formula (11) can be completely recycled to the 13# nickel-tin salt coloring tank;

6) and treating the filtrate to recover nickel phosphate and reuse the coloring and cleaning water. According to the formula (9), the nickel hydroxide has the solubility of 130mg/L which is far higher than the discharge standard of 0.5mg/L, needs secondary treatment and can reach the standard for recycling. (9) The filtrate of the formula (I) contains ammonium sulfate and ammonium tartrate, and contains 130mg/L of nickel hydroxide, and the concentration needs to be reduced to below 0.5 mg/L; adding phosphoric acid with the concentration of 85 wt.% into the filtrate, adjusting the pH value to be 8.5-9.0 to be 6.5-7.5, and reacting:

3Ni²⁺+2H₃PO₄＝(Ni)₃(PO₄)₂↓+6H²⁺ (12)

the solubility of the nickel phosphate is minus 31 times of 5 times 10, and the filtrate far reaches the recycling standard; filtering the nickel phosphate again, rinsing and drying to obtain a nickel phosphate product; the filtrate is an N-P compound fertilizer containing ammonium phosphate, ammonium sulfate and ammonium tartrate, and is used as a plant greening fertilizer to realize the recycling of coloring water.

Second, experimental results of recovery of colorant by coloring nickel tin salt

The series of experiments respectively examine the coloring ability of the nickel-tin salt colorant produced according to the formula (11) according to the coloring control index of the nickel-tin salt provided by the formula (1).

1. The effect of the stannous sulfate concentration (actually the colorant concentration according to equation (11)) on tintability. Taking stannous sulfate with the pH value of 1.0, the temperature of 25 ℃, 4g/L, 6g/L, 8g/L, 10g/L, 12g/L and 14 g/L; the thickness of the oxide film was 15 μm, the coloring time was 4 minutes, and the color of the aluminum material appearance was observed, and the results are shown in Table 1:

TABLE 1 Effect of stannous sulfate concentration on tinting strength

2. The effect of the coloration time on the coloration color. Taking 10g/L stannous sulfate (25 g/L nickel sulfate and 8g/L tartaric acid) according to the formula (11), keeping the temperature at 25 ℃, and keeping the pH value at 1.0; the thickness of the oxide film was taken to be 15 μm, and the coloring time was taken to be 6, 8, 10, 12, 14, and 16 minutes, and the results are shown in Table 2:

TABLE 2 Effect of different tinting times on color

Third, analysis of experimental results of coloring recycled colorant of nickel-tin salt and utilization of reclaimed water

According to the formulas (1) to (12) and experiments 1 to 2 and the detection results, the following analysis can be made:

1. according to the formula (9), adding liquid ammonia, carrying out online individual treatment on the collected nickel-tin-containing wastewater at the pH value of 8.5-9.0, recovering a solid mixture of tin hydroxide, stannous hydroxide and nickel hydroxide, converting the nickel-tin-containing solid hazardous waste into a high-value chemical raw material, and realizing the resource utilization of the solid hazardous waste;

2. adding sulfuric acid according to the formula (10), converting a recovered tin hydroxide, stannous hydroxide and nickel hydroxide solid mixture into a stannous sulfate and nickel sulfate mixed solution, and under the condition that tin powder and sulfuric acid are excessive, the reaction end point is 0.8-1.0 of the pH value, so that the requirement of subsequent conversion into a nickel-tin salt coloring agent is met;

3. converting a mixed solution of stannous sulfate and nickel sulfate into a liquid nickel-tin salt colorant according to the formula (11) by utilizing the principle that coloring agents are compatible with each other, and directly adding the liquid nickel-tin salt colorant into a 13# nickel-tin salt coloring tank; the manufacturing cost of the colorant is greatly saved;

4. according to the results of the series of experiments 1-2, the nickel tin salt colorant prepared according to the formula (11) can completely meet the coloring requirement within the control index range specified by the formula (1);

5. in the formula (12) in the presence of tin hydroxide, hydrogen oxideAdding phosphoric acid into the filtrate obtained after solid-liquid separation of the stannous chloride and nickel hydroxide solid mixture to convert residual Ni²⁺The residual nickel phosphate concentration is negative 31 th power of 5 multiplied by 10, and the filtrate far reaches the recycling standard; filtering the nickel phosphate again, rinsing and drying to obtain a nickel phosphate product; the filtrate is an N-P compound fertilizer containing ammonium phosphate, ammonium sulfate and ammonium tartrate, and is used as a plant greening fertilizer to realize the recycling of water for coloring the nickel-tin salt; and the fertilizer filter residue is nickel phosphate and is retained in the reaction container to wait for next recovery.

Example (b):

a method and a system for recycling coloring agent and reclaimed water by coloring and sealing nickel-tin salt relate to a large source of toxic waste residues generated in the aluminum processing industry, namely the toxic waste residues containing nickel and tin generated by oxidizing, coloring and sealing holes. The invention utilizes an online classification recovery method to intercept and collect coloring hole sealing cleaning water, recover and convert the coloring agent into coloring agent, recycle reclaimed water, block the pollution of nickel-tin-containing wastewater to a wastewater treatment center and reduce the discharge of industrial hazardous waste.

2000 ten thousand tons of extruded aluminum products are produced every year in China, the oxidation coloring hole sealing material accounts for more than 800 ten thousand tons, 4800 ten thousand tons of water is consumed for coloring hole sealing, 13.5 ten thousand tons of nickel-tin-containing waste residues are produced, and the problem of waste water and waste residues is very outstanding! The invention provides a brand new process design, nickel-containing wastewater is collected in an online classified manner, and 13.5 ten thousand tons of nickel hydroxide and stannous hydroxide are recovered and converted into a nickel-tin salt colorant; 4800 million tons of reclaimed water after recycling and treatment is converted into liquid N-P compound fertilizer, and the recycling of toxic waste is realized.

Example 1:

pumps

Further, in the 13# nickel tin salt coloring tank, the concentration of stannous sulfate is controlled to be 6-12g/L, the concentration of nickel sulfate is controlled to be 20-30g/L, the concentration of sulfuric acid is controlled to be 15-20g/L, the concentration of tartaric acid is controlled to be 8-10g/L, the pH value is controlled to be 0.8-1.0, the temperature is controlled to be 20-25 ℃, the treatment time is controlled to be 30s-15min, and the voltage is controlled to be 14-16V;

in No. 14 flowing water washing tank, pH is controlled to be pH > 3.0;

in # 15 running water wash tank, pH was controlled to pH > 5.5.

Furthermore, the flow of the water inlet of the No. 15 flowing water washing tank is adjusted according to the control indexes set by the No. 14 flowing water washing tank and the No. 15 flowing water washing tank, so that the water consumption for coloring and cleaning is reduced; intercepting the nickel-tin-containing wastewater of 14# flowing rinsing bath and 15# flowing rinsing bath, collecting coloring nickel-tin wastewater from a water outlet at the bottom of the 14# flowing rinsing bath, treating the nickel-tin-containing wastewater on line and independently, avoiding the trouble of retreating massive nickel-tin-containing wastewater after mixing with water used in other processes, and greatly reducing the environmental protection cost for treating the waste residue of the nickel-tin-containing wastewater.

Further, under the condition that the weight of pure water/the weight of the solid mixture is 3 and the tin powder is in proper excess, the saturated concentration of the stannous sulfate and the nickel sulfate in the reaction liquid is far lower, so that the stannous sulfate and the nickel sulfate are prevented from crystallizing and precipitating in the reaction liquid.

Further, the concentration of nickel sulfate and stannous sulfate is titrated, the concentration of stannous sulfate is about 177g/L, the concentration of nickel sulfate is about 577g/L, and the concentration is lower than a saturation point, so that crystallization is avoided; adding corresponding agents according to the concentration of nickel sulfate/stannous sulfate of 2.5 and the concentration of nickel sulfate/tartaric acid of 25/8, adjusting the components of the agents, preparing a nickel-tin salt coloring liquid, and recycling the nickel-tin salt coloring liquid to a 13# nickel-tin salt coloring tank to meet the coloring quality requirement of the aluminum alloy.

Furthermore, the solid mixture is only rinsed and not dried, and directly reacts with sulfuric acid after adding tin powder and pure water, so that the drying cost is greatly saved.

Furthermore, after the liquid nickel-tin salt colorant is reformed by using the mixed solution of stannous sulfate and nickel sulfate, the liquid nickel-tin salt colorant is not concentrated and crystallized and is directly used for slotting and adding a 13# nickel-tin salt coloring tank, so that the crystallization, separation and drying costs of the colorant are greatly saved.

A system for tints recovery of colorants and recycled water comprising: a nickel-tin wastewater collection system, a nickel-tin separation system, a nickel phosphate recovery system and an N-P compound fertilizer recovery system;

The system for the nickel-tin salt coloring recovery coloring agent and the reclaimed water utilization method comprises the following steps: a No. 14 flowing water washing tank, a pump 1, a coloring nickel tin wastewater collecting tank and a pump 2; the 14# flowing rinsing bath, the pump 1, the coloring nickel-tin wastewater collecting tank and the pump 2 are adjacently and sequentially connected; the No. 14 flowing water washing tank is filled with nickel-tin wastewater;

the compound fertilizer recovery tank is used for collecting secondary filtrate of the 2# filter press and sending the secondary filtrate to the filter; the pump 5 is used for collecting the secondary filtrate after the filter treatment to the greening fertilizer collector. The collected greening fertilizer can be transmitted to the green land needing to be cultivated, and the nutrition is provided for the vegetation at the green land.

Example 2 (working ability test of Nickel tin salt coloring solution produced by recovery)

According to figure 2, continuously producing the colored aluminum material, and continuously adding the recycled and manufactured coloring liquid into a 13# nickel-tin salt coloring tank according to the formula (1) control index; taking the coloring liquid with pH of 1.0, temperature of 25 deg.C, and stannous sulfate 5-10 g/L (other components calculated according to formula (12)); the thickness of the oxide film was taken to be 15 μm and the coloring time was taken to be 10 minutes, and the results are shown in the following Table 3:

TABLE 3 coloring effect of stannous sulfate of different concentrations on aluminum materials

The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.

Claims

1. The method for utilizing the coloring recovered coloring agent and the reclaimed water of the nickel-tin salt is characterized by comprising the following steps of: nickel-tin wastewater treatment operation, nickel phosphate recovery operation and N-P compound fertilizer recovery operation;

(2) the nickel phosphate recovery operation comprises: closing the valve 9 and the valve 11, opening the valve 8 and the valve 10, starting the pumps 4 and 2# to electrically stir, and circulating the reaction liquid; slowly opening the valve 9, sucking phosphoric acid in the phosphoric acid tank into the pump 4, and fully mixing the reaction liquid by utilizing the high-speed rotation of the pump 4; adding phosphoric acid, detecting the pH value of the reaction solution, closing the valve 9 when the pH value reaches 6.5-7.5, stopping adding the chemicals, and continuously and circularly stirring for 1 hour; opening the No. 2 filter press, opening the valve 11, closing the valve 10, and performing solid-liquid separation on the nickel phosphate and the secondary filtrate; repeatedly spraying and rinsing the nickel phosphate solid for 10 minutes, recovering a nickel phosphate product, and enabling secondary filtrate to flow into a compound fertilizer recovery tank;

2. The tinplate colorant recovery and mid-water utilization process as claimed in claim 1, wherein the pH is controlled to a pH >3.0 in a 14# running water wash tank.

3. The coloring recovery coloring agent for nickel-tin salt and the method for utilizing the medium water according to claim 1, wherein in the nickel-tin wastewater treatment operation, the nickel-tin solid contains tin hydroxide, stannous hydroxide and nickel hydroxide solid, and pure water, tin powder and sulfuric acid are added to the recovered nickel-tin solid and converted into stannous sulfate and nickel sulfate; adding proper excess sulfuric acid, wherein the reaction end point is that the pH value reaches 0.8-1.0; under the condition that (pure water weight/solid mixture weight) is 3 and tin powder is in proper excess, precipitating and filtering reaction liquid to obtain an unsaturated solution and filter residue which are mixed by stannous sulfate and nickel sulfate; the pH value of the unsaturated solution is 0.8-1.0, the content is lower than the saturation point, and the liquid nickel-tin salt colorant can be prepared; and the filter residue is tin powder and is retained in the reactor to wait for the next reaction.

4. The method for utilizing coloring recovered coloring agent and reclaimed water of nickel-tin salt according to claim 3, wherein in the operation of treating the nickel-tin wastewater, the liquid coloring agent of nickel-tin salt is prepared by using stannous sulfate and nickel sulfate, the content of the unsaturated mixed solution of stannous sulfate and nickel sulfate is titrated, and then the ratio of the chemical agent is adjusted according to the ratio of (nickel sulfate concentration/stannous sulfate concentration) being 2.5 and (nickel sulfate concentration/tartaric acid concentration) being 25/8, so as to convert the unsaturated mixed solution of stannous sulfate and nickel sulfate into the liquid coloring agent of nickel-tin salt.

5. The method for utilizing the coloring recovered coloring agent and the reclaimed water of the nickel-tin salt according to claim 4, wherein when the recovered nickel-tin solid is converted into the mixed solution of the stannous sulfate and the nickel sulfate, the recovered nickel-tin solid is directly reacted with the sulfuric acid after rinsing, adding the tin powder and the pure water.

6. The method for utilizing the recycled coloring agent and the reclaimed water of the nickel-tin salt according to claim 5, wherein the liquid coloring agent of the nickel-tin salt is prepared by using the mixed solution of the stannous sulfate and the nickel sulfate, and is directly used for slotting and adding a 13# coloring tank of the nickel-tin salt without concentration and crystallization.

7. A system for implementing the nickel tin salt coloring recovery colorant and the method for utilizing reclaimed water according to any one of claims 1 to 6, which comprises: a nickel-tin wastewater collection system, a nickel-tin separation system, a nickel phosphate recovery system and an N-P compound fertilizer recovery system;

the N-P compound fertilizer recovery system is used for collecting secondary filtrate, and collecting the collected secondary filtrate into a greening fertilizer after filtering operation;

nickel tin effluent collecting system includes: a No. 14 flowing water washing tank, a pump 1, a coloring nickel tin wastewater collecting tank and a pump 2; the 14# flowing rinsing bath, the pump 1, the coloring nickel-tin wastewater collecting tank and the pump 2 are adjacently and sequentially connected; the No. 14 flowing water washing tank is filled with nickel-tin wastewater;

8. The system for the coloring recovery colorant of nickel-tin salt and the utilization method of reclaimed water as claimed in claim 7, wherein the recovery tank for nickel-tin salt is provided with # 1 electric stirring, and the recovery tank for nickel phosphate is provided with # 2 electric stirring.