CN109097807A

CN109097807A - The method of single nickel salt coloring recycling hole sealing agent and Waste water utilization

Info

Publication number: CN109097807A
Application number: CN201810843402.6A
Authority: CN
Inventors: 熊映明
Original assignee: FOSHAN SANSHUI XIONGYING INNOVATIVE CENTER FOR ALUMINUM SURFACE TECHNOLOGIES Co Ltd
Current assignee: FOSHAN SANSHUI XIONGYING INNOVATIVE CENTER FOR ALUMINUM SURFACE TECHNOLOGIES Co Ltd
Priority date: 2018-07-27
Filing date: 2018-07-27
Publication date: 2018-12-28

Abstract

The method of single nickel salt coloring recycling hole sealing agent and Waste water utilization, includes the following steps: that (1) retains nickeliferous cleaning waste water by retaining rinsing bowl online, is collected in nickeliferous cleaning waste water reaction tank；(2) liquefied ammonia is added, and at pH value 8.5-9.0, recycles Ni²⁺, it is separated by solid-liquid separation the first filtrate of solid nickel hydroxide and liquid；(3) pure water and acetic acid is added, precipitating, filtering obtain liquid acetic acid nickel solution；And liquid acetic acid nickel solution is converted to liquid medium temperature hole sealing agent；(4) phosphoric acid will be added in the first filtrate, and adjusts pH value to 6.5-7.5, convert remnants Ni²⁺For nickel phosphate, it is separated by solid-liquid separation the second filtrate of solid nickel phosphate and liquid；(5) by the pH value of the second filtrate between 6.5-7.5, for being used as N-P compound fertilizer；The present invention utilizes online classification recovery method, and nickeliferous cleaning waste water is collected in retention, and recycling is converted to sealing of hole medicament, and water in recycling blocks pollution of the nickel-containing waste water to wastewater treatment center, reduces industrial dangerous waste discharge.

Description

The method of 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 the sides of single nickel salt coloring recycling hole sealing agent and Waste water utilization Method.

Background technique

Aluminium alloy has many advantages, such as that processing performance is excellent, corrosion resistance is good, surface aesthetic, the rate of recovery are high, in building, traffic The industries such as transport, machinery, electric power are applied widely.In recent years, aluminium is for copper, aluminium generation wood, aluminium for steel, expansion aluminium application model The trend enclosed is more obvious.Aluminium processing industry is both conventional industries, is even more full of the rising industry of vitality.According to statistics, American-European Developed country consumes aluminium alloy 32kg or more year per capita, and China only has 13kg or so per capita, only the three of developed country/ One or so, there are also huge growth spaces for domestic aluminium alloy consumption.But aluminium processing industry energy consumption is high, total amount of pollutants discharged Greatly, the low common problem of resource recycling rate highlights to restrict the bottleneck and obstacle of industry development.

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

One, Aluminum waste residue source

1, electrolysis founding aluminium ash

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

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

2, compressive surface handles waste water and dregs

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

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

Extruding die for aluminum shaped material will be put into high-concentration alkali liquor after and carry out pot mould, and the reactive aluminum in die cavity is corroded Fall.The concentration for stewing sodium hydroxide in mould liquid reaches 200-300g/L, and with the progress of reaction, aluminium composition is constantly increased, when reaching When being substantially reduced to 60-70g/L or more, reaction speed, it must will just stew mould liquid and exhaust, as shown in Figure 2.In the waste liquid exhausted Containing a large amount of aluminium ion and sodium hydroxide, potential economic value is very big.The processing for stewing mould waste liquid is generally taken " with useless Control useless " mode, direct emission is into waste water center, the spent acid neutralisation treatment that generates with oxidation operation.This processing mode generates Waste residue amount it is very big, stew mould waste residue can account for 28% or so of the total quantity of slag of enterprise；Meanwhile a large amount of sodium ions enter waste water Center, water in pollution, a possibility that thoroughly breaking off Treated sewage reusing.This coarse processing mode of mould liquid is stewed, enterprise does not have not only Using its economic value, increase cost instead, waste water, waste residue are treated as heavy environmental burden.

2.2, surface treatment waste water waste residue

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

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

The waste water of waste water central collection, contains Al³⁺、Na⁺、NH₄ ⁺、Ni²⁺、Sn²⁺、Cr⁶⁺Equal cations, SO₄ ^2-、F^-、NO₃ ^-、 NO₂ ^-、S^2-、Cl^-, tartrate anion, glucose acid group, anion and the organic phenol, surfactant and acrylic acid such as acetate Organic matters such as resin etc..Acid waste water, alkaline waste water are usually to mix neutralisation treatment, and chromate waste water, nickel-containing waste water must be single It stays alone reason.Oxidation electrophoresis material ratio decline in recent years, but most of aluminum material factories or acid waste water are more than alkaline waste water, soda acid Water all mixes processing, in acidity after waste water mixing, needs to put into a large amount of piece alkali, lime and PAC, PAM, produces A large amount of waste residues.The useful resources such as a large amount of metallic aluminiums, acid, alkali in waste residue are not utilized, and cause the huge wasting of resources.It is useless Slag belongs to hazardous waste, has containing aluminium hydroxide, fluoride, sulfide, nickel salt, phenol, nitrate, nitrite etc. are a variety of Malicious harmful substance, environmental hazard is huge, can not fill, and has great environmental hazard.Waste water center processing is separated by solid-liquid separation Afterwards, middle water contain sodium ion, ammonium ion, sulfate radical, nitrate anion, nitrite anions, acetate, tartrate anion, thiosulfate anion, Chloride ion, sulphion, fluorine ion etc., can not reuse.Current Environmental Protection Situation forces enterprise to follow to energy-saving and emission-reduction and resource Ring utilization orientation Transformation Development, but lack the technology of mature and reliable.Water fully recovering, zero output of waste residue, resource benefit in realization With value maximization, there is great environmental benefit, Social benefit and economic benefit.

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

Two, Aluminum Solid state fermentation and utilize status

1, electrolysis founding aluminium ash handles and utilizes status

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

1.1, aluminium ash recycles

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

1.2, aluminium ash comprehensively utilizes

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

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

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

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

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

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

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

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

1.2, oxidation solution aluminium ion and retrieval of sulfuric acid

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

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

1.3, spraying pretreated waste water recycling

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

1.4, contain chromium and nickel-containing waste water

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

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

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

1.5, the recovery processing of polishing fluid

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

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

1.6, compressive surface handles waste water and dregs integrated treatment

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

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

2, compressive surface processing waste water and dregs comprehensive utilization

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

2.1, the comprehensive utilization of aluminium slag

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

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

2.2, chromium slag and nickel slag for comprehensive utilize

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

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

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

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

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

Three, Aluminum aluminium ash and aluminium slag minimizing recycling direction

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

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

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

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

Summary of the invention

It is an object of the invention to propose a kind of method of single nickel salt coloring recycling hole sealing agent and Waste water utilization, using Nickeliferous cleaning waste water is collected in line classified reclaiming method, retention, and recycling is converted to sealing of hole medicament, and water in recycling blocks nickeliferous Pollution of the waste water to wastewater treatment center reduces industrial dangerous waste discharge.

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

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

(1) nickeliferous cleaning waste water is retained by retaining rinsing bowl online, and be collected in nickeliferous cleaning waste water reaction tank；

(2) liquefied ammonia is added into nickel-containing waste water reactor tank, hybrid reaction generates primary reaction liquid, and in pH value 8.5-9.0 Under, recycle Ni²⁺, after separation of solid and liquid, recycle the first filtrate of solid nickel hydroxide and liquid；

(3) pure water and acetic acid will be added in the nickel hydroxide of recycling, precipitating, filtering obtain pH value >=6.0, nickel acetate contains Amount is lower than the liquid acetic acid nickel solution of saturation point；And according to nickel acetate/triethanolamine=10, nickel acetate/isobutanol=10 weight Ratio is measured, triethanolamine and isobutanol is added respectively, liquid acetic acid nickel solution is made to be converted to liquid medium temperature hole sealing agent；

(4) phosphoric acid will be added in the first filtrate of step (2), hybrid reaction generates secondary reaction liquid, and pH value is adjusted To 6.5-7.5, remnants Ni is converted²⁺For nickel phosphate, after separation of solid and liquid, the second filtrate of solid nickel phosphate and liquid is recycled；

(5) step (4) obtain the second filtrate in containing ammonium phosphate, ammonium sulfate, ammonium borate, ammonium acetate, triethanolamine and Isobutanol, pH value is between 6.5-7.5, for being used as N-P compound fertilizer.A kind of single nickel salt coloring recycling proposed by the present invention The method of hole sealing agent and Waste water utilization devises a kind of completely new technological design, that is, utilizes online classification recovery method, retention Nickeliferous cleaning waste water is collected, recycling is converted to sealing of hole medicament, and water in recycling blocks nickel-containing waste water to wastewater treatment center Pollution, reduce industrial dangerous waste discharge.Wherein, nickel hydroxide can be recycled up to 7.5 ten thousand tons, be effectively converted into medium temperature hole sealing agent； Recycling water during treated, up to 24,000,000 tons, be effectively converted into liquid N-P compound fertilizer makes for afforesting plant area vegetation The effective recycling of color water realizes that the resource recycling of toxic waste utilizes.

Wherein, in step (3), the content of liquid nickel acetate is titrated first, further according to nickel acetate/triethanolamine=10, vinegar The weight ratio of sour nickel/isobutanol=10 adds triethanolamine and isobutanol respectively, liquid acetic acid nickel solution is made to be converted to liquid Medium temperature hole sealing agent, and the liquid medium temperature hole sealing agent not condensing crystallizing, can be added directly into medium temperature sealing of hole slot, meet aluminium conjunction Golden sealing quality requirement, substantially saves crystallization, the separation, drying cost of medium temperature hole sealing agent.In step (4), due to remaining Ni²⁺ For phosphoric acid nickel concentration be 5 multiplied by 10 minus 31 power, therefore the first filtrate much reaches recycling using standard, by nickel phosphate mistake It filters, rinse, drying, nickel phosphate product can be obtained.

It further illustrates, the online retention rinsing bowl is by single nickel salt colouring function slot, the first flowing rinsing bowl and second Flow rinsing bowl composition；Two flowing rinsing bowls are located at behind the single nickel salt colouring function slot, and differential concatenation is arranged, Nickeliferous cleaning waste water are retained by two flowing rinsing bowls, and are collected to by the slot bottom water outlet of the first flowing rinsing bowl nickeliferous clear It washes in waste water reaction tank.

It further illustrates, controls the nickeliferous cleaning waste water in the second flowing rinsing bowl of the online retention rinsing bowl PH value flows into nickel-containing waste water reactor tank between 5.5-6.5, and through the first flowing rinsing bowl.By controlling second Index in dynamic rinsing bowl is pH value 5.5-6.5, and the stream of the water outlet of the first flowing rinsing bowl is further controlled according to the pH value Amount reduces the total amount of the nickeliferous cleaning waste water of the water outlet retention recycling of the first flowing rinsing bowl, reduces processing pressure, section About cost of investment.

It further illustrates, contains nickel sulfate, the single nickel salt colouring function in each slot of the online retention rinsing bowl The Con trolling index of the nickeliferous cleaning waste water of slot are as follows: nickel sulfate 140-160g/L, boric acid 40-60g/L, pH value 3.5-4.5, temperature 20-25 DEG C, coloration time 0.5-15min；

The Con trolling index of the nickeliferous cleaning waste water of the first flowing rinsing bowl are as follows: nickel sulfate 0.3-0.6g/L, boric acid 0.1-0.2g/L, pH value 5.0-6.5；

The Con trolling index of the nickeliferous cleaning waste water of the second flowing rinsing bowl are as follows: pH value 5.5-6.5.

It further illustrates, in step (3), after the liquid acetic acid nickel solution of acquisition is filtered, its filter residue is resided in into reaction In container, as nickel hydroxide starting material, the conversion of liquid acetic acid nickel next time is carried out.

It further illustrating, in step (3), the acetic acid additive amount is 95% of addition weight needed for chemical reaction completely, Nickel hydroxide is excessive, makes pH value >=6.0 of mixed liquor, and under conditions of pure water weight/weight of nickel hydroxide=10, vinegar The content of sour nickel makes liquid acetic nickel solution without nickel acetate knot for 14.5-15.5wt.% far below the saturated concentration of nickel acetate Partial crystallization goes out.

It further illustrates, in step (3), the solid-state nickel hydroxide of recycling is only rinsed, is not dried, pure water is added And acetic acid directly and acetic acid reaction generates liquid acetic acid nickel solution.The solid-state nickel hydroxide of recycling is only rinsed, and is not dried It is dry, liquid acetic acid nickel solution is directly obtained, to substantially save the drying cost of nickel hydroxide.

Beneficial effects of the present invention:

1, Con trolling index of the present invention according to the second flowing rinsing bowl setting, the water inlet of adjustment the second flowing rinsing bowl Flow reduces coloring cleaning water consumption；And by the nickel-containing waste water of the first, second flowing rinsing bowl retention, from the first circulating water The slot bottom water outlet of washing trough flows into nickeliferous cleaning waste water reaction tank, and effectively realization is online, individually handles these nickel-containing waste waters, keeps away Exempt from after being mixed with other processes with water, reprocess the trouble of magnanimity nickel-containing waste water, the ring of processing nickel-containing waste water waste residue is greatly reduced Guaranteed cost；

2, 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.

3, 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；

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

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

6, after when the present invention is converted to liquid acetic nickel using the nickel hydroxide of recycling, only rinsing, do not dry, adding pure water Directly and acetic acid reaction, the drying cost of nickel hydroxide is substantially saved；

7, 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；

8, 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；

9, the Con trolling index that the present invention sets the second flowing rinsing bowl for the first time controls second by pH value as pH value 5.5-6.5 Rinsing bowl water inlet flow is flowed, the nickel-containing waste water total amount of the water outlet recycling of the first flowing rinsing bowl slot bottom is reduced, at reduction Manage 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 heat tinting process flow chart；

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

Tu5Lv processing enterprise waste residue source pie chart；

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

The existing chromate waste water process flow of Fig. 7；

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

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

Specific embodiment

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

Aluminium processing industry generates the big source of toxic waste residue one, the i.e. nickeliferous toxic waste residue of heat-tinting generation, such waste residue The 5% of Zhan Lv processing enterprise surface treatment waste residue total amount, about 7.5 ten thousand tons, while being related to about 24,000,000 tons of nickeliferous water, 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, Subsequent 14,15#, which flows rinsing bowl and takes nickel-containing waste water out of, enters wastewater treatment center, and 2.25 hundred million tons of pollution whole industry water generates 1500000 tons of toxic waste residues of nickeliferous mixing.The present invention relates to 13#-15# slot, 24,000,000 tons of nickeliferous coloring cleanings are collected in retention With water, nickel-contained waste slag is individually recycled, 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:

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 washed with flowing pure water；In addition, heavy metal nickel, which may be put into, to be forbidden making 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 to contain Nickel waste water increases environmental protection treatment pressure.

Through last 100 years application, the drawbacks of heat-tinting, is completely exposed already.Especially emphasize the present that cleaning is carried out production strictly in line with rules and regulations It, 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, It brings nickel-containing waste water into waste water center, pollutes the water for cleaning of whole oxidation line other processes；After mixing, reprocesses these and contain Nickel waste water, and qualified discharge, difficulty as one can imagine, cost is surprising.This mode can be returned there is an urgent need to improve with online classification It receives, individually handles, replace traditional mixed processing mode, reduce environmentally friendly cost；

2, the passive processing waste water and dregs theory for needing abandoning tradition, handles nickel-containing waste water from the angle of recycling Waste residue, change dangerous waste are valuable chemical resource, and processing cost is both greatly reduced, and realize what nickeliferous chemical products value utilized It maximizes.Prior art design theory is unreasonable, and 13# is nickeliferous tank liquor, is directly entered bis- stream of 14#, 15# after aluminium sealing of hole Dynamic rinsing bowl, brings nickel-containing waste water into waste water center, pollutes the water for cleaning of whole oxidation line other processes；Waste water center pair These waste water are neutralized, are precipitated, filters pressing, obtain nickeliferous solid slag；Meanwhile it is useless

Still nickel hydroxide 130mg/L is remained in water, the discharge standard much higher than 0.5mg/L；These magnanimity nickel-containing waste waters Waste residue, clear stipulaties are dangerous waste for State Ministry of Environmental Protection；These nickeliferous dangerous wastes are handled, enterprise and society need are paid high Environmentally friendly cost, while wasting valuable nickel resources.This extensive production method can configure special equipment there is an urgent need to improve, Nickeliferous product is actively recycled online, is turned waste into wealth, realizes dangerous waste resource utilization；

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

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, society Expensive environmentally friendly cost will be paid thus, and there is an urgent need to develop new technologies, and individually processing colours process nickel-containing waste water.

The method of single nickel salt coloring recycling hole sealing agent and Waste water utilization proposed by the present invention is to fully realize aluminium processing The production of enterprise is puzzled, is researched and developed for many years, at, the huge coloring of environmental protection pressure big to existing aluminium processing enterprise waste water and dregs amount Science and engineering sequence, 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 contained by coloring liquid It brings 14#, 15# flowing rinsing bowl into, pollutes the water for cleaning of flowing；13# single nickel salt colours the pH 3.5-4.5,15# slot of slot The pH value of water inlet 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 cut (equipped with nickel reclaimer, nickel content can be further decreased in trapped fluid for most of producer) is stayed in 14#, 15# rinse bath；

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.

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:

It is slowly added liquefied ammonia, stirring while adding, pH value is stepped up, there is following variation:

When pH value is lower than 7.0, tank liquor is clear, no precipitating, no precipitate；

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

NH₃+H₂O=NH₄OH

Ni²⁺+2NH₄OH=2NH₄ ⁺+Ni(OH)₂↓ (4)

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

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

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

When pH is between 9.0-10.0, tank liquor is muddy, and green crystal precipitate nickel hydroxide is not further added by, takes PH8.5-9.0 is reaction end；

2) ammonium sulfate 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 In；

3) it is separated by solid-liquid separation, separates ammonium sulfate and ammonium borate with filtrate, recycle solid nickel hydroxide.By (4) formula, will react Product is separated by solid-liquid separation.Ammonium sulfate and ammonium borate are flowed out with filtrate, obtain solid nickel hydroxide；It rinsed, dried, obtained Meet the technical grade nickel hydroxide product of national standard；Nickel hydroxide solubility 130mg/L in filtrate, much higher than 0.5mg/L's Discharge 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 is wet, and being slowly added concentration is 98% acetic acid, reacts as follows:

Ni(OH)₂+2CH₃COOH

=Ni (CH₃COO)₂+2H₂O (5)

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

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

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

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

6) filtrate is handled, nickel phosphate is recycled, recycles coloring water for cleaning.By (4) formula, nickel hydroxide solubility 130mg/L, the discharge standard much higher than 0.5mg/L, needs secondary treatment, up to standard can recycle.(4) filtrate of formula contains Ammonium sulfate and ammonium borate, while 130mg/L containing nickel hydroxide need to be reduced to 0.5mg/L or less；Concentration is added in filtrate For 85wt.% phosphoric acid, pH value 8.5-9.0 is adjusted to 6.5-7.5, reaction are as follows:

3Ni²⁺+2H₃PO₄=(Ni)₃(PO₄)₂↓+6H²⁺ (7)

The solubility of nickel phosphate be 5 multiplied by 10 minus 31 power, filtrate much reaches recycling using standard；It filters again Nickel phosphate, rinsing, drying, obtains nickel phosphate product；Filtrate is the N-P compound fertilizer of phosphoric acid ammonium, ammonium sulfate and ammonium borate, as Plant area afforests Fertilizer application, realizes that coloring is recycled with water.

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

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

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

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

2, influence of the sealing of hole slot pH value to sealing quality.Taking nickel acetate 5g/L, (triethanolamine and isobutanol are dense for nickel acetate / 10th of degree, similarly hereinafter), 55 DEG C of temperature, pH4.5,5.0,5.5,6.0,6.5,7.0；Taking oxide thickness is 15 microns, The sealing of hole time is 15 minutes, detects sealing quality by ISO3210 international standard, as a result as 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, Nickel-containing waste water is collected in 14# slot slot bottom water outlet, controls nickel-containing waste water total amount to be processed；

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

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

4, (6) formula is pressed, nickel acetate solution is converted to liquid hole sealing agent, is added directly into 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 phosphoric acid Nickel, remaining phosphoric acid nickel concentration be 5 multiplied by 10 minus 31 power, filtrate much reaches recycling using standard；Phosphoric acid is filtered again 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；Filter residue is nickel phosphate, is resided in reaction vessel, and waiting is returned next time It receives.

The method of embodiment-single nickel salt coloring recycling hole sealing agent and Waste water utilization of the invention, includes the following steps:

(5) step (4) obtain the second filtrate in containing ammonium phosphate, ammonium sulfate, ammonium borate, ammonium acetate, triethanolamine and Isobutanol, pH value is between 6.5-7.5, for being used as N-P compound fertilizer.

Embodiment 1 (nickel-containing waste water retention is collected)

By the Con trolling index that (2) formula is set, 15# slot water inlet flow is adjusted, reduces coloring water for cleaning；Retention is collected 14, the nickel-containing waste water of 15# rinsing bowl is into spare in reactor tank, avoid in Fig. 3 with other mixed with water after reprocess these magnanimity The environmentally friendly cost of processing nickel-containing waste water is greatly reduced in the trouble of waste water；

Embodiment 2 (nickel-containing waste water processing, recycling nickel hydroxide)

Liquefied ammonia is added in reactor tank nickel-containing waste water, presses (4) formula, at pH value 8.5-9.0, recycles Ni2+, reaction generates Nickel hydroxide is separated by solid-liquid separation, and rinsing, drying must meet the nickel hydroxide product of national standard；It is spare to recycle filtrate；

Embodiment 3 (conversion nickel hydroxide, production nickel acetate solution)

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

Embodiment 4 (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 sealing of hole slot；During sealing of hole slot is Warm sealing of hole has certain evaporation capacity, and liquid hole sealing agent just supplements drug concentration and liquid level, saves drying nickel hydroxide, evaporation The trouble of Acetic Acid Glacil nickel solution substantially saves the cost of manufacture of hole sealing agent；

Embodiment 5 (with phosphoric acid handle in water, recycling nickel phosphate, water in recycling)

In the filtrate after nickel hydroxide separation of solid and liquid, (7) formula is pressed, phosphoric acid is added, by filtrate pH value by 8.5-9.0 tune It is whole to 6.5-7.5, conversion remnants Ni2+ is 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；Filtrate is phosphoric acid ammonium, ammonium sulfate With the N-P compound fertilizer of ammonium borate, Fertilizer application is afforested as plant area, realizes that coloring is recycled with water；

Embodiment 6 (the hole sealing agent ability to work of remanufacture detects)

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

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

Claims

1. the method for single nickel salt coloring recycling hole sealing agent and Waste water utilization, characterized by the following steps:

(2) liquefied ammonia is added into nickel-containing waste water reactor tank, hybrid reaction generates primary reaction liquid, and at pH value 8.5-9.0, returns Receive Ni²⁺, after separation of solid and liquid, recycle the first filtrate of solid nickel hydroxide and liquid；

(3) pure water and acetic acid will be added in the nickel hydroxide of recycling, precipitating, filtering, acquisition pH value >=6.0, acetic acid nickel content are low In the liquid acetic acid nickel solution of saturation point；And according to nickel acetate/triethanolamine=10, nickel acetate/isobutanol=10 weight ratio, Triethanolamine and isobutanol are added respectively, and liquid acetic acid nickel solution is made to be converted to liquid medium temperature hole sealing agent；

(4) will be added phosphoric acid in the first filtrate of step (2), hybrid reaction generates secondary reaction liquid, and by pH value adjust to 6.5-7.5 converts remnants Ni²⁺For nickel phosphate, after separation of solid and liquid, the second filtrate of solid nickel phosphate and liquid is recycled；

(5) contain ammonium phosphate, ammonium sulfate, ammonium borate, ammonium acetate, triethanolamine and isobutyl in the second filtrate that step (4) obtains Alcohol, pH value is between 6.5-7.5, for being used as N-P compound fertilizer.

2. the method for single nickel salt coloring recycling hole sealing agent and Waste water utilization according to claim 1, it is characterised in that: described Online retention rinsing bowl is made of single nickel salt colouring function slot, the first flowing rinsing bowl and the second flowing rinsing bowl；Two flowings Rinsing bowl is located at behind the single nickel salt colouring function slot, and differential concatenation is arranged, nickeliferous by two flowing rinsing bowl retentions Waste water is cleaned, and is collected in nickeliferous cleaning waste water reaction tank by the slot bottom water outlet of the first flowing rinsing bowl.

3. the method for single nickel salt coloring recycling hole sealing agent and Waste water utilization according to claim 2, it is characterised in that: control The pH value of nickeliferous cleaning waste water in second flowing rinsing bowl of the online retention rinsing bowl passes through between 5.5-6.5 First flowing rinsing bowl flows into nickel-containing waste water reactor tank.

4. the method for single nickel salt coloring recycling hole sealing agent and Waste water utilization according to claim 3, it is characterised in that: described Contain nickel sulfate in each slot of online retention rinsing bowl, the control of the nickeliferous cleaning waste water of the single nickel salt colouring function slot refers to It is designated as: nickel sulfate 140-160g/L, boric acid 40-60g/L, pH value 3.5-4.5, temperature 20-25, DEG C coloration time 0.5-15min；

The Con trolling index of the nickeliferous cleaning waste water of the first flowing rinsing bowl are as follows: nickel sulfate 0.3-0.6g/L, boric acid 0.1- 0.2g/L, pH value 5.0-6.5；

5. the method for single nickel salt coloring recycling hole sealing agent and Waste water utilization according to claim 1, it is characterised in that: step (3) in, after the liquid acetic acid nickel solution of acquisition is filtered, its filter residue is resided in reaction vessel, as nickel hydroxide starting material, Carry out the conversion of liquid acetic acid nickel next time.

6. the method for single nickel salt coloring recycling hole sealing agent and Waste water utilization according to claim 1, it is characterised in that: step (3) in, the acetic acid additive amount is 95% of addition weight needed for chemical reaction completely, and nickel hydroxide is excessive, makes mixed liquor PH value >=6.0, and under conditions of pure water weight/weight of nickel hydroxide=10, the content of nickel acetate is 14.5- 15.5wt.% crystallizes liquid acetic nickel solution without nickel acetate and is precipitated far below the saturated concentration of nickel acetate.

7. the method for single nickel salt coloring recycling hole sealing agent and Waste water utilization according to claim 1, it is characterised in that: step (3) in, the solid-state nickel hydroxide of recycling is only rinsed, is not dried, pure water and acetic acid is added, it is directly and acetic acid reaction, raw At liquid acetic acid nickel solution.