CN108191107A - The recovery system and method for single nickel salt coloring and medium temperature sealing of hole medicament in aluminium processing - Google Patents

Abstract

The recovery system and method for single nickel salt coloring and medium temperature sealing of hole medicament in aluminium processing, the system includes nickel-containing waste water retention unit, nickel-containing waste water collector unit and basic nickel carbonate recovery unit, the 18# flowing external tap water of rinsing bowl in nickel-containing waste water retention unit, 14# flowings rinsing bowl, 15# flowings rinsing bowl, 17# flow rinsing bowl and 18# flowing rinsing bowl differential concatenation settings, and 13# single nickel salts colour slot and are compatible with setting to 16# medium temperature sealing of holes slot；Nickel-containing waste water collector unit includes nickel-containing waste water collecting pit A and the water outlet of nickel-containing waste water collecting pit B, 14# flowing rinsing bowl is equipped with the pipeline for connecting with nickel-containing waste water collecting pit A and being connect with nickel-containing waste water collecting pit B；Basic nickel carbonate recovery unit includes 1# pumps, recycling can, centrifuge, secondary crystallization tank and 2# pumps；The present invention can online classification collect nickel-containing waste water, on the basis of medicament compatibility, recycle basic nickel carbonate containing nickel product, be converted to medium temperature hole sealing agent, realize the recycling of toxic waste and recycle.

Description

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

Technical field

The present invention relates to single nickel salt coloring in aluminum processing technology field, more particularly to aluminium processing and times of medium temperature sealing of hole medicament Receive System and method for.

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.With the development of economy, aluminium scrap ash amount of savings will increase considerably year by year, if not finding economical and effective, innoxious Method is pocessed, and will increasingly highlight its serious threat to environment.The recycling of China's aluminium ash at present is still in the starting stage, Lack that technology maturation is reliable, recovery method of good economy performance, the aluminium ash processing rate of recovery is low, energy consumption and waste are big, utilizes way Diameter is few.Even if still containing a large amount of harmful substances in treated aluminium ash, still can only stockyard stockpiling or burial processing, with pole Big environmental hazard, while producer carries huge illegal risk.Execution from 1 day January in 2018《Chinese people's republicanism 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.Containing a large amount of in the waste liquid exhausted Aluminium ion and sodium hydroxide, potential economic value are very big.The mode of " treatment of wastes with processes of wastes against one another " is generally taken in the processing for stewing mould waste liquid: 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 with regard to that can account for enterprise 30% or so of total quantity of slag.Not only without using its economic value, increasing cost instead, waste water, waste residue are processed into for enterprise For 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 Anion, and organic matters such as 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.Oxidation electrophoresis material ratio declines, but most of aluminiums in recent years More than alkaline waste water, soda acid water all mixes processing, in acidity after waste water mixing, needs input greatly for factory or acid waste water The piece alkali of amount, lime and PAC, PAM, produce a large amount of waste residues.

The latest edition of August execution from 1 day in 2016《National Hazard waste register》Acid and alkaline waste water waste residue is arranged Enter register management, waste classification is HW34, HW35 respectively.The execution from 1 day January in 2018《People's Republic of China's environment Protect tax law》Regulation, enterprise must pay 1000 yuan/ton of wastewater treatment sludge environment-friendly tax.

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, such as Fig. 2, are that certain is large-scale Aluminum material factory Aluminiferous waste slag source situation.Waste residue belongs to hazardous waste, has great environmental hazard.Existing situation forces enterprise Will be to energy-saving and emission-reduction and resource circulation utilization direction Transformation Development, but lack the technology of mature and reliable.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.The artificial of small workshop mode fries ash Method is also largely using, this method is open type operation, generates a large amount of dust smog.Other methods also have squeeze absorption method, etc. from The instant method of son, 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, for the Transport And Transformation of the harmful elements such as aluminium ash processing procedure fluorine and heavy metal Mechanism lacks more deep discussion.

In the case of resource scarcity, environmental pollution getting worse, the development of aluminium processing industry faces the huge of resource and environment Pressure, energy-saving and emission-reduction, resource circulation utilization are following developing direction and the only way.Accomplish aluminium ash resource " zero is useless Abandon ", it is necessary to change utilization of resources thinking, make full use of the various composition in aluminium ash, carry out harmless treatment, resource maximizationization It utilizes.This work is very urgent, needs specific direction, standard guidance, multiparty collaboration, 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, such as the Crystalfix chemical recovery systems of Italy, but because flow is complicated, comprehensive benefit is not high, it is practical to answer It is few.Aluminium processing enterprise processing stew mould waste liquid common practice be:Mould waste water is stewed to neutralize with the spent acid that oxidation operation generates Precipitation post-processes slag processed, only stews the waste residue that mould waste liquid generates and just accounts for 30% or so of the total quantity of slag of enterprise.Enterprise does not have back not only It receives using the useful resources such as sodium hydroxide, aluminium ion in mould waste liquid are stewed, increases cost instead, waste water, waste residue are processed into For 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, can only stop production manual cleaning at this time, take time and effort.There is a small amount of producer to come into operation online soda recovery unit, because of recovering effect not It is good, of high cost, it has given it up mostly.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, and part of the manufacturer is using, but efficiency is low and generates a large amount of condensed waters, Effect is equally preferable not to the utmost.The processing of nickel-containing waste water uses the precipitation method, adds in sodium hydroxide and PAM, adjusts pH, reaction generation hydrogen Nickel oxide precipitates, and nickel slag is obtained after dewatering and filtering mud.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 summary, 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, Chinese patent CN 1319302C discloses a kind of method using fluorine-containing acid sludge preparing hydrogen aluminium oxide, this patented technology Shuo Jia producers are practical should With achieving fabulous economic benefit, while solve the processing problem of acid sludge.

Except the technology that aluminium hydroxide is produced using acid sludge is succeeded in addition to, other major part methods do not have scale Using the comprehensive utilization ratio of aluminium slag is very low, and main cause or technology are immature, added value of product is low, cost is higher.Exhausted big portion Point waste residue is all that aluminum material factory's payment process of spending is fallen, and pile up like a mountain for the waste residue of many aluminum material factories now, into the one of aluminum material factory A hot Chinese yam.

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 summary, aluminium processing industry waste water and dregs processing domestic at present is particularly thorny, and integrated treatment difficulty is larger, cost Height, recovery utilization rate are low, have both caused a large amount of wastes of resource, and 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 to propose aluminium processing in single nickel salt coloring and medium temperature sealing of hole medicament recovery system, using Line classification recycling and compatibility method, selected dosage component, ingenious configuration system, it is ensured that the nickeliferous product reuse of recycling to sealing of hole Slot.

It is another object of the present invention to propose the recovery method of single nickel salt coloring and medium temperature sealing of hole medicament in aluminium processing, As a kind of completely new technological design, online classification collects nickel-containing waste water, on the basis of medicament compatibility, recycles alkali containing nickel product Formula nickelous carbonate is converted to medium temperature hole sealing agent, realizes the purpose that the resource recycling of toxic waste utilizes.

The present invention uses following technical scheme:

The recovery system of single nickel salt coloring and medium temperature sealing of hole medicament in aluminium processing includes Nickel-bearing Waste successively from upstream to downstream Water retention unit, nickel-containing waste water collector unit and basic nickel carbonate recovery unit；The nickel-containing waste water retention unit includes sequence 13# single nickel salts coloring slot, 14# flowings rinsing bowl, 15# flowings rinsing bowl, 16# medium temperature sealing of holes slot, the 17# flowing rinsing bowls of configuration Rinsing bowl is flowed with 18#；The 18# flows the external tap water of rinsing bowl, the 14# flows rinsing bowl, 15# flows rinsing bowl, 17# flows rinsing bowl and 18# flowing rinsing bowl differential concatenation settings, and the 13# single nickel salts coloring slot is simultaneous to 16# medium temperature sealing of hole slots It is installed with and puts；

The nickel-containing waste water collector unit includes nickel-containing waste water collecting pit A and nickel-containing waste water collecting pit B, the 14# flowings The water outlet of rinsing bowl is respectively equipped with the nickel-containing waste water collecting pit A pipelines connected and connects with nickel-containing waste water collecting pit B Pipeline；

The basic nickel carbonate recovery unit includes the 1# pumps, recycling can, centrifuge, secondary crystallization tank and the 2# that are arranged in order Pump, the 1# pump the nickel-containing waste water of nickel-containing waste water collecting pit A and nickel-containing waste water collecting pit B being pumped into the recycling can, institute Recycling can is stated to be used for the Ni in nickel-containing waste water²⁺Solid basic nickel carbonate is converted into, the centrifuge is solid for detaching The nickel-containing waste water of basic nickel carbonate and liquid, the secondary crystallization tank is for the Ni in the nickel-containing waste water after separation²⁺Secondary knot Crystalline substance, 2# pump for by the secondary crystallization object in the secondary crystallization tank be pumped into the recycling can and by after crystallization without nickel Clear liquid is pumped into subsequent treatment unit for waste water.

Further illustrate, in nickel-containing waste water retention unit, the water inlet of the 18# flowings rinsing bowl it is external originally The pipeline of water is equipped with 1# valves, and water outlet and the 17# of the 18# flowings rinsing bowl flow the pipeline that the water inlet of rinsing bowl connects 2# one-way valves are equipped with, the 15# flows to be set on the pipeline that the water inlet of rinsing bowl and the water outlet of 17# flowing rinsing bowls connect There are 3# one-way valves, 4# one-way valves are equipped between the water outlet of the 15# flowings rinsing bowl and the water inlet of 14# flowing rinsing bowls.

It further illustrates, in the nickel-containing waste water collector unit, the water inlet of the nickel-containing waste water collecting pit A described contains It is connected between the water outlet of the water inlet of nickel waste water collecting pit B and 14# flowing rinsing bowls by three-way pipe, and described three Siphunculus is equipped with 5# valves with one end that 14# flowing rinsing bowls connect, and the three-way pipe is connected with the nickel-containing waste water collecting pit A One end be equipped with 6# valves, one end that the three-way pipe connect with the nickel-containing waste water collecting pit B is equipped with 7# valves；

The pipeline that the water outlet of the nickel-containing waste water collecting pit A is connected with the 1# water inlets pumped is equipped with 8# valves, described nickeliferous The pipeline that the water outlet of wastewater collection pond B is connected with the 1# water inlets pumped is equipped with 9# valves.

It further illustrates, in the basic nickel carbonate recovery unit, the water outlet of the 1# pumps and the water inlet of recycling can The pipeline of connection is equipped with 10# valves, and the pipeline that the water outlet of the recycling can is connected with the water inlet of centrifuge is equipped with 11# valves, institute Centrifuge is stated equipped with solid-state separation material mouth and Liquid segregation material mouth, the Liquid segregation material mouth of the centrifuge passes through pipeline and secondary The water inlet connection of crystallizing tank；

The middle part of the secondary crystallization tank is equipped in the first supernatant delivery outlet, the second supernatant delivery outlet and third vertically Clear liquid delivery outlet, the bottom of the secondary crystallization tank are equipped with crystallization delivery outlet；The first supernatant output of the secondary crystallization tank Mouth is equipped with 12# valves with the pipeline that the water inlet of 2# pumps connects, the second supernatant delivery outlet and the 2# pump of the secondary crystallization tank The pipeline of water inlet connection is equipped with 13# valves, and the third supernatant delivery outlet of the secondary crystallization tank is connected with the 2# water inlets pumped Pipeline be equipped with 14# valves, the pipeline that the crystallization delivery outlet of the secondary crystallization tank is connected with the 2# water inlets pumped equipped with 15# valves, The pipeline that first water outlet of the 2# pumps is connected with the water inlet of recycling can is equipped with 16# valves, the second water outlet of the 2# pumps The pipeline connected with the water inlet of the treatment unit for waste water is equipped with 17# valves.

It further illustrates, the recycling can is internally provided with the stirring of 1# electricity, and the secondary crystallization tank is internally provided with 2# electricity stirs.

The recovery method of single nickel salt coloring and medium temperature sealing of hole medicament in aluminium processing, includes the following steps:

Step 1:Retain nickel-containing waste water:It opens 1# valves and 5# valves, water is entered by 1# valves, and followed by 2# valves Door, 3# valves, 4# valves flow into 14# flowing rinsing bowls, then are flowed out by 5# valves, only one of ejected wash water differential concatenation flowing；It will Aluminium alloy is after the coloring slot coloring of 13# single nickel salts, drip 30s；Into 14# flowings rinsing bowl, 15# flowing rinsing bowls, cleaning 60s, drip 30s；Into 16# medium temperature sealing of hole slots, sealing of hole 15min, drip 30s；Into 17# flowings rinsing bowl, 18# flowing washings Slot cleans 60s, drip 30s；

Step 2:Collect nickel-containing waste water:6# valves or 7# valves are opened, by the waste water by being flowed out in 14# flowing rinsing bowls It flows into nickel-containing waste water collecting pit A or B；

Step 3:Recycle basic nickel carbonate:8# valves or 9# valves are opened, No. 1 pump is opened, and open 10# valves, closes Waste water in nickel-containing waste water collecting pit A or B is pumped into recycling can by 11# valves；The stirring of 1# electricity is opened, is slowly added to sodium carbonate simultaneously Detection pH value on one side until when pH value is 9.0, stops adding in sodium carbonate, continues to stir 30min, recycle Ni²⁺, reaction generation alkali Formula nickelous carbonate；11# valves are opened, open centrifuge, make nickel-containing waste water separation of solid and liquid, recycle solid basic nickelous carbonate, liquid It is spare that nickel-containing waste water flows into secondary crystallization tank；

Step 4:Prepare nickel acetate solution:By basic nickel carbonate after rinsing, after adding in pure water moistening, it is slowly added ice Acetic acid (98%), under conditions of basic nickel carbonate excess, reaction generation nickel acetate solution；

Step 5:Hole sealing agent is transformed:According to medium temperature sealing of hole Con trolling index, concentration, three second of addition of nickel acetate solution are titrated Hydramine and isobutanol form the hole sealing agent that can be added directly in 16# medium temperature sealing of hole slots.

It further illustrates, in step 5, the ratio between concentration of the nickel acetate solution and triethanolamine is 10:1st, the acetic acid The ratio between concentration of nickel solution and isobutanol is 10:1.

It further illustrates, in step 3, further includes recycling wastewater treatment and secondary crystallization step:Open 12# valves or 13# Valve or 14# valves open pump 2, open 17# valves, close 15# valves and 16# valves, by secondary crystallization tank without on nickel Clear liquid is pumped into wastewater treatment center, is neutralized；12# valves or 13# valves or 14# valves are closed, closes 17# valves, 15# valves and 16# valves are opened, the stirring of 2# electricity is opened, the secondary crystallization object of secondary crystallization pot bottom is pumped into recycling can again In, for carrying out secondary recovery basic nickel carbonate.

It further illustrates, in step 4, the pH value of the nickel acetate solution of generation is more than 6.

It further illustrates, the oxide thickness of the aluminum alloy surface is 15 microns.

Beneficial effects of the present invention:

1st, setting nickel-containing waste water retains unit for the first time, makes when production colours sealing of hole aluminium, rinsing bowl retention nickel-containing waste water, Individually processing, avoid with other mixed with water after reprocess the troubles of these magnanimity waste water, processing nickel-containing waste water is greatly reduced Environmentally friendly cost；

2nd, for the first time in nickel-containing waste water retains unit using coloring sealing of hole water differential concatenation mode, production is made to colour sealing of hole During aluminium, flowing rinsing bowl is configured after 13# single nickel salts colour slot, flowing rinsing bowl, two sets of cleanings are matched after 16# medium temperature sealing of hole slots Water is independent mutually, and ton material water consumption is at 4 tons or more, 16,000,000 tons of whole industry water consumption；The present invention is for the first time by sealing of hole and coloring water Differential concatenation can effectively reduce half water, and solid foundation has been established for online individually processing nickel-containing waste water, device miniaturization；

The 3rd, nickel-containing waste water collector unit is set online for the first time, avoid being mixed with other with water, individually to handle；

The 4th, basic nickel carbonate recovery unit is set online for the first time, the waste water of nickel-containing waste water collecting pit A or B are pumped into reaction Tank recycles Ni²⁺, reaction generation basic nickel carbonate, realization separation of solid and liquid；

5th, for the first time in the retort of basic nickel carbonate recovery unit, sodium carbonate is added in, Ni is recycled with sodium carbonate²⁺, reaction Basic nickel carbonate is generated, and is conducive to the recycling of basic nickel carbonate as reaction end when being 9.0 using pH value；

6th, it is equipped with wastewater treatment for the first time and secondary crystallization recycles, the supernatant in secondary crystallization tank is pumped into wastewater treatment The secondary crystallization object of secondary crystallization pot bottom is pumped into retort, realizes secondary recovery basic nickel carbonate by heart neutralisation treatment again；

7th, it only rinses, dry, and and glacial acetic acid using the basic nickel carbonate of basic nickel carbonate recovery unit recycling for the first time (98%) it reacts, under conditions of basic nickel carbonate excess, effecting reaction generation pH value is more than 6 nickel acetate solution；

8th, principle is compatible with using medicament for the first time, nickel acetate solution of the pH value for reacting generation more than 6 is transformed into hole sealing agent, Fluting and addition for 16# medium temperature sealing of hole slots realize that solid dangerous waste resource recycling utilizes.

Description of the drawings

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 existing conventional oxidation coloring hole-sealing technology flow and slot position layout drawing；

Fig. 7 be one embodiment of the invention aluminium processing in the recovery system of single nickel salt coloring and medium temperature sealing of hole medicament show It is intended to.

Specific embodiment

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

The present invention relates to aluminium processing industries to generate toxic one big source of waste residue, i.e. heat-tinting sealing of hole generates nickeliferous toxic Waste residue, the 4% of such waste residue Zhan Lv processing enterprises surface treatment waste residue total amount, about 40,000 tons, while it is related to about 16,000,000 tons of use Water, waste water and dregs problem are very prominent.

The present invention is by following theoretical foundation, the recovery system of single nickel salt hole sealing agent, recovery method and quantitative and qualitative analysis Come what is realized:

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

Conventional oxidation colours hole-sealing technology flow and slot position layout drawing is as shown in Figure 6, and each work nest matches two circulating waters Washing trough, oxidation processes need 18 slot positions, and containing nickel salt, follow-up rinsing bowl is taken out of nickeliferous for wherein 13# coloring slots and 16# sealing of holes slot Waste water enters wastewater treatment center, generates nickeliferous toxic waste residue.13#-18 slots function of the present invention is as follows:

13# colours slot

The purpose for setting this slot is in order to which oxidizing film is painted, and improves the dicoration of aluminium alloy.Generally using single nickel salt, list 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:

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

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:

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 need to select appropriate chelating agent, thoroughly stablize stannous sulfate.Sulfuric acid rises and prevents Pink salt hydrolyzes and improves the double action of conductance, and free sulfuric acid control 15-20g/L is advisable.The relatively low glossiness of sulfuric acid is quite a lot of, sulfuric acid Too high coloring speed and gloss decline, and only have ater just to rise to 25g/L, to prevent surface from generating hydroxide.Some nickel Tin salt-mixture coloring liquid adds boric acid, it plays cushioning effect in hole, is conducive to electrodeposition of nickel, improves uniformity and improves color Sense, is advisable, too high colour cast is dark with 20-25g/L.

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 can increase local ph as cathode, evolving hydrogen reaction, 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 phenol, sulfuric acid, boric acid are added in, also need to add in oxidation retarder, such as:It is anti- Bad hematic acid, phenylbenzene, quinhydrones etc..The wherein acidificable solution of sulfuric acid reduces pH value；Boric acid has buffering and complexing, winestone Acid, citric acid, ammonium tartrate can not only improve the electric conductivity of solution, moreover it is possible to play cushioning effect to pH value.Add sulphur urine or sulphur Sour diamine can play reduction to tetravalence tin ion.Addition replaces the medicament that divalent tin ion is aoxidized, such as ferrous ion is worked as When divalent tin ion and ferrous ion coexist, in divalent tin ion before the oxidation reaction of tetravalence tin ion, Asia first has occurred The oxidation reaction of iron ion, so as to control transformation of the divalent tin ion to tetravalence tin ion.Here the additive added in is all Some substances with cushioning effect, complexing and antioxidation, can be complexed Sn²⁺Ion, or can be preferentially by solution Dissolved oxygen aoxidizes, 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 desired to which 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

Experiment proves that the time of electrolytic coloring will be accurate to be calculated by the second, and 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).

Electrolytic coloring slot tank liquor temperature may be designated as 20-25 DEG C.When colouring tank liquor temperature raising, coloring liquid conductivity increases Greatly, 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 0.8-1.0 is the generation uniform face of champagne aluminium section bar 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.

14# and 15# flowing rinsing bowls

The purpose for setting this twice rinsing bowl is the residual colorant that cleaning coloring slot is taken out of, protects sealing of hole slot.Equally, certainly Water is from 15# slots into 14# slots go out, differential concatenation, and water consume is 2.0-3.0 tons/ton material or so, and water consumption is too big, and what is discharged is Stanniferous and nickel waste water, increases environmental protection treatment pressure.

16# sealing of hole slots

The purpose for setting this slot is to seal the micropore of oxidation film, it is ensured that its corrosion resistance.Also it can be replaced with electrophoresis tank and sealed Hole slot.Method for sealing by operating temperature be divided into high temperature, in mild normal-temperature hole sealing.High temperature hole sealing is pure water of the aluminium at 95-100 DEG C Middle processing, sealing quality is preferable, but high energy consumption, and evaporated quantity of water is big, easy dust, and easy foreign ion poisoning need to often replace 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, and few dust is not split Film, but it is nickeliferous, it is unfavorable for environmental protection；Normal-temperature hole sealing uses nickel fluoride doping method, is handled at 25-35 DEG C, sealing of hole speed Comparatively fast, 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 with medium temperature sealing of hole For main methods.Medium temperature sealing of hole Con trolling index is:

17# and 18# flowing rinsing bowls

The purpose that this twice rinsing bowl is set be cleaning sealing of hole slot take nickeliferous residual medicament out of, protect aluminium manufacture after not by Corrosion.Equally, tap water is from 18# slots into 17# slots go out, differential concatenation, and water consume is 2.0-3.0 tons/ton material or so, and water consumption is too Greatly, and what is discharged is nickel-containing waste water, increases environmental protection treatment pressure.

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 Changing line 13-18# slots has 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# and 16# are nickeliferous tank liquor, and 14#, 15#, 17#, 18# tetra- is directly entered after aluminium coloring and sealing of hole Road flows rinsing bowl, brings nickel-containing waste water into waste water center, pollutes the water for cleaning of whole oxidation line other processes；After mixing, These nickel-containing waste waters are reprocessed, and qualified discharge, difficulty well imagine that cost is surprising.This mode can be used there is an urgent need to improve Online classification is individually handled, and 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.The mesh of 14#, 15# twice rinsing bowl is set after 13# coloring slots Be the residual colorant taken out of of cleaning coloring slot, protect sealing of hole slot.Tap water is from 15# slots into 14# slots go out, differential concatenation, water Consume for 2.0-3.0 tons/ton material or so, water consumption is too big, and discharge be stanniferous and nickel waste water, increase environmental protection treatment pressure； The purpose that 17#, 18# twice rinsing bowl are set after 16# sealing of hole slots is that cleaning sealing of hole slot takes nickeliferous residual medicament out of, and protection aluminium goes out It is not corroded after factory.Tap water is from 18# slots into 17# slots go out, differential concatenation, and water consume is 2.0-3.0 tons/ton material or so, water consumption It is too big, and what is discharged is nickel-containing waste water, increases environmental protection treatment pressure.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, is given up from the angle processing nickel-containing waste water of recycling Slag, change dangerous waste are valuable chemical resource, and processing cost is both greatly reduced, and realize the maximum that nickeliferous chemical products value utilizes Change.Prior art design theory is unreasonable, and 13# and 16# are nickeliferous tank liquor, be directly entered after aluminium coloring and sealing of hole 14#, 15#, 17#, 18# tetra- flows rinsing bowl, brings nickel-containing waste water into waste water center, and the cleaning for polluting whole oxidation line other processes is used Water；Waste water center neutralizes these waste water, is precipitated, press filtration, obtains nickeliferous solid slag；These magnanimity nickel-contained waste slags, country Clear stipulaties are dangerous waste for Chinese Ministry of Environmental Protection；These nickeliferous dangerous wastes are handled, high environmentally friendly cost is paid in enterprise and society need, together When the valuable nickel resources of waste.This extensive mode of production can configure special equipment there is an urgent need to improve, online actively to recycle Nickeliferous product, turns waste into wealth, and realizes dangerous waste recycling.

Modern aluminum processing enterprise, the nickel-containing waste water waste residue for having the generation of heat-tinting sealing of hole is in need of immediate treatment, and traditional cleaning It is too simple with the method reprocessed after the big mixing of water, the nickel-contained waste slag of magnanimity is generated, handles these waste residues, society will be this pair Go out expensive environmentally friendly cost.

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

1) processing is collected separately in, coloring washing.By (1) formula, single nickel salt coloring Con trolling index is:Nickel sulfate 150g/L, boron Sour 50g/L, pH 3.5-4.5,20-25 DEG C of temperature, time 30s-15min.Single nickel salt colouring slot liquid is highly stable, but requirementization It is high to learn medicament purity, contamination resistance is weak, it is desired to which 12#, 11# rinsing bowl before coloring are washed with flowing pure water；Aluminium presses 30s- It after the 15min times colour, rises and hangs drip 30s, flow rinsing bowl into 14#, clean 1min, rise and hang drip 30s, flowed into 15# Dynamic rinsing bowl, cleans 1min, rises and hangs drip 30s, into 16# sealing of hole slots, completes coloring and washing process.When being cleaned after coloring, Nickel sulfate and boric acid contained by coloring liquid bring 14#, 15# flowing rinsing bowl into, pollute the water for cleaning of flowing；13# coloring slots PH value is that the pH value of the water inlet of 3.5-4.5,15# slots is 6.0-7.0, therefore 14#, 15#pH value is between 3.5-7.0, this section Nickel sulfate and boric acid are stablized, and do not decompose, processing can be collected separately.

2), sealing of hole washing individually recycling.

It is by (7) formula, medium temperature sealing of hole Con trolling index:Nickel acetate 5g/L, triethanolamine 0.5g/L, isobutanol 0.5g/L, PH5.5-6.5,50-60 DEG C of temperature, time 10-25min.It after aluminium presses 10-25min time sealing of holes, rises and hangs drip 30s, enter 17# flows rinsing bowl, cleans 1min, rises and hangs drip 30s, flows rinsing bowl into 18#, cleans 1min, rises and hang drip 30s, into Enter air drying area, complete sealing of hole and washing process.When being cleaned after sealing of hole, nickel acetate, triethanolamine and isobutanol contained by pore-sealing liquid It brings 17#, 18# flowing rinsing bowl into, pollutes the water for cleaning of flowing；The pH value of 16# sealing of hole slots is the water inlet of 5.5-6.5,18# slots The pH value of mouth is 6.0-7.0, therefore 17#, 18#pH value, between 5.5-7.0, this section nickel acetate, triethanolamine and isobutanol are steady It is fixed, it does 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 coloring, nickel sulfate and boric acid contained by coloring liquid bring 14#, 15# flowing rinsing bowl into；14#、15#pH It is worth between 3.5-7.0, this section nickel sulfate and boric acid are stablized, and do not decompose；When being cleaned after sealing of hole, the acetic acid contained by pore-sealing liquid Nickel, triethanolamine and isobutanol bring 17#, 18# flowing rinsing bowl into；17#, 18#pH value are between 5.5-7.0, this section acetic acid Nickel, triethanolamine and isobutanol are stablized, and do not decompose.The tap water inlets of 15# slots are closed, by the water for cleaning of 17# slot water outlets Reverse phase is connected serially to the water inlet of 15# slots, realize ejected wash water enter from 18# slots, through 17# slots, 15# slots and 14# slots, finally from 14# The reversed big series connection of the water outlet outflow of slot.Such series system, nickel acetate, three ethyl alcohol contained by 17#, 18# flowing rinsing bowl Amine and isobutanol bring 15# slots and 14# slots into, need to investigate two aspects:First, whether 14#, 15# slot are muddy, make aluminium dust； Two are whether to influence the sealing of hole ability of 16# slots.

A, the stability analysis of 14#, 15# slot.

For 14#, 15#pH value between 3.5-7.0, this section nickel sulfate, boric acid, nickel acetate, triethanolamine and isobutanol are non- Often stablize, no muddy object generates, and aluminium is it is not possible that dust, differential concatenation washing are feasible；

B, impact analysis of 14#, 15# slot to sealing of hole slot.

When being cleaned after coloring, nickel sulfate and boric acid contained by coloring liquid bring 14#, 15# flowing rinsing bowl into；14#、15#pH It is worth between 3.5-7.0, during sealing of hole, micro nickel sulfate and boric acid can bring sealing of hole slot into, and sealing quality is qualified；Differential concatenation is washed Afterwards, nickel acetate, triethanolamine and the isobutanol that 17#, 18# are flowed contained by rinsing bowl bring 15# slots and 14# slots into, equally, micro vinegar Sour nickel, triethanolamine and isobutanol can take back 16# sealing of hole slots, these are the proper constituent of sealing of hole slot in itself, and principle is compatible with by oneself, The sealing of hole ability of 16# can never be influenced, reverse phase washing series-connection is feasible.

2nd, single nickel salt coloring and the quantitative and qualitative analysis of sealing of hole ejected wash water remanufacture hole sealing agent

After reverse phase washing series-connection, 14# water outlet sulfur acids nickel, boric acid, nickel acetate, triethanolamine and isobutanol, by (1), (7) formula and aluminium per ton take 50Kg tank liquors out of, 2.5 tons of water for cleaning of consumption calculate, 14# water outlets drug concentration for coloring slot and 2% or so of sealing of hole slot concentration, i.e. nickel sulfate 3g/L, boric acid 1g/L nickel acetate 0.1g/L, triethanolamine 0.01g/L, isobutanol 0.01g/L.Nickel retracting device is generally fitted provided in view of single nickel salt coloring, the nickel sulfate actually taken out of is much lower.Eachization The processing mode for learning component is as follows:

1st, the nickeliferous crystallization of nickel sulfate and nickel acetate institute is precipitated.

By (1), (7) control coloring and sealing of hole slot, differential concatenation washing production coloring sealing of hole material takes 14# water outlets to clean Water 1L, test agents are a concentration of:

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 triethanolamine, 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↓ (9)

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.

2nd, boric acid, triethanolamine and isobutanol do not react, and retain in liquid.

By (8) formula, with the addition of sodium carbonate, pH is constantly increased, by (9) formula, Ni²⁺Constantly reaction generation NiCO₃、Ni (OH)₂Or NiCO₃-2Ni(OH)₂-4H₂O, but boric acid, triethanolamine and isobutanol pH value be no more than 9 under conditions of, regardless of Solution, does not precipitate, retains in liquid.

3rd, separation of solid and liquid isolates boric acid, triethanolamine and isobutanol with liquid, recycles solid basic nickelous carbonate.

By (9) formula, reaction product is subjected to separation of solid and liquid.Boric acid, triethanolamine and isobutanol are flowed out with liquid, consolidate Body basic nickel carbonate；Through rinsing, drying, the technical grade basic nickel carbonate product for meeting national standard is obtained.

4th, principle is compatible with by medicament, regenerates hole sealing agent, realize that solid dangerous waste resource recycling utilizes.

The basic nickel carbonate product 100g obtained after rinsing is dried is weighed (to dry when only laboratory is measured, when producing greatly Rinsed clean, it is not necessary to dry, save production cost), 100g pure water is added to moisten, is slowly added acetic acid (98%), reaction is such as Under:

NiCO₃.2Ni(OH)₂.4H₂O+6CH₃COOH=3Ni (CH₃COO)₂+9H₂O+CO₂↑ (10)

100g basic nickel carbonates, the reaction was complete needs to add glacial acetic acid (98%) 97.7g.Take glacial acetic acid 95g, basic carbonate Nickel is excessive, that is, beaker bottom has a small amount of solid residue after the completion of reacting；The pH value 6.19 of nickel acetate solution is detected, meets medium temperature envelope Agent pH in hole is more than 6.0 requirement；

It is that the nickel reactant recycled from 14# rinsing bowls generates due to the nickel acetate liquid that (10) formula obtains, 14#, 15# slot pair The sealing of hole capacity of 16# sealing of hole slots is limited, substantially compatible, thus by the production of (10) formula nickel acetate completely can by hole sealing agent into Row transformation, reuse to sealing of hole slot.By (7) formula, remodeling method is:

By the hole sealing agent that (11) are transformed, with reference to (7) formula, fluting that completely can be as 16# sealing of hole slots and addition；It considers The working index of 16# slots is pH5.5-6.5,50-60 DEG C of temperature, and the nickel acetate of (10) formula recycling has met pH value requirement；Temperature During 50-60 DEG C of sealing of hole, there is a large amount of water evaporation, liquor of hole- sealing tank position shoals, when being added by the liquid hole sealing agent of (11) formula production, just Drug concentration and liquid level are supplemented well.

3rd, single nickel salt coloring and the experimental result of sealing of hole ejected wash water remanufacture hole sealing agent

The present invention by (9) formula, obtains basic nickel carbonate first, then produces nickel acetate by (10), finally presses (11) formula tune With medium temperature hole sealing agent.This serial experiment presses the medium temperature sealing of hole slot Con trolling index that (7) formula provides, and is investigated respectively by the production of (11) formula The sealing of hole ability of medium temperature hole sealing agent.

1st, influence of the sealing of hole agent concentration to sealing quality.

Take 55 DEG C of pH6.0, temperature, nickel acetate 2,3,4,5,6, (triethanolamine and isobutanol are acetic acid nickel concentration to 7g/L 1/10th, similarly hereinafter)；It is 15 microns to take oxide thickness, and the sealing of hole time is 15 minutes, detects and seals by ISO3210 international standards Hole quality, the results are shown in Table 1:

Influence of the 1 sealing of hole agent concentration of table to sealing quality

2nd, influence of the sealing of hole slot pH value to sealing quality.

Take nickel acetate 5g/L (triethanolamine and isobutanol are 1/10th of acetic acid nickel concentration, similarly hereinafter), 55 DEG C of temperature, pH4.5、5.0、5.5、6.0、6.5、7.0；It is 15 microns to take oxide thickness, and the sealing of hole time is 15 minutes, by the ISO3210 worlds Standard detection sealing quality, the results are shown in Table 2:

Influence of the 2 sealing of hole slot pH value of table to sealing quality

3rd, influence of the sealing of hole temperature to sealing quality.

Take nickel acetate 5g/L (triethanolamine and isobutanol are 1/10th of acetic acid nickel concentration, similarly hereinafter), pH6.0, temperature 40、45、50、55、60、65℃；It is 15 microns to take oxide thickness, and the sealing of hole time is 15 minutes, is examined by ISO3210 international standards Sealing quality is surveyed, the results are shown in Table 3:

Influence of the 3 sealing of hole temperature of table to sealing quality

4th, influence of the sealing of hole time to sealing quality.

Take nickel acetate 5g/L (triethanolamine and isobutanol are 1/10th of acetic acid nickel concentration, similarly hereinafter), pH6.0, temperature 55℃；It is 15 microns to take oxide thickness, and the sealing of hole time is 5,8,11,14,17,20 minutes, is detected by ISO3210 international standards Sealing quality, the results are shown in Table 4:

Influence of the 4 sealing of hole time of table to sealing quality

4th, single nickel salt coloring and the analysis of experimental results of sealing of hole ejected wash water remanufacture hole sealing agent

By reaction equation (8)-(11) and experiment 1-4 and testing result, following analysis can be done:

1st, by formula (8), the principle that be compatible with using sealing of hole washing to sealing of hole slot itself can be by sealing of hole water differential concatenation extremely Color water, two sets of washings are combined into one, and save half water, and recycling nickel-containing waste water is retained in 14# slots water outlet；

2nd, by (9) formula, the nickel-containing waste water of retention can individually be handled online, recycles the basic nickel carbonate of technical grade, will contain Nickel solid dangerous waste is converted into the industrial chemicals of high value, realizes the recycling of solid dangerous waste；

3rd, by (10) formula, the basic nickel carbonate of recycling can be converted to nickel acetate solution, in the item of basic nickel carbonate excess Under part, the pH value of reaction product is more than 6.0, meets requirement of the subsequent transformation into hole sealing agent；

4th, by (11) formula, it can be converted to liquid hole sealing agent by nickel acetate solution by (7) formula requirement, be added directly into sealing of hole Slot；Sealing of hole slot is medium temperature sealing of hole, there is certain evaporation capacity, and liquid hole sealing agent just supplements drug concentration and liquid level, saves devaporation The trouble of Acetic Acid Glacil nickel solution substantially saves the cost of manufacture of hole sealing agent；

5th, it is understood by serial experiment result 1-4, as defined in (7) formula in the range of Con trolling index, in being made by (11) formula Warm hole sealing agent is fully able to meet sealing of hole requirement.

5th, aluminium processing in single nickel salt coloring and medium temperature sealing of hole medicament recovery system and method foundation reaction equation (8)- (11), 1-4 and testing result are tested, practical with reference to coloring sealing of hole quantity-produced, medicament recycling the factors such as retains with water, with And slot position is how many etc., Aluminum subtract slag single nickel salt coloring remanufacture hole sealing agent and water-saving configuration it is as shown in Figure 7:

In order to realize long-term large-scale production using water wisely, online recycling nickel-containing waste water, individually convert nickeliferous solid dangerous waste Target, 6 slot positions are configured in Fig. 7, containing two pharmacy slots, 4 flowing rinsing bowls, the part contacted with tank liquor, all by acidproof Design.

The recovery system of single nickel salt coloring and medium temperature sealing of hole medicament in aluminium processing of the present invention, includes successively from upstream to downstream Nickel-containing waste water retention unit, nickel-containing waste water collector unit and basic nickel carbonate recovery unit；The nickel-containing waste water retains unit packet Include the 13# single nickel salts coloring slot being arranged in order, 14# flowings rinsing bowl, 15# flowings rinsing bowl, 16# medium temperature sealing of holes slot, 17# flowings Rinsing bowl and 18# flowing rinsing bowls；The 18# flows the external tap water of rinsing bowl, the 14# flowings rinsing bowl, 15# circulating waters Washing trough, 17# flowing rinsing bowls and 18# flowing rinsing bowl differential concatenation settings, the 13# single nickel salts coloring slot seal 16# medium temperatures Hole slot compatibility setting；

The nickel-containing waste water collector unit includes nickel-containing waste water collecting pit A and nickel-containing waste water collecting pit B, the 14# flowings The water outlet of rinsing bowl is respectively equipped with the nickel-containing waste water collecting pit A pipelines connected and connects with nickel-containing waste water collecting pit B Pipeline；

The basic nickel carbonate recovery unit includes the 1# pumps, recycling can, centrifuge, secondary crystallization tank and the 2# that are arranged in order Pump, the 1# pump the nickel-containing waste water of nickel-containing waste water collecting pit A and nickel-containing waste water collecting pit B being pumped into the recycling can, institute Recycling can is stated to be used for the Ni in nickel-containing waste water²⁺Solid basic nickel carbonate is converted into, the centrifuge is solid for detaching The nickel-containing waste water of basic nickel carbonate and liquid, the secondary crystallization tank is for the Ni in the nickel-containing waste water after separation²⁺Secondary knot Crystalline substance, 2# pump for by the secondary crystallization object in the secondary crystallization tank be pumped into the recycling can and by after crystallization without nickel Clear liquid is pumped into subsequent treatment unit for waste water.

On the basis of medicament compatibility, the present invention is responsible for retention 13# single nickel salts and by the way that nickel-containing waste water is set to retain unit The medicament that color slot and 16# medium temperature sealing of hole slots are taken out of, reside in 14,15,17, in 18# flowing rinsing bowls, avoid and use water with other The trouble of these magnanimity waste water is reprocessed after mixing, the environmentally friendly cost of processing nickel-containing waste water is greatly reduced；It is retained in nickel-containing waste water Using coloring sealing of hole water differential concatenation mode in unit, by sealing of hole and coloring water differential concatenation, reduce half water, be Line individually handles nickel-containing waste water, device miniaturization has established solid foundation；And by setting basic nickel carbonate recycling single online Member is responsible for recycling Ni²⁺, reaction generation basic nickel carbonate, and pore-sealing liquid is transformed into, realize that solid dangerous waste resource recycling utilizes.

Further illustrate, in nickel-containing waste water retention unit, the water inlet of the 18# flowings rinsing bowl it is external originally The pipeline of water is equipped with 1# valves, and water outlet and the 17# of the 18# flowings rinsing bowl flow the pipeline that the water inlet of rinsing bowl connects 2# one-way valves are equipped with, the 15# flows to be set on the pipeline that the water inlet of rinsing bowl and the water outlet of 17# flowing rinsing bowls connect There are 3# one-way valves, 4# one-way valves are equipped between the water outlet of the 15# flowings rinsing bowl and the water inlet of 14# flowing rinsing bowls.

It further illustrates, in the nickel-containing waste water collector unit, the water inlet of the nickel-containing waste water collecting pit A described contains It is connected between the water outlet of the water inlet of nickel waste water collecting pit B and 14# flowing rinsing bowls by three-way pipe, and described three Siphunculus is equipped with 5# valves with one end that 14# flowing rinsing bowls connect, and the three-way pipe is connected with the nickel-containing waste water collecting pit A One end be equipped with 6# valves, one end that the three-way pipe connect with the nickel-containing waste water collecting pit B is equipped with 7# valves；

The pipeline that the water outlet of the nickel-containing waste water collecting pit A is connected with the 1# water inlets pumped is equipped with 8# valves, described nickeliferous The pipeline that the water outlet of wastewater collection pond B is connected with the 1# water inlets pumped is equipped with 9# valves.

It further illustrates, in the basic nickel carbonate recovery unit, the water outlet of the 1# pumps and the water inlet of recycling can The pipeline of connection is equipped with 10# valves, and the pipeline that the water outlet of the recycling can is connected with the water inlet of centrifuge is equipped with 11# valves, institute Centrifuge is stated equipped with solid-state separation material mouth and Liquid segregation material mouth, the Liquid segregation material mouth of the centrifuge passes through pipeline and secondary The water inlet connection of crystallizing tank；

The middle part of the secondary crystallization tank is equipped in the first supernatant delivery outlet, the second supernatant delivery outlet and third vertically Clear liquid delivery outlet, the bottom of the secondary crystallization tank are equipped with crystallization delivery outlet；The first supernatant output of the secondary crystallization tank Mouth is equipped with 12# valves with the pipeline that the water inlet of 2# pumps connects, the second supernatant delivery outlet and the 2# pump of the secondary crystallization tank The pipeline of water inlet connection is equipped with 13# valves, and the third supernatant delivery outlet of the secondary crystallization tank is connected with the 2# water inlets pumped Pipeline be equipped with 14# valves, the pipeline that the crystallization delivery outlet of the secondary crystallization tank is connected with the 2# water inlets pumped equipped with 15# valves, The pipeline that first water outlet of the 2# pumps is connected with the water inlet of recycling can is equipped with 16# valves, the second water outlet of the 2# pumps The pipeline connected with the water inlet of the treatment unit for waste water is equipped with 17# valves.

It further illustrates, the recycling can is internally provided with the stirring of 1# electricity, and the secondary crystallization tank is internally provided with 2# electricity stirs.

Rely on above system setting, the present invention can online processing aluminium processing industry heat-tinting sealing of hole generate nickel-containing waste water About 16,000,000 tons, nickeliferous about 40,000 tons of toxic waste residue is converted, generates about 50,000 tons of basic nickel carbonate.Operating process of the present invention, including Following steps:

Step 1:Retain nickel-containing waste water:It opens 1# valves and 5# valves, water is entered by 1# valves, and followed by 2# valves Door, 3# valves, 4# valves flow into 14# flowing rinsing bowls, then are flowed out by 5# valves, only one of ejected wash water differential concatenation flowing；It will Aluminium alloy is after the coloring slot coloring of 13# single nickel salts, drip 30s；Into 14# flowings rinsing bowl, 15# flowing rinsing bowls, cleaning 60s, drip 30s；Into 16# medium temperature sealing of hole slots, sealing of hole 15min, drip 30s；Into 17# flowings rinsing bowl, 18# flowing washings Slot cleans 60s, drip 30s；

Step 2:Collect nickel-containing waste water:6# valves or 7# valves are opened, by the waste water by being flowed out in 14# flowing rinsing bowls It flows into nickel-containing waste water collecting pit A or B；

Step 3:Recycle basic nickel carbonate:8# valves or 9# valves are opened, No. 1 pump is opened, and open 10# valves, closes Waste water in nickel-containing waste water collecting pit A or B is pumped into recycling can by 11# valves；The stirring of 1# electricity is opened, is slowly added to sodium carbonate simultaneously Detection pH value on one side until when pH value is 9.0, stops adding in sodium carbonate, continues to stir 30min, recycle Ni²⁺, reaction generation alkali Formula nickelous carbonate；11# valves are opened, open centrifuge, make nickel-containing waste water separation of solid and liquid, recycle solid basic nickelous carbonate, liquid It is spare that nickel-containing waste water flows into secondary crystallization tank；

Step 4:Prepare nickel acetate solution:By basic nickel carbonate after rinsing, after adding in pure water moistening, it is slowly added ice Acetic acid (98%), under conditions of basic nickel carbonate excess, reaction generation nickel acetate solution；

Step 5:Hole sealing agent is transformed:According to medium temperature sealing of hole Con trolling index, concentration, three second of addition of nickel acetate solution are titrated Hydramine and isobutanol form the hole sealing agent that can be added directly in 16# medium temperature sealing of hole slots.

It further illustrates, in step 5, the ratio between concentration of the nickel acetate solution and triethanolamine is 10:1st, the acetic acid The ratio between concentration of nickel solution and isobutanol is 10:1.

It further illustrates, in step 3, further includes recycling wastewater treatment and secondary crystallization step:Open 12# valves or 13# Valve or 14# valves open pump 2, open 17# valves, close 15# valves and 16# valves, by secondary crystallization tank without on nickel Clear liquid is pumped into wastewater treatment center, is neutralized；12# valves or 13# valves or 14# valves are closed, closes 17# valves, 15# valves and 16# valves are opened, the stirring of 2# electricity is opened, the secondary crystallization object of secondary crystallization pot bottom is pumped into recycling can again In, for carrying out secondary recovery basic nickel carbonate.

It further illustrates, in step 4, the pH value of the nickel acetate solution of generation is more than 6.

It further illustrates, the oxide thickness of the aluminum alloy surface is 15 microns.

Embodiment

On the basis of ejected wash water and medicament compatibility, in order to realize that water for cleaning halves and recycle basic nickel carbonate, making The target of pore-sealing liquid, the operation (such as Fig. 7) of each system, is the key that present invention is implemented as work(.

Embodiment 1 (operation of retention nickel-containing waste water)

It opens 1# valves and 5# valves, water is entered by 1# valves, and flowed into followed by 2# valves, 3# valves, 4# valves 14# flows rinsing bowl, then is flowed out by 5# valves, only one of ejected wash water differential concatenation flowing；15 microns of aluminium of thickness of oxidation film is closed Gold is after the coloring slot coloring of 13# single nickel salts, drip 30s；Into 14# flowings rinsing bowl, 15# flowing rinsing bowls, 60s, drop are cleaned Flow 30s；Into 16# medium temperature sealing of hole slots, sealing of hole 15min, drip 30s；Rinsing bowl is flowed into 17# flowings rinsing bowl, 18#, clearly 60s, drip 30s are washed, completes nickel-containing waste water retention operation；

Embodiment 2 (operation for collecting nickel-containing waste water)

Open 6# valves or 7# valves, by by the waste water flowed out in 14# flowing rinsing bowls flow into nickel-containing waste water collecting pit A or In B, complete nickel-containing waste water and collect operation；

Embodiment 3 (operation of recycling basic nickel carbonate)

8# valves or 9# valves are opened, No. 1 pump is opened, and open 10# valves, closes 11# valves, nickel-containing waste water is collected Waste water in pond A or B is pumped into recycling can；The stirring of 1# electricity is opened, be slowly added to sodium carbonate and detects pH value on one side, until pH value is When 9.0, stop adding in sodium carbonate, continue to stir 30min, recycle Ni²⁺, reaction generation basic nickel carbonate；11# valves are opened, are opened Centrifuge is opened, makes nickel-containing waste water separation of solid and liquid, recycles solid basic nickelous carbonate, the nickel-containing waste water inflow secondary crystallization tank of liquid is standby With；Complete basic nickel carbonate reclaimer operation；

Embodiment 4 (operation of recycling wastewater treatment and secondary crystallization)

12# valves or 13# valves or 14# valves are opened, opens pump 2, opens 17# valves, closes 15# valves and 16# valves Door, will be pumped into wastewater treatment center without nickel supernatant in secondary crystallization tank, is neutralized；Close 12# valves or 13# valves Door or 14# valves close 17# valves, open 15# valves and 16# valves, the stirring of 2# electricity are opened, by secondary crystallization pot bottom Secondary crystallization object is pumped into recycling can again, for carrying out secondary recovery basic nickel carbonate, completes wastewater treatment and secondary crystallization Reclaimer operation；

Embodiment 5 (using the basic nickel carbonate of recycling, makes the nickel acetate solution for meeting hole sealing agent requirement)

The basic nickel carbonate product 100g obtained after rinsing is dried is weighed (to dry when only laboratory is measured, when producing greatly Rinsed clean, it is not necessary to dry, save production cost), 100g pure water is added to moisten, by reaction equation

NiCO₃.2Ni(OH)₂.4H₂O+6CH₃COOH=3Ni (CH₃COO)₂+9H₂O+CO₂↑

100g basic nickel carbonates, the reaction was complete needs to add glacial acetic acid (98%) 97.7g.95g glacial acetic acid is slowly added, Under conditions of basic nickel carbonate excess, that is, beaker bottom has a small amount of solid residue after the completion of reacting；Detect the pH of nickel acetate solution Value 6.19 meets the requirement that medium temperature hole sealing agent pH is more than 6.0；

Embodiment 6 (is transformed into medium temperature hole sealing agent)

According to medium temperature sealing of hole Con trolling index, the nickel acetate solution of making is titrated, obtains a concentration of 28.2g/L of nickel acetate；By (7) The ratio between concentration of formula, nickel acetate solution and triethanolamine is 10:1st, the ratio between concentration of the nickel acetate solution and isobutanol is 10: 1, addition triethanolamine 2.82g/L, isobutanol 2.82g/L complete the hole sealing agent transformation of nickel acetate solution.

With reference to (7) formula, this hole sealing agent is added to 16# sealing of hole slots；Working index in view of 16# slots is pH5.5-6.5, This hole sealing agent has met pH value requirement；In 50-60 DEG C of sealing of hole of temperature, there is a large amount of water evaporation, liquor of hole- sealing tank position shoals, addition This hole sealing agent just supplements drug concentration and liquid level.

Embodiment 7 (detection to the hole sealing agent ability to work of remanufacture)

By Fig. 7, continuous production coloring sealing of hole aluminium, 16# sealing of holes slot constantly adds making of the present invention by (7) formula Con trolling index Hole sealing agent；Take 55 DEG C of liquor of hole- sealing tank pH6.0, temperature, nickel acetate 4-6g/L；It is 15 microns to take oxide thickness, the sealing of hole time It is 15 minutes, continuously detects sealing quality by ISO3210 international standards, the results are shown in table below:

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 recovery system of single nickel salt coloring and medium temperature sealing of hole medicament in aluminium processing includes nickel-containing waste water successively from upstream to downstream Retain unit, nickel-containing waste water collector unit and basic nickel carbonate recovery unit, it is characterised in that:

The nickel-containing waste water retention unit includes the 13# single nickel salts being arranged in order coloring slot, 14# flowings rinsing bowl, 15# circulating waters Washing trough, 16# medium temperature sealing of holes slot, 17# flowing rinsing bowls and 18# flowing rinsing bowls；The 18# flows the external tap water of rinsing bowl, The 14# flowings rinsing bowl, 15# flowings rinsing bowl, 17# flowing rinsing bowls and 18# flowing rinsing bowl differential concatenation settings, it is described 13# single nickel salts colour slot and are compatible with setting to 16# medium temperature sealing of holes slot；

The nickel-containing waste water collector unit includes nickel-containing waste water collecting pit A and nickel-containing waste water collecting pit B, the 14# flowings washing The water outlet of slot is respectively equipped with and the nickel-containing waste water collecting pit A pipelines connected and the pipeline connected with nickel-containing waste water collecting pit B；

The basic nickel carbonate recovery unit includes the 1# pumps being arranged in order, recycling can, centrifuge, secondary crystallization tank and 2# pumps, 1# pump by the nickel-containing waste water of nickel-containing waste water collecting pit A and nickel-containing waste water collecting pit B for being pumped into the recycling can, described time Closed cans is used for the Ni in nickel-containing waste water²⁺Solid basic nickel carbonate is converted into, the centrifuge is used to detach solid alkali formula The nickel-containing waste water of nickelous carbonate and liquid, the secondary crystallization tank is for the Ni in the nickel-containing waste water after separation²⁺Secondary crystallization, institute State 2# pump for by the secondary crystallization object in the secondary crystallization tank be pumped into the recycling can and by after crystallization without nickel supernatant It is pumped into subsequent treatment unit for waste water.

2. the recovery system of single nickel salt coloring and medium temperature sealing of hole medicament in aluminium processing according to claim 1, feature exist In:In the nickel-containing 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# Valve, the water outlet of the 18# flowings rinsing bowl are equipped with 2# one-way valves with the pipeline that the water inlet of 17# flowing rinsing bowls connects, The water inlet of the 15# flowings rinsing bowl is equipped with 3# one-way valves with the pipeline that the water outlet of 17# flowing rinsing bowls connects, described 4# one-way valves are equipped between the water outlet of 15# flowing rinsing bowls and the water inlet of 14# flowing rinsing bowls.

3. the recovery system of single nickel salt coloring and medium temperature sealing of hole medicament in aluminium processing according to claim 2, feature exist In:In the nickel-containing waste water collector unit, the water inlet of the nickel-containing waste water collecting pit A, the nickel-containing waste water collecting pit B into It is connected between the water outlet of the mouth of a river and 14# flowing rinsing bowls by three-way pipe, and the three-way pipe and 14# flowings One end of rinsing bowl connection is equipped with 5# valves, and one end that the three-way pipe is connected with the nickel-containing waste water collecting pit A is equipped with 6# valves, institute It states one end that three-way pipe is connected with the nickel-containing waste water collecting pit B and is equipped with 7# valves；

The pipeline that the water outlet of the nickel-containing waste water collecting pit A is connected with the 1# water inlets pumped is equipped with 8# valves, the nickel-containing waste water The pipeline that the water outlet of collecting pit B is connected with the 1# water inlets pumped is equipped with 9# valves.

4. the recovery system of single nickel salt coloring and medium temperature sealing of hole medicament in aluminium processing according to claim 3, feature exist In:In the basic nickel carbonate recovery unit, the pipeline that the water outlet of the 1# pumps is connected with the water inlet of recycling can is equipped with 10# Valve, the pipeline that the water outlet of the recycling can is connected with the water inlet of centrifuge are equipped with 11# valves, and the centrifuge is equipped with solid-state point From material mouth and Liquid segregation material mouth, the Liquid segregation material mouth of the centrifuge is connected by the water inlet of pipeline and secondary crystallization tank It connects；

The middle part of the secondary crystallization tank is equipped with the first supernatant delivery outlet, the second supernatant delivery outlet and third supernatant vertically Delivery outlet, the bottom of the secondary crystallization tank are equipped with crystallization delivery outlet；First supernatant delivery outlet of the secondary crystallization tank and The pipeline of the water inlet connection of 2# pumps is equipped with 12# valves, the water inlet of the second supernatant delivery outlet and the 2# pump of the secondary crystallization tank The pipeline of mouthful connection is equipped with 13# valves, the pipe that the third supernatant delivery outlet of the secondary crystallization tank is connected with the 2# water inlets pumped Road is equipped with 14# valves, and the pipeline that the crystallization delivery outlet of the secondary crystallization tank is connected with the 2# water inlets pumped is equipped with 15# valves, described The pipeline that first water outlet of 2# pumps is connected with the water inlet of recycling can is equipped with 16# valves, the second water outlet of the 2# pumps and institute The pipeline for stating the water inlet connection for the treatment of unit for waste water is equipped with 17# valves.

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

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

6. in the aluminium processing as described in any one in claim 5 the recovery system of single nickel salt coloring and medium temperature sealing of hole medicament Recovery method, it is characterised in that:Include the following steps:

Step 1:Retain nickel-containing waste water:It opens 1# valves and 5# valves, water is entered by 1# valves, and followed by 2# valves, 3# Valve, 4# valves flow into 14# flowing rinsing bowls, then are flowed out by 5# valves, only one of ejected wash water differential concatenation flowing；By aluminium alloy After the coloring slot coloring of 13# single nickel salts, drip 30s；Into 14# flowings rinsing bowl, 15# flowing rinsing bowls, 60s, drip are cleaned 30s；Into 16# medium temperature sealing of hole slots, sealing of hole 15min, drip 30s；Into 17# flowings rinsing bowl, 18# flowing rinsing bowls, cleaning 60s, drip 30s；

Step 2:Collect nickel-containing waste water:6# valves or 7# valves are opened, will be flowed by the waste water flowed out in 14# flowing rinsing bowls In nickel-containing waste water collecting pit A or B；

Step 3:Recycle basic nickel carbonate:8# valves or 9# valves are opened, No. 1 pump is opened, and open 10# valves, closes 11# Waste water in nickel-containing waste water collecting pit A or B is pumped into recycling can by valve；The stirring of 1# electricity is opened, is slowly added to sodium carbonate and one side PH value is detected, until when pH value is 9.0, stops adding in sodium carbonate, continues to stir 30min, recycle Ni²⁺, reaction generation alkali formula carbon Sour nickel；Open 11# valves, open centrifuge, make nickel-containing waste water separation of solid and liquid, recycle solid basic nickelous carbonate, liquid it is nickeliferous It is spare that waste water flows into secondary crystallization tank；

Step 4:Prepare nickel acetate solution:By basic nickel carbonate after rinsing, after adding in pure water moistening, it is slowly added glacial acetic acid (98%), under conditions of basic nickel carbonate excess, reaction generation nickel acetate solution；

Step 5:Hole sealing agent is transformed:According to medium temperature sealing of hole Con trolling index, concentration, the addition triethanolamine of nickel acetate solution are titrated And isobutanol, form the hole sealing agent that can be added directly in 16# medium temperature sealing of hole slots.

7. the recovery method of single nickel salt coloring and medium temperature sealing of hole medicament in aluminium processing according to claim 6, feature exist In:In step 5, the ratio between concentration of the nickel acetate solution and triethanolamine is 10:1st, the nickel acetate solution and isobutanol The ratio between concentration is 10:1.

8. the recovery method of single nickel salt coloring and medium temperature sealing of hole medicament in aluminium processing according to claim 6, feature exist In:In step 3, recycling wastewater treatment and secondary crystallization step are further included:

12# valves or 13# valves or 14# valves are opened, opens pump 2, opens 17# valves, closes 15# valves and 16# valves, it will Wastewater treatment center is pumped into without nickel supernatant in secondary crystallization tank, is neutralized；Close 12# valves or 13# valves or 14# valves close 17# valves, open 15# valves and 16# valves, the stirring of 2# electricity are opened, by the secondary of secondary crystallization pot bottom Crystal is pumped into recycling can again, for carrying out secondary recovery basic nickel carbonate.

9. the recovery method of single nickel salt coloring and medium temperature sealing of hole medicament in aluminium processing according to claim 6, feature exist In:In step 4, the pH value of the nickel acetate solution of generation is more than 6.

10. the recovery method of single nickel salt coloring and medium temperature sealing of hole medicament in aluminium processing according to claim 6, feature exist In:The oxide thickness of the aluminum alloy surface is 15 microns.