CN108193251A - The medicament recovery system and method for the coloring of nickel pink salt and medium temperature sealing of hole in aluminium processing - Google Patents

Abstract

The medicament recovery system and method for the coloring of nickel pink salt and medium temperature sealing of hole in being processed the invention discloses aluminium, include nickeliferous tin waste water retention unit, nickeliferous tin wastewater collection unit, tin ion recovery unit and nickel ion recovery unit successively from upstream to downstream, the nickeliferous tin waste water retention unit includes the 13# nickel pink salt being arranged in order coloring slot, 14# flowings rinsing bowl, 15# high-pressure atomizations spray groove, 16# medium temperature sealing of holes slot, 17# flowing rinsing bowls and 18# flowing rinsing bowls.The toxic waste residue of nickeliferous tin that heat-tinting sealing of hole generates in being processed for aluminium; utilize online classification recycling and compatibility method, selected dosage component, ingenious configuration system; ensure that nickeliferous tin product reuse to the 13# nickel pink salt of recycling colours slot, realize that the resource recycling of toxic waste utilizes.Can heat-tinting sealing of hole generates in the processing of online processing aluminium about 16,000,000 tons of nickeliferous tin waste water, convert about 40,000 tons of the toxic waste residue of nickeliferous tin, about 100,000 tons of generation nickel pink salt colorant.

Description

The medicament recovery system and method for the coloring of nickel pink salt and medium temperature sealing of hole in aluminium processing

Technical field

The present invention relates to the medicaments of the coloring of nickel pink salt and medium temperature sealing of hole in aluminium manufacture field more particularly to aluminium processing to recycle system System and method.

Background technology

Aluminium and aluminium alloy have many advantages, such as that processing performance is excellent, corrosion resistance is good, surface aesthetic, the rate of recovery are high, in building, hand over The industries such as logical transport, machinery, electric power are applied widely, and it is more obvious to expand aluminium application trend for steel in recent years with aluminium.Aluminium Processing industry is conventional industries, even more the rising industry full of vitality.According to statistics, year consumes aluminium per capita for European and American developed countries More than 32kg, and China only has 13kg or so per capita, only 1/3rd or so of developed country, domestic aluminium consumption are also huge Big growth space, but the problem of under economic new normality, energy consumption is high, total amount of pollutants discharged is big, resource recycling rate is low As the bottleneck and obstacle of industry development.

Aluminium industry production includes the processes such as electrolysis, founding, pressure processing, surface treatment, and each process can difference during production Degree generates waste water, waste residue.A large amount of aluminium ash is generated when electrolysis and founding, extrusion process, which has, stews mould alkaline waste liquor, surface treatment Process generates all kinds of waste water and dregs containing the complicated components such as acid, alkali, treatment agent and chromium, nickel heavy metal ion.

(1) Aluminum waste residue source

1st, electrolysis founding aluminium ash

Aluminium ash results from the electrolysis, melting and casting process of aluminium and aluminium alloy, and aluminium total losses amount is in 1- caused by aluminium ash 12%.Often process one ton of primary aluminum, about generate 20-40kg aluminium ash, yield is less during molten aluminum direct founding, during aluminium ingot remelting amount compared with It is more, and regenerate one ton of aluminium scrap and about generate 100-250kg aluminium ash.Aluminium ash can be divided into two kinds：One kind is secondary aluminium ash, is former in electrolysis Aluminium and casting etc. do not add the scum silica frost generated during salt flux and skimming, and main component is metallic aluminium and aluminum oxide, and aluminium contains Amount is differed up to 15%-70%, and color is white；Another kind is Quadratic aluminum dust, is that a secondary aluminium ash carries the waste after alum recovery, Aluminium content is low compared with a secondary aluminium ash, generally in grey black.Quadratic aluminum dust complicated component contains metallic aluminium (5-30%), aluminium oxide (30-70%), silica and di-iron trioxide (5-15%), the chloride (10-30%) of potassium sodium calcium and magnesium and nitrogen fluorine arsenic etc. Poisonous and harmful element.If Fig. 1 is aluminium ash composition examining report.Alleged aluminium ash refers both to Quadratic aluminum dust below.

National 32,500,000 tons of electrolytic aluminium yield in 2016, squeezes and calendering processing aluminum materials yield is more than 20,000,000 tons, every year The aluminium ash quantity conservative estimation in the whole nation more has data to think aluminium ash total amount in ten thousand tons of 600-850 at 2,000,000 tons or more.Aluminium ash is one The reproducible resource of kind, there is higher comprehensive reutilization to be worth, but do not obtain enough attention always, causes huge The wasting of resources.Simultaneously because, containing poisonous and harmful substances such as fluoride, ammonia nitrogen, arsenic, being listed in danger wastes in aluminium lime-ash, Version in 2016《National Hazard waste register》The waste classification of middle aluminium ash is HW48, hazard property T (Toxicity)-toxicity risk Waste.The recycling of China's aluminium ash at present lacks that technology maturation is reliable, recovery method of good economy performance still in the starting stage, aluminium The ash processing rate of recovery is low, energy consumption and waste are big, and utilization ways are few.Execution from 1 day January in 2018《The Chinese people are total to With state's environmental protection tax law》Regulation, aluminium ash discharge enterprise will pay 1000 yuan/ton of environment protection tax.

2nd, compressive surface processing waste water and dregs

The production of aluminium fabricated product will consume a large amount of water, often produce 1 ton of aluminium and at least consume 15 tons of water, the life of whole industry year 10,000,000 tons of squeeze wood is produced, nearly 300,000,000 tons of waste discharge generates about 3,000,000 tons of waste residue after wastewater treatment, quantity is extremely surprising.

2.1st, it squeezes and stews mould waste liquid waste water and dregs

Extruding die for aluminum shaped material will be put into high-concentration alkali liquor after and carry out pot mould, and the reactive aluminum in die cavity is corroded Fall.The concentration of sodium hydroxide in mould liquid is stewed up to 250-350g/L, with the progress of reaction, aluminium composition constantly increases, when up to To more than 60-70g/L, when reaction speed is substantially reduced, it must will just stew mould waste liquid and exhaust.The processing for stewing mould waste liquid is generally taken The mode of " treatment of wastes with processes of wastes against one another "：It is neutralized with the spent acid that oxidation operation generates, the waste residue amount that this processing mode generates is very big, stews mould Waste residue is with regard to that can account for 30% or so of the total quantity of slag of enterprise.Enterprise not only without using its economic value, increasing cost, giving up instead Water, waste residue are treated as heavy environmental burden.

2.2nd, surface treatment waste water waste residue

Aluminium is enhancing anti-corrosive properties and decoration performance, to be surface-treated.Common surface treatment mode has anodic oxygen Change coloring, electrophoretic coating, powder spray, F-C paint spraying etc..Surface treatment process generates the waste water of a large amount of complicated components.

It is divided by process, the waste water and dregs of anodic oxidation and electrophoretic coating process have：The alkaline waste water that Alkaline etchant generates gives up Slag accounts for the 20% of total quantity of slag；The acid waste water waste residue that oxidation solution generates, accounts for the 30% of total quantity of slag；The acidity that spraying process generates Waste water and dregs account for the 20% of total quantity of slag.Aluminium processing enterprise waste water center aluminium slag source is subdivided into：It stews mould waste liquid alkaline residue and accounts for total quantity of slag 30%, Alkaline etchant alkaline residue accounts for the 20% of total quantity of slag, and oxidation solution acid sludge accounts for the 30% of total quantity of slag, and spraying acid waste residue accounts for total quantity of slag 20%.

Contain Al in waste water³⁺、Na⁺、NH₄ ⁺、Ni₂ ⁺、Sn²⁺、Cr⁶⁺Wait cations, SO₄ ^2-、F^-、NO^3-、NO₂ ^-、S^2-、Cl^-Deng Organic matters such as anion and organic phenol, surfactant and acrylic resin etc..Acid waste water, alkaline waste water usually mix Post processing, and chromate waste water, nickel-containing waste water must be handled individually.Soda acid water all mixes processing, in acid after waste water mixing Property, it needs to put into a large amount of piece alkali, lime and PAC, PAM, produces a large amount of waste residues.

The recycling rate of waterused of current aluminium processing industry water generates a large amount of waste residues less than 30% after wastewater treatment.On the one hand it is useless The useful resources such as a large amount of metallic aluminiums, acid, alkali in slag are not utilized, and cause the huge wasting of resources, if Fig. 2 is certain Large size Aluminium Material factory Aluminiferous waste slag source situation.Waste residue belongs to hazardous waste, has great environmental hazard.It realizes wastewater zero discharge, give up Zero output of slag, utilization of resources value maximization have great environmental benefit, Social benefit and economic benefit.

(2) Aluminum Solid state fermentation and present situation is utilized

1st, electrolysis founding aluminium ash handles and utilizes present situation

The method for developing many aluminium ash recycling and recycling in succession both at home and abroad, recycles in recent years about aluminium ash Patent it is also in rising trend but most of in the experimental study stage, technology is confined to hot conditions extraction metallic aluminium, prepares The inorganic material and steelmaking ingredient etc. such as aluminium oxide, aluminium chloride, aluminum sulfate, also have from industrialization, scale with a certain distance from.

1.1st, aluminium ash recycles

The method of recycling aluminium ash can be divided into heat treating process and cold-treating process at present, all only recycle the metal in aluminium ash Aluminium.Domestic large-scale regeneration aluminium manufacturer is mostly using rotary kiln facture of fascinating：(it is typically sodium chloride, chlorine aluminium ash and additive salt Change the mixture of potassium and a small amount of calcirm-fluoride) be placed on heated in the rotary kiln that fascinates after detach metallic aluminium, but removal process has flue gas It generates, metal recovery rate is relatively low, and content of residual aluminum is higher in aluminium ash, still there is further recycling space.Other methods, which also have, squeezes back The instant method of receipts method, plasma, electrical concentration, MRM methods, ALUREC methods etc..

1.2nd, aluminium ash comprehensively utilizes

Because aluminium ash composition and bauxite are basically identical, the product that can be produced with bauxite, all someone are carried out with aluminium ash Overtesting is studied.Mainly there are three routes in terms of the recycling of current aluminium ash：(1) recycling aluminium oxide returns electrolysis, recycles chlorine Salt is used as founding refining agent, but the main component in aluminium ash is α-Al₂O₃, poor activity, more multipotency need to be consumed by being ionized Amount, causes tank voltage to increase.(2) acid system or alkaline process processing removal of impurities, production synthesis Brown Alundum, Sialon ceramics and refractory material etc. Inorganic material produces the water-purifying materials such as aluminium polychloride and aluminum sulfate, produces steel-making slag making desulfurizing agent, but because cost is than existing Also height, fail realize industrialized production.(3) building materials or road-making material are produced, such as aluminate cement, calcium aluminate powder, clear water brick, And road-making material etc., but the fluoride, the villaumite that contain have an impact performance, while added value of product is low, limit practical answer With.There are the shortcomings of product purity is low, added value is low, waste secondary pollution for application in terms of three above.Aluminium ash recycles Waste after utilization can only be filled or be stored up still containing great amount of soluble salt and fluoride or dangerous waste, environmental hazard There is no reductions.

Due to containing high temperature resistants, corrosion resistance, the toxics such as a certain amount of villaumite (NaCl, KCl etc.) and fluoride in aluminium ash Etc. components, conventional method be difficult to realize the recycling of full ingredient, increase the cost and technical difficulty of aluminium ash recycling so that The Industrialization Progress of aluminium ash processing is slow.In addition, the Transport And Transformation for harmful elements such as aluminium ash processing procedure fluorine and heavy metals Mechanism lacks more deep discussion.

Accomplish " zero discarded " of aluminium ash resource, it is necessary to change utilization of resources thinking, make full use of in aluminium ash it is various into Point, carry out harmless treatment, resource maximizationization utilizes.This work is very urgent, needs specific direction, standard guidance, more Fang Xiezuo strives obtaining real-time breakthrough early.

2nd, compressive surface processing waste water and dregs handle and utilize present situation

1. waste water and dregs are recycled, comprehensive utilization includes two aspect contents：First, the recycling of water；Second is that waste residue Comprehensive utilization of resources.

1.1st, it squeezes and stews mould waste liquid and oxidation pre-treatment Alkaline etchant recycling

It squeezes pot mould waste liquid and contains a large amount of sodium hydroxide and aluminium ion, have many research in terms of stewing mould devil liquor recovery Report and patent.Aluminium processing enterprise processing stew mould waste liquid common practice be：It stews in the spent acid that mould waste water is generated with oxidation operation Slag processed is post-processed with precipitation, the waste residue that mould waste liquid generates only is stewed and just accounts for 30% or so of the total quantity of slag of enterprise.Enterprise does not have not only The useful resources such as sodium hydroxide, the aluminium ion stewed in mould waste liquid are recycled, increase cost, the processing of waste water, waste residue instead As heavy environmental burden.

The recycling of oxidation pre-treatment Alkaline etchant recycles sodium hydroxide generally using crystallization, but sodium hydroxide granularity it is relatively thin, Purity is not high, economic value is low.In addition, aluminium ion is maintained at low concentration (being less than 30g/L) by crystallization, it is thick to easily cause section bar The defects of crystalline substance, coarse sand, excessive erosion, and aluminium consumption is too high.Crystallization is higher to operation and technological requirement, and management is bad will to precipitate knot Dirt takes time and effort.There is a small amount of producer to come into operation online soda recovery unit, because recovering effect is bad, of high cost, abandoned mostly no With.Add corrosion inhibiter, the alkaline etching tank liquor of complexing agent does not apply to soda recovery unit, also limit the application of the technology.

1.2nd, oxidation solution aluminium ion and retrieval of sulfuric acid

Aluminium ion in aluminium alloy anode oxide liquid directly affects the electric conductivity and film quality of tank liquor, Optimal Control Concentration should be between 3-10g/L ranges.Aluminium ion constantly accumulates raising with the increase of output, and film quality is deteriorated, power consumption Raising, but in view of reagent cost and environmental protection pressure, aluminium ion concentration general control is in 15-20g/L areas in enterprise practical production Between.After reaching the upper limit, it is necessary to reduce aluminium composition.It is to exhaust half tank liquor to reduce aluminum ions usual way, supplements sulfuric acid After continue to produce.This method is simple, but has the following disadvantages：First, having lost sulfuric acid, aluminium ion is wasted, sulfuric acid consumption reaches More than 60kg/t；Second is that processing spent acid increases sizable cost；Third, flood tide waste residue causes environmental hazard.

Retrieval of sulfuric acid machine using diffusion dialysis principle was once the aluminum ions means of control being widely used.Retrieval of sulfuric acid Machine is aluminum ions stabilising arrangement, reaches recycling sulfuric acid using diffusion dialysis amberplex, removes aluminum ions purpose.In reality In the operation of border, there are recovering effect is poor, high energy consumption, efficiency is low, the quantity of slag is not reduced the deficiencies of.In view of the above-mentioned grain of retrieval of sulfuric acid machine The using effect of cake, most of aluminium processing enterprise gradually deactivate the device, have restored the tradition side of the oxidation of falling half tank liquor Method.

1.3rd, spraying pretreated waste water recycling

The market share of powder spray alloy product significantly increases in recent years, has accounted for aluminum alloy surface processing product More than 60%.The purpose of sprayed surface pretreatment is to generate one layer of fine and close conversion film in aluminium material surface, by base material and sprayed coating Firm connection is together.To ensure the quality of conversion film, process control needs are very strict, and exceeded tank liquor and washings are necessary It exhausts.Waste water contains a large amount of Cr VI, fluotitanic acid, fluorine zirconic acid root and fluorine ion in acidity.A large amount of spent acid processing both increased Entreprise cost, and resource is wasted, also with environmental hazard.Spraying pretreatment and wastewater processing technology are in progress without apparent, It still uses conventional methods, neutralizes, precipitates, a large amount of waste residues are formed after filter-press dehydration.Waste residue belongs to the hazardous waste of stringent management and control, Qualified third party must be transferred to and carry out the harmless processing that standardizes.

1.4th, containing chromium and nickel-containing waste water

Chromium, nickel belong to a class of pollutant, and processing, chromium slag (HW21) and nickel slag must be individually separated containing chromium or nickel-containing waste water (HW17) belong to hazardous waste.

The recycling of hexavalent chromium is still a problem, can not now realize online recycling medicament containing chromium.Chromate waste water is present Processing method be：The reducing agents such as sodium pyrosulfite or sodium hydrogensulfite are added in, by hexavalent chrome reduction into the lower trivalent of toxicity Chromium, then adds alkali, PAM carries out reaction precipitation, and chromium slag is obtained after dewatering and filtering mud.Exemplary process such as Fig. 3.

Nickel ion, which recycles, is only limitted to coloring slot, and the nickel ion in sealing of hole waste water is because of the low direct emission of content.Nickel ion returns It receives using RO retracting devices, principle is identical with acid recovery, but efficiency is low and generates a large amount of condensed waters.The processing of nickel-containing waste water Using the precipitation method, sodium hydroxide and PAM are added in, adjusts pH, reaction generates nickel hydroxide precipitate, nickel is obtained after dewatering and filtering mud Slag.Exemplary process such as Fig. 4.

1.5th, compressive surface processing waste water and dregs integrated treatment

Many aluminium section bar producers have carried out various aspects in terms of water-saving and waste water treatment and have tried to explore and effective practice, obtain Certain effect.Aluminum current processing industry waste water is still generally adjusted using neutralization and coagulant sedimentation processing, process flow are： Acidic and alkaline waste water neutralizes mutually, adjusts pH to the formation hydroxide precipitation such as neutrality, cation A l3+.The waste water of neutralized precipitation is beaten Enter in coagulation tank, add in flocculant PAC, PAM, precipitation tank, standard emission of clear or reuse are entered after flocculation, water-containing sludge is through pressure Aluminiferous waste slag is formed after filter press filtration.Waste residue moisture content 80% or so, quantity is very big.Waste residue exemplary process such as Fig. 5.

In conclusion conventional waste water Solid state fermentation mode has following deficiency：When after wastewater treatment can qualified discharge, but in Reusing rate is low；Second is that cost for wastewater treatment is high, increase artificial, medicament, power consumption；Third, a large amount of soda acid, metallic aluminium, change The useful resources such as medicament are learned to be wasted；Fourth, waste residue belongs to dangerous waste, disposal costs are high, need to pay environmentally friendly tax.

2nd, compressive surface processing waste water and dregs comprehensive utilization

Comprehensive utilization includes two aspect contents：First, the recycling of water；Second is that the comprehensive utilization of resources to waste residue.Recycling Very undesirable using present situation, preceding to have addressed, the recycling rate of waterused of water is less than 30%, way that aluminium slag, chromium slag, nickel slag for comprehensive utilize Diameter and method are limited.

2.1st, the comprehensive utilization of aluminium slag

Carry out for many years, there is considerable article and patented technology, recycling profit to the utilization of resources research of Aluminiferous waste slag Technology Ways and aluminium ash are essentially identical, mainly there is following several respects：(1) aluminium hydroxide or aluminium oxide are directly recycled；(2) it closes Into the ceramics such as mullite, cordierite, preparing ceramic clinker, artificial resin marble or refractory material；(3) water-purifying material, such as aluminium are produced Sour calcium, aluminium polychloride (iron), polyaluminium sulfate etc.；(4) chemical products such as aluminium hydroxide, ammonia-alum are produced in reaction, such as China Patent CN 1350065A disclose it is a kind of using alkaline residue extracting sulfuric acid aluminium ammonium, aluminum sulfate, aluminium hydroxide method, Chinese patent CN 101186282B, which disclose a kind of hardening oxidation sulfuric acid tank liquor, reduces aluminium ion and the method for producing ammonium alum, this patented technology In Shuo Jia producers practical application, fabulous economic benefit is achieved, while solves the processing problem of acid sludge.

Except the technology that aluminium hydroxide is produced using acid sludge is succeeded in addition to, the comprehensive utilization ratio of aluminium slag is very low, main Want that reason or technology are immature, added value of product is low, cost is higher.Most waste residues are all that aluminum material factory spends payment process Fall, pile up like a mountain for the waste residue of many aluminum material factories now, into a hot Chinese yam of aluminum material factory.

2.2nd, chromium slag and nickel slag for comprehensive utilize

According to open source information, chromium slag can be used as glass colorant and crystallization promoter, but practical situations are unknown.It has no There is the open source information of nickel slag recycling.Chromium slag, nickel slag common practice are to go to the third-party institution to carry out at innoxious burial Reason.

3rd, there are problems for the processing of compressive surface processing waste water and dregs

First, water consume is high, lack ripe water-saving technology, the reclamation rate of water is low；Second is that online classification waste water fails before becoming Program is put, causes waste residue yield big；Third, the comprehensive utilization effect of waste residue is little, Solid state fermentation becomes business burden and environmental protection Risk.

Currently, Solid state fermentation there are problems that three aspect conspicuous contradictions and：First, country carries out enterprise pollution object discharge permit Card management controls the gross contamination emission of enterprise, and the actual waste water waste residue amount of enterprise is much larger than allowable emission；It is second is that useless Slag must legal transfer disposed to qualified third party, but disposing capacity is significantly inadequate, can not legal processes such flood tides Waste residue；Third, by dangerous waste specification handles waste residue, flow is complicated, efficiency is low, of high cost.

In conclusion aluminium processing industry waste water and dregs processing domestic at present is particularly thorny, integrated treatment difficulty is larger, cost Height, recovery utilization rate are low, have not only caused a large amount of wastes of resource, but also seriously pollute environment.Therefore for aluminium processing industry, waste water zero Discharge and the research and development of resource comprehensive utilization technology have bright prospects and huge environmental benefit, society to imitate with popularization and application Benefit and economic benefit.

(3) Aluminum aluminium ash and aluminium slag minimizing recycling direction

1st, the principle followed：Minimizing control, harmless treatment, recycling, it is necessary to government driving, enterprise dominate, Resource is configured in third party's marketization, and the unification of three power could obtain positive progress；

2nd, source controls, and classifies to each pharmacy slot and retains, online to convert, and recycling reduces waste water and dregs discharge capacity；

3rd, environmentally friendly process for treating surface is promoted and applied.For the pollution problem of oxidation line, promote and apply nothing and add Add agent alkaline etching, without techniques such as nickel free-floride sealing of holes；

4th, strengthen Enterprises Universities Researches Union, expand thinking and the field of waste residue comprehensive utilization, realize that comprehensive utilization value maximizes.

Invention content

It is an object of the invention in order to overcome drawbacks described above, propose the medicine of the coloring of nickel pink salt and medium temperature sealing of hole in aluminium processing Agent recovery system and method are contained using online classification recycling and compatibility method, selected dosage component, ingenious configuration system, realization The resource recycling of malicious waste utilizes, and the stannic hydroxide of acquisition and basic nickel carbonate are transformed into nickel pink salt colorant, Realize recycling for solid dangerous waste resource.

For this purpose, the present invention uses following technical scheme：

The medicament recovery system of the coloring of nickel pink salt and medium temperature sealing of hole in a kind of aluminium processing includes containing successively from upstream to downstream Nickel tin waste water retention unit, nickeliferous tin wastewater collection unit, tin ion recovery unit and nickel ion recovery unit, feature exist In：

The nickeliferous tin waste water retention unit includes the 13# nickel pink salt being arranged in order coloring slot, 14# flowings rinsing bowl, 15# High-pressure atomization spray groove, 16# medium temperature sealing of holes slot, 17# flowing rinsing bowls and 18# flowing rinsing bowls, the 18# are flowed outside rinsing bowl Water is connected to, the 14# flowings rinsing bowl, 15# high-pressure atomizations spray groove, 17# flowing rinsing bowls and 18# flowing rinsing bowls are reversed It is arranged in series, the 16# medium temperatures sealing of hole slot is to the coloring slot compatibility setting of 13# nickel pink salt；

The nickeliferous tin wastewater collection unit includes nickeliferous tin wastewater collection pond A and nickeliferous tin wastewater collection pond B, described The water outlet of 14# flowing rinsing bowls is respectively equipped with the nickeliferous tin wastewater collection pond A pipelines connected and is received with nickeliferous tin waste water Collect the pipeline of pond B connections；

The tin ion recovery unit include be arranged in order 1# pumps, tin recycling can, 1# centrifuges, tin secondary crystallization tank and 2# is pumped, and the 1# pumps the nickeliferous tin waste water of nickeliferous tin wastewater collection pond A and nickeliferous tin wastewater collection pond B being pumped into the tin Recycling can, the tin recycling can are used for the Sn in nickeliferous tin waste water²⁺Solid stannic hydroxide is converted into, the 1# centrifuges are used In the nickeliferous tin waste water for detaching solid stannic hydroxide and liquid, the tin secondary crystallization tank is for the nickeliferous tin waste water after separation In Sn²⁺Secondary crystallization, 2# pump returns for the tin secondary crystallization object in the tin secondary crystallization tank to be pumped into the tin Closed cans；

The nickel ion recovery unit includes the nickel recycling being arranged in order, 2# centrifuges, nickel secondary crystallization tank and 3# pumps, The 2# pumps are additionally operable to the nickeliferous supernatant in the tin secondary crystallization tank being pumped into the nickel recycling can, and the nickel recycling can is used In by the Ni in the nickeliferous supernatant²⁺Solid basic nickel carbonate is converted into, the 2# centrifuges are used to detach solid alkali The nickeliferous supernatant of formula nickelous carbonate and liquid, the nickel secondary crystallization tank is for the Ni in the nickeliferous supernatant after separation²⁺Two Secondary crystallization, the 3# pump that the nickel secondary crystallization object in the nickel secondary crystallization tank is pumped into the nickel recycling can and will be crystallized Afterwards be pumped into subsequent treatment unit for waste water without nickel supernatant.

Preferably, in the nickeliferous tin waste water retention unit, the external tap water of the water inlet of the 18# flowings rinsing bowl Pipeline be equipped with 1# valves, on the pipeline that the water outlet and the water inlet of 17# flowing rinsing bowls of 18# flowing rinsing bowl connect Equipped with 2# check valves, 4# high is equipped between the water outlet of water inlet and 17# the flowing rinsing bowl of the 15# high-pressure atomizations spray groove Press pump, the pipeline that the water outlet of the 17# flowings rinsing bowl is connected with the water inlet of 4# high-pressure pumps is equipped with 3# check valves, described 5# is equipped between the water inlet of water outlet and 14# the flowing rinsing bowl of 15# high-pressure atomization spray grooves to pump.

Preferably, in the nickeliferous tin wastewater collection unit, the water inlet of the nickeliferous tin wastewater collection pond A described contains It is connected between the water outlet of the water inlet of nickel tin wastewater collection pond B and 14# flowing rinsing bowls by three-way pipe, and described One end connected with 14# flowing rinsing bowls of three-way pipe is equipped with 5# valves, and the three-way pipe and described nickeliferous tin waste water is received The one end for collecting pond A connections is equipped with 6# valves, and one end connected with the nickeliferous tin wastewater collection pond B of the three-way pipe is equipped with 7# Valve；

The pipeline that the water outlet of the nickeliferous tin wastewater collection pond A is connected with the 1# water inlets pumped is equipped with 8# valves, described to contain The pipeline that the water outlet of nickel tin wastewater collection pond B is connected with the 1# water inlets pumped is equipped with 9# valves.

Preferably, in the tin ion recovery unit, what the water outlet of 1# pump was connected with the water inlet of tin recycling can Pipeline is equipped with 10# valves, and the pipeline that the water outlet of the tin recycling can is connected with the water inlet of 1# centrifuges is equipped with 11# valves, described 1# centrifuges are equipped with solid-state separation material mouth and Liquid segregation material mouth, the Liquid segregation material mouth of the 1# centrifuges pass through pipeline and tin The water inlet connection of secondary crystallization tank；

The middle part of the tin secondary crystallization tank is equipped with the first supernatant delivery outlet, the second supernatant delivery outlet and third vertically Supernatant delivery outlet, the bottom of the tin secondary crystallization tank are equipped with the first crystallization delivery outlet, and the first of the tin secondary crystallization tank The pipeline that supernatant delivery outlet is connected with the 2# water inlets pumped is equipped with 12# valves, and the second supernatant of the tin secondary crystallization tank is defeated It exports the pipeline connected with the 2# water inlets pumped and is equipped with 13# valves, the third supernatant delivery outlet and 2# of the tin secondary crystallization tank The pipeline of the water inlet connection of pump is equipped with 14# valves, the first crystallization delivery outlet of the tin secondary crystallization tank and the water inlet of 2# pumps The pipeline of connection is equipped with 15# valves, and the pipeline that the first water outlet of the 2# pumps is connected with the water inlet of tin recycling can is equipped with 16# Valve, the pipeline that the second water outlet of the 2# pumps is connected with the water inlet of nickel recycling can are equipped with 17# valves；

The tin recycling can is internally provided with 1# electricity blenders, and the 2# electricity that is internally provided with of the tin secondary crystallization tank stirs Mix device.

Preferably, in the nickel ion recovery unit, the water outlet of the nickel recycling can and the water inlet of 2# centrifuges connect The pipeline connect is equipped with 18# valves, and the 2# centrifuges are equipped with solid-state separation material mouth and Liquid segregation material mouth, the liquid of the 2# centrifuges State separation material mouth is connected by pipeline with the water inlet of nickel secondary crystallization tank；

The middle part of the nickel secondary crystallization tank is equipped with the 4th supernatant delivery outlet, the 5th supernatant delivery outlet and the 6th vertically Supernatant delivery outlet, the bottom of the nickel secondary crystallization tank are equipped with the second crystallization delivery outlet, and the 4th of the nickel secondary crystallization tank the The pipeline that supernatant delivery outlet is connected with the 3# water inlets pumped is equipped with 19# valves, and the 5th supernatant of the nickel secondary crystallization tank is defeated It exports the pipeline connected with the 3# water inlets pumped and is equipped with 20# valves, the 6th supernatant delivery outlet and 3# of the nickel secondary crystallization tank The pipeline of the water inlet connection of pump is equipped with 21# valves, the second crystallization delivery outlet of the nickel secondary crystallization tank and the water inlet of 3# pumps The pipeline of connection is equipped with 22# valves, and the pipeline that the first water outlet of the 3# pumps is connected with the water inlet of nickel recycling can is equipped with 23# Valve, the pipeline that the second water outlet of the 3# pumps is connected with the water inlet of the treatment unit for waste water are equipped with 24# valves；

The nickel recycling can is internally provided with 3# electricity blenders, and the 4# electricity that is internally provided with of the nickel secondary crystallization tank stirs Mix device.

Preferably, the recovery method of the medicament recovery system of the coloring of nickel pink salt and medium temperature sealing of hole in being processed using the aluminium：

Step 1, opens the 1# valves, and tap water enters the 18# and flows rinsing bowl, then through the 2# check valves into Enter the 17# flowings rinsing bowl；The 4# high-pressure pumps are opened, water flows through the 3# check valves and enters 15# high-pressure atomization spray grooves； The 5# pumps are opened, the water of the 15# high-pressure atomizations spray groove is pumped into 14# flowing rinsing bowls；The 5# valves are opened, it is described The water of 14# flowing rinsing bowls is flowed out through the 5# valves；

Step 2, the aluminium alloy for being wrapped with oxidation film is first after 13# nickel pink salt coloring slot is coloured, drip 30s；So Enter the 14# flowing rinsing bowl cleanings 60s, drip 30s afterwards；Enter back into the 15# high-pressure atomizations spray groove cleaning 60s, drop Flow 30s；Subsequently enter 16# medium temperatures sealing of hole slot the sealing of hole 15min, drip 30s；Enter 17# flowing rinsing bowl cleanings therewith 60s, drip 30s finally enter 18# flowing rinsing bowl cleanings 60s, drip 30s；

Step 3, opens the 6# valves, and the nickeliferous tin waste water of the 14# flowings rinsing bowl outflow gives up into the nickeliferous tin Water collecting pit A；Alternatively, opening 7# valves, the nickeliferous tin waste water of the 14# flowings rinsing bowl outflow enters the nickeliferous tin waste water and receives Collect pond B；

Step 4 opens the 8# valves or 9# valves and opens the 10# valves, closes the 11# valves, opens the 1# pumps, The nickeliferous tin waste water of nickeliferous tin wastewater collection pond A or nickeliferous tin wastewater collection ponds B is pumped into the tin recycling can；Open the 1# Electric blender is slowly added to sodium carbonate, by the Sn in nickeliferous tin waste water toward the tin recycling can²⁺It is converted into solid hydroxide Tin；The 1# centrifuges are opened, open the 11# valves, carry out separation of solid and liquid, recycle solid stannic hydroxide, and by liquid Nickeliferous tin waste water flows into the tin secondary crystallization tank and carries out crystallization treatment；

After crystallization, the 12# valves, 13# valves or 14# valves are opened, closes 15# valves and 16# valves, the 2# pumps are opened, by institute It states the nickeliferous supernatant in tin secondary crystallization tank and is pumped into the nickel recycling can；Then, close the 12# valves, 13# valves, 14# valves and 17# valves open 15# valves and 16# valves, open the 2# pumps and 2# electricity blenders, and the tin in the tin secondary crystallization tank is secondary Crystal is pumped into the tin recycling can, carries out the secondary recovery of tin；

Step 5 opens the 3# electricity blender, sodium carbonate is slowly added to toward the nickel recycling can, by the nickeliferous supernatant Ni in liquid²⁺It is converted into solid basic nickel carbonate；The 2# centrifuges are opened, open the 18# valves, carry out separation of solid and liquid, Solid basic nickel carbonate is recycled, and the nickeliferous supernatant of liquid is flowed into the tin secondary crystallization tank and carries out crystallization treatment；

After crystallization, open the 19# valves, 20# valves or 21# valves and open 24# valves, close 22# valves and 23# valves, open institute 3# pumps are stated, are neutralized subsequent treatment unit for waste water is pumped into without nickel supernatant in the nickel secondary crystallization tank； Then, the 19# valves, 20# valves, 21# valves and 24# valves are closed, opens 22# valves and 23# valves, opens the 3# pumps and the stirring of 4# electricity Nickel secondary crystallization object in the nickel secondary crystallization tank is pumped into the nickel recycling can, carries out the secondary recovery of nickel by device.

Preferably, it is further comprising the steps of：

Step 6 after the stannic hydroxide rinsed clean for obtaining the step 4, after adding in pure water moistening, is slowly added sulphur Sour (98%), under conditions of excess sulfuric acid, reaction generation stannous sulfate solution, and the pH value of the stannous sulfate solution when generation Stop reaction when=0.8；

Step 7 after the basic nickel carbonate rinsed clean for obtaining the step 5, after adding in pure water moistening, is slowly added Sulfuric acid (98%), under conditions of excess sulfuric acid, reaction generation sulfuric acid Asia nickel solution, and set the sulfuric acid Asia nickel solution of generation PH value=0.8 is reaction end；

Step 8, the nickel pink salt that slot is coloured according to the 13# nickel pink salt colour Con trolling index, titrated sulfuric acid stannous solution Concentration and the concentration of sulfuric acid Asia nickel solution add tartaric acid, form the nickel tin that can be added directly to the 13# nickel pink salt coloring slot Salt colorant.

Preferably, the nickel pink salt coloring Con trolling index of the 13# nickel pink salt coloring slot is：Stannous sulfate 10g/L, nickel sulfate 25g/L, sulfuric acid 18g/L, tartaric acid 8g/L, pH value 0.8-1.2, temperature are 20-25 DEG C, processing time 30s-15min, electricity It presses as 14-16V.

Preferably, in the step 4, while being slowly added to sodium carbonate toward the tin recycling can, the tin recycling is detected The pH value of solution in tank when the pH value of the solution in the tin recycling can reaches 4.8, stops adding in sodium carbonate, continues to stir Mix 30min；In the step 5, while being slowly added to sodium carbonate toward the nickel recycling can, detect in the nickel recycling can The pH value of solution when the pH value of the solution in the nickel recycling can reaches 9.0, stops adding in sodium carbonate, continues to stir 30min。

Preferably, the medium temperature sealing of hole index of the 16# medium temperatures sealing of hole slot is nickel acetate 5g/L, triethanolamine 0.5g/L, different Butanol 0.5g/L, pH value 5.5-6.5, temperature are 50-60 DEG C, processing time 10-25min；The oxygen of the aluminum alloy surface The thickness for changing film is 15 microns.

The medicament recovery system of the coloring of nickel pink salt and medium temperature sealing of hole is sealed for heat-tinting in aluminium processing in the aluminium processing Hole generate the toxic waste residue of nickeliferous tin, using online classification recycling and compatibility method, selected dosage component, ingenious configuration system, Ensure that nickeliferous tin product reuse to the 13# nickel pink salt of recycling colours slot, realize that the resource recycling of toxic waste utilizes.It is described Aluminium processing in nickel pink salt coloring and medium temperature sealing of hole medicament recovery system can online processing aluminium processing in heat-tinting sealing of hole generate About 16,000,000 tons of nickeliferous tin waste water, convert about 40,000 tons of the toxic waste residue of nickeliferous tin, about 100,000 tons of generation nickel pink salt colorant.

Description of the drawings

The present invention will be further described for attached drawing, but the content in attached drawing does not form any limitation of the invention.

Fig. 1 is the examining report figure of existing aluminium ash component；

Fig. 2 is the cake chart in certain existing large-scale aluminum material factory Aluminiferous waste slag source；

Fig. 3 is the flow chart of existing chromate waste water processing；

Fig. 4 is the flow chart of existing nickel-containing waste water processing；

Fig. 5 is the flow chart of existing waste water and dregs processing；

Fig. 6 is the conventional oxidation coloring hole-sealing technology flow of the one of embodiment of the present invention and slot position layout drawing；

Fig. 7 is the medicament recovery system of the coloring of nickel pink salt and medium temperature sealing of hole during the aluminium of the one of embodiment of the present invention is processed Structure chart.

Specific embodiment

Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.

The present embodiment is by following theoretical foundation, nickel pink salt colorant recovery system, recovery method and quantitative and qualitative analysis Come what is realized：

First, the coloring of nickel pink salt and the theoretical foundation of sealing of hole ejected wash water remanufacture colorant

Conventional oxidation colours hole-sealing technology flow and slot position arrangement as shown in fig. 6, each work nest is washed with two flowings Slot, 18 slot positions of oxidation processes needs, wherein 13# nickel pink salt coloring slot and 16# medium temperature sealing of hole slots are nickeliferous, pink salt, follow-up water Washing trough takes nickeliferous tin waste water out of and enters wastewater treatment center, generates the toxic waste residue of nickeliferous tin.13# nickel pink salt of the present invention Colour slot, 14# flowings rinsing bowl, 15# high-pressure atomizations spray groove, 16# medium temperature sealing of holes slot, 17# flowing rinsing bowls and 18# circulating waters The function of washing trough is as follows：

The purpose of 13# nickel pink salt coloring slot is in order to which oxidizing film is painted, and improves the dicoration of aluminium alloy.It is general to use list Nickel salt, single pink salt or the coloring of nickel tin salt-mixture, and add the additives such as phenols, organic acid, boric acid and stablize coloring liquid.Single nickel salt Color control index is：

Nickel sulfate 150g/L, boric acid 50g/L, pH value 3.5-4.5, temperature are 20-25 DEG C, processing time 30s- 15min (1)；

Single nickel salt colouring slot liquid is highly stable, but requires chemical agent purity high, and contamination resistance is weak, it is desirable that before coloring 12# flows rinsing bowl and 11# flowing rinsing bowls are washed with flowing pure water；In addition, with the raising of environmental requirement, heavy metal nickel may It is put into the catalogue being forbidden to use.

Single pink salt colouring slot liquid is unstable, easily muddy, but fluting concentration is low, and about 15g/L or so, contamination resistance is strong, Colour system enriches.In view of the trend that nickel salt may be prohibited from using, it is badly in need of developing novel coloring stabilizer, thoroughly stablizes pink salt.

Nickel tin salt-mixture electrolytic coloring, in addition to bronzing system, also can artificial stainless steel colour, champagne and ater. Nickel tin mixed salt electrolytic colouring liquid has good color dispersion, and color film uniform color, the elegance of formation are luxurious, have good resistance to Solarization property, corrosion resistance and wearability, coloring liquid have stronger stain resistance in itself.It is suitble to the control parameter of large-scale production For：Stannous sulfate 10g/L, nickel sulfate 25g/L, sulfuric acid 18g/L, tartaric acid 8g/L, pH value 0.8-1.2, temperature 20-25 DEG C, processing time 30s-15min, voltage is 14-16V (2)；

It is coloured with nickel tin mixing salt electrolyte, not only at low cost, usage time is long, and can obtain individual nickel salt Or the pink salt not getable color of institute and quality, thus deep favored by vast aluminium producer.But such as single pink salt coloring one Sample, the stannous ion in nickel tin salt-mixture electrolytic coloring system are extremely unstable.Even if in the acid solution of pH=1.0, also hold The oxygen easily released by the oxygen in air or hydroxyl electrolysis, is oxidized to high price tin ion, and then hydrolysis generation white occurs Stannic acid precipitates, and gently then influences the quality of coloring film, heavy then make coloring liquid entirely ineffective.So the emphasis of control mainly ensures Asia In addition the stabilization of tin ion is the control of tone.

Nickel pink salt colours, based on pink salt, since competition reduction improves colouring speeds and uniformity when the two coexists.Nickel tin Salt is fewer and more stable than single pink salt dosage, thoroughly red more good-looking in tone Huang.Nickel salt is advisable with 20-25g/L, and too high colour cast is dark, but Being that ater is appropriate to the occasion rises to 45g/L.General tin salt 6-8g/L is advisable.Summer removes the limit, the winter upper limit, and ater needs to rise To 10-12g/L.Additive, which plays, improves uniformity and the effects that prevent stannous from hydrolyzing, but at present coloring slot energy is complexed Power is inadequate, stannous in the same old way can oxydrolysis, therefore add tartaric acid, be complexed stannous ion.Sulfuric acid, which rises, prevents pink salt from hydrolyzing and improving The double action of conductance, free sulfuric acid control 15-20g/L are advisable.The relatively low glossiness of sulfuric acid is quite a lot of, sulfuric acid too high coloring speed and Gloss declines, and only has ater just to rise to 25g/L, to prevent surface from generating hydroxide.Some nickel tin salt-mixture coloring liquids Add boric acid, it plays cushioning effect in hole, is conducive to electrodeposition of nickel, improves uniformity and improves color sensation, using 20-25g/L as Preferably, too high colour cast is dark.

Sn²⁺Ion is easily aoxidized by all oxidants, is then hydrolyzed into gelatinous Sn (OH)₂With Sn (OH)₄It is deposited in slot Bottom is suspended within solution.In coloring process, several situations can all facilitate Sn below²⁺Oxidation and hydrolysis：

1st, it is aoxidized caused by tank liquor stirring

In order to make the temperature of tank liquor, even concentration, reply colouring slot liquid is stirred during production, although avoiding straight with air It connects stirring and takes circulating pump, the chance that tank liquor is contacted with air can still increased, divalent can occur in being contacted with air Tin is easily oxidized to stannic reaction：

SnSO₄+H₂SO₄+ O=H₂O+Sn(SO₄)₂↓ (3)；

2nd, the oxidation and hydrolysis occurred during electrode reaction

When electrode is in anode half cycle, the reaction of hydroxyl betatopic generation oxygen can occur:

4OH^-- 4e=2O+2H₂O (4)；

In coloring process, Sn²⁺The oxygen effect generated in easily being reacted in electrode reaction with (4) formula, aoxidizes, by (3) Formula generates muddy object.In addition, aluminium alloy, as cathode, evolving hydrogen reaction can increase local ph, promote the Sn in slot²⁺And Sn^{4 +}Ion hydrolysis：

Sn²⁺+2OH^-=Sn (OH)₂↓ (5)；

Sn⁴⁺+4OH^-=Sn (OH)₄↓ (6)；

Due to the presence reacted above and Sn²⁺Stabilizer complexing power not enough etc. factors, tank liquor service life is longer, hang Floating muddiness is more serious.Good additive should have certain integration capability, both anti-Sn²⁺Ion precipitation hydrolyzes, and also to have acceleration Ionization improves the effect of dispersibility.Otherwise, complexing coordinates bad, Sn with ionization dynamic equilibrium in coloring process²⁺Ion It is bad in inner hole deposition product condition, coloration efficiency and coloring tone can be influenced.

The additives such as magnesium sulfate, aluminum sulfate, ATS (Ammonium thiosulphate) are added in coloring liquid surface to be made uniformly to be coloured Effect.Electrolytic colouring liquid based on pink salt, most important problem are how to prevent or slow down stannous oxidation, improve electrolysis The stability and service life of liquid.In addition to the additives such as tartaric acid, phenol, sulfuric acid, boric acid are added in, also need to add in oxidation retarder, Such as：Ascorbic acid, phenylbenzene, quinhydrones etc..The wherein acidificable solution of sulfuric acid reduces pH value；There is boric acid buffering and complexing to make With stannous ion can be not only complexed in tartaric acid, citric acid, ammonium tartrate, moreover it is possible to play cushioning effect to pH value.Add sulphur urine or Hydrazine sulfate can play reduction to tetravalence tin ion.The medicament that addition is aoxidized instead of divalent tin ion, such as ferrous ion, i.e., When divalent tin ion and ferrous ion coexist, in divalent tin ion before the oxidation reaction of tetravalence tin ion, first have occurred The oxidation reaction of ferrous ion, so as to control transformation of the divalent tin ion to tetravalence tin ion.Here the additive added in is all It is some substances with cushioning effect, complexing and antioxidation, Sn can be complexed²⁺Ion can be preferentially by solution Dissolved oxygen oxidation, to prevent Sn²⁺Ion is oxidised with air to Sn⁴⁺, and then generate Sn (OH)₄White precipitate influences coloring.

Consider any of the above factor, the formula design of coloring stabilizer must satisfy four point requirements：1st, coloring is improved Uniform performance；2nd, white dot and crack are prevented；3rd, stablize tin salt；4th, the electric conductivity of electrolyte is improved.

In order to obtain the uniformity of stainless steel colored champagne colour system aluminium section bar color, need strictly to control the work of anodizing tank Skill parameter, it is desirable that the thickness of oxidation film reaches unanimity, and deviation is the smaller the better, and preferably control is 12 μm.It will be according to anodizing tank Technological parameter situation determine anodizing time.In addition, colouring parameters must be controlled：

(1) time and temperature

It is calculated it is demonstrated experimentally that the time of electrolytic coloring will be accurate to by the second, determining for time, is according to electrolytic coloring slot The situation of various technological parameters and it is determining.The coloration time difference of one second has significantly the color of champagne electrophoretic coating aluminium section bar It influences, coloration time extends, and Sn contents increase in oxidation film, and oxidation film color also gradually deepens.Oxidation film Sn contents with when Between extend and linearly increase, relational expression is：

W=4.4+2.5t (1≤t≤5).

The tank liquor temperature of electrolytic coloring slot may be designated as 20-25 DEG C.When colouring tank liquor temperature raising, coloring liquid conductivity Increase, and Sn²⁺Precipitation reaction speed is accelerated, and colouring speeds is promoted to accelerate.In addition, the raising of coloring liquid temperature is unfavorable for Sn²⁺It is steady It is fixed.Sn²⁺Oxidation reaction speed with coloring liquid temperature increase and accelerate.Therefore, in order to ensure champagne electrophoretic coating aluminium Section bar consistency of colour, will control colouring slot liquid temperature, and fluctuation range is the smaller the better.

(2) pH value

At 1.0 or so, colouring speeds are basically unchanged colouring slot liquid pH value.Work as pH>When 1.1, colouring speeds are quickly, it is difficult to Control；If pH value is too small, and influences coloring film corrosion resistance.Therefore, pH value is that generation champagne aluminium section bar is uniform for 0.8-1.0 An important factor for color.

(3) voltage

Coloring liquid voltage control 14-16V (stainless steel colored 10-13V), current density is 0.6-0.8A/dm², no-voltage guarantor Hold 1-1.5min.Boosting rectifier control is critically important, about every 3s raising voltages 1V.To colouring speeds when voltage is less than 14V or more than 16V It influences very big.

(4) it washes

Be not allowed to park in first of rinsing bowl after anodic oxidation, in second rinsing bowl the storage period be no more than 2min enters coloring, to avoid harmful effect of the sulfuric acid in rinsing bowl to oxidation film.Second rinsing bowl requires pH >=3.It After color timing, it should lift by crane immediately and be transferred to lower road rinsing bowl again to color, can not be stopped in slot is coloured, stringent control is aerial to be risen Hang transfer time.Rinsing bowl after coloring also requires pH >=3.In water-washing process, the coloring metal salt in fenestra is highly prone to The etch of water middle acid substance causes to fade.

From the point of view of coloring effect, the color using nickel tin salt-mixture, be relatively used alone nickel salt or pink salt color Will be beautiful, heat resistance and light resistance have reached requirement.When stannous sulfate is less than 2/L, colouring speeds are relatively slow, when When being increased to more than 5/L, colouring speeds are significantly accelerated；The concentration range of nickel sulfate is broader.

The purpose of the 14# flowing rinsing bowls and 15# high-pressure atomization spray grooves is the residual coloring that cleaning coloring slot is taken out of Sealing of hole slot is protected in agent.Equally, tap water is from 15# high-pressure atomizations spray groove into 14# flowing rinsing bowls go out, differential concatenation, water consume For 2.0-3.0 tons/ton material, water consumption is too big, and what is discharged is stanniferous and nickel waste water, increases environmental protection treatment pressure.

The purpose of 16# medium temperature sealing of hole slots is to seal the micropore of oxidation film, it is ensured that its corrosion resistance.Also it can be taken with electrophoresis tank For sealing of hole slot.Method for sealing by operating temperature be divided into high temperature, in mild normal-temperature hole sealing.High temperature hole sealing is aluminium at 95-100 DEG C It is handled in pure water, sealing quality is preferable, but high energy consumption, and evaporated quantity of water is big, easy dust, and easy foreign ion poisoning need to be replaced often Tank liquor；Medium temperature sealing of hole generally using the additivated method of nickel acetate, is handled at 55-65 DEG C, and sealing of hole speed is fast, few dust, Film, but nickeliferous tin are not split, is unfavorable for environmental protection；Normal-temperature hole sealing uses nickel fluoride doping method, is handled at 25-35 DEG C, seals Hole speed, few dust, low energy consumption, easy to use.But film easy to crack, and fluorine-containing and nickel is unfavorable for environmental protection.Now, the country is in Warm sealing of hole is main methods.Medium temperature sealing of hole Con trolling index is：

Nickel acetate 5g/L, triethanolamine 0.5g/L, isobutanol 0.5g/L, pH value 5.5-6.5, temperature are 50-60 DEG C, place The reason time is 10-25min (7)；

17# flows rinsing bowl and 18# flowing rinsing bowls, and the purpose for setting this twice rinsing bowl is to clean sealing of hole slot and take out of to contain Nickel remains medicament, and aluminium is protected not to be corroded after dispatching from the factory.Equally, tap water flows rinsing bowl into 17# flowing rinsing bowls from 18# Go out, differential concatenation, water consume is 2.0-3.0 tons/ton material, and water consumption is too big, and what is discharged is nickel-containing waste water, increases environmental protection treatment pressure Power.

After aluminium is handled by 18 slot positions, manufacture can be packed, completes anodized.

Through last 100 years application, the drawbacks of oxidation line, is completely exposed already.Particularly emphasize today that cleaning is carried out production strictly in line with rules and regulations, oxygen Change line 13# nickel pink salt coloring slot, 14# flowings rinsing bowl, 15# high-pressure atomizations spray groove, 16# medium temperature sealing of holes slot, 17# flowing washings Slot and 18# flowing rinsing bowls have following several respects needs to be greatly improved：

1st, reprocessing after traditional ejected wash water is mixed is needed to be changed to classification processing, processing cost is greatly reduced.Traditional work Skill design concept is unreasonable, and 13# nickel pink salt coloring slot and 16# medium temperature sealing of holes slot are nickeliferous, molten tin bath liquid, after aluminium coloring and sealing of hole 14# flowings rinsing bowl, 15# high-pressure atomizations spray groove, 17# flowing rinsing bowls and 18# flowing rinsing bowls four is directly entered to flow Rinsing bowl brings nickeliferous tin waste water into waste water center, pollutes the water for cleaning of whole oxidation line other processes；After mixing, then locate These nickeliferous tin waste water are managed, and qualified discharge, difficulty well imagine that cost is surprising.This mode can be used in there is an urgent need to improve Line grouping sheet is stayed alone reason, replaces traditional mixed processing mode, reduces environmentally friendly cost；

2nd, it needs traditional ejected wash water Two In and Two Out, is changed to one-in-and-one-out, water for cleaning is greatly reduced, saving is processed into This, takes a firm foundation for online classification processing, device miniaturization.Rinsing bowl after two function troughs is respectively independent, two water inlets Mouth, two discharge outlet, water consumption are too big.4 rinsing bowls, total water consumption are 4-6 tons/ton material.Except in addition to water cost, these are useless The processing and discharge of water, are required for additionally paying cost.This cleaning way can reversely be gone here and there there is an urgent need to improve with ejected wash water The rinsing bowl connection mode of connection, one-in-and-one-out replaces traditional two sets to wash independent, Two In and Two Out cleaning way mutually, section About half uses water, reduces environmentally friendly cost；

3rd, the passive processing waste water and dregs theory of abandoning tradition is needed, nickeliferous tin waste water is handled from the angle of recycling Waste residue, change dangerous waste are valuable chemical resource, and processing cost is not only greatly reduced, but also realize what nickeliferous tin chemical products value utilized It maximizes.Prior art design theory is unreasonable, brings nickeliferous tin waste water into waste water center, pollutes whole oxidation line other processes Water for cleaning；Waste water center neutralizes these waste water, is precipitated, press filtration, obtains nickeliferous tin solid slag；These magnanimity are nickeliferous Tin waste residue, clear stipulaties are dangerous waste for State Ministry of Environmental Protection；These nickeliferous tin dangerous wastes are handled, enterprise and society need are paid high Environmentally friendly cost, while waste valuable nickel resources.This extensive mode of production can configure special set there is an urgent need to improve It is standby, nickeliferous tin product is actively recycled online, is turned waste into wealth, and realizes dangerous waste recycling.

Modern aluminum processing enterprise, the nickeliferous tin waste water and dregs for having the coloring sealing of hole generation of nickel pink salt are in need of immediate treatment, and traditional The method reprocessed after the big mixing of water for cleaning is too simple, generates the nickeliferous tin waste residue of magnanimity, handles these waste residues, and society will Expensive environmentally friendly cost is paid thus.

The medicament recovery system and method for the coloring of nickel pink salt and medium temperature sealing of hole in aluminium processing are to fully realize aluminium processing enterprise The production puzzlement of industry, through researching and developing for many years, the nickel pink salt big to existing aluminium processing enterprise waste water and dregs amount, environmental protection pressure is huge coloring Hole-sealing treatment process, after having carried out unprecedented system research, a new process of birth：

1), processing is collected separately in nickel tin complex salt coloring washing.

By (2) formula, nickel pink salt colouring slot liquid less stable is easily decomposes, needs to add tartaric acid complexing stannous ion, and Sulfuric acid is added, reduces pH value to 0.8-1.2.It after aluminium is coloured by the 30s-15min times, rises and hangs drip 30s, flowed into 14# Rinsing bowl cleans 1min, rises and hangs drip 30s, into 15# high-pressure atomization spray grooves, cleans 1min, rises and hang drip 30s, enters 16# medium temperature sealing of hole slots complete coloring and washing process.When being cleaned after coloring, the nickel sulfate contained by coloring liquid, stannous sulfate, wine Stone acid and sulfuric acid bring 14# flowings rinsing bowl, 15# high-pressure atomization spray grooves into, pollute the water for cleaning of flowing；13# nickel pink salts The pH value of color slot is 0.8-1.2, and the pH value of the water inlet of 15# slots is 6.0-7.0, therefore the pH value of 14# flowing rinsing bowls is 1.5- Between 3.5, this section stannous sulfate is unstable, starts to decompose, and generates stannic hydroxide；The pH value of 15# slots between 3.5-6.0, This section stannous sulfate is more unstable, resolves into stannic hydroxide completely；

2), sealing of hole washing individually recycling.

It by (7) formula, after aluminium presses 10-25min time sealing of holes, rises and hangs drip 30s, flow rinsing bowl, cleaning into 17# 1min rises and hangs drip 30s, flows rinsing bowl into 18#, cleans 1min, rises and hang drip 30s, into air drying area, complete sealing of hole with Washing process.When being cleaned after sealing of hole, nickel acetate, triethanolamine and isobutanol contained by pore-sealing liquid bring into 17# flowing rinsing bowl and 18# flows rinsing bowl, pollutes the water for cleaning of flowing；The pH value of 16# medium temperature sealing of hole slots is 5.5-6.5,18# flowing rinsing bowls The pH value of water inlet is 6.0-7.0, therefore 17# flowing rinsing bowls and 18# flow the pH value of rinsing bowl between 5.5-7.0, this area Between nickel acetate, triethanolamine and isobutanol stablize, do not decompose, processing can be collected separately.

3), coloring washing is handled with sealing of hole washing reverse phase series hybrid collection.

When being cleaned after aluminium coloring, stannous sulfate, nickel sulfate, tartaric acid and sulfuric acid contained by coloring liquid bring 14# flowings into Rinsing bowl and 15# high-pressure atomization spray grooves；For the pH value of 14# flowing rinsing bowls between 1.5-3.5, this section stannous sulfate is unstable It is fixed, start to decompose, generate stannic hydroxide；The pH value of 15# high-pressure atomization spray grooves is between 3.5-6.0, this section stannous sulfate It is more unstable, stannic hydroxide is resolved into completely；When being cleaned after aluminium sealing of hole, nickel acetate, triethanolamine contained by pore-sealing liquid and different Butanol brings 17# flowing rinsing bowls and 18# flowing rinsing bowls into；It is 5.5- that 17#, which flows rinsing bowl and the pH value of 18# flowing rinsing bowls, Between 7.0, this section nickel acetate, triethanolamine and isobutanol are stablized, and do not decompose.Close 15# high-pressure atomizations spray groove originally The water for cleaning reverse phase of the water outlet of 17# flowing rinsing bowls is connected serially to the water inlet of 15# high-pressure atomization spray grooves by water inlet, Realize that ejected wash water enters from 18# flowing rinsing bowls, through 17# flowings rinsing bowl, 15# high-pressure atomizations spray groove and 14# flowing washings Slot, the reversed big series connection finally flowed out from the water outlet of 14# flowing rinsing bowls.Such series system, 17# flowing rinsing bowl and Nickel acetate, triethanolamine and isobutanol contained by 18# flowing rinsing bowls bring 14# flowing rinsing bowls and 15# high-pressure atomizations spray into Slot needs to investigate two aspects：First, whether 14# flowing rinsing bowls and 15# high-pressure atomizations spray groove are muddy, make aluminium dust； Two are whether to influence the sealing of hole ability of 16# medium temperature sealing of hole slots.

A, 14# flows the stability analysis of rinsing bowl and 15# high-pressure atomization spray grooves.

For the pH value of 14# flowing rinsing bowls between 1.5-3.5, this section stannous sulfate is unstable, starts to decompose, and generates hydrogen Tin oxide；For the pH value of 15# high-pressure atomization spray grooves between 3.5-6.0, this section stannous sulfate is more unstable, resolves into completely Stannic hydroxide；The two rinsing bowls are muddy, the easy dust of aluminium, need to improve cleaning way, be sprayed using 15# high-pressure atomizations Slot is drenched, water for cleaning is greatly reduced in high-efficiency water-saving cleaning, and spray-water then is pumped into 14# streams from 15# high-pressure atomization spray grooves Dynamic rinsing bowl, then the water outlet through 14# flowing rinsing bowls flow out.Since spray-water is water-saving, the pH value of 14# flowing rinsing bowls is low In 2.0, stannous sulfate is temporarily uncertain, and aluminium material surface is clean, avoids the risk of dust；

B, impact analysis of the 15# high-pressure atomizations spray groove to sealing of hole slot.

The water for cleaning of 17# flowing rinsing bowl water outlets is extracted with 4# high-pressure pumps, is pumped into 15# high-pressure atomization spray grooves, clearly Aluminium is washed, micro pore-sealing liquid can bring 16# medium temperature sealing of hole slots into aluminium, these are the proper constituent of 16# medium temperature sealing of hole slots in itself, By from compatible principle, the sealing of hole ability of 16# medium temperature sealing of hole slots can never be influenced, reverse phase washing series-connection is feasible.

2nd, the medicament recovery system and method for the coloring of nickel pink salt and medium temperature sealing of hole in aluminium processing

Practical with reference to coloring sealing of hole quantity-produced, medicament recycling retains etc. factors with water and slot position is how many etc., aluminium In processing nickel pink salt coloring and medium temperature sealing of hole medicament recovery system as shown in fig. 7,

Include nickeliferous tin waste water retention unit, nickeliferous tin wastewater collection unit, tin ion recycling successively from upstream to downstream Unit and nickel ion recovery unit；

The nickeliferous tin waste water retention unit includes the 13# nickel pink salt being arranged in order coloring slot, 14# flowings rinsing bowl, 15# High-pressure atomization spray groove, 16# medium temperature sealing of holes slot, 17# flowing rinsing bowls and 18# flowing rinsing bowls, the 18# are flowed outside rinsing bowl Water is connected to, the 14# flowings rinsing bowl, 15# high-pressure atomizations spray groove, 17# flowing rinsing bowls and 18# flowing rinsing bowls are reversed It is arranged in series, the 16# medium temperatures sealing of hole slot is to the coloring slot compatibility setting of 13# nickel pink salt；

The nickeliferous tin wastewater collection unit includes nickeliferous tin wastewater collection pond A and nickeliferous tin wastewater collection pond B, described The water outlet of 14# flowing rinsing bowls is respectively equipped with the nickeliferous tin wastewater collection pond A pipelines connected and is received with nickeliferous tin waste water Collect the pipeline of pond B connections；

The tin ion recovery unit include be arranged in order 1# pumps, tin recycling can, 1# centrifuges, tin secondary crystallization tank and 2# is pumped, and the 1# pumps the nickeliferous tin waste water of nickeliferous tin wastewater collection pond A and nickeliferous tin wastewater collection pond B being pumped into the tin Recycling can, the tin recycling can are used for the Sn in nickeliferous tin waste water²⁺Solid stannic hydroxide is converted into, the 1# centrifuges are used In the nickeliferous tin waste water for detaching solid stannic hydroxide and liquid, the tin secondary crystallization tank is for the nickeliferous tin waste water after separation In Sn²⁺Secondary crystallization, 2# pump returns for the tin secondary crystallization object in the tin secondary crystallization tank to be pumped into the tin Closed cans；

The nickel ion recovery unit includes the nickel recycling being arranged in order, 2# centrifuges, nickel secondary crystallization tank and 3# pumps, The 2# pumps are additionally operable to the nickeliferous supernatant in the tin secondary crystallization tank being pumped into the nickel recycling can, and the nickel recycling can is used In by the Ni in the nickeliferous supernatant²⁺Solid basic nickel carbonate is converted into, the 2# centrifuges are used to detach solid alkali The nickeliferous supernatant of formula nickelous carbonate and liquid, the nickel secondary crystallization tank is for the Ni in the nickeliferous supernatant after separation²⁺Two Secondary crystallization, the 3# pump that the nickel secondary crystallization object in the nickel secondary crystallization tank is pumped into the nickel recycling can and will be crystallized Afterwards be pumped into subsequent treatment unit for waste water without nickel supernatant.

In the nickeliferous tin waste water retention unit, the pipeline of the external tap water of the water inlet of the 18# flowings rinsing bowl 1# valves are equipped with, the water outlet of the 18# flowings rinsing bowl is equipped with 2# with the pipeline that the water inlet of 17# flowing rinsing bowls connects Check valve, the 15# high-pressure atomizations spray groove water inlet and 17# flowing rinsing bowl water outlet between be equipped with 4# high-pressure pumps, The pipeline that the water outlet of the 17# flowings rinsing bowl is connected with the water inlet of 4# high-pressure pumps is equipped with 3# check valves, the 15# high It presses and is equipped with 5# pumps between the water outlet of atomizing spray slot and the water inlet of 14# flowing rinsing bowls.

In the nickeliferous tin wastewater collection unit, water inlet, the nickeliferous tin waste water of the nickeliferous tin wastewater collection pond A It is connected between the water outlet of the water inlet of collecting pit B and 14# flowing rinsing bowls by three-way pipe, and the three-way pipe The one end connected with 14# flowing rinsing bowls is equipped with 5# valves, and the three-way pipe is connected with the nickeliferous tin wastewater collection pond A One end be equipped with 6# valves, one end connect with the nickeliferous tin wastewater collection pond B of the three-way pipe is equipped with 7# valves；

The pipeline that the water outlet of the nickeliferous tin wastewater collection pond A is connected with the 1# water inlets pumped is equipped with 8# valves, described to contain The pipeline that the water outlet of nickel tin wastewater collection pond B is connected with the 1# water inlets pumped is equipped with 9# valves.

In the tin ion recovery unit, the water outlet of the 1# pumps is equipped with the pipeline that the water inlet of tin recycling can connects 10# valves, the pipeline that the water outlet of the tin recycling can is connected with the water inlet of 1# centrifuges are equipped with 11# valves, the 1# centrifuges Material mouth is detached equipped with solid-state and Liquid segregation material mouth, the Liquid segregation material mouth of the 1# centrifuges pass through pipeline and tin secondary crystallization The water inlet connection of tank；

The middle part of the tin secondary crystallization tank is equipped with the first supernatant delivery outlet, the second supernatant delivery outlet and third vertically Supernatant delivery outlet, the bottom of the tin secondary crystallization tank are equipped with the first crystallization delivery outlet, and the first of the tin secondary crystallization tank The pipeline that supernatant delivery outlet is connected with the 2# water inlets pumped is equipped with 12# valves, and the second supernatant of the tin secondary crystallization tank is defeated It exports the pipeline connected with the 2# water inlets pumped and is equipped with 13# valves, the third supernatant delivery outlet and 2# of the tin secondary crystallization tank The pipeline of the water inlet connection of pump is equipped with 14# valves, the first crystallization delivery outlet of the tin secondary crystallization tank and the water inlet of 2# pumps The pipeline of connection is equipped with 15# valves, and the pipeline that the first water outlet of the 2# pumps is connected with the water inlet of tin recycling can is equipped with 16# Valve, the pipeline that the second water outlet of the 2# pumps is connected with the water inlet of nickel recycling can are equipped with 17# valves；

The tin recycling can is internally provided with 1# electricity blenders, and the 2# electricity that is internally provided with of the tin secondary crystallization tank stirs Mix device.

In the nickel ion recovery unit, pipeline that the water outlet of the nickel recycling can is connected with the water inlet of 2# centrifuges Equipped with 18# valves, the 2# centrifuges are equipped with solid-state separation material mouth and Liquid segregation material mouth, the Liquid segregation material of the 2# centrifuges Mouth is connected by pipeline with the water inlet of nickel secondary crystallization tank；

The middle part of the nickel secondary crystallization tank is equipped with the 4th supernatant delivery outlet, the 5th supernatant delivery outlet and the 6th vertically Supernatant delivery outlet, the bottom of the nickel secondary crystallization tank are equipped with the second crystallization delivery outlet, and the 4th of the nickel secondary crystallization tank the The pipeline that supernatant delivery outlet is connected with the 3# water inlets pumped is equipped with 19# valves, and the 5th supernatant of the nickel secondary crystallization tank is defeated It exports the pipeline connected with the 3# water inlets pumped and is equipped with 20# valves, the 6th supernatant delivery outlet and 3# of the nickel secondary crystallization tank The pipeline of the water inlet connection of pump is equipped with 21# valves, the second crystallization delivery outlet of the nickel secondary crystallization tank and the water inlet of 3# pumps The pipeline of connection is equipped with 22# valves, and the pipeline that the first water outlet of the 3# pumps is connected with the water inlet of nickel recycling can is equipped with 23# Valve, the pipeline that the second water outlet of the 3# pumps is connected with the water inlet of the treatment unit for waste water are equipped with 24# valves；

The nickel recycling can is internally provided with 3# electricity blenders, and the 4# electricity that is internally provided with of the nickel secondary crystallization tank stirs Mix device.

The nickeliferous tin waste water retention unit is set, is responsible for retention 13# nickel pink salt coloring slot and 16# medium temperature sealing of hole slots is taken out of Medicament, make its reside in 14# flowing rinsing bowl, 15# high-pressure atomizations spray groove, 17# flowing rinsing bowl and 18# flowing rinsing bowl In, avoid with other mixed with water after reprocess the troubles of these magnanimity waste water, the ring for handling nickeliferous tin waste water is greatly reduced Guaranteed cost；The nickeliferous tin waste water retention unit using coloring sealing of hole water differential concatenation mode, by 16# medium temperature sealing of hole slots and 13# nickel pink salt coloring slot uses water differential concatenation, reduces half water, small-sized individually to handle nickeliferous tin waste water, equipment online Solid foundation has been established in change.

The nickeliferous tin that the nickeliferous tin wastewater collection unit is responsible for being collected separately the water outlet outflow of 14# flowing rinsing bowls gives up Water avoids being mixed with other with water, individually to handle.

The tin ion recovery unit recycles the Sn in nickeliferous tin waste water²⁺, it is reacted and is converted into solid stannic hydroxide, Realize the primary recycling of tin, reaction solution can be sodium carbonate；The nickel ion recovery unit recycles the Ni in nickeliferous tin waste water²⁺, will Its reaction is converted into solid basic nickel carbonate, realizes the primary recycling of nickel, and reaction solution can be sodium carbonate.The tin secondary crystallization Tank carries out tin secondary crystallization, and the tin secondary crystallization object after crystallization is pumped into the tin recycling can, realizes the secondary recovery of tin；It is described Nickel secondary crystallization tank carries out nickel secondary crystallization, and the nickel secondary crystallization object after crystallization is pumped into the nickel recycling can, realizes the two of nickel Secondary recycling.And the stannic hydroxide of acquisition and basic nickel carbonate are transformed into nickel pink salt colorant, realize solid dangerous waste resource It recycles.

The recovery method of the medicament recovery system of the coloring of nickel pink salt and medium temperature sealing of hole in being processed using the aluminium：

Step 1, opens the 1# valves, and tap water enters the 18# and flows rinsing bowl, then through the 2# check valves into Enter the 17# flowings rinsing bowl；The 4# high-pressure pumps are opened, water flows through the 3# check valves and enters 15# high-pressure atomization spray grooves； The 5# pumps are opened, the water of the 15# high-pressure atomizations spray groove is pumped into 14# flowing rinsing bowls；The 5# valves are opened, it is described The water of 14# flowing rinsing bowls is flowed out through the 5# valves, only one of ejected wash water differential concatenation flowing, completes a whole set of washing；

Step 2, the aluminium alloy for being wrapped with oxidation film is first after 13# nickel pink salt coloring slot is coloured, drip 30s；So Enter the 14# flowing rinsing bowl cleanings 60s, drip 30s afterwards；Enter back into the 15# high-pressure atomizations spray groove cleaning 60s, drop Flow 30s；Subsequently enter 16# medium temperatures sealing of hole slot the sealing of hole 15min, drip 30s；Enter 17# flowing rinsing bowl cleanings therewith 60s, drip 30s finally enter 18# flowing rinsing bowl cleaning 60s, drip 30s, complete nickeliferous tin waste water retention unit operation；

Step 3, opens the 6# valves, and the nickeliferous tin waste water of the 14# flowings rinsing bowl outflow gives up into the nickeliferous tin Water collecting pit A；Alternatively, opening 7# valves, the nickeliferous tin waste water of the 14# flowings rinsing bowl outflow enters the nickeliferous tin waste water and receives Collect pond B, complete nickeliferous tin wastewater collection unit operation；

Step 4 opens the 8# valves or 9# valves and opens the 10# valves, closes the 11# valves, opens the 1# pumps, The nickeliferous tin waste water of nickeliferous tin wastewater collection pond A or nickeliferous tin wastewater collection ponds B is pumped into the tin recycling can；Open the 1# Electric blender is slowly added to sodium carbonate, by the Sn in nickeliferous tin waste water toward the tin recycling can²⁺It is converted into solid hydroxide Tin；The 1# centrifuges are opened, open the 11# valves, carry out separation of solid and liquid, recycle solid stannic hydroxide, and by liquid Nickeliferous tin waste water flows into the tin secondary crystallization tank and carries out crystallization treatment；

After crystallization, the 12# valves, 13# valves or 14# valves are opened, closes 15# valves and 16# valves, the 2# pumps are opened, by institute It states the nickeliferous supernatant in tin secondary crystallization tank and is pumped into the nickel recycling can；Then, close the 12# valves, 13# valves, 14# valves and 17# valves open 15# valves and 16# valves, open the 2# pumps and 2# electricity blenders, and the tin in the tin secondary crystallization tank is secondary Crystal is pumped into the tin recycling can, carries out the secondary recovery of tin, completes the operation of tin ion recovery unit；

Step 5 opens the 3# electricity blender, sodium carbonate is slowly added to toward the nickel recycling can, by the nickeliferous supernatant Ni in liquid²⁺It is converted into solid basic nickel carbonate；The 2# centrifuges are opened, open the 18# valves, carry out separation of solid and liquid, Solid basic nickel carbonate is recycled, and the nickeliferous supernatant of liquid is flowed into the tin secondary crystallization tank and carries out crystallization treatment；

After crystallization, open the 19# valves, 20# valves or 21# valves and open 24# valves, close 22# valves and 23# valves, open institute 3# pumps are stated, are neutralized subsequent treatment unit for waste water is pumped into without nickel supernatant in the nickel secondary crystallization tank； Then, the 19# valves, 20# valves, 21# valves and 24# valves are closed, opens 22# valves and 23# valves, opens the 3# pumps and the stirring of 4# electricity Nickel secondary crystallization object in the nickel secondary crystallization tank is pumped into the nickel recycling can by device, carries out the secondary recovery of nickel, completes nickel Ion recovery unit operates；

Step 6 after the stannic hydroxide rinsed clean for obtaining the step 4, after adding in pure water moistening, is slowly added sulphur Sour (98%), under conditions of excess sulfuric acid, reaction generation stannous sulfate solution, and the pH value of the stannous sulfate solution when generation Stop reaction when=0.8；Detection mark stannous sulfate concentration；

Step 7 after the basic nickel carbonate rinsed clean for obtaining the step 5, after adding in pure water moistening, is slowly added Sulfuric acid (98%), under conditions of excess sulfuric acid, reaction generation sulfuric acid Asia nickel solution, and set the sulfuric acid Asia nickel solution of generation PH value=0.8 is reaction end；Detection mark sulfuric acid Asia nickel concentration；

Step 8, the nickel pink salt that slot is coloured according to the 13# nickel pink salt colour Con trolling index, titrated sulfuric acid stannous solution Concentration and the concentration of sulfuric acid Asia nickel solution add tartaric acid, and the nickel pink salt that formation can be added directly to 13# nickel pink salt coloring slot Toner.

The nickeliferous tin that nickel pink salt colorant recovery method generates for heat-tinting sealing of hole in aluminium processing in the aluminium processing Toxic waste residue, utilize online classification recycling and compatibility method, selected dosage component, ingenious configuration system, it is ensured that recycling it is nickeliferous Tin product reuse to 13# nickel pink salt colours slot, realizes that the resource recycling of toxic waste utilizes.And by the hydroxide of acquisition Tin and basic nickel carbonate are transformed into nickel pink salt colorant, realize recycling for solid dangerous waste resource.

The nickel pink salt of the 13# nickel pink salt coloring slot colours Con trolling index and is：Stannous sulfate 10g/L, nickel sulfate 25g/L, Sulfuric acid 18g/L, tartaric acid 8g/L, pH value 0.8-1.2, temperature are 20-25 DEG C, processing time 30s-15min, and voltage is 14-16V。

In the step 4, while being slowly added to sodium carbonate toward the tin recycling can, detect in the tin recycling can The pH value of solution when the pH value of the solution in the tin recycling can reaches 4.8, stops adding in sodium carbonate, continues to stir 30min；

In the step 5, while being slowly added to sodium carbonate toward the nickel recycling can, detect in the nickel recycling can The pH value of solution when the pH value of the solution in the nickel recycling can reaches 9.0, stops adding in sodium carbonate, continues to stir 30min。

The medium temperature sealing of hole index of the 16# medium temperatures sealing of hole slot be nickel acetate 5g/L, triethanolamine 0.5g/L, isobutanol 0.5g/L, pH value 5.5-6.5, temperature are 50-60 DEG C, processing time 10-25min；

The thickness of the oxidation film of the aluminum alloy surface is 15 microns.

3rd, the quantitative and qualitative analysis of the coloring of nickel pink salt and sealing of hole ejected wash water remanufacture colorant

After reverse phase washing series-connection, the 14# flowings water outlet sulfur acid nickel of rinsing bowl, stannous sulfate, nickel acetate, sulfuric acid, three Ethanol amine and isobutanol take 50Kg tank liquors out of by (2), (7) formula and aluminium per ton, 2.5 tons of water for cleaning of consumption calculate, 14# streams The drug concentration of the water outlet of dynamic rinsing bowl colours 2% or so of slot and 16# medium temperature sealing of hole slot concentration, i.e. sulphur for 13# nickel pink salt Sour nickel 0.5g/L, stannous sulfate 0.2g/L, tartaric acid 0.16g/L, sulfuric acid 0.36g/L, nickel acetate 0.1g/L, triethanolamine 0.01g/L, isobutanol 0.01g/L.The processing mode of each chemical constituent is as follows：

1st, stannous ion crystallization is precipitated contained by stannous sulfate.By (2), (7) control 13# nickel pink salt coloring slot and 16# medium temperatures Sealing of hole slot, differential concatenation washing production coloring sealing of hole material, takes 14# to flow the ejected wash water 1L of the water outlet of rinsing bowl, test agents It is a concentration of：

Stannous sulfate 0.22g/L, nickel sulfate 0.53g/L, tartaric acid 0.17g/L, nickel acetate 0.12g/L, triethanolamine 0.01g/L, isobutanol 0.01g/L, pH value are 1.86 (8)；

Sodium carbonate is slowly added, pH value is stepped up, and following variation occurs：

When pH value is less than 2.0, due to the complexing of tartaric acid, tank liquor is clear, no precipitation, no precipitate；

When pH is between 2.0-3.0, tank liquor starts muddiness, a small amount of white precipitate stannous hydroxide occurs：

Sn²⁺+2OH^-=Sn (OH)₂↓ (9)；

When pH is between 3.0-4.0, tank liquor is muddy, and white precipitate stannous hydroxide increases；

When pH is between 4.0-4.5, tank liquor is muddy, and white precipitate stannous hydroxide continues to increase；

When pH is between 4.5-5.0, tank liquor is muddy, and white precipitate stannous hydroxide is not further added by.Separation of solid and liquid, drift It washes, dry, the yellowish crystalline powder stannous hydroxide of technical grade of national standard must be met.

2nd, nickel ion crystallization is precipitated contained by nickel sulfate and nickel acetate.

By (9) formula, separation of solid and liquid is carried out, the drug concentration for detecting liquid is：

Nickel sulfate 0.52g/L, nickel acetate 0.11g/L, tartaric acid 0.15g/L, triethanolamine 0.01g/L, isobutanol 0.01g/L, pH value are 4.85 (10)；

Sodium carbonate is slowly added, pH value is stepped up, and following variation occurs：

When pH value is less than 7.0, due to the complexing of tartaric acid, tank liquor is clear, no precipitation, no precipitate；

When pH is between 7.0-7.5, tank liquor starts muddiness, a small amount of white precipitate basic nickel carbonate occurs：

3Ni²⁺+4OH^-+CO₃ ^2-+4H₂O=NiCO₃.2Ni(OH)₂.4H₂O↓ (11)；

When pH is between 7.5-8.0, tank liquor is muddy, and white precipitate basic nickel carbonate increases；

When pH is between 8.0-8.5, tank liquor is muddy, and white precipitate basic nickel carbonate continues to increase；

When pH is between 8.5-9.0, tank liquor is muddy, and white precipitate basic nickel carbonate is not further added by.

3rd, tartaric acid, triethanolamine and isobutanol do not react, and retain in liquid.By (11) formula, with adding for sodium carbonate Add, pH is constantly increased, Ni²⁺Constantly reaction generation NiCO₃、Ni(OH)₂、NiCO₃-2Ni(OH)₂-4H₂O, but tartaric acid, three ethyl alcohol Amine and isobutanol are not decomposed, are not precipitated, retain in liquid under conditions of pH value is no more than 9.

4th, separation of solid and liquid isolates tartaric acid, triethanolamine and isobutanol with liquid, recycles solid basic nickelous carbonate.It presses (11) reaction product is carried out separation of solid and liquid by formula.Tartaric acid, triethanolamine and isobutanol are flowed out with liquid, obtain solid basic Nickelous carbonate；Through rinsing, drying, the technical grade basic nickel carbonate product for meeting national standard is obtained.

5th, principle is compatible with by medicament, regenerates nickel pink salt colorant, realize that solid dangerous waste resource recycling utilizes.

1) stannous sulfate solution, is produced.Weigh stannous hydroxide product 100g (the only laboratories obtained after rinsing is dried Dried during metering, rinsed clean when producing greatly, it is not necessary to dry, save production cost) and appropriate glass putty, add 100g pure water wet Profit, is slowly added sulfuric acid (98%), and reaction is as follows：

Sn(OH)₂+H₂SO₄=SnSO₄+2H₂O；

By reaction equation (3) to (6), the part tetravalent tin generated is restored with glass putty：

Sn+Sn(OH)₄+2H₂SO₄=2SnSO₄+4H₂O (12)；

Take excess sulfuric acid, when detecting the pH value of stannous sulfate solution=0.8, as reaction end；It is dense to detect stannous sulfate It spends spare；

2) nickel sulfate solution, is produced.Weigh basic nickel carbonate product 100g (the only laboratory meters obtained after rinsing is dried Dried during amount, rinsed clean when producing greatly, it is not necessary to dry, save production cost), 100g pure water is added to moisten, is slowly added Sulfuric acid (98%), reaction are as follows：

NiCO₃.2Ni(OH)₂.4H₂O+3H₂SO₄=3NiSO₄+9H₂O+CO₂↑ (13)；

Excess sulfuric acid is taken, when detecting the pH value of nickel sulfate solution=0.8, as reaction end；It is standby to detect concentration of nickel sulfate With；

3) nickel pink salt coloring liquid, is prepared.The stannous sulfate solution that (12) formula is taken to produce, the nickel sulfate of (13) formula production are molten Liquid, by (2) formula, nickel pink salt coloring slot Con trolling index is：Stannous sulfate 10g/L, nickel sulfate 25g/L, sulfuric acid 18g/L, tartaric acid 8g/L, pH value 0.8-1.2, temperature are 20-25 DEG C, processing time 30s-15min, voltage 14-16V.

Remodeling method is：

Concentration of nickel sulfate/stannous sulfate concentration=25/10 (g/L)

Concentration of nickel sulfate/tartaric acid concentration=25/8 (g/L) (14)；

First by (9) formula, stannous hydroxide is obtained, basic nickel carbonate is produced by (11) formula；Then sulphur is produced by (12) formula Sour stannous produces nickel sulfate by (13) formula；Finally, by (14) formula, nickel pink salt coloring liquid is prepared.Due to 16# medium temperature sealing of hole slots Chemical agent is compatible with 13# nickel pink salt coloring slot substantially, therefore by the nickel pink salt colorant of (14) formula production, it completely can be with reuse Slot is coloured to 13# nickel pink salt.

4th, the coloring of nickel pink salt and the experimental result of sealing of hole ejected wash water remanufacture nickel pink salt colorant

The nickel pink salt coloring Con trolling index that experiment 1 and 2 is provided by (2) formula, investigates the nickel pink salt by the production of (14) formula respectively The colorability of colorant.

The influence of experiment 1, stannous sulfate concentration (practical is colorant concentration) to colorability.PH value is taken as 1.0, temperature It is 25 DEG C, stannous sulfate 4,6,8,10,12,14g/L；It is 15 microns to take oxide thickness, and coloration time is 4 minutes, observes aluminium Material appearance color, the results are shown in Table 1：

Table 1

The influence of experiment 2, coloration time to coloring color.By (14) formula, taking stannous sulfate 10g/L, (nickel sulfate is at this time 25g/L, tartaric acid 8g/L), 25 DEG C of temperature, pH value 1.0；Oxide thickness is taken as 15 microns, coloration time 6,8,10, 12nd, 14,16 minutes, the results are shown in Table 2：

Table 2

5th, the coloring of nickel pink salt and the analysis of experimental results of sealing of hole ejected wash water remanufacture nickel pink salt colorant

By reaction equation (8) to (14) and experiment 1 to 2 and testing result, following analysis can be done：

1st, by formula (8), the principle being compatible with using sealing of hole washing to 16# medium temperature sealing of holes slot itself can be used sealing of hole with water conservancy The method of high-pressure atomization spray washing, differential concatenation to coloring water, two sets of washings are combined into one, and half water are saved, in 14# Nickeliferous tin waste water is recycled in the water outlet retention for flowing rinsing bowl；

By (9) formula, the nickeliferous tin waste water of retention can individually be handled online, recycle the stannous hydroxide of technical grade, will contain Nickel tin solid dangerous waste is converted into the industrial chemicals of high value, realizes the recycling of solid dangerous waste；

By (11) formula, the nickeliferous tin waste water of retention can individually be handled online, recycle the basic nickel carbonate of technical grade, will contain Nickel tin solid dangerous waste is converted into high value industrial chemicals, realizes the recycling of solid dangerous waste；

By (12) formula, the stannous hydroxide of recycling can be further processed, stannous sulfate solution be produced, by nickeliferous tin solid Dangerous waste is converted into the industrial chemicals of high value, realizes the recycling of solid dangerous waste；

By (13) formula, the basic nickel carbonate of recycling can be further processed, produce nickel sulfate solution, nickeliferous tin solid is endangered The useless industrial chemicals for being converted into high value realizes the recycling of solid dangerous waste；

By (14) formula, stannous sulfate, nickel sulfate solution that can be to conversion by (2) formula, be configured to nickel pink salt coloring liquid, return With to coloring slot, resource circulation utilization is realized；

Empirically 1 and 2 result is it is found that in the nickel pink salt in the range of Con trolling index, made as defined in (2) formula by (14) formula Colorant is fully able to the coloring requirement for meeting 13# nickel pink salt coloring slot.

As shown in Figure 7, continuous production coloring sealing of hole aluminium, 13# nickel pink salt coloring slot are constantly added by (2) formula Con trolling index The coloring liquid that the present embodiment recycling makes；The pH value for taking coloring liquid is 1.0, temperature is 25 DEG C, stannous sulfate 6-10g/L；Take oxygen It is 15 microns to change film thickness, and coloration time is 10 minutes, as a result as shown in table 3 below：

Table 3

There is the medicament recovery system of the coloring of nickel pink salt and medium temperature sealing of hole with following with method in the aluminium processing of the present embodiment Beneficial effect：

The 1st, nickeliferous tin waste water retention unit is set for the first time, be responsible for retention 13# nickel pink salt coloring slot and 16# medium temperature sealing of hole slot bands The medicament gone out.By Fig. 7, during production coloring sealing of hole aluminium, rinsing bowl retains nickeliferous tin waste water, individually handles, avoid and other The trouble of these magnanimity waste water is reprocessed after being mixed with water, the environmentally friendly cost for handling nickeliferous tin waste water is greatly reduced；

2nd, for the first time in nickeliferous tin waste water retention system using coloring sealing of hole water differential concatenation mode.As shown in Figure 6, it passes When system mode produces coloring sealing of hole aluminium, two sets ejected wash waters independence mutually, ton material water consumption is at 4 tons or more, whole industry water consumption 16000000 tons；As shown in Figure 7, sealing of hole and coloring water differential concatenation are reduced into half water for the first time, contained for online individually processing Nickel tin waste water, stable stannous, device miniaturization have established solid foundation；

The 3rd, nickeliferous tin wastewater collection unit is set online for the first time, be responsible for being collected separately the water outlet stream of 14# flowing rinsing bowls The nickeliferous tin waste water gone out, avoids being mixed with other with water, individually to handle；

The 4th, tin ion recovery unit is set online for the first time, be responsible for the waste water of nickeliferous tin wastewater collection pond being pumped into tin recycling Tank recycles Sn²⁺, reaction generation stannous hydroxide, realization separation of solid and liquid；Supernatant in tin secondary crystallization tank is pumped into nickel recycling The secondary crystallization object of tin secondary crystallization pot bottom is pumped into tin recycling can, carries out secondary recovery by tank again；

The 5th, nickel ion recovery unit is set online for the first time, be responsible for recycling Ni²⁺, reaction generation basic nickel carbonate, realization solid-liquid Separation；Supernatant in nickel secondary crystallization tank is pumped into wastewater treatment center neutralisation treatment, by the two of nickel secondary crystallization pot bottom Secondary crystal is pumped into nickel recycling can again, carries out secondary recovery；

6th, the stannous hydroxide of recycling is further processed for the first time, produces stannous sulfate solution, nickeliferous tin solid is endangered The useless industrial chemicals for being converted into high value realizes the recycling of solid dangerous waste；

7th, the basic nickel carbonate of recycling is further processed for the first time, nickel sulfate solution is produced, by nickeliferous tin solid dangerous waste The industrial chemicals of high value is converted into, realizes the recycling of solid dangerous waste；

8th, for the first time to the stannous sulfate of conversion, nickel sulfate solution, coloring liquid requirement is configured to nickel pink salt coloring liquid, reuse To coloring slot, resource circulation utilization is realized.

The technical principle of the present invention is described above in association with specific embodiment.These descriptions are intended merely to explain the present invention's Principle, and it cannot be construed to limiting the scope of the invention in any way.Based on explanation herein, the technology of this field Personnel would not require any inventive effort the other specific embodiments that can associate the present invention, these modes are fallen within Within protection scope of the present invention.

Claims (10)

1. the medicament recovery system of the coloring of nickel pink salt and medium temperature sealing of hole in a kind of aluminium processing includes nickeliferous successively from upstream to downstream Tin waste water retention unit, nickeliferous tin wastewater collection unit, tin ion recovery unit and nickel ion recovery unit, it is characterised in that：

The nickeliferous tin waste water retention unit includes the 13# nickel pink salt being arranged in order coloring slot, 14# flowings rinsing bowl, 15# high pressures Atomizing spray slot, 16# medium temperature sealing of holes slot, 17# flowing rinsing bowls and 18# flowing rinsing bowls, the 18# flowings rinsing bowl are external certainly Water, the 14# flowings rinsing bowl, 15# high-pressure atomizations spray groove, 17# flowing rinsing bowls and 18# flowing rinsing bowl differential concatenations Setting, the 16# medium temperatures sealing of hole slot is to the coloring slot compatibility setting of 13# nickel pink salt；

The nickeliferous tin wastewater collection unit includes nickeliferous tin wastewater collection pond A and nickeliferous tin wastewater collection pond B, the 14# streams The water outlet of dynamic rinsing bowl be respectively equipped with the nickeliferous tin wastewater collection pond A pipelines connected and with nickeliferous tin wastewater collection pond B The pipeline of connection；

The tin ion recovery unit includes the 1# pumps, tin recycling can, 1# centrifuges, tin secondary crystallization tank and the 2# that are arranged in order Pump, the 1# pumps return for the nickeliferous tin waste water of nickeliferous tin wastewater collection pond A and nickeliferous tin wastewater collection pond B to be pumped into the tin Closed cans, the tin recycling can are used for the Sn in nickeliferous tin waste water²⁺Solid stannic hydroxide is converted into, the 1# centrifuges are used for Solid stannic hydroxide and the nickeliferous tin waste water of liquid are detached, the tin secondary crystallization tank is in the nickeliferous tin waste water after separation Sn²⁺Secondary crystallization, 2# pump recycles for the tin secondary crystallization object in the tin secondary crystallization tank to be pumped into the tin Tank；

The nickel ion recovery unit includes the nickel recycling being arranged in order, 2# centrifuges, nickel secondary crystallization tank and 3# pumps, described 2# pumps are additionally operable to the nickeliferous supernatant in the tin secondary crystallization tank being pumped into the nickel recycling can, and the nickel recycling can is used for will Ni in the nickeliferous supernatant²⁺Solid basic nickel carbonate is converted into, the 2# centrifuges are used to detach solid alkali formula carbon The nickeliferous supernatant of sour nickel and liquid, the nickel secondary crystallization tank is for the Ni in the nickeliferous supernatant after separation²⁺Secondary knot Crystalline substance, 3# pump by the nickel secondary crystallization object in the nickel secondary crystallization tank for being pumped into the nickel recycling can and will be after crystallization No nickel supernatant is pumped into subsequent treatment unit for waste water.

2. the medicament recovery system of the coloring of nickel pink salt and medium temperature sealing of hole in aluminium processing according to claim 1, feature exist In：In the nickeliferous tin waste water retention unit, the pipeline of the external tap water of the water inlet of the 18# flowings rinsing bowl is equipped with 1# valves, the pipeline that the water outlet and the water inlet of 17# flowing rinsing bowls of the 18# flowings rinsing bowl connect are unidirectional equipped with 2# Valve, the 15# high-pressure atomizations spray groove water inlet and 17# flowing rinsing bowl water outlet between be equipped with 4# high-pressure pumps, it is described The pipeline that the water outlet of 17# flowing rinsing bowls is connected with the water inlet of 4# high-pressure pumps is equipped with 3# check valves, the 15# high pressures mist Change and be equipped with 5# pumps between the water outlet of spray groove and the water inlet of 14# flowing rinsing bowls.

3. the medicament recovery system of the coloring of nickel pink salt and medium temperature sealing of hole in aluminium processing according to claim 2, feature exist In：

In the nickeliferous tin wastewater collection unit, the water inlet of the nickeliferous tin wastewater collection pond A, the nickeliferous tin wastewater collection The water inlet of pond B and the 14# flowing rinsing bowl water outlet between connected by three-way pipe, and the three-way pipe and institute State 14# flowing rinsing bowl connection one end be equipped with 5# valves, connected with the nickeliferous tin wastewater collection pond A the one of the three-way pipe End is equipped with 6# valves, and one end connected with the nickeliferous tin wastewater collection pond B of the three-way pipe is equipped with 7# valves；

The pipeline that the water outlet of the nickeliferous tin wastewater collection pond A is connected with the 1# water inlets pumped is equipped with 8# valves, the nickeliferous tin The pipeline that the water outlet of wastewater collection pond B is connected with the 1# water inlets pumped is equipped with 9# valves.

4. the medicament recovery system of the coloring of nickel pink salt and medium temperature sealing of hole in aluminium processing according to claim 3, feature exist In：

In the tin ion recovery unit, the pipeline that the water outlet of the 1# pumps is connected with the water inlet of tin recycling can is equipped with 10# Valve, the pipeline that the water outlet of the tin recycling can is connected with the water inlet of 1# centrifuges are equipped with 11# valves, and the 1# centrifuges are equipped with Solid-state detaches material mouth and Liquid segregation material mouth, and the Liquid segregation material mouths of the 1# centrifuges passes through pipeline and tin secondary crystallization tank Water inlet connects；

The middle part of the tin secondary crystallization tank is equipped with the first supernatant delivery outlet, the second supernatant delivery outlet and third supernatant vertically Liquid delivery outlet, the bottom of the tin secondary crystallization tank are equipped with the first crystallization delivery outlet, the first supernatant of the tin secondary crystallization tank The pipeline that liquid delivery outlet is connected with the 2# water inlets pumped is equipped with 12# valves, the second supernatant delivery outlet of the tin secondary crystallization tank The pipeline connected with the water inlet of 2# pumps is equipped with 13# valves, third supernatant delivery outlet and the 2# pump of the tin secondary crystallization tank The pipeline of water inlet connection is equipped with 14# valves, and the first crystallization delivery outlet of the tin secondary crystallization tank is connected with the 2# water inlets pumped Pipeline be equipped with 15# valves, the pipeline that the first water outlet of the 2# pump connect with the water inlet of tin recycling can is equipped with 16# valves, institute It states the pipeline that the second water outlet that 2# is pumped is connected with the water inlet of nickel recycling can and is equipped with 17# valves；

The tin recycling can is internally provided with 1# electricity blenders, and the tin secondary crystallization tank is internally provided with the stirring of 2# electricity Device.

5. the medicament recovery system of the coloring of nickel pink salt and medium temperature sealing of hole in aluminium processing according to claim 4, feature exist In：

In the nickel ion recovery unit, the water outlet of the nickel recycling can is equipped with the pipeline that the water inlet of 2# centrifuges connects 18# valves, the 2# centrifuges are equipped with solid-state separation material mouth and Liquid segregation material mouth, the Liquid segregation material mouth of the 2# centrifuges are led to Piping is connected with the water inlet of nickel secondary crystallization tank；

The middle part of the nickel secondary crystallization tank is equipped with the 4th supernatant delivery outlet, the 5th supernatant delivery outlet and the 6th supernatant vertically Liquid delivery outlet, the bottom of the nickel secondary crystallization tank are equipped with the second crystallization delivery outlet, the 4th supernatant of the nickel secondary crystallization tank The pipeline that liquid delivery outlet is connected with the 3# water inlets pumped is equipped with 19# valves, the 5th supernatant delivery outlet of the nickel secondary crystallization tank The pipeline connected with the water inlet of 3# pumps is equipped with 20# valves, the 6th supernatant delivery outlet and the 3# pump of the nickel secondary crystallization tank The pipeline of water inlet connection is equipped with 21# valves, and the second crystallization delivery outlet of the nickel secondary crystallization tank is connected with the 3# water inlets pumped Pipeline be equipped with 22# valves, the pipeline that the first water outlet of the 3# pump connect with the water inlet of nickel recycling can is equipped with 23# valves, institute It states the pipeline that the second water outlet that 3# is pumped is connected with the water inlet of the treatment unit for waste water and is equipped with 24# valves；

The nickel recycling can is internally provided with 3# electricity blenders, and the nickel secondary crystallization tank is internally provided with the stirring of 4# electricity Device.

6. use the recycling side of the medicament recovery system of the coloring of nickel pink salt and medium temperature sealing of hole in the aluminium processing described in claim 5 Method, it is characterised in that：

Step 1 opens the 1# valves, and tap water enters the 18# and flows rinsing bowl, then enters institute through the 2# check valves State 17# flowing rinsing bowls；The 4# high-pressure pumps are opened, water flows through the 3# check valves and enters 15# high-pressure atomization spray grooves；It opens The water of the 15# high-pressure atomizations spray groove is pumped into 14# flowing rinsing bowls by the 5# pumps；Open the 5# valves, the 14# streams The water of dynamic rinsing bowl is flowed out through the 5# valves；

Step 2, the aluminium alloy for being wrapped with oxidation film is first after 13# nickel pink salt coloring slot is coloured, drip 30s；Then into Enter 14# flowings rinsing bowl the cleaning 60s, drip 30s；Enter back into the 15# high-pressure atomizations spray groove cleaning 60s, drip 30s；Subsequently enter 16# medium temperatures sealing of hole slot the sealing of hole 15min, drip 30s；Enter 17# flowing rinsing bowl cleaning 60s therewith, Drip 30s finally enters 18# flowing rinsing bowl cleanings 60s, drip 30s；

Step 3, opens the 6# valves, and the nickeliferous tin waste water of the 14# flowings rinsing bowl outflow enters the nickeliferous tin waste water and receives Collect pond A；Alternatively, opening 7# valves, the nickeliferous tin waste water of the 14# flowings rinsing bowl outflow enters the nickeliferous tin wastewater collection pond B；

Step 4 opens the 8# valves or 9# valves and opens the 10# valves, closes the 11# valves, opens the 1# pumps, will contain The nickeliferous tin waste water of nickel tin wastewater collection pond A or nickeliferous tin wastewater collection ponds B is pumped into the tin recycling can；The 1# electricity is opened to stir Device is mixed, sodium carbonate is slowly added to toward the tin recycling can, by the Sn in nickeliferous tin waste water²⁺It is converted into solid stannic hydroxide；It opens The 1# centrifuges are opened, open the 11# valves, carry out separation of solid and liquid, recycle solid stannic hydroxide, and by the nickeliferous tin of liquid Waste water flows into the tin secondary crystallization tank and carries out crystallization treatment；

After crystallization, the 12# valves, 13# valves or 14# valves are opened, closes 15# valves and 16# valves, the 2# pumps are opened, by the tin Nickeliferous supernatant in secondary crystallization tank is pumped into the nickel recycling can；Then, the 12# valves, 13# valves, 14# valves and 17# are closed Valve opens 15# valves and 16# valves, the 2# pumps and 2# electricity blenders is opened, by the tin secondary crystallization in the tin secondary crystallization tank Object is pumped into the tin recycling can, carries out the secondary recovery of tin；

Step 5 opens the 3# electricity blender, and sodium carbonate is slowly added to toward the nickel recycling can, will be in the nickeliferous supernatant Ni²⁺It is converted into solid basic nickel carbonate；The 2# centrifuges are opened, open the 18# valves, carry out separation of solid and liquid, recycling Solid basic nickel carbonate, and the nickeliferous supernatant of liquid is flowed into the tin secondary crystallization tank and carries out crystallization treatment；

After crystallization, open the 19# valves, 20# valves or 21# valves and open 24# valves, close 22# valves and 23# valves, open the 3# Pump, is neutralized subsequent treatment unit for waste water is pumped into without nickel supernatant in the nickel secondary crystallization tank；Then, The 19# valves, 20# valves, 21# valves and 24# valves are closed, opens 22# valves and 23# valves, opens the 3# pumps and 4# electricity blenders, it will Nickel secondary crystallization object in the nickel secondary crystallization tank is pumped into the nickel recycling can, carries out the secondary recovery of nickel.

7. the recycling side of the medicament recovery system of the coloring of nickel pink salt and medium temperature sealing of hole in aluminium processing according to claim 6 Method, which is characterized in that further comprising the steps of：

Step 6 after the stannic hydroxide rinsed clean for obtaining the step 4, after adding in pure water moistening, is slowly added sulfuric acid (98%), under conditions of excess sulfuric acid, reaction generation stannous sulfate solution, and the pH value of stannous sulfate solution that ought be generated= Stop reaction when 0.8；

Step 7 after the basic nickel carbonate rinsed clean for obtaining the step 5, after adding in pure water moistening, is slowly added sulfuric acid (98%), under conditions of excess sulfuric acid, reaction generation sulfuric acid Asia nickel solution, and set the pH value of the sulfuric acid Asia nickel solution of generation =0.8 is reaction end；

Step 8, the nickel pink salt that slot is coloured according to the 13# nickel pink salt colour Con trolling index, the concentration of titrated sulfuric acid stannous solution Concentration with sulfuric acid Asia nickel solution adds tartaric acid, and the nickel pink salt of the 13# nickel pink salt coloring slot can be added directly to by, which being formed, Toner.

8. the recycling side of the medicament recovery system of the coloring of nickel pink salt and medium temperature sealing of hole in aluminium processing according to claim 7 Method, which is characterized in that the nickel pink salt of the 13# nickel pink salt coloring slot colours Con trolling index and is：Stannous sulfate 10g/L, nickel sulfate 25g/L, sulfuric acid 18g/L, tartaric acid 8g/L, pH value 0.8-1.2, temperature are 20-25 DEG C, processing time 30s-15min, electricity It presses as 14-16V.

9. the recycling side of the medicament recovery system of the coloring of nickel pink salt and medium temperature sealing of hole in aluminium processing according to claim 6 Method, it is characterised in that：

In the step 4, while being slowly added to sodium carbonate toward the tin recycling can, the solution in the tin recycling can is detected PH value, when the pH value of the solution in the tin recycling can reaches 4.8, stop add in sodium carbonate, continue stir 30min；

In the step 5, while being slowly added to sodium carbonate toward the nickel recycling can, the solution in the nickel recycling can is detected PH value, when the pH value of the solution in the nickel recycling can reaches 9.0, stop add in sodium carbonate, continue stir 30min.

10. the recycling side of the medicament recovery system of the coloring of nickel pink salt and medium temperature sealing of hole in aluminium processing according to claim 6 Method, it is characterised in that：

The medium temperature sealing of hole index of the 16# medium temperatures sealing of hole slot be nickel acetate 5g/L, triethanolamine 0.5g/L, isobutanol 0.5g/L, PH value is 5.5-6.5, and temperature is 50-60 DEG C, processing time 10-25min；

The thickness of the oxidation film of the aluminum alloy surface is 15 microns.