CN104310647A - Recycling method for treating stainless steel pickling acid pickle and wastewater - Google Patents

Recycling method for treating stainless steel pickling acid pickle and wastewater Download PDF

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CN104310647A
CN104310647A CN201410577338.3A CN201410577338A CN104310647A CN 104310647 A CN104310647 A CN 104310647A CN 201410577338 A CN201410577338 A CN 201410577338A CN 104310647 A CN104310647 A CN 104310647A
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acid
stainless steel
neutralization reaction
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waste
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CN104310647B (en
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徐超群
陈云华
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Shanghai Doctoral High Environmental Protection Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/04—Surfactants, used as part of a formulation or alone

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

The invention relates to a recycling method for treating stainless steel pickling acid pickle and wastewater, belonging to the field of treatment of industrial acid pickle and wastewater in iron and steel and metallurgy industries. The acid pickle and wash wastewater generated during stainless steel pickling are collected according to quality and category and the acid pickle is subjected to acid recycling. The acid pickle and wash wastewater are treated through fractional precipitation by adopting lime as a neutralizing agent. Calcium sulfate or calcium fluoride or a mixture of calcium sulfate and calcium fluoride is obtained through precipitation under the acidic condition (the pH value is equal to 3.0+/-0.5) and can serve as a cement filler or a material for brickmaking or a building material after heavy metal polluted calcium salt is removed. A metal hydroxide is obtained through precipitation under the alkaline condition (the pH value is not more than 9.0) and can serve as a stainless steel smelting raw material as the quality of the product is better than that of the imported laterite-nickel ores in China. The calcium nitrate containing wastewater obtained after the acid pickle is treated is not needed to be discharged or treated and can be recycled. After being treated, the wash wastewater can be reused as production line wash water.

Description

The resource utilization method of waste acid from stainless steel acid washing liquid and wastewater treatment
Technical field
The present invention relates to the treatment process of a kind of metal finishing spent acid solution and waste water, more specifically to the resource utilization method of a kind of waste acid from stainless steel acid washing liquid and wastewater treatment, belong to iron and steel and metallurgy industry industrial waste acid and field of waste water treatment.
Background technology
Stainless steel can carry out style by purposes, chemical composition and metallographic structure.With the stainless steel-like of austenite class by 18% chromium-8% nickel for essentially consist, the difference of the add-on of each element change, and develop the type of stainless steel of various uses.
Stainless steel, owing to having many advantages such as acid corrosion-resistant, good heat resistance, high temperature oxidation resistance be good, is therefore widely used in the fields such as oil, chemical industry, power, nuclear engineering, aerospace, medical machinery, light industrial goods, individual housing decoration, luxurious hotel's facility.Stainless steel is in shaping and heat treatment process, surface can produce the oxide skin of one deck black, this kind of oxide skin compact structure, strong with matrix adhesive force, containing Fe, Cr, Ni, a small amount of C and Si, may be there is Mn, Ti, Mo, Cu and elements such as w in some product, oxide structure is: iron protoxide, ferric oxide, Z 250, chromic oxide, nickel oxide, silicon-dioxide, picotite (Cr 2o 3and nickel spinel (NiOFe FeO) 2o 3) etc.Stainless steel oxidation skin not only destroys the aesthetic property of steel surface, can accelerate again the galvanic corrosion of metallic surface, and its surface stress existed can accelerate the stress corrosion of steel surface.Therefore, the oxide skin of stainless steel surface must be removed totally before following process.
In engineering, the normal oxide skin used in the formation of stainless steel steel surface in acid cleaning process removal hot rolling and annealing process, carries out Passivation Treatment to stainless steel surface simultaneously, makes it have more solidity to corrosion.
Acid washing process for stainless steel is actually and is made up of acid cleaning process and passivation technology two techniques.In acid cleaning process, main employing sulfuric acid or nitric hydrofluoric acid mixing acid, carry out the removal of iron scale to the stainless steel of unlike material and peel off.In the production process of reality, stainless steel surface passivation is the nitric acid adopting concentration higher, and chromium metal is insoluble in concentrated nitric acid, because metallic surface generates the Cr of one deck densification very soon 2o 3thin film layer, prevents proceeding of reaction.So in nitric hydrofluoric acid mixing acid washing lotion, concentration of nitric acid can not be too high.
In acid cleaning process, main exist two class acid waste liquids.One is sulfuric acid washing spent acid solution, and it two is nitric hydrofluoric acid mixing spent acid solution.According to the difference of acid cleaning process, spent acid solution Free Acid content and metal ion content different.Automatically generating on line, because needs are enhanced productivity, the nitric hydrofluoric acid mix acid liquor concentration of acid cleaning process preparation suitably improves.When in pickle solution, iron concentration reaches 40-50g/l, the efficiency of scale removal can reduce, and needs to change eo-acid.At this moment, in solution, the concentration of nitric acid still has 12-18%, hydrofluoric acid concentration 3-5%.When adopting the pre-pickling of sulfuric acid, when in acid solution, iron concentration is greater than 60g/l, the efficiency of scale removal can reduce, and whole pickling speed is slack-off, must change eo-acid.At this moment, residual in waste pickle liquor sulfuric acid concentration still has 15-20%.After acid cleaning process terminates, must rinse metallic surface with water, washing water quantity is comparatively large, this part water acid content and amount of metal ion all relatively less, the pH of flushing waste water is mostly between 1-4.
International and domestic, spraying burning method (Ruthner method) is mainly contained to the processing mode of nitric hydrofluoric acid mix acid liquor recovered acid, the method is that Austrian Andritz company initiates, this method is that after spent acid solution spraying being burned, acid solution is reclaimed in condensation, be mainly used in the recovery of volatile hydrochloric acid and nitric hydrofluoric acid mixing acid, product is corresponding acid solution and metal oxide.This kind of method advantage is that resource is well recycled, shortcoming processes these corrosive inorganic acids under the high temperature conditions, very high to the requirement for anticorrosion of equipment, facility investment and working cost, maintenance cost are large, general enterprises is difficult to bear, and domestic at present only have several large iron and steel enterprise such as Baosteel and Taiyuan Iron and Steel Co. to adopt.
Exchange resin method is the method for selecting to exchange or adsorb recovered acid by Special Resin.The representative enterprise of this method is SCANACON company of Sweden, and this method advantage is that free acid in spent acid solution can major part be recycled, investment and running cost low.Shortcoming is that comparatively burning method is low for sour recovery utilization rate, and what also have equal volume needs process containing sour salt bearing liquid wastes simultaneously.The method both can process single spent acid also can process nitration mixture, has certain superiority to the high boiling Waste Sulfuric Acid of recovery.
Filter membrane method is separated free acid in spent acid and metal-salt, hydrochlorate good separating effect, but facility investment is comparatively large, and single complete equipment processing power is less, the same with resin method have need to process containing sour salt bearing liquid wastes.
Sulfate substitution distillation under vacuum carries out acid recovery to nitric hydrofluoric acid mixing spent acid solution, namely uses sulfate substitution nitrate radical and fluorion, produces lower boiling nitric acid and hydrofluoric acid, reclaim these lower boiling mix acid liquors by underpressure distillation.The method waste acidity recovery effect is high, greatly reduces nitric acid and nitrate enters waste water processing station, and reduce Determination of Total Nitrogen in Waste Water content, and waste acidity recovery is effective, cost of investment is moderate.
At present, most of spent acid solution process adopts lime one step moderate water-cut stage, by the remnants acid neutralization in water, forms the co-precipitation mud of calcium sulfate or Calcium Fluoride (Fluorspan) or metal hydroxides.The method advantage is that technique is simple, and facility investment is few, and effluent quality is better, and saltiness is lower.Shortcoming is in pH=6-9 scope, and part metals precipitation of hydroxide is incomplete, and the sludge quantity that water treatment produces is more, and containing plurality of heavy metal in throw out, need manage by industrial dangerous waste, sludge disposal expense is large.
" Chinese water supply and drainage " the 25th volume the 10th phase disclosed " the sludge emission reduction technology in stainless steel acid cleaning waste water process ", Shanghai City company limited of Electromechanical Design institute (highlighted), " the 8th (2011) China Steel nd Annual Meeting collection ", Baoshan Iron & Steel Co., Ltd technique center (Shi Lei etc.), adopt this type of high density pickling waste waters of step-by-step precipitation method process, sludge quantity has larger minimizing than step precipitator method, the acid-bearing wastewater of the method mainly in process metal surfaces treating processes, utilize the first precipitate metal ion of sodium hydroxide, again with lime slurry precipitation fluorion and sulfate ion, two kinds of mud are precipitated respectively, separately treatment and utilization.Its shortcoming is that select sodium hydroxide to originate as hydroxide radical, cost of water treatment is high when precipitating metal sludge.Removing in fluorine process with lime slurry, in order to ensure the pH of waste water, a large amount of hydrochloric acid need be added, its essence is exactly add calcium chloride, containing a large amount of sodium sulfate sodium-chlor SODIUMNITRATE salinities in waste water after process, should not use as reuse water, cause a large amount of water resource waste and saltiness waste water to enter water body.Meanwhile, containing SODIUMNITRATE in processed waste water, discharge water total nitrogen content severe overweight, must do after in-depth process further could qualified discharge, and water treatment running cost is high.
Because in water treatment, running cost is high, water resource waste is large, and the high and defect of total nitrogen severe overweight of discharge water salinity, is difficult to be widely applied in industrial application.
The invention solves the high and discharge water of water treatment running cost and contain the defect that salinity is high and total nitrogen maximum discharge is high, accomplish the recycling of water resources and sludge resource.
In prior art, no matter be step precipitator method or the two step precipitator method, adopt sodium-hydroxide treatment spent acid waste water, although mud has certain decrement, but there is the discharge of supersalinity and high total nitrogen waste water, process these waste water working costs high, the waste water processed can not be recycled.
The resource utilization method of waste acid from stainless steel acid washing liquid of the present invention and wastewater treatment, compared with prior art, the neutralization precipitation agent used is lime, low price, except fluorine sulfate radical is effective, the water quality saliferous rate after process is low, pickling lines can be returned reuse as wash-down water, not only energy-conservation but also reduce discharging, water technology is simple, and working cost is low; The different spent acid solution of dual treatment, precipitated sulfur acid group and fluorion can be come by nitrocalcite in recycle waste water, minimizing lime consumption and the high salinity water that contains discharge or process, precipitate metal sulfate and metal fluoride simultaneously, avoid metal hydroxides and calcium sulfate Calcium Fluoride (Fluorspan) to produce co-precipitation, improve the relative abundance of metallic element in metal hydroxides.By using the sulfonitric washings washing calcium salt mud of pH=3 ± 0.2, reducing unwanted toxic substances content in mud, making it to meet available industrial by-products.Resource utilization method of the present invention has more effects of energy saving and emission reduction than the cement kiln burning method adopted at present, it also avoid sulfurous gas that high temperature incineration method disposing sludge produces and the secondary pollution that hydrofluoric acid brings.
The resource utilization method of waste acid from stainless steel acid washing liquid of the present invention and wastewater treatment is a kind of environmental friendliness, energy-saving and emission-reduction, the mud that running cost is low and the method that waste water resource utilizes, its remarkable economic and social benefits.In waste acid recycling, particularly effective displacement is carried out to nitrate radical in spent acid solution and fluorion and reclaimed, improve acid recovery amount, decreased measuring with acid of acid washing process for stainless steel, reduce pickling cost.Determination of Total Nitrogen in Waste Water amount reduces greatly simultaneously, decreases denitrogenation expense, can accomplish that the qualified discharge of water treatment and water resources utilize under low operating cost.
Summary of the invention
The object of the present invention is to provide the resource utilization method of a kind of stainless steel acid-washing waste liquid and wastewater treatment, it solve waste and the water treatment running cost problem of environmental protection problem and the resource existed in existing acid washing process for stainless steel.
The invention provides the resource utilization method of spent acid solution and the wastewater treatment produced in a whole set of acid washing process for stainless steel, comprise the resource utilization method of spent acid solution process wastewater treatment and mud.
Of the present inventionly to be achieved through the following technical solutions: the spent acid solution first stainless steel sulfuric acid refining production line produced and the categorised collection of flushing waste water sub-prime, to classify and then and acid recovery process and wastewater treatment are carried out to spent acid solution.The present invention, by nitric hydrofluoric acid mixing spent acid solution individual curing, adopts sulfate substitution distillation under vacuum to reclaim nitric hydrofluoric acid mixing acid, adopts the sulfuric acid in exchange resin method waste acid recovery liquid, and the raffinate waste liquid of discharge mixes or individual curing.This spent acid raffinate treatment process benefit is that in waste water, the solid content of mud is high, press filtration is got final product without the need to carrying out sludge settling concentration process after reacting completely, thereafter can reuse nitrocalcite wherein when precipitating the waste water of press filtration metal sludge, supersalinity waste water does not need discharge.When mixing spent acid solution and flushing waste water regardless of qualitative classification process, the nitrocalcite in waste water is difficult to be fully utilized, and bring difficulty also can to denitrogenation of waste water desalination, water treatment running cost increases.The independent collection and treatment of wash-down water, its waste water treatment technology is substantially identical, and difference is that the wash-down water water yield is large, and pollutent is few, and the sludge quantity of wastewater treatment precipitation is few, and in waste water, the solid content of mud is low, and mud need carry out precipitating and sludge condensation process.Benefit of the present invention is, the waste water total nitrogen after wash-down water process and saltiness very low, be beneficial to waste water reclamation utilize and low cost denitrogenation processing.Spent acid solution of the present invention and wastewater treatment use inexpensive lime as neutralization precipitation agent, and water treatment running cost is low, and effluent quality is good.When wastewater sludge recycling, the calcium precipitation mud obtained respectively is calcium sulfate or Calcium Fluoride (Fluorspan) or calcium sulfate calcium fluoride mixture and precipitate metal hydroxides mud.Calcium sulfate or Calcium Fluoride (Fluorspan) or its mixture mud wash through sour water, the heavy metal ion of removing trace, obtain calcium sulfate that heavy metal free pollutes or Calcium Fluoride (Fluorspan) or its mixture mud, can be used as general industry by-product utilized.Main application is cement filler or brickmaking or building materials raw material.Metal hydroxides Ni and Cr contained iron content is higher, and its quality is better than import red soil nickel ore, can be used as stainless steel metallurgical raw material.Using lime slurry as waste water neutralize precipitation agent, when precipitate metal hydroxide mud, also can add a small amount of sodium carbonate solution or sodium sulfide solution, make nickel or manganese in waste water precipitate completely, meet the requirement of discharge of wastewater national standard, reach the requirement of acid cleaning process wash water simultaneously.
The resource utilization method of waste acid from stainless steel acid washing liquid of the present invention and wastewater treatment, can be used for the process of waste liquid after recovered acid, also can mix the wastewater treatment after collection to the process of the mixed spent acid solution of non-recovered acid or spent acid waste water.According to the selection of the method for acid pickle of acid washing recovered acid, the sludge components that one-level neutralization precipitation obtains is different, but one-level neutralization reaction is carried out all in acid condition, precipitated product is the mixture of single calcium salt or two kinds of calcium salts, when needs obtain single calcium sulfate or Calcium Fluoride (Fluorspan) and metal hydroxides, it comprises the following steps:
A) the sulfuric acid waste liquid in pickling tank or nitric hydrofluoric acid mixing acid waste liquid are collected separately, first carry out acid recovery process if desired, raffinate after recovered acid carries out fractionation precipitation process again, flushing waste water is collected separately rear direct feeding wastewater equalization pond and is processed, one-level neutralization reaction is carried out in acid condition with lime slurry, obtain calcium sulfate or Calcium Fluoride (Fluorspan) or its mixture, in the basic conditions precipitate metal ion, obtain metal hydroxides;
B) added by lime slurry in sulfuric acid waste liquid, one-level neutralization reaction lime slurry is neutralized to pH=3.0 ± 0.5, prevents Hydrolysis Reactions of Metal-ions precipitation in waste water.During first set reaction, should add and the nitrocalcite of metal ion equivalent or calcium chloride, make sulfate radical and precipitate with the form of calcium sulfate, and now metal nitrate or muriate do not precipitate, the present invention preferably adopts nitrocalcite.One-level neutralization-precipitation reaction 0.5-2.0 hour, press filtration precipitating sludge, the sulfonitric solution washing of mud pH=3 ± 0.20, how many according to the content of metal in sludge ion, determine washing times.Generally, after washing 1-3 time, Of Heavy Metal Level In Sludge leaches venomous injurant standard lower than National Hazard refuse, pH=6-9 is regulated again with lime slurry, press filtration obtains the calcium sulfate product that heavy metal free pollutes, product reaches the standard of country " industry by-product gypsum in cement " GB/T21371-2008, and can be used as cement filler or building materials or other industrial chemicals and use, washings enters wash-down water treatment system.The waste water of metal ion enters the neutralization precipitation process that second-level settling pond carries out metal sludge.The present invention pays the utmost attention to use nitrocalcite, and when using calcium chloride, in processed waste water, chloride ion content is higher, one, is not suitable for as the wash water of reuse water for stainless steel part; Its two, mud is not suitable for using in cement, there are certain requirements chloride ion content as gypsum for cement.The resource utilization method of waste acid from stainless steel acid washing liquid of the present invention and wastewater treatment, continue with the metal ion in lime slurry neutralization precipitation waste water, press filtration throw out obtains metal hydroxides mud.Containing a large amount of nitrocalcite composition in pressing filtering liquid, collect storage and recycle, starch for calcification or directly return in waste sulfuric acid equalizing tank.During waste water after recycle precipitate metal ion, nitrocalcite and metal sulfate generation replacement(metathesis)reaction, formation calcium sulfate salt precipitates, the pH of waste water is constant, make the relatively good control of reaction system acidity, sulfate radical can be removed again, with the amount of spent acid solution Free Acid during the lime slurry added is only, save large quantities of lime.
C) joined by lime slurry in the mixing spent acid solution containing nitric hydrofluoric acid, control pH=3.0 ± 0.5, prevents Hydrolysis Reactions of Metal-ions from precipitating, and fluorine element in hydrofluoric acid and metal fluoride is precipitated with the form of Calcium Fluoride (Fluorspan).One-level neutralization-precipitation reaction 0.5-1 hour, press filtration calcium fluoride precipitate mud, the sulfonitric solution washing of mud pH=3 ± 0.2, content according to metal in sludge ion determines washing times, generally, after washing 1-3 time, pH=6-9 is regulated with lime slurry, obtain the Calcium Fluoride (Fluorspan) product that heavy metal free pollutes, this product can be used for metallurgy industry or the dry rear raw material as manufacturing hydrofluoric acid.The pressing filtering liquid waste water of metal ion enters secondary neutralization reaction settling tank.
The resource utilization method of waste acid from stainless steel acid washing liquid of the present invention and wastewater treatment, the metal-containing salt filtrate that sulfuric acid waste liquid and nitric hydrofluoric acid spent acid solution one-level neutralization reaction are collected, its precipitated product is all metal hydroxides, can merging treatment when secondary neutralization reaction.With the metal ion in lime slurry neutralization precipitation waste water, press filtration throw out obtains metal hydroxides mud.
D) by step B) and step C) one-level neutralization-precipitation reaction filtrate, use lime slurry neutralization reaction further, between control pH=8.5 ± 0.2, most metal ion is precipitated with the form of oxyhydroxide, after this, add sodium carbonate or the sodium sulphite of Manganese in Waste Water ionic theory residual quantity 1.0-1.5 times of equivalent again, regulate pH≤9.0, metal ion is precipitated completely.Press filtration precipitating sludge, obtains metal hydroxide mixture, this moisture percentage in sewage sludge 50%, nickel content 1.8-3.0%, chromium content 3.5-6.0%, iron level 18-22%, and its quality is better than red soil nickel ore, can be used as stainless steel metallurgical raw material.When using sodium sulphite precipitation trace metal, it is excessive to control as far as possible, causes the sulfide of waste water to exceed standard.
The resource utilization method of waste acid from stainless steel acid washing liquid of the present invention and wastewater treatment, when acid pickle of acid washing and flushing waste water are mixed collections, the waste water of sulfur acid and vitriol and all enter equalizing tank containing the mixing acid waste water of nitric hydrofluoric acid and corresponding salt, treatment process of the present invention comprises the following steps:
E) lime slurry is joined in the first order reaction pond of composite waste, control pH=3.0 ± 0.5, the amount that first time should add nitrocalcite will decide according to free nitric acid amount, when using useless acid-treated secondary neutralization reaction filtrate, nitrocalcite in graywater carrys out the negatively charged ion in precipitated sulfur hydrochlorate or fluorochemical, form the throw out of calcium sulfate Calcium Fluoride (Fluorspan), without the need to additional nitrocalcite.Mud is through solid-liquid separation and sludge washing, obtain the calcium sulfate Calcium Fluoride (Fluorspan) mixing sludge that heavy metal free pollutes, quality product reaches the standard of country " industry by-product gypsum in cement " GB/T21371-2008, can be used as cement filler or brickmaking or other industrial chemicals and uses;
F) by step e) one-level neutralization-precipitation reaction filtrate, use lime slurry neutralization reaction further, between control pH=8.5 ± 0.2, most metal ion is precipitated with the form of oxyhydroxide, after this, add sodium carbonate or the sodium sulphite of Manganese in Waste Water ionic theory residual quantity 1.0-1.5 times of equivalent again, regulate pH≤9.0, metal ion is precipitated completely.Press filtration precipitating sludge, obtains metal hydroxide mixture, this moisture percentage in sewage sludge 50%, nickel content 1.8-3.0%, chromium content 3.5-6.0%, iron level 18-22%, and its quality is better than red soil nickel ore, can be used as stainless steel metallurgical raw material.When only using lime slurry as neutralization precipitation agent, under the condition of pH=9, waste water mn ion severe overweight after process, only has control ph more than 10.2, and at this moment mn ion can precipitate completely, but the consequence brought has a large amount of calcium hydroxide unreacted complete, sludge quantity strengthens, and the waste water after process must adjust back pH with sulfuric acid, produces calcium sulfate precipitation again simultaneously, reaction tank and settling tank need be increased, make water technology become complicated.
When using sodium sulphite precipitation trace metal, it is excessive to control as far as possible, causes the waste water sulfide discharge beyond standards after process.Waste water after filtering, saltiness is low, can be used for acid washing process for stainless steel and uses as wash-down water.
The resource utilization method of waste acid from stainless steel acid washing liquid of the present invention and wastewater treatment, the treatment process of its flushing waste water adopts identical one-level neutralization reaction precipitation to obtain calcium salt mud, and secondary neutralization reaction precipitation obtains metal hydroxides mud.
The resource utilization method of waste acid from stainless steel acid washing liquid of the present invention and wastewater treatment, when flushing waste water process, the add-on of second order reaction pond sodium carbonate is sodium carbonate or the sodium sulphite of mn ion theoretical residual amount 1.0-1.5 times of equivalent, guarantee that metal ion precipitates completely, excessively add calcium carbonate sodium, a large amount of precipitation of calcium carbonate can be formed, and too much consume the amount of sodium carbonate, increase water treatment running cost, excessively add sodium-chlor, the waste water sulfide after process can be made to exceed standard.
The resource utilization method of waste acid from stainless steel acid washing liquid of the present invention and wastewater treatment, its further technical scheme can also be can add poly aluminum chloride (PAC) or bodied ferric sulfate (PFS) or polyacrylamide (PAM) as coagulating agent or flocculation agent in described wastewater treatment process, strengthen the sedimentation effect of mud.
The resource utilization method of waste acid from stainless steel acid washing liquid of the present invention and wastewater treatment, its further technical scheme adopts sulfate substitution distillation under vacuum or exchange resin method process recovered acid, preferred method adopts sulfate substitution distillation under vacuum to reclaim nitric acid in nitric hydrofluoric acid mixing acid or hydrofluoric acid, the evaporation boiling temperature of mix acid liquor controls at 50-70 DEG C, and exchange resin method recovered acid carries out at normal temperature.
Step B) its reaction equation of method as follows:
The process of sulfuric acid waste liquid (Me is in pickle solution+divalent or+3 valence metal ions, this reaction equation is for+divalent metal ion):
H 2SO 4+Ca(OH) 2＝CaSO 4↓+2H 2O
MeSO 4+Ca(NO 3) 2＝CaSO 4↓+Me(NO 3) 2
MeSO 4+CaCl 2＝CaSO 4↓+MeCl 2
Step C) its reaction equation of method as follows:
2HNO 3+Ca(OH) 2＝Ca(NO 3) 2+2H 2O
2HF+Ca(OH) 2＝CaF 2↓+2H 2O
MeF 2+Ca(NO 3) 2＝CaF 2↓+Me(NO 3) 2
Step B) or step C) first time neutralization reaction time, appropriate nitrocalcite or calcium chloride should be added, pay the utmost attention to use nitrocalcite.When not using nitrocalcite or calcium chloride, after in the free acid in waste water and completely, in waste water, pH can raise rapidly, causes metal hydroxides co-precipitation.As about pH=3 in waste water, lime adding amount is inadequate, and the sulfate radical in metal sulfate cannot form calcium sulfate precipitation.In spent acid solution, sulfate radical often in metal-salt is more than the sulfate radical in free acid, when not using the recycle waste water containing nitrocalcite, major part sulfate radical can not precipitate, in post precipitation metal hydroxides reaction process, when adding lime slurry to pH=6-9, a large amount of calcium salt mud and metal sludge form co-precipitation, affect quality and the recycling of metal sludge.Its reaction formula is as follows:
MeSO 4+Ca(OH) 2＝CaSO 4↓+Me(OH) 2↓
MeF 2+Ca(OH) 2＝CaF 2↓+Me(OH) 2↓
Me(NO 3) 2+Ca(OH) 2＝Me(OH) 2↓+Ca(NO 3) 2
These two kinds of mud form co-precipitation cannot be separated, and metal in sludge relative abundance reduces, and utility value is not high, even will as Hazardous Wastes Management, and disposal costs is high, the recycling after being more unfavorable for.
Step D) its reaction equation of method as follows:
Me(NO 3) 2+Ca(OH) 2 -＝Me(OH) 2↓+Ca(NO 3) 2
Me(NO 3) 2+Na 2CO 3＝MeCO 3↓+2NaNO 3
Me(NO 3) 2+Na 2S＝MeS↓+2NaNO 3
When only using lime slurry neutralization reaction, pH value should be adjusted to more than 10.2, now calcium hydroxide solubility property is poor, want complete precipitate metal ion, what must increase lime slurry adds consumption, the sludge quantity brought also increases thereupon, is mixed with a large amount of undissolved calcium hydroxide in metal hydroxides mud.The waste water processed often needs to regulate acidity to use with sulfuric acid, also needs increase reaction tank and settling tank to process the throw out of calcium sulfate.
Step e) its reaction equation of method as follows:
H 2SO 4+Ca(OH) 2＝CaSO 4↓+2H 2O
2HNO 3+Ca(OH) 2＝Ca(NO 3) 2+2H 2O
MeSO 4+Ca(NO 3) 2＝CaSO 4↓+Me(NO 3) 2
2HF+Ca(OH) 2＝Ca?F 2↓+2H 2O
MeF 2+Ca(NO 3) 2＝Ca?F 2↓+Me(NO 3) 2
Step F) its reaction equation of method as follows:
Me(NO 3) 2+Ca(OH) 2＝Me(OH) 2↓+Ca(NO 3) 2
Step F) nitrocalcite that produces is in step B) or step C) reused in technique, reduce the consumption of lime slurry simultaneously, reduce cost of water treatment.
As pH=8.5, iron ion, chromium ion concentration is at below 1mg/l, and nickel ion concentration is at 6mg/l, manganese ion concentration at about 100mg/l, although in precipitation process, manganous hydroxide can produce co-precipitation, but Manganese in Waste Water ionic concn is all at more than 50mg/l, reach the emission request of below 2mg/l, the pH of solution should more than 10.2.So according to Manganese in Waste Water content, should add the sodium carbonate of 1.0-1.5 times of equivalent, form the precipitation of manganous carbonate and nickelous carbonate, guarantee that manganese ion concentration is less than 2mg/l, nickel ion concentration is less than 1mg/l.
The present invention adopts exchange resin method recovered acid or sulfate substitution distillation under vacuum to reclaim nitric hydrofluoric acid mixing acid, pickling lines recycle is turned back to by reclaiming the acid solution obtained, realize energy-saving and emission-reduction and resource regeneration, reduce the load of water treatment and the minimizing of sludge quantity simultaneously.The present invention preferentially selects sulfate substitution distillation under vacuum to reclaim nitric hydrofluoric acid mixing spent acid, and exchange resin method reclaims the free sulfuric acid in waste sulfuric acid.The difference of different according to type of stainless steel from pickling mode, the preparation of pickle solution has larger difference, be stainless steel automatization pickling lines for 300, adopt sulfuric acid, nitric hydrofluoric acid mixing acid acid cleaning process, the spent acid solution of discharging in pickling tank, the concentration of metal ions 50-80g/L of sulfuric acid waste, free acid concentration is at 150-200g/L; In nitric hydrofluoric acid mixing spent acid solution, concentration of metal ions 45-60g/L, concentration of nitric acid at 120-180g/L, hydrofluoric acid 30-50g/L.
The resource utilization method of waste acid from stainless steel acid washing liquid of the present invention and wastewater treatment, in the calcium sulfate mud produced in spent acid solution process and waste water treatment process or calcium fluoride sludge or its mixture mud, sludge water content contains certain poisonous and harmful heavy metallic chromium, nickel, manganese element, must thoroughly remove these harmful elements, the Leaching of mud is made to meet " Hazardous wastes judging standard-leaching characteristic identification " (GB5085.3-2007) requirement, each constituent concentration limit value: Ni5mg/L in leach liquor, total Cr15mg/L, sexavalence Cr5mg/L.Adopt the similar sour water of the leach liquor of sulfonitric method repeatedly to wash mud, washing times should decide according to the amount of poisonous and harmful element in mud, and general washing times can meet the demands at 1-3 time.According to national standard, in mud during venomous injurant quality detection, the solid-to-liquid ratio of dewatered sludge and leach liquor is 1: 10, and the original concentration namely remaining in hazardous substance in mud must not be higher than: Ni50mg/L, total Cr150mg/L, sexavalence Cr50mg/L.
Compared with prior art the present invention also has following beneficial effect:
Embodiment
The present invention is described in further detail for embodiment below, allly all belongs to scope of the present invention based on the technical scheme described by content of the present invention, and can not be interpreted as that the present invention is only limitted to following embodiment.Adopt sulfate substitution distillation under vacuum to reclaim nitric hydrofluoric acid spent acid, the nitric hydrofluoric acid rate of recovery is more than 90%, and adopt exchange resin method to reclaim waste sulfuric acid, the spent acid solution Free Acid rate of recovery is more than 80%, and the clearance of metal ion is more than 75%.
Embodiment 1
Get nitric hydrofluoric acid mixing acid to give up spent pickle liquor 1m 3, after testing, concentration of nitric acid is at 150g/L, hydrofluoric acid 45g/L, iron concentration 45g/L, the vitriol oil 100L adding 98% carries out underpressure distillation, select graphite evaporator and the condenser of dipping tetrafluoroethylene, control spent acid evaporation boiling temperature at 50-70 DEG C, after condensation recovered acid, after testing, nitric acid is 204Kg, total nitric acid rate of recovery is 92.3%, and hydrofluoric acid is 62Kg, and total hydrofluoric acid rate of recovery is 93.9%.
Embodiment 2
Get sulfuric acid pickling waste liquid 1m 3, after testing, sulfuric acid concentration at 180g/L, iron concentration 61g/L, exchange resin method is adopted to reclaim the sulfuric acid of waste sulfuric acid, after measured, reclaim(ed) sulfuric acid 152Kg, retrieval of sulfuric acid rate is 84.4%, iron ion content 12Kg in the sulfuric acid of recovery, metal ion clearance 80.3%.Raffinate 1.1m 3, iron concentration is 45.5g/L, and sulfuric acid concentration is 25.5g/L.
Embodiment 3
Get acid-washing stainless steel waste sulfuric acid 1m 3, after testing, sulfuric acid concentration at 180g/L, iron concentration 61.8g/L, total chromium 16.0g/L, nickel ion 6.7g/L, mn ion 0.72g/L.For the lime slurry concentration 10-15% of water treatment, nitrocalcite concentration 20%.
Add above-mentioned lime slurry to pH=3.0 ± 0.2 under stirring in first order reaction pond, more quantitatively add concentration 20% ca nitrate soln 1400Kg, react after one hour, press dry moisture with pressure filter, sludge quantity is 962Kg, water ratio 50%.In filtrate, each concentration of metal ions is: iron concentration 10.3g/L, total chromium 2.67g/L, nickel ion 1.12g/L, mn ion 0.12g/L.With the sulfonitric washing water 4m of pH=3.0 ± 0.2 3after washing once, press filtration is to moisture 50% mud, and detecting concentration of metal ions in filtrate is: iron concentration 740mg/L, total chromium 192mg/L, nickel ion 81mg/L, mn ion 9mg/L.With the sulfonitric washing water 4m of pH=3.0 ± 0.2 3after washing secondary, press filtration is to moisture 50% mud, and detecting concentration of metal ions in filtrate is: iron concentration 53.3mg/L, total chromium 13.8mg/L, nickel ion 6.0mg/L, mn ion 1mg/L.After second time washing, the concentration of harm composition is lower than the standard of perfection of Hazardous wastes.With the reuse water 3m after water treatment 3(pH=9.0) wash mud, then regulate pH=6-7 with lime slurry, detect pressing filtering liquid, iron concentration 10.5mg/L, total chromium 0mg/L, nickel ion 1.2mg/L, the mud of water ratio 50% is weighed 962Kg.Utilize as general industry by-product gypsum.
One-level neutralization reaction throw out filtrate, continuation lime slurry is neutralized to pH=9.0, reacts 1 hour, through the moisture 50% metal hydroxides 269Kg that press filtration obtains.Filtrate 4m 3collection storage, nitrocalcite concentration 67.6g/L in waste water, makes calcification slurry and one-level neutralization reaction supplements nitrocalcite and regulating pondage uses.Mud is nickel content 2.3% after testing, chromium content 5.5%, Fe content 0.25%, iron level 21.4%, and its quality is better than red soil nickel ore, can be used as stainless steel metallurgical raw material.
Embodiment 4
Get the raffinate 1.0m that exchange resin method reclaims waste sulfuric acid 3, iron concentration is 45.5g/L, and sulfuric acid concentration is 25.5g/L.With the second order reaction filtrate 2.0m of embodiment 3 3lime slurrying, 1.5m 3for regulating the consumption of nitrocalcite, add above-mentioned lime slurry to pH=3.0 ± 0.2, first order reaction 45 minutes, press filtration throw out obtains the 417.4Kg calcium sulfate mud of moisture 50%, detecting concentration of metal ions in filtrate is: iron concentration 7.02g/L, total chromium 1.82g/L, nickel ion 0.76g/L.With the sulfonitric washing water 2m of pH=3.0 ± 0.2 3after washing once, press filtration is to moisture 50% mud, and detecting concentration of metal ions in filtrate is: iron concentration 400mg/L, total chromium 104mg/L, nickel ion 43.3mg/L, the reuse water 2m of mud after water treatment 3(pH=9.0) wash, regulate pH=6-7 with lime slurry, detect pressing filtering liquid, iron concentration 38.2mg/L, total chromium 0mg/L, nickel ion 4.1mg/L, the mud of water ratio 50% is weighed 417Kg.Utilize as general industry by-product gypsum.
One-level neutralization reaction throw out filtrate, continuation lime slurry is neutralized to pH=9.0, reacts 1 hour, through the moisture 50% metal hydroxides 198Kg that press filtration obtains.Filtrate 4m 3collection storage, nitrocalcite concentration 50.7g/L in waste water, makes calcification slurry and one-level neutralization reaction supplements nitrocalcite and regulating pondage uses.Mud is nickel content 2.2% after testing, chromium content 5.4%, Fe content 0.26%, iron level 21.5%, and its quality is better than red soil nickel ore, can be used as stainless steel metallurgical raw material.
Embodiment 5
Get nitric hydrofluoric acid mixing spent acid solution 1m 3after testing, concentration of nitric acid is at 150g/L, hydrofluoric acid 45g/L, iron concentration 45g/L, under agitation adds above-mentioned lime slurry to pH=3.0 ± 0.2, first order reaction 0.5 hour, press filtration throw out obtains the 272Kg calcium fluoride sludge of moisture 50%, with the sulfonitric washing water 2m of pH=3.0 ± 0.2 3after washing once, press filtration is to moisture 50% mud, and detecting concentration of metal ions in filtrate is: iron concentration 955mg/L, total chromium 253mg/L, nickel ion 105mg/L.The sulfonitric washing water 2m of mud pH=3.0 ± 0.2 3after washing secondary, press filtration is to moisture 50% mud, and detecting concentration of metal ions in filtrate is: iron concentration 62mg/L, total chromium 16.4mg/L, nickel ion 6.8mg/L.The wash-down water 2m of mud after water treatment 3(pH=9.0) wash, regulate pH=6-7 with lime slurry, detect pressing filtering liquid, iron concentration 2.5mg/L, total chromium 0mg/L, nickel ion 0.5mg/L.The mud of water ratio 50% is weighed 271Kg.Utilize as general industry by-product Calcium Fluoride (Fluorspan).
One-level neutralization reaction throw out filtrate, continues to use lime slurry neutralization reaction 45 minutes, through the moisture 50% metal hydroxides 269Kg that press filtration obtains.Filtrate 4m 3collection storage, nitrocalcite concentration 67.6g/L in waste water, makes calcification slurry and one-level neutralization reaction supplements nitrocalcite and regulating pondage uses.Mud is nickel content 2.2% after testing, chromium content 5.4%, Fe content 0.24%, iron level 21.8%, and its quality is better than red soil nickel ore, can be used as stainless steel metallurgical raw material.
Embodiment 6
Get the mixed waste water 1m of spent acid solution without acid recovery and wash-down water 3, after measured, pH=0.8, iron 6800mg/L, chromium 1300mg/L, nickel 590mg/L, manganese 520mg/L.Under agitation add lime slurry to pH=2.8 ± 0.2, react after 45 minutes, press filtration throw out, obtain the mud 38Kg that water ratio is 50%.With the sulfonitric washing water washing mud of 200 liters of pH=3.0 ± 0.2, press filtration is to moisture 50% mud, and detecting concentration of metal ions in filtrate is: iron concentration 560mg/L, total chromium 105mg/L, nickel ion 49mg/L.Mud with reuse water (pH=9.0) washing after water 200 liters of wastewater treatments, regulates pH=6-7 with lime slurry, detects pressing filtering liquid, iron concentration 50mg/L, total chromium 0mg/L, nickel ion 4.3mg/L again.The mud obtaining water ratio 50% after press filtration is weighed 37.6Kg.Mud main component is the mixture of calcium sulfate and Calcium Fluoride (Fluorspan), utilizes as general industry by-product fluorgypsum.
One-level neutralization reaction throw out filtrate, continues to use lime slurry neutralization reaction 1 hour, through the moisture 50% metal hydroxides 29.6Kg that press filtration obtains.Mud is nickel content 1.9% after testing, chromium content 4.3%, Fe content 1.7%, iron level 22.4%, and its quality is better than red soil nickel ore, can be used as stainless steel metallurgical raw material.
Embodiment 7
Individual curing flushing waste water, gets acid cleaning process and mixes wash-down water 1m 3, after measured, pH=2.0, iron 430mg/L, chromium 96mg/L, nickel 64mg/L, manganese 23mg/L.What store after direct use process spent acid solution contains nitrocalcite wastewater sedimentation calcium salt mud, nitrocalcite concentration 50.7g/L in waste water, taking 35L adds in waste water, pH=3 is regulated with lime slurry, quiescent setting, filter and obtain moisture 50% throw out of 5.8Kg, mud directly washs with 20 liters of reuse waters (pH=9.0), regulate pH=6-7 with lime slurry, press filtration obtains the mixing sludge 5.8Kg of moisture 50% calcium sulfate Calcium Fluoride (Fluorspan).Filtrate continues to be neutralized to pH=9.0 with lime slurry, and aeration 2 as a child quiescent setting or the sodium carbonate solution that adds 400 gram 10% stirs quiescent setting after 0.5 hour, filters and obtains moisture 50% metal hydroxides 2Kg.Waste water saltiness after process is low, nitrocalcite concentration 1.8g/L, total nitrogen content 30gmg/L, returns pickling lines and does wash-down water use.The detected level of metal ion in this waste water, can reach " Iron And Steel Industry wastewater pollutants emission standard " (GB13456-2012) directly emission request, but total nitrogen will reach the direct emission standard of 15mg/L, must do denitrogenation processing.

Claims (3)

1. a resource utilization method for waste acid from stainless steel acid washing liquid and wastewater treatment, the spent acid that the method process acid washing process for stainless steel produces or flushing waste water or its mixed waste water, is characterized in that:
A) by the spent acid solution of acid-washing stainless steel and the categorised collection of flushing waste water sub-prime, spent acid solution carries out acid recovery, recovered acid returns production line to be continued to use, raffinate after acid recovery or flushing waste water or its mixed waste water lime slurry do further wastewater grading precipitation process, one-level neutralization reaction is to acid, obtain calcium sulfate or Calcium Fluoride (Fluorspan) or its mixture product, secondary neutralization reaction, to alkalescence, obtains metal Strong oxdiative produce thing;
B) by steps A) waste sulfuric acid or reclaim(ed) sulfuric acid after Waste Sulfuric Acid raffinate lime slurry do the process of classification neutralization precipitation, obtain calcium sulfate in acid condition, more specifically method is that one-level neutralization reaction lime slurry is neutralized to pH=3.0 ± 0.5, reaction times controls at 0.5-2.0 hour, obtain calcium sulfate product, filtrate enters secondary neutralization reaction;
C) by steps A) waste nitric acid hydrofluoric acid mix acid liquor lime do the process of classification neutralization precipitation, obtain Calcium Fluoride (Fluorspan) in acid condition, more specifically method is that one-level neutralization reaction lime slurry is neutralized to pH=3.0 ± 0.5, reaction times controls at 0.5-2.0 hour, obtain Calcium Fluoride (Fluorspan) product, filtrate enters secondary neutralization reaction;
D), by step B) or step C) the sulfonitric solution washing of product pH=2.5-3.5 that obtains in one-level neutralization reaction 1-3 time, preferred washings pH=3.0 ± 0.2, remove the poisonous and harmful metal ion in product, wash with reuse water again, lime slurry regulates pH=6-7, and press filtration obtains calcium sulfate or Calcium Fluoride (Fluorspan) or its mix product;
E), just step B) or step C) one-level neutralization reaction filtrate be neutralized to alkalescence, precipitate metal ion, obtain Metal hydroxide product, more specifically method is that secondary neutralization reaction lime slurry is neutralized to pH≤9.0, reaction times controls at 0.5-2.0 hour, and press filtration obtains metal hydroxides product;
F), by steps A) flushing waste water or mixed waste water lime do the process of classification neutralization precipitation, obtain calcium sulfate or Calcium Fluoride (Fluorspan) or its mixture product in acid condition, more specifically method is that one-level neutralization reaction lime slurry is neutralized to pH=3.0 ± 0.5, reaction times controls at 0.5-2.0 hour, obtain calcium precipitation product, the sulfonitric solution washing of throw out pH=2.5-3.5 0-1 time, preferred washings pH=3.0 ± 0.2, remove the poisonous and harmful metal ion in precipitated product, wash with reuse water again, lime slurry regulates pH=6-7, press filtration obtains calcium sulfate calcium fluoride mixture product, precipitation obtains metal hydroxides product in the basic conditions, more specifically method is that secondary neutralization reaction lime slurry is when being neutralized to pH=8.5 ± 0.2, add sodium carbonate or the sodium sulphite demanganization of now mn ion equivalent 1.0-1.5 times again, reaction times controls at 0.5-2.0 hour, or secondary neutralization reaction control pH≤9.0, Air Exposure 1-3 hour demanganization, press filtration throw out obtains metal hydroxides product, and supernatant liquor or pressing filtering liquid do the recycling of pickling lines wash-down water.
2. the resource utilization method of waste acid from stainless steel acid washing liquid according to claim 1 and wastewater treatment, it is characterized in that the filtrate of spent acid solution secondary neutralization reaction is without the need to discharge and process, nitrocalcite in recycle filtrate, for one-level neutralization reaction cementation removing sulfate radical or fluorion, Application way adopts secondary neutralization reaction filtrate as calcification slurry or directly adds in one-level neutralization reaction pond more specifically, under the acidic conditions of pH=3.0 ± 0.5, precipitate the sulfate radical in removal metal sulfate or fluorochemical and fluorion.
3. the resource utilization method of waste acid from stainless steel acid washing liquid according to claim 1 and wastewater treatment, it is characterized in that adopting sulfate substitution distillation under vacuum or exchange resin method process recovered acid, preferred method adopts sulfate substitution distillation under vacuum to reclaim nitric acid in nitric hydrofluoric acid mixing acid or hydrofluoric acid, and the evaporation boiling temperature of mix acid liquor controls at 50-70 DEG C; Adopt the sulfuric acid in exchange resin method recovery waste sulfuric acid.
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