CN104131285B - The recovery method of ferric trichloride etching waste liquor - Google Patents

Abstract

The invention provides the useless recovery method carving liquid of a kind of ferric trichloride erosion, use film electrolysis and extraction integrated technology, being provided with amberplex in a cell and electrolytic cell segmentation is formed anode chamber and cathode chamber, negative electrode and anode lay respectively at cathode chamber and the anode chamber of amberplex both sides；In cathode chamber, add ferric trichloride etching waste liquor, carry out film electrolysis, by Fe³⁺Ion reduction is Fe²⁺Ion；Solution after being electrolysed cathode chamber carries out extracting imurity-removal metal, is extracted phase solution and demetalization impurity phase solution, and demetalization impurity phase solution is delivered to anode chamber and carried out film electrolysis, by Fe²⁺Ionic oxide formation is Fe³⁺Ion；The solution that anode chamber's electrolysis obtains reclaims.Compared with existing ferric trichloride etching waste liquor treatment technology, technological process is short and simple, non-secondary pollution produce, there is no three waste discharge, production cost is low, it is adaptable to process on a large scale, year treating capacity can have good environmental benefit and economic benefit more than ten thousand tons.

Description

The recovery method of ferric trichloride etching waste liquor

Technical field

The present invention relates to a kind of ferric trichloride etching waste liquor recovery method, particularly relate to a kind of containing foreign metal from The recovery method of the ferric trichloride etching waste liquor of son.

Background technology

Etching method is applicable to high-volume, multi items, the thin metal material processing of big plane and surface of metal product Handicraft decorative (half corrosion).Now be applied to various circuit lead frame and fluorescent display screen display, aperture plate, Secondary filter net, encoder grating, microelectrode, mask plate, integrated circuit cover plate, shadow mask, surface The products such as attachment (SMT) tin cream wire mark plate, etching method manufacturing process is often applied to high-tech area.

Liquor ferri trichloridi has certain oxidisability and acidity, and iron, nickel are had good corrosiveness, because of And by the substantial amounts of metal etch that is applied to, as in the etching of fine circuit pattern, microelectronics Packaging at ferric trichloride Etching nickel and stainless steel shadow mask process.In etching process, FeCl₃It is reduced into FeCl by nickel and stainless steel₂, the most a small amount of Metallic nickel can be oxidized with Ni²⁺Form enters etching solution.In etching process, along with FeCl in etching solution₃Concentration Reduction and Ni²⁺The rising of concentration, the efficiency of etching can decline.Additionally, Ni in etching solution²⁺Concentration Raise the tendency being also easy to cause product etching surface the most coarse.The most a large amount of used FeCl₃Etching solution by Discharge with waste liquid form from etch system in can not meet etch process requirement.

FeCl₃Etching waste liquor composition is mainly ferric trichloride 40%, frerrous chloride 10%, also has nickel chloride 20%, If this waste liquid is the most treated and discharge as danger wastes, not only results in the pollution of environment, and cause money The significant wastage in source, thus the how highly efficient regeneration of nickeliferous ferric trichloride etching solution to utilize be generally to close both at home and abroad at present The problem of note.

At present the processing method of Ni from waste etching FeCl 3 solution containing mainly has following several: selective precipitation, molten Agent extraction, crystallization roasting method, direct electrolysis method, metal deoxidization, membrane electrolysis etc..As: CN1166816C The renovation process of disclosed Ni from waste etching FeCl 3 solution containing, first with iron scale or iron powder by Fe³⁺It is reduced into Fe²⁺, It is subsequently adding H₂S precipitates Ni²⁺, the most backward mother liquor is passed through chlorine, by FeCl₂It is oxidized to FeCl₃； The disclosed method processing ferric trichloride etching waste liquor of CN101497484B, with sec-octyl alcohol, secondary octyl benzene oxygen second Acid etc. carries out first paragraph extraction as extractant, then with 2-hydroxyl-4-secondary octyl-diphenyl-ketoxime as extractant Carry out second segment extraction, it is achieved the separation of ferronickel；CN100485091C is disclosed separates liquor ferri trichloridi The method of middle nickel ion, including being heated to 110-115 DEG C, being cooled to 30 DEG C, stirred crystallization, is subsequently adding Calcium phosphate+ forage nickel ion, ferric trichloride is by flowing out as solution after back extraction.

Wherein, the principle of membrane electrolysis is made by membrane electrolysis cells and realizes the iron ion of different valence state in etching waste liquor and divide Oxidation and reduction reaction is not occurred to reach the purpose processing, disposing in the anode chamber of electrolytic cell and cathode chamber.Its In mainly make the Fe in solution at cathode chamber³⁺It is reduced to Fe²⁺Ion；In anode chamber by Fe in etching waste liquor²⁺From Son is oxidized to Fe³⁺Ion, and anode chamber's etchant concentration is adjusted the requirement reaching etch process, make etching solution Regenerated.Ion-exchange membrane electrolysis regeneration is used to process ferric trichloride etching waste liquor to the Appropriate application of resource and ring Border protection has great importance, and is the most day by day paid attention to by domestic and international enterprise.

Study to compare many at the relevant ion-exchange membrane electrolysis of Japan at present, and applied for many patents.East China is managed Work university research paired electrolysis technology regeneration ferric trichloride invar etching solution technique.By Electrode material and The structure of electrolytic cell, electrolyte composition, the current density impact on electrolysis, electrode assembling uses bipolar type, Arrived can the cell reaction technique of industrialized production, technique can realize serialization, automated production.This technique Use continuously, classification tandem removes nickel technique, and in the iron nickel powder obtained, the content of nickel is up to 50%.Regeneration Etching solution constituent content is: FeCl₃45～48%, FeCl₂< 0.2%, NiCl₂< 0.1%, reach reuse quality Requirement.But the postorder that the method exists iron nickel powder is disposed and the problem of technology controlling and process.

Owing to nickel and stainless steel requirement on machining accuracy is high, therefore the purity requirement to ferric trichloride etching solution is the highest. According to enterprise-quality requirement, its constituent content of the etching solution of regeneration should reach following level requirement: wherein tri-chlorination Iron content controls about 45%, frerrous chloride content controls about 0.3%, nickel content controls 0.1% Left and right, free acid content control about 0.24%.Current domestic type of industry is mostly by refuses such as etching waste liquors Take the mode taken out, specialized company be acted upon and recycle.It should be noted that and on the one hand need in etching Enterprise compares the area of concentration, sets up scale bigger, technique and the more advanced professional recovery company of equipment, anti- Only during changing waste into resources, cause secondary pollution；On the other hand, it is necessary to make the production of etching and processing industry Gradually decrease discharge waste, walk " cleaning produces " and the road of recycling economy.

The method that etching solution is taked by general enterprises is instant regeneration method, and the circulation of etching solution is the tightest Close, regeneration method require simple, rapidly, economy, material balance, the kind of interpolation material and quantity is few, Discharge safety etc..Currently used certain methods is at aspects such as the cost of technology, security and comprehensive utilizations of resources There are some problems the most to some extent.Therefore, a kind of simple, economic nickeliferous ferric trichloride etching solution is sought Renovation process be the most necessary.

Summary of the invention

For the problem existing for the ferric trichloride etching waste liquor recovery method of current contaminating metal ion, this Bright provide a kind of ferric trichloride etching solution recovery method, use film electrolysis and extraction integrated technology, it is achieved with Few operating cost obtains the target of high-quality regenerating etchant.This kind of technology is useless with the etching of existing ferric trichloride Liquid treatment technology is compared, and its technological process is short and simple, and in regenerative process, non-secondary pollution produces, and has well Environmental benefit and economic benefit.

The invention provides the useless recovery method carving liquid of a kind of ferric trichloride erosion, step includes:

Step 1, it is provided that at least one electrolytic cell, is provided with amberplex and electrolytic cell segmentation is formed sun in electrolytic cell Room, pole and cathode chamber, negative electrode and anode lay respectively at cathode chamber and the anode chamber of amberplex both sides；

Step 2, adds ferric trichloride etching waste liquor in cathode chamber, carries out film electrolysis, by Fe in cathode chamber³⁺From Son is reduced to Fe²⁺Ion；

Step 3, the solution after being electrolysed cathode chamber carries out extracting imurity-removal metal, is extracted phase solution and removing impurities Matter metal phase solution, de-foreign metal phase solution is delivered to anode chamber and is carried out film electrolysis, by Fe²⁺Ion reduction is Fe³⁺Ion；The solution that anode chamber's electrolysis obtains reclaims as regenerated liquid.

Wherein, described foreign metal can be any metal ion produced in etching process, is preferably etched The ion of substrate metal, most preferably nickel.

In step 3 extraction process can extractant such as 4-methyl-2 pentanone, sec-octyl alcohol, secondary octyl benzene oxygen second Acid, any one or a few in organic phosphine extractant (such as extraction).

In first preferred embodiment of recovery method of the present invention, also include: in step 3, extraction mixes Liquid carries out back extraction, obtains foreign metal salt and extractant.

In the preferred embodiment shown, it is highly preferred that the solution after extractant is electrolysed with follow-up cathode chamber mixes, Proceed to extract the step of imurity-removal metal.

Wherein, described negative electrode material can be graphite, titanium, iron, stainless steel, copper, nickel etc., and preferably stone Ink and titanium, more preferably titanium (Ti cathode).

Wherein, during described anode can be insoluble anode, graphite anode, precious metal anode any one or Several；And preferably insoluble anode；More preferably with Titanium as substrate, surface is coated with ruthenic oxide And/or the anode of titanium dioxide, most preferably with Titanium as substrate, surface coating ruthenic oxide and titanium dioxide The anode of titanium；Most preferably, TiO₂For the intermediate layer of anode, at TiO₂Surface coating RuO₂。

Wherein, described amberplex is selected from out-phase cation-exchange membrane, homogeneous phase cation exchange film, out-phase the moon Any one or a few combination in amberplex, homogeneous-phase anion exchange film.Described amberplex is more Be preferably anion-exchange membrane, most preferably homogeneous-phase anion exchange film, can be strong basicity or alkalescent cloudy from Proton exchange, the present invention is preferably alkalescent homogeneous-phase anion exchange film.

Described amberplex basement membrane be preferably in polymers of vinyl monomers, polyphenylene oxide, polysulfones any one Or several combinations, described vinyl monomer such as ethene, vinyl chloride, vinylidene chloride, vinylidene, styrene, Ring-alkylated styrenes, isobutene, divinylbenzene.Described amberplex basement membrane is more preferably vinyl monomer and gathers Compound, can be copolymer or homopolymers, more preferably polyethylene, polyvinyl fluoride, polyvinyl chloride, polyphenyl second Any one or a few combination in alkene.

In method of the present invention, electrolytic cell quantity can be one or be more than one, and the combination of electrolytic cell can To be bipolar type or acyclic type, the present invention is preferably bipolar type.

In second preferred embodiment of the present invention, each electrolytic cell matrix is arranged, wherein, and a in matrix_i,jPosition The anode of electrolytic cell and a_(i+1),jPosition anode electrolytic cell electrical connection, a_(i+1),jPosition electric tank cathode and a_(i+2),jPosition Electric tank cathode connects；In matrix, the first row electric tank cathode is in parallel, and in matrix, last column anode electrolytic cell is also Connection.

In two preferred embodiments, described matrix is preferably n × m matrix, and wherein, n is 2-10, preferably For 2-8, more preferably 3-6, such as 4,5；Wherein, m is 2-10, preferably 2-8, more preferably 3-6, Such as 4,5；M and n can be identical or different.

In the 3rd preferred embodiment of the present invention, each electrolytic cell matrix is arranged, wherein, and each electrolytic cell square Battle array arrangement, wherein, a in matrix_i,jThe anode chamber of position electrolytic cell and a_(i+1),jPosition electrolyzer anode chamber fluid is even Logical, a_(i+1),jThe cathode chamber of position electrolytic cell and a_(i+2),jElectric tank cathode room, position is in fluid communication；In matrix first The anolyte flow circuit of row electric tank cathode room is in parallel, the anolyte flow circuit of last column electrolyzer anode chamber in matrix In parallel.

In three preferred embodiments, described matrix is preferably n × m matrix, and wherein, n is 2-10, preferably For 2-8, more preferably 3-6, such as 4,5；Wherein, m is 2-10, preferably 2-8, more preferably 3-6, Such as 4,5；M and n can be identical or different.

In the 4th preferred embodiment of the present invention, described anode and negative electrode composition bipolar type electrode structure, tool Body structure is as follows: arrange substrate between anode and negative electrode, and anode and negative electrode two ends are connected on substrate.

In the 4th preferred embodiment, more preferably: described substrate is preferably titanium-base, and described anode is preferred For described insoluble anode, described negative electrode is preferably Ti cathode.

In the 5th preferred embodiment of the present invention, place multiple such as the 4th in each electrolytic cell and be preferable to carry out Bipolar type electrode described in example, and the negative electrode of electrode is towards same direction, between adjacent bipolar type electrode Separate with described amberplex.

In the 5th preferred embodiment, more preferably: in each electrolytic cell, power supply output line and input line It is just connected on the male or female at electrolytic cell two ends.

In any means that the present invention is above-mentioned, the pole frame of anode chamber and/or cathode chamber arranges cloth tank, room, pole Inlet opening and the position diagonal relationship each other of apopore.

Wherein, frame both sides, pole also set up dividing plate, are provided with mesh in the middle of dividing plate.

Wherein, mesh grid is elected in described network optimization as, and material is preferably plastics, such as polyethylene, polypropylene, polyphenyl second Alkene, polyvinyl chloride, polyester, polyamide, polyacrylonitrile, preferably polypropylene.

Wherein, described pole frame material is preferably plastics, as polyethylene, polypropylene, polystyrene, polyvinyl chloride, Polyester, polyamide, polyacrylonitrile, preferably polypropylene.

Wherein, the cell wall of described electrolytic cell is preferably plastics, such as polyethylene, polypropylene, polystyrene, polychlorostyrene Ethene, polyester, polyamide, polyacrylonitrile, preferably polypropylene.

In any means that the present invention is above-mentioned, the preferably rectangular battery lead plate of electrode, electric current entry and exit point lays respectively at square The diagonal position of shape plate.

In any means that the present invention is above-mentioned, the decomposition voltage of electrolytic cell is preferably >=1V, more preferably >= 1.5V, more preferably >=2V, more preferably >=2.5V, such as 3-10V, 3.5-8V, 4-6V, be more preferably 2.5-5V.More preferably 3-4V.Described electrolytic process is most preferably constant voltage.

In any means that the present invention is above-mentioned, the electrolytic current density of electrolytic cell is preferably >=50A/m², more It is preferably >=80A/m², more preferably >=100A/m², more preferably higher than equal to 120A/m², as 150-400A/m², more preferably 150-30A/m², more preferably 150-250A/m², such as 190-200A/m²。

In the above-mentioned any means of the present invention, the electrolysis time of electrolytic cell is preferably >=0.5h, more preferably >=1h, More preferably >=1.5h, such as 1.5-10h, more preferably 1.5-6h, more preferably 1.5-4h, such as 2-3h, as 2.5h。

In the above-mentioned any means of the present invention, the electrolysis temperature of electrolytic cell is preferably 10-80 DEG C, more preferably 15-75 DEG C, more preferably 20-70 DEG C, more preferably 25-70 DEG C, more preferably 30-70 DEG C.

It should be appreciated that various preferred embodiments and preferable case in foregoing of the present invention, can not be subject to The mutual any combination limited.

The invention provides a kind of new regeneration etching waste liquor method, use film electrolysis and extraction integrated technology, real The target of high-quality regenerating etchant is now obtained with minimum operating cost.This kind of technology and existing ferric trichloride Etching waste liquor treatment technology is compared, and its technological process is short and simple, and in regenerative process, non-secondary pollution produces, and does not has Three waste discharge, production cost is low, it is adaptable to process on a large scale, year treating capacity can have very well more than ten thousand tons Environmental benefit and economic benefit.

Accompanying drawing explanation

Fig. 1 is the nickeliferous useless recovery method workflow schematic diagram carving liquid of ferric trichloride erosion of the present invention；

Fig. 2 is electric tank working schematic diagram of the present invention；

Fig. 3 is one preferred electrode structural representation of the present invention；

Fig. 4 is one preferred electrode mount structure schematic diagram of the present invention；

Fig. 5 is one preferred separator structural representation of the present invention；

Fig. 6 is a kind of preferably electrolytic tank electrode assembling mode schematic diagram of the present invention；

Fig. 7 is a kind of preferably electrolytic cell distribution figure of the present invention；

Fig. 8 is electrolyte circulation figure between a kind of preferably electrolytic cell of the present invention.

Detailed description of the invention

As it is shown in figure 1, carve returning of liquid with Ni from waste etching FeCl 3 solution containing in order to the erosion of, ferric trichloride of the present invention is useless Receiving method is as follows:

Step 1

Electrolytic cell 4 is provided to be electrolysed described etching waste liquor for film.Wherein, electrolytic cell 4 is provided with ion exchange Electrolytic cell segmentation is formed anode chamber 1 and cathode chamber 2 by film 3, and negative electrode 20 and anode 10 lay respectively at ion Cathode chamber 2 and the anode chamber 1 of exchange membrane 3 both sides.

Fig. 2 gives a kind of two Room membrane electrolysis cells fundamental diagrams, can connect between negative electrode 20 and anode 10 It is connected to rectifier 5.Solution in anolyte storage tank 11 sends into anode chamber 1 by water pump 12；Catholyte storage tank Solution in 21 sends into anode chamber's (or extremely indoor electrolyte being sent into storage tank by pump) by water pump 22.

Ferric trichloride etching solution is a kind of liquid with acidity, strong oxidizing property, and regenerates etching solution requirement not New impurity can be introduced, so must have as anode material: good chemistry and electrochemical stability, conduction Performance is good, good mechanical property, have relatively low overpotential, light, aboundresources, low price.Preferably In embodiment, select insoluble anode, with Titanium as substrate, Coating TiO₂、RuO₂, or also It is coated with catalyst (catalyst such as Pt, Ir, Co₃O₄、PbO₂Deng), have corrosion-resistant, dimensionally stable, The advantages such as life-span length, compared with modal graphite electrode, analysis chlorine overpotential is the lowest, and overpotential for oxygen evolution is high, Good conductivity, it is possible to decrease power consumption.Owing to, in membrane electrolysis regeneration ferric trichloride etching solution, anode does not analyse chlorine Or analyse the oxidation of chlorine, mainly ferrous ion less, therefore anode electrode current potential is mainly running less than chlorine evolution potential, Injury to electrode coating is very little, and the service life of electrode is the longest.

It is highly preferred that with TiO₂For intermediate layer, on titanium-base, i.e. first coat TiO₂, at TiO₂Surface is coated with RuO₂.Although TiO₂Belonging to ceramic material, electric conductivity is very poor, but the ionic radius of ruthenium, titanium connects very much Closely, lattice structure and space belong to same type, and electrode of the present invention can be firm as pottery in forming process Adhere to titanium-based, the RuO of formation₂-TiO₂It is the solid solution of a kind of firm stable, and electric conductivity carries significantly High.

General cathode material will not be by electrochemical corrosion in electrolytic process of the present invention, and many materials are available for choosing Select, have as comparatively ideal: iron, graphite, stainless steel, titanium, nickel or active nickel and other most metals. But, at cathode chamber, Fe³⁺It is reduced into Fe²⁺, reduction potential is the lowest, and reduction efficiency is high, simultaneously Fe³⁺ Having the strongest oxidisability, negative electrode does not such as have current protection, many electrode materials will be corroded, therefore, in reality In electrolysis, electrolytic cell power-off can occur unavoidably, damage, need maintenance etc. to stop transport operation, the selection of cathode material The reason injury to electrode that happens suddenly will be considered.One layer of high-resistance oxide-film of the oxidizable formation in titanium surface, even if When electrolytic cell is stopped transport, electrolyte can make electrolytic cell be equivalent to an electrochmical power source or capacitor, now electrode direction Reversing, Ti cathode becomes anode, and surface is quickly generated high-resistance oxide-film, and makes Ti electrode be protected. In the present invention, negative electrode is selected from Ti cathode.

In one preferred embodiment of the present invention, as it is shown on figure 3, the anode of the present invention and negative electrode composition bipolar type Electrode structure, including the substrate 6 in centre position, titanium-base both sides are respectively Ti cathode, and titanium-based RuO₂-TiO₂Anode.Fig. 6 gives multiple bipolar type electrode structure situation for single electrolytic cell, multipole The negative electrode of formula electrode structure is all towards right side, and anode is all towards left side, and the input of power supply only exists with output connection On the anode at the two ends of electrolytic cell and negative electrode, substantial amounts of copper bar can be saved, reduce investment.

In film is electrolysed, owing to needing barrier film to be separated with catholyte by anolyte between cathode chamber, anode chamber, In order to avoid current efficiency declines.In the present invention, cation-exchange membrane or anion-exchange membrane can serve as paired electricity Solve barrier film, as homogeneous phase cation exchange film (homogeneous anode membrane), out-phase cation-exchange membrane (out-phase anode membrane), Homogeneous-phase anion exchange film (homogeneous cavity block), out-phase anion-exchange membrane (out-phase cavity block), select in the present embodiment Select anion-exchange membrane, especially weak alkaline ionexchange memberanes, such as homogeneous-phase anion exchange film.

Electrolytic cell selects filter press-type, anode chamber 1, cathode chamber 2 to use identical electrode frame structure (electrode frame knot Structure is as shown in Figure 4), cell wall and electrode frame all use polypropylene material, and without any inserts. Cloth tank opens covered conduit, and cross section, hole is 3mm × 10mm, exports as trumpet type, extremely indoor water outlet duct and water inlet Diagonal angle each other, duct.Equally, in a cell, it is also possible to take the mode at electric current turnover wiring diagonal angle.

Prepare as it is shown in figure 5, the dividing plate 7 of electrode frame both sides is also polypropylene material, thickness of slab 0.8mm, interior If polypropylene woven net 71.It is possible to prevent film directly to contact electrode, and plays turbulent flow.

Step 2

In cathode chamber 2, add a certain amount of etching waste liquor, carry out film electrolysis.

After the regular hour is electrolysed, the Fe in cathode chamber 2³⁺Almost all is reduced into Fe²⁺, reaction is such as Under:

Fe³⁺+e→Fe²⁺

In anode chamber 1, initial time can add FeCl₂Solution, FeCl₃Solution or described etching waste liquor, this is right It is known from the point of view of those skilled in the art.

Step 3

Solution (cathode chamber electrolyte) after being electrolysed cathode chamber carries out extracting nickel removal, and the method for extraction of nickel is this Known to the skilled person, typically use organic extractant, after separation, form the aqueous phase of nickel removal and nickeliferous Organic phase.Aqueous phase is again sent electrolytic cell (such as anode chamber) back to and is proceeded film electrolysis.Available extractant is such as 4-methyl-2 pentanone, sec-octyl alcohol, secondary octyl phenoxy acetic acid, organic phosphine extractant (such as extraction).

In anode chamber, Fe²⁺Ion is oxidized to Fe³⁺Ion；React as follows:

Fe²⁺+e→Fe³⁺

The solution that anode chamber's electrolysis obtains reclaims.

Nickeliferous organic phase can carry out back extraction with hydrochloric acid, due to Cl^-A large amount of appearance, NiCl can be induced₂Heavy Form sediment, thus by NiCl₂Separating, and regain extractant or the solution containing extractant, extractant can be with rear Extraction step is proceeded after continuous cathode chamber electrolyte mixing.

For electrochemical reactor, the production capacity of separate unit is limited, and therefore, it is same that the present invention assembles multiple stage electrolytic cell Shi Yunhang, wherein, electrolytic cell is arranged in array.

In another embodiment, as it is shown in fig. 7, electrolytic cell composition 4 × 4 matrixes, in same row electrolytic cell, The first row electric tank cathode connects power supply, and anode connects the anode of the second row electrolytic cell；The moon of second row electrolytic cell Pole connects the negative electrode of the 3rd electrolytic cell, i.e. a_i,jThe anode of position electrolytic cell and a_(i+1),jPosition anode electrolytic cell electricity Connect, a_(i+1),jPosition electric tank cathode and a_(i+2),jPosition electric tank cathode connects, last anode electrolytic cell Connect power supply.4 row electrolytic cells all use aforesaid way to connect, and the electric tank cathode of the first row is in parallel, last The anode of row electrolytic cell is in parallel.

Electric current between electrolytic cell is uniform particularly significant, and electrolysis power is divided into D.C. regulated power supply, DC constant current electricity Source, according to Ohm's law, D.C. regulated power supply output voltage is constant, and electric current affects with system resistance, resistance liter Gao Shi, electric current declines；Otherwise, electric current raises.DC current stabilized power supply constant output current, tank voltage is with resistance Raising and raise, in practical operation, several factors can cause the change of system resistance, and constant current can cause and be The instability of system operation, the particularly appearance of electrolytic polarization can cause and greatly endanger.Therefore this technique uses permanent electricity The mode of pressure, operates safe, easy to control.

In another embodiment, the distribution of electrolyte is also adopted by the mode that above-described embodiment is similar.Such as Fig. 8 Shown in, electrolytic cell composition 4 × 4 matrixes, in same row electrolytic cell, the first row electric tank cathode room and catholyte Storage tank fluidly connects, and anode chamber connects the anode chamber of the second row electrolytic cell；The cathode chamber of the second row electrolytic cell connects The cathode chamber of the 3rd electrolytic cell, i.e. a_i,jThe anode chamber of position electrolytic cell and a_(i+1),jPosition electrolyzer anode chamber flows Body connects, a_(i+1),jElectric tank cathode room, position and a_(i+2),jElectric tank cathode room, position fluidly connects, last Electrolyzer anode chamber's jointed anode liquid storage tank.

4 row electrolytic cells all use aforesaid way to connect, and the anolyte flow circuit of the electric tank cathode room of the first row is also Connection, the anolyte flow circuit of the anode chamber of last column electrolytic cell is in parallel.

Detection method:

1, iron chloride assay

Reagent and material: KI；Hydrochloric acid solution (1+1)；Sodium thiosulfate standard titration solution 0.1mol/L Left and right；The starch indicator of 1%.

Taking 25ml cathode chamber and anode chamber's solution is respectively placed in 250ml volumetric flask, constant volume is solution A.With Pipette takes solution A 5ml, in 250ml iodine flask, adds 2g KI and 5ml hydrochloric acid solution, adds Suitable quantity of water, builds bottle stopper, shakes up, in dark place 20min.With sodium thiosulfate standardized titration to faint yellow, add Enter 1ml starch indicator, continue to be titrated to blue disappearance.Do blank assay simultaneously.

Iron chloride content, in terms of the mass fraction ω of iron chloride, is calculated as follows:

$\mathrm{\&omega;}=\frac{c\&times;(V-V_0)\&times;M}{m\&times;5}\&times;10\&times;100\%$

The numerical value of the volume of the sodium thiosulfate standard titration solution that V titration consumes, units/ml

V₀The numerical value of the volume of the sodium thiosulfate standard titration solution that blank assay consumes, units/ml

The exact value of c sodium thiosulfate standard titration solution concentration, unit mol/L

The quality of m 1L test portion, density is multiplied by volume, unit g

The molecular weight of M iron chloride, 162.2

2, frerrous chloride assay

Phosphoric acid；Sulfuric acid solution (1+5)；Potassium bichromate standard titration solution: c(1/6K₂CrO₇) about 0.05mol/L；Diphenylamine sulfonic acid sodium salt: 5g/L.

10ml(negative electrode is taken with pipette) or 20ml(anode) liquid A, it is placed in 250ml conical flask, 5ml sulfuric acid and 2ml phosphoric acid and 3～4 diphenylamine sulfonic acid sodium salts, be titrated to potassium bichromate standard titration solution Bluish violet.It is calculated as follows:

$\mathrm{\&omega;}=\frac{c\&times;V\&times;M}{m\&times;V_1}\&times;10\&times;100\%$

The numerical value of the volume of the potassium bichromate standard titration solution that V titration consumes, units/ml

V₁Taken liquid A volume, units/ml

The exact value of c potassium bichromate standard titration solution concentration, unit mol/L

The quality of m 1L test portion, i.e. density are multiplied by volume, unit g

The molecular weight of M frerrous chloride, 126.8

3, free acid content measures

Fluorinse: 40g/L；Standard Volumetric Solutions for Sodium Hydroxide: c(NaOH) about 0.05mol/L； Instructions phenolphthalein solution: 10g/L.

Take above-mentioned solution A 20ml in the volumetric flask of 100ml, add the Fluorinse of 60-70ml, Constant volume, stands 10-20 minute.Filter with Medium speed filter paper to the beaker of dried and clean, discard filtrate before 10ml, Pipette 40ml and be placed in conical flask, add instructions phenolphthalein solution, be titrated to blush with NaOH titrand, 30s is colour-fast；Calculate the content (mol/L) of free acid in sample.It is calculated as follows:

$c_{H^{+}}=\frac{c\&times;V}{40}\&times;50$

C concentration of sodium hydroxide solution, unit mol/L

V consumes the volume of sodium hydroxide solution, units/ml

4, chlorine ion content determination

Standard Volumetric Solutions for Sodium Hydroxide: c(NaOH) about 0.05mol/L；Instructions phenolphthalein solution: 10g/L； Silver nitrate 0.01mol/L；Potassium chromate 5%.

Take the above-mentioned filtered fluid of 10ml in 50ml volumetric flask, constant volume.Take 2ml and be placed in conical flask, add 50ml The deionized water of left and right, drips instructions phenolphthalein solution, with NaOH and nitric acid (1+130) be transferred to micro-red Look just takes off.The potassium chromate 1ml adding 5%, under fully shake, uses AgNO₃Standard liquid is titrated to dense Liquid is brick-red, is terminal.According to sample size, AgNO₃The concentration of standard liquid and the volume consumed, Calculate the content mol/L of chlorine in sample.It is calculated as follows:

$c_{{\mathrm{Cl}}^{-}}=\frac{c\&times;V}{2}\&times;250$

C silver nitrate solution concentration, unit mol/L

V consumes the volume of silver nitrate solution, units/ml

5, nickel ion assay

Reagent and material: 30% sodium citrate；30% ammonium chloride；The dimethylglyoxime ethanol solution of 1%；20% Sodium thiosulfate；The murexide of murexide indicator: 0.1g and the finely ground mixing of 10g sodium chloride； The EDTA solution of 0.02615mol/L.

Taking 5ml solution A, add the sodium citrate of 10ml30%, heating water bath is to 70-80 DEG C, more constantly Stirring under, add 30% ammonium chloride 10ml, dimethylglyoxime 25ml, add ammoniacal liquor to micro-ammonia taste, nickel starts to sink Form sediment, be incubated 10-30 minute.Filter, with hot water wash 8～10 times, dissolve with hydrochloric acid (1+1), be heated to It is evaporated soon, uses hot water injection's wall of cup, by ammoniacal liquor tune pH value to 5, the sodium thiosulfate 10ml adding 20%, And add water to 100ml, add ammoniacal liquor 2ml, and add indicator murexide 0.2g, be titrated to purple with EDTA Redness is terminal.Calculate the content of nickel content, unit mol/L in sample.It is calculated as follows:

$c_{{\mathrm{Ni}}^{2+}}=\frac{c\&times;V}{5}\&times;10$

The concentration of c EDTA solution, unit mol/L

V consumes the volume of EDTA solution, units/ml

Etching waste liquor forms

New etching solution is the product of etching solution factory supply, and old etching solution is that the etching solution processed without regeneration is given up Liquid, spent etching solution 1 is that etching workshop added the sodium hypochlorite regeneration process used useless erosion of Posterior circle in waste liquid Carving liquid, spent etching solution 2,3 is that etching workshop did not added sodium hypochlorite regeneration process Posterior circle use in waste liquid The spent etching solution crossed, its composition analysis result is as shown in table 1.Spent etching solution composition from the point of view of analysis result from table Data fluctuate within the specific limits.

Table 1, etching solution composition analysis result table

Embodiment 1

It is separately added into 1L spent etching solution in cathode chamber reservoir in the anode chamber being made up of electrolytic cell out-phase anode membrane 1, at room temperature measure film polarization curve, it is known that voltage is linearly increasing with electric current.In order to be better understood by electrolysis The voltage impact on electrolysis effectiveness, respectively 2.5,3.0,3.5, the electrolyzer electric pressure of 4.0V is electrolysed Test, samples 25mL respectively in anode chamber with cathode chamber every half an hour in process of the test, analyzes in sample Ferrous ion, iron ion, total electrolysis time is 3.0h, be electrolysed 3 hours post analysis free acids and chlorine from Sub-concentration, uses negative electrode Fe respectively²⁺The variable quantity calculating current efficiency of material.Experimental result such as table 1-1, table 1-2, Table 1-3.

Table 1-1, Fe in cathode and anode reservoir in electrolytic process²⁺Change in concentration table

Table 1-2, Fe in cathode and anode reservoir in electrolytic process³⁺Change in concentration table

Table 1-3, cloudy current efficiency and current density change table in electrolytic process

From table 1-1, data understand the rising with bath voltage, and electrolytic speed increases, if tank voltage is 4V Time, half an hour inner anode liquid can't detect Fe²⁺.Fe in catholyte is understood by data in table 1-2³⁺Concentration subtracts In a small amount, increase with the increase of bath voltage.From table 1-3 data, increase electric current effect with electrolysis time Rate declines, but the electrolysis effectiveness under different voltage relatively in when tank voltage is 3V current efficiency the highest, to sum up The above results bath voltage is defined as 3V.

Embodiment 2

The spent etching solution 1 of 1L is added in anode chamber with cathode chamber.Select different amberplexes, at groove Voltage stabilizing electrolysis under voltage 3.0V, total electrolysis time is 3.0h.In experiment, per half an hour is respectively at anode liquid storage Groove, negative electrode reservoir sample 25mL, analyzes ferrous ion therein, iron ion, and be electrolysed 3 hours After free acid and chlorine ion concentration calculate Faradaic current efficiency, in its result such as table 2-1,2-2.From table 2-1,2-2 understand in out-phase anode membrane composition electrolytic cell has Fe ion permeable anode membrane to cathode chamber transport phenomena, electricity Solving the preferably homogeneous cavity block electrolytic cell of effect out-phase anode membrane electrolytic cell to take second place, out-phase cavity block electrolytic cell is worst.From free From the point of view of acid concentration (table 2-3), using homogeneous cavity block as diaphragm, anode free acid concentration is minimum, and out-phase is cloudy Membrane electrolysis cells effect is worst.

Fe in cathode and anode reservoir in table 2-1 electrolytic process²⁺Change in concentration table

Fe in cathode and anode reservoir in table 2-2 electrolytic process³⁺Change in concentration table

Table 2-3 is electrolysed chlorine ion concentration and free acid concentration after 3 hours

Embodiment 3

Spent etching solution 2 do not has Na⁺With H in acid⁺As conductive ion, so selecting cavity block composition electrolytic cell to enter Row current stabilization is tested.In anode reservoir, add 3L spent etching solution 2, negative electrode reservoir adds 600ml and gives up Etching solution 2, under current stabilization state, the highest electric current 5.6A under is electrolysed after being electrolysed 2 hours under first low current 3.60A 3 hours, the ferrous ion of reaction to anode is all oxidized to iron ion to be terminated.Period, have every 1h or 2h( Body problem is specifically chosen) in anode chamber with cathode chamber, sample 25ml and 10ml respectively, analyze the Asia in sample Iron ion, iron ion, and electrolysis terminate after the free acid of solution and chlorine ion concentration calculate in each reservoir Current efficiency.The results are shown in Table 3-1.

Table 3-1,5.60A current stabilization electrolytic trial result table

Electrolysis time (h)	1.0	2.0	3.0	4.0	5.0
						Voltage (V)	6.95	6.69	8.36	8.40	8.47
Electric current (A)	3.60	3.60	5.60	5.60	5.60
						Electrolyzer temperature (DEG C)	25	32	40	45	45
Catholyte Fe2+Concentration (mol/L)		0.6540	0.9522	1.2831	1.5963
						Catholyte Fe3+Concentration (mol/L)		3.2166	2.4630	1.9815	1.6822
Anolyte Fe2+Concentration (mol/L))	0.4050	0.3218	0.2130	0.0931	0.0000
						Anolyte Fe3+Concentration (mol/L)	3.2461	3.2756	3.3551	3.4277	3.4686
Current efficiency (%)			84.19	91.53	85.45
						Current density (A/m2)	103.49	104.65	163.95	162.79	162.79

Table 3-2,3.56A current stabilization electrolytic trial result table

Electrolysis time (h)	0.0	0.5	1.0	1.5	2.0
						Voltage (V)	7.60	6.90	6.20	6.10	5.90
Electric current (A)	3.56	3.56	3.56	3.56	3.56
						Catholyte Fe2+Concentration (mol/L)	0.4866	0.5805	0.6721	0.7759	0.8793
Catholyte Fe3+Concentration (mol/L)	3.1213	3.0078	2.7694	2.5401	2.4558
						Anolyte Fe2+Concentration (mol/L))	0.2294	0.1982	0.1953	0.1923	0.1664
Anolyte Fe3+Concentration (mol/L)	3.3710	3.4005	3.4232	3.2042	3.2147
						Current efficiency (%)		83.48	79.93	89.14	87.15
Current density (A/m2)	103.49	103.49	103.49	103.49	103.49

Can be seen that decomposition voltage is constant at 45 DEG C with electrolyzer temperature from table 3-1, decomposition voltage is stable at 8.4V, Fe in anolyte²⁺Concentration is zero, and current efficiency can reach more than 91%.Table 3-2 is to repeat current stabilization at 3.56A Electrolysis result, it can be seen that iron concentration is diluted in anolyte, illustrates Cl in catholyte^-With hydration Ionic species migrates to anode through cavity block, and this impact is negligible, and current efficiency equally reaches More than 87%.

Embodiment 4

Being separately added into the spent etching solution 3 of 1L in anode reservoir with negative electrode reservoir, test voltage is with electric current The polarization curve of change, it is known that optimal electrolytic cell currents is 6.0A.Selecting Faradaic current is that 6.0A carries out current stabilization Electrolysis, electrolysis total time is 6h.

In anode chamber with cathode chamber, sample 25ml respectively every 2h, analyze the ferrous ion in sample, iron Ion, free acid, chlorion and nickel ion, calculate its catholyte current efficiency, in its result such as table 4-1.

Tank voltage kept stable in electrolytic process, catholyte Cl^-Concentration has reduction trend, illustrates to be electrolysed Cl in journey^-Migrated to anode by negative electrode, Fe in anode chamber after electrolysis 2h²⁺Quickly oxidation is completely.After electrolysis completely The Fe of anolyte³⁺Concentration can reach 2.7067mol/L, and this spent etching solution is 191.86A/m in current density² Electrolytic condition under, current stabilization Faradaic current efficiency can reach the ideal effect of more than 97%.

Table 4-1, current stabilization electrolytic trial result table

Embodiment 5

With titanium-based ruthenic oxide as anode, titanium is negative electrode, and homogeneous cavity block is amberplex, and current density is 200A/m², tank voltage is 6.0V, and electrolysis procedure temperature is 30-70 DEG C, is electrolysed, and current efficiency is 97%。

Ionic membrane runs nearly 45h continuously under running conditions, wherein through repeatedly tearing groove, power failure test, ion open Exchange membrane property retention is intact.Seeing from the above, electrolysis with ion-exchange film method regenerates 304 steel waste liquids in skill It is feasible in art.

The extraction of nickel is carried out according to the method that the present invention is above-mentioned.

Embodiment 5 reclaiming FeCl₃The moment performance of etching solution

New etching solution is the product of etching solution factory supply, and online etching solution is to etch online liquid, and regenerated loses Carving liquid is that etching workshop spent etching solution processes after etching liquid, its composition analysis result such as table 5 through film electrolytic regeneration Shown in.The oxidizing potential regenerating etching solution from table from the point of view of analysis result is identical with new etching solution.

Table 5, etching solution forms

	New etching solution	Online etching solution	Regeneration etching solution
				Fe2+(mol/L)	0.0027	0.2740	0.0000
Fe3+(mol/L)	4.0950	3.2050	3.5108
				Free acid (mol/L)	0.0100	0.0800	0.0476
Cl-(mol/L)	12.42	11.78	11.57
				Ni2+(mol/L)	0.000	0.210	0.210
Oxidizing potential (V)	1.0710	0.9204	1.0759
				Reduction potential (V)	0.0694	0.1413	0.0980
Density ((g/mL)	1.43596	1.39964	1.45653

Take respectively 100g regeneration etching solution, new etching solution, online etching solution in 100ml beaker, and will burn Cup is placed in constant temperature in 50 DEG C of thermostats.Weigh three 40mm × 40mm × 0.2mm's respectively with electronic balance Iron plate, the etching solution being added separately to stationary temperature is etched.Often etch 10min, take out iron plate with tweezers, Clean, and dry on electric furnace, carry out weighing its quality.Until it is the most of poor quality the most constant.To three kinds of erosions Carve liquid and do etch-rate etching period curve.The etching speed after etching solution regeneration is can be seen that by done curve map With the etching speed line similar trend of online etching solution, and in figure, the etching speed Trendline of regenerated liquid is online The top of the etching speed line trend of etching solution, illustrates that regenerated liquid performance fully meets etching requirement.

Being described in detail the specific embodiment of the present invention above, but it is intended only as example, the present invention is also It is not restricted to particular embodiments described above.To those skilled in the art, any the present invention is carried out Equivalent modifications and substitute the most all among scope of the invention.Therefore, without departing from the spirit of the present invention and model Enclose lower made impartial conversion and amendment, all should contain within the scope of the invention.

Claims (11)

1. the recovery method of a ferric trichloride etching waste liquor, it is characterised in that step includes:

Step 1, it is provided that at least one electrolytic cell, is provided with amberplex and electrolytic cell segmentation is formed anode chamber and cathode chamber in electrolytic cell, negative electrode and anode lay respectively at cathode chamber and the anode chamber of amberplex both sides；

Step 2, adds ferric trichloride etching waste liquor in cathode chamber, carries out film electrolysis, by Fe in cathode chamber³⁺Ion reduction is Fe²⁺Ion；

Step 3, the solution after being electrolysed cathode chamber carries out extracting imurity-removal metal, is extracted phase solution and de-foreign metal phase solution, and de-foreign metal phase solution is delivered to anode chamber and carried out film electrolysis, by Fe²⁺Ionic oxide formation is Fe³⁺Ion；The solution that anode chamber's electrolysis obtains reclaims；

Wherein, any one or a few in 4-methyl-2 pentanone, sec-octyl alcohol, the secondary octyl phenoxy acetic acid of the extractant in step 3；

Wherein, in step 3, extraction phase solution hydrochloric acid carries out back extraction, obtains foreign metal salt and extractant；

Wherein, the solution after extractant is electrolysed with follow-up cathode chamber mixes, and proceeds to extract nickel removal step.

Method the most according to claim 1, it is characterised in that the solution after extractant is electrolysed with follow-up cathode chamber mixes, proceeds to extract the step of imurity-removal metal.

Method the most according to claim 1, it is characterised in that the decomposition voltage of electrolytic cell is 3-10V, the electrolytic current density of electrolytic cell is 150-250A/m², the electrolysis temperature of electrolytic cell be 10-80 DEG C.

Method the most according to claim 1, it is characterised in that described amberplex is homogeneous-phase anion exchange film.

Method the most according to claim 1, it is characterised in that described negative electrode material is titanium；Described anode is insoluble anode, and described insoluble anode is with titanium as substrate, and surface coats ruthenic oxide and titanium dioxide.

Method the most according to claim 1, it is characterised in that electrolytic cell quantity is more than one, each electrolytic cell matrix is arranged, wherein, a in matrix_i,jThe anode chamber of position electrolytic cell and a_(i+1),jPosition electrolyzer anode chamber is in fluid communication, a_(i+1),jThe cathode chamber of position electrolytic cell and a_(i+2),jElectric tank cathode room, position is in fluid communication；In matrix, the anolyte flow circuit of the first row electric tank cathode room is in parallel, and in matrix, the anolyte flow circuit of last column electrolyzer anode chamber is in parallel.

Method the most according to claim 1, it is characterised in that electrolytic cell quantity is more than one, each electrolytic cell matrix is arranged, wherein, a in matrix_i,jThe anode of position electrolytic cell and a_(i+1),jPosition anode electrolytic cell electrical connection, a_(i+1),jPosition electric tank cathode and a_(i+2),jPosition electric tank cathode connects；In matrix, the first row electric tank cathode is in parallel, and in matrix, last column anode electrolytic cell is in parallel.

Method the most according to claim 1, it is characterised in that described anode and negative electrode composition bipolar type electrode structure, described bipolar type electrode structure is: arrange substrate between anode and negative electrode, and anode and negative electrode two ends are connected on substrate.

Method the most according to claim 8, it is characterised in that place multiple described bipolar type electrode in each electrolytic cell, and the negative electrode of electrode is towards same direction, separates with described amberplex between adjacent bipolar type electrode.

Method the most according to claim 1, it is characterised in that the preferably rectangular battery lead plate of electrode, electric current entry and exit point lays respectively at the diagonal position of rectangular slab.

11. methods according to claim 1, it is characterised in that the position diagonal relationship each other of cloth tank, inlet opening, room, pole and apopore is set in the pole frame of anode chamber and/or cathode chamber.