CN109160628A - The on-line system and method for single nickel salt coloring recycling hole sealing agent and Waste water utilization - Google Patents

Abstract

The on-line system and method for single nickel salt coloring recycling hole sealing agent and Waste water utilization, the system include 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；Nickel-containing waste water retention unit includes the 13# single nickel salt coloring slot, 14# flowing pure water rinse bath and 15# flowing pure water rinse bath being arranged in order；Nickel-containing waste water collector unit includes coloring nickel-containing waste water collecting tank and pump 1；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；N-P compound fertilizer recovery unit includes compound fertilizer's recycling can and filter；The present invention is configured using the on-line system, recycles nickel-containing waste water waste residue, and recycling 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

The on-line system and method for single nickel salt coloring 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 recycling hole sealing agent and Waste water utilization it is online System and method for.

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, when aluminium ingot remelting amount compared with It is more, and regenerate one ton of aluminium scrap and about generate 100-250kg aluminium ash.Aluminium ash can be divided into two kinds: be former in electrolysis one is secondary aluminium ash Aluminium and casting etc. do not add the dross generated during salt flux and skimming, and main component is metallic aluminium and aluminum oxide, and aluminium contains It measures and is differed up to 15%-70%, color is white；Another kind is Quadratic aluminum dust, is that a secondary aluminium ash mentions the waste after alum recovery, Aluminium content is low compared with a secondary aluminium ash, generally in grey black.Quadratic aluminum dust complicated component contains metallic aluminium (5-30%), aluminium oxide (30-70%), silica and di-iron trioxide (5-15%), the chloride (10-30%) of potassium sodium calcium and magnesium and nitrogen fluorine arsenic etc. Poisonous and harmful element.Lower Fig. 1 is aluminium ash composition examining report.Alleged aluminium ash refers both to Quadratic aluminum dust below.Whole nation electricity in 2016 32,500,000 tons of aluminium yield of solution, squeezes and calendering processing aluminum materials yield is more than 20,000,000 tons, the aluminium ash quantity conservative estimation in the annual whole nation 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 resource, have compared with High comprehensive reutilization value, but enough attention are not obtained always, cause the huge wasting of resources.Simultaneously because of aluminium lime-ash In containing the poisonous and harmful substances such as fluoride, ammonia nitrogen, arsenic, danger wastes are listed in, in version " National Hazard waste name in 2016 Record " in aluminium ash waste classification be HW48, hazard property T (Toxicity)-toxicity risk waste.With the development of economy, it gives up Aluminium ash amount of savings will increase considerably year by year, will be more and more convex if not finding economical and effective, innoxious method is pocessed It is shown to seriously threaten environment.

The recycling of China's aluminium ash at present still in its infancy, lacks that technology maturation is reliable, recovery method of good economy performance, Aluminium ash handles the low rate of recovery, energy consumption and waste greatly, and utilization ways are few.Even if still containing largely having in treated aluminium ash Evil substance, still can only stockyard stockpiling or burial processing, have great environmental hazard, while producer carry it is huge disobey Method 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, and whole industry year is raw 20,000,000 tons of squeeze wood are produced, nearly 2.25 hundred million tons of waste discharge, about 1,500,000 tons of waste residue are generated after wastewater treatment, quantity is extremely surprising.

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.Contain in the waste liquid exhausted There are 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 " to be controlled with useless It is useless " mode, direct emission is into waste water center, the spent acid neutralisation treatment generated with oxidation operation.What this processing mode generated Waste residue amount is very big, and 28% or so of the total quantity of slag of enterprise can be accounted for by stewing mould waste residue；Meanwhile a large amount of sodium ions enter in waste water The heart, water in pollution, a possibility that thoroughly breaking off Treated sewage reusing.This coarse processing mode of mould liquid is stewed, enterprise is not only without benefit With 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 Fig. 6 It is shown.

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 tree such as acetate Organic matters such as rouge etc..Acid waste water, alkaline waste water are usually to mix neutralisation treatment, and chromate waste water, nickel-containing waste water must be independent Processing.Oxidation electrophoresis material ratio decline in recent years, but most of aluminum material factories or acid waste water are more than alkaline waste water, and soda acid water is complete Portion 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 useless Slag.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.Waste residue belongs to danger Dangerous waste contains a variety of venomous injurants such as aluminium hydroxide, fluoride, sulfide, nickel salt, phenol, nitrate, nitrite Matter, environmental hazard is huge, can not fill, and has great environmental hazard.After waste water center processing, separation of solid and liquid, middle water contains Have sodium ion, ammonium ion, sulfate radical, nitrate anion, nitrite anions, acetate, tartrate anion, thiosulfate anion, chloride ion, sulphur from Son, fluorine ion etc., can not reuse.Current Environmental Protection Situation forces enterprise to turn to energy-saving and emission-reduction and resource circulation utilization direction Type development, but lack the technology of mature and reliable.Water fully recovering, zero output of waste residue, utilization of resources value maximization in realization, tool There are 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 " National Hazard waste Register ".

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

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 about aluminium ash in recent years Patent it is also in rising trend, but it is most of be in the experimental study stage, technology is confined to hot conditions and extracts metallic aluminium, preparation The inorganic material and steelmaking ingredient etc. such as aluminium oxide, aluminium chloride, aluminum sulfate, from industrialization, scale there are also with a certain distance from.

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 produces the water-purifying materials such as aluminium polychloride and aluminum sulfate, produces steel-making slag making desulfurizing agent, but because cost is than existing Also height, be 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 and actually answers With.There is the disadvantages of product purity is low, added value is low, waste secondary pollution in the application in terms of three above.The recycling of aluminium ash Waste after utilization still contains great amount of soluble salt and fluoride or dangerous waste, can only fill or store up, environmental hazard There is no reductions.

Due to containing high temperature resistants, corrosion resistance, the toxics such as a certain amount of villaumite (NaCl, KCl etc.) and fluoride in aluminium ash Etc. components, conventional method be difficult to realize the recycling of full ingredient, increase the cost and technical difficulty of aluminium ash recycling so that The Industrialization Progress of aluminium ash processing is slow.In addition, for the Transport And Transformation of the harmful elements such as aluminium ash treatment process fluorine and heavy metal Mechanism 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, makes full use of the various composition in aluminium ash, carry out harmless treatment, resource maximizationization It utilizes.This work is very urgent, needs specific direction, standard guidance, multiparty collaboration, strives obtaining real-time breakthrough early.

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 resource of waste residue 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 And patent, such as the Crystalfix chemical recovery system of Italy, but because process is complicated, comprehensive benefit is not high, practical application Seldom.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 stews mould The waste residue that liquid generates just accounts for 28% or so of the total quantity of slag of enterprise.Enterprise not only without recycle stew mould liquid in sodium ion, The useful resources such as 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-oxygen Change aluminium particle size compared with thin, economic value is low.In addition, aluminium ion is maintained at low concentration (being less than 30g/L) by crystallization, type is easily caused The defects of material coarse-grain, coarse sand, excessive erosion, and aluminium consumption is too high.Crystallization is run to equipment and technique is more demanding, and management is bad just Fouling can be precipitated, can only stop production manual cleaning at this time, take time and effort.There is a small amount of producer to come into operation online soda recovery unit, because returning It receives ineffective, at high cost, has given it up mostly.It joined corrosion inhibiter, the alkaline etching tank liquor of complexing agent is not suitable for alkali collection dress It sets, 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, film quality variation, power consumption with the increase of output It increases, but considers reagent cost and environmental protection pressure, aluminium ion concentration general control is in the area 15-20g/L in enterprise practical production Between.After reaching the upper limit, it is necessary to reduce aluminium composition.Reducing aluminum ions usual way is to exhaust half tank liquor, supplements sulfuric acid After continue to produce.This method is simple, but has the disadvantage that first is that have lost sulfuric acid, wastes aluminium ion, sulfuric acid consumption reaches 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.Sulfuric acid Recycling machine is aluminum ions stabilising arrangement, reaches recycling sulfuric acid using diffusion dialysis amberplex, removes aluminum ions purpose. 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 on retrieval of sulfuric acid machine Bad using effect is stated, most of aluminium processing enterprise gradually deactivates the device, restored the tradition of the oxidation of falling half tank liquor 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 spray coating Firm connection is together.For the quality for guaranteeing conversion film, process control needs are very strict, and exceeded tank liquor and rinse water are necessary It exhausts.Waste water contains a large amount of Cr VI, fluotitanic acid, fluorine zirconic acid root and fluorine ion in acidity.A large amount of waste acid treatment both increased Entreprise cost, and resource is wasted, also there is environmental hazard.Spraying pretreatment and wastewater processing technology are in progress without obvious, It still uses conventional methods, neutralizes, precipitates, forming a large amount of waste residues after filter-press dehydration.Waste residue belongs to the hazardous waste strictly managed, Qualified third party must be transferred to 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 is as shown in Figure 7.

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 condensed waters of generation, Effect is 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, and reaction generates hydrogen Nickel oxide precipitates, and obtains nickel slag 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, and all kinds of electronic product casings, high-speed rail interior decoration, bathroom are set It is standby etc., it 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 polishing of every production Material consumes three acid 250-350Kg with subsequent rinse bath and is discharged into waste water center.This extensive production method harm is huge Greatly, 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 quite Big 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 are huge Greatly, cost should not be overlooked；Container for evaporation corrosion is too fast, every two years needs replacing once, investment is too many.Three acid recovery actual motions In, 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, most of aluminium 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, obtain Certain effect.Aluminum current processing industry waste water still generallys use neutralization adjusting and coagulant sedimentation processing, and process flow is: Acidic and alkaline waste water neutralizes mutually, adjusts pH to neutrality, cation A l³⁺It is precipitated etc. hydroxide is formed.The waste water of neutralized precipitating is beaten Enter in coagulation tank, flocculant PAC, PAM is added, precipitation tank, standard emission of clear or reuse is entered after flocculation, water-containing sludge is through pressing Aluminiferous waste slag is formed after filter filters pressing.Waste residue moisture content 80% or so, quantity is very big, waste water and dregs process flow such as Fig. 9 institute Show.

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, based on 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 ", " the Chinese people are total With state's Law on Environmental Protection " it is implemented on January 1st, 2018, impose effluent charge.Waste water by 1.4-14 member/T, waste residue by 1000 yuan/ T, dangerous waste is paid taxes by 2000 yuan/T.Whole industry waste water pay taxes 22.5 hundred million yuan, waste residue pay taxes 1,500,000,000 yuan, dangerous waste pays taxes 3,000,000,000 yuan.

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.It recycles Status is very undesirable, preceding to have addressed, and middle salinity water value is much higher than seawater, is unable to reuse；Waste residue ingredient is excessively complicated, comprehensive benefit Approach and method are 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) it closes At the ceramics such as mullite, cordierite, preparing ceramic clinker, artificial resin marble or refractory material；(3) water-purifying material, such as aluminium are produced Sour calcium, aluminium polychloride (iron), polyaluminium sulfate etc.；(4) chemical products such as aluminium hydroxide, ammonia-alum are produced in reaction, such as China Patent CN 1350065A discloses a kind of method using alkaline residue extracting sulfuric acid aluminium ammonium, aluminum sulfate, aluminium hydroxide, Chinese patent 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 answered Shuo Jia producer is practical With 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 application With 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.The overwhelming majority 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 one of aluminum material factory Scald one's hand 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.It has no There is the open source information of nickel slag resource utilization.Chromium slag, nickel slag common practice are to go to the third-party institution to carry out at innoxious burial Reason.

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 before becoming Program is set, the big mixed sludge of yield is caused, increases huge technical difficulty for subsequent processing；Third is that the comprehensive utilization of waste residue at Less, Solid state fermentation becomes enterprise can't bear the financial burden born and environmentally friendly risk to effect.

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 useless Slag 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, cost Height, recovery utilization rate are low, have not only caused a large amount of wastes of resource, but also seriously pollute environment.Therefore for aluminium processing industry, waste water zero Discharge and the research and development of resource comprehensive utilization technology and popularization and application have bright prospects and huge environmental benefit, society to imitate 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, and 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 maximizes.

Summary of the invention

It is an object of the invention to propose the on-line system of a kind of single nickel salt coloring recycling hole sealing agent and Waste water utilization, utilize On-line system configuration recycles nickel-containing waste water waste residue, and coloring water for cleaning is collected in retention, and recycling is converted to sealing of hole medicament, Water in recycling is converted to N-P compound liquid fertilizer, blocks pollution of the nickel-containing waste water to wastewater treatment center, reduces industry Dangerous waste.

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

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

The on-line system of single nickel salt coloring recycling hole sealing agent and Waste water utilization, successively includes nickel-containing waste water from upstream to downstream Retain unit, nickel-containing waste water collector unit, nickel hydroxide recovery unit, nickel phosphate recovery unit and N-P compound fertilizer recovery unit；

Nickel-containing waste water retention unit include the 13# single nickel salt coloring slot being arranged in order, 14# flowing pure water rinse bath and 15# flows pure water rinse bath；The 14# flowing pure water rinse bath and 15# flowing pure water rinse bath differential concatenation setting, it is described 15# flows the external tap water of water inlet of pure water rinse bath, and the water outlet of the 14# flowing pure water rinse bath is connected to described contain Nickel waste water collector unit；

The nickel-containing waste water collector unit includes coloring nickel-containing waste water collecting tank and pump 1；The coloring nickel-containing waste water is collected Tank is used to collect the coloring nickel-containing waste water from 14# flowing pure water rinse bath；It is described pump 1 for incite somebody to action coloring nickel-containing waste water It is pumped into the coloring 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 nickel-containing waste water；It is described pump 3 for recycle in nickel hydroxide recycling can Color nickel-containing waste water, and the primary reaction liquid pump after reaction is entered in 1# filter press；The ammonia tank is used to return to nickel hydroxide Liquefied ammonia is added in closed cans, is reacted with coloring nickel-containing waste water and obtains primary reaction liquid；The 1# filter press is for separating primary reaction The first filtrate of solid-state nickel hydroxide and liquid in 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 used for the first filtrate in recycled phosphoric acid nickel recycling can, and will be after reaction Secondary reaction liquid pump enter in 2# filter press；The phosphoric acid tank is for being added phosphoric acid into nickel phosphate recycling can, with the first filtrate Reaction obtains secondary reaction liquid；The 2# filter press is used to separate solid-state nickel phosphate and the filter of liquid second in secondary reaction liquid Liquid；

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 for It filters the second filtrate and obtains liquid N-P compound fertilizer.

The present invention proposes the on-line system of a kind of single nickel salt coloring recycling hole sealing agent and Waste water utilization, provides a kind of completely new On-line system configuration, recycle nickel-containing waste water waste residue configured using online classification recovery method by above system, cut Collection coloring water for cleaning is stayed, recycling is converted to sealing of hole medicament, water in recycling, wherein can recycle nickel hydroxide 7.5 ten thousand Ton, is converted to medium temperature hole sealing agent；24,000,000 tons of water during treated is recycled, N-P compound liquid fertilizer is converted to, is used for factory The fertilising of area's land use for greening, makes the effective recycling of coloring water, blocks pollution of the nickel-containing waste water to wastewater treatment center, reduces Industrial dangerous waste discharge realizes that the resource recycling of toxic waste utilizes.

In addition, the present invention is retained by nickel-containing waste water individually sets the pH value control that 15# flows pure water rinse bath in unit Index precisely adjusts the water inlet flow of 15# flowing pure water rinse bath, reduces coloring cleaning water consumption；Make to be flowed by 14# pure The nickel-containing waste water of water rinse bath and 15# flowing pure water rinse bath retention, concentrates 14# slot slot bottom water outlet to flow into coloring Nickel-bearing Waste Water collecting tank, it is more simple that nickel-containing waste water retains cellular construction, effectively realize more rapidly, it is steadily online, individually handle these Nickel-containing waste water avoids after being mixed with other processes with water, reprocesses the trouble of magnanimity nickel-containing waste water, processing Nickel-bearing Waste is greatly reduced The environmentally friendly cost of water waste residue.

It further illustrates, in the nickel-containing waste water retention unit, the pipe of the 15# flowing external tap water of pure water rinse bath Road is equipped with valve 14, and the water outlet of the 15# flowing pure water rinse bath is connect with the water inlet of 14# flowing pure water rinse bath Pipeline be equipped with one-way valve 15.

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；The water outlet of the coloring nickel-containing waste water collecting tank and the water inlet of the pump 2 connect The pipeline connect is equipped with valve 2.

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

It further illustrates, in the nickel phosphate recovery unit, the water outlet of the water outlet, phosphoric acid tank of the nickel phosphate recycling can Mouthful, between the water inlet of pump 4 by tee tube connection, and the tee tube is connected with the water outlet of the nickel phosphate recycling can One end be equipped with valve 8, one end that the tee tube connect with the water outlet of the phosphoric acid tank is equipped with valve 9；The water outlet of the pump 4 The pipeline connecting with the water inlet of the nickel phosphate recovery unit is equipped with valve 10；The water outlet of the pump 4 and 2# filter press The pipeline of water inlet connection 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.

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

Step 1: operation nickel-containing waste water retains unit: opening valve 14, cleaning tap water flows pure water rinse bath stream by 15# Into through one-way valve 15, differential concatenation is flow in 14# flowing pure water rinse bath, and going out from the slot bottom of 14# flowing pure water rinse bath Mouth of a river outflow；

By aluminium after 13# single nickel salt coloring slot coloring 0.5-15min, rises and hang drip 30s, it is clear into 14# flowing pure water 1min is cleaned in washing trough, is risen and is hung drip 30s, is flowed pure water rinse bath into 15#, is cleaned 1min, rise and hang drip 30s, completes coloring With washing；When cleaning after colouring aluminium, the coloring liquid containing nickel sulfate, boric acid is retained in 14# flowing pure water rinse bath and 15# It flows in pure water rinse bath；Meanwhile the flow of the valve 14 of the water inlet of 15# flowing pure water rinse bath is adjusted, control the 15# stream PH value in dynamic pure water rinse bath is between 5.5-6.5；

Step 2: collecting nickel-containing waste water, opens valve 1, opens pump 1, and the slot bottom water outlet of 14# flowing pure water rinse bath is arranged Coloring nickel-containing waste water out is pumped into coloring nickel-containing waste water collecting tank；

Step 3: recycling nickel hydroxide opens valve 2, valve 3, closes valve 4, opens pump 2, and coloring 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 4: 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, opening valve 11 closes valve 10, is separated by solid-liquid separation secondary reaction liquid, sprays, is rinsed admittedly repeatedly 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 5: 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 delivered to land use for greening, uses as N-P compound fertilizer.

It further illustrates, in step 3, 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, vinegar The weight ratio of sour nickel/isobutanol=10 adds triethanolamine and isobutanol respectively, is converted to liquid acetic acid nickel solution in liquid Warm hole sealing agent.

Wherein, the acetic acid additive amount is 95% of addition weight needed for chemical reaction completely, and nickel hydroxide is excessive, makes to mix Close pH value >=6.0 of liquid；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 it recycles Solid-state nickel hydroxide only rinse, do not dry, be added into after pure water directly and acetic acid reaction, substantially save the baking of nickel hydroxide Dry cost；After the liquid acetic acid nickel solution of acquisition is filtered simultaneously, its filter residue is resided in reaction vessel, as nickel hydroxide Raw material, waiting convert next time.

In addition, the content of liquid nickel acetate is titrated first, further 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 medium temperature hole sealing agent, and And the liquid medium temperature hole sealing agent not condensing crystallizing, it can be added directly into 16# medium temperature sealing of hole slot, meet aluminium alloy sealing quality and want It asks, substantially saves crystallization, the separation, drying cost of medium temperature hole sealing agent.

It further illustrates, in step 4, 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 cleaning Sewage treatment Online Processing System to the present invention for the first time, utilizes online classification recycling side Method is configured by above system, and coloring water for cleaning is collected in retention, is recycled nickel hydroxide, is converted to medium temperature hole sealing agent；Recycling benefit With treated, middle water, is converted to N-P compound liquid fertilizer, blocks pollution of the nickel-containing waste water to wastewater treatment center, reduces work The discharge of industry dangerous waste realizes that the resource recycling of toxic waste utilizes.

2, the pH value control that the present invention flows pure water rinse bath by individually setting 15# in nickel-containing waste water retention unit refers to Mark precisely adjusts the water inlet flow of 15# flowing pure water rinse bath, reduces coloring cleaning water consumption；Make to flow pure water by 14# The nickel-containing waste water of rinse bath and 15# flowing pure water rinse bath retention, concentrates 14# slot slot bottom water outlet to flow into coloring nickel-containing waste water Collecting tank, it is more simple that nickel-containing waste water retains cellular construction, effectively realize more rapidly, it is steadily online, individually handle these and contain Nickel waste water avoids after being mixed with other processes with water, reprocesses the trouble of magnanimity nickel-containing waste water, processing nickel-containing waste water is greatly reduced The environmentally friendly cost of waste residue；

3, 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；

4, 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；

5, the present invention adds three second according to nickel acetate/triethanolamine=10, nickel acetate/isobutanol=10 weight ratio for the first time Nickel acetate solution is converted to liquid medium temperature hole sealing agent, directly inserts medium temperature sealing of hole slot by hydramine and isobutanol, meets aluminium alloy envelope Hole quality requirement；

6, 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 It adjusts to 6.5-7.5, converts remnants Ni²⁺For nickel phosphate；Remaining phosphoric acid nickel concentration be 5 multiplied by 10 minus 31 power, filtrate is much Reach recycling and uses standard；Nickel phosphate is filtered again, and rinsing, drying obtain nickel phosphate product；Filter residue is nickel phosphate, is resided in anti- Container is answered, waiting is recycled next time；

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

8, 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；

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

10, 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 15# and flows pure water rinse bath water inlet flow, be further reduced containing for 14# flowing pure water rinse bath slot bottom water outlet recycling Nickel 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 signal of the single nickel salt coloring recycling hole sealing agent of one implementation of the present invention and the on-line system of Waste water utilization Figure；

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 material accounts for 8,000,000 tons or more, and aluminium processing industry generates toxic useless The nickeliferous toxic waste residue that the big source of slag one, i.e. heat-tinting generate, such waste residue Zhan Lv processing enterprise are surface-treated waste residue total amount 5%, about 7.5 ten thousand tons, while it is nickeliferous with water to be related to about 24,000,000 tons, therefore waste water and dregs problem is very prominent！

Wherein, heat tinting process process is as shown in Figure 3, and 1#, 4#, 7#, 10#, 13#, 16# slot are work nest, Mei Gegong Make slot with two flowing rinsing bowls, oxidation processes need 18 slot positions, and wherein 13# is single nickel salt coloring slot, sulfur acid nickel, thereafter Continuous 14,15# flowing rinsing bowl takes nickel-containing waste water out of and enters wastewater treatment center, and 2.25 hundred million tons of pollution whole industry water generates 150 Ten thousand tons of toxic waste residues of nickeliferous mixing.The present invention relates to 13#-15# slot, retention collects 24,000,000 tons of nickeliferous colorings and cleans use Water individually recycles nickel-contained waste slag, is converted into hole sealing agent, realizes the zero-emission of nickel-containing waste water waste residue.13#-15# function is as follows:

13# single nickel salt colours slot

The purpose that this slot is arranged is to improve the dicoration of aluminium alloy for the colouring of oxidizing film.Single nickel salt color control refer to It is designated as:

Nickel sulfate 140-160g/L

Boric acid 40-60g/L (1)

pH 3.5-4.5

20-25 DEG C of temperature

Time 30s-15min

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

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 nickeliferous Waste water increases environmental protection treatment pressure.

Through last 100 years application, the drawbacks of heat-tinting, is completely exposed already.Especially emphasize today that cleaning is carried out production strictly in line with rules and regulations, Oxidation line 13-15# 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# is nickeliferous tank liquor, is directly entered 14#, 15# bis- after aluminium coloring and flows rinsing bowl, will Nickel-containing waste water brings waste water center into, pollutes the water for cleaning of whole oxidation line other processes；After mixing, these Nickel-bearing Wastes are reprocessed Water, and qualified discharge, difficulty as one can imagine, cost is surprising.This mode can be recycled there is an urgent need to improve with online classification, single It stays alone reason, replaces traditional mixed processing mode, reduce environmentally friendly cost；

2, it is useless to handle nickel-containing waste water from the angle of recycling for the passive processing waste water and dregs theory for needing abandoning tradition Slag, change dangerous waste are valuable chemical resource, and processing cost is both greatly reduced, and realize that nickeliferous chemical products are worth the maximum utilized Change.Prior art design theory is unreasonable, and 13# is nickeliferous tank liquor, and the flowing washing of 14#, 15# bis- is directly entered after aluminium sealing of hole Slot brings nickel-containing waste water into waste water center, pollutes the water for cleaning of whole oxidation line other processes；Waste water center is to these waste water It neutralized, precipitated, filters pressing, obtaining nickeliferous solid slag；Meanwhile nickel hydroxide 130mg/L is still remained in waste water, it is much higher than The discharge standard of 0.5mg/L；These magnanimity nickel-containing waste water waste residues, clear stipulaties are dangerous waste for State Ministry of Environmental Protection；Handle these High environmentally friendly cost is paid in nickeliferous dangerous waste, enterprise and society need, while wasting valuable nickel resources.This extensive production Mode can configure special equipment, actively recycle nickeliferous product online, turn waste into wealth there is an urgent need to improve, and realize dangerous waste recycling It utilizes；

3, it presses 2010 " Cu, Ni and Co emission of industrial pollutants standard " (GB25467-2010), the discharge standard of nickel-containing waste water For total nickel content 0.5mg/L.Reach the discharge standard of 0.5mg/L, itself there is sizable processing difficulty, if by coloring water It is reprocessed after being mixed with other processes with water, processing difficulty can infinitely amplify, and processing cost is significantly increased；Meanwhile by Fig. 9, The nickel-contained waste slag of color 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# slot, individually handles these Nickel-bearing Wastes Water recycles nickel, is converted to hole sealing agent, reuse into 16# medium temperature sealing of hole slot；Water in recycling, by coloring process water and waste water Center is completely isolated.

Modern aluminum processing enterprise, the nickel-containing waste water waste residue for having heat-tinting to generate is in need of immediate treatment, and traditional water for cleaning The method reprocessed after big mixing is too simple, generates the nickel-containing waste water waste residue of magnanimity, to handle these waste water and dregs, and society will Expensive environmentally friendly cost is paid thus, and there is an urgent need to develop new technologies, and individually processing colours process nickel-containing waste water.

The on-line system and method for single nickel salt coloring recycling hole sealing agent and Waste water utilization proposed by the present invention, are sufficiently to recognize The production of Shi Lv processing enterprise is puzzled, is researched and developed for many years, big to existing aluminium processing enterprise waste water and dregs amount, environmental protection pressure is huge Coloring treatment process, 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 water for cleaning retains collection method

1) rinsing bowl individually retains after colouring.By Fig. 3 and (1) formula, tap water is cleaned from 15# into differential concatenation to 14# Slot is flowed out from 14# slot.Slot is coloured after aluminium is by 30s-15min coloring by (1) formula control 13# single nickel salt to rise and hang drip 30s, Rinsing bowl is flowed into 14#, cleans 1min, rises and hangs drip 30s, rinsing bowl is flowed into 15#, cleans 1min, rise and hang drip 30s completes coloring and washing process into sealing of hole slot.When being cleaned after aluminium coloring, nickel sulfate and boric acid band contained by coloring liquid Enter 14#, 15# flowing rinsing bowl, pollutes the water for cleaning of flowing；13# single nickel salt colour slot pH 3.5-4.5,15# slot into The pH value at the mouth of a river is 6.0-7.0, therefore 14#, 15# slot pH value < 7.0, this section nickel sulfate and boric acid are stablized, and do not decompose, can retain In 14#, 15# rinse bath (equipped with nickel reclaimer, nickel content can be further decreased in trapped fluid for most of producer)；

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

By Fig. 3,15# slot inlet valve is adjusted, it is clear by the control coloring of (2) formula under conditions of ensuring to colour cleaning quality Wash water dosage, the nickeliferous water for cleaning for collecting outflow from 14# slot slot bottom water outlet are spare to reactor tank.Wherein, the control of 14# slot Index is 0.3-0.6g/L, boric acid 0.1-0.2g/L and pH 5.0-6.5.

Two, 13# single nickel salt coloring ejected wash water collects production hole sealing agent and middle water recycles quantitative and qualitative analysis

1) the recovered liquid 1L of reactor tank, sulfur acid nickel and boric acid, test agents concentration are taken are as follows:

Nickel sulfate 0.3g/L

Boric acid 0.1g/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, and takes pH8.5- 9.0 be reaction end；

2) ammonium sulfate and ammonium borate do not precipitate, and retain in liquid.By (3) formula, with the addition of liquefied ammonia, pH is constantly risen Height presses (4) formula, Ni²⁺Constantly reaction generates Ni (OH)₂But ammonium sulfate and ammonium borate do not decompose, and do not precipitate, and retain in liquid；

3) it is separated by solid-liquid separation, separates ammonium sulfate and ammonium borate with filtrate, recycle solid nickel hydroxide.By (4) formula, reaction is produced Object is separated by solid-liquid separation.Ammonium sulfate and ammonium borate are flowed out with filtrate, obtain solid nickel hydroxide；It rinsed, dried, met The technical grade nickel hydroxide product of national standard；Nickel hydroxide solubility 130mg/L in filtrate, the discharge much higher than 0.5mg/L Standard needs secondary treatment, up to standard can recycle；

4) nickel hydroxide is converted, reaction generates nickel acetate.The nickel hydroxide product obtained after rinsing drying is weighed, is added pure Water-wet profit, being slowly added concentration is 98% acetic acid, is reacted 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.By vinegar Sour nickel 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 add 132.1 × 95%=125.5g of acetic acid on the rocks 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 nickel acetate Saturated crystallization is precipitated；By 95% addition of acetic acid additive amount, nickel hydroxide is excessive, i.e., beaker bottom has a small amount of hydrogen after the reaction was completed Nickel oxide solid residue, can ensure that the pH proximity values 6.28 of nickel acetate solution, and pH >=6.0 meet medium temperature hole sealing agent pH greater than 5.5 Sealing quality requirement；Remaining filter residue is the nickel hydroxide solid not reacted completely, is resided in reactor, and waiting turns next time Change；

5) hole sealing agent is produced, realizes that useless nickel resourcesization utilize.It due to the nickel acetate liquid that (5) formula obtains, is washed from 14# The nickeliferous waste liquid of slot recycling, which reacts, to be generated, and after the ammonium sulfate 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；In view of 16# The working index of slot is pH5.5-6.5, and the nickel acetate of (5) formula recycling has met pH value requirement；When sealing of hole, 50-60 DEG C of temperature, have A large amount of water evaporation, liquor of hole- sealing tank position shoal, by (6) formula production liquid hole sealing agent addition when, just supplement drug concentration and Liquid level saves the cost of manufacture of the nickel acetate condensing crystallizing of (5) formula recycling；In addition, the nickel hydroxide of (4) formula recycling, rinsing are dry It is net, it 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) the filtrate sulfur-bearing of formula Sour ammonium and ammonium borate, while 130mg/L containing nickel hydroxide need to be reduced to 0.5mg/L or less；Concentration is added in filtrate is 85wt.% phosphoric acid adjusts pH value 8.5-9.0 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；Phosphorus is filtered again Sour nickel, rinsing, drying, obtains nickel phosphate product；Filtrate is the N-P compound fertilizer of phosphoric acid ammonium, ammonium sulfate and ammonium borate, as plant area Fertilizer application is afforested, 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 sealing of hole of the medium temperature hole sealing agent by the production of (6) formula respectively 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, when sealing of hole Between be 15 minutes, by ISO3210 international standard detection sealing quality, 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, envelope The 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 analysis of experimental results that 13# single nickel salt coloring water for cleaning remanufacture hole sealing agent and middle water recycle

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 water for cleaning online；15# slot flow of inlet water is adjusted, 14# slot slot bottom water outlet collects nickel-containing waste water, 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 sealing of hole slot；Sealing of hole slot is medium temperature Sealing of hole has certain evaporation capacity, and liquid hole sealing agent just supplements drug concentration and liquid level, saves drying nickel hydroxide, evaporation knot The trouble of brilliant 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, adds phosphoric acid, conversion remnants Ni2+ is 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 the N-P compound fertilizer of phosphoric acid ammonium, ammonium sulfate and ammonium borate, afforests fertilizer as plant area Material uses, and realizes that coloring is recycled with water；Filter residue is nickel phosphate, is resided in reaction vessel, and waiting is recycled next time.

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

It is practical in conjunction with heat-tinting quantity-produced by formula (1)-(7) and experiment 1-4 and testing result, single nickel salt coloring It recycles hole sealing agent and Waste water utilization method and configuration 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 5 big systems:

The on-line system of single nickel salt coloring recycling hole sealing agent and Waste water utilization of the present invention, successively includes containing from upstream to downstream Nickel waste water retains unit, nickel-containing waste water collector unit, nickel hydroxide recovery unit, nickel phosphate recovery unit and N-P compound fertilizer and returns Receive unit；

Nickel-containing waste water retention unit include the 13# single nickel salt coloring slot being arranged in order, 14# flowing pure water rinse bath and 15# flows pure water rinse bath；The 14# flowing pure water rinse bath and 15# flowing pure water rinse bath differential concatenation setting, it is described 15# flows the external tap water of water inlet of pure water rinse bath, and the water outlet of the 14# flowing pure water rinse bath is connected to described contain Nickel waste water collector unit；

The nickel-containing waste water collector unit includes coloring nickel-containing waste water collecting tank and pump 1；The coloring nickel-containing waste water is collected Tank is used to collect the coloring nickel-containing waste water from 14# flowing pure water rinse bath；It is described pump 1 for incite somebody to action coloring nickel-containing waste water It is pumped into the coloring 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 nickel-containing waste water；It is described pump 3 for recycle in nickel hydroxide recycling can Color nickel-containing waste water, and the primary reaction liquid pump after reaction is entered in 1# filter press；The ammonia tank is used to return to nickel hydroxide Liquefied ammonia is added in closed cans, is reacted with coloring nickel-containing waste water and obtains primary reaction liquid；The 1# filter press is for separating primary reaction The first filtrate of solid-state nickel hydroxide and liquid in 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 used for the first filtrate in recycled phosphoric acid nickel recycling can, and will be after reaction Secondary reaction liquid pump enter in 2# filter press；The phosphoric acid tank is for being added phosphoric acid into nickel phosphate recycling can, with the first filtrate Reaction obtains secondary reaction liquid；The 2# filter press is used to separate solid-state nickel phosphate and the filter of liquid second in secondary reaction liquid Liquid；

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 for It filters the second filtrate and obtains liquid N-P compound fertilizer.

It further illustrates, in the nickel-containing waste water retention unit, the pipe of the 15# flowing external tap water of pure water rinse bath Road is equipped with valve 14, and the water outlet of the 15# flowing pure water rinse bath is connect with the water inlet of 14# flowing pure water rinse bath Pipeline be equipped with one-way valve 15.

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；The water outlet of the coloring nickel-containing waste water collecting tank and the water inlet of the pump 2 connect The pipeline connect is equipped with valve 2.

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

It further illustrates, in the nickel phosphate recovery unit, the water outlet of the water outlet, phosphoric acid tank of the nickel phosphate recycling can Mouthful, between the water inlet of pump 4 by tee tube connection, and the tee tube is connected with the water outlet of the nickel phosphate recycling can One end be equipped with valve 8, one end that the tee tube connect with the water outlet of the phosphoric acid tank is equipped with valve 9；The water outlet of the pump 4 The pipeline connecting with the water inlet of the nickel phosphate recovery unit is equipped with valve 10；The water outlet of the pump 4 and 2# filter press The pipeline of water inlet connection 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.

The present invention utilizes online classification recovery method, configures by above system, and coloring water for cleaning, recycling are collected in retention 7.5 ten thousand tons of nickel hydroxide, it is converted to medium temperature hole sealing agent；24,000,000 tons of water during treated is recycled, N-P complex liquid is converted to Body fertilizer blocks pollution of the nickel-containing waste water to wastewater treatment center, reduces industrial dangerous waste discharge, realizes the resource of toxic waste Change recycles, and operation of the present invention process includes the following steps:

Step 1: operation nickel-containing waste water retains unit: opening valve 14, cleaning tap water flows pure water rinse bath stream by 15# Into through one-way valve 15, differential concatenation is flow in 14# flowing pure water rinse bath, and going out from the slot bottom of 14# flowing pure water rinse bath Mouth of a river outflow；

By aluminium after 13# single nickel salt coloring slot coloring 0.5-15min, rises and hang drip 30s, it is clear into 14# flowing pure water 1min is cleaned in washing trough, is risen and is hung drip 30s, is flowed pure water rinse bath into 15#, is cleaned 1min, rise and hang drip 30s, completes coloring With washing；When cleaning after colouring aluminium, the coloring liquid containing nickel sulfate, boric acid is retained in 14# flowing pure water rinse bath and 15# It flows in pure water rinse bath；Meanwhile the flow of the valve 14 of the water inlet of 15# flowing pure water rinse bath is adjusted, control the 15# stream PH value in dynamic pure water rinse bath is between 5.5-6.5；

Step 2: collecting nickel-containing waste water, opens valve 1, opens pump 1, and the slot bottom water outlet of 14# flowing pure water rinse bath is arranged Coloring nickel-containing waste water out is pumped into coloring nickel-containing waste water collecting tank；

Step 3: recycling nickel hydroxide opens valve 2, valve 3, closes valve 4, opens pump 2, and coloring 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 4: 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, opening valve 11 closes valve 10, is separated by solid-liquid separation secondary reaction liquid, sprays, is rinsed admittedly repeatedly 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 5: 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 delivered to land use for greening, uses as N-P compound fertilizer.

It further illustrates, in step 3, 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, vinegar The weight ratio of sour nickel/isobutanol=10 adds triethanolamine and isobutanol respectively, is converted to liquid acetic acid nickel solution in liquid Warm hole sealing agent.

It further illustrates, in step 4, 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.

Embodiment

Embodiment 1 (nickel-containing waste water retention system operatio)

Nickel-containing waste water retains system operatio process: opening valve 14, cleans tap water from 15# slot into through one-way valve 15, reversely It is connected serially to 14# slot, is flowed out from 14# slot slot bottom, through valve 1, pump 1, coloring nickel-containing waste water collecting tank is pumped into, completes nickel-containing waste water and cut It stays；Aluminium after 13# coloring, is risen by 30s-15min and hangs drip 30s, is flowed rinsing bowl into 14#, is cleaned 1min, rises and hang drip 30s flows rinsing bowl into 15#, cleans 1min, rises and hang drip 30s, into sealing of hole slot, completes coloring and washing process；Aluminium When cleaning after coloring, nickel sulfate contained by coloring liquid, boric acid are brought into, are retained in 14#, 15# flowing rinsing bowl；By 15# slot PH5.5-6.5, the flow of whole valve 14；When 15# slot pH value is between 5.5-6.5, fixed valve 14 completes nickel-containing waste water retention System operatio process；

Embodiment 2 (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 nickel-containing waste water is pumped into nickel-containing waste water collecting tank；Complete nickel-containing waste water collection system operating process；

Embodiment 3 (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-oxygen Change nickel 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, benefit With 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 8.5- When 9.0, valve 5 is closed, stops dosing, continues cycling through stirring 1 hour；1# filter press is opened, valve 7 is opened, closes valve 6,8, Gu Liquid separates nickel hydroxide；It sprays repeatedly, rinse nickel hydroxide solid after ten minutes, recycle nickel hydroxide product, complete hydroxide Nickel recovery system operating process；

Embodiment 4 (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；Add phosphoric acid, side in side The pH value for detecting reaction solution closes valve 9 when pH value reaches 6.5-7.5, stops dosing, continues cycling through stirring 1 hour；It opens 2# filter press is opened, valve 11 is opened, closes valve 10, is separated by solid-liquid separation nickel phosphate；It sprays repeatedly, rinse nickel phosphate solid after ten minutes, Nickel phosphate product is recycled, nickel phosphate recovery system operating process is completed；

Embodiment 5 (operation of N-P compound fertilizer recovery system)

N-P compound fertilizer recovery system operating process: opening valve 12,13, opens pump 5, after recovered liquid is filtered, 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 6 (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 required in the acetic acid weight of addition Under the conditions of weight 95%, nickel hydroxide are excessive, it is ensured that reacting liquid pH value >=6.0；In pure water weight/weight of nickel hydroxide=10 Under the conditions of, reaction solution acetic acid nickel content is 14.5-15.5wt.%, far below the saturated concentration of nickel acetate, it is ensured that reaction solution is without vinegar Sour nickel crystallization is precipitated；

Embodiment 7 (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 8 (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 of the 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, the technology of this field Personnel can associate with other specific embodiments of the invention without creative labor, these modes are fallen within Within protection scope of the present invention.

Claims (10)

1. the on-line system of single nickel salt coloring recycling hole sealing agent and Waste water utilization, it is characterised in that: successively wrapped from upstream to downstream It is compound to include nickel-containing waste water retention unit, nickel-containing waste water collector unit, nickel hydroxide recovery unit, nickel phosphate recovery unit and N-P Fertile recovery unit；

The nickel-containing waste water retention unit includes 13# single nickel salt coloring slot, 14# flowing pure water rinse bath and the 15# being arranged in order Flow pure water rinse bath；The 14# flowing pure water rinse bath and 15# flowing pure water rinse bath differential concatenation setting, the 15# stream The water outlet of the external tap water of water inlet of dynamic pure water rinse bath, the 14# flowing pure water rinse bath is connected to the Nickel-bearing Waste Water collector unit；

The nickel-containing waste water collector unit includes coloring nickel-containing waste water collecting tank and pump 1；The coloring nickel-containing waste water collecting tank is used In coloring nickel-containing waste water of the collection from 14# flowing pure water rinse bath；It is described pump 1 for incite somebody to action coloring nickel-containing waste water be pumped into In the coloring 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 nickel-containing waste water will be coloured；Coloring of the pump 3 for recycling in nickel hydroxide recycling can contains Nickel waste water, and the primary reaction liquid pump after reaction is entered in 1# filter press；The ammonia tank is used for nickel hydroxide recycling can Middle addition liquefied ammonia reacts with coloring nickel-containing waste water and obtains primary reaction liquid；The 1# filter press is for separating in primary reaction liquid The first filtrate of solid-state nickel hydroxide and 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 recycling hole sealing agent and Waste water utilization according to claim 1, it is characterised in that: In the nickel-containing waste water retention unit, the pipeline of the 15# flowing external tap water of pure water rinse bath is equipped with valve 14, described The pipeline that the water outlet of 15# flowing pure water rinse bath is connect with the water inlet of 14# flowing pure water rinse bath is equipped with single-pass Valve 15.

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

4. the on-line system of single nickel salt coloring recycling hole sealing agent and Waste water utilization according to claim 3, it is characterised in that: In the nickel hydroxide recovery unit, the pipeline that connect of water outlet of the water inlet of the nickel hydroxide recycling can and the pump 2 It 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 pass through three Siphunculus connection, and one end that the tee tube is connected with the water outlet of the nickel hydroxide recycling can is equipped with valve 4, the threeway One end of the water outlet of pipe and the ammonia tank is equipped with valve 5；The water outlet of the pump 3 and the water inlet of nickel hydroxide recycling can connect The pipeline connect 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 recycling hole sealing agent and Waste water utilization according to claim 4, it is characterised in that: In the nickel phosphate recovery unit, the water outlet of the nickel phosphate recycling can, phosphoric acid tank water outlet, pump between 4 water inlet It is connected by tee tube, and one end that the tee tube is connected with the water outlet of the nickel phosphate recycling can is equipped with valve 8, it is described One end that tee tube is connected with the water outlet of the phosphoric acid tank is equipped with valve 9；The water outlet of the pump 4 and nickel phosphate recycling are single The pipeline of the water inlet connection of member is equipped with valve 10；On the pipeline that the water outlet of the pump 4 is connect with the water inlet of 2# filter press Equipped with valve 11.

6. the on-line system of single nickel salt coloring recycling hole sealing agent and Waste water utilization according to claim 5, it is characterised in that: In N-P compound fertilizer recovery unit, it is arranged on the pipeline that the water outlet of compound fertilizer's recycling can is connect with the water inlet of the pump 5 There is 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 recycling hole sealing agent and Waste water utilization according to claim 6, it is characterised in that: The nickel hydroxide recycling can is internally provided with the stirring of 1# electricity, and the nickel phosphate recycling can is internally provided with the stirring of 2# electricity.

8. the recovery method of the on-line system of single nickel salt coloring recycling hole sealing agent as claimed in claim 7 and Waste water utilization, It is characterized in that: including the following steps:

Step 1: operation nickel-containing waste water retains unit: opening valve 14, cleaning tap water is flowed by 15# flowing pure water rinse bath, passed through One-way valve 15, differential concatenation are flow in 14# flowing pure water rinse bath, and the water outlet of the slot bottom from 14# flowing pure water rinse bath Outflow；

By aluminium after 13# single nickel salt coloring slot coloring 0.5-15min, rises and hangs drip 30s, flow pure water rinse bath into 14#, 1min is cleaned, rises and hangs drip 30s, pure water rinse bath is flowed into 15#, cleans 1min, rise and hang drip 30s, complete coloring and water It washes；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 In pure water rinse bath；Meanwhile the flow of the valve 14 of the water inlet of 15# flowing pure water rinse bath is adjusted, it is pure to control the 15# flowing PH value in water rinse bath is between 5.5-6.5；

Step 2: 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 nickel-containing waste water is pumped into coloring nickel-containing waste water collecting tank；

Step 3: recycling nickel hydroxide opens valve 2, valve 3, closes valve 4, opens pump 2, and coloring nickel-containing waste water is pumped into hydroxide Nickel 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 nickel hydroxide recycling can Middle addition liquefied ammonia, using the high speed rotation of pump 3, reaction generates primary reaction liquid；The pH of side liquid feeding ammonia frontier inspection survey primary reaction liquid Value closes valve 5 when pH value reaches 8.5-9.0, stops dosing, continues cycling through stirring 1h；1# filter press is opened, valve is opened 7, valve 6,8 is closed, primary reaction liquid is separated by solid-liquid separation, sprays repeatedly, rinse solid nickel hydroxide after ten minutes, recycle solid Nickel hydroxide；And the first filtrate of liquid is flowed into nickel phosphate recycling can；

Step 4: 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 5: 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 recovery method of the on-line system of single nickel salt coloring recycling hole sealing agent according to claim 8 and Waste water utilization, It is characterized by:, by the solid-state nickel hydroxide of recycling, pure water and acetic acid is added in step 3, precipitating is filtered, acquisition 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/different The weight ratio of butanol=10 adds triethanolamine and isobutanol respectively, liquid acetic acid nickel solution is made to be converted to liquid medium temperature sealing of hole Agent.

10. the recovery method of the on-line system of single nickel salt coloring recycling hole sealing agent according to claim 8 and Waste water utilization, It is characterized by: being separated by solid-liquid separation secondary reaction liquid in step 4, after receiving solid-state nickel phosphate, the liquid second of acquisition is filtered Contain ammonium phosphate, ammonium sulfate, ammonium borate, ammonium acetate, triethanolamine and isobutanol in liquid, pH value is used between 6.5-7.5 As N-P compound fertilizer.