CN109183118A - Nickel pink salt colours sealing of hole recycling colorant and Waste water utilization method and Configuration Online - Google Patents

Abstract

Nickel pink salt colours sealing of hole recycling colorant and Waste water utilization method and Configuration Online, includes: the water-saving operation of differential concatenation, nickel tin waste water retention operation, nickel tin wastewater treatment operations, nickel phosphate reclaimer operation and N-P compound fertilizer reclaimer operation using method；Its Configuration Online includes: the useless water generation system of nickel tin, nickel tin wastewater collection system, nickel tin separation system, nickel phosphate recovery system and N-P compound fertilizer recovery system；The present invention utilizes online classification recovery method, and by the Configuration Online of the design, the water of coloring and sealing of hole cleaning is collected in retention, recycles nickel tin solid mixture, is converted to nickel pink salt colorant；Water during treated is recycled, and is converted to N-P compound liquid fertilizer, blocks pollution of the nickeliferous tin waste water to wastewater treatment center, reduces industrial dangerous waste discharge, realizes that the resource recycling of toxic waste utilizes.

Description

Nickel pink salt colours sealing of hole recycling colorant and Waste water utilization method and Configuration Online

Technical field

The present invention relates to aluminum processing technology field more particularly to nickel pink salt coloring sealing of hole recycling colorants and Waste water utilization Method and Configuration Online.

Background technique

Aluminium alloy has many advantages, such as that processing performance is excellent, corrosion resistance is good, surface aesthetic, the rate of recovery are high, in building, traffic The industries such as transport, machinery, electric power are applied widely.In recent years, aluminium is for copper, aluminium generation wood, aluminium for steel, expansion aluminium application model The trend enclosed is more obvious.Aluminium processing industry is both conventional industries, is even more full of the rising industry of vitality.But in economy Under new normality, the common problem that aluminium processing industry energy consumption is high, total amount of pollutants discharged is big, resource recycling rate is low is highlighted as system The about bottleneck and obstacle of industry development.

Aluminium industry production includes the processes such as electrolysis, founding, pressure processing, surface treatment, and each process can generate when production Different degrees of exhaust gas, waste water, waste residue.A large amount of aluminium ash is generated when electrolysis and founding, it is useless that extrusion process generates pot mould alkalinity Liquid, it is useless that surface treatment process generates all kinds of waste water containing the complicated components such as acid, alkali, treatment agent and chromium, nickel heavy metal ion Slag.

Aluminum waste residue source

1, electrolysis founding aluminium ash and aluminium ash results from the electrolysis, melting and casting process of aluminium and aluminium alloy, caused by aluminium ash Aluminium total losses amount is in 1-12%.One ton of primary aluminum of every processing, about generation 20-40kg aluminium ash, when molten aluminum direct founding yield compared with Few, when aluminium ingot remelting, measures more, and regenerates one ton of aluminium scrap about to generate 100-250kg aluminium grey.

Aluminium ash can be divided into two kinds: be during electrolysis primary aluminum and casting etc. do not add salt flux one is secondary aluminium ash The dross of generation and skimming, main component are metallic aluminium and aluminum oxide, and for aluminium content up to 15%-70% etc., color is white Color；Another kind is Quadratic aluminum dust, is that a secondary aluminium ash mentions the waste after alum recovery, aluminium content is low compared with a secondary aluminium ash, generally in ash Black.Quadratic aluminum dust complicated component contains metallic aluminium (5-30%), aluminium oxide (30-70%), silica and three oxidations two The poisonous and harmful elements such as iron (5-15%), the chloride (10-30%) of potassium sodium calcium and magnesium and nitrogen fluorine arsenic.Alleged aluminium ash is equal below Refer to Quadratic aluminum dust.

National 32,500,000 tons of yield of electrolytic aluminium 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 at ten thousand tons of 600-850 at 2,000,000 tons or more.Aluminium ash is one The reproducible resource of kind, comprehensive reutilization value with higher, but enough attention are not obtained always, it 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, The waste classification of aluminium ash is HW48, hazard property T (Toxicity)-toxicity in 2016 version " National Hazard waste register " Hazardous waste.With the development of economy, aluminium scrap ash amount of savings will increase considerably year by year, if not finding economical and effective, nothing The method of evilization is pocessed, and is seriously threatened it is increasingly highlighted to environment.The recycling of China's aluminium ash has still been at present Step section, lacks that technology maturation is reliable, recovery method of good economy performance, and aluminium ash handles the low rate of recovery, energy consumption and waste Greatly, utilization ways are few.Even if treated, aluminium ash is interior still contains a large amount of harmful substances, still can only stockyard stockpiling or burial Processing has great environmental hazard, while producer carries huge illegal risk.Execution from January 1st, 2018 " People's Republic of China's environmental protection tax law " regulation, aluminium ash discharge enterprise will pay 1000 yuan/ton of environment protection tax.

2, compressive surface handles waste water and dregs

The production of aluminium fabricated product will consume a large amount of water, and 1 ton of aluminium of every production at least consumes 15 tons of water, whole industry year 20,000,000 tons of squeeze wood of production, generates about 1,500,000 tons of waste residue, quantity is extremely frightened by nearly 2.25 hundred million tons of waste discharge after wastewater treatment People.

2.1, 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 for stewing sodium hydroxide in mould liquid reaches 200-300g/L, and with the progress of reaction, aluminium composition is constantly increased, when reaching When being substantially reduced to 60-70g/L or more, reaction speed, it must will just stew mould 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 side of " treatment of wastes with processes of wastes against one another " is generally taken in the processing for stewing mould waste liquid Formula, direct emission is into waste water center, the spent acid neutralisation treatment generated with oxidation operation.The waste residue amount that this processing mode generates Very big, 28% or so of the total quantity of slag of enterprise can be accounted for by stewing mould waste residue；Meanwhile a large amount of sodium ions enter waste water center, pollution Middle water, a possibility that thoroughly breaking off Treated sewage reusing.This coarse processing mode of mould liquid is stewed, enterprise is not only without utilizing its warp Ji value, increase cost instead, and waste water, waste residue are treated as heavy environmental burden.

2.2, surface treatment waste water waste residue

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

Divide by technique, the waste water and dregs that anode oxidation process generates have: the alkaline waste water waste residue that Alkaline etchant generates accounts for The 18% of total quantity of slag；The acid waste water waste residue that oxidation solution generates, accounts for the 29% of total quantity of slag, and coloring generates nickeliferous with pore-sealing liquid Waste residue accounts for total quantity of slag 9%；The acid waste water waste residue that spraying process generates, accounts for the 18% of total quantity of slag.In aluminium processing enterprise waste water Heart aluminium slag source subdivision are as follows: stew mould liquid alkaline slag and account for the 28% of total quantity of slag, Alkaline etchant alkaline residue accounts for the 18% of total quantity of slag, oxidation solution acid Slag accounts for the 29% of total quantity of slag, and coloring accounts for total quantity of slag 9% with pore-sealing liquid nickel slag；Spraying acid waste residue accounts for the 18% of total quantity of slag.This Outside, Some Enterprises production polishing aluminium, generates a large amount of polishing slag.

The waste water of waste water central collection, containing cations such as Al3+, Na+, NH4+, Ni2+, Sn2+, Cr6+, SO42-, The anion such as F-, NO3-, NO2-, S2-, Cl-, tartrate anion, glucose acid group, acetate and organic phenol, surface-active Organic matters such as agent and acrylic resin etc..Acid waste water, alkaline waste water are usually to mix neutralisation treatment, and chromate waste water, nickeliferous Waste water must be handled individually.Oxidation electrophoresis material ratio decline in recent years, but most of aluminum material factories or acid waste water are more than alkalinity Waste water, soda acid water all mix processing, in acidity after waste water mixing, need to put into a large amount of piece alkali, lime and PAC, PAM produces a large amount of waste residues.The useful resources such as a large amount of metallic aluminiums, acid, alkali in waste residue are not utilized, and are caused huge The wasting of resources.Waste residue belongs to hazardous waste, contains aluminium hydroxide, fluoride, sulfide, nickel salt, phenol, nitrate, nitrous acid A variety of poisonous and harmful substances such as salt, environmental hazard is huge, can not fill, and has great environmental hazard.At waste water center Reason, be separated by solid-liquid separation after, middle water contain sodium ion, ammonium ion, sulfate radical, nitrate anion, nitrite anions, acetate, tartrate anion, Thiosulfate anion, chloride ion, sulphion, fluorine ion etc., can not reuse.Current Environmental Protection Situation forces enterprise to subtract to energy conservation Row and resource circulation utilization direction Transformation Development, but lack the technology of mature and reliable.Water fully recovering, waste residue zero produce in realization Out, utilization of resources value maximization has great environmental benefit, Social benefit and economic benefit.

The latest edition " National Hazard waste register " of execution from August 1st, 2016 arranges acid and alkaline waste water waste residue Enter register management, waste classification is HW34, HW35 respectively.Acid, alkaline residue, chromium slag, nickel slag have been included in latest edition, and " National Hazard is useless Name record ".

The Law on Environmental Protection of the People's Republic of China implemented on January 1st, 2018, imposed effluent charge.Waste water presses 1.4- 14 yuan/T, waste residue pays taxes by 2000 yuan 1000 yuan/T, dangerous waste/T.Whole industry waste water pay taxes 22.5 hundred million yuan, dangerous waste pay taxes 3,000,000,000 Member.

Summary of the invention

It is an object of the invention to propose that nickel pink salt coloring sealing of hole recycling colorant and Waste water utilization method, this method are used In recycling coloring and sealing of hole water for cleaning, it is converted to nickel pink salt colorant.

The present invention also proposes that the Configuration Online of nickel pink salt coloring sealing of hole recycling colorant and middle water, the Configuration Online are used for Recycling coloring and sealing of hole water for cleaning, are converted to nickel pink salt colorant.

To achieve this purpose, the present invention adopts the following technical scheme:

Nickel pink salt colours sealing of hole recycling colorant and Waste water utilization method, comprising: the water-saving operation of differential concatenation, nickel tin are useless Water retains operation, nickel tin wastewater treatment operations, nickel phosphate reclaimer operation and N-P compound fertilizer reclaimer operation；

(1) the water-saving operation of the differential concatenation includes: to open valve 14, logical from tap water water inlet to 18# flowing rinsing bowl Enter tap water, enter 17# through valve 15 and flow rinsing bowl, enter 15# through valve 16 and flow rinsing bowl, enters 14# circulating water through valve 17 Washing trough, through valve 1 and pump 1, into coloring sealing of hole nickel tin wastewater collection tank；

(2) the nickel tin waste water retention operation includes: to colour aluminium using coloring liquid in 13# nickel pink salt coloring slot 30s-15min rises and hangs drip at least 30s；Aluminium after coloring is entered into 14# flowing rinsing bowl cleaning at least 1min, rises and hangs drop It is flow to few 30s, and cleans at least 1min after going to 15# flowing rinsing bowl, rises and hangs drip at least 30s, wherein aluminium is in 13# nickel Pink salt coloring slot coloring after can by nickel sulfate, stannous sulfate and the tartaric acid in coloring liquid bring into 14# flow rinsing bowl and 15# flows rinsing bowl, the nickel tin waste water after forming coloring；Aluminium is gone in 16# medium temperature sealing of hole slot, using pore-sealing liquid to aluminium Material carries out sealing pores 10-25min, rises after hanging drip at least 30s, sequentially enters 17# flowing rinsing bowl and 18# flowing washing Slot, each slot, which is respectively washed at least 1min and rises, hangs a drip at least 30s, wherein aluminium in 16# medium temperature sealing of hole slot when sealing of hole, The nickel acetate, triethanolamine and isobutanol of pore-sealing liquid can be brought into 17# flowing rinsing bowl and 18# flowing rinsing bowl, form envelope Nickel tin waste water behind hole；The 17# nickel tin waste water flowed in rinsing bowl and 18# flowing rinsing bowl after sealing of hole is reversely flowed into 15# stream Dynamic rinsing bowl and 14# flow rinsing bowl, form the nickel tin waste water of mixing, and adjustment 18# flowing rinsing bowl is passed through originally water management 14# flows pH > 3.0 of rinsing bowl and pH > 5.5 of 15# flowing rinsing bowl, fixed valve 14；

(3) the nickel tin wastewater treatment operations include: to open valve 1, open pump 1, and the slot bottom of 14# flowing rinsing bowl is gone out It is spare that the nickel tin waste water of mouth of a river discharge is pumped into coloring sealing of hole nickel tin wastewater collection tank；Valve 2 and valve 3 are opened, valve 4 is closed, opens pump 2, nickel tin solid recycling can is pumped into using nickel tin waste water as reaction solution；Valve 4 and valve 6 are opened, pump 3 and 1# electricity stirring, circulation are opened Reaction solution；Valve 5 is slowly opened, the liquefied ammonia suction pump 3 of ammonia tank is sufficiently mixed reaction solution using the high speed rotation of pump 3；Side Liquefied ammonia is added, frontier inspection surveys the pH value of reaction solution, when pH value reaches 8.5-9.0, closes valve 5, stops that liquefied ammonia is added, continues to follow Ring stirs 1 hour；1# filter press is opened, valve 7 is opened, closes valve 6 and valve 8, is separated by solid-liquid separation nickel tin solid and first-time filtrate；Instead Multiple spray, rinsing nickel tin solid after ten minutes, recycle nickel tin solid, and first-time filtrate flows into nickel phosphate recycling can；

(4) the nickel phosphate reclaimer operation includes: to close valve 9 and valve 11, opens valve 8 and valve 10, opens pump 4 and 2# electricity Stirring, circular response liquid；Valve 9 is slowly opened, the phosphoric acid suction pump 4 of phosphoric acid tank is sufficiently mixed using the high speed rotation of pump 4 Reaction solution；Phosphoric acid is added on side, and frontier inspection surveys the pH value of reaction solution, when pH value reaches 6.5-7.5, closes valve 9, stops dosing, Continue cycling through stirring 1 hour；2# filter press is opened, valve 11 is opened, closes valve 10, is separated by solid-liquid separation nickel phosphate and secondary filtrate；Instead Multiple spray, rinsing nickel phosphate solid after ten minutes, recycle nickel phosphate product, and secondary filtrate flows into compound fertilizer's recycling can；

(5) N-P compound fertilizer reclaimer operation includes: to open valve 12 and valve 13, pump 5 is opened, by secondary filtrate through filtering After device filtering, it is delivered to land use for greening, is used as nitrogenous and phosphorus N-P compound fertilizer, the filter residue of filter is nickel phosphate, is stayed It is stored in nickel phosphate recycling can, waiting is recycled next time.

It further explains, 13# nickel pink salt colours in slot, and the concentration control of stannous sulfate is 6-12g/L, nickel sulfate Concentration control is 20-30g/L, and the concentration control of sulfuric acid is 15-20g/L, and the concentration control of tartaric acid is 8-10g/L, pH control For 0.8-1.0, temperature control is 20-25 DEG C, and the control of processing time is 30s-15min, and voltage control is 14-16V；

In 16# medium temperature sealing of hole slot, the concentration control of nickel acetate is 4-6g/L, and the concentration control of triethanolamine is 0.4- 0.6g/L, the concentration control of isobutanol are 0.4-0.6g/L, and pH control is 5.5-6.5, and temperature control is 50-60 DEG C, time control It is made as 10-25min.

It further explains, in the nickel tin wastewater treatment operations, nickel tin solid bag contains stannic hydroxide, stannous hydroxide With nickel hydroxide solid, into the nickel tin solid of recycling, addition pure water, glass putty and sulfuric acid are converted to stannous sulfate and sulfuric acid Nickel；Sulfuric acid addition is appropriate excessive, and reaction end is that pH reaches=0.8-1.0；In (pure water weight/solid mixture weight)=3 With glass putty it is appropriate it is excessive under the conditions of, precipitating and filtering reacting liquid obtain the unsaturated solution of stannous sulfate and nickel sulfate mixing And filter residue；Unsaturated solution pH value=the 0.8-1.0, content lower than saturation point and can make liquid nickel pink salt colorant；Filter residue It for glass putty, resides in reactor, waits next secondary response.

It further explains, in the nickel tin wastewater treatment operations, configures liquid nickel using stannous sulfate and nickel sulfate Pink salt colorant, first titrated sulfuric acid stannous and nickel sulfate mixing unsaturated solution content, then by (concentration of nickel sulfate/sulfuric acid is sub- Tin is dense)=2.5 and (concentration of nickel sulfate/tartaric acid concentration)=25/8, dosages distribution is adjusted, stannous sulfate and nickel sulfate are mixed It closes unsaturated solution and is converted to liquid nickel pink salt colorant, be added directly into 13# nickel pink salt coloring slot.

It further explains, when the nickel tin solid of recycling is converted to stannous sulfate and nickel sulfate mixed liquor, the nickel tin of recycling After solid rinse plus glass putty and pure water, directly and sulfuric acid reaction.

It further explains, it is not dense after being prepared into liquid nickel pink salt colorant using stannous sulfate and nickel sulfate mixed liquor Sheepshank is brilliant and is directly used in the fluting of 13# nickel pink salt coloring slot and addition.

It further explains, comprising: nickel tin gives up water generation system, nickel tin wastewater collection system, nickel tin separation system, phosphorus Sour nickel recovery system and N-P compound fertilizer recovery system；

The useless water generation system of the nickel tin is used to handle cleaning and sealing pores after aluminium coloring, coloring, generates and colours Afterwards with the nickel tin waste water after sealing of hole, and the nickel tin waste water of generation is sent to the nickel tin wastewater collection system；

The nickel tin wastewater collection system is used to collect the nickel tin and gives up the nickel tin waste water of water generation system, and by nickel tin Waste water is sent to nickel tin separation system；

The nickel tin separation system is used to handle the nickel tin waste water of the nickel tin wastewater collection system, and liquefied ammonia reaction is added Generate nickel tin solid mixture；The nickel tin separation system is equipped with No.1 separation equipment, and the No.1 separation equipment is for handling After nickel tin solid mixture, nickel tin solid and first-time filtrate are isolated；The nickel tin separation system be also used to isolate one Secondary filtrate is sent to the nickel phosphate recovery system；

The nickel phosphate recovery system handles the first-time filtrate of the nickel tin separation system, and phosphatase reaction is added and generates phosphorus Sour nickel mixture；The nickel phosphate recovery system is additionally provided with No. two separation equipments, and No. two separation equipments are for handling phosphoric acid After nickel mixture, nickel phosphate solid and secondary filtrate are isolated；The nickel phosphate recovery system is also used to secondary by what is isolated Filtrate is sent to N-P compound fertilizer recovery system；

The secondary filtrate being collected into is filtered behaviour for collecting secondary filtrate by N-P compound fertilizer recovery system After work, collect into greening fertilizer.

It further explains, the useless water generation system of the nickel tin includes: 13# nickel pink salt coloring slot, No.1 flowing washing Slot, 16# medium temperature sealing of hole slot, No. two flowing rinsing bowls and tap water water inlet；The 13# nickel pink salt colours slot, No.1 circulating water Washing trough, 16# medium temperature sealing of hole slot, No. two flowing rinsing bowls and tap water water inlet is adjacent is sequentially connected；

No. two flowings rinsing bowl is also attached to the No.1 flowing rinsing bowl, which is equipped with valve 16；

The No.1 flowing rinsing bowl is connected to the nickel tin wastewater collection system, and the connecting line is equipped with pump 1；Institute 13# nickel pink salt coloring slot is stated to be used to colour for aluminium；The No.1 flowing rinsing bowl is used to clean the aluminium after coloring, obtains Nickel tin waste water after coloring；The 16# medium temperature sealing of hole slot is used to be aluminium sealing pores；No. two flowings rinsing bowl is used for Aluminium after cleaning sealing of hole, the nickel tin waste liquid after obtaining sealing of hole；The pump 1 is for flowing described No. two the sealing of hole of rinsing bowl Waste liquid, which is pumped through valve 16 to the No.1, flows rinsing bowl, and flows in rinsing bowl with the No.1 and pump together with nickel tin waste water to institute State nickel tin wastewater collection system.

It further explains, the No.1 flowing rinsing bowl includes: 14# flowing rinsing bowl and 15# flowing rinsing bowl；Institute Stating No. two flowing rinsing bowls includes: 17# flowing rinsing bowl and 18# flowing rinsing bowl；

The 13# nickel pink salt coloring slot, 14# flowing rinsing bowl, 15# flowing rinsing bowl, 16# medium temperature sealing of hole slot, 17# flowing Rinsing bowl, 18# flowing rinsing bowl and tap water water inlet is adjacent is sequentially connected；The 17# flowing rinsing bowl and 15# stream Dynamic rinsing bowl connection, and it is equipped with the valve 16；17# flowing rinsing bowl described in 18# flowing rinsing bowl be equipped with single-pass to valve 15；14# flowing rinsing bowl described in 15# flowing rinsing bowl be equipped with single-pass to valve 17；The 14# flowing rinsing bowl connection In the pump 1.

It further explains, the nickel tin wastewater collection system includes: coloring sealing of hole nickel tin wastewater collection tank and pump 2；Institute Pump 1, coloring sealing of hole nickel tin wastewater collection tank and pump 2 is stated adjacent to be sequentially connected；

The coloring sealing of hole nickel tin wastewater collection tank is connected to the nickel tin separation system by the pump 2；The pump 2 Nickel tin waste water pump for collecting the coloring sealing of hole nickel tin wastewater collection tank is to the nickel tin solid recycling can；

The nickel tin separation system includes: nickel tin solid recycling can, pump 3, ammonia tank and 1# filter press；The ammonia tank Equipped with liquefied ammonia；

The pump 2 is connected to the nickel tin solid recycling can；The bottom of the nickel tin solid recycling can, the pump 3 and institute State that 1# filter press is adjacent to be sequentially connected；The ammonia tank is equipped with pipeline and is connected to the nickel tin solid recycling can and the pump 3 Connecting line on；The pump 3 is additionally provided with the pipeline being connected at the top of the nickel tin solid recycling can；

The nickel phosphate recovery system includes: nickel phosphate recycling can, pump 4, phosphoric acid tank and 2# filter press；The ammonia tank Equipped with phosphoric acid；

The 1# filter press is connected to the nickel phosphate recycling can；The bottom of the nickel phosphate recycling can, 4 and of the pump The 2# filter press is adjacent to be sequentially connected；The phosphoric acid tank is equipped with the connection for being connected to the nickel phosphate recycling can and the pump 4 On pipeline；The pump 4 is additionally provided with the pipeline being connected at the top of the nickel phosphate recycling can；

The 2# filter press is used to that nickel phosphate solid and secondary filtrate will to be isolated with the first-time filtrate after phosphatase reaction, And secondary filtrate is sent to N-P compound fertilizer recovery system；

N-P compound fertilizer recovery system includes: compound fertilizer's recycling can, filter, pump 5 and greening fertilizer collector；

Fertilizer collector is adjacent is sequentially connected for the 2# filter press, compound fertilizer's recycling can, filter, pump 5 and greening；

Compound fertilizer's recycling can is used to collect the secondary filtrate of the 2# filter press, and secondary filtrate is sent to described Filter；The pump 5 is for collecting the secondary filtrate after the filter process to the greening fertilizer collector；

It is equipped with 1# electricity in the nickel tin solid recycling can to stir, 2# electricity is equipped in the nickel phosphate recycling can and is stirred.

Beneficial effects of the present invention:

1, the present invention utilizes online classification recovery method, and by the Configuration Online of the design, coloring and sealing of hole are collected in retention The water of cleaning recycles nickel tin solid mixture, is converted to nickel pink salt colorant；Water during treated is recycled, and is converted At N-P compound liquid fertilizer, pollution of the nickeliferous tin waste water to wastewater treatment center is blocked, reduces industrial dangerous waste discharge, realization contains The resource recycling of malicious waste utilizes.

2, the present invention is by 14# flowing rinsing bowl, the pH value Con trolling index of 15# flowing rinsing bowl setting, adjustment 18# flowing Rinsing bowl water inlet flow reduces coloring sealing of hole cleaning water consumption；The nickeliferous tin waste water for retaining 14# flowing rinsing bowl, from 14# Flowing rinsing bowl slot bottom water outlet is collected into coloring sealing of hole nickel tin wastewater collection tank, and it is useless online, individually to handle these nickeliferous tin Water avoids after being mixed with other processes with water, reprocesses the trouble of the nickeliferous tin waste water of magnanimity, and it is useless that the nickeliferous tin of processing is greatly reduced The environmentally friendly cost of water waste residue.

Detailed description of the invention

Fig. 1 is the nickel tin separation system, nickel phosphate recovery system and N-P compound fertilizer recovery system connection structure of the design Figure；

Fig. 2 is the useless water generation system of nickel tin and nickel tin wastewater collection system connection structure diagram of the design；

Fig. 3 is the conventional oxidation coloring hole-sealing technology process and slot position layout drawing of the one of embodiment of the present invention；

Specific embodiment

To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.

One, 13# nickel pink salt coloring slot and the retention of 16# medium temperature sealing of hole slot water for cleaning and collection method

Heat-tinting hole-sealing technology process is as shown in figure 3,1#, 4#, 7#, 10#, 13#, 16# slot are work nest, Mei Gegong Make slot with two flowing rinsing bowls, oxidation processes need 18 slot positions, and wherein 13# is that nickel pink salt colours slot, sulfur acid nickel, sulphur Sour stannous and tartaric acid；16# slot is medium temperature sealing of hole slot, contains nickel acetate, triethanolamine and isobutanol；Its subsequent 14,15#, 17#, 18# flowing rinsing bowl takes nickeliferous tin waste water out of and enters wastewater treatment center, and 2.25 hundred million tons of pollution whole industry water generates 1,500,000 The toxic waste residue of mixing of the nickeliferous tin of ton.The present invention relates to 13#-18# slot, the coloring sealing of hole of 48,000,000 tons of nickeliferous tin is collected in retention Water for cleaning individually recycles nickeliferous tin waste residue, is converted into nickel pink salt colorant, realizes nickeliferous tin waste water and dregs zero-emission. 13#-18# function is as follows:

13# nickel pink salt colours slot (hereinafter referred to as 13#)

Nickel pink salt electrolytic coloring, in addition to bronzing system, can also artificial stainless steel colour, champagne and ater.Nickel tin Salt electrolytic colouring liquid has a good color dispersion, the color film uniform color of formation, graceful luxurious, have good light resistance, Corrosion resistance and wearability, coloring liquid itself have stronger stain resistance.It is suitble to the control parameter of large-scale production are as follows:

Stannous sulfate 6-12g/L；Nickel sulfate 20-30g/L (contains 6 crystallizations water)；Sulfuric acid 15-20g/L；

Tartaric acid 8-10g/L；PH=0.8-1.0；20-25 DEG C of temperature；Time 30s-15min；Voltage 14-16V；

(1) formula

Coloured with nickel pink salt electrolyte, it is not only at low cost, it is long using the time, and can obtain individual nickel salt or The not getable color of pink salt institute and quality, thus the deep favor by vast aluminium producer.But such as single pink salt coloring one Sample, the stannous ion in nickel pink salt electrolytic coloring system are extremely unstable.Even if being also easy quilt in the acid solution of pH=1.0 Oxygen or hydroxyl in air are electrolysed the oxygen released, are oxidized to high price tin ion, and then the stannic acid that hydrolysis generates white occurs Precipitating, gently then influences the quality of coloring film, heavy then keep coloring liquid entirely ineffective.So the emphasis of control mainly guarantees stannous In addition the stabilization of 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 Pink salt is fewer and more stable than single pink salt dosage, thoroughly red more good-looking in tone Huang.Nickel salt is advisable with 20-30g/L, and too high colour cast is dark, But ater is appropriate to the occasion to rise to 45g/L.General tin salt 6-8g/L is advisable.Summer removes the limit, the winter upper limit, ater 10-12g/L need to be risen to.Additive, which plays, improves uniformity and the effects of prevent stannous from hydrolyzing, but at present coloring slot network Conjunction ability is inadequate, stannous in the same old way can oxydrolysis, therefore add tartaric acid, be complexed stannous ion.Sulfuric acid rise prevent pink salt hydrolysis and The double action of conductance is improved, 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, only have ater just to rise to 25g/L, to prevent surface from generating hydroxide.Some nickel pink salts Color liquid adds boric acid, it is worked as a buffer in hole, is conducive to electrodeposition of nickel, improves uniformity and improves color sensation, with 20- 25g/L is advisable, and too high colour cast is dark.

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

1, oxidation caused by tank liquor stirring

In order to make temperature, the even concentration of tank liquor, reply colouring slot liquid is stirred when production, although avoiding using air The chance for directly stirring and taking circulating pump, but tank liquor can be made to contact with air increases, and can occur in contacting with air Bivalent Tin is oxidized to stannic reaction

SnSO₄+H₂SO₄+ O=H₂O+Sn(SO₄)₂↓ (2) formula

2, the oxidation and hydrolysis occurred when electrode reaction

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

4OH^--4e^-=2O+2H₂O (3) formula

In coloring process, Sn²⁺The oxygen effect generated in easily reacting with (3) formula in electrode reaction, aoxidizes, presses (2) Formula generates muddy object.In addition, aluminium alloy, as cathode, evolving hydrogen reaction can be such that local pH value increases, promote the Sn in slot²⁺With Sn⁴⁺Ion hydrolysis

Sn²⁺+2OH^-=Sn (OH)²↓ (4) formula

Sn⁴⁺+4OH^-=Sn (OH)⁴↓ (5) formula

Due to the presence reacted above and Sn²⁺The stabilizer complexing power factors such as not enough, tank liquor service life is longer, It suspends muddy more serious.Good additive should have certain integration capability, both anti-Sn²⁺Ion precipitation hydrolysis, will also have and add Speed ionization, improves the effect of dispersibility.Otherwise, complexing and bad, the Sn of ionization dynamic equilibrium coordination in coloring process²⁺ It is bad in inner hole deposition product condition, it will affect coloration efficiency and coloring tone.

The additives such as magnesium sulfate, aluminum sulfate, ATS (Ammonium thiosulphate) are added in coloring liquid so that surface is uniformly coloured Effect.Electrolytic colouring liquid based on pink salt, most important problem are how to prevent or slow down stannous oxidation, improve electricity Solve the stability and service life of liquid.In addition to the additives such as tartaric acid, phenol, sulfuric acid, boric acid are added, also need that oxidizing and depressing is added Agent, such as: ascorbic acid, phenylbenzene, quinhydrones etc..The wherein acidificable solution of sulfuric acid reduces pH value；Boric acid has buffering and network Cooperation is used, and stannous ion can be not only complexed in tartaric acid, citric acid, ammonium tartrate, moreover it is possible to play buffer function to pH value.Addition Sulphur urine or hydrazine sulfate can play reduction to tetravalence tin ion.The medicament that addition replaces divalent tin ion to be oxidized, it is such as ferrous Ion, i.e., when divalent tin ion and ferrous ion coexist, in divalent tin ion to before the oxidation reaction of tetravalence tin ion, The oxidation reaction of ferrous ion first has occurred, to control transformation of the divalent tin ion to tetravalence tin ion.Here it is added Additive is all some substances with buffer function, complexing and antioxidation, and Sn can be complexed²⁺Ion, or can be preferential By the dissolved oxygen oxidation in solution, to prevent Sn²⁺Ion is oxidised with air to Sn⁴⁺, and then generate Sn (OH)₄White precipitate shadow Ring coloring.

Comprehensively consider the above various factors, the formula design of coloring stabilizer must satisfy four point requirements: 1, improving coloring Uniform performance；2, white dot and crack are prevented；3, stablize tin salt；4, the electric conductivity of electrolyte is improved.

In order to obtain the uniformity of stainless steel colored champagne colour system aluminum profile color, strict control anodizing tank is needed Technological parameter, it is desirable that the thickness of oxidation film reaches unanimity, and deviation is the smaller the better, and preferably control is 12 μm.It will be according to anodic oxidation The technological parameter situation of slot determines anodizing time.In addition, colouring parameters must be controlled:

(1) time and temperature

It is calculated it is demonstrated experimentally that the time of electrolytic coloring will be accurate to by the second, the determination of time is according to electrolytic coloring The situations of the various technological parameters of slot and determination.One second difference of coloration time has the color of champagne electrophoretic coating aluminum profile It significantly affects, coloration time extends, and Sn content increases in oxidation film, and oxidation film color also gradually deepens.Oxidation film Sn content with The time extend linearly increase, relational expression are as follows: 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 Increase, and Sn²⁺Precipitation reaction speed is accelerated, and colouring speeds is promoted to accelerate.In addition, the raising of coloring liquid temperature is unfavorable for Sn²⁺'s Stablize.Sn²⁺Oxidation reaction speed with coloring liquid temperature increase and accelerate.Therefore, in order to guarantee champagne electrophoretic coating Aluminum profile 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.As pH > 1.1, colouring speeds are quickly, difficult With control；If pH value is too small, and influences coloring film corrosion resistance.Therefore, pH value 0.8-1.0 is that generation champagne aluminum profile is equal An important factor for even color.

(3) voltage

Coloring liquid voltage controls 14-16V (stainless steel colored 10-13V), and current density is 0.6-0.8A/dm², no-voltage guarantor Hold 1-1.5min.Boosting rectifier control is critically important, about increases voltage 1V every 3s.To coloring speed when voltage is less than 14V or is greater than 16V Degree influences very big.

(4) it washes

It is not allowed to park in first of rinsing bowl after anodic oxidation, the storage period is no more than in second rinsing bowl 2min enters coloring, the adverse effect to avoid sulfuric acid in rinsing bowl to oxidation film.Second rinsing bowl requires pH >=3. After colouring timing, it should lift by crane immediately and be transferred to lower road rinsing bowl again to color, can not be stopped in coloring slot, strict control is empty Middle lifting transfer time.Rinsing bowl after coloring also requires pH >=3.In water-washing process, the coloring metal salt in fenestra is easily By the etch of water middle acid substance, cause to fade.

From the point of view of coloring effect, using the color of nickel pink salt, be relatively used alone nickel salt or pink salt color will Beauty, heat resistance and light resistance have reached requirement.When stannous sulfate is less than 2g/L, colouring speeds are relatively slow, when mentioning When height is to 5g/L or more, colouring speeds are obviously accelerated；The concentration range of nickel sulfate is broader.

14# flows rinsing bowl and 15# flowing rinsing bowl (hereinafter referred to as 14# and 15#)

The purpose that this twice rinsing bowl is arranged is the residual coloring liquid for cleaning coloring slot and taking out of, protects sealing of hole slot.Tap water From 15# slot into 14# slot goes 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 be discharged is to contain Nickel tin waste water increases environmental protection treatment pressure.It is suitble to the control parameter of large-scale production are as follows: 14# flows rinsing bowl pH > 3.0；15# Flow rinsing bowl pH > 5.5；(6) formula

16# sealing of hole slot (hereinafter referred to as 16#)

The purpose that this slot is arranged is the micropore for sealing oxidation film, it is ensured that its corrosion resistance.It can also be replaced with electrophoresis tank and be sealed Hole slot.Method for sealing by operating temperature be divided into high temperature, in mild normal-temperature hole sealing.It is pure at 95-100 DEG C that high temperature hole sealing is aluminium It is handled in water, sealing quality is preferable, but energy consumption is high, and evaporated quantity of water is big, easy dust, and easy foreign ion poisoning need to often replace slot Liquid；Medium temperature sealing of hole generally uses the additivated method of nickel acetate, handles at 55-65 DEG C, and sealing of hole speed is fast, few dust, no Film, but nickeliferous tin are split, environmental protection is unfavorable for；Normal-temperature hole sealing uses nickel fluoride doping method, handles at 25-35 DEG C, sealing of hole Fast speed, few dust, low energy consumption, easy to use.But film easy to crack, and fluorine-containing and nickel is unfavorable for environmental protection.Now, the country is in Warm sealing of hole is main methods.Medium temperature sealing of hole Con trolling index are as follows:

Nickel acetate 4-6g/L；Triethanolamine 0.4-0.6g/L；Isobutanol 0.4-0.6g/L；

PH=5.5-6.5；50-60 DEG C of temperature；Time 10-25min；(7) formula

17# flows rinsing bowl and 18# flowing rinsing bowl (hereinafter referred to as 17# and 18#)

The purpose that this twice rinsing bowl is arranged is that cleaning sealing of hole slot takes nickeliferous residual medicament out of, after protecting aluminium to dispatch from the factory not It is corroded.Equally, tap water is from 18# slot into 17# slot goes 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 be discharged is nickel-containing waste water, increases environmental protection treatment pressure.

Aluminium can pack factory after 18 slot positions are handled, and complete anodized.

Two, 13# nickel pink salt coloring slot and 16# medium temperature sealing of hole slot ejected wash water collect production nickel pink salt colorant and middle water returns It receives and utilizes quantitative and qualitative analysis

1), take coloring sealing of hole nickel tin wastewater collection tank recovered liquid 1L, sulfur acid stannous, nickel sulfate, tartaric acid, sulfuric acid, Nickel acetate, triethanolamine and isobutanol, test agents concentration are as follows:

Stannous sulfate 0.2g/L；Nickel acetate 0.1g/L；Nickel sulfate 0.5g/L；Triethanolamine 0.01g/L；Tartaric acid 0.0.16g/L, isobutanol 0.01g/L, pH=3.15；(8) formula

It is slowly added liquefied ammonia, stirring while adding, pH value is stepped up, there is following variation: when pH value is lower than 7.0, tank liquor Muddiness, precipitating increase, and press (4) (5) formula, and stannous hydroxide and stannic hydroxide is precipitated；When pH is between 7.0-7.5, tank liquor is more Muddiness, precipitate nickel hydroxide containing green crystal:

NH₃+H₂O=NH₄OH

Sn²⁺+ 2OH=Sn (OH)₂↓ (9) formula

Sn⁴⁺+ 4OH=Sn (OH)₄↓

Ni²⁺+2NH₄OH=2NH₄ ⁺+Ni(OH)₂↓

When pH is between 7.5-8.0, tank liquor is muddy, and green crystal precipitate nickel hydroxide increases；

When pH is between 8.0-8.5, tank liquor is muddy, and green crystal precipitate nickel hydroxide increases；

When pH is between 8.5-9.0, tank liquor is muddy, and green crystal precipitate nickel hydroxide is not further added by；

When pH is between 9.0-10.0, tank liquor is muddy, and green crystal precipitate nickel hydroxide is not further added by.

By above-mentioned experimental result, the first reaction end pH5.5-6.0 can use, be separated by solid-liquid separation, recycle stannic hydroxide and hydrogen-oxygen Change stannous, filtrate sulfur acid nickel and nickel acetate；Continue annex solution ammonia in filtrate, take the second reaction end pH8.5-9.0, returns Receive nickel hydroxide.In view of the first section stage of reaction pH3.0-6.0, when adding liquefied ammonia, reaction solution local ph can be can exceed that 7.5, there is the risk for generating nickel hydroxide, in the stannic hydroxide and stannous hydroxide of recycling, nickel hydroxide may be mixed, it is bad Separation；In addition, the stannic hydroxide and stannous hydroxide of recycling, need to rinse, water consumption is too big, recycles for subsequent middle water Excessively high threshold is preset, therefore the present invention uses single step reaction, taking pH8.5-9.0 is reaction end, directly recycling stannic hydroxide, hydrogen Stannous oxide and nickel hydroxide solid mixture are spare；

2), ammonium sulfate, ammonium tartrate, ammonium acetate, triethanolamine and isobutanol do not precipitate, and retain in liquid.

By (9) formula, with the addition of liquefied ammonia, pH is constantly increased, and stannic hydroxide, stannous hydroxide and nickel hydroxide are continuous Precipitation but ammonium sulfate, ammonium tartrate, ammonium acetate, triethanolamine and isobutanol, do not decompose, do not precipitate, retain in liquid；

3) it, is separated by solid-liquid separation, filters out ammonium sulfate, ammonium tartrate, ammonium acetate, triethanolamine and isobutanol with filtrate, recycle hydrogen Tin oxide, stannous hydroxide and nickel hydroxide solid mixture.

By (9) formula, reaction product is separated by solid-liquid separation.Ammonium sulfate, ammonium tartrate, ammonium acetate, triethanolamine and isobutyl Alcohol is flowed out with filtrate, obtains stannic hydroxide, stannous hydroxide and nickel hydroxide solid mixture；It rinsed, dried, mixed Close object solid；Nickel hydroxide solubility 130mg/L in filtrate, the discharge standard much higher than 0.5mg/L, needs secondary treatment, side It up to standard can recycle；

4) sulfuric acid (concentration 98%), is added, conversion stannic hydroxide, stannous hydroxide and nickel hydroxide solid mixture, instead Stannous sulfate and nickel sulfate mixing unsaturated solution should be generated.

Weigh stannic hydroxide, stannous hydroxide and the nickel hydroxide solid mixture 100g obtained after rinsing drying (only Laboratory is dried when measuring, rinsed clean when mass production, it is not necessary to be dried, be saved production cost), the medicine provided by (8) formula Agent concentration, 100g hybrid solid about contain stannous hydroxide 38g, nickel hydroxide 61g, stannic hydroxide 1g, and it is sub- that reaction generates sulfuric acid Tin about 53g, nickel sulfate (containing 6 crystallizations water) about 173g.By stannous sulfate solubility 330g/L, nickel sulfate (contains 6 crystallizations water) Solubility 625g/L designs reaction solution.Glass putty 1g is added, 300g pure water is added, is uniformly mixed, is slowly added sulfuric acid (concentration 98%), reaction is following (restoring tetravalent tin with glass putty):

Sn(OH)₂+H₂SO₄=SnSO₄+2H₂O

Ni(OH)₂+H₂SO₄=NiSO₄+2H₂O (10) formula

Sn+Sn(OH)₄+2H₂SO₄=2SnSO₄+4H₂O

Taking excess sulfuric acid, side is added frontier inspection and is surveyed, as pH value=0.8-1.0 of reaction solution, as reaction end.Filtering Reaction solution, filter residue are residual glass putty, reside in reactor, wait next secondary response；Filtrate is that stannous sulfate and nickel sulfate are mixed Unsaturated solution is closed, is stored for future use；

5) nickel pink salt coloring liquid, is prepared.

The stannous sulfate and nickel sulfate mixing unsaturated solution for taking (10) formula to produce, the 13# nickel pink salt provided by (1) formula Colour slot Con trolling index, remodeling method are as follows:

Concentration of nickel sulfate/stannous sulfate concentration=25/10 (g/L) (11)

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

Titrated sulfuric acid nickel and stannous sulfate concentration, stannous sulfate concentration are 177g/L or so, concentration of nickel sulfate 577g/L Left and right, is below saturation point, avoids crystallization and is precipitated；Corresponding medicament is added by (11) formula, dosage component is adjusted, is configured to nickel Pink salt coloring liquid, reuse to 13# nickel pink salt colour slot；

6) filtrate, is handled, nickel phosphate is recycled, recycles coloring sealing of hole water for cleaning.By (9) formula, nickel hydroxide dissolution 130mg/L is spent, the discharge standard much higher than 0.5mg/L needs secondary treatment, up to standard can recycle.(9) filtrate of formula Liquid containing ammonium sulfate, ammonium tartrate, ammonium acetate, triethanolamine and isobutanol, while 130mg/L containing nickel hydroxide need to be reduced to 0.5mg/L or less；It is 85wt.% phosphoric acid that concentration is added in filtrate, and pH value 8.5-9.0 is adjusted to 6.5-7.5, reaction are as follows:

3Ni²⁺+2H₃PO₄=(Ni)₃(PO₄)₂↓+6H²⁺ (12)

The solubility of nickel phosphate be 5 multiplied by 10 minus 31 power, filtrate much reaches recycling using standard；It filters again Nickel phosphate, rinsing, drying, obtains nickel phosphate product, it is spare that filtrate is stored in compound fertilizer's recycling can；Filtrate is liquid containing ammonium sulfate, winestone The N-P compound fertilizer of sour ammonium, ammonium acetate, triethanolamine and isobutanol afforests Fertilizer application as plant area, realizes that coloring is returned with water It receives and utilizes.

Three, the experimental result of nickel pink salt coloring sealing of hole recycling colorant

This serial experiment colours Con trolling index by the nickel pink salt that (1) formula provides, and investigates the nickel tin by the production of (11) formula respectively The colorability of salt colorant.

1, influence of the stannous sulfate concentration (being colorant concentration by (11) formula, reality) to colorability.

Take 25 DEG C of pH1.0, temperature, stannous sulfate 4,6,8,10,12,14g/L；Oxide thickness is 15 microns, when coloring Between be 4 minutes, observe aluminium appearance color, the results are shown in Table 1:

Influence of the 1 stannous sulfate concentration of table to colorability

2, influence of the coloration time to coloring color.

By (11) formula, take stannous sulfate 10g/L (nickel sulfate is 25g/L, tartaric acid 8g/L at this time), 25 DEG C of temperature, pH1.0；Taking oxide thickness is 15 microns, and coloration time 6,8,10,12,14,16 minutes, the results are shown in Table 2:

Influence of the different coloration times of table 2 to color

Four, the analysis of experimental results of nickel pink salt coloring sealing of hole recycling colorant and Waste water utilization

By formula (1)-(12) and experiment 1-2 and testing result, following analysis can be done:

1, the standard provided by formula (6) formula can retain nickel pink salt coloring sealing of hole water for cleaning online；Adjust the water inlet of 18# slot Flow controls nickeliferous tin waste water total amount to be processed；Nickeliferous tin waste water is collected into coloring sealing of hole nickel tin waste water in 14# slot water outlet Collecting tank；

By (9) formula, adds liquefied ammonia and the nickeliferous tin waste water of collection is individually handled online at pH value 8.5-9.0, recycle Stannic hydroxide, stannous hydroxide and nickel hydroxide solid mixture, the chemical industry for converting high value for nickeliferous tin solid dangerous waste are former Material realizes the resource utilization of solid dangerous waste；

By (10) formula, sulfuric acid is added, recycling stannic hydroxide, stannous hydroxide and nickel hydroxide solid mixture are converted For stannous sulfate and nickel sulfate mixing unsaturated solution, under conditions of glass putty and excess sulfuric acid, reaction end is pH value 0.8- 1.0, meet subsequent transformation into the requirement of nickel pink salt colorant；

2, (11) formula is pressed, stannous sulfate and nickel sulfate mixing unsaturated solution are converted to liquid nickel pink salt colorant, directly It connects and is added to 13# nickel pink salt coloring slot；Substantially save the cost of manufacture of colorant；

3, serial experiment result 1-2 is pressed it is found that pressing the nickel of (11) formula production within the scope of the Con trolling index as defined in (1) formula Pink salt colorant is fully able to meet coloring requirement；

4, (12) formula is pressed, the filtrate after stannic hydroxide, stannous hydroxide and nickel hydroxide solid mixture separation of solid and liquid In, phosphoric acid is added, remnants Ni is converted²⁺For nickel phosphate, remaining phosphoric acid nickel concentration be 5 multiplied by 10 minus 31 power, filtrate much reaches Standard is used to recycling；Nickel phosphate is filtered again, and rinsing, drying obtain nickel phosphate product, filtrate is stored in compound fertilizer's recycling can It is spare；Filtrate is the N-P compound fertilizer of liquid containing ammonium sulfate, ammonium tartrate, ammonium acetate, triethanolamine and isobutanol, is afforested as plant area Fertilizer application realizes that nickel pink salt coloring sealing of hole is recycled with water；Fertilizer filter residue is nickel phosphate, is resided in reaction vessel, etc. To recycle next time.

Embodiment

Nickel pink salt colours sealing of hole recycling colorant and Waste water utilization method and Configuration Online, is related to the generation of aluminium processing industry The toxic waste residue of nickeliferous tin that the big source of toxic waste residue one, i.e. heat-tinting sealing of hole generate.The present invention utilizes online classification recycling side Coloring sealing of hole water for cleaning is collected in method, retention, and recycling is converted to coloring medicament, and water in recycling blocks nickeliferous tin waste water pair The pollution at wastewater treatment center reduces industrial dangerous waste discharge.

The whole nation produces 20000000 tons of extruded aluminum per year, and heat-tinting sealing of hole material accounts for 8,000,000 tons or more, colours sealing of hole consumptive use 48,000,000 tons of water, 13.5 ten thousand tons of nickeliferous tin waste residue is generated, waste water and dregs problem is very prominent！The present invention provides a kind of completely new Technological design, online classification collects nickel-containing waste water, recycles nickel hydroxide and 13.5 ten thousand tons of stannous hydroxide, be converted to nickel tin Salt colorant；48,000,000 tons of water during treated is recycled, liquid N-P compound fertilizer is converted to, realizes the money of toxic waste Source recycles.

Embodiment 1

Nickel pink salt colours sealing of hole recycling colorant and Waste water utilization method, comprising: the water-saving operation of differential concatenation, nickel tin are useless Water retains operation, nickel tin wastewater treatment operations, nickel phosphate reclaimer operation and N-P compound fertilizer reclaimer operation；

(1) the water-saving operation of the differential concatenation includes: to open valve 14, logical from tap water water inlet to 18# flowing rinsing bowl Enter tap water, enter 17# through valve 15 and flow rinsing bowl, enter 15# through valve 16 and flow rinsing bowl, enters 14# circulating water through valve 17 Washing trough, through valve 1 and pump 1, into coloring sealing of hole nickel tin wastewater collection tank；The water-saving operation of differential concatenation is responsible for collecting seals into coloring Hole nickel tin wastewater collection tank；Nickeliferous tin wastewater collection amount is greatly decreased, reduces online equipment investment, reduces treating capacity and processing Cost；

(2) the nickel tin waste water retention operation includes: to colour aluminium using coloring liquid in 13# nickel pink salt coloring slot 30s-15min rises and hangs drip at least 30s；Aluminium after coloring is entered into 14# flowing rinsing bowl cleaning at least 1min, rises and hangs drop It is flow to few 30s, and cleans at least 1min after going to 15# flowing rinsing bowl, rises and hangs drip at least 30s, wherein aluminium is in 13# nickel Pink salt coloring slot coloring after can by nickel sulfate, stannous sulfate and the tartaric acid in coloring liquid bring into 14# flow rinsing bowl and 15# flows rinsing bowl, the nickel tin waste water after forming coloring；Aluminium is gone in 16# medium temperature sealing of hole slot, using pore-sealing liquid to aluminium Material carries out sealing pores 10-25min, rises after hanging drip at least 30s, sequentially enters 17# flowing rinsing bowl and 18# flowing washing Slot, each slot, which is respectively washed at least 1min and rises, hangs a drip at least 30s, wherein aluminium in 16# medium temperature sealing of hole slot when sealing of hole, The nickel acetate, triethanolamine and isobutanol of pore-sealing liquid can be brought into 17# flowing rinsing bowl and 18# flowing rinsing bowl, form envelope Nickel tin waste water behind hole；The 17# nickel tin waste water flowed in rinsing bowl and 18# flowing rinsing bowl after sealing of hole is reversely flowed into 15# stream Dynamic rinsing bowl and 14# flow rinsing bowl, form the nickel tin waste water of mixing, and adjustment 18# flowing rinsing bowl is passed through originally water management 14# flows pH > 3.0 of rinsing bowl and pH > 5.5 of 15# flowing rinsing bowl, fixed valve 14；

(3) the nickel tin wastewater treatment operations include: to open valve 1, open pump 1, and the slot bottom of 14# flowing rinsing bowl is gone out It is spare that the nickel tin waste water of mouth of a river discharge is pumped into coloring sealing of hole nickel tin wastewater collection tank；Valve 2 and valve 3 are opened, valve 4 is closed, opens pump 2, nickel tin solid recycling can is pumped into using nickel tin waste water as reaction solution；Valve 4 and valve 6 are opened, pump 3 and 1# electricity stirring, circulation are opened Reaction solution；Valve 5 is slowly opened, the liquefied ammonia suction pump 3 of ammonia tank is sufficiently mixed reaction solution using the high speed rotation of pump 3；Side Liquefied ammonia is added, frontier inspection surveys the pH value of reaction solution, when pH value reaches 8.5-9.0, closes valve 5, stops that liquefied ammonia is added, continues to follow Ring stirs 1 hour；1# filter press is opened, valve 7 is opened, closes valve 6 and valve 8, is separated by solid-liquid separation nickel tin solid and first-time filtrate；Instead Multiple spray, rinsing nickel tin solid after ten minutes, recycle nickel tin solid, and first-time filtrate flows into nickel phosphate recycling can；

(4) the nickel phosphate reclaimer operation includes: to close valve 9 and valve 11, opens valve 8 and valve 10, opens pump 4 and 2# electricity Stirring, circular response liquid；Valve 9 is slowly opened, the phosphoric acid suction pump 4 of phosphoric acid tank is sufficiently mixed using the high speed rotation of pump 4 Reaction solution；Phosphoric acid is added on side, and frontier inspection surveys the pH value of reaction solution, when pH value reaches 6.5-7.5, closes valve 9, stops dosing, Continue cycling through stirring 1 hour；2# filter press is opened, valve 11 is opened, closes valve 10, is separated by solid-liquid separation nickel phosphate and secondary filtrate；Instead Multiple spray, rinsing nickel phosphate solid after ten minutes, recycle nickel phosphate product, and secondary filtrate flows into compound fertilizer's recycling can；

(5) N-P compound fertilizer reclaimer operation includes: to open valve 12 and valve 13, pump 5 is opened, by secondary filtrate through filtering After device filtering, it is delivered to land use for greening, is used as nitrogenous and phosphorus N-P compound fertilizer, the filter residue of filter is nickel phosphate, is stayed It is stored in nickel phosphate recycling can, waiting is recycled next time.

It further explains, the present invention utilizes online classification recovery method, and by the system configuration of the design, retention is received Collection coloring sealing of hole water for cleaning, recycles nickel tin solid mixture, is converted to nickel pink salt colorant；It recycles during treated Water, and it is converted to N-P compound liquid fertilizer, pollution of the nickeliferous tin waste water to wastewater treatment center is blocked, industrial dangerous waste row is reduced It puts, realizes that the resource recycling of toxic waste utilizes.

It further explains, which is characterized in that 13# nickel pink salt colours in slot, and the concentration control of stannous sulfate is 6-12g/ L, the concentration control of nickel sulfate are 20-30g/L, and the concentration control of sulfuric acid is 15-20g/L, and the concentration control of tartaric acid is 8- 10g/L, pH control are 0.8-1.0, and temperature control is 20-25 DEG C, and the control of processing time is 30s-15min, and voltage control is 14-16V；

In 16# medium temperature sealing of hole slot, the concentration control of nickel acetate is 4-6g/L, and the concentration control of triethanolamine is 0.4- 0.6g/L, the concentration control of isobutanol are 0.4-0.6g/L, and pH control is 5.5-6.5, and temperature control is 50-60 DEG C, time control It is made as 10-25min.

It further explains, by 14# flowing rinsing bowl, the pH value Con trolling index of 15# flowing rinsing bowl setting, adjusts 18# Rinsing bowl water inlet flow is flowed, coloring sealing of hole cleaning water consumption is reduced；The nickeliferous tin waste water for retaining 14# flowing rinsing bowl, from 14# flowing rinsing bowl slot bottom water outlet is collected into coloring sealing of hole nickel tin wastewater collection tank, these nickeliferous tin online, are individually handled Waste water avoids after being mixed with other processes with water, reprocesses the trouble of the nickeliferous tin waste water of magnanimity, and the nickeliferous tin of processing is greatly reduced The environmentally friendly cost of waste water and dregs；

It further explains, in the nickel tin wastewater treatment operations, nickel tin solid bag contains stannic hydroxide, stannous hydroxide With nickel hydroxide solid, into the nickel tin solid of recycling, addition pure water, glass putty and sulfuric acid are converted to stannous sulfate and sulfuric acid Nickel；Sulfuric acid addition is appropriate excessive, and reaction end is that pH reaches=0.8-1.0；In (pure water weight/solid mixture weight)=3 With glass putty it is appropriate it is excessive under the conditions of, the content of reaction solution is far below the saturated concentration of stannous sulfate and nickel sulfate, it is ensured that reaction Liquid is precipitated without stannous sulfate and nickel sulfate crystallization；Precipitating and filtering reacting liquid obtain the insatiable hunger of stannous sulfate and nickel sulfate mixing With solution and filter residue；Unsaturated solution pH value=the 0.8-1.0, content lower than saturation point and can make the coloring of liquid nickel pink salt Agent；Filter residue is glass putty, is resided in reactor, and next secondary response is waited.

It further explains, in the nickel tin wastewater treatment operations, configures liquid nickel using stannous sulfate and nickel sulfate Pink salt colorant, first titrated sulfuric acid stannous and nickel sulfate mixing unsaturated solution content, then by (concentration of nickel sulfate/sulfuric acid is sub- Tin is dense)=2.5 and (concentration of nickel sulfate/tartaric acid concentration)=25/8, dosages distribution is adjusted, stannous sulfate and nickel sulfate are mixed It closes unsaturated solution and is converted to liquid nickel pink salt colorant, be added directly into 13# nickel pink salt coloring slot.

It further explains, titrated sulfuric acid nickel and stannous sulfate concentration, stannous sulfate concentration is 177g/L or so, sulfuric acid Nickel concentration is 577g/L or so, is below saturation point, avoids crystallization and is precipitated；It is dense by concentration of nickel sulfate/stannous sulfate)=2.5 Corresponding medicament is added in (concentration of nickel sulfate/tartaric acid concentration)=25/8, adjusts dosage component, is configured to nickel pink salt coloring liquid, Reuse to 13# nickel pink salt colours slot, meets alloy colouring quality requirement.

It further explains, when the nickel tin solid of recycling is converted to stannous sulfate and nickel sulfate mixed liquor, the nickel tin of recycling After solid rinse plus glass putty and pure water, directly and sulfuric acid reaction.

Further explain, solid mixture only rinse, do not dry, add glass putty and pure water after, directly and sulfuric acid reaction, The drying cost substantially saved.

It further explains, it is not dense after being prepared into liquid nickel pink salt colorant using stannous sulfate and nickel sulfate mixed liquor Sheepshank is brilliant and is directly used in the fluting of 13# nickel pink salt coloring slot and addition.

It further explains, it is not dense after being transformed into liquid nickel pink salt colorant using stannous sulfate and nickel sulfate mixed liquor Sheepshank is brilliant, is directly used in fluting and the addition of 13# nickel pink salt coloring slot, substantially saves the crystallization of colorant, separate, be dried into This；

Nickel pink salt colours the Configuration Online of sealing of hole recycling colorant and Waste water utilization method, comprising: nickel tin waste water generates system System, nickel tin wastewater collection system, nickel tin separation system, nickel phosphate recovery system and N-P compound fertilizer recovery system；

The useless water generation system of the nickel tin is used to handle cleaning and sealing pores after aluminium coloring, coloring, generates and colours Afterwards with the nickel tin waste water after sealing of hole, and the nickel tin waste water of generation is sent to the nickel tin wastewater collection system；

The nickel tin wastewater collection system is used to collect the nickel tin and gives up the nickel tin waste water of water generation system, and by nickel tin Waste water is sent to nickel tin separation system；

The nickel tin separation system is used to handle the nickel tin waste water of the nickel tin wastewater collection system, and liquefied ammonia reaction is added Generate nickel tin solid mixture；The nickel tin separation system is equipped with No.1 separation equipment, and the No.1 separation equipment is for handling After nickel tin solid mixture, nickel tin solid and first-time filtrate are isolated；The nickel tin separation system be also used to isolate one Secondary filtrate is sent to the nickel phosphate recovery system；

The nickel phosphate recovery system handles the first-time filtrate of the nickel tin separation system, and phosphatase reaction is added and generates phosphorus Sour nickel mixture；The nickel phosphate recovery system is additionally provided with No. two separation equipments, and No. two separation equipments are for handling phosphoric acid After nickel mixture, nickel phosphate solid and secondary filtrate are isolated；The nickel phosphate recovery system is also used to secondary by what is isolated Filtrate is sent to N-P compound fertilizer recovery system；

The secondary filtrate being collected into is filtered behaviour for collecting secondary filtrate by N-P compound fertilizer recovery system After work, collect into greening fertilizer, the greening fertilizer of collection can reach the greenery patches for needing to cultivate, provide nutrition for the vegetation at this.

It further explains, the useless water generation system of the nickel tin includes: 13# nickel pink salt coloring slot, No.1 flowing washing Slot, 16# medium temperature sealing of hole slot, No. two flowing rinsing bowls and tap water water inlet；The 13# nickel pink salt colours slot, No.1 circulating water Washing trough, 16# medium temperature sealing of hole slot, No. two flowing rinsing bowls and tap water water inlet is adjacent is sequentially connected；

No. two flowings rinsing bowl is also attached to the No.1 flowing rinsing bowl, which is equipped with valve 16；

The No.1 flowing rinsing bowl is connected to the nickel tin wastewater collection system, and the connecting line is equipped with pump 1；Institute 13# nickel pink salt coloring slot is stated to be used to colour for aluminium；The No.1 flowing rinsing bowl is used to clean the aluminium after coloring, obtains Nickel tin waste water after coloring；The 16# medium temperature sealing of hole slot is used to be aluminium sealing pores；No. two flowings rinsing bowl is used for Aluminium after cleaning sealing of hole, the nickel tin waste liquid after obtaining sealing of hole；The pump 1 is for flowing described No. two the sealing of hole of rinsing bowl Waste liquid, which is pumped through valve 16 to the No.1, flows rinsing bowl, and flows in rinsing bowl with the No.1 and pump together with nickel tin waste water to institute State nickel tin wastewater collection system.

It further explains, the No.1 flowing rinsing bowl includes: 14# flowing rinsing bowl and 15# flowing rinsing bowl；Institute Stating No. two flowing rinsing bowls includes: 17# flowing rinsing bowl and 18# flowing rinsing bowl；

The 13# nickel pink salt coloring slot, 14# flowing rinsing bowl, 15# flowing rinsing bowl, 16# medium temperature sealing of hole slot, 17# stream Dynamic rinsing bowl, 18# flowing rinsing bowl and tap water water inlet is adjacent is sequentially connected；The 17# flowing rinsing bowl and the 15# Rinsing bowl connection is flowed, and is equipped with the valve 16；17# flowing rinsing bowl described in 18# flowing rinsing bowl be equipped with single-pass to Valve 15；14# flowing rinsing bowl described in 15# flowing rinsing bowl be equipped with single-pass to valve 17；The 14# flowing rinsing bowl connects It is connected to the pump 1.

It further explains, the nickel tin wastewater collection system includes: coloring sealing of hole nickel tin wastewater collection tank and pump 2；Institute Pump 1, coloring sealing of hole nickel tin wastewater collection tank and pump 2 is stated adjacent to be sequentially connected；

The coloring sealing of hole nickel tin wastewater collection tank is connected to the nickel tin separation system by the pump 2；The pump 2 Nickel tin waste water pump for collecting the coloring sealing of hole nickel tin wastewater collection tank is to the nickel tin solid recycling can；

The nickel tin separation system includes: nickel tin solid recycling can, pump 3, ammonia tank and 1# filter press；The ammonia tank Equipped with liquefied ammonia；

The pump 2 is connected to the nickel tin solid recycling can；The bottom of the nickel tin solid recycling can, the pump 3 and institute State that 1# filter press is adjacent to be sequentially connected；The ammonia tank is equipped with pipeline and is connected to the nickel tin solid recycling can and the pump 3 Connecting line on；The pump 3 is additionally provided with the pipeline being connected at the top of the nickel tin solid recycling can；

The nickel phosphate recovery system includes: nickel phosphate recycling can, pump 4, phosphoric acid tank and 2# filter press；The ammonia tank Equipped with phosphoric acid；

The 1# filter press is connected to the nickel phosphate recycling can；The bottom of the nickel phosphate recycling can, 4 and of the pump The 2# filter press is adjacent to be sequentially connected；The phosphoric acid tank is equipped with the connection for being connected to the nickel phosphate recycling can and the pump 4 On pipeline；The pump 4 is additionally provided with the pipeline being connected at the top of the nickel phosphate recycling can；

The 2# filter press is used to that nickel phosphate solid and secondary filtrate will to be isolated with the first-time filtrate after phosphatase reaction, And secondary filtrate is sent to N-P compound fertilizer recovery system；

N-P compound fertilizer recovery system includes: compound fertilizer's recycling can, filter, pump 5 and greening fertilizer collector；

Fertilizer collector is adjacent is sequentially connected for the 2# filter press, compound fertilizer's recycling can, filter, pump 5 and greening；

Compound fertilizer's recycling can is used to collect the secondary filtrate of the 2# filter press, and secondary filtrate is sent to described Filter；The pump 5 is for collecting the secondary filtrate after the filter process to the greening fertilizer collector；

It is equipped with 1# electricity in the nickel tin solid recycling can to stir, 2# electricity is equipped in the nickel phosphate recycling can and is stirred.

Embodiment 2 (the nickel pink salt coloring liquid ability to work of remanufacture detects)

By Fig. 3, continuous production colours aluminium, and 13# nickel pink salt coloring slot constantly adds the present invention by (1) formula Con trolling index Recycle the coloring liquid of production；25 DEG C of coloring liquid pH=1.0, temperature are taken, (other compositions press (12) formula to stannous sulfate 5-10g/L It calculates)；Taking oxide thickness is 15 microns, and coloration time is 10 minutes, as a result as shown in table 3 below:

Coloration effects of the stannous sulfate of 3 various concentration of table to aluminium

The technical principle of the invention is described above in combination with a specific embodiment.These descriptions are intended merely to explain the present invention Principle, and shall not be construed in any way as a limitation of the scope of protection of the invention.Based on the explanation herein, this field Technical staff can associate with other specific embodiments of the invention without creative labor, these modes are all It will fall under the scope of the present invention.

Claims (10)

1. nickel pink salt colours sealing of hole recycling colorant and Waste water utilization method characterized by comprising the water-saving behaviour of differential concatenation Make, nickel tin waste water retains operation, nickel tin wastewater treatment operations, nickel phosphate reclaimer operation and N-P compound fertilizer reclaimer operation；

(1) the water-saving operation of the differential concatenation includes: to open valve 14, is passed through certainly from tap water water inlet to 18# flowing rinsing bowl Water enters 17# through valve 15 and flows rinsing bowl, enters 15# through valve 16 and flows rinsing bowl, enters 14# through valve 17 and flows rinsing bowl, Through valve 1 and pump 1, into coloring sealing of hole nickel tin wastewater collection tank；

(2) the nickel tin waste water retention operation includes: that aluminium is coloured 30s- using coloring liquid in 13# nickel pink salt coloring slot 15min rises and hangs drip at least 30s；Aluminium after coloring is entered into 14# flowing rinsing bowl cleaning at least 1min, rises and hangs drip extremely Few 30s, and at least 1min is cleaned after going to 15# flowing rinsing bowl, it rises and hangs drip at least 30s, wherein aluminium is in 13# nickel pink salt Nickel sulfate, stannous sulfate and the tartaric acid in coloring liquid can be brought into after coloring slot coloring and flow rinsing bowl and 15# flowing in 14# Rinsing bowl, the nickel tin waste water after forming coloring；Aluminium is gone in 16# medium temperature sealing of hole slot, aluminium is sealed using pore-sealing liquid Hole handles 10-25min, rises after hanging drip at least 30s, sequentially enters 17# flowing rinsing bowl and 18# flowing rinsing bowl, each slot It is respectively washed at least 1min and rises and hang a drip at least 30s, wherein aluminium, can be by pore-sealing liquid in 16# medium temperature sealing of hole slot when sealing of hole Nickel acetate, triethanolamine and isobutanol bring into 17# flowing rinsing bowl and 18# flowing rinsing bowl in, formed sealing of hole after nickel tin Waste water；By 17# flow the nickel tin waste water in rinsing bowl and 18# flowing rinsing bowl after sealing of hole reversely flow into 15# flowing rinsing bowl and 14# flows rinsing bowl, forms the nickel tin waste water of mixing, and adjustment 18# flowing rinsing bowl is passed through originally water management 14# and flows rinsing bowl PH > 3.0 and 15# flowing rinsing bowl pH > 5.5, fixed valve 14；

(3) the nickel tin wastewater treatment operations include: to open valve 1, open pump 1, and the slot bottom water outlet of 14# flowing rinsing bowl is arranged It is spare that nickel tin waste water out is pumped into coloring sealing of hole nickel tin wastewater collection tank；Valve 2 and valve 3 are opened, valve 4 is closed, pump 2 is opened, by nickel Tin waste water is pumped into nickel tin solid recycling can as reaction solution；Valve 4 and valve 6 are opened, pump 3 and 1# electricity stirring, circular response liquid are opened； Valve 5 is slowly opened, the liquefied ammonia suction pump 3 of ammonia tank is sufficiently mixed reaction solution using the high speed rotation of pump 3；Side annex solution Ammonia, frontier inspection surveys the pH value of reaction solution, when pH value reaches 8.5-9.0, closes valve 5, stops that liquefied ammonia is added, continues cycling through stirring 1 Hour；1# filter press is opened, valve 7 is opened, closes valve 6 and valve 8, is separated by solid-liquid separation nickel tin solid and first-time filtrate；It sprays, float repeatedly It washes nickel tin solid after ten minutes, recycles nickel tin solid, first-time filtrate flows into nickel phosphate recycling can；

(4) the nickel phosphate reclaimer operation includes: to close valve 9 and valve 11, opens valve 8 and valve 10, opens pump 4 and 2# electricity stirring, Circular response liquid；Valve 9 is slowly opened, the phosphoric acid suction pump 4 of phosphoric acid tank is sufficiently mixed reaction using the high speed rotation of pump 4 Liquid；Phosphoric acid is added on side, and frontier inspection surveys the pH value of reaction solution, when pH value reaches 6.5-7.5, closes valve 9, stops dosing, continues Circulation stirring 1 hour；2# filter press is opened, valve 11 is opened, closes valve 10, is separated by solid-liquid separation nickel phosphate and secondary filtrate；It sprays repeatedly Leaching, rinsing nickel phosphate solid after ten minutes, recycle nickel phosphate product, and secondary filtrate flows into compound fertilizer's recycling can；

(5) N-P compound fertilizer reclaimer operation includes: to open valve 12 and valve 13, pump 5 is opened, by secondary filtrate through filter mistake After filter, it is delivered to land use for greening, is used as nitrogenous and phosphorus N-P compound fertilizer, the filter residue of filter is nickel phosphate, resides in phosphorus Sour nickel recycling can, waiting are recycled next time.

2. nickel pink salt coloring sealing of hole recycling colorant and Waste water utilization method according to claim 1, which is characterized in that 13# Nickel pink salt colours in slot, and the concentration control of stannous sulfate is 6-12g/L, and the concentration control of nickel sulfate is 20-30g/L, sulfuric acid Concentration control is 15-20g/L, and the concentration control of tartaric acid is 8-10g/L, and pH control is 0.8-1.0, and temperature control is 20-25 DEG C, the control of processing time is 30s-15min, and voltage control is 14-16V；

In 16# medium temperature sealing of hole slot, the concentration control of nickel acetate is 4-6g/L, and the concentration control of triethanolamine is 0.4-0.6g/L, The concentration control of isobutanol is 0.4-0.6g/L, and pH control is 5.5-6.5, and temperature control is 50-60 DEG C, and time control is 10- 25min。

3. nickel pink salt coloring sealing of hole recycling colorant and Waste water utilization method according to claim 1, which is characterized in that described In nickel tin wastewater treatment operations, nickel tin solid bag contains stannic hydroxide, stannous hydroxide and nickel hydroxide solid, to the nickel tin of recycling In solid, addition pure water, glass putty and sulfuric acid are converted to stannous sulfate and nickel sulfate；Sulfuric acid addition is appropriate excessive, and reaction end is PH reaches=0.8-1.0；Under the conditions of (pure water weight/solid mixture weight)=3 and glass putty are appropriate excessive, precipitating and mistake Reaction solution is filtered, the unsaturated solution and filter residue of stannous sulfate and nickel sulfate mixing are obtained；Unsaturated solution pH value=the 0.8- 1.0, content lower than saturation point and can make liquid nickel pink salt colorant；Filter residue is glass putty, is resided in reactor, is waited next Secondary response.

4. nickel pink salt coloring sealing of hole recycling colorant and Waste water utilization method according to claim 3, which is characterized in that described In nickel tin wastewater treatment operations, liquid nickel pink salt colorant, first titrated sulfuric acid stannous are configured using stannous sulfate and nickel sulfate With nickel sulfate mixing unsaturated solution content, (concentration of nickel sulfate/stannous sulfate is dense)=2.5 and (concentration of nickel sulfate/wine are then pressed Stone acid concentration)=25/8, dosages distribution is adjusted, stannous sulfate and nickel sulfate mixing unsaturated solution are converted to liquid nickel pink salt Colorant is added directly into 13# nickel pink salt coloring slot.

5. nickel pink salt coloring sealing of hole recycling colorant and Waste water utilization method according to claim 4, which is characterized in that recycling Nickel tin solid when being converted to stannous sulfate and nickel sulfate mixed liquor, after the nickel tin solid rinse of recycling plus glass putty and pure water, directly It connects and sulfuric acid reaction.

6. nickel pink salt coloring sealing of hole recycling colorant and Waste water utilization method according to claim 5, which is characterized in that utilize After stannous sulfate and nickel sulfate mixed liquor are prepared into liquid nickel pink salt colorant, without condensing crystallizing and it is directly used in 13# nickel tin Salt colours fluting and the addition of slot.

7. any the nickel pink salt coloring sealing of hole recycling colorant and Waste water utilization method is online according to claim 1~6 Configuration characterized by comprising nickel tin give up water generation system, nickel tin wastewater collection system, nickel tin separation system, nickel phosphate time Receipts system and N-P compound fertilizer recovery system；

The nickel tin give up water generation system be used for handle aluminium coloring, coloring after cleaning and sealing pores, generate coloring after and Nickel tin waste water after sealing of hole, and the nickel tin waste water of generation is sent to the nickel tin wastewater collection system；

The nickel tin wastewater collection system is used to collect the nickel tin waste water of the useless water generation system of the nickel tin, and nickel tin waste water is sent To nickel tin separation system；

The nickel tin separation system is used to handle the nickel tin waste water of the nickel tin wastewater collection system, and liquefied ammonia reaction is added and generates nickel Tin solid mixture；The nickel tin separation system is equipped with No.1 separation equipment, and the No.1 separation equipment is solid for handling nickel tin After body mixture, nickel tin solid and first-time filtrate are isolated；The first-time filtrate that the nickel tin separation system is also used to isolate It send to the nickel phosphate recovery system；

The nickel phosphate recovery system handles the first-time filtrate of the nickel tin separation system, and it is mixed that phosphatase reaction generation nickel phosphate is added Close object；The nickel phosphate recovery system is additionally provided with No. two separation equipments, and No. two separation equipments are for handling nickel phosphate mixing After object, nickel phosphate solid and secondary filtrate are isolated；The secondary filtrate that the nickel phosphate recovery system is also used to isolate is sent To N-P compound fertilizer recovery system；

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

8. nickel pink salt coloring sealing of hole recycling colorant according to claim 7 and Waste water utilization method and Configuration Online, It is characterized in that, the useless water generation system of the nickel tin includes: 13# nickel pink salt coloring slot, No.1 flowing rinsing bowl, 16# medium temperature sealing of hole Slot, No. two flowing rinsing bowls and tap water water inlet；The 13# nickel pink salt coloring slot, No.1 flowing rinsing bowl, 16# medium temperature envelope Hole slot, No. two flowing rinsing bowls and tap water water inlet is adjacent is sequentially connected；

No. two flowings rinsing bowl is also attached to the No.1 flowing rinsing bowl, which is equipped with valve 16；

The No.1 flowing rinsing bowl is connected to the nickel tin wastewater collection system, and the connecting line is equipped with pump 1；The 13# Nickel pink salt colours slot and is used to colour for aluminium；The No.1 flowing rinsing bowl is used to clean the aluminium after coloring, after being coloured Nickel tin waste water；The 16# medium temperature sealing of hole slot is used to be aluminium sealing pores；No. two flowing rinsing bowls are for cleaning sealing of hole Aluminium afterwards, the nickel tin waste liquid after obtaining sealing of hole；The pump 1 is for flowing described No. two the sealing of hole waste liquid of rinsing bowl through valve 16 Pump to the No.1 flows rinsing bowl, and pumps together with nickel tin waste water in No.1 flowing rinsing bowl to the nickel tin waste water and receive Collecting system.

9. nickel pink salt coloring sealing of hole recycling colorant according to claim 8 and Waste water utilization method and Configuration Online, It is characterized in that, the No.1 flowing rinsing bowl includes: 14# flowing rinsing bowl and 15# flowing rinsing bowl；No. two flowings washing Slot includes: 17# flowing rinsing bowl and 18# flowing rinsing bowl；

The 13# nickel pink salt coloring slot, 14# flowing rinsing bowl, 15# flowing rinsing bowl, 16# medium temperature sealing of hole slot, 17# flowing washing Slot, 18# flowing rinsing bowl and tap water water inlet is adjacent is sequentially connected；The 17# flowing rinsing bowl and 15# flowing washing Slot connection, and it is equipped with the valve 16；17# flowing rinsing bowl described in 18# flowing rinsing bowl be equipped with single-pass to valve 15；It is described 15# flow rinsing bowl described in 14# flowing rinsing bowl be equipped with single-pass to valve 17；The 14# flowing rinsing bowl is connected to the pump 1。

10. nickel pink salt coloring sealing of hole recycling colorant according to claim 9 and Waste water utilization method and Configuration Online, It is characterized in that, the nickel tin wastewater collection system includes: coloring sealing of hole nickel tin wastewater collection tank and pump 2；The pump 1, coloring envelope Hole nickel tin wastewater collection tank is adjacent with pump 2 to be sequentially connected；

The coloring sealing of hole nickel tin wastewater collection tank is connected to the nickel tin separation system by the pump 2；The pump 2 is used for will The nickel tin waste water pump that the coloring sealing of hole nickel tin wastewater collection tank is collected is to the nickel tin solid recycling can；

The nickel tin separation system includes: nickel tin solid recycling can, pump 3, ammonia tank and 1# filter press；The ammonia tank is equipped with liquid Ammonia；

The pump 2 is connected to the nickel tin solid recycling can；The bottom of the nickel tin solid recycling can, the 3 and 1# of the pump Filter press is adjacent to be sequentially connected；The ammonia tank is equipped with pipeline and is connected to the company of the nickel tin solid recycling can and the pump 3 Adapter tube road；The pump 3 is additionally provided with the pipeline being connected at the top of the nickel tin solid recycling can；

The nickel phosphate recovery system includes: nickel phosphate recycling can, pump 4, phosphoric acid tank and 2# filter press；The ammonia tank is equipped with phosphorus Acid；

The 1# filter press is connected to the nickel phosphate recycling can；The bottom of the nickel phosphate recycling can, the 4 and 2# of the pump Filter press is adjacent to be sequentially connected；The phosphoric acid tank is equipped on the connecting line for being connected to the nickel phosphate recycling can and the pump 4； The pump 4 is additionally provided with the pipeline being connected at the top of the nickel phosphate recycling can；

The 2# filter press is used to that nickel phosphate solid and secondary filtrate will to be isolated with the first-time filtrate after phosphatase reaction, and by two Secondary filtrate is sent to N-P compound fertilizer recovery system；

N-P compound fertilizer recovery system includes: compound fertilizer's recycling can, filter, pump 5 and greening fertilizer collector；

Fertilizer collector is adjacent is sequentially connected for the 2# filter press, compound fertilizer's recycling can, filter, pump 5 and greening；

Compound fertilizer's recycling can is used to collect the secondary filtrate of the 2# filter press, and secondary filtrate is sent to the filtering Device；The pump 5 is for collecting the secondary filtrate after the filter process to the greening fertilizer collector；

It is equipped with 1# electricity in the nickel tin solid recycling can to stir, 2# electricity is equipped in the nickel phosphate recycling can and is stirred.