CN109179736A

CN109179736A - Single nickel salt colours the on-line system and method for sealing of hole recycling hole sealing agent and Waste water utilization

Info

Publication number: CN109179736A
Application number: CN201810843439.9A
Authority: CN
Inventors: 熊映明
Original assignee: FOSHAN SANSHUI XIONGYING INNOVATIVE CENTER FOR ALUMINUM SURFACE TECHNOLOGIES Co Ltd
Current assignee: FOSHAN SANSHUI XIONGYING INNOVATIVE CENTER FOR ALUMINUM SURFACE TECHNOLOGIES Co Ltd
Priority date: 2018-07-27
Filing date: 2018-07-27
Publication date: 2019-01-11

Abstract

Single nickel salt colours the on-line system and method for sealing of hole recycling hole sealing agent and Waste water utilization, which includes the water-saving subsystem of flowing pure water cleaning differential concatenation, nickel-containing waste water retention unit, nickel-containing waste water collector unit, nickel hydroxide recovery unit, nickel phosphate recovery unit and N-P compound fertilizer recovery unit；The flowing pure water cleaning water-saving subsystem of differential concatenation includes several flowing pure water rinse baths of sequence differential concatenation setting；Nickel-containing waste water retention unit includes 13# single nickel salt coloring slot and 16# medium temperature sealing of hole slot；Nickel hydroxide recovery unit includes pump 2, pump 3, nickel hydroxide recycling can, ammonia tank and 1# filter press；Nickel phosphate recovery unit includes nickel phosphate recycling can, pump 4, phosphoric acid tank and 2# filter press；Invention designs completely new on-line system configuration, and the nickel-containing waste water waste residue of synchronous recycling heat-tinting sealing of hole is converted to sealing of hole medicament, and water in recycling is converted to N-P compound liquid fertilizer, realizes that the resource recycling of toxic waste utilizes.

Description

Single nickel salt colours the on-line system and method for sealing of hole recycling hole sealing agent and Waste water utilization

Technical field

The present invention relates to aluminum processing technology field more particularly to single nickel salt coloring sealing of hole recycling hole sealing agents and Waste water utilization On-line system and method.

Background technique

One, Aluminum waste residue source

1, electrolysis founding aluminium ash

Aluminium ash results from the electrolysis, melting and casting process of aluminium and aluminium alloy, because aluminium ash caused by aluminium total losses amount in 1- 12%.One ton of primary aluminum of every processing, about generation 20-40kg aluminium ash, yield is less when molten aluminum direct founding, and when aluminium ingot remelting measures It is more, and regenerate one ton of aluminium scrap and about generate 100-250kg aluminium ash.Aluminium ash can be divided into two kinds: one is secondary aluminium ashes, are in electricity Solution primary aluminum and casting etc. do not add the dross generated during salt flux and skimming, and main component is metallic aluminium and aluminum oxide, For aluminium content up to 15%-70% etc., color is white；Another kind is Quadratic aluminum dust, and it is useless after alum recovery to be that a secondary aluminium ash mentions Gurry, aluminium content are low compared with a secondary aluminium ash, generally in grey black.Quadratic aluminum dust complicated component contains metallic aluminium (5-30%), oxygen Change the chloride (10-30%) and nitrogen fluorine of aluminium (30-70%), silica and di-iron trioxide (5-15%), potassium sodium calcium and magnesium The poisonous and harmful elements such as arsenic.Lower Fig. 1 is aluminium ash composition examining report.Alleged aluminium ash refers both to Quadratic aluminum dust below.2016 32,500,000 tons of national electrolytic aluminium yield, squeezes and calendering processing aluminum materials yield is more than 20,000,000 tons, and the aluminium ash quantity in the annual whole nation is protected Estimation is kept at 2,000,000 tons or more, more there are data to think aluminium ash total amount at ten thousand tons of 600-850.Aluminium ash is a kind of reproducible money Source, comprehensive reutilization value with higher, but enough attention are not obtained always, cause the huge wasting of resources.Together When because containing the poisonous and harmful substances such as fluoride, ammonia nitrogen, arsenic in aluminium lime-ash, danger wastes are listed in, in version " state in 2016 Family Hazardous Waste List " in aluminium ash waste classification be HW48, hazard property T (Toxicity)-toxicity risk waste.With Expanding economy, aluminium scrap ash amount of savings will increase considerably year by year, if not finding economical and effective, innoxious method is subject to Processing, seriously threatens environment for it is increasingly highlighted.

The recycling of China's aluminium ash at present still in its infancy, lacks that technology maturation is reliable, recycling side of good economy performance Method, aluminium ash handle the low rate of recovery, energy consumption and waste greatly, and utilization ways are few.Even if treated, aluminium ash is interior still containing big Measure harmful substance, still can only stockyard stockpiling or burial processing, have great environmental hazard, while producer carry it is huge Big illegal risk.

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, as shown in Figure 2.In the waste liquid exhausted Containing a large amount of aluminium ion and sodium hydroxide, potential economic value is very big.The processing for stewing mould waste liquid is generally taken " with useless Control useless " mode, direct emission is into waste water center, the spent acid neutralisation treatment that generates with oxidation operation.This processing mode generates Waste residue amount it is very big, stew mould waste residue can account for 28% or so of the total quantity of slag of enterprise；Meanwhile a large amount of sodium ions enter waste water Center, water in pollution, a possibility that thoroughly breaking off Treated sewage reusing.This coarse processing mode of mould liquid is stewed, enterprise does not have not only Using its economic value, increase cost instead, 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, electrophoretic coating, powder spray, F-C paint spraying etc..Surface treatment process generates the waste water of a large amount of complicated components.

Divide by technique, the waste water and dregs that anode oxidation process (Fig. 3) generates have: the alkaline waste water that Alkaline etchant generates is useless Slag accounts for the 18% of total quantity of slag；The acid waste water waste residue that oxidation solution generates, accounts for the 27% of total quantity of slag, and coloring is generated with pore-sealing liquid Nickel-contained waste slag accounts for total quantity of slag 9%；The acid waste water waste residue that spraying process (Fig. 4) generates, accounts for the 18% of total quantity of slag.Aluminium processing enterprise Industry waste water center aluminium slag source subdivision are as follows: stew mould liquid (Fig. 2) alkaline residue and account for the 28% of total quantity of slag, Alkaline etchant alkaline residue accounts for total quantity of slag 18%, oxidation solution acid sludge accounts for the 27% 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 total slag The 18% of amount, waste residue source is as shown in Figure 5.In addition, Some Enterprises production polishing aluminium, generates a large amount of polishing slag, such as schemes Shown in 6.

The waste water of waste water central collection, contains Al³⁺、Na⁺、NH₄ ⁺、Ni²⁺、Sn²⁺、Cr⁶⁺Equal cations, SO₄ ^2-、F^-、NO₃ ^-、 NO₂ ^-、S^2-、Cl^-, tartrate anion, glucose acid group, anion and the organic phenol, surfactant and acrylic acid such as acetate Organic matters such as resin etc..Acid waste water, alkaline waste water are usually to mix neutralisation treatment, and chromate waste water, nickel-containing waste water must be single It stays alone reason.Oxidation electrophoresis material ratio decline in recent years, but most of aluminum material factories or acid waste water are more than alkaline waste water, soda acid Water all mixes processing, in acidity after waste water mixing, needs 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 cause the huge wasting of resources.It is useless Slag belongs to hazardous waste, has containing aluminium hydroxide, fluoride, sulfide, nickel salt, phenol, nitrate, nitrite etc. are a variety of Malicious harmful substance, environmental hazard is huge, can not fill, and has great environmental hazard.Waste water center processing is separated by solid-liquid separation Afterwards, 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 follow to energy-saving and emission-reduction and resource Ring utilization orientation Transformation Development, but lack the technology of mature and reliable.Water fully recovering, zero output of waste residue, resource benefit in realization With value maximization, there is 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 ".

Two, Aluminum Solid state fermentation and utilize status

1, electrolysis founding aluminium ash handles and utilizes status

The method for developing many aluminium ash recycling and resource utilization in succession both at home and abroad, recycles benefit about aluminium ash in recent years Patent is also in rising trend, but most of in the experimental study stage, and technology is confined to hot conditions and extracts metallic aluminium, The inorganic material and steelmaking ingredient etc. such as aluminium oxide, aluminium chloride, aluminum sulfate are prepared, there are also certain from industrialization, scale Distance.

1.1, aluminium ash recycles

The method of recycling aluminium ash can be divided into heat treating process and cold-treating process at present, all only recycle the metal in aluminium ash Aluminium.Domestic large-scale regeneration aluminium manufacturer mostly uses rotary kiln facture of fascinating, aluminium ash and additive salt (usually sodium chloride, chlorine Change the mixture of potassium and a small amount of calcirm-fluoride) be placed on heated in the rotary kiln that fascinates after separate metallic aluminium, but removal process has flue gas It generates, metal recovery rate is lower, and content of residual aluminum is higher in aluminium ash, still there is further recycling space.The artificial stir-fry ash of small workshop mode Method is also largely using, this method is open type operation, generates a large amount of dust smog.Other methods also squeeze absorption method, etc. from The instant method of son, electrical concentration, MRM method, ALUREC method etc..

1.2, aluminium ash comprehensively utilizes

Because aluminium ash composition and bauxite are almost the same, the product being able to produce with bauxite, all someone are carried out with aluminium ash Overtesting research.Mainly there are three routes in terms of the resource utilization of current aluminium ash: (1) recycling aluminium oxide and return electrolysis, recycle chlorine Salt is used as founding refining agent, but the main component in aluminium ash is α-Al₂O₃, poor activity, more multipotency need to be consumed by being ionized Amount, causes tank voltage to increase.(2) acid system or alkaline process processing removal of impurities, production synthesis Brown Alundum, Sialon ceramics and refractory material Etc. inorganic material, produce the water-purifying materials such as aluminium polychloride and aluminum sulfate, steel-making slag making desulfurizing agent produced, but because of cost ratio Existing also height, is not able to achieve industrialized production.(3) building materials or road-making material are produced, such as aluminate cement, calcium aluminate powder, clear Water brick and road-making material etc., but the fluoride, the villaumite that contain have an impact to performance, while added value of product is low, limits Practical application.There is the disadvantages of product purity is low, added value is low, waste secondary pollution in the application in terms of three above.Aluminium Waste after ash recycles still contains great amount of soluble salt and fluoride or dangerous waste, can only fill or store up, ring There is no reduce for border harmfulness.

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

In the case where resource scarcity, environmental pollution are got worse, the development of aluminium processing industry faces the huge of resource and environment Pressure, energy-saving and emission-reduction, resource circulation utilization are following developing direction and the only way.Accomplish aluminium ash resource " zero is useless Abandon ", it is necessary to change utilization of resources thinking, make full use of the various composition in aluminium ash, carries out harmless treatment, resource maximizes Change and utilizes.This work is very urgent, needs specific direction, standard guidance, multiparty collaboration, strives that obtaining real-time early dashes forward It is broken.

2, compressive surface processing waste water and dregs handle and utilize status

1. waste water and dregs are recycled, comprehensive utilization includes two aspect contents: first is that Treated sewage reusing；Second is that the money of waste residue Source comprehensive utilization.

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

It squeezes pot mould liquid and contains a large amount of sodium hydroxide and aluminium ion, stewing mould liquid recycling aspect has many research reports Road and patent, such as the Crystalfix chemical recovery system of Italy, but because process is complicated, comprehensive benefit is not high, practical application It is few.The common practice that the processing of aluminium processing enterprise stews mould waste liquid is the spent acid for neutralizing oxidation operation and generating, and generates alkaline residue, only It stews the waste residue that mould liquid generates and just accounts for 28% or so of the total quantity of slag of enterprise.Enterprise is not only without recycling the sodium stewed in mould liquid The useful resources such as ion, aluminium ion, increase cost instead；Water in sodium ion pollution, limits Treated sewage reusing.

The recycling of oxidation pre-treatment Alkaline etchant generally uses crystallization, recycles aluminium hydroxide, reuse sodium hydroxide.But hydrogen Aluminum oxide grain size is compared with thin, economic value is low.In addition, aluminium ion is maintained at low concentration (being less than 30g/L), Yi Zao by crystallization The defects of forming material coarse-grain, coarse sand, excessive erosion, and aluminium consumption is too high.Crystallization is run to equipment and technique is more demanding, management Bad to precipitate fouling, can only stop production manual cleaning at this time, take time and effort.There is a small amount of producer to come into operation online alkali collection dress It sets, because recovering effect is bad, at high cost, has given it up mostly.It is not applicable to joined corrosion inhibiter, the alkaline etching tank liquor of complexing agent Soda recovery unit also limits the application of the technology.

1.2, oxidation solution aluminium ion and retrieval of sulfuric acid

Aluminium ion in aluminium alloy anode oxide liquid directly affects the electric conductivity and film quality of tank liquor, Optimal Control Concentration should be between 3-10Kg/L range.Aluminium ion constantly accumulates raising with the increase of output, and film quality is deteriorated, is electric Consumption increases, but considers reagent cost and environmental protection pressure, and aluminium ion concentration general control is in 15-20g/L in enterprise practical production Section.After reaching the upper limit, it is necessary to reduce aluminium composition.Reducing aluminum ions usual way is to exhaust half tank liquor, supplements sulphur Continue to produce after acid.This method is simple, but has the disadvantage that first is that have lost sulfuric acid, wastes aluminium ion, sulfuric acid consumption reaches To 60kg/t or more；Second is that processing spent acid increases sizable cost；Third is that flood tide waste residue causes environmental hazard.

Retrieval of sulfuric acid machine using diffusion dialysis principle was once the aluminum ions effective means of control being widely used.Sulphur Acid recovery machine is aluminum ions stabilising arrangement, reaches recycling sulfuric acid using diffusion dialysis amberplex, removes aluminum ions mesh 's.In actual operation, there are poor recovery effect, high energy consumption and efficiency is low, the quantity of slag is not reduced the deficiencies of.In view of retrieval of sulfuric acid The using effect of the above-mentioned bad luck of machine, most of aluminium processing enterprise gradually deactivate the device, have restored the oxidation of falling half tank liquor Conventional method.

1.3, spraying pretreated waste water recycling

The market share of powder spray alloy product obviously increases in recent years, has accounted for aluminum alloy surface processing product 60% or more.The pretreated purpose of sprayed surface is to generate one layer of fine and close conversion film in aluminium material surface, by substrate and spraying Layer firm connection is together.For the quality for guaranteeing conversion film, process control needs are very strict, exceeded tank liquor and rinse water It must exhaust.Waste water contains a large amount of Cr VI, fluotitanic acid, fluorine zirconic acid root and fluorine ion in acidity.A large amount of waste acid treatment Not only entreprise cost is increased, but also wastes resource, also there is environmental hazard.Spraying pretreatment and wastewater processing technology are without bright Aobvious progress, still uses conventional methods, neutralizes, precipitates, forming a large amount of waste residues after filter-press dehydration.Waste residue, which belongs to, strictly to be managed Hazardous waste, it is necessary to be transferred to qualified third party and carry out the harmless processing that standardizes.

1.4, contain chromium and nickel-containing waste water

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

The recycling of hexavalent chromium is still a problem, now cannot achieve online recycling medicament containing chromium.Chromate waste water is present Processing method be: be added the reducing agents such as sodium pyrosulfite or sodium hydrogensulfite, by hexavalent chrome reduction at the lower trivalent of toxicity Chromium, then adds alkali, PAM carries out reaction precipitating, obtains chromium slag after dewatering and filtering mud.Exemplary process such as Fig. 7 institute Show.

Nickel ion recycling is only limitted to single nickel salt coloring slot, and the nickel ion in sealing of hole waste water is because of the low direct emission of content.Nickel from Son uses RO recyclable device, and principle is identical as acid recovery, and part of the manufacturer is using, but low efficiency and a large amount of concentrations of generation Water, effect are equally ideal not to the utmost.The processing of nickel-containing waste water uses the precipitation method, and sodium hydroxide and PAM is added, and adjusts pH, reaction life At nickel hydroxide precipitate, nickel slag is obtained after dewatering and filtering mud.Exemplary process such as Fig. 8.

1.5, the recovery processing of polishing fluid

Aluminium alloy polishing is to produce the important means of high-grade aluminium, all kinds of electronic product casings, high-speed rail interior decoration, bathroom Equipment etc. is general to select polishing aluminium.In addition to atmosphere pollution, bigger pollution is the pollution of three sour waters for polishing.One ton of throwing of every production Finish consumes three acid 250-350Kg with subsequent rinse bath and is discharged into waste water center.This extensive production method harm It is huge, first is that having lost three acid, metallic aluminium is wasted, three acid consumption reach 300kg/t or more；Second is that processing spent acid increases Sizable cost；Third is that flood tide waste residue causes environmental hazard.

Being retained polishing fluid using non-mobile water washing trough after polishing, be evaporated reuse once is the section acid hand being widely used Section.But the sour evaporation process of retention three generates a large amount of smog, pollutes environment, processing cost is huge；Three sour evaporation process energy consumptions Huge, cost should not be overlooked；Container for evaporation corrosion is too fast, every two years needs replacing once, investment is too many.Three acid recoverys are practical In operation, there is the deficiencies of pollution is big, high energy consumption and efficiency is low, cost is big.In view of the bad using effect of three acid recoverys, big portion Fen Lv processing enterprise, gradually deactivate three acid recoverys, restored direct emission into waste water center conventional method.

1.6, compressive surface handles waste water and dregs integrated treatment

Many aluminum profile producers have carried out various aspects in terms of water-saving and waste water treatment and have tried to explore and effective practice, take Obtained certain effect.Aluminum current processing industry waste water still generallys use neutralization adjusting and coagulant sedimentation processing, process flow Be: acidic and alkaline waste water neutralizes mutually, adjusts pH to neutrality, cation A l³⁺It is precipitated etc. hydroxide is formed.Neutralized precipitating is given up Water is squeezed into coagulation tank, and flocculant PAC, PAM is added, and precipitation tank, standard emission of clear or reuse, aqueous dirt are entered after flocculation Mud forms Aluminiferous waste slag after filter press filters pressing.Waste residue moisture content 80% or so, quantity is very big, waste water and dregs process flow As shown in Figure 9.

Conventional waste water Solid state fermentation mode has following deficiency: first is that waste residue contains aluminium hydroxide, fluoride, sulfide, nickel A variety of poisonous and harmful substances such as salt, phenol, nitrate, nitrite, environmental hazard is huge, can not fill, it is necessary to give money The specialized company of matter is handled.It is calculated by national annual 1500000 tons of waste residue of generation, by 3000 yuan per ton, Solid state fermentation cost is 45 Hundred million yuan.Second is that middle water contains sodium ion, ammonium ion, sulfate radical, nitrate anion, nitrite anions, acetate, tartrate anion, thio sulphur Acid group, chloride ion, sulphion, fluorine ion etc., can not reuse.By national annual 2.25 hundred million tons of waste water of generation, press 100 yuan per ton It calculates, cost for wastewater treatment is 22,500,000,000 yuan.In addition, waste residue has been included in latest edition " National Hazard waste register ".

2, compressive surface processing waste water and dregs comprehensive utilization

Comprehensive utilization includes two aspect contents: first is that Treated sewage reusing；Second is that the comprehensive utilization of resources to waste residue.Recycling benefit Very undesirable with status, preceding to have addressed, middle salinity water value is much higher than seawater, is unable to reuse；Waste residue ingredient is excessively complicated, comprehensive It closes the approach utilized and method is limited.

2.1, the comprehensive utilization of aluminium slag

Carry out for many years, there is considerable article and patented technology, recycling benefit to the utilization of resources research of Aluminiferous waste slag Technology Ways and aluminium ash are essentially identical, mainly there is following several respects: (1) directly recycling aluminium hydroxide or aluminium oxide；(2) The ceramics such as mullite synthesizing, cordierite, preparing ceramic clinker, artificial resin marble or refractory material；(3) water-purifying material is produced, such as Calcium aluminate, aluminium polychloride (iron), polyaluminium sulfate etc.；(4) chemical products such as aluminium hydroxide, ammonia-alum are produced in reaction, as in State patent CN 1350065A discloses a kind of method using alkaline residue extracting sulfuric acid aluminium ammonium, aluminum sulfate, aluminium hydroxide, and China is specially Sharp CN 101186282B discloses a kind of method that hardening oxidation sulfuric acid tank liquor reduces aluminium ion and produces ammonium alum, Chinese patent CN 1319302C discloses a kind of method using fluorine-containing acid sludge preparing ice spar, this patented technology is in Shuo Jia producer reality Using achieving fabulous economic benefit, while solving the processing problem of acid sludge.

Except the technology for being produced ice crystal using acid sludge is succeeded in addition to, other major part methods do not have scale Using the comprehensive utilization ratio of aluminium slag is very low, and main cause or technology are immature, added value of product is low, higher cost.It is big absolutely Part waste residue is all that aluminum material factory spends landfill disposal of paying, and pile up like a mountain for the waste residue of many aluminum material factories now, at aluminum material factory One hot Chinese yam.

2.2, chromium slag and nickel slag for comprehensive utilize

According to open source information, chromium slag can be used as glass colorant and crystallization promoter, but practical situations are unknown.Not See the open source information for having nickel slag resource utilization.Chromium slag, nickel slag common practice are to go to the third-party institution to carry out innoxious burial Processing.

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

First is that water consume is high, lack mature water-saving technology, Treated sewage reusing rate is low；Second is that online classification waste water fails to become Preposition program leads to the big mixed sludge of yield, increases huge technical difficulty for subsequent processing；Third is that the comprehensive benefit of waste residue Little with effect, Solid state fermentation, which becomes enterprise, can't bear the financial burden born and environmentally friendly risk.

Currently, Solid state fermentation there are problems that three aspect conspicuous contradictions and: first is that country carry out enterprise pollution object discharge permit Card management controls the gross contamination emission of enterprise, and the actual waste water waste residue amount of enterprise is much larger than allowable emission；Second is that Waste residue must legal transfer disposed to qualified third party, but disposing capacity is obviously inadequate, can not the such flood tide of legal processes Waste residue；Process complexity, low efficiency, at high cost third is that press dangerous waste specification handles waste residue, aluminium processing industry will can't bear the heavy load.

In conclusion aluminium processing industry waste water and dregs processing domestic at present is particularly thorny, integrated treatment difficulty is larger, at This height, recovery utilization rate are low, have not only caused a large amount of wastes of resource, but also seriously pollute environment.Therefore it for aluminium processing industry, gives up The research and development of water zero discharge and resource comprehensive utilization technology and popularization and application have bright prospects and huge environmental benefit, Social benefit and economic benefit.

Three, Aluminum aluminium ash and aluminium slag minimizing recycling direction

1, the principle followed: minimizing control, harmless treatment, resource utilization, it is necessary to government driving, enterprise be leading, Third party's marketization configures resource, and the unification of three power could obtain positive progress；

2, source controls, and classifies to each pharmacy slot and retains, online to convert, resource utilization, reduces waste water and dregs discharge Amount；

3, surface treatment reagent combination is improved, nontoxic, less toxic, the easy recycling of use, the chemical constituent substitution of easy-clear are traditional Contain Na⁺、NH₄ ⁺、Ni²⁺、Sn²⁺、Cr⁶⁺、NO₂ ^-、NO₃ ^-、Cl^-、F^-、CH₃COO^-, glucose acid group, tartrate anion, S₂O₃ ^2-Deng Byproduct is done from source, reduces waste water recycling and solid waste is innoxious, technical threshold of resource utilization；

4, reinforce Enterprises Universities Researches Union, expand thinking and the field of waste residue comprehensive utilization, realize that comprehensive utilization value is maximum Change.

Summary of the invention

It is an object of the invention to propose a kind of single nickel salt coloring sealing of hole recycling hole sealing agent and Waste water utilization in linear system System, designs completely new on-line system configuration, the nickel-containing waste water waste residue of effective recycling heat-tinting sealing of hole, and synchronous retention is received Collection coloring sealing of hole water for cleaning, recycling are converted to sealing of hole medicament, and water in recycling is converted to N-P compound liquid fertilizer, real The resource recycling of existing toxic waste utilizes.

It is another object of the present invention to propose a kind of single nickel salt coloring sealing of hole recycling hole sealing agent and Waste water utilization The recovery method of linear system system.

For up to this purpose, the invention adopts the following technical scheme:

Single nickel salt colours the on-line system of sealing of hole recycling hole sealing agent and Waste water utilization, successively includes stream from upstream to downstream Dynamic pure water cleans the water-saving subsystem of differential concatenation, nickel-containing waste water retention unit, nickel-containing waste water collector unit, nickel hydroxide recycling Unit, nickel phosphate recovery unit and N-P compound fertilizer recovery unit；

The flowing pure water cleaning water-saving subsystem of differential concatenation includes the 12# flowing pure water of sequence differential concatenation setting Rinse bath, 11# flowing pure water rinse bath, 18# flowing pure water rinse bath, 17# flowing pure water rinse bath, 15# flowing pure water cleaning Slot and 14# flow pure water rinse bath；The 12# flowing pure water rinse bath is provided with pure water water inlet；

The nickel-containing waste water retention unit includes 13# single nickel salt coloring slot and 16# medium temperature sealing of hole slot；The 13# single nickel salt Slot is coloured to be arranged between the 12# flowing pure water rinse bath and 14# flowing pure water rinse bath；The 16# medium temperature sealing of hole slot setting It is flowed between pure water rinse bath and 17# flowing pure water rinse bath in the 15#；

The nickel-containing waste water collector unit includes coloring sealing of hole nickel-containing waste water collecting tank and pump 1；The coloring sealing of hole is nickeliferous Wastewater collection tank is used to collect the coloring sealing of hole nickel-containing waste water from 14# flowing pure water rinse bath；The pump 1 is used for will Coloring sealing of hole nickel-containing waste water is pumped into the coloring sealing of hole nickel-containing waste water collecting tank；

The nickel hydroxide recovery unit includes pump 2, pump 3, nickel hydroxide recycling can, ammonia tank and 1# filter press；It is described Pump 2 is pumped into nickel hydroxide recycling can for that will colour sealing of hole nickel-containing waste water；The pump 3 is for recycling nickel hydroxide recycling can In coloring sealing of hole nickel-containing waste water, and the primary reaction liquid pump after reaction is entered in 1# filter press；The ammonia tank be used for Liquefied ammonia is added in nickel hydroxide recycling can, is reacted with coloring sealing of hole nickel-containing waste water and obtains primary reaction liquid；The 1# filter press is used The first filtrate of solid-state nickel hydroxide and liquid in separation primary reaction liquid；

The nickel phosphate recovery unit includes nickel phosphate recycling can, pump 4, phosphoric acid tank and 2# filter press；The nickel phosphate returns Closed cans is used for the first filtrate of recovering liquid；The pump 4 is for the first filtrate in recycled phosphoric acid nickel recycling can, and will react Secondary reaction liquid pump afterwards enters in 2# filter press；The phosphoric acid tank is for being added phosphoric acid into nickel phosphate recycling can, with the first filter Liquid reaction obtains secondary reaction liquid；The 2# filter press is used to separate the solid-state nickel phosphate and liquid second in secondary reaction liquid Filtrate；

N-P compound fertilizer recovery unit includes compound fertilizer's recycling can, pump 5 and filter；Compound fertilizer's recycling can is used In recycling the second filtrate；The pump 5 is for being pumped into filter for the second filtrate in compound fertilizer's recycling can；The filter is used Liquid N-P compound fertilizer is obtained in filtering the second filtrate.

The present invention proposes the on-line system of a kind of single nickel salt coloring sealing of hole recycling hole sealing agent and Waste water utilization, provides one The completely new on-line system configuration of kind, recycles the nickel-containing waste water waste residue of heat-tinting sealing of hole, utilizes online classification recycling side Method is configured by above system, and coloring sealing of hole water for cleaning is collected in retention, is recycled and is converted to sealing of hole medicament, in recycling Water is converted to medium temperature hole sealing agent in which it is possible to recycle nickel hydroxide up to 13.5 ten thousand tons；Water 4 during treated is recycled to reach 8000000 tons, it is converted to N-P compound liquid fertilizer, applies fertilizer for plant area's land use for greening, makes the effective recycling of coloring water, Pollution of the nickel-containing waste water to wastewater treatment center is blocked, industrial dangerous waste discharge is reduced, realizes the resource recycling of toxic waste It utilizes.

The water-saving subsystem of differential concatenation is cleaned by the way that the flowing pure water is arranged, realizes and more effectively collects coloring sealing of hole Nickel-containing waste water receipts are greatly decreased according to the structure design characteristic of the flowing pure water cleaning water-saving subsystem of differential concatenation in nickel-containing waste water Collection amount improves the treatment effeciency of nickel-containing waste water, reduces online equipment investment, reduces treating capacity and processing cost.

In addition, the present invention can also individually set the pH value Con trolling index of 15# flowing pure water rinse bath, directly adjustment 12# The flow for flowing pure water rinse bath water inlet valve 14 can effectively reduce coloring sealing of hole cleaning water consumption；By 14#, 15#, 17#, 18# flowing pure water rinse bath synchronize retention coloring sealing of hole nickel-containing waste water, and 14# slot slot bottom water outlet is concentrated to flow into Colour in sealing of hole nickel-containing waste water collecting tank, to realize online, synchronous, independent processing coloring sealing of hole nickel-containing waste water, avoid and its After the mixing of his process water, reprocess the trouble of magnanimity nickel-containing waste water, be greatly reduced the environmental protection of processing nickel-containing waste water waste residue at This.

It further illustrates, in the flowing pure water cleaning water-saving subsystem of differential concatenation, the 12# flowing pure water cleaning The pipeline of the pure water water inlet of slot is equipped with valve 14；The water outlet of the 12# flowing pure water rinse bath flows pure with the 11# The pipeline of the water inlet connection of water rinse bath is equipped with one-way valve 15；The water outlet and 18# of the 11# flowing pure water rinse bath The pipeline for flowing the water inlet connection of pure water rinse bath is equipped with valve 16；The water outlet of 18# flowing pure water rinse bath with The pipeline that 17# flows the water inlet connection of pure water rinse bath is equipped with one-way valve 17；The 17# flowing pure water rinse bath goes out The pipeline that the mouth of a river is connect with the water inlet of 15# flowing pure water rinse bath is equipped with valve 18；The 5# flowing pure water rinse bath goes out The pipeline that the mouth of a river is connect with the water inlet of 14# flowing pure water rinse bath is equipped with one-way valve 19.

It further illustrates, in the nickel-containing waste water collector unit, the water inlet and 14# of the pump 1 flow pure water rinse bath Water outlet connection pipeline be equipped with valve 1；It is described coloring sealing of hole nickel-containing waste water collecting tank water outlet and it is described pump 2 into The pipeline of mouth of a river connection is equipped with valve 2.

It further illustrates, in the nickel hydroxide recovery unit, the water inlet and the pump of the nickel hydroxide recycling can The pipeline of 2 water outlet connection is equipped with valve 3；The water outlet, described of the water outlet of the nickel hydroxide recycling can, ammonia tank It is connected between the water inlet of pump 3 by tee tube, and the tee tube is connected with the water outlet of the nickel hydroxide recycling can One end be equipped with valve 4, one end of the water outlet of the tee tube and the ammonia tank is equipped with valve 5；It is described pump 3 water outlet with The pipeline of the water inlet connection of nickel hydroxide recycling can is equipped with valve 6；The water outlet of the pump 3 and the water inlet of 1# filter press The pipeline of connection is equipped with valve 7.

It further illustrates, in the nickel phosphate recovery unit, the water outlet of the nickel phosphate recycling can, phosphoric acid tank go out The mouth of a river pumps between 4 water inlet through tee tube connection, and the water outlet of the tee tube and the nickel phosphate recycling can One end of connection is equipped with valve 8, and one end that the tee tube is connected with the water outlet of the phosphoric acid tank is equipped with valve 9；The pump 4 The pipeline that water outlet is connect with the water inlet of the nickel phosphate recovery unit is equipped with valve 10；The water outlet and 2# of the pump 4 are pressed The pipeline of the water inlet connection of filter is equipped with valve 11.

Further illustrate, in N-P compound fertilizer recovery unit, the water outlet of compound fertilizer's recycling can and the pump 5 into Valve 12 is provided on the pipeline of mouth of a river connection；The pipeline of the water outlet of the pump 5 is equipped with valve 13.

It further illustrates, the nickel hydroxide recycling can is internally provided with the stirring of 1# electricity, the nickel phosphate recycling can It is internally provided with the stirring of 2# electricity.

Single nickel salt colours the recovery method of the on-line system of sealing of hole recycling hole sealing agent and Waste water utilization, includes the following steps:

Step 1: operation flowing pure water cleans the water-saving subsystem of differential concatenation, opens valve 14, and cleaning pure water is flowed by 12# The pure water water inlet of pure water rinse bath is successively pure by 12# flowing pure water rinse bath, 11# flowing pure water rinse bath, 18# flowing Water rinse bath, 17# flowing pure water rinse bath, 15# flowing pure water rinse bath and 14# flow pure water rinse bath, are finally flowed by 14# The water outlet outflow of the slot bottom of dynamic pure water rinse bath；

Step 2: operation nickel-containing waste water retains unit, by aluminium after 13# single nickel salt coloring slot coloring 0.5-15min, It rises and hangs drip 30s, sequentially enter in 14# flowing rinsing bowl and 15# flowing rinsing bowl, be respectively washed 1min, rise and hang drip 30s, When cleaning after colouring aluminium, the coloring liquid containing nickel sulfate, boric acid is retained in 14# flowing pure water rinse bath and 15# flowing is pure In water rinse bath；Aluminium is gone successively in 16# medium temperature sealing of hole slot after medium temperature sealing of hole 10-25min；Rise hang drip 30s, successively into Enter in 17# flowing rinsing bowl and 18# flowing rinsing bowl, is respectively washed 1min, rises and hang drip 30s, cleaned after making aluminium sealing of hole When, the pore-sealing liquid of nickel acetate, triethanolamine and isobutanol is retained in 17# flowing pure water rinse bath and 18# flowing pure water rinse bath In, and flow into 14# flowing pure water rinse bath and 15# flowing pure water rinse bath, aluminium goes successively to air drying area, completes coloring Sealing of hole and washing；

Meanwhile the flow of the valve 14 of the water inlet of 12# flowing pure water rinse bath is adjusted, it is clear to control the 15# flowing pure water PH value in washing trough is between 5.5-6.5；

Step 3: collecting nickel-containing waste water, opens valve 1, opens pump 1, by the slot bottom water outlet of 14# flowing pure water rinse bath The coloring sealing of hole nickel-containing waste water of discharge is pumped into coloring sealing of hole nickel-containing waste water collecting tank；

Step 4: recycling nickel hydroxide opens valve 2, valve 3, closes valve 4, opens pump 2, will colour sealing of hole Nickel-bearing Waste water pump Enter nickel hydroxide recycling can；Valve 4, valve 6 are opened, pump 3, the stirring of 1# electricity, circular response liquid are opened；Valve 5 is slowly opened, to hydrogen-oxygen Change in nickel recycling can and liquefied ammonia is added, using the high speed rotation of pump 3, reaction generates primary reaction liquid；Side liquid feeding ammonia frontier inspection is surveyed primary The pH value of reaction solution closes valve 5 when pH value reaches 8.5-9.0, stops dosing, continues cycling through stirring 1h；Open 1# pressure Filter opens valve 7, closes valve 6,8, is separated by solid-liquid separation primary reaction liquid, sprays, rinses solid nickel hydroxide 10 minutes repeatedly Afterwards, solid nickel hydroxide is recycled；And the first filtrate of liquid is flowed into nickel phosphate recycling can；

Step 5: recycling nickel phosphate closes valve 9,11, opens valve 8,10, opens pump 4, the stirring of 2# electricity, circular response liquid； Valve 9 is slowly opened, phosphoric acid is added into nickel phosphate recycling can, using the high speed rotation of pump 4, reaction generates secondary reaction liquid；Side Add phosphoric acid frontier inspection to survey the pH value of secondary reaction liquid, when pH value reaches 6.5-7.5, closes valve 9, stop 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 secondary reaction liquid, sprays, rinse repeatedly Solid-state nickel phosphate after ten minutes, recycles solid-state nickel phosphate, and the second filtrate of liquid is flowed into compound fertilizer's recycling can；

Step 6: recycling N-P compound fertilizer opens valve 12,13, opens pump 5, obtain after the second filtrate is filtered Liquid N-P compound fertilizer is obtained, land use for greening is delivered to, is used as N-P compound fertilizer.

It further illustrates, in step 4, by the solid-state nickel hydroxide of recycling, pure water and acetic acid is added, precipitating, filtering obtain Obtain pH value >=6.0, acetic acid nickel content is lower than the liquid acetic acid nickel solution of saturation point；And according to nickel acetate/triethanolamine=10, Nickel acetate/isobutanol=10 weight ratio adds triethanolamine and isobutanol respectively, liquid acetic acid nickel solution is made to be converted to liquid Body medium temperature hole sealing agent.

Wherein, the acetic acid additive amount is 95% of addition weight needed for chemical reaction completely, and nickel hydroxide is excessive, is made PH value >=6.0 of mixed liquor；And under conditions of pure water weight/weight of nickel hydroxide=10, the content of nickel acetate is 14.5-15.5wt.%, far below the saturated concentration of nickel acetate, it is ensured that liquid acetic nickel solution is crystallized without nickel acetate and is precipitated.And And the solid-state nickel hydroxide of recycling is only rinsed, is not dried, is added into after pure water directly and acetic acid reaction, is substantially saved hydrogen-oxygen Change the drying cost of nickel；After the liquid acetic acid nickel solution of acquisition is filtered simultaneously, its filter residue is resided in reaction vessel, is made For nickel hydroxide starting material, waiting converts next time.

In addition, the content for titrating liquid nickel acetate first, further according to nickel acetate/triethanolamine=10, nickel acetate/isobutyl The weight ratio of alcohol=10 adds triethanolamine and isobutanol respectively, liquid acetic acid nickel solution is made to be converted to liquid medium temperature sealing of hole Agent, and the liquid medium temperature hole sealing agent not condensing crystallizing, can be added directly into 16# medium temperature sealing of hole slot, meet aluminium alloy sealing Quality requirement substantially saves crystallization, the separation, drying cost of medium temperature hole sealing agent.

It further illustrates, in step 5, secondary reaction liquid is separated by solid-liquid separation, after receiving solid-state nickel phosphate, the liquid of acquisition Contain ammonium phosphate, ammonium sulfate, ammonium borate, ammonium acetate, triethanolamine and isobutanol in the second filtrate of state, pH value is in 6.5-7.5 Between, for being used as N-P compound fertilizer.

Beneficial effects of the present invention:

1, setting single nickel salt colours sealing of hole cleaning Sewage treatment Online Processing System to the present invention for the first time, utilizes online classification Recovery method is configured by above system, and coloring sealing of hole water for cleaning is collected in synchronous retention, recycles nickel hydroxide up to 13.5 ten thousand Ton, is converted to medium temperature hole sealing agent；It recycles water during treated and is converted to N-P compound liquid fertilizer up to 48,000,000 tons, hinder Disconnected pollution of the nickel-containing waste water to wastewater treatment center reduces industrial dangerous waste discharge, realizes the resource recycling benefit of toxic waste With；

2, the present invention cleans the water-saving subsystem of differential concatenation by the way that the flowing pure water is arranged, and realization is more effectively collected Sealing of hole nickel-containing waste water is coloured, according to the structure design characteristic of the flowing pure water cleaning water-saving subsystem of differential concatenation, is greatly decreased and contains Nickel waste water collecting amount improves the treatment effeciency of nickel-containing waste water, reduces online equipment investment, reduces treating capacity and processing cost；

3, the present invention flows the pH value Con trolling index of pure water rinse bath by setting 15#, and directly adjustment 12# flows pure water The flow of rinse bath water inlet valve 14 can effectively reduce coloring sealing of hole cleaning water consumption；It is flowed by 14#, 15#, 17#, 18# Dynamic pure water rinse bath synchronizes retention coloring sealing of hole nickel-containing waste water, concentrates 14# slot slot bottom water outlet to flow into coloring sealing of hole and contains In nickel waste water collecting tank, to realize online, synchronous, independent processing coloring sealing of hole nickel-containing waste water, avoid and other processes water After mixing, the trouble of magnanimity nickel-containing waste water is reprocessed, the environmentally friendly cost of processing nickel-containing waste water waste residue is greatly reduced；

4, liquefied ammonia is added in the nickel-containing waste water that the present invention is collected to reactor tank for the first time, and at pH value 8.5-9.0, recycling Ni²⁺, reaction generation nickel hydroxide, separation of solid and liquid, rinsing, drying must meet the nickel hydroxide product of national standard；

5, the present invention adds pure water and acetic acid for the first time into the nickel hydroxide of recycling, is converted to nickel acetate, precipitating, filtering Reaction solution obtains pH value >=6.0, the nickel acetate solution that content is lower than saturation point, can make medium temperature hole sealing agent；

6, the present invention is for the first time according to nickel acetate/triethanolamine=10, nickel acetate/isobutanol=10 weight ratio addition three Nickel acetate solution is converted to liquid medium temperature hole sealing agent, directly inserts medium temperature sealing of hole slot by ethanol amine and isobutanol, meets aluminium conjunction Golden sealing quality requirement；

7, in the filtrate after the present invention is separated by solid-liquid separation to nickel hydroxide for the first time, phosphoric acid is added, by filtrate pH value by 8.5- 9.0 adjust to 6.5-7.5, convert remnants Ni²⁺For nickel phosphate；Remaining phosphoric acid nickel concentration be 5 multiplied by 10 minus 31 power, filtrate Much reach recycling and uses standard；Nickel phosphate is filtered again, and rinsing, drying obtain nickel phosphate product；Filter residue is nickel phosphate, is retained In reaction vessel, waiting is recycled next time；

8, when the present invention is converted to liquid acetic nickel using the nickel hydroxide of recycling, only it can rinse, not dry plus is pure After water directly and acetic acid reaction, the drying cost of nickel hydroxide is substantially saved；

9, after the present invention is transformed into liquid medium temperature hole sealing agent using nickel acetate, condensing crystallizing, is not directly used in medium temperature sealing of hole Crystallization, the separation, drying cost of medium temperature hole sealing agent are substantially saved in the fluting of slot and addition；

10, the present invention nickel phosphate is separated by solid-liquid separation for the first time after filtrate, be converted into phosphoric acid ammonium, ammonium sulfate, ammonium borate, N-P compound fertilizer of the pH value between 6.5-7.5 applies fertilizer for plant area's afforestation vegetation, realizes that coloring is recycled with water；

11, the present invention Con trolling index for setting 15# flowing pure water rinse bath independent for the first time is pH value 5.5-6.5, by pH value It controls 12# and flows pure water rinse bath water inlet flow, be further reduced 14# flowing pure water rinse bath slot bottom water outlet recycling Nickel-containing waste water total amount reduces processing pressure, investment reduction cost.

Detailed description of the invention

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

Fig. 2 is the schematic diagram that existing pot mould liquid is emitted into waste water center；

Fig. 3 is heat tinting process flow chart；

Fig. 4 is schematic diagram of the spraying coating line discharge of wastewater to waste water center；

Fig. 5 is aluminium processing enterprise waste residue source pie chart；

Fig. 6 is schematic diagram of the polish line discharge of wastewater to waste water center；

Fig. 7 is existing chromate waste water process flow；

Fig. 8 is existing nickel-containing waste water process flow；

Fig. 9 is existing waste water and dregs process flow diagram；

Figure 10 is the schematic diagram of the flowing pure water cleaning water-saving subsystem of differential concatenation of one implementation of the present invention；

Figure 11 is the on-line system of single nickel salt coloring sealing of hole the recycling hole sealing agent and Waste water utilization of one implementation of the present invention Schematic diagram；

Specific embodiment

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

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, and aluminium processing industry has The nickeliferous toxic waste residue that the big source of malicious waste residue one, i.e. heat-tinting sealing of hole generate, the surface treatment of such waste residue Zhan Lv processing enterprise 9% or more of waste residue total amount, about 13.5 ten thousand tons, while being related to about 48,000,000 tons of nickeliferous water, therefore waste water and dregs problem is very It is prominent！

Wherein, heat-tinting hole-sealing technology process is as shown in Figure 3, and 1#, 4#, 7#, 10#, 13#, 16# slot are work nest, often A work nest matches two flowing rinsing bowls, and oxidation processes need 18 slot positions, and wherein 13# is that single nickel salt colours slot, sulfur acid nickel And boric 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 nickel-containing waste water out of and enters wastewater treatment center, 2.25 hundred million tons of pollution whole industry water, generate 1,500,000 tons it is nickeliferous Mix toxic waste residue.The present invention relates to 13#-18# slot, 48,000,000 tons of nickeliferous coloring water for cleaning are collected in retention, are individually recycled Nickel-contained waste slag is converted into hole sealing agent, realizes the zero-emission of nickel-containing waste water waste residue.13#-18# function is as follows:

13# single nickel salt colours slot and 16# medium temperature sealing of hole slot

The purpose that 13#, 16# slot is arranged is to improve the decorative and anti-corrosion of aluminium alloy in order to which oxidizing film colours sealing of hole Property.Single nickel salt coloring and medium temperature sealing of hole slot Con trolling index are as follows:

13# single nickel salt colours slot: the purpose that this slot is arranged is coloured to aluminium, is increased decorative.Single nickel salt coloring liquid is non- Often stablize, but require chemical agent with high purity, contamination resistance is weak, it is desired to 12#, 11# rinsing bowl flowing pure water before coloring It washes；In addition, heavy metal nickel may be put into the catalogue being forbidden to use with the raising of environmental requirement.

14# and 15# flows rinsing bowl

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 waste water increases environmental protection treatment pressure.

16# medium temperature sealing of hole slot: the purpose that this slot is arranged is the micropore for sealing oxidation film, it is ensured that its corrosion resistance, it can also Replace sealing of hole slot with electrophoresis tank.

17# and 18# flows rinsing bowl: the purpose that this twice rinsing bowl is arranged is the nickeliferous residual cleaning sealing of hole slot and taking out of Medicament is not corroded after protecting aluminium to dispatch from the factory.Tap water is from 18# slot into 17# slot goes out, differential concatenation, water consume 2.0-3.0 Ton/ton material or so, water consumption is too big, and what is be discharged is nickel-containing waste water, increases environmental protection treatment pressure.

National annual consumption coloring sealing of hole is nickeliferous to use 48,000,000 tons of water, generates about 13.5 ten thousand tons of nickel-contained waste slag；By Fig. 9, this A little nickel-containing waste waters are mixed with aluminum fabrication plant other processes waste water, and pollution 2.25 hundred million tons of water of the whole industry generates nickeliferous dangerous waste 150 Ten thousand tons；Nickel-contained waste slag processing cost is 4,500,000,000 yuan (3000 yuan of calculating per ton), and nickel-containing waste water processing cost is 22,500,000,000 yuan (per ton 100 yuan of calculating).In addition, waste residue has been included in latest edition " National Hazard waste register ".Meanwhile 2.25 hundred million tons of waste water center magnanimity Waste water, after simple neutralisation treatment, in addition to generating 1,500,000 tons of aluminium hydroxides and nickel hydroxide mixed sludge, hydrogen in waste water Nickel oxide solubility is 130mg/L, and the discharge standard much higher than 0.5mg/L needs secondary specially treated, can be up to standard, is increased 22,500,000,000 yuan of nickel-containing waste water processing cost.

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

Through last 100 years application, the drawbacks of oxidation line, is completely exposed already.Especially emphasize today that cleaning is carried out production strictly in line with rules and regulations, Oxidation line 13-18# slot has following several respects needs to be greatly improved:

1, need will traditional ejected wash water mix after reprocessing be changed to grouping sheet and stay alone reason, processing cost is greatly reduced.It passes Suggestion of process design of uniting is unreasonable, and 13#, 16# are nickeliferous tank liquor, is directly entered 14#, 15#, 17#, 18# after aluminium coloring sealing of hole Four flowing rinsing bowls, bring nickel-containing waste water into waste water center, pollute the water for cleaning of whole oxidation line other processes；Mixing Afterwards, these nickel-containing waste waters, and qualified discharge are reprocessed, difficulty as one can imagine, cost is surprising.This mode there is an urgent need to improve, It can be recycled with online classification, individually be handled, replace traditional mixed processing mode, reduce environmentally friendly cost；

2, the passive processing waste water and dregs theory for needing abandoning tradition, handles nickel-containing waste water from the angle of recycling Waste residue, change dangerous waste are valuable chemical resource, and processing cost is both greatly reduced, and realize what nickeliferous chemical products value utilized It maximizes.Prior art design theory is unreasonable, brings nickel-containing waste water into waste water center, pollutes whole oxidation line other processes Water for cleaning；Waste water center neutralizes these waste water, precipitated, filters pressing, obtains nickeliferous solid slag；Meanwhile in waste water still So residual nickel hydroxide 130mg/L, the discharge standard much higher than 0.5mg/L；These magnanimity nickel-containing waste water waste residues, national environmental protection Clear stipulaties are dangerous waste in portion；These nickeliferous dangerous wastes are handled, high environmentally friendly cost is paid in enterprise and society need, simultaneously Waste valuable nickel resources.This extensive production method can configure special equipment there is an urgent need to improve, online actively to recycle Nickeliferous product, turns waste into wealth, and realizes dangerous waste resource utilization；

3, it presses 2010 " Cu, Ni and Co emission of industrial pollutants standard " (GB25467-2010), the discharge mark of nickel-containing waste water Standard is total nickel content 0.5mg/L.Reach the discharge standard of 0.5mg/L, itself there is sizable processing difficulty, if by sealing of hole It is reprocessed after being mixed with other processes with water with water, processing difficulty can infinitely amplify, and processing cost is significantly increased；Meanwhile by figure 9, the nickel-contained waste slag of sealing of hole is mixed with the waste residue of other processes, generates the industrial dangerous waste of magnanimity, to handle these industrial dangerous wastes, Enterprise and society will pay high environmentally friendly cost；Unique correctly selection is to retain 14#, 15#, 17#, 18# slot, individually It handles these nickel-containing waste waters, recycles nickel, be converted to hole sealing agent, reuse into 16# medium temperature sealing of hole slot；Water in recycling will colour Sealing of hole process water and waste water center are completely isolated.

Modern aluminum processing enterprise, the nickel-containing waste water waste residue for having heat-tinting sealing of hole to generate is in need of immediate treatment, and traditional cleaning It is too simple with the method reprocessed after the big mixing of water, the nickel-containing waste water waste residue of magnanimity is generated, these waste water and dregs are handled, Society will pay expensive environmentally friendly cost thus, and there is an urgent need to develop new technologies, and individually processing colours sealing of hole process Nickel-bearing Waste Water.

The on-line system and method for single nickel salt proposed by the present invention coloring sealing of hole recycling hole sealing agent and Waste water utilization, be The production for fully realizing aluminium processing enterprise is puzzled, is researched and developed for many years, and, environmental protection big to existing aluminium processing enterprise waste water and dregs amount is pressed The huge coloring sealing pores process of power, after having carried out unprecedented system research, a new technology of birth.

The present invention is the realization that is converted by following theoretical foundation, quantitative and qualitative analysis, medicament:

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

1) rinsing bowl differential concatenation individually retains after colouring sealing of hole.Figure 10 and (1) formula, cleaning pure water flow direction be 12# slot → 11# slot → 18# slot → 17# slot → 15# slot → 14# slot is flowed out from 14# slot slot bottom, cleans pure water differential concatenation, by 3 sets of tradition Water for cleaning, differential concatenation is 1 set of nickeliferous water for cleaning, through valve 1 and pump 1, is collected into coloring sealing of hole nickel-containing waste water collecting tank； Nickel-containing waste water collecting amount is greatly decreased, reduces online equipment investment, reduces treating capacity and processing cost；13# single nickel salt colours slot Con trolling index are as follows: nickel sulfate 140-160g/L, boric acid 40-60g/L, pH3.5-4.5,20-25 DEG C of temperature, time 30s- 15min；16# medium temperature sealing of hole slot Con trolling index are as follows: nickel acetate 4-6g/L, triethanolamine 0.4-0.6g/L, isobutanol 0.4- 0.6g/L, pH5.5-6.5,50-60 DEG C of temperature, time 10-25min；Aluminium after the coloring of 13# slot, is risen and is hung by 30s-15min Drip 30s, flows rinsing bowl into 14#, cleans 1min, rise and hang drip 30s, flows rinsing bowl into 15#, cleans 1min, rises Drip 30s is hung, into sealing of hole slot, after aluminium coloring when cleaning, nickel sulfate contained by coloring liquid, boric acid brought into, be retained in 14#, 15# flows in rinsing bowl；Aluminium after 16# slot medium temperature sealing of hole, is risen by 10-25min and hangs drip 30s, is flowed and is washed into 17# Slot cleans 1min, rises and hangs drip 30s, flows rinsing bowl into 18#, cleans 1min, rises and hangs drip 30s, complete into air drying area At coloring sealing of hole and washing process；When being cleaned after aluminium sealing of hole, nickel acetate contained by pore-sealing liquid, triethanolamine and isobutanol band Enter, be retained in 17#, 18# flowing rinsing bowl, differential concatenation flows into 14#, 15# slot；By 15# slot pH5.5-6.5,12# slot is adjusted The flow of water inlet valve 14；When 15# slot pH value is between 5.5-6.5, fixed valve 14 completes nickel-containing waste water retention；

2) water lotion is collected separately after colouring sealing of hole.It detects 15# and flows rinsing bowl pH value, strict control 15# flowing washing The pH value of slot are as follows: 15# slot pH5.5-6.5 (2)

By Figure 10,12# slot inlet valve is adjusted, water consumption is cleaned by (2) formula control coloring sealing of hole, goes out from 14# slot slot bottom The mouth of a river, the nickeliferous water for cleaning for collecting outflow through valve 1, pump 1 are spare to coloring sealing of hole nickel-containing waste water collecting tank.

Two, 13# single nickel salt coloring slot and 16# medium temperature sealing of hole slot ejected wash water collect production hole sealing agent and middle water recycles Quantitative and qualitative analysis

1) the recovered liquid 1L of coloring sealing of hole nickel-containing waste water collecting tank, sulfur acid nickel, boric acid, nickel acetate, isobutanol and three are taken Ethanol amine, test agents concentration are as follows:

Nickel sulfate 0.3g/L boric acid 0.1g/L nickel acetate 0.1g/L

Triethanolamine 0.01g/L isobutanol 0.01g/L (3)

pH 5.85

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 is clear, no precipitating, no precipitate；

When pH is between 7.0-7.5, tank liquor starts muddiness, and green crystal nickel hydroxide is precipitated:

NH₃+H₂O=NH₄OH

Ni²⁺+2NH₄OH=2NH₄ ⁺+Ni(OH)₂↓ (4)

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, takes PH8.5-9.0 is reaction end；

2) ammonium sulfate, ammonium acetate, ammonium borate, triethanolamine and isobutanol do not precipitate, and retain in liquid.By (3) formula, With the addition of liquefied ammonia, pH is constantly increased, and presses (4) formula, Ni²⁺Constantly reaction generates Ni (OH)₂But ammonium sulfate, ammonium acetate, boron Sour ammonium, isobutanol and triethanolamine, are not decomposed, and are not precipitated, and are retained in liquid；

3) it is separated by solid-liquid separation, with filtrate separation ammonium sulfate, ammonium borate, ammonium acetate, isobutanol and triethanolamine, recycles solid Nickel hydroxide.By (4) formula, reaction product is separated by solid-liquid separation.Ammonium sulfate, ammonium borate, ammonium acetate, isobutanol and three ethyl alcohol Amine is flowed out with filtrate, obtains solid nickel hydroxide；It rinsed, dried, the technical grade nickel hydroxide for obtaining meeting national standard produces Product；Nickel hydroxide solubility 130mg/L in filtrate, the discharge standard much higher than 0.5mg/L, needs secondary treatment, can be up to standard It recycles；

4) nickel hydroxide is converted, reaction generates nickel acetate.The nickel hydroxide product obtained after rinsing drying is weighed, is added Pure water is wet, and being slowly added concentration is 98% acetic acid, reacts as follows:

Ni(OH)₂+2CH₃COOH

=Ni (CH₃COO)₂+2H₂O (5)

100g nickel hydroxide, completely reaction need to add glacial acetic acid (98%) 132.1g, generate nickel acetate 190.7g.It presses Nickel acetate solubility 182g/L (20 DEG C), pH6.28 design recovery scheme.

Nickel hydroxide 100g is taken, pure water 1000mL is added, pure water weight/weight of nickel hydroxide=10 stirs evenly；Slowly 132.1 × 95%=125.5g of glacial acetic acid is added, generates nickel acetate close to 190.7 × 95%=181.2g；Reaction solution total weight 1225.5g, acetic acid nickel content is 181.2/1225.5=14.8wt.%, lower than the saturated concentration of nickel acetate, it is ensured that without acetic acid Nickel saturated crystallization is precipitated；By 95% addition of acetic acid additive amount, nickel hydroxide is excessive, i.e., beaker bottom has less after the reaction was completed Nickel hydroxide solid residue is measured, can ensure that the pH proximity values 6.28 of nickel acetate solution, it is big to meet medium temperature hole sealing agent pH for pH >=6.0 In 5.5 sealing quality requirement；Remaining filter residue is the nickel hydroxide solid not reacted completely, is resided in reactor, under waiting Primary conversion；

5) hole sealing agent is produced, realizes that useless nickel resourcesization utilize.It is from 14# water due to the nickel acetate liquid that (5) formula obtains The nickeliferous waste liquid of washing trough recycling, which reacts, to be generated, and after the ammonium sulfate, ammonium acetate and ammonium borate rinsed clean of remaining, presses (1) formula, Remodeling method are as follows:

A, acetic acid nickel concentration is titrated, X (g/L) is obtained；

B, triethanolamine X/10 (g/L) (6) are added

C, isobutanol X/10 (g/L) is added

By the hole sealing agent that (6) are transformed, the fluting and addition medicament of 16# medium temperature sealing of hole slot can be used as completely；It considers The working index of 16# slot is pH5.5-6.5, and the nickel acetate of (5) formula recycling has met pH value requirement；When sealing of hole, temperature 50-60 DEG C, there is a large amount of water evaporation, liquor of hole- sealing tank position shoals, and when adding by the liquid hole sealing agent of (6) formula production, just supplements medicament Concentration and liquid level save the cost of manufacture of the nickel acetate condensing crystallizing of (5) formula recycling；In addition, the nickel hydroxide of (4) formula recycling, Rinsed clean not dry, because (5) formula needs to add a large amount of water when reacting, save cost of manufacture；

6) filtrate is handled, nickel phosphate is recycled, recycles coloring water for cleaning.By (4) formula, nickel hydroxide solubility 130mg/L, the discharge standard much higher than 0.5mg/L, needs secondary treatment, up to standard can recycle.(4) filtrate of formula contains Ammonium sulfate, ammonium borate, ammonium acetate, isobutanol and triethanolamine, 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⁺ (7)

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；Filtrate is phosphoric acid ammonium, ammonium sulfate, ammonium borate, ammonium acetate, isobutanol and three The N-P compound fertilizer of ethanol amine afforests Fertilizer application as plant area, realizes that coloring is recycled with water.

Three, the sealing of hole capacity experimental of 13# single nickel salt coloring water for cleaning remanufacture hole sealing agent

The present invention presses (4) formula first, obtains nickel hydroxide, then produces nickel acetate by (5), finally by the allotment of (6) formula Warm hole sealing agent.This serial experiment presses medium temperature sealing of hole slot Con trolling index, investigates the envelope of the medium temperature hole sealing agent by the production of (6) formula respectively Hole ability.

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

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

2, influence of the sealing of hole slot pH value to sealing quality.Taking nickel acetate 5g/L, (triethanolamine and isobutanol are dense for nickel acetate / 10th of degree, similarly hereinafter), 55 DEG C of temperature, pH4.5,5.0,5.5,6.0,6.5,7.0；Taking oxide thickness is 15 microns, The sealing of hole time is 15 minutes, detects sealing quality by ISO3210 international standard, the results are shown in Table 2:

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

3, influence of the sealing of hole temperature to sealing quality.Taking nickel acetate 5g/L, (triethanolamine and isobutanol are acetic acid nickel concentration 1/10th, similarly hereinafter), pH6.0,40,45,50,55,60,65 DEG C of temperature；Taking oxide thickness is 15 microns, the sealing of hole time It is 15 minutes, detects sealing quality by ISO3210 international standard, the results are shown in Table 3:

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

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

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

Four, the experimental result point that 13# single nickel salt coloring sealing of hole water for cleaning remanufacture hole sealing agent and middle water recycle Analysis

By formula (1)-(7) and experiment 1-4 and testing result, following analysis can be done:

1, the standard provided by formula (2) formula can retain collection coloring sealing of hole water for cleaning online；Adjust 12# slot feed water flow Amount collects nickel-containing waste water in 14# slot slot bottom water outlet, controls nickel-containing waste water total amount to be processed；

2, (4) formula is pressed, addition liquefied ammonia individually handles the nickel-containing waste water of retention online at pH value 8.5-9.0, recycles The nickel hydroxide of technical grade converts nickeliferous solid dangerous waste to the industrial chemicals of high value, realizes the recycling benefit of solid dangerous waste With；

3, (5) formula is pressed, converts nickel acetate solution for the nickel hydroxide of recycling, under the conditions of nickel hydroxide is excessive, instead It answers the pH value of product to be greater than 6.0, meets subsequent transformation into the requirement of hole sealing agent；

4, (6) formula is pressed, nickel acetate solution is converted to liquid hole sealing agent, is added directly into 16# medium temperature sealing of hole slot；Sealing of hole Slot is medium temperature sealing of hole, has certain evaporation capacity, liquid hole sealing agent just supplements drug concentration and liquid level, saves drying hydroxide The trouble of nickel, evaporative crystallization nickel acetate solution substantially saves the cost of manufacture of hole sealing agent；

5, it by known to serial experiment result 1-4, within the scope of the Con trolling index as defined in medium temperature sealing of hole slot, is made by (6) formula Medium temperature hole sealing agent be fully able to meet sealing of hole requirement；

6, (7) formula is pressed, in the filtrate after nickel hydroxide separation of solid and liquid, phosphoric acid is added, converts remnants Ni²⁺For nickel phosphate, Remaining phosphoric acid nickel concentration be 5 multiplied by 10 minus 31 power, filtrate much reaches recycling using standard；Nickel phosphate is filtered again, is floated It washes, dry, obtain nickel phosphate product；Filtrate is phosphoric acid ammonium, ammonium sulfate, ammonium borate, ammonium acetate, isobutanol and triethanolamine N-P compound fertilizer afforests Fertilizer application as plant area, realizes that coloring sealing of hole is recycled with water；Filter residue is nickel phosphate, is resided in In reaction vessel, waiting is recycled next time.

Five, the on-line system and method for single nickel salt coloring sealing of hole recycling hole sealing agent and Waste water utilization

It is practical in conjunction with heat-tinting sealing of hole quantity-produced by formula (1)-(7) and experiment 1-4 and testing result, single nickel salt It colours sealing of hole recycling hole sealing agent and Waste water utilization method and Configuration Online is as shown in Figure 10:

In order to realize long-term large-scale production water conservation, online recycling nickel-containing waste water, individually convert nickeliferous solid dangerous waste Target, Figure 10 configure 6 big systems:

The on-line system of single nickel salt coloring sealing of hole recycling hole sealing agent and Waste water utilization of the present invention, successively from upstream to downstream Unit, nickel-containing waste water collector unit, hydroxide are retained including the water-saving subsystem of flowing pure water cleaning differential concatenation, nickel-containing waste water Nickel recovery unit, nickel phosphate recovery unit and N-P compound fertilizer recovery unit；

The present invention utilizes online classification recovery method, configures by above system, and retention is collected coloring sealing of hole cleaning and used Water recycles 13.5 ten thousand tons of nickel hydroxide, is converted to medium temperature hole sealing agent；48,000,000 tons of water during treated is recycled, is converted to N-P compound liquid fertilizer blocks pollution of the nickel-containing waste water to wastewater treatment center, reduces industrial dangerous waste discharge, realizes toxic useless The resource recycling of gurry utilizes, and operation of the present invention process includes the following steps:

Embodiment

Embodiment 1 (operation of flowing pure water cleaning differential concatenation water-saving system)

It flows pure water and cleans differential concatenation water-saving system operating process: opening valve 14, cleaning pure water is from 12# slot into warp 12# slot → 11# slot → 18# slot → 17# slot → 15# slot → 14# slot is flowed out from 14# slot slot bottom, cleans pure water differential concatenation, will Traditional 3 sets of water for cleaning, differential concatenation are 1 set of nickeliferous water for cleaning；Complete flowing pure water cleaning differential concatenation water-saving system behaviour Make process；

Embodiment 2 (nickel-containing waste water retention system operatio)

Nickel-containing waste water retain system operatio process: open valve 14, cleaning pure water from 12# slot into, through 12# slot → 11# slot → 18# slot → 17# slot → 15# slot → 14# slot is flowed out from 14# slot slot bottom, cleans pure water differential concatenation, and 3 sets of cleanings of tradition are used Water, differential concatenation are 1 set of nickeliferous water for cleaning；Then through valve 1, pump 1, it is pumped into coloring sealing of hole nickel-containing waste water collecting tank, completes to contain Nickel waste water retention；Aluminium after 13# coloring, is risen by 30s-15min and hangs drip 30s, flows rinsing bowl, cleaning into 14# 1min rises and hangs drip 30s, flows rinsing bowl into 15#, cleans 1min, rises and hang drip 30s, into sealing of hole slot；Aluminium coloring After when cleaning, nickel sulfate contained by coloring liquid, boric acid are brought into, are retained in 14#, 15# flowing rinsing bowl；Aluminium presses 10- 25min rises after 16# medium temperature sealing of hole and hangs drip 30s, flows rinsing bowl into 17#, cleans 1min, rise and hang drip 30s, enters 18# flows rinsing bowl, cleans 1min, rises and hangs drip 30s, into air drying area, completes coloring sealing of hole and washing process；Aluminium envelope When cleaning behind hole, nickel acetate contained by pore-sealing liquid, triethanolamine and isobutanol are brought into, are retained in 17#, 18# flowing rinsing bowl, Differential concatenation flows into 14#, 15# slot；By 15# slot pH5.5-6.5, the flow of 12# slot water inlet valve 14 is adjusted；When 15# slot pH value When between 5.5-6.5, fixed valve 14 completes nickel-containing waste water and retains system operatio process；

Embodiment 3 (operation of nickel-containing waste water collection system)

Nickel-containing waste water collection system operating process: opening valve 1, opens pump 1, the coloring that 14# slot slot bottom water outlet is discharged It is spare that sealing of hole nickel-containing waste water is pumped into coloring sealing of hole nickel-containing waste water collecting tank；Complete nickel-containing waste water collection system operating process；

Embodiment 4 (operation of nickel hydroxide recovery system)

Nickel hydroxide recovery system operating process: opening valve 2,3, closes valve 4, opens pump 2, nickel-containing waste water is pumped into hydrogen Nickel oxide recycling can；Valve 4,6 is opened, pump 3, the stirring of 1# electricity, circular response liquid are opened；Valve 5 is slowly opened, by liquefied ammonia suction pump 3, using the high speed rotation of pump 3, it is sufficiently mixed reaction solution；Liquefied ammonia is added on side, and frontier inspection surveys the pH value of reaction solution, when pH value reaches When 8.5-9.0, valve 5 is closed, stops dosing, continues cycling through stirring 1 hour；Unlatching 1# filter press, opening valve 7, closing valve 6, 8, it is separated by solid-liquid separation nickel hydroxide；It sprays repeatedly, rinse nickel hydroxide solid after ten minutes, recycle nickel hydroxide product, complete hydrogen Nickel oxide recovery system operating process；

Embodiment 5 (operation of nickel phosphate recovery system)

Nickel phosphate recovery system operating process: closing valve 9,11, opens valve 8,10, opens pump 4, the stirring of 2# electricity, and circulation is anti- Answer liquid；Valve 9 is slowly opened, phosphoric acid suction pump 4 is sufficiently mixed reaction solution using the high speed rotation of pump 4；Phosphoric acid is added on side, Frontier inspection surveys the pH value of reaction solution, when pH value reaches 6.5-7.5, closes valve 9, stops dosing, continues 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；It sprays, rinse nickel phosphate solid 10 minutes repeatedly Afterwards, nickel phosphate product is recycled, nickel phosphate recovery system operating process is completed；

Embodiment 6 (operation of N-P compound fertilizer recovery system)

N-P compound fertilizer recovery system operating process: opening valve 12,13, opens pump 5, recovered liquid is filtered Afterwards, it is delivered to land use for greening, is used as N-P compound fertilizer, N-P compound fertilizer recovery system operating process is completed；

Embodiment 7 (conversion nickel hydroxide, production nickel acetate solution)

In the nickel hydroxide of recycling, pure water and acetic acid are added, nickel acetate is converted to.It is institute in the acetic acid weight of addition Under the conditions of needing weight 95%, nickel hydroxide excessive, it is ensured that reacting liquid pH value >=6.0；In pure water weight/weight of nickel hydroxide Under the conditions of=10, reaction solution acetic acid nickel content is 14.5-15.5wt.%, far below the saturated concentration of nickel acetate, it is ensured that reaction Liquid is crystallized without nickel acetate and is precipitated；

Embodiment 8 (produces liquid medium temperature hole sealing agent with nickel acetate solution)

Nickel acetate solution is converted to liquid medium temperature hole sealing agent by (6) formula, is added directly into 16# medium temperature sealing of hole slot；Sealing of hole Slot is medium temperature sealing of hole, has certain evaporation capacity, liquid hole sealing agent just supplements drug concentration and liquid level, saves drying hydroxide The trouble of nickel, evaporative crystallization nickel acetate solution substantially saves the cost of manufacture of hole sealing agent；

Embodiment 9 (the hole sealing agent ability to work of remanufacture detects)

By Fig. 3, continuous production sealing of hole aluminium, 16# sealing of hole slot constantly adds the present invention by (6) formula by (1) formula Con trolling index The hole sealing agent of production；Take 55 DEG C of liquor of hole- sealing tank pH6.0, temperature, nickel acetate 4-6g/L；Taking oxide thickness is 15 microns, sealing of hole Time is 15 minutes, continuously detects sealing quality by ISO3210 international standard, as a result as shown in the table:

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

1. single nickel salt colour sealing of hole recycling hole sealing agent and Waste water utilization on-line system, it is characterised in that: from upstream to downstream according to Secondary includes the water-saving subsystem of flowing pure water cleaning differential concatenation, nickel-containing waste water retention unit, nickel-containing waste water collector unit, hydroxide Nickel recovery unit, nickel phosphate recovery unit and N-P compound fertilizer recovery unit；

The flowing pure water cleaning water-saving subsystem of differential concatenation includes the 12# flowing pure water cleaning of sequence differential concatenation setting Slot, 11# flowing pure water rinse bath, 18# flowing pure water rinse bath, 17# flowing pure water rinse bath, 15# flowing pure water rinse bath and 14# flows pure water rinse bath；The 12# flowing pure water rinse bath is provided with pure water water inlet；

The nickel-containing waste water retention unit includes 13# single nickel salt coloring slot and 16# medium temperature sealing of hole slot；The 13# single nickel salt coloring Slot is arranged between the 12# flowing pure water rinse bath and 14# flowing pure water rinse bath；The 16# medium temperature sealing of hole slot is set to institute It states between 15# flowing pure water rinse bath and 17# flowing pure water rinse bath；

The nickel-containing waste water collector unit includes coloring sealing of hole nickel-containing waste water collecting tank and pump 1；The coloring sealing of hole nickel-containing waste water Collecting tank is used to collect the coloring sealing of hole nickel-containing waste water from 14# flowing pure water rinse bath；The pump 1 will be for that will colour envelope Hole nickel-containing waste water is pumped into the coloring sealing of hole nickel-containing waste water collecting tank；

The nickel hydroxide recovery unit includes pump 2, pump 3, nickel hydroxide recycling can, ammonia tank and 1# filter press；The pump 2 is used It is pumped into nickel hydroxide recycling can in sealing of hole nickel-containing waste water will be coloured；It is described pump 3 for recycle in nickel hydroxide recycling can Color sealing of hole nickel-containing waste water, and the primary reaction liquid pump after reaction is entered in 1# filter press；The ammonia tank is used for hydroxide Liquefied ammonia is added in nickel recycling can, is reacted with coloring sealing of hole nickel-containing waste water and obtains primary reaction liquid；The 1# filter press is for separating The first filtrate of solid-state nickel hydroxide and liquid in primary reaction liquid；

The nickel phosphate recovery unit includes nickel phosphate recycling can, pump 4, phosphoric acid tank and 2# filter press；The nickel phosphate recycling can For the first filtrate of recovering liquid；The pump 4 is used for the first filtrate in recycled phosphoric acid nickel recycling can, and will be secondary after reaction Order reaction liquid pump enters in 2# filter press；The phosphoric acid tank is reacted for phosphoric acid to be added into nickel phosphate recycling can with the first filtrate Obtain secondary reaction liquid；The 2# filter press is used to separate the second filtrate of solid-state nickel phosphate and liquid in secondary reaction liquid；

N-P compound fertilizer recovery unit includes compound fertilizer's recycling can, pump 5 and filter；Compound fertilizer's recycling can is used for back Receive the second filtrate；The pump 5 is for being pumped into filter for the second filtrate in compound fertilizer's recycling can；The filter is for filtering Second filtrate obtains liquid N-P compound fertilizer.

2. the on-line system of single nickel salt coloring sealing of hole recycling hole sealing agent and Waste water utilization according to claim 1, feature It is: in the flowing pure water cleaning water-saving subsystem of differential concatenation, the pure water water inlet of the 12# flowing pure water rinse bath Pipeline is equipped with valve 14；The water outlet of the 12# flowing pure water rinse bath and the water inlet of 11# flowing pure water rinse bath connect The pipeline connect is equipped with one-way valve 15；The water inlet of the water outlet and 18# flowing pure water rinse bath of the 11# flowing pure water rinse bath The pipeline of mouth connection is equipped with valve 16；The water inlet of the water outlet and 17# flowing pure water rinse bath of the 18# flowing pure water rinse bath The pipeline of mouth connection is equipped with one-way valve 17；The water outlet and 15# of the 17# flowing pure water rinse bath flow pure water rinse bath The pipeline of water inlet connection is equipped with valve 18；The water outlet and 14# of the 5# flowing pure water rinse bath flow pure water rinse bath The pipeline of water inlet connection is equipped with one-way valve 19.

3. the on-line system of single nickel salt coloring sealing of hole recycling hole sealing agent and Waste water utilization according to claim 2, feature It is: in the nickel-containing waste water collector unit, what the water inlet of the pump 1 was connect with the water outlet of 14# flowing pure water rinse bath Pipeline is equipped with valve 1；On the pipeline that the water outlet of the coloring sealing of hole nickel-containing waste water collecting tank is connect with the water inlet of the pump 2 Equipped with valve 2.

4. the on-line system of single nickel salt coloring sealing of hole recycling hole sealing agent and Waste water utilization according to claim 3, feature Be: in the nickel hydroxide recovery unit, the water inlet of the nickel hydroxide recycling can is connect with the water outlet of the pump 2 Pipeline is equipped with valve 3；The water outlet of the nickel hydroxide recycling can, the water outlet of ammonia tank, the pump 3 water inlet between lead to Tee tube connection is crossed, and one end that the tee tube is connected with the water outlet of the nickel hydroxide recycling can is equipped with valve 4, it is described One end of the water outlet of tee tube and the ammonia tank is equipped with valve 5；The water inlet of the water outlet and nickel hydroxide recycling can of the pump 3 The pipeline of mouth connection is equipped with valve 6；The pipeline that the water outlet of the pump 3 is connect with the water inlet of 1# filter press is equipped with valve 7.

5. the on-line system of single nickel salt coloring sealing of hole recycling hole sealing agent and Waste water utilization according to claim 4, feature Be: in the nickel phosphate recovery unit, the water outlet of the nickel phosphate recycling can, phosphoric acid tank water outlet, pump 4 water inlet Between connected by tee tube, and one end for connect with the water outlet of the nickel phosphate recycling can of the tee tube is equipped with valve 8, One end that the tee tube is connected with the water outlet of the phosphoric acid tank is equipped with valve 9；The water outlet and the nickel phosphate of the pump 4 return The pipeline for receiving the water inlet connection of unit is equipped with valve 10；The pipe that the water outlet of the pump 4 is connect with the water inlet of 2# filter press Road is equipped with valve 11.

6. the on-line system of single nickel salt coloring sealing of hole recycling hole sealing agent and Waste water utilization according to claim 5, feature It is: in N-P compound fertilizer recovery unit, the pipeline that connect of water inlet of the water outlet of compound fertilizer's recycling can and the pump 5 On be provided with valve 12；The pipeline of the water outlet of the pump 5 is equipped with valve 13.

7. the on-line system of single nickel salt coloring sealing of hole recycling hole sealing agent and Waste water utilization according to claim 6, feature Be: the nickel hydroxide recycling can is internally provided with the stirring of 1# electricity, and the nickel phosphate recycling can is internally provided with 2# electricity Stirring.

8. the recycling side of the on-line system of single nickel salt coloring sealing of hole recycling hole sealing agent as claimed in claim 7 and Waste water utilization Method, characterized by the following steps:

Step 1: operation flowing pure water cleans the water-saving subsystem of differential concatenation, opens valve 14, cleans pure water by 12# and flows pure water The pure water water inlet of rinse bath is successively clear by 12# flowing pure water rinse bath, 11# flowing pure water rinse bath, 18# flowing pure water Washing trough, 17# flowing pure water rinse bath, 15# flowing pure water rinse bath and 14# flow pure water rinse bath, finally flow pure water by 14# The water outlet of the slot bottom of rinse bath flows out；

Step 2: operation nickel-containing waste water retains unit, by aluminium after 13# single nickel salt coloring slot coloring 0.5-15min, rises and hangs drop 30s is flowed, is sequentially entered in 14# flowing rinsing bowl and 15# flowing rinsing bowl, is respectively washed 1min, rises and hang drip 30s, make aluminium When cleaning after coloring, the coloring liquid containing nickel sulfate, boric acid is retained in 14# flowing pure water rinse bath and 15# flowing pure water cleaning In slot；Aluminium is gone successively in 16# medium temperature sealing of hole slot after medium temperature sealing of hole 10-25min；It rises and hangs drip 30s, sequentially enter 17# stream In dynamic rinsing bowl and 18# flowing rinsing bowl, it is respectively washed 1min, rises and hangs drip 30s, when making to clean after aluminium sealing of hole, nickel acetate, The pore-sealing liquid of triethanolamine and isobutanol is retained in 17# flowing pure water rinse bath and 18# flowing pure water rinse bath, and is flowed into 14# flows in pure water rinse bath and 15# flowing pure water rinse bath, and aluminium goes successively to air drying area, completes coloring sealing of hole and washing；

Meanwhile the flow of the valve 14 of the water inlet of 12# flowing pure water rinse bath is adjusted, control the 15# flowing pure water rinse bath In pH value between 5.5-6.5；

Step 3: collecting nickel-containing waste water, opens valve 1, opens pump 1, by the slot bottom water outlet discharge of 14# flowing pure water rinse bath Coloring sealing of hole nickel-containing waste water is pumped into coloring sealing of hole nickel-containing waste water collecting tank；

Step 4: recycling nickel hydroxide opens valve 2, valve 3, closes valve 4, opens pump 2, and coloring sealing of hole nickel-containing waste water is pumped into hydrogen Nickel oxide recycling can；Valve 4, valve 6 are opened, pump 3, the stirring of 1# electricity, circular response liquid are opened；Valve 5 is slowly opened, is returned to nickel hydroxide Liquefied ammonia is added in closed cans, using the high speed rotation of pump 3, reaction generates primary reaction liquid；Side liquid feeding ammonia frontier inspection surveys primary reaction liquid PH value, when pH value reaches 8.5-9.0, close valve 5, stop dosing, continue cycling through stirring 1h；1# filter press is opened, is beaten Valve opening 7 closes valve 6,8, is separated by solid-liquid separation primary reaction liquid, sprays repeatedly, rinses solid nickel hydroxide after ten minutes, recycling is solid The nickel hydroxide of state；And the first filtrate of liquid is flowed into nickel phosphate recycling can；

Step 5: recycling nickel phosphate closes valve 9,11, opens valve 8,10, opens pump 4, the stirring of 2# electricity, circular response liquid；Slowly Valve 9 is opened, phosphoric acid is added into nickel phosphate recycling can, using the high speed rotation of pump 4, reaction generates secondary reaction liquid；While adding phosphorus Sour frontier inspection surveys the pH value of secondary reaction liquid, 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 secondary reaction liquid, sprays repeatedly, rinse solid state of phosphorous Sour nickel after ten minutes, recycles solid-state nickel phosphate, and the second filtrate of liquid is flowed into compound fertilizer's recycling can；

Step 6: recycling N-P compound fertilizer opens valve 12,13, opens pump 5, obtain liquid after the second filtrate is filtered N-P compound fertilizer, is delivered to land use for greening, uses as N-P compound fertilizer.

9. the recycling side of the on-line system of single nickel salt coloring sealing of hole recycling hole sealing agent according to claim 8 and Waste water utilization Method, it is characterised in that: in step 4, by the solid-state nickel hydroxide of recycling, pure water and acetic acid is added, precipitating, filtering obtain pH value >=6.0, acetic acid nickel content is lower than the liquid acetic acid nickel solution of saturation point；And according to nickel acetate/triethanolamine=10, nickel acetate/ The weight ratio of isobutanol=10 adds triethanolamine and isobutanol respectively, and liquid acetic acid nickel solution is made to be converted to liquid medium temperature envelope Hole agent.

10. the recycling of the on-line system of single nickel salt coloring sealing of hole recycling hole sealing agent according to claim 8 and Waste water utilization Method, it is characterised in that: in step 5, secondary reaction liquid is separated by solid-liquid separation, after receiving solid-state nickel phosphate, the liquid of acquisition the In two filtrates contain ammonium phosphate, ammonium sulfate, ammonium borate, ammonium acetate, triethanolamine and isobutanol, pH value between 6.5-7.5, For as N-P compound fertilizer.