CN109137037B - Nickel-tin salt coloring recovery coloring agent and reclaimed water utilization method - Google Patents
Nickel-tin salt coloring recovery coloring agent and reclaimed water utilization method Download PDFInfo
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- CN109137037B CN109137037B CN201810842559.7A CN201810842559A CN109137037B CN 109137037 B CN109137037 B CN 109137037B CN 201810842559 A CN201810842559 A CN 201810842559A CN 109137037 B CN109137037 B CN 109137037B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/14—Producing integrally coloured layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/20—Electrolytic after-treatment
- C25D11/22—Electrolytic after-treatment for colouring layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
- C25D21/18—Regeneration of process solutions of electrolytes
Abstract
The method for utilizing the coloring recovered coloring agent and the reclaimed water of the nickel-tin salt comprises the following steps: steps (1) to (4); wherein, the control indexes of the step (1) are as follows: 13# nickel tin salt staining bath: controlling the concentration of stannous sulfate to be 6-12g/L, the concentration of nickel sulfate to be 20-30g/L, the concentration of sulfuric acid to be 15-20g/L, the concentration of tartaric acid to be 8-10g/L, the pH to be 0.8-1.0, the temperature to be 20-25 ℃, the treatment time to be 30s-15min and the voltage to be 14-16V; pH >3.0 in # 14 running water wash tank; pH >5.5 in No. 15 running water wash tank; the method can be used for online and independent treatment of the nickel-tin-containing wastewater according to the set control index, avoids the trouble of treating massive nickel-tin-containing wastewater after mixing with water used in other processes, and reduces the environmental protection cost for treating the waste residue of the nickel-tin-containing wastewater.
Description
Technical Field
The invention relates to the technical field of aluminum material processing, in particular to a method for coloring and recycling a nickel-tin salt coloring colorant and neutralizing water.
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 construction, 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. 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 of aluminum industry includes the procedures of electrolysis, casting, pressure processing, surface treatment and the like, and all the procedures can generate waste gas, waste water and waste residues with different degrees 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.
Modern aluminum processing enterprises have urgent need for treatment of nickel-containing wastewater and waste residue generated by oxidation hole sealing, while the traditional method for mixing and then treating cleaning water is too simple, a large amount of nickel-containing wastewater and waste residue are generated, the society pays expensive environmental protection cost for treating the wastewater and waste residue, and new technology is urgently required to be developed for treating the nickel-containing wastewater in the hole sealing process independently.
Disclosure of Invention
The invention aims to provide a method for utilizing coloring recovery coloring agent and reclaimed water of nickel-tin salt, which solves the problems.
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:
(1) setting control indexes for a 13# nickel-tin salt coloring tank, a 14# flowing rinsing tank and a 15# flowing rinsing tank, adjusting the flow of a water inlet of the 15# tank, and reducing the water consumption for coloring and cleaning;
(2) intercepting the nickel-tin-containing wastewater in the No. 13 nickel-tin salt coloring tank in a No. 14 flowing water washing tank and a No. 15 flowing water washing tank, and collecting the wastewater into a reaction tank from a water outlet at the bottom of the No. 14 flowing water washing tank;
(3) adding liquid ammonia into the nickel-tin-containing wastewater collected by the reaction tank, and reacting to generate a solid-liquid mixture containing stannic hydroxide, stannous hydroxide and nickel hydroxide at a pH value of 8.5-9.0;
(4) carrying out solid-liquid separation, rinsing and drying on the solid-liquid mixture obtained in the step (3) to obtain a solid mixture of tin hydroxide, stannous hydroxide and nickel hydroxide;
wherein, the control indexes of the step (1) are as follows: 13# nickel tin salt staining bath: 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 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; 14# running water wash at pH > 3.0; in # 15 running water wash tank, pH > 5.5.
Further, adding pure water, tin powder and sulfuric acid to the solid mixture of tin hydroxide, stannous hydroxide and nickel hydroxide in the step (4) to convert 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 unsaturated solution and filter residue 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.
Furthermore, the liquid nickel-tin salt colorant is prepared by using stannous sulfate and nickel sulfate, the content of the mixed unsaturated solution of stannous sulfate and nickel sulfate is firstly titrated, 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, the mixed unsaturated solution of stannous sulfate and nickel sulfate is converted into the liquid nickel-tin salt colorant, and the liquid nickel-tin salt colorant is directly added into the 13# nickel-tin salt colorant tank.
Further, phosphoric acid is added into the filtrate after the solid-liquid separation of the solid mixture of tin hydroxide, stannous hydroxide and nickel hydroxide, the pH value of the filtrate is adjusted to 6.5-7.5, and residual Ni is converted2+Is nickel phosphate, and the concentration of the residual nickel phosphate is 5 × 10-31(ii) a Filtering the nickel phosphate, rinsing and drying to obtain a nickel phosphate product.
Further, the filtrate after the solid-liquid separation of the nickel phosphate is converted into an N-P compound fertilizer containing ammonium phosphate, ammonium sulfate and ammonium tartrate and having a pH value of between 6.5 and 7.5, and the N-P compound fertilizer is used for plant area greening vegetation fertilization.
Furthermore, when the solid-liquid separation of the nickel phosphate is carried out, the filter residue is kept in the reaction vessel as the nickel phosphate and waits for the next recovery.
Further, when the solid mixture of tin hydroxide, stannous hydroxide and nickel hydroxide in the step (4) 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, and drying is not needed.
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 directly used for slotting and adding a 13# nickel-tin salt coloring tank without concentration and crystallization.
The invention has the beneficial effects that:
according to the control indexes set by the 13# nickel-tin salt coloring tank, the 14# flowing water washing tank and the 15# flowing water washing tank, the flow of the water inlet of the 15# flowing water washing tank is adjusted, and the water consumption for coloring and cleaning is reduced; intercepting the nickel-tin-containing wastewater of the 14# flowing water washing tank and the 15# flowing water washing tank, collecting the nickel-tin-containing wastewater from a water outlet at the bottom of the 14# flowing water washing tank into a reaction tank, treating the nickel-tin-containing wastewater on line and independently, avoiding the trouble of treating the nickel-tin-containing wastewater in large quantities after mixing with other process water, and greatly reducing the environmental protection cost for treating the waste residue of the nickel-tin-containing wastewater.
Drawings
FIG. 1 is a flow chart of a process for recovering colorants for nickel tin salt coloration and for utilizing mid-water;
FIG. 2 is a schematic illustration of the discharge of oxidation line wastewater to a wastewater center for one 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 5 percent of the total amount of the waste residues generated by surface treatment of aluminum processing enterprises, about 7.5 ten thousand tons, and simultaneously relate to 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 the 13# is a nickel-tin salt coloring tank containing stannous sulfate and nickel sulfate, the subsequent 14# and 15# flowing water washing tanks bring nickel-tin-containing wastewater into a wastewater treatment center, 2.25 million tons of water in the whole industry are polluted, and 150 million tons of mixed toxic wastewater 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 waste residues containing nickel and tin, converts the waste residues into a nickel and tin salt coloring agent, and realizes zero discharge of waste water and waste residues containing nickel and tin. The function of # 13-18 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 color film has uniform color, elegance and nobility, good sun resistance, corrosion resistance and wear resistance, and the coloring liquid has strong anti-pollution 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)
Sulfuric acid 15-20g/L
Tartaric acid 8-10g/L
pH 0.8-1.0 (1)
The temperature is 20-25 DEG C
The time is 30s-15min
Voltage 14-16V
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 groups is easily oxidized to high-valent tin ions, and further hydrolyzed to form white stannic acid precipitates, which may adversely affect the quality of the colored film and may lead to complete failure of 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 and 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 prior coloring tank has insufficient complexing ability, and the stannous can be oxidized and hydrolyzed as usual, so that 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 color is pure black, 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 during the contact with air
SnSO4+H2SO4+O＝H2O+Sn(SO4)2↓ (2)
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)
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)
Sn4++4OH＝Sn(OH)4↓ (5)
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 combinationAbility to prevent both 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 conditions for ion deposition in the pores affect coloring efficiency and coloring hue.
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 the quaternary tin ions. An agent, such as ferrous ion, is added to replace the oxidation of the stannous ion, that is, when the divalent stannic ion and the ferrous ion coexist, the oxidation of the ferrous ion occurs before the oxidation of the divalent stannic ion to the tetravalent stannic ion, thereby controlling the conversion of the divalent stannic ion to the tetravalent stannic ion. The additives are substances with buffering, complexing and antioxidant effects, 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 coloring time of one second has obvious influence on the color of champagne electrophoretic painting aluminum sections, 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+ 2.5 t (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 profiles, the temperature of the coloring bath solution is well controlled, and the smaller the fluctuation range, the better.
(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 fast and 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 2/L, the coloring speed is relatively slow, and when the coloring speed is increased to more than 5/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 and protecting the hole sealing tank. Tap water enters from the No. 15 tank and exits from the No. 14 tank and is reversely connected in series, 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 washing tank and No. 15 flowing water washing tank
pH>3.0 pH>5.5 (6)
16# hole sealing groove (also called 16# groove)
The purpose of the groove is to seal the micropores of the oxide film and ensure the corrosion resistance. An electrophoresis tank may be used instead of the well sealing 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 medium-temperature hole sealing control indexes are as follows:
17# and 18# running water washing tanks (also called 17# tank and 18# tank)
The two rinsing baths are arranged for cleaning the hole sealing bath to bring out a residual agent containing nickel, so that the aluminum product is protected from being corroded after leaving the factory. Similarly, tap water enters from the No. 18 tank and exits from the No. 17 tank and is reversely connected in series, 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-containing wastewater increases the environmental protection treatment pressure.
After the aluminum material is processed by 18 slots, the aluminum material can be packaged and delivered out of a factory to finish the anodic oxidation treatment.
The invention is realized according to the following theoretical basis, quantitative and qualitative analysis and medicament compatible design.
Quantitative and qualitative analysis of utilization of coloring recovery coloring agent and reclaimed water of nickel-tin salt
1) Taking 1L of recovery liquid of the reaction tank, containing stannous sulfate, nickel sulfate, tartaric acid and sulfuric acid, and detecting the concentration of the medicament:
stannous sulfate 0.2g/L
Nickel sulfate 0.5g/L (containing 6 crystal water)
Tartaric acid 0.16g/L (8)
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:
NH3+H2O＝NH4OH
Sn2++2OH＝Sn(OH)2↓ (9)
Sn4++4OH＝Sn(OH)4↓
Ni2++2NH4OH＝2NH4 ++Ni(OH)2↓
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 the tin hydroxide, the stannous hydroxide and the nickel hydroxide. According to the formula (9), the reaction product is subjected to solid-liquid separation. The ammonium sulfate and the tartaric acid ammonium flow out along with the filtrate to obtain a solid mixture of tin hydroxide, stannous hydroxide and 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. 100g of solid mixture of tin hydroxide, stannous hydroxide and nickel hydroxide obtained after rinsing and drying is weighed (only drying is carried out during laboratory measurement, rinsing is carried out during mass production, drying is not needed, and the production cost is saved), 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, stannous sulfate is generated through reaction, and about 63g of nickel sulfate (containing 6 crystal water) is generated. 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. Adding 1g of tin powder, adding 300g of pure water, uniformly mixing, slowly adding sulfuric acid (with the concentration of 98%), and reacting 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. Because the chemical agent recovered from the 14# tank is compatible with the 13# nickel-tin salt coloring tank, 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.
Experimental results of coloring and recovering coloring agent by 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 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 results of taking the oxide film with a thickness of 15 μm and coloring times of 6, 8, 10, 12, 14 and 16 minutes are shown in Table 2:
TABLE 2 Effect of different tinting times on color
Fourth, 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 standard provided by the formula (6), the water for coloring and cleaning the nickel-tin salt can be intercepted on line; adjusting the inlet water flow of the No. 15 tank, and controlling the total amount of the nickel-tin containing wastewater to be treated; collecting nickel-tin-containing wastewater at a water outlet of the No. 14 tank, and feeding the nickel-tin-containing wastewater into a reaction tank;
2. 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;
3. 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;
4. 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;
5. 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);
6. according to the formula (12), phosphoric acid is added into the filtrate obtained after the solid-liquid separation of the solid mixture of tin hydroxide, stannous hydroxide and nickel hydroxide 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 the nickel phosphate productPreparing a product; the filtrate is an N-P compound fertilizer containing ammonium phosphate, ammonium sulfate and ammonium tartrate, and is used as a green fertilizer material in a plant area 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 1:
the method for utilizing the coloring recovered coloring agent and the reclaimed water of the nickel-tin salt comprises the following steps:
(1) setting control indexes for a 13# nickel-tin salt coloring tank, a 14# flowing rinsing tank and a 15# flowing rinsing tank, adjusting the flow of a water inlet of the 15# tank, and reducing the water consumption for coloring and cleaning;
(2) intercepting the nickel-tin-containing wastewater in the No. 13 nickel-tin salt coloring tank in a No. 14 flowing water washing tank and a No. 15 flowing water washing tank, and collecting the wastewater into a reaction tank from a water outlet at the bottom of the No. 14 flowing water washing tank;
(3) adding liquid ammonia into the nickel-tin-containing wastewater collected by the reaction tank, and reacting to generate a solid-liquid mixture containing stannic hydroxide, stannous hydroxide and nickel hydroxide at a pH value of 8.5-9.0;
(4) carrying out solid-liquid separation, rinsing and drying on the solid-liquid mixture obtained in the step (3) to obtain a solid mixture of tin hydroxide, stannous hydroxide and nickel hydroxide;
wherein, the control indexes of the step (1) are as follows: 13# nickel tin salt staining bath: 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 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; 14# running water wash at pH > 3.0; in # 15 running water wash tank, pH > 5.5.
Further, adding pure water, tin powder and sulfuric acid to the solid mixture of tin hydroxide, stannous hydroxide and nickel hydroxide in the step (4) to convert 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 unsaturated solution and filter residue 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.
Furthermore, the liquid nickel-tin salt colorant is prepared by using stannous sulfate and nickel sulfate, the content of the mixed unsaturated solution of stannous sulfate and nickel sulfate is firstly titrated, 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, the mixed unsaturated solution of stannous sulfate and nickel sulfate is converted into the liquid nickel-tin salt colorant, and the liquid nickel-tin salt colorant is directly added into the 13# nickel-tin salt colorant tank.
Further, phosphoric acid is added into the filtrate after the solid-liquid separation of the solid mixture of tin hydroxide, stannous hydroxide and nickel hydroxide, the pH value of the filtrate is adjusted to 6.5-7.5, and residual Ni is converted2+Is nickel phosphate, and the concentration of the residual nickel phosphate is 5 × 10-31(ii) a Filtering the nickel phosphate, rinsing and drying to obtain a nickel phosphate product.
Further, the filtrate after the solid-liquid separation of the nickel phosphate is converted into an N-P compound fertilizer containing ammonium phosphate, ammonium sulfate and ammonium tartrate and having a pH value of between 6.5 and 7.5, and the N-P compound fertilizer is used for plant area greening vegetation fertilization.
Furthermore, when the solid-liquid separation of the nickel phosphate is carried out, the filter residue is kept in the reaction vessel as the nickel phosphate and waits for the next recovery.
Further, when the solid mixture of tin hydroxide, stannous hydroxide and nickel hydroxide in the step (4) 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, and drying is not needed.
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 directly used for slotting and adding a 13# nickel-tin salt coloring tank without concentration and crystallization.
Example 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 coloring liquid, pH1.0, temperature 25 deg.C, stannous sulfate 5-10 g/L (other components calculated according to formula (12)); the results are shown in the following table, taking an oxide film thickness of 15 μm and a coloration time of 10 minutes:
TABLE 3 Effect of stannous sulfate on appearance color
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 other specific embodiments of the present invention without inventive efforts, which shall fall within the scope of the present invention.
Claims (6)
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:
(1) setting control indexes for a 13# nickel-tin salt coloring tank, a 14# flowing rinsing tank and a 15# flowing rinsing tank, adjusting the flow of a water inlet of the 15# tank, and reducing the water consumption for coloring and cleaning;
(2) intercepting the nickel-tin-containing wastewater in the No. 13 nickel-tin salt coloring tank in a No. 14 flowing water washing tank and a No. 15 flowing water washing tank, and collecting the wastewater into a reaction tank from a tank bottom water outlet of the No. 14 flowing water washing tank;
(3) adding liquid ammonia into the nickel-tin-containing wastewater collected by the reaction tank, and reacting to generate a solid-liquid mixture containing tin hydroxide, stannous hydroxide and nickel hydroxide at a pH value of 8.5-9.0;
(4) carrying out solid-liquid separation, rinsing and drying on the solid-liquid mixture obtained in the step (3) to obtain a solid mixture of tin hydroxide, stannous hydroxide and nickel hydroxide; adding phosphoric acid into the filtrate obtained after solid-liquid separation of the solid mixture of tin hydroxide, stannous hydroxide and nickel hydroxide, adjusting the pH value of the filtrate to 6.5-7.5, and converting residual Ni2+Is nickel phosphate; filtering the nickel phosphate, rinsing and drying to obtain a nickel phosphate product; the filtrate after solid-liquid separation of nickel phosphate is converted into ammonium phosphate, ammonium sulfate and ammonium tartrate with pH value of 6.5-7.5The N-P compound fertilizer is used for plant greening vegetation fertilization;
wherein, the control indexes of the step (1) are as follows: 13# nickel tin salt staining bath: controlling the concentration of stannous sulfate to be 6-12g/L, the concentration of nickel sulfate to be 20-30g/L, the concentration of sulfuric acid to be 15-20g/L, the concentration of tartaric acid to be 8-10g/L, the pH to be 0.8-1.0, the temperature to be 20-25 ℃, the treatment time to be 30s-15min and the voltage to be 14-16V; 14# running water wash at pH > 3.0; in # 15 running water wash tank, pH > 5.5.
2. The coloring recovery colorant for nickel tin salts and the method for utilizing reclaimed water according to claim 1, characterized in that pure water, tin powder and sulfuric acid are added to the solid mixture of tin hydroxide, stannous hydroxide and nickel hydroxide in the step (4) to be converted into stannous sulfate and nickel sulfate; the sulfuric acid is added in a suitable excess, the end point of the reaction is that the pH reaches = 0.8-1.0; under the conditions that the weight of pure water/the weight of the solid mixture =3 and the tin powder is in proper excess, precipitating and filtering the reaction liquid to obtain an unsaturated solution and filter residue mixed by stannous sulfate and nickel sulfate; the unsaturated solution has pH value =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.
3. The method for utilizing the reclaimed coloring agent and the reclaimed water according to claim 2 is characterized in that stannous sulfate and nickel sulfate are utilized to prepare a liquid nickel-tin salt coloring agent, the content of a mixed unsaturated solution of the stannous sulfate and the nickel sulfate is firstly titrated, then the ratio of the agent is adjusted according to the concentration of the nickel sulfate/the concentration of the stannous sulfate being 2.5 and the concentration of the nickel sulfate/the concentration of the tartaric acid being 25/8, the mixed unsaturated solution of the stannous sulfate and the nickel sulfate is converted into the liquid nickel-tin salt coloring agent, and the liquid nickel-tin salt coloring agent is directly added into a 13# nickel-tin salt coloring tank.
4. The method for utilizing coloring recovered coloring agent and reclaimed water of nickel-tin salt according to claim 1, wherein the filter residue is retained in the reaction vessel as nickel phosphate during solid-liquid separation of nickel phosphate, and is waited for the next recovery.
5. The method for utilizing the coloring recovered colorant and reclaimed water of the nickel-tin salt according to claim 2, wherein when the solid mixture of the tin hydroxide, the stannous hydroxide and the nickel hydroxide in the step (4) is converted into the mixed solution of the stannous sulfate and the nickel sulfate, the recovered nickel-tin solid is directly reacted with sulfuric acid after rinsing, adding tin powder and pure water, and drying is not needed.
6. The method for utilizing the recycled coloring agent and the reclaimed water for the nickel-tin salt according to claim 2, wherein the liquid coloring agent for the nickel-tin salt is prepared from a mixed solution of stannous sulfate and nickel sulfate, and is directly used for grooving and adding a 13# coloring tank for the nickel-tin salt without concentration and crystallization.
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| CN108193251A (en) * | 2017-12-29 | 2018-06-22 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | The medicament recovery system and method for the coloring of nickel pink salt and medium temperature sealing of hole in aluminium processing |
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| CN101636353A (en) * | 2007-03-27 | 2010-01-27 | 麦克德米德尖端有限公司 | Method of recycling electroless nickel waste |
| CN108193251A (en) * | 2017-12-29 | 2018-06-22 | 佛山市三水雄鹰铝表面技术创新中心有限公司 | The medicament recovery system and method for the coloring of nickel pink salt and medium temperature sealing of hole in aluminium processing |
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