CN105884156A - Resource utilization method for metal surface treatment sludge - Google Patents
Resource utilization method for metal surface treatment sludge Download PDFInfo
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- CN105884156A CN105884156A CN201510027612.4A CN201510027612A CN105884156A CN 105884156 A CN105884156 A CN 105884156A CN 201510027612 A CN201510027612 A CN 201510027612A CN 105884156 A CN105884156 A CN 105884156A
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Abstract
The invention relates to a resource utilization method for metal surface treatment sludge, in particular to resource utilization of stainless steel acid pickling sludge or electroplating sludge, and belongs to sludge pollutant treatment in the steel and metallurgy industry. Hydrochloric acid or nitric acid is adopted as pickle liquor, metal elements in the sludge are acidized and leached, calcium salt sludge hard to dissolve is separated through filter pressing under the condition that the pH is controlled to range from 1.8 to 3.0, the sediment is washed 1-3 times with a diluted hydrochloric acid solution with the pH equal to 3.0+/-0.2, a slightly soluble calcium salt sludge product free of heavy metal pollution is obtained, and the sludge can be used as cement filler or a brickmaking or building material. Furthermore, metal ions in acid leaching filtrate are neutralized with lime emulsion, and a metal hydroxide sludge product is obtained and can be used as a stainless steel smelting material or used for separating single metal elements. Filtrate obtained after metal hydroxide is subjected to filter pressing, and after recycling is carried out 3-5 times, when the concentration of calcium chloride is larger than 20%, evaporation and crystallization are carried out to recycle a calcium chloride product.
Description
Technical field
The present invention relates to the resource utilization method of a kind of Treatment of Metal Surface mud, more specifically to a kind of acid-washing stainless steel
Mud and the resource utilization method of electroplating sludge, belong to iron and steel and metallurgy industry industrial residue and field of sludge treatment.
Background technology
Stainless steel is shaping and in heat treatment process, and surface can produce the oxide skin of one layer of black, this kind of oxide skin compact structure,
Strong with matrix adhesive force, containing Fe, Cr, Ni, a small amount of C and Si, some product there may be Mn, Ti, Mo, Cu
And elements such as w, oxide structure is: ferrous oxide, ferrum oxide, ferroso-ferric oxide, chromium oxide, nickel oxide, silicon dioxide,
Picotite (Cr2O3And nickel spinelle (NiO Fe FeO)2O3) etc..Stainless steel oxidation skin has not only broken up U.S. of steel surface
The property seen, can accelerate again the electrochemical corrosion of metal surface, and its surface stress existed can accelerate the stress corrosion of steel surface.
Therefore, the oxide skin of stainless steel surfaces must be removed totally before following process.In engineering, acid cleaning process is often used to remove hot rolling
And the oxide skin formed at rustless steel steel surface in annealing process, it is passivated stainless steel surfaces processing so that it is more simultaneously
Corrosion resistance.
In acid cleaning process, it is primarily present two class acid waste liquids.One be in descaling bath pickling produce acid pickle, its two for rinsing
Or flushing waste water.Most metals surface processes acid pickle and waste water is all that unified collection processes at present, uses Calx one step to neutralize
The sedimentation method, neutralize the residual acid in water, form calcium sulfate or the co-precipitation mud of calcium phosphate or calcium fluoride or metal hydroxides.
The method advantage is that technique is simple, and equipment investment is few, and effluent quality is preferable, and the waste water salinity after process is relatively low.Shortcoming be
PH=6-9 scope, not exclusively, in the waste water after process, part metals ion exceeds standard part metals hydroxide precipitation, and water processes and produces
Raw sludge quantity is more, and containing plurality of heavy metal in precipitate, need to manage by industrial dangerous waste, and disposal costs is big.
These mud currently processed mainly uses three kinds of approach: one is to send hazardous waste landfill to fill after solidification and stabilization, and two
Being to use cement kiln to work in coordination with incineration disposal, mud uses as cement filler, three be mix in clay burned brick or with cement mixing
Make non-burning brick.Owing to containing plurality of heavy metal element in this mud, needing to manage with reference to industrial dangerous waste, direct brickmaking is disposed
Method is restricted, and solidification and stabilization disposal options mud occurs quantitation, and disposal costs is higher, burns harmlessness disposing expense
Height, heavy metal has made stable harmlessness disposing, belongs to more low-grade recycling mode.
Process at present these mud and mainly use three kinds of approach: one is to send hazardous waste landfill to fill after solidification and stabilization, and two are
Using cement kiln to coordinate incineration disposal, uses as cement filler, three is to mix in clay burned brick or mix to make with cement and exempt from
Baking bricks, owing to this mud belongs to hazardous waste, direct occupation mode is limited.Nanjing University Liu Fu by force wait application " one is not
With sludge heavy-metal its recovery method as resource in rust steel pickling waste waters ", number of patent application CN201210141865.0, use acidleach,
Oxidation, ion exchanges, and neutralization precipitation reclaims nickel hydroxide, and due to complex process, in mud, Ni-Cr-Mn content is the highest, ferrum nickel chromium triangle
The cost recovery of manganese is high, the recovery benefit extreme difference of its metal itself, and the mud still suffering from containing in a large number heavy metal needs to dispose, unfavorable
In large batch of sludge treatment.
" in producing stainless steel process, nickel-containing wastes is comprehensive for the paper that Shanghai Baosteel company limited-steel company Han Wei delivers
Utilize " (" bao steel technology ", the third phase in 2009), describe method and the treasured of several extensive process acid-washing stainless steel mud
Steel processes the application practice of this mud, and the utilization rate of metal in sludge is high, but under hot conditions, sulfate and fluoride can decompose,
Sulfur dioxide in flue gas, fluohydric acid content is higher, it is necessary to flue gas carries out purified treatment, and fume treatment cost is high.The present invention adopts
Use acidleach mode, dissolve the metallic element in mud, solid-liquid separation in acid condition, obtain slightly solubility calcium salt mud, utilize
Lime slurry further neutralization precipitation metal ion, obtains metal hydroxides mud.Solve the mixed of Treatment of Metal Surface generation
Closing the technical problem of the recycling of precipitating sludge, the various metals in mud are all recycled utilization, and utilization rate is 99%
Above.
Summary of the invention
It is an object of the invention to provide the Sludge resource utilization method that a kind of Treatment of Metal Surface produces, it is applicable to rustless steel
The resource utilization method of the mud that pickling waste waters and electroplating wastewater processing produce.Its core be exactly by the metallic element in mud with
Slightly solubility gypsum material is effectively separated in the case of relatively low expense, and two class materials after separation can sufficiently be provided
Sourceization utilizes.Within 2013, China's stainless steel output accounts for whole world half, whole nation rustless steel crude steel yield (54 main steel mills) 2253
Ten thousand tons (stainless steel 21,400,000 tons), wherein 200 is yield 7,460,000 tons, accounts for the 33.10% of total output, and 300 is yield 1122
Ten thousand tons, accounting for the 49.80% of total output, 400 is yield 3,850,000 tons, accounts for the 17.09% of total output.Often it is only acid-washing stainless steel to produce
Raw chemically precipitated sludge about 2,000,000 tons, needs further harmless treatment, if metallic element therein is the most effectively returned
Receiving, be equivalent to reclaim 60,000 tons of stainless steel materials every year, economic benefit, social benefit, environmental benefit are considerable.
The present invention is achieved through the following technical solutions: first in Treatment of Metal Surface production process produce containing metal
Mixing sludge hydrochloric acid or nitric acid dousing, leach metallic element therein, when in pickle liquor, acid concentration is bigger, be conducive to dirt
Metal hydroxides or metal-oxide fast reaction in mud, generate the respective metal ion of solubility, it is achieved the sulphuric acid in mud
Calcium or the effective of the slightly solubility calcium salt such as calcium fluoride or calcium phosphate separate.In order to improve acidity and acidifying efficiency, the initial acidleach used
Liquid is excessive, free acid unnecessary in neutralisation treatment leachate, can consume more alkali liquor, causes sludge treatment cost to raise.
The present invention uses the method that pending mud replaces alkali liquor, the excessive hydrochloric acid added when neutralizing mud acidifying, had both decreased alkali liquor and has used
Amount, has processed again mud.In terms of selecting pickle liquor, in order to control Treatment of Sludge cost and environmental conservation and Treatment of Sludge mistake
The economic treatment method of the sewage that self produces in journey, the present invention preferentially selects hydrochloric acid to be reasonable selection as pickle liquor.Adopt
With nitric acid as pickle liquor, cost of raw is big, and Determination of Total Nitrogen in Waste Water content is high, processes the waste water produced in production process
Difficulty is big.Acid-base neutralization course of reaction is exothermic reaction, and the present invention is in order to reduce the issuable volatilization of hydrochloric acid in reaction, highly concentrated
Degree hydrochloric acid is the most first configured to the examination pickle liquor that concentration is 5-15% and is advisable.When leaching metal in sludge, acid in acidleach pond
Acidity is preferably maintained in pH and is less than 1, is slowly stirred mud 1-3 hour, makes metal in sludge element all leach.Then in stirring
Lower this kind of sludge slurry of addition, neutralizes the free hydrochloric acid in the pickle liquor of excess in acidleach pond, Controlled acidity between pH=1.9-3,
Continue reaction 1-2 hour, carry out solid-liquid separation.For the mud that pilling up time is longer, part ferrous oxidising one-tenth ferric iron,
The acidity of leachate is preferably controlled in below pH=2, prevents ferric hydrolysis, affects the recovery of ferrum, filter pressing mud suspension,
Obtain mud and the metal chloride solutions of calcium sulfate, calcium fluoride or calcium phosphate.The hydrochloric acid of the solid pH=3 that filter pressing obtains or
Sulfuric acid solution washs 1-3 time, then regulates pH to 6-9 with lime slurry, and filter pressing obtains content of beary metal less than hazardous waste standard
General industry by-product gypsum, the Leaching of this mud be less than " hazardous waste judging standard-leaching characteristic identification "
(GB5085.3-2007) requirement, can in cement plant, Building Materials Factory's (plasterboard or brickmaking) or roadbed material use.Slightly solubility calcium
The washes of salt enters supporting sewage treatment facility further acid-base neutralization precipitate metal ion, and precipitating sludge is back to acidleach
Pond acidification, the waste water after process, recycle aborning or the rear discharge up to standard of a small amount of remaining water.
Metal chloride solutions continues to use lime slurry neutralization precipitation, and filter pressing separates, and obtains precipitate metal hydroxides and chloride containing
The solution of calcium.In acid washing process for stainless steel produce mud as a example by, due to be all-metal element reclaim, in metal hydroxides
The relative abundance of metallic element is close with metallic element composition in rustless steel, three be stainless steel surfaces process mud quality be better than into
Mouth lateritic nickel ore, as rustless steel metallurgical raw material after drying pelletize, it is achieved the full recycling of metal in sludge element, metal
The utilization rate of element reaches more than 99%.The solution of chloride containing calcium uses for pickle liquor preparating acid immersion, reuses 1-4 time
After, when Chlorine in Solution calcium concentration is more than 20%, not in use by, calcium chloride product is reclaimed in evaporation, can be as general chemicals pin
Sell, so can greatly reduce evaporation expense, reduce sludge treatment cost.
The resource utilization method of the Treatment of Metal Surface mud of the present invention, can process stainless steel surfaces and process the mud and electricity produced
Plating mud.Its further processing method comprises the following steps:
A) mud is thrown in acidproof pond (acidleach pond), add the hydrochloric acid pickle liquor that concentration is 5-15% of excess, control
PH is less than 1, mud quickly softens and metal hydroxides or metal-oxide is generated the metal chloride of solubility, is stirring
React 1-3 hour under the conditions of mixing, add the sludge slurry that the present invention is pending, neutralize free acid too much in acidleach pond,
Controlling pH=1.5-3, preferred Acidity Range is pH=1.9-2.5, reacts 1-2 hour.Filter pressing suspension, obtains solid calcium salt
Mixture and metal chloride solutions.Solid pH=3.0 ± 0.2 hydrochloric acid or sulfuric acid solution washing, filter pressing, repeat 1-3 time,
To reduce the content of metallic element, until less than the content of heavy metal in National Hazard refuse, regulating to pH=6-9 with lime slurry,
Filter pressing obtains slightly solubility calcium salt mud side-product.In mud acidleach pond, slightly solubility weight of calcium salt controls between 5-10% (i.e. containing solid
Rate 5-10%), this mud need not concentration, can directly use pressure filter filter pressing, saves the facility such as sedimentation tank and sludge concentration tank
Investment.Generation object according to Treatment of Metal Surface mud is different, the calcium salt product that the present invention obtains, be mainly composed of calcium sulfate,
Calcium fluoride or calcium phosphate, reach the standard of country " industry by-product gypsum in cement " GB/T21371-2008, can conduct
General industry by-product gypsum utilizes.Also can use as building materials or other industrial chemicals.
Mud acidleach process reaction equation is following (Me is metallic element):
CaSO4 CaF2Ca3(PO4)2 Me(OH)2↓+2HCl=CaSO4CaF2Ca3(PO4)2↓+MeCl2+2H2O
B) being neutralized by the lime slurry of the pressing filtering liquid containing metal chloride, pH is between 8.0-8.5 in control, makes overwhelming majority gold
Belong to ion to precipitate with the form of hydroxide, hereafter, add sodium carbonate or the sulfur of manganese ion theoretical residual amount 1.2-2.0 times equivalent
Changing sodium, pH is between 8.5-9.0 in regulation, makes metal ion precipitate completely.Filter pressing precipitating sludge, obtains metal hydroxides and mixes
Compound, this moisture percentage in sewage sludge 50%, when processing acid-washing stainless steel mud, metal in sludge constituent content is mainly by stainless steel
Matter determine, general two be three be mixing pickling system, substantially nickel content 1.0-3.0%, chromium content 3.5-7.0%, iron content 18-22%,
Can be as rustless steel metallurgical raw material.When in rustless steel containing manganese element, when only using lime slurry as neutralization precipitation agent,
Under conditions of pH=9, the waste water manganese ion severe overweight after process, only control ph is more than 10.2, and at this moment manganese ion is
Can precipitate completely.But the consequence brought is to have a large amount of calcium hydroxide unreacted complete, and sludge quantity increases, and the waste water after process must
PH to 6-9 must be adjusted back with sulphuric acid, produce again calcium sulfate precipitation, it is necessary to do further precipitate separating treatment, make follow-up simultaneously
Water treatment technology becomes complicated.
Metal chloride neutralization by lime equation is following (Me is metallic element):
MeCl2+Ca(OH)2=Me (OH)2↓+CaCl2
C) solution of chloride containing calcium after precipitation solid-liquid separation, repeats to prepare as pickle liquor, after utilizing 3-5 time, and calcium chloride concentration
Reaching more than 20%, this solution obtains crystallization of calcium chloride side-product through evaporative crystallization, can sell as general chemical raw material.Evaporation
The repeatable utilization of water reclaimed.
Compared with prior art the present invention also has the advantages that
The resource utilization method of the Treatment of Metal Surface mud of the present invention, compared with prior art, technique is simple, metallic element
Recovery utilization rate high, processing cost is low.Using hydrochloric acid to process mud as pickle liquor, metal in sludge Elements Leaching rate is high,
Realize the full recycling of metal in sludge element.The calcium salt mud of slightly solubility can the most convenient separate with metallic element.In acidleach
In the selection of liquid, not using nitric acid to make leachate, because after using nitric acid, the Determination of Total Nitrogen in Waste Water content of washing mud is difficult to as far as possible
Processing, and total nitrogen removing process is complicated, denitrogenation cost is high.Through measuring and calculating, often 30 tons of acid-washing stainless steel mud of process, recyclable 1
Ton stainless steel smelting needed raw material, resource recycles and is worth height, has appreciable economic worth.With the dirt of the present invention
Mud processing method, metallic element is fully used, the slightly solubility calcium salt mud of isolated also can recycling, processed
Journey non-secondary pollution and refuse produce.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, all equal based on the technical scheme described by present invention
Belong to the scope of the present invention, and should not be understood to convey that the invention be limited solely to below example.At the mud that the process resting period is longer
Time, the bivalence ferrous iron in mud can be gradually oxidized to ferric iron by the oxygen in air, now when processing this mud, should carry
The acidity of high pickle liquor, pH should control at 1.8-2.3, increases ferric leaching rate as far as possible and prevents ferric ion from hydrolyzing.
Embodiment 1
This mud be 200 be acid-washing stainless steel water process produce mud, moisture content about 46%.Sludge components: Fe (OH)2
14.60%；Cr(OH)34.60%；Ni(OH)20.44%；Mn(OH)21.38%；Cu(OH)20.37%；Calcium sulfate 10.05-12.45%；
Calcium fluoride 20.2-22%；Take this mud 1000Kg, be added in reaction tank, be computed iron content 90.8Kg in mud, chromium 23.0
Kg, nickel 2.8Kg, manganese 8.5Kg, copper 2.4Kg, from dewatered sludge elemental analysis data, metal sludge content 21.4%, no
Dissolubility calcium salt sludge content 30.4-34.5%, adds the hydrochloric acid solution 1.5m of 15%3Soaking mud, treat that mud softens, stirring is anti-
Answering 1 hour, now acidity is about pH=0.5, continues under agitation to add in this kind of sludge slurry and part free acid, controls
PH=2.0, stopping addition mud, this suspension of filter pressing after reacting 2 hours, the salt acid elution of the solid pH=3 obtained after filter pressing,
After filter pressing washes twice, in neutralization pond, addition lime slurry is to pH=6-9 in solid input, and filter pressing obtains content of beary metal less than state
The general industry solid waste of family's hazardous waste standard.When mud acidifying or washing, the addition of pickle liquor or cleaning mixture presses solid-to-liquid ratio
=1: 10-20 is more suitable, preferred solid-to-liquid ratio=1: 10.Cleaning mixture enters Waste Water Treatment, processes with Calx acid-base neutralization,
The a small amount of sludge slurry produced returns in acidleach pond, uses for neutralizing the free acid of excess.Mud acidleach pond reaction terminate after,
Containing a large amount of metallic elements in pressing filtering liquid, continue to use lime white neutralization precipitation, precipitation pH to control about 9.0.Filter pressing precipitates,
To precipitate metal hydroxides, in this precipitate, the relative abundance of metallic element is close with the metallic element composition of pickling of stainless steel,
Can be as stainless metallurgical raw material.After the suspension filter pressing of metal hydroxides, solution returns to mud acidleach pond, as configuration
Pickle liquor is reused 3-5 time, when calcium chloride concentration is more than 20%, stops reuse, and calcium chloride side-product is reclaimed in evaporation.
Process this mud of 1000Kg, obtain aqueous 50% insoluble calcium phosphate mud about 630Kg, obtain the hydroxide of aqueous 50%
Thing mud 430Kg, iron content 21.0% in mud, chromium 5.2%, nickel 0.87%, manganese 1.9%, copper 0.53%.CALCIUM CHLORIDE DIHYDRATE
300Kg。
Embodiment 2
This mud be 200 be 300 be mixing acid-washing stainless steel water process produce mud, moisture content about 68%.Sludge components:
Sludge components: iron-holder 5.62%；Chrome content 0.53%；Nickel content 0.31%；Manganese content 0.36%；Mix in wet mud, gold
Belong to hydroxide and account for 11.7%, calcium sulfate Calcium Fluoride Content 20.3%, take this mud 1000Kg, be added in reaction tank, through meter
Calculate iron content 56.2Kg in mud, chromium 5.3Kg, nickel 3.1Kg, manganese 3.6Kg, add the hydrochloric acid solution 1.2m of 15%3Soak dirt
Mud, treats that mud softens, stirring reaction 1 hour, and now acidity is about pH=0.5, continues under agitation to add this kind of mud mud
Slurry, neutralizes part free acid, controls pH=3.0, stops adding mud, this suspension of filter pressing after reacting 1.5 hours, and solid is used
The salt acid elution of pH=3, after filter pressing washes twice, solid adds lime slurry to pH=6-9 in neutralization pond, and filter pressing obtains a huge sum of money
Belong to the content general industry solid waste less than National Hazard refuse standard.When mud acidifying or washing, pickle liquor or the addition of cleaning mixture
Amount is more suitable by solid-to-liquid ratio=1: 10-20, preferred solid-to-liquid ratio=1: 10.The cleaning mixture of insoluble calcium phosphate mud enters waste water and processes
System, uses lime slurry neutralisation treatment, and a small amount of sludge slurry of generation uses as neutralizing the free acid of excess in acidleach pond, reaction
After end, pressing filtering liquid contains a large amount of metallic elements, continues to use lime slurry neutralization precipitation, precipitation pH to control about 9.0.Filter pressing
Precipitate, obtains precipitate metal hydroxides, and in this precipitate, the relative abundance of metallic element and the composition of pickling of stainless steel are close,
Can be as stainless metallurgical raw material.The pressing filtering liquid of precipitate metal hydroxides, returns to mud acidleach pond, as configuration pickle liquor
Reusing 3-5 time, when calcium chloride concentration is more than 20%, stop reuse, calcium chloride is reclaimed in evaporation.
Process this mud of 1000Kg, obtain aqueous 50% insoluble calcium phosphate mud about 410Kg, obtain the hydroxide of aqueous 50%
Thing mud 234Kg, (moisture content 50%) iron content 22%, chromium 2.2%, nickel 1.3%, manganese 1.5%, CALCIUM CHLORIDE DIHYDRATE in mud
180Kg。
Embodiment 3
Treatment of Industrial Park of Plating mud 1000Kg, moisture content 70% calculates, and is mainly calcium sulfate, calcium phosphate and metallic hydrogen in solid matter
Hopcalite.According to elementary analysis, tenor is about 60-75Kg, and the amount of equivalent metal hydroxides is
In 92-115Kg, 300Kg solid, about 200Kg is insoluble calcium salt mud, and 100Kg is metal hydroxides mud.Add
Enter the hydrochloric acid solution 1.2m of 15%3Soak mud, treat that mud softens, stirring reaction 1 hour, now acidity is about pH=0.5,
Continuing under agitation to add in this kind of sludge slurry and part free acid, control pH=3.0, stop adding mud, reaction 1.5 is little
This suspension of filter pressing time after, the salt acid elution of solid pH=3, after filter pressing washes twice, solid adds Calx in neutralization pond
Emulsion is to pH=6-9, and filter pressing obtains the content of beary metal general industry solid waste less than National Hazard refuse standard.Mud is acidified or washes
When washing, the addition of pickle liquor or cleaning mixture is more suitable by solid-to-liquid ratio=1: 10-20, preferred solid-to-liquid ratio=1: 10.Insoluble calcium
The cleaning mixture of salt mud enters Waste Water Treatment, processes with Calx acid-base neutralization, a small amount of sludge slurry of generation, as neutralizing acid
In soaking pit, the free acid of excess uses, and after reaction terminates, filter pressing obtains containing a large amount of metallic element solution, and this solution continues to use Calx
Slurry neutralization precipitation, precipitation pH controls about 9.0.Filter pressing precipitates, and obtains precipitate metal hydroxides, metal in this precipitate
The relative abundance of element is close with the composition of pickling of stainless steel, can be as stainless metallurgical raw material.After filter pressing metal hydroxides
Solution return mud acidleach pond, as configuration pickle liquor reuse 1-4 time, when calcium chloride concentration more than 20% time, stopping
Reuse, calcium chloride is reclaimed in evaporation.
Process this mud of 1000Kg, obtain aqueous 50% insoluble calcium phosphate mud about 420Kg, obtain the metallic hydrogen of aqueous 50%
Oxide mud 230Kg, CALCIUM CHLORIDE DIHYDRATE 160Kg.Obtain single metallic element, must also separating treatment further.
Embodiment 4
This mud be 200 be 300 be mixing acid-washing stainless steel water process produce mud, deposit a period of time, moisture content 65%
Left and right, mud is bronzing, and part ferrous iron autoxidation becomes ferric iron.Sludge components: sludge components: iron-holder 5.88%；
Chrome content 0.56%；Nickel content 0.32%；Manganese content 0.38%；Mixing in wet mud, metal hydroxides accounts for 11.7%, sulphuric acid
Calcium Calcium Fluoride Content 20.3%, takes this mud 1000Kg, is added in reaction tank, is computed iron content 58.8Kg in mud, chromium 5.6
Kg, nickel 3.2Kg, manganese 3.8Kg, add the hydrochloric acid solution 1.2m of 15%3Soak mud, treat that mud softens, stir reaction 1
Hour, now acidity is about pH=0.5, continues under agitation to add this kind of sludge slurry, neutralizes part free acid, controls
PH=1.8-2.3, stops adding mud, and improving acidity purpose in mud is to prevent ferric precipitation, filter pressing after reacting 1.5 hours
This suspension, the salt acid elution of solid pH=3, after filter pressing washes twice, solid adds lime slurry extremely in neutralization pond
PH=6-9, filter pressing obtains the content of beary metal general industry solid waste less than National Hazard refuse standard.When mud acidifying or washing,
The addition of pickle liquor or cleaning mixture is more suitable by solid-to-liquid ratio=1: 10-20, preferred solid-to-liquid ratio=1: 10.Cleaning mixture enters waste water
Processing system, processes with Calx acid-base neutralization, and a small amount of sludge slurry of generation uses as neutralizing the free acid of excess in acidleach pond.
After reaction terminates, the pressing filtering liquid in acidleach pond, containing a large amount of metallic elements, continues to use lime white neutralization precipitation, precipitation pH to control
9.0 left and right.Filter pressing precipitates, and obtains precipitate metal hydroxides, the relative abundance of metallic element and pickling of stainless steel in this precipitate
Composition close, can be as stainless metallurgical raw material.Solution after filter pressing metal hydroxides returns to mud acidleach pond, as
Configuration pickle liquor is reused 3-5 time, when calcium chloride concentration is more than 20%, stops reuse, and calcium chloride is reclaimed in evaporation.
Process this mud of 1000Kg, obtain aqueous 50% insoluble calcium phosphate mud about 420Kg, obtain the hydroxide of aqueous 50%
Thing mud 236Kg, (aqueous 50%) iron content 22.8%, chromium 2.3%K, nickel 1.3%, manganese 1.6%, two chloride hydrate in mud
Calcium 190Kg.
Embodiment 5
This mud be 300 be acid-washing stainless steel water process produce mud, deposit a period of time, moisture content about 65%.Mud
Composition: sludge components: iron-holder 5.72%；Chrome content 1.06%；Nickel content 0.52%；Take this mud 1000Kg, be added to acid
In soaking pit pond, it is computed iron content 57.2Kg in mud, chromium 10.6Kg, nickel 5.2Kg.Add the hydrochloric acid solution 1.2m of 15%3
Soaking mud, treat that mud softens, stirring reaction 1 hour, now acidity is about pH=0.5, continues under agitation to add this kind
Sludge slurry, neutralization part free acid, control pH=2.0-2.3, stopping addition mud, this suspension of filter pressing after reacting 1.5 hours,
The salt acid elution of solid pH=3, after filter pressing washes twice, solid is thrown in addition lime slurry in neutralization pond and is regulated to pH=6-9,
Filter pressing obtains the content of beary metal general industry solid waste less than National Hazard refuse standard.Mud acidifying or washing time, pickle liquor or
The addition of cleaning mixture is more suitable by solid-to-liquid ratio=1: 10-20, preferred solid-to-liquid ratio=1: 10.Cleaning mixture enters Waste Water Treatment,
Processing with Calx acid-base neutralization, a small amount of sludge slurry of generation uses as neutralizing the free acid of excess in acidleach pond.After reaction terminates,
The pressing filtering liquid in acidleach pond, containing a large amount of metallic elements, continues to use lime white neutralization precipitation, precipitation pH to control about 9.0.Filter pressing
Precipitation, obtains precipitate metal hydroxides, and in this precipitate, the relative abundance of metallic element and the composition of pickling of stainless steel are close,
Can be as stainless metallurgical raw material.Solution after filter pressing metal hydroxides, returns to mud acidleach pond as configuration pickle liquor weight
Using 3-5 time again, when calcium chloride concentration is more than 20%, stop reuse, calcium chloride is reclaimed in evaporation.
Process this mud of 1000Kg, obtain aqueous 50% insoluble calcium phosphate mud about 430Kg, obtain the hydroxide of aqueous 50%
Thing mud 270Kg, (aqueous 50%) iron content 21.0%, chromium 6.1%K, nickel 1.9%, CALCIUM CHLORIDE DIHYDRATE 196Kg in mud.
Claims (4)
1. a resource utilization method for Treatment of Metal Surface mud, the method uses the acid-hatching of young eggs to leach metal in sludge element, it is characterised in that:
A) the mud hydrochloric acid containing metal or nitric acid are acidified immersion, the hydrochloric acid of preferably 5-15% makees pickle liquor, leaching the metallic element in mud, by slightly solubility calcium salt and metallic element solid-liquid separation, filter pressing obtains slightly solubility calcium salt sewage sludge solid and metal chloride or nitrate solution；
B) by step A) slightly solubility calcium salt sewage sludge solid pH=3.0 ± 0.2 dilute hydrochloric acid solution washing, filter pressing, wash again, filter pressing again, repeat 1-3 time, remove the poisonous and harmful metal ion of residual in solid, rinsing to pH=6-8 with lime slurry regulation, filter pressing obtains calcium sulfate or calcium fluoride or calcium phosphate or its mix product again；
C) by step A) metal chloride solutions that obtains, it is neutralized to pH≤9.0 with lime slurry, precipitate metal ion in the basic conditions, obtain metal hydroxides, more specifically method is to neutralize with lime slurry, response time controls at 0.5-2.0 hour, and filter pressing separates, and obtains metal hydroxides product；
D) step C) filtrate be that configuration pickle liquor is used repeatedly, when Chlorine in Solution calcium reaches finite concentration, discharge, evaporation reclaim calcium chloride product.
The resource utilization method of Treatment of Metal Surface mud the most according to claim 1, it is characterized in that step A controls between 0.5-1.0 at pH, stirring reaction 1-3 hour, metal ion in Ore Leaching mud, then the hydrochloric acid of excess is neutralized with pending sludge slurry, control solid-to-liquid ratio between 1: 10-20, pH controls between 1.8-3.0, continuing stirring reaction 1-2 hour, after reaction stops, filter pressing obtains calcium sulfate or calcium fluoride or calcium phosphate or its mix product.
The resource utilization method of Treatment of Metal Surface mud the most according to claim 1 and 2, uses dilute hydrochloric acid to make cleaning mixture, it is characterised in that the consumption of cleaning mixture controls to control between 1: 10-20 in solid-to-liquid ratio.
The resource utilization method of Treatment of Metal Surface mud the most according to claim 1, it is characterised in that the filtrate cycle of step C is used for configuring pickle liquor 3-5 time, when in filtrate, calcium chloride concentration is more than 20%, calcium chloride product is reclaimed in evaporation.
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| CN201510027612.4A CN105884156A (en) | 2015-01-20 | 2015-01-20 | Resource utilization method for metal surface treatment sludge |
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| CN201510027612.4A CN105884156A (en) | 2015-01-20 | 2015-01-20 | Resource utilization method for metal surface treatment sludge |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106746391A (en) * | 2016-11-16 | 2017-05-31 | 环境保护部南京环境科学研究所 | A kind of phosphatization recycling sludge method of disposal |
| CN107140799A (en) * | 2017-04-26 | 2017-09-08 | 天津壹新环保工程有限公司 | A kind of online decrement treatment method and apparatus of sludge |
| CN108863014A (en) * | 2018-04-28 | 2018-11-23 | 广西博世科环保科技股份有限公司 | A method of applied to the molten leaching slurry drainage of nickeliferous electroplating sludge acid |
| CN109133549A (en) * | 2018-09-04 | 2019-01-04 | 许晓原 | The processing method of acid washing phosphorization sludge |
| CN109400035A (en) * | 2018-11-06 | 2019-03-01 | 泰州华昊废金属综合利用有限公司 | The method for preparing concrete brick using Treatment of Metal Surface waste |
| CN109897954A (en) * | 2019-03-27 | 2019-06-18 | 东北师范大学 | A kind of purification process for cold rolling iron cement |
| CN111088412A (en) * | 2019-12-16 | 2020-05-01 | 霸州环瑞节能科技有限公司 | Acid pickling sludge resource utilization method |
| CN112358148A (en) * | 2020-11-04 | 2021-02-12 | 昆明理工大学 | Resourceful treatment method for domestic sludge |
| CN112573786A (en) * | 2020-10-12 | 2021-03-30 | 江苏荣信环保科技有限公司 | Treatment process for waste sulfuric acid sludge on surface of metal product |
| CN112573580A (en) * | 2020-10-12 | 2021-03-30 | 江苏荣信环保科技有限公司 | Recovery treatment process of ferric trichloride sludge on surface of metal product |
| CN112573581A (en) * | 2020-10-12 | 2021-03-30 | 江苏荣信环保科技有限公司 | Recovery treatment process of waste acid ferric trichloride on surface of metal product |
| CN115180791A (en) * | 2022-07-12 | 2022-10-14 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for washing and desalting iron-containing acidic sludge |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106746391A (en) * | 2016-11-16 | 2017-05-31 | 环境保护部南京环境科学研究所 | A kind of phosphatization recycling sludge method of disposal |
| CN107140799A (en) * | 2017-04-26 | 2017-09-08 | 天津壹新环保工程有限公司 | A kind of online decrement treatment method and apparatus of sludge |
| CN108863014B (en) * | 2018-04-28 | 2021-08-06 | 广西博世科环保科技股份有限公司 | Method for assisting in filtering acid-soluble leached slurry of nickel-containing electroplating sludge |
| CN108863014A (en) * | 2018-04-28 | 2018-11-23 | 广西博世科环保科技股份有限公司 | A method of applied to the molten leaching slurry drainage of nickeliferous electroplating sludge acid |
| CN109133549A (en) * | 2018-09-04 | 2019-01-04 | 许晓原 | The processing method of acid washing phosphorization sludge |
| CN109400035A (en) * | 2018-11-06 | 2019-03-01 | 泰州华昊废金属综合利用有限公司 | The method for preparing concrete brick using Treatment of Metal Surface waste |
| CN109897954A (en) * | 2019-03-27 | 2019-06-18 | 东北师范大学 | A kind of purification process for cold rolling iron cement |
| CN111088412A (en) * | 2019-12-16 | 2020-05-01 | 霸州环瑞节能科技有限公司 | Acid pickling sludge resource utilization method |
| CN112573786A (en) * | 2020-10-12 | 2021-03-30 | 江苏荣信环保科技有限公司 | Treatment process for waste sulfuric acid sludge on surface of metal product |
| CN112573580A (en) * | 2020-10-12 | 2021-03-30 | 江苏荣信环保科技有限公司 | Recovery treatment process of ferric trichloride sludge on surface of metal product |
| CN112573581A (en) * | 2020-10-12 | 2021-03-30 | 江苏荣信环保科技有限公司 | Recovery treatment process of waste acid ferric trichloride on surface of metal product |
| CN112358148A (en) * | 2020-11-04 | 2021-02-12 | 昆明理工大学 | Resourceful treatment method for domestic sludge |
| CN115180791A (en) * | 2022-07-12 | 2022-10-14 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for washing and desalting iron-containing acidic sludge |
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