CN102992513A - Method for producing ferric salt-series purifiers by recycling and comprehensive utilizing stainless steel waste etching solution - Google Patents

Method for producing ferric salt-series purifiers by recycling and comprehensive utilizing stainless steel waste etching solution Download PDF

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CN102992513A
CN102992513A CN2012104647030A CN201210464703A CN102992513A CN 102992513 A CN102992513 A CN 102992513A CN 2012104647030 A CN2012104647030 A CN 2012104647030A CN 201210464703 A CN201210464703 A CN 201210464703A CN 102992513 A CN102992513 A CN 102992513A
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China
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stainless steel
nickel
waste liquor
iron
etching waste
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CN2012104647030A
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Chinese (zh)
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王富鑫
张秀媛
王柳洋
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天津市聚鑫源水处理技术开发有限公司
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Publication of CN102992513A publication Critical patent/CN102992513A/en

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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention relates to a method for producing ferric salt-series purifiers by recycling and comprehensive utilizing a stainless steel waste etching solution, which is developed for overcoming the defects of high production cost, halfway separation and complicated operation existing in the traditional stainless steel waste etching solution regeneration and nickel recovery technology. The method comprises the following steps of: firstly performing component analysis on the waste etching solution, additionally adding a certain amount of ferrous sulfate heptahydrate crystal according to the contents of nickel and chromium, and then oxidizing by using ozone; when Fe<2+> in a mixture is all oxidized to Fe<3+>, moving the mixture to a crystallization kettle, and adding hydrochloric acid to regulate pH value; forming hydrated sulfate and chlorate crystallized substances containing nickel and chromium ions by controlling the crystallization temperature and time, stirring speed and pH value; performing solid-liquid seperation on the crystallized substances, and then performing secondary crystallization when the contents of nickel and chromium in a filtrate are proper until the contents of the nickel and chromium in the filtrate are less than 100PPM; obtaining ferric chloride as a chemical component of the filtrate after separation, and producing other ferric salt-series purifiers by adjusting the amounts of ferrous sulfate and the hydrochloric acid.

Description

A kind of stainless steel etching waste liquor comprehensive utilization of resources is produced the method for molysite series water purification agent
Technical field
The invention belongs to the comprehensive utilization of resource and environment field waste, the application technology as the second resource that relates to the etching waste liquor that produces in a kind of stainless steel surface etching and processing particularly relates to and a kind of the nickel that contains in the stainless steel etching waste liquor, chromium ion is separated removal, filtrate for the production of the method for molysite series water purification agent product with crystalline hydrate thing form from mixture.
Background technology
Stainless steel is because of surface and the excellent processing characteristics of its superior solidity to corrosion, uniqueness, and the production application development is swift and violent.The stainless steel plate any surface finish has higher plasticity, toughness and physical strength, and the corrosion of acid-and base-resisting, gas and other media is widely used in industry, decoration and the life.
Development along with electronics, mechanics of communication, the little increase in demand of high performance essence, the super-thin workpiece that stainless steel Cellphone Accessories, the electrical fittings take nickel, chromium element as alloy base material more and more need many complex geometry, precision requirement high mechanical workout to be difficult to realize.Stainless Steel Products decorative pattern, pattern, artwork, stainless steel label are good, attractive in appearance because of antiseptic property, more and more are applied to such as places such as elevator door, subway, warning signs.The stainless steel processing method because easily reach parts smooth, without burr, figure is numerous and diverse, the degree of depth is controlled requirement, and the process-cycle is short, cost is low, has become the precise machining process that is rising.
At present, the most frequently used etching reagent of the etching of Stainless Steel Alloy is iron trichloride, and, etching cycle low because of its price grown, controlled etch depth easily, has become and has made electrical fittings, communication stainless steel accessory, the indispensable etching solution of stainless steel surface processing patterns.
Iron trichloride etching solution etching metal is to utilize FeCI 3Middle high price Fe 3+Ion has the principle that stronger oxidisability and the metal in the alloy carry out chemical reaction, makes metal in the alloy be oxidized to ion and is dissolved into the etching solution from substrate.Liquor ferri trichloridi is as follows as the chemical equation of metal in etching reagent and the alloy:
2FeCI 3+Fe→3FeCI 2
2FeCl 3+Ni→NiCI 2+2FeCI 2
3FeCl 3+Cr→CrCI 3+3FeCI 2
By chemical principle as can be known, enter in the etching solution with ionic forms after the metal in the etching process interalloy is reduced.Carry out the Fe of high price along with etched 3+Ionic concn is more and more lower, Fe in the etching solution 2+, Ni 2+, Cr 3+Plasma concentration is more and more higher.Along with the accumulation of the concentration of metal ions under etched, etching solution all significantly descends to corrosion speed, etch capabilities, the etching efficiency of metal alloy, continues to use to cause etched surfaces coarse the etching quality variation again.This moment, etching solution also just lost etch capabilities, the etching solution that need carry out manipulation of regeneration or more renew the etching solution that lost efficacy.
To the manipulation of regeneration of inefficacy etching solution, the on-the-spot oxidation of general employing is regenerated on the technique.Main method has directly logical chlorine or adds the strong oxidizers such as hydrogen peroxide makes the ferrous iron in the inefficacy etching solution become ferric iron, etch functions is recovered after making the concentration of iron trichloride reach finite concentration.But so that product is improved quality at etching performance with to the etch effect of machining object descends very soon, the twice later etch effect of regenerate degenerates with regard to detail because of accumulation that the accumulation of iron, nickel, chromium ion, especially nickel, chromium are arranged in the etching solution.Etching solution can not be realized permanent regeneration, therefore will constantly discharge the ferric trichloride etching waste liquor of iron content, nickel, chromium ion on the stable production line, the etching solution that more renews.The disposal of ferric trichloride etching waste liquor has become the difficult problem of stainless steel etching and processing industry.
At present both at home and abroad to the disposal of stainless steel etching waste liquor mainly concentrate on the regeneration of etching waste liquor, the removal Separation and Recovery of nickel is utilized, studying more main renovation process has facture that iron replacement reduction method, film electrolytic regeneration method, extraction process, evaporating, concentrating and crystallizing method, the neutralizing hydrolysis precipitator method and several method combine etc.These methods are the Shortcomings part separately.
The iron replacement reduction method is utilized the metal displacement reaction principle, excessive high reactivity reduced iron powder is joined in the etching waste liquor nickel is cemented out and is attached on the iron powder surface, by solid-liquid separation the nickel that displaces is removed.Iron powder is reduced and is converted into ferrous ion and enters and form solution of ferrous chloride in the solution.Such as CN02116014.7 " the nickel method of removing of Ni from waste etching FeCl 3 solution containing ".This patent is the nickel method of removing for the ferric trichloride etching waste liquor of wiring board, television picture tube shadow mask etching generation.High-purity iron powder with excessive 100~150% or squamous iron sheet join and carry out reduction reaction in the Ni from waste etching FeCl 3 solution containing, reacted 20~180 minutes, and heated mixt to 55~95 ℃, again toward wherein adding iron powder and SULPHUR POWDER or arsenide or antimony compounds, carry out the precipitin reaction of nickelous, then filter, nickel is separated from ferric trichloride etching waste liquor.The weak point of this method is to have consumed a large amount of iron powders, wherein the overwhelming majority consume with waste liquid in ferric chloride reaction generate on the iron protochloride, and the nickel displacement is not thorough, still containing nickel ion in the solution of ferrous chloride can not thoroughly separate, produce hydrogen with the acid-respons that dissociates in the displacement, this method needs to carry out under heating simultaneously, has consumed a large amount of energy, and is high to this cost.
Extraction separation method CN03131945.9 " extraction separating method of Ni from waste etching FeCl 3 solution containing " utilizes the solvent selection principle that mixes, and forms water and oil phase.Pass into first chlorine and make oxidation of divalent become ferric iron, the waste liquid after the oxidation joins in the extracting system, and iron trichloride enters oil phase, and nickelous chloride enters water, realizes the separation of nickel.Need in oil phase, to add a large amount of sour waters but strip, make iron trichloride enter water with low levels.The low levels iron trichloride needs evaporation concentration just can reach the concentration that re-uses, and still contains the nickel ion of higher concentration in the iron trichloride.Evaporation concentration can produce a large amount of acid waste water in addition, and passes into chlorine and cause security to be subject to danger, and the technological operation difficulty is large, cost recovery is high.
Film electrolytic regeneration method is to utilize ionic membrane or barrier film to carry out electrolytic separation, and nickel ion is separated with iron.Although this technique does not consume new chemical feedstocks, the method equipment is complicated, needs a large amount of electric energy during electrolysis, processes comprehensive cost more than 1400 yuan/m3 etching solution, and processing cost is high, and nickel, chromium, iron separates limitedly, is not suitable for suitability for industrialized production.
Evaporation concentration crystallisation by cooling method patent CN200310120087.8 " renovation process of Ni from waste etching FeCl 3 solution containing " is the waste liquid that produces for only " invar " etching nickeliferous, iron that the television picture tube shadow mask uses, the evaporation concentration crystallisation by cooling method of employing.At first waste liquid is concentrated to 70~80% of initial volume, is cooled to 40~50 ℃, and then add 1.5~2 times waste liquid stoste, and mixture is cooled to≤below 17 ℃, crystallization 24~60 hours obtains containing the FeCl of micro-nickel 3.6H 2The O crystal carries out solid-liquid separation and goes out crystallisate, adds a certain amount of water again and again is made into the iron trichloride etching solution.The method is separated not thorough, contains a large amount of FeCl in the stoste 2, FeCl 2Solubleness be lower than FeCl 3, can preferential FeCl 3Crystallize out FeCl 3.6H 2Can contain a large amount of FeCl in the O crystal 2.4H 2O and nickelous chloride crystal.
The neutralizing hydrolysis precipitator method; adjust PH to weakly alkaline with alkaline matter (sodium hydroxide, yellow soda ash); forming the precipitations such as ironic hydroxide, nickel hydroxide separates; throw out need to wash, separates, drying; the a large amount of industrial chemicals of this method consumption, and can produce the higher waste water of a large amount of saltiness, cause secondary pollution; and processing cost is higher, and large-scale production is unrealistic.
Present stage, the base material that electron trade and stainless steel decoration industry are commonly used is 304# (0Cr19Ni9) stainless steel nickeliferous, chromium.Ni accounts for 8.0~11.0% in its chemical ingredients, Cr accounts for 17.0~19.0%, Fe and account for 65~70.0%.Contain Ni2+, Cr3+, Fe in the waste liquid after the etching 2+Ion and unreacted FeCl 3, hydrochloric acid.If the not treated direct discharging of etching waste liquor can cause the pollution of water surrounding, and a large amount of valuable nickel, chromium, iron resources are by slatterning in vain.And the cost that qualified discharge can increase scale wastewater treatment is processed in the etching waste liquor water treatment, and therefore, the method for seeking a kind of economy, effectively stainless steel etching waste liquor comprehensive utilization is very necessary.
Summary of the invention
The object of the invention is to overcome the deficiency of existing etching waste liquid regeneration, recovery nickel technology production cost height, complicated operation, in line with the principle of resource reutilization, invent the method that a kind of stainless steel etching waste liquor comprehensive utilization of resources is produced iron series water purifier.
Principle of the present invention is to utilize metallic compound deliquescent difference under differing temps, different PH, in the different solutions, makes nickel in the etching waste liquor, chromium ion with the form solid-liquid separation of hydrated sulfate, chlorination crystallisate by crystallization control temperature, time, stirring velocity.Liquid phase after the separation is that iron chloride salt can be produced iron system (iron trichloride, poly-ferric chloride, poly-ferric sulfate chloride, ferric chloride (FeCl36H2O) etc.) water purification agent, nickel, chromium can be used as stainless raw materials for metallurgy and further utilize than the ratio near element in the stainless steel in the hydrated sulfate that solid phase nickel after the separation, chromium, iron ion form, the chlorination crystalline mixture.
The inventive method realizes by following technique.At first etching waste liquor is carried out the component content analysis, add a certain amount of iron vitriol crystal according to nickel, chromium content size.The ozone that sends with ozonizer carries out oxidation to etching waste liquor, rely on oxidation heat liberation that mixeding liquid temperature is raise, speed by the control oxidation, make temperature slowly rise to certain insulation, after the ferrous ion in the etching waste liquor mixture all is oxidized to ferric ion, well-oxygenated etching waste liquor mixture is moved on in the crystallization kettle.According to etching solution mixture acidity situation, add acidity regulator, regulate the pH value of etching waste liquor mixture to certain limit.By temperature, time, stirring velocity, the pH value of crystallization control process, form nickeliferous, the hydrated sulfate of chromium ion, chlorate crystallisate.The crystallisate that obtains carries out solid-liquid separation with whizzer.Detect nickel, chromium content in the filtrate, carry out again in case of necessity secondary crystal, until nickel, chromium content are lower than 100PPM in the filtrate.
This project technical matters is simple, strong operability, do not increase more other ions and enter in the etching waste liquor, the oxidized rear ferric iron that all is converted into of the ferrous ion that adds, nickel, chromium ion are with form and the liquid separation of vitriol, hydration chlorination crystallisate, filtrate product chemical ingredients is iron(ic) chloride, meets GB4482-2006 ferric chloride purifying agent II class standard index.Also can produce other molysite water clarifiers by proportioning or the evaporation concentration of adjusting ferrous sulfate, acidity, realize the purpose of the treatment of wastes with processes of wastes against one another, cleaner production, resource reutilization.
Embodiment
The etching waste liquor that produces take certain electronic enterprise etching 304# stainless steel plate is as raw material, and comprehensive utilization of resources is produced molysite series flocculants product.Main component in the etching waste liquor is FeCI by analysis 3: 16.3%; FeCl 2: 18.6%; Ni:0.41%; Cr:0.83%; HCI:0.25%; Insolubles: 0.03%; Surplus is water.
Embodiment one:
1, with in the 1000L stills for air blowing of squeezing into after 1000 kilograms of meterings of etching waste liquor with temperature-controlled, starts stirring, add 5 kilograms of iron vitriol crystal 4s, make its under agitation constantly dissolving.
2, start ozonizer, the ozone that goes out is passed in the stills for air blowing, along with the carrying out of oxidation heat liberation, temperature can raise slowly, control ozone generating capacity, and insulation reaction when temperature is elevated to 55~60 ℃ is until ferrous sulfate all dissolves.
3, the ferrous ion content in the detection etching waste liquor stops ozone oxidation until ferrous ion approaches when all being oxidized to ferric ion, and mixture is squeezed in the crystallization kettle.
4, the hydrochloric acid soln of adding an amount of 30% in the crystallization kettle adjust mixture PH between 0.2~0.5, and it is constant to remain on this scope.
5, the crystallization kettle stirring velocity is adjusted to 20~30 rev/mins, and under this temperature, stirring velocity, be incubated 5~6 hours, the crystalline particulate deposits yields is arranged.
6, with filter-cloth filtering, isolate crystallisate, crystallisate is separated with whizzer, obtain the crystalline mixture of seven water single nickel salts, Hexaaquachromium chloride, Iron dichloride tetrahydrate, four hydration nickelous chlorides.
7, the filtrate after filtrate and the centrifugation is merged to be driven in second crystallization kettle carry out secondary crystal.35~40 ℃ of lower insulations 5~6 hours, and be interrupted and stir, the control stirring velocity has crystallisate to produce at 10~15 rev/mins.
8, the filtering separation crystallisate separates crystallisate with whizzer, again obtains the crystalline mixture of seven water single nickel salts, Hexaaquachromium chloride, Iron dichloride tetrahydrate, four hydration nickelous chlorides.
9, twice crystallisate is merged, the crystallisate of nickeliferous, chromium, iron ion is sold to the smeltery as the raw material of stainless steel smelting carries out deep processing.
10, filtrate is squeezed in the storage tank, obtain the solution of iron trichloride content more than 38%.Testing product adds an amount of hydrochloric acid in case of necessity to adjust free acid content at acceptability limit.
Iron trichloride product technology parameter
? Index name Index request Detected result
1 Outward appearance Reddish-brown liquid Reddish-brown liquid
2 Iron(ic) chloride (FeCl 3), content 〉= 38.0 39.42
3 Iron protochloride (FeCl 2) content≤ 0.40 0.12
4 Insolubles content≤ 0.50 0.05
5 Free acid (in HCI) content≤ 0.50 0.12
6 Arsenic (As) content≤ 0.002 Qualified
7 Plumbous (pb) content≤ 0.004 Qualified
Embodiment two:
1, with in the 1000L stills for air blowing of squeezing into after 1000 kilograms of meterings of etching waste liquor with temperature-controlled, starts stirring, add 5 kilograms of iron vitriol crystal 4s, make its under agitation constantly dissolving.
2, start ozonizer, the ozone that goes out is passed in the stills for air blowing, along with the carrying out of oxidation heat liberation, temperature can raise slowly, control ozone generating capacity, and insulation reaction when temperature is elevated to 55~60 ℃ is until ferrous sulfate all dissolves.
3, the ferrous ion content in the detection etching waste liquor until ferrous ion approaches the oxidation that stops ozonizer when all being oxidized to ferric ion, is squeezed into mixture in the crystallization kettle.
4, the hydrochloric acid soln of adding an amount of 30% in the crystallization kettle adjust mixture PH between 0.5~1, and it is constant to remain on this scope.
5, the crystallization kettle stirring velocity is adjusted to 20~30 rev/mins, and under this temperature, stirring velocity, be incubated 5~6 hours, the crystalline particulate deposits yields is arranged.
6, with filter-cloth filtering, isolate crystallisate, crystallisate is separated with whizzer, obtain the crystalline mixture of seven water single nickel salts, Hexaaquachromium chloride, Iron dichloride tetrahydrate, four hydration nickelous chlorides.
7, the filtrate after filtrate and the centrifugation is merged to be driven in second crystallization kettle carry out secondary crystal.35~40 ℃ of lower insulations 5~6 hours, and be interrupted and stir, the control stirring velocity has crystallisate to produce at 10~15 rev/mins.
8, the filtering separation crystallisate separates crystallisate with whizzer, again obtains the crystalline mixture of seven water single nickel salts, Hexaaquachromium chloride, Iron dichloride tetrahydrate, four hydration nickelous chlorides.
9, twice crystallisate is merged, the crystallisate of nickeliferous, chromium, iron ion is sold to the smeltery as the raw material of stainless steel smelting carries out deep processing.
10, filtrate is squeezed in the storage tank, testing product obtains iron(ic) chloride content and is the poly-ferric chloride solution with low polymerization degree more than 38%.
The poly-ferric chloride technical target of the product
Sequence number Index name Indication range Detected result
1 Outward appearance Reddish brown~brown liquid Brown liquid
2 Density (g/cm 320℃)≥ 1.28 1.41
3 All iron content % 〉= 11.0 13.52
4 Reductibility is (with Fe 2+Count) %≤ 0.20 0.08
5 Basicity % 9.0~20.0 10.2
6 Insolubles content (%)≤ 0.3 0.08
7 PH (1% aqueous solution) 2.0~3.0 2.1
8 Heavy metal in lead (Pb) content %≤ 0.0005 Qualified
9 Arsenic (As) content %≤ 0.0001 Qualified
Embodiment three:
1, with in the 1000L stills for air blowing of squeezing into after 1000 kilograms of meterings of etching waste liquor with temperature-controlled, starts stirring, add 100 kilograms in iron vitriol crystal, make its under agitation constantly dissolving.
2, start ozonizer, the ozone that goes out is passed in the stills for air blowing, along with the carrying out of oxidation heat liberation, temperature can raise slowly, control ozone generating capacity, and insulation reaction when temperature is elevated to 55~60 ℃ is until ferrous sulfate all dissolves.
3, the ferrous ion content in the detection etching waste liquor until ferrous ion approaches the oxidation that stops ozonizer when all being oxidized to ferric ion, is squeezed into mixture in the crystallization kettle.
4, the hydrochloric acid soln of adding an amount of 30% in the crystallization kettle adjust mixture PH between 0.5~1.0, and it is constant to remain on this scope.
5, the crystallization kettle stirring velocity is adjusted to 20~30 rev/mins, and under this temperature, stirring velocity, be incubated 5~6 hours, the crystalline particulate deposits yields is arranged.
6, with filter-cloth filtering, isolate crystallisate, crystallisate is separated with whizzer, obtain the crystalline mixture of seven water single nickel salts, Hexaaquachromium chloride, Iron dichloride tetrahydrate, four hydration nickelous chlorides.
7, the filtrate after filtrate and the centrifugation is merged to be driven in second crystallization kettle carry out secondary crystal.35~40 ℃ of lower insulations 5~6 hours, and be interrupted and stir, the control stirring velocity has crystallisate to produce at 10~15 rev/mins.
8, the filtering separation crystallisate separates crystallisate with whizzer, again obtains the crystalline mixture of seven water single nickel salts, Hexaaquachromium chloride, Iron dichloride tetrahydrate, four hydration nickelous chlorides.
9, twice crystallisate is merged, the crystallisate of nickeliferous, chromium, iron ion is sold to the smeltery as the raw material of stainless steel smelting carries out deep processing.
10, filtrate is squeezed in the storage tank, the testing product technical indicator obtains all iron content and is the poly-ferric sulfate chloride solution with low polymerization degree more than 13%.
The poly-ferric sulfate chloride technical target of the product
Sequence number Index subjet Indication range Detected result
1 Outward appearance The red-brown thick liquid The red-brown thick liquid
2 All iron content % 〉= 11.0 13.80
3 Reductibility is (with Fe 2+Count) %≤ 0.10 0.08
4 Basicity % 8~12 10.15
5 Chlorination degree % 18~22 20
6 Viscosity (20 ℃)/mPa.S 11~15 14
7 Water insoluble matter content %≤ 0.2 0.08
8 PH (1% aqueous solution) 0.5~2.5 1.5
9 Heavy metal in lead (Pb) content %≤ 0.0005 Qualified
10 Arsenic (As) content %≤ 0.0001 Qualified
Embodiment four:
1, with in the 1000L stills for air blowing of squeezing into after 1000 kilograms of meterings of etching waste liquor with temperature-controlled, starts stirring, add 5 kilograms of iron vitriol crystal 4s, make its under agitation constantly dissolving.
2, start ozonizer, the ozone that goes out is passed in the stills for air blowing, along with the carrying out of oxidation heat liberation, temperature can raise slowly, control ozone generating capacity, and insulation reaction when temperature is elevated to 55~60 ℃ is until ferrous sulfate all dissolves.
3, the ferrous ion content in the detection etching waste liquor until ferrous ion approaches the oxidation that stops ozonizer when all being oxidized to ferric ion, is squeezed into mixture in the crystallization kettle.
4, the hydrochloric acid soln of adding an amount of 30% in the crystallization kettle adjust mixture PH between 0.2~0.5, and it is constant to remain on this scope.
5, the crystallization kettle stirring velocity is adjusted to 20~30 rev/mins, and under this temperature, stirring velocity, be incubated 5~6 hours, the crystalline particulate deposits yields is arranged.
6, with filter-cloth filtering, isolate crystallisate, crystallisate is separated with whizzer, obtain the crystalline mixture of seven water single nickel salts, Hexaaquachromium chloride, Iron dichloride tetrahydrate, four hydration nickelous chlorides.
7, the filtrate after filtrate and the centrifugation is merged to be driven in second crystallization kettle carry out secondary crystal.35~40 ℃ of lower insulations 5~6 hours, and be interrupted and stir, the control stirring velocity has crystallisate to produce at 10~15 rev/mins.
8, the filtering separation crystallisate separates crystallisate with whizzer, again obtains the crystalline mixture of seven water single nickel salts, Hexaaquachromium chloride, Iron dichloride tetrahydrate, four hydration nickelous chlorides.
9, twice crystallisate is merged, the crystallisate of nickeliferous, chromium, iron ion is sold to the smeltery as the raw material of stainless steel smelting carries out deep processing.
10, filtrate is squeezed into carry out evaporation concentration in the evaporating kettle, control vacuum tightness is at-0.08MP, and vaporization temperature is at 85~90 ℃, when enriched material proportion reaches 1.60 when above, stop evaporation concentration, be cooled to obtain crystallisate below 30 ℃, centrifugation obtains the ferric chloride (FeCl36H2O) crystal to crystallisate.The mother liquor reuse continues evaporation concentration.
The ferric chloride (FeCl36H2O) technical target of the product
? Index name Index request Detected result
1 Outward appearance Orange-yellow crystal Orange-yellow crystal
2 Iron(ic) chloride (FeCI 3.6H 2O), content 〉= 96 97.16
3 Iron protochloride (FeCI 2) content≤ 0.50 0.20
4 Water insoluble matter content≤ 0.50 0.02
5 Free acid (in HCI) content≤ 0.50 0.18
6 Arsenic (As) content≤ 0.002 0.001
7 Plumbous (pb) content≤ 0.004 0.002

Claims (10)

1. the method that stainless steel etching waste liquor comprehensive utilization of resources is produced molysite series water purification agent is characterized in that comprising the steps:
(1) will carry out the component content analysis from the etching waste liquor that produces in the stainless steel etching and processing production process, and according to the content of nickel, chromium, make a gesture of measuring according to the sulfate radical mole that formation sulphate crystal thing needs, calculating need to be added the molysite consumption of containing sulfate radicals.
(2) with in the stills for air blowing of squeezing into after the etching waste liquor metering with temperature-controlled, start stirring, add the molysite of the containing sulfate radicals of metering, make it under agitation constantly be dissolved into the etching waste liquor mixture.
(3) the etching waste liquor mixture is carried out oxidation, stop oxidation until detect when ferrous ion is approaching all to be oxidized to ferric ion, the mixture after the oxidation is squeezed in the crystallization kettle.
(4) in crystallization kettle, add an amount of PH conditioning agent, adjust mixing speed and crystallization kettle temperature, make nickel, chromium ion in the mixture form the crystalline hydrate composition granule.Filter, separate crystalline hydrate composition granule nickeliferous, chromium ion.Filtrate being contains the water purification agent of iron trichloride, as obtaining the Iron trichloride hexahydrate crystal after the evaporation concentration.
2. a kind of stainless steel etching waste liquor comprehensive utilization of resources according to claim 1 is produced the method for molysite series water purification agent, it is characterized in that described stainless steel etching waste liquor is take iron trichloride as etching solution stainless steel to be carried out the waste liquid that produces after the etching, the composition in the etching waste liquor contains metal and the salt acid ions such as ferrous iron, ferric iron, nickel, chromium by stainless material difference.The content of nickel, chromium ion also use discarded degree relevant with etching solution, but the mol ratio in its mol ratio and the stainless steel is close except outside the Pass having with stainless steel.
3. a kind of stainless steel etching waste liquor comprehensive utilization of resources according to claim 1 is produced the method for molysite series water purification agent, the molysite that it is characterized in that adding sulfate radical can be a kind of or mixture in ferrous sulfate, the ferric sulfate, can be that solid also can be liquid, preferred iron vitriol solid.
4. a kind of stainless steel etching waste liquor comprehensive utilization of resources according to claim 1 is produced the method for molysite series water purification agent, it is characterized in that to the employed oxygenant of mixture oxidation can be hydrogen peroxide, sodium chlorate, oxygen, sodium perchlorate, ozone etc., preferably by the on-the-spot ozone that occurs of ozonizer.
5. a kind of stainless steel etching waste liquor comprehensive utilization of resources according to claim 1 is produced the method for molysite series water purification agent, it is characterized in that the PH conditioning agent that adds can be hydrochloric acid, sulphuric acid soln, preferred hydrochloric acid.
6. a kind of stainless steel etching waste liquor comprehensive utilization of resources according to claim 1 is produced the method for molysite series water purification agent, it is characterized in that in the crystallisation process that the stirring tank mixing speed is that 20~30 rev/mins, temperature are 55~60 ℃, crystallization time is 5~6 hours, to form macrobead crystalline hydrate thing as purpose.
7. a kind of stainless steel etching waste liquor comprehensive utilization of resources according to claim 1 is produced the method for molysite series water purification agent, it is characterized in that the crystalline hydrate thing is the crystalline mixture of four hydration nickelous chlorides, single nickel salts, Hexaaquachromium chloride, Iron dichloride tetrahydrate, carries out solid-liquid separation with filter-cloth filtering, whizzer.
8. a kind of stainless steel etching waste liquor comprehensive utilization of resources according to claim 1 is produced the method for molysite series water purification agent, it is characterized in that filtrate is the liquor ferri trichloridi that nickel, chromium content are lower than 100PPM.Can produce the poly-ferric chloride of different polymerization degree by the amount of adjusting hydrochloric acid, produce the poly-ferric sulfate chloride solution of different chlorination degrees by adjusting the amount that adds iron vitriol, or filtrate evaporation concentration crystallisation by cooling is obtained the ferric chloride (FeCl36H2O) crystal.
9. filtrate according to claim 8 is the liquor ferri trichloridi that nickel, chromium content are lower than 100PPM.It is characterized in that and to realize by the method for secondary crystal.Realize that by reduction Tc, prolongation crystallization time, control stirring velocity purpose is to obtain macrobead crystalline hydrate thing.Preferred 35~40 ℃ of secondary crystal temperature, insulation 5~6 hours, and be interrupted and stir, stirring velocity is at 10~15 rev/mins.
10. according to claim 8 filtrate evaporation concentration crystallisation by cooling is obtained the ferric chloride (FeCl36H2O) crystal.It is characterized in that can carry out heating vacuum vaporation to filtrate by evaporating kettle concentrates.The vacuum tightness of control in the evaporating kettle-0.06~-0.08MP, vaporization temperature is at 85~90 ℃, when filtrate enriched material proportion reaches 1.60 when above, stops evaporation concentration, is cooled to obtain below 30 ℃ the ferric chloride (FeCl36H2O) crystal.
CN2012104647030A 2012-11-19 2012-11-19 Method for producing ferric salt-series purifiers by recycling and comprehensive utilizing stainless steel waste etching solution CN102992513A (en)

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CN104591465A (en) * 2015-01-30 2015-05-06 深圳市危险废物处理站有限公司 Method for recycling and processing ammonia-nitrogen-containing wastewater in circuit board etching waste liquor recycling industry
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CN107522366A (en) * 2017-10-13 2017-12-29 林翔 The sewage disposal device that a kind of convenience is handled organic matter
CN109292828A (en) * 2018-11-06 2019-02-01 徐州清流水环保科技有限公司 A kind of preparation method of poly-iron chloride
CN110791651A (en) * 2019-10-31 2020-02-14 昆明理工大学 Resource utilization method for crystallized salt mud in stainless steel pickling wastewater

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104098148A (en) * 2013-04-08 2014-10-15 兰州大学 Processing method for recovering nickel, chromium and iron from stainless steel factory waste residue
CN104098148B (en) * 2013-04-08 2015-11-18 兰州大学 A kind for the treatment of process reclaiming nickel, chromium, iron from stainless steel plant's waste residue
CN104591465A (en) * 2015-01-30 2015-05-06 深圳市危险废物处理站有限公司 Method for recycling and processing ammonia-nitrogen-containing wastewater in circuit board etching waste liquor recycling industry
CN104591465B (en) * 2015-01-30 2017-04-05 深圳市危险废物处理站有限公司 A kind of circuitboard etching waste liquid reclaims industry nitrogen-containing wastewater recycling and the method for processing
CN104986805A (en) * 2015-06-23 2015-10-21 河北冀泽生物科技有限公司 Production method for polyferric chloride sulfate
CN105836862A (en) * 2016-04-01 2016-08-10 郑州轻工业学院 Comprehensive treatment method for recovery dust produced in production of titanium tetrachloride through boiling chlorination
CN105836862B (en) * 2016-04-01 2018-12-18 郑州轻工业学院 A kind of fluidizing chlorination method produces the integrated conduct method of collected ash during titanium tetrachloride
CN107522366A (en) * 2017-10-13 2017-12-29 林翔 The sewage disposal device that a kind of convenience is handled organic matter
CN109292828A (en) * 2018-11-06 2019-02-01 徐州清流水环保科技有限公司 A kind of preparation method of poly-iron chloride
CN110791651A (en) * 2019-10-31 2020-02-14 昆明理工大学 Resource utilization method for crystallized salt mud in stainless steel pickling wastewater

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