CN101348916A - Electrolytic oxidation method of etching waste liquor - Google Patents
Electrolytic oxidation method of etching waste liquor Download PDFInfo
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- CN101348916A CN101348916A CNA200810096179XA CN200810096179A CN101348916A CN 101348916 A CN101348916 A CN 101348916A CN A200810096179X A CNA200810096179X A CN A200810096179XA CN 200810096179 A CN200810096179 A CN 200810096179A CN 101348916 A CN101348916 A CN 101348916A
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Abstract
The invention provides a method for conducting etching exhaust liquid containing ferric chloride or copper chloride into an electrolyte tank as electrolyte to electrolytically oxidize the low-vament ions into high-valent ions. The method can inhibit overoxidation of the etching exhaust liquid on the anode surface, prevent chlorine generated from the electrolyte tank, and electrolytically oxidize the etching exhaust liquid effectively with the equipment investment and operation cost. A method for conducting etching exhaust liquid containing ferric chloride or copper chloride as electrolyte into an electrolyte tank which is formed by an anode chamber and a cathode chamber divided by a diaphragm is characterized in: using a special electrolyte tank, supplying the etching exhaust liquid into the electrolyte tank, using 15-50% of the anode chamber liquor drainage as the supplying liquid to circulate, controlling the oxidation-reduction potential management value of the anode chamber liquor drainage between 550 and 800mV, and using the silver-silver chloride electrode as the reference of oxidation-reduction potential.
Description
Technical field
The present invention relates to the electrolytic oxidation method of etching waste liquor, more specifically, the etching waste liquor that relates to contain iron(ic) chloride or cupric chloride feeds the method that the low price ion electrolysis that makes in the electrolyzer in this etching waste liquor is oxidized to high valence ion as electrolytic solution, this method is suppressed at the peroxidation of the etching waste liquor of anode surface, prevent that chlorine from producing from electrolyzer, and electrolytic oxidation etching waste liquor effectively.
Background technology
In the past, in the method that from the waste material that contains multiple metal or alloy, reclaims valuable metal or in manufacturing procedure, used the etching solution dissolution of metals, then separating metal from lysate with the dissolving metal operation.For example, in the manufacturing of the lead frame that becomes the semiconductor integrated circuit base stage, etching solution uses usually and contains the acidic aqueous solution of the high valence ion of cupric chloride and/or iron(ic) chloride as main component, extensively adopts the etch processes that the dissolving of metal sheets such as copper is processed as the regulation shape.At this moment, the acidic aqueous solution that reduces for the dissolving metal ability that makes after the etch processes, the dissolving power that so-called etching waste liquor improves metal are separated dissolution of metals, and make the regeneration of dissolving metal ability and utilize.
, the high valence ion because of cupric chloride or iron(ic) chloride in etch processes leaches metal, carries out to the reaction of low price ion reductive, so the change of the low price ion of the acidic aqueous solution that the dissolving metal ability after the etch processes reduces, so-called etching waste liquor is many.Therefore, for the dissolving metal ability of the etching waste liquor of regenerating, be that the iron ion of divalent or the cupric ion selective oxidation of 1 valency are that high valence ion is that the iron ion of 3 valencys or the cupric ion of divalent get final product with the low price ion that is contained in the solution.
For this reason, carried out oxidation regeneration by in etching waste liquor, being blown into chlorine in the past.But chlorine is poisonous, from the transportation of factory, store, be provided with etc. in the management and need exactissima diligentia.In addition, because of the corrodibility of chlorine is obvious, so can not ignore the safety such as management of the selected and ambiance that is used to prevent the pipe arrangement material revealed and the consideration and the investment of environment aspect.
In addition, as the renovation process that does not directly use the etching waste liquor of chlorine, the method for known employing electrolytic oxidation.Use electrolyzer in this method, switch on the electrolytic oxidation etching waste liquor between the anode of portion's setting within it and the negative electrode.But if carry out oxidation in anode side, then naturally in cathode side generation reduction reaction, so oxidation and reduction are offset, oxidation efficiency reduces, and solution can not be regenerated.
For this reason, proposed to adopt near the membrane electrolysis that can prevent gas that anode side generates and ion etc. diffuse to cathode side, come the method (for example, with reference to patent documentation 1,2) of electrolysis oxide etch waste liquid by the electrolyzer that will separate and be divided into anolyte compartment and cathode compartment between anode and the negative electrode with ion-exchange membrane.
But, on the problem of membranous problem and generation chlorine, have the serious problems that solve in this method.Promptly, be not only high price of ion-exchange membrane at first as membranous problem, and be easy to generate as etching waste liquor in the occasion of oxide precipitation, produce or stop up or the exchange of film sees through ability and reduces and make lifetime or impedance increase make disadvantageous problem on management such as bath voltage rising and the cost.And, in the electrolyzer that in the method for electrolytic oxidation etching waste liquor, uses, having the anodic structure of in the case that separates with barrier film, packing into usually, this structure is very complicated, has problems in investment and management.
Next, be in order to prevent from electrolytic oxidation, to produce the related problem of control method of chlorine as the problem that produces chlorine.That is, during the electrolytic oxidation etching waste liquor, if form than the higher peroxidation state of low price ion formation high valence ion degree at anode surface, then chlorine generates from electrode surface as gas.Influence environment for fear of the chlorine that is produced, must reclaim, neutralize and remove by the environment for use smoke collecting device, cause costs such as this investment and reagent expense to rise.
In addition, by the magnitude of current or the logical liquid measure in the control electrolysis,, can prevent that this type of chlorine from producing by being suppressed at the peroxidation state of anode surface.But, because control the above-mentioned magnitude of current or logical liquid measure, be difficult to keep the homogeneity of electrolyzer electrolyte inside, when the chlorine that for example suppresses to cause because of the peroxidation at anode surface excessively produces, might discharge the not enough electrolytic solution of oxidation.For example, in electrolyzer electrolyte inside homogenizing, proposed liquid stream in the overflow mode and stirred near the anode method (for example with reference to patent documentation 3), but from installing space, the cost of a plurality of machines etc. is set, might not be practical.
And then, the structure of electrolyzer also there are a plurality of problems that solve.For example, even in the electrolytic oxidation of etching waste liquor, in order to handle tank solution, adopted in the past in electrolysis for production of metal etc. normally used with a plurality of anodes and negative electrode with narrow interval alternately closely be encased in the electrolyzer mode (for example, with reference to patent documentation 4), in this type of mode, because be used for the complex structure of anode side and cathode side both sides confession row electrolytic solution, so cost of investment also increases.In addition, consider, a plurality of liquid that flow to the electrode case are flowed supply also is very difficult after the complete homogenizing from operation and management.
According to above situation, regenerate in the method for etching waste liquor by electrolytic oxidation, seek to solve the relevant problem of equipment as described above or control, prevent that chlorine from producing and the method for electrolytic oxidation etching waste liquor effectively from electrolyzer.
Patent documentation 1: the spy opens flat 6-207281 communique (page 1, page 2)
Patent documentation 2: the spy opens flat 10-18062 communique (page 1, page 2)
Patent documentation 3: the spy opens 2000-303192 communique (page 1, page 2)
Patent documentation 4: the spy opens flat 7-70784 communique (page 1, page 2, Fig. 1)
Summary of the invention
Problem points in view of above-mentioned conventional art, the object of the present invention is to provide: the etching waste liquor that will contain iron(ic) chloride or cupric chloride feeds the method that in the electrolyzer low price ion electrolysis in this etching waste liquor is oxidized to high valence ion as electrolytic solution, this method is suppressed at the peroxidation of anode surface etching waste liquor, prevent that chlorine from producing from electrolyzer, and on facility investment and running cost electrolytic oxidation etching waste liquor effectively.
In order to achieve the above object, the inventor etc. will be to containing iron(ic) chloride, the etching waste liquor of cupric chloride etc. feeds the method that in the electrolyzer that is formed by anolyte compartment that separates with barrier film and cathode compartment the low price ion electrolysis in this etching waste liquor is oxidized to high valence ion and has carried out wholwe-hearted research repeatedly as electrolytic solution, found that, use possesses specific barrier film material, regulate unit for discharge opeing, the unit of controlled oxidation reduction potential and the electrolyzer of regulating the power supply unit of electrical current, this etching waste liquor is supplied to electrolyzer, the discharge opeing from the anolyte compartment with specified quantitative circulates as feed flow, and will be from the oxidation reduction potential control of anolyte compartment's discharge opeing at particular value, can be suppressed at the peroxidation of the etching waste liquor of anode surface, can prevent that chlorine from producing, and the method for electrolytic oxidation etching waste liquor effectively, thereby finished the present invention.
Promptly, according to first invention of the present invention, a kind of electrolytic oxidation method of etching waste liquor is provided, the etching waste liquor that will contain iron(ic) chloride feeds in the electrolyzer that is formed by anolyte compartment that separates with barrier film and cathode compartment as electrolytic solution the low price ion electrolysis in this etching waste liquor is oxidized to high valence ion, it is characterized in that, use following electrolyzer (A) or electrolyzer (B), supply with described etching waste liquor to electrolyzer, to circulate as feed flow from 15～50% of anolyte compartment's lifting rate, and will be controlled at 550～800mV from the management value of the redox potential (is benchmark with silver/silver chloride electrode) of the discharge opeing of anolyte compartment.
Electrolyzer (A) is to be made of with anolyte compartment and the cathode compartment that filter cloth system barrier film separates the electrode pair that anode that is provided with in the case and negative electrode form, possess: this anolyte compartment and this cathode compartment be separately individually for row's electrolytic solution, and the discharge opeing of anolyte compartment is returned to the adjusting of the feed flow unit for discharge opeing; Discharge opeing side in this anolyte compartment detects redox potential, by increasing and decreasing the unit that the feed flow flow or the electrical current of electrolyzer are controlled this redox potential (is benchmark with silver/silver chloride electrode) management value; And the power supply unit of regulating electrical current.
Electrolyzer (B) is to be made of with anolyte compartment and the cathode compartment that filter cloth system barrier film separates at least 2 above electrode pairs that anode column that is provided with in the OBL case and cathode columns form, described anode column long side direction is provided with the anode more than at least 2, this anode is arranged in series on electrode wide cut direction, described cathode columns is at the one-sided negative electrode that equates with this anode quantity that is provided with of anode column, and this negative electrode is the relative mode arranged in series of single face with the electrode surface of anode and negative electrode; This electrolyzer (B) possesses: this anolyte compartment and this cathode compartment are supplied with electrolytic solution and discharge from opposition side from being listed as a vertical side individually separately with each, and the discharge opeing of anolyte compartment is returned to the unit that supplies discharge opeing to the adjusting of feed flow; The unit that discharge opeing side in this anolyte compartment detects redox potential and controls; Set the unit of the pole span of this anode column and this cathode columns; And the power supply unit of each electrode pair being regulated electrical current.
In addition, according to second invention of the present invention, a kind of electrolytic oxidation method of etching waste liquor is provided, it is characterized in that, the adjusting of above-mentioned electrolyzer (B) is for the unit of discharge opeing in first invention, carry out following control: can carry out circulation and self the round-robin reservoir of solution to electrolysis of solutions groove by discharge opeing and the solution of accepting described anolyte compartment, continuing to carry out this discharge opeing fixes up to the redox potential of the solution of anolyte compartment and reservoir to the circulation of feed flow, thereafter, in order to continue electrolytic oxidation, the solution that electrolytic oxidation is finished is expelled to from reservoir outside the system, the new etching waste liquor of the solution a great deal of that the electrolytic oxidation of accepting and being discharged finishes.
In addition,, provide a kind of electrolytic oxidation method of etching waste liquor, it is characterized in that in first or second invention, the electrode pair of above-mentioned electrolyzer (B) is 2～6 according to the 3rd invention of the present invention.
In addition, according to the 4th invention of the present invention, a kind of electrolytic oxidation method of etching waste liquor is provided, it is characterized in that, in any invention in first to the 3rd, above-mentioned electrolyzer (B) uses cancellous anode, and and then possesses to make along the electrolyte flow of electrode surface in the anolyte compartment and become the baffle plate that crosses this anode mesh.
In addition, according to the 5th invention of the present invention, a kind of electrolytic oxidation method of etching waste liquor is provided, it is characterized in that, in any invention in first to the 3rd, the detection of above-mentioned electrolyzer (B) and the unit of controlled oxidation reduction potential by increase and decrease to the management value of the electrical current of electrolyzer control from the redox potential of anolyte compartment's discharge opeing.
In addition, according to the 6th invention of the present invention, a kind of electrolytic oxidation method of etching waste liquor is provided, it is characterized in that, in any invention in first to the 3rd, the power supply unit of the adjusting electrical current of above-mentioned electrolyzer (B) is regulated electrical current to each electrode pair.
In addition,, provide a kind of electrolytic oxidation method of etching waste liquor, it is characterized in that in the 6th invention, described electrical current is set at high value at the electrode place of feed flow side, be set at low value at the electrode place of discharge opeing side on the other hand according to the 7th invention of the present invention.
In addition, according to the 8th invention of the present invention, a kind of electrolytic oxidation method of etching waste liquor is provided, it is characterized in that, in any invention in first to the 3rd, the unit of the setting pole span of above-mentioned electrolyzer (B) is according to the set(ting)value of the selected pole span of specific conductivity of etching waste liquor.
In addition, according to the 9th invention of the present invention, provide a kind of electrolytic oxidation method of etching waste liquor, it is characterized in that, in any invention in first to the 3rd, configuration in parallel of above-mentioned electrolyzer or configured in series have plural at least electrolyzer (B).
In addition, according to the tenth invention of the present invention, a kind of electrolytic oxidation method of etching waste liquor is provided, it is characterized in that, in the 9th invention, in the described configuration in parallel, carry out power supply to each electrolyzer (B) with independent electric supply installation or with at least two electric supply installations that are connected in series to power in whole electrolyzers or each electrolyzer, on the other hand, the feed flow to each electrolyzer (B) is the etching waste liquor that contains iron(ic) chloride to be cut apart the back anolyte compartment and the cathode compartment of each electrolyzer are supplied with respectively.
In addition, according to the 11 invention of the present invention, a kind of electrolytic oxidation method of etching waste liquor is provided, it is characterized in that, in any invention in first to the 3rd, further possess urgent unit, this unit is according to the alarm value of the indicator value of the redox potential of electrolyzer (A) or electrolyzer (B) or set chlorine gas concentration meter, to pack in the anolyte compartment from the discharge opeing of cathode compartment, the redox potential of regulating this anolyte compartment is to described management value.
In addition, according to the 12 invention of the present invention, a kind of electrolytic oxidation method of etching waste liquor is provided, it is characterized in that, in the electrolytic oxidation method of the etching waste liquor of any invention in the first to the 11, etching waste liquor contains cupric chloride and replaces iron(ic) chloride, and redox potential (is benchmark with silver/silver chloride electrode) is 400～800mV.
The electrolytic oxidation method of etching waste liquor of the present invention is to feed the method that in the electrolyzer low price ion electrolysis in this etching waste liquor is oxidized to high valence ion as electrolytic solution with the etching waste liquor that contains iron(ic) chloride or cupric chloride, can be suppressed at the peroxidation of the etching waste liquor of anode surface, can prevent that chlorine from producing from electrolyzer, and electrolytic oxidation etching waste liquor effectively on facility investment and running cost is so its industrial value is very big.
And then, if use the OBL electrolyzer (B) that constitutes by plural electrode pair, especially here, if use following unit, electrolytic oxidation more effectively just, so it is more favourable, described unit can carry out self round-robin reservoir by accepting this discharge opeing and solution, the discharge opeing that continues to carry out the anolyte compartment is fixed until the redox potential of the solution of anolyte compartment and reservoir to the circulation of feed flow, thereafter, solution as regeneration ending is expelled to from reservoir outside the system, and the new etching waste liquor of the solution a great deal of of the regeneration ending of accepting and being discharged is regulated the discharge opeing that supplies of electrolyzer by such control.
Description of drawings
Fig. 1 is that expression contains the redox potential of the aqueous solution of iron(ic) chloride and cupric chloride and the graph of a relation of dissolution rate.
Fig. 2 is a sectional view of representing to show when electrode pair is 4 long side direction that signal is constructed.
Fig. 3 is that the electrolyzer that is formed by 4 electrode pairs is used in expression, at the ORP variation diagram of energising discharge opeing in the time of 60 hours.
Fig. 4 is the electrolyzer longitdinal cross-section diagram that is illustrated in a kind of mode that baffle plate is set in the anolyte compartment.
Fig. 5 is the ORP variation diagram that has or not the anode discharge opeing under energising that baffle plate is set in the expression anolyte compartment.
Fig. 6 is that expression has electrolyzer (B) and accepts the discharge opeing of electrolyzer and can carry out the sectional view of solution to the electrolyzer of the circulation of electrolyzer and self round-robin reservoir.
Fig. 7 is the figure of an example of expression electrolyzer (B) configuration in parallel.
Fig. 8 is the figure of an example of expression electrolyzer (B) configured in series.
Fig. 9 is the graph of a relation of the ORP of the expression electrical current amount of comparative example 1 and bath voltage and anolyte compartment.
(nomenclature)
1 volume pump
2 initial liquid baths
3 sump pits
4 ORP meter
5 anolyte compartments
6 baffle plates
7 cathode compartments
8 electrolyte flow
9 anodes
10 electrolyzers (B)
11 reservoirs
12 water level gauges
The receiving port of 13 etching waste liquors
14 handle the relief outlet of back solution
15 feed flows to each anolyte compartment and cathode compartment
Embodiment
Below, the electrolytic oxidation method of etching waste liquor of the present invention is elaborated.
The electrolytic oxidation method of etching waste liquor of the present invention is to feed the method that in the electrolyzer that the anolyte compartment that separated by barrier film and cathode compartment form the low price ion electrolysis in this etching waste liquor is oxidized to high valence ion as electrolytic solution with the etching waste liquor that contains iron(ic) chloride, the method is characterized in that, use following electrolyzer (A) or electrolyzer (B), supply with described etching waste liquor to electrolyzer, to circulate as feed flow from 15～50% of anolyte compartment's lifting rate, and will be controlled at 550～800mV from the management value of the redox potential (is benchmark with silver/silver chloride electrode) of the discharge opeing of anolyte compartment.
Electrolyzer (A) is to be made of with anolyte compartment and the cathode compartment that filter cloth system barrier film separates the electrode pair that anode that is provided with in the case and negative electrode form, possess: this anolyte compartment and this cathode compartment be separately individually for row's electrolytic solution, and the discharge opeing of anolyte compartment is returned to the adjusting of the feed flow unit for discharge opeing; Discharge opeing side in this anolyte compartment detects redox potential, by increasing and decreasing the unit that the feed flow flow or the electrical current of electrolyzer are controlled the management value of this redox potential (is benchmark with silver/silver chloride electrode); And the power supply unit of regulating electrical current.
Electrolyzer (B) is to be made of with anolyte compartment and the cathode compartment that filter cloth system barrier film separates at least 2 above electrode pairs that anode column that is provided with in the OBL case and cathode columns form, described anode column long side direction is provided with the anode more than at least 2, this anode is arranged in series on electrode wide cut direction, described cathode columns is at the one-sided negative electrode that equates with this anode quantity that is provided with of anode column, and this negative electrode is the relative mode arranged in series of single face with the electrode surface of anode and negative electrode; This electrolyzer (B) possesses: this anolyte compartment and this cathode compartment are supplied with electrolytic solution and discharge from opposition side from being listed as a vertical side individually separately with each, and the discharge opeing of anolyte compartment is returned to the unit that supplies discharge opeing to the adjusting of feed flow; The unit that discharge opeing side in this anolyte compartment detects redox potential and controls; Set the unit of the pole span of this anode column and this cathode columns; And the power supply unit of each electrode pair being regulated electrical current.
Important meaning of the present invention is, use electrolyzer (A) or electrolyzer (B), supply with etching waste liquor to electrolyzer, to circulate as feed flow from 15～50% of anolyte compartment's lifting rate, and will be controlled at 550～800mV from the management value of the redox potential (is benchmark with silver/silver chloride electrode) of the discharge opeing of anolyte compartment.
That is, at first, the first, make separately circulation of elecrolyte at anolyte compartment and cathode compartment, it is important especially will circulating as feed flow from 15～50%, preferred 25～50% of anolyte compartment's lifting rate.That is, return to the feed flow side, increase relative solution flow in the electrolyzer, forcibly eliminate the uneven liquid stream in the electrolyzer by a part with discharge opeing.Thus,, also can suppress to inferior limit the mixing of two Room solution, finish practicality and go up no problem oxidation efficiency, so do not need the ion-exchange membrane of high price even use cheap common filter cloth as barrier film.If common filter cloth then has the needed material cost of exchange and reduces significantly, even and produce to stop up, to advantages such as the influence of flow control are also little.
Here, if from 15% of the not enough lifting rate of the internal circulating load of anolyte compartment's discharge opeing, when flow being reduced, can not prevent to produce the situation of chlorine because of peroxidation because of the variable error of pump or the management leeway in the actually operating.On the other hand,, then not only the effect of homogenizing is improved less than higher, spend power cost on the contrary more if surpass 50% of lifting rate from the internal circulating load of anolyte compartment's discharge opeing.
The second, will be controlled at 550～800mV from the management value of the redox potential (is benchmark with silver/silver chloride electrode) of anolyte compartment's discharge opeing, preferred 580～700mV is important.For this reason, use electrolyzer (A) or electrolyzer (B), in the discharge opeing portion from the anolyte compartment electrode of measuring redox potential (the following ORP that is also referred to as sometimes) is set, the discharge opeing side in the anolyte compartment detects redox potential, the control electrical current makes this value reach the management value.Thus, can effectively prevent the generation of chlorine.
Also have, as the etching waste liquor that contains iron(ic) chloride used in the above-mentioned electrolytic oxidation method, the etching solution of that the acidic aqueous solution of 3 valency iron(ic) chloride as the oxidation leaching agent forms by mainly containing, the so-called iron of employing system, when metals such as etch processes copper, generate, contain the iron(ic) chloride and the etching dissolved metal of divalent and 3 valencys usually.In addition, in the manipulation of regeneration of this etching waste liquor, because with institute's dissolved metal before saturated in the Separation and Recovery solution, so also use Separation and Recovery metal solution afterwards.The separation and recovery method of this metal, different and different according to metal species, adopt methods such as solvent extraction, electrowinning, displacement.Can enumerate when for example metal is copper the substitution method of being undertaken by metallic iron, the perhaps method that by cathodic reaction its electrolysis is separated out electrolytic oxidation the time.
That is, described iron is in the electrolytic oxidation of etching waste liquor, even the iron ion in the solution 100% becomes high valence ion, chlorine can moltenly be stored in the solution during, do not produce chlorine yet, surrounding environment is not almost had influence.Also have, the chlorine of this molten nonresident portion is during circulate soln, because of the unreacted low price ion of oxidation easily and effectively is consumed.Find that in addition the scope that chlorine can moltenly be stored in the solution is roughly 700～1000mV with ORP value (is benchmark with silver/silver chloride electrode) expression.But the ORP value when switching on usually (is benchmark with silver/silver chloride electrode) can rise to the scope that surpasses 1000mV rapidly from 700mV, is difficult to it is carried out strictness control in practicality.Therefore, in order to control in the mode that does not reach 1000mV well-to-doly, the management value as from the redox potential (is benchmark with silver/silver chloride electrode) of anolyte compartment's discharge opeing is limited to 800mV on it, be preferably 700mV.
On the other hand, be limited to 550mV under it, be preferably 580mV.That is, according to the mensuration of copper coin dissolution rate, when using as etching solution, dissolution rate reduces rapidly during not enough 550mV.In addition, when 580mV is above,, on the dissolution rate of copper coin, does not almost have difference yet, thereby be preferably even compare with the situation of using the fresh sample solution that forms by 100% iron trichloride.
Here, the mensuration of described copper coin dissolution rate is following carries out.
Using with regulation mixed iron trichloride and iron protochloride makes concentration of iron make the copper chloride solution of copper concentration as 80g/L as the ferric chloride in aqueous solution of 180g/L with regulation mixed dichloride copper and cuprous chloride, adjust the solution of different ORP, each 100mL is put into beaker, putting into therein thickness is that the copper coin of 0.3mm is that the mode of 10g is cut off the copper coin that gets and stirred 15 minutes down at 60 ℃ with weight, through picking up washing and dry after the specified time, obtain meltage according to weight, calculate every liter of solution dissolution rate hourly.The result is illustrated among Fig. 1.
Fig. 1 represents the relation of redox potential and dissolution rate.As shown in Figure 1, be boundary with ORP (is benchmark with silver/silver chloride electrode) 550～580mV substantially, dissolution rate reduces rapidly during ORP below this, and then does not almost have dissolving power when being lower than 400mV at ORP (is benchmark with silver/silver chloride electrode).
The electrolyzer (A) that is used for aforesaid method is made of with anolyte compartment and the cathode compartment that filter cloth system barrier film separates the electrode pair that anode that is provided with in the case and negative electrode form, possess: this anolyte compartment and this cathode compartment be separately individually for row's electrolytic solution, and the discharge opeing of anolyte compartment is returned to the adjusting of the feed flow unit for discharge opeing; Discharge opeing side in this anolyte compartment detects redox potential, by increasing and decreasing the unit that the feed flow flow or the electrical current of electrolyzer are controlled the management value of this redox potential (is benchmark with silver/silver chloride electrode); And the power supply unit of regulating electrical current.
As the unit of above-mentioned control ORP, increase and decrease electrical current or feed flow flow get final product.That is, ORP rises when too much, in order to prevent peroxidation, reduces electric current or increases the feed flow flow, reduces the electric current that per unit solution is applied.On the contrary, ORP descends when too much, in order to prevent dysoxidation, reduces the feed flow flow or increases electric current.
Also has the available following formula of relation (1) expression of electrical current and minimum essential feed flow flow.
V＝(2.08×A)/(60×C
Fe)......(1)
(in the formula, V represents feed flow flow (L/min), and A represents electrical current (A), C
FeIron (II) concentration (g/L) of expression feed flow.)
For example, suppose that A is 4.73A, C
FeDuring for 20g/L, V=8.2mL/min then.
But in the electrolyzer (A), increase and decrease need so just make cost uprise with umformer way such as control pump fine to the feed flow flow of electrolyzer.And, viewpoint from the minimizing of holding liquid measure and solution insulation, be preferably the regeneration of in the etching production line, carrying out etching waste liquor as far as possible continuously, and from guaranteeing the viewpoint of the necessary solution of etching operation, the increase and decrease of feed flow flow becomes operational key sometimes.Solve countermeasure as this, the preferred following OBL electrolyzer (B) that constitutes by 2 above electrode pairs.
The electrolyzer (B) that is used for aforesaid method is that at least 2 above electrode pairs that the anode column that is provided with in the case by OBL box and cathode columns form constitute with anolyte compartment and the cathode compartment that filter cloth system barrier film separates, described anode column long side direction is provided with the anode more than at least 2, this anode is arranged in series on electrode wide cut direction, described cathode columns is at the one-sided negative electrode that equates with this anode quantity that is provided with of anode column, and this negative electrode is the relative mode arranged in series of single face with the electrode surface of anode and negative electrode; This electrolyzer possesses: this anolyte compartment and this cathode compartment are supplied with electrolytic solution and discharge from opposition side from being listed as a vertical side individually separately with each, and the discharge opeing of anolyte compartment is returned to the unit that supplies discharge opeing to the adjusting of feed flow; The unit that discharge opeing side in this anolyte compartment detects redox potential and controls; Set the unit of the pole span of this anode column and this cathode columns; And the power supply unit of each electrode pair being regulated electrical current.
The electrode pair of above-mentioned electrolyzer (B) does not limit especially, is at least more than 2, and preferred especially 2～6, more preferably 2～4.That is, the electrode pair problem that the number of devices of groove increases that produces electrolysis when being 1, when surpassing 6 pairs on the other hand, the influence of worrying the electrolyzer long side direction becomes excessive and bias current takes place solution in the groove easily, the local chlorine that produces.
In the above-mentioned electrolyzer (B), electrolytic solution from the opposition side discharge opeing, for this reason, forms the electrolyte flow along a plurality of anode surfaces from respectively being listed as a vertical side feed flow with above-mentioned, keeps the few feed flow of deflection that is caused by each anode.Therefore, management value from the redox potential of anolyte compartment's discharge opeing can be controlled to the electrical current of electrolyzer by increase and decrease in the unit of the redox potential of control electrolyzer (B).Here, about the increase and decrease of electrical current, as power supply unit, can be by each electrode pair fine adjustments electrical current be carried out.For example, if with the electrode in the feed flow side serves as that high value is that the mode of low value is set at the electrode of discharge opeing side on the other hand, then in the anode of feed flow, there are a large amount of unoxidized ions than nearside, so can switch on strong current, on the other hand, unoxidized ion reduces in the anode of discharge opeing side, prevents peroxidation so can reduce electrical current.
Here, describe with the control of electrolyzer (B) the redox potential in the OBL electrolyzer of characteristic.Here, for the effect that makes the oblong-shaped electrolyzer obvious, do not use discharge opeing with the anolyte compartment to return to unit to feed flow, under the condition of following (1)～(3), begin the fixing logical flow quantity feed flow of an electrode from initial liquid bath with the flow of 8.2mL/min, discharge opeing be flow into sump pit once pass through solution.In addition, be 4.725A to an electrifying electrodes.Also have, current density is 500A/m
2
(1) electrolyzer: use following case, be that the length of the direction of 90mm and anode of facing mutually and negative electrode is that 70mm is as benchmark with the length of electrode wide cut direction promptly with the size of a corresponding electrolyzer of electrode pair, the number of electrode pair is become 2～6, only on electrode wide cut direction, prolong the case that gets owing to its number.Here, the degree of depth of electrolyzer is 160mm.In addition, on the position of anode side 30mm and cathode side 40mm, use and to wash Telon system filter cloth and separate the long side direction of electrolyzer, anolyte compartment and cathode compartment are set as barrier film.In addition, leakage fluid dram from electrolyzer is installed downwards in 15mm and the cathode compartment downwards on the position of 10mm from the electrolyzer upper end from electrolyzer upper end in the anolyte compartment.Fig. 2 illustrates an example of electrolyzer.Fig. 2 is the sectional view of the long side direction of the expression electrode pair signal structure that shows electrolyzer (B) 10 when being 4.Here, electrolytic solution, is discharged to sump pit 3 from initial liquid bath 2 feed flows by volume pump 1.In addition, the variation of writing down redox potentials with the ORP meter 4 that is arranged on anolyte compartment's relief outlet.
(2) anode and negative electrode:, use chlorine generation type insoluble anode (mesh-shape) to make that with being with to shelter electrode area is the anode of 70 * 135mm with PERMELEC ELECTRODE (strain) system as anode; As negative electrode, use the titanium plate of thick 1mm sheltered in the same mode of electrode area and anode and must negative electrode.Here, the desired location of anode and negative electrode is that 20mm and the distance from the barrier film to the negative electrode are that the mode of 40mm is fixed with distance from the barrier film to the anodic.Keep intact in the described anodic back side, the back side of negative electrode is for sheltering all surfaces.
(3) electrolytic solution: consistent with the composition substantially of etching waste liquor in the actually operating, it is 107g/L that dissolving iron trichloride reagent makes concentration of iron, it is 53g/L that dissolving chlorination phenanthroline makes concentration of iron, and dissolving dichloride Tong Shiji makes that copper concentration is 60g/L, and adjusting pH with hydrochloric acid is about-0.3.Also having the feed flow temperature of electrolytic solution is 60 ℃.
Its result as can be known, any one situation in the electrolyzer that forms by 2～6 electrode pairs, the ORP of discharge opeing is controlled at below the 1000mV with being stabilized, can suppress the generation of chlorine.Fig. 3 illustrates one of them example.Fig. 3 represents to use the electrolyzer that is formed by 4 electrode pairs, and the ORP of the discharge opeing 60 hours time of switching on changes.As shown in Figure 3, redox potential is through stably passing after the time at initial stage.Hence one can see that, if use OBL electrolyzer (B), then can realize the control of redox potential by regulating electrical current.
The anode that is used for above-mentioned electrolyzer (B) does not limit especially, uses various insoluble anodes, and can enumerate commercially available graphite, cover the platinum titanium, cover the ruthenium oxide titanium and cover the titanium etc. of iridium oxide class, but the preferred type of making the chlorine generation type that is covered with ruthenium oxide of using.In addition, as shape use tabular, perforation is tabular, bar-shaped, curtain shape and mesh-shape etc., but preferred cancellous shape.That is, only make anode when face-off, because the back side does not have help to reaction one-sided, so it is inefficent etc. that worry can cause the using method of short circuit, electrode, if use the electrode that is shaped as mesh-type, then because of also fully carrying out oxidation overleaf, so also can not have problems.
And then this moment, preferably in the anolyte compartment, have to be used for becoming and cross the such mobile baffle plate of anode mesh by the electrolyte flow along electrode surface of supply electrolytic solution formation.Thus, obtain higher oxidation efficiency.Relevant this is elaborated by concrete example below point.
Use the OBL electrolyzer that forms by two electrode pairs as electrolyzer (B), when in the anolyte compartment, being provided with baffle plate and baffle plate not being set, with identical liquid supply rate and identical electrical current, the solution of composition of supplying with ferric iron and be 125g/L and ferrous iron and be 55g/L is as the initial liquid and the energising of electrolytic solution.Fig. 4 is the electrolyzer longitdinal cross-section diagram that a kind of mode of baffle plate is set in the expression anolyte compartment.Here, in the cathode compartment 7 baffle plate is not set.Illustrated among Fig. 4 by baffle plate 6 is set in anolyte compartment 5, the electrolyte flow 8 that dots becomes flowing of the mesh that crosses anode 9.The ORP that measures the anode discharge opeing of this moment under energising changes.Fig. 5 is illustrated in and has or not the ORP that the anode discharge opeing under energising that baffle plate causes is set to change in the anolyte compartment.As shown in Figure 5, for identical liquid supply rate and identical electrical current, when baffle plate is set the rising of ORP very fast, have only such oxidation efficiency height.
The unit of the setting pole span of above-mentioned electrolyzer (B) does not limit especially, but can select the set(ting)value of pole span according to the specific conductivity of etching waste liquor.Promptly, in the electrolyzer (B), because can on position arbitrarily, set the interval of anode column and cathode columns, so can be according to the only pole span of the conductivity setpoint of etching waste liquor, thus, has undesigned fault such as the short circuit that can avoid anode and negative electrode and then improve the advantages such as operability of electrode.
The adjusting of above-mentioned electrolyzer (B) does not limit especially for the unit of discharge opeing, preferably carry out following control: can carry out circulation and self the round-robin reservoir of solution to electrolyzer by accepting discharge opeing and solution, the discharge opeing that continues to carry out described anolyte compartment is fixed until the redox potential of the solution of anolyte compartment and reservoir to the circulation of feed flow, thereafter, in order to proceed electrolytic oxidation, the solution that electrolytic oxidation is finished is expelled to from reservoir outside the system, the new etching waste liquor of the solution a great deal of that the electrolytic oxidation of accepting and being discharged finishes.By carrying out this control, carry out electrolytic oxidation continuously, so can enroll the etching operation production line.
Fig. 6 illustrates the sectional view that expression uses the signal of a kind of electrolyzer of described control to construct.Among Fig. 6, electrolyzer comprises the electrolyzer (B) 10 that is formed by 4 electrode pairs and accepts the discharge opeing of electrolyzer and can carry out circulation and self the round-robin reservoir 11 of solution to electrolyzer, be provided with ORP meter 4 in the electrolyzer (B) 10, be provided with the receiving port 13 of water level gauge 12, etching waste liquor and the relief outlet 14 of handling back solution in the reservoir 11.
Promptly, by a part of discharge opeing is returned to the feed flow side, increase the relative solution flow in the electrolyzer, forcibly eliminate the uneven liquid stream in the electrolyzer, therefore electrolyzer self is enlarged, in fact and to circulate between the reservoir of other setting be effective this has any problem on multiple major causes such as space, so.With the integrated electrolyzer that forms of above-mentioned the same reservoir in switch on, the ORP of the solution of electrolyzer and reservoir can almost stably pass on the fixed value, with in the past with once different by the situation of leading to liquid, have the advantage that need not strict control feed flow flow.And then, shorten in the residence time of electrolyzer body part, and the adding the control of gentle cooling equitemperature and can in reservoir, carry out of the electrolytic solution that carries out as required, thus have can the simplified apparatus structure advantage.
And then as required, the electrolyzer that is used for aforesaid method can possess: according to the alarm value of the management value of the oxidation-reduction potentiometer of electrolyzer (A) or electrolyzer (B) or set chlorine gas concentration meter, to the redox potential of this anolyte compartment be adjusted to the urgent unit of described management value from the discharge opeing of the cathode compartment anolyte compartment of packing into.That is, in the electrolytic oxidation method that is undertaken by the present invention, can prevent that substantially chlorine from producing, however be not to imagine the situation that makes the unusual generation of chlorine because of multiple reason.Guard against this situation that the equipment that the discharge opeing from cathode compartment can be added drop-wise to anolyte compartment's liquid level preferably is set, make the oxidation-reduction potentiometer or the chlorine alarm interlock of itself and electrolyzer (A) or electrolyzer (B).
The cathode compartment that is used for the electrolyzer of aforesaid method must lead to liquid with certain flow.That is,, then carry out reduction with the cathode solution of same charge a great deal of if carry out oxidation in anode side.Therefore, in the time of will containing the etching waste liquor feeding cathode compartment of copper, superfluous ground over reduction makes the copper electrolysis probably, contacts with anode to produce short circuit, and hinders electrolysis, so flow that need be certain.For example, in the etching waste liquor in the actually operating, according to the composition of iron ion in the etching waste liquor, can be to the feed flow flow of cathode compartment the anode chamber the feed flow flow about 1/9.
The anode that is used for the electrolyzer of aforesaid method does not limit especially, uses various insoluble anodes, and can enumerate commercially available graphite, cover the platinum titanium, cover the ruthenium oxide titanium and cover the titanium etc. of iridium oxide class, but the preferred type of using the chlorine generation type that is covered with ruthenium oxide.In addition, as shape use tabular, perforation is tabular, bar-shaped, curtain shape and mesh-shape etc., but preferred cancellous shape.
The negative electrode that is used for the electrolyzer of aforesaid method preferably has the titanium of erosion resistance at mordant ferric chloride Solution.As its shape use tabular, perforation is tabular, bar-shaped, curtain shape and expanded metal (expand metal) shape etc.
The filter cloth that is used for the electrolyzer of aforesaid method does not limit especially, for example use the filter cloth of making by materials such as polypropylene, polyester, acrylic resin, modified acroleic acid resinoid, tetrafluoroethylene and polyvinylidene difluoride (PVDF), among this, the filter cloth that the preferred especially mode that reduces with thin, the permeable degree of eye is made into.Permeable degree does not limit especially, is preferably 0.04～0.15L/m when handling iron ion
2The scope of s.
The electrolyzer that is used for aforesaid method can use configuration in parallel or configured in series that the electrolyzer of at least two above electrolyzers (B) is arranged as required.That is, poor hour of the ORP of the ORP before the electrolytic oxidation and the target value of electrolytic oxidation is arranged in parallel and makes the increase of treatment soln amount, and when the ORP difference was enough big, preferred longitudinal tensile strain carried out with uniform flux.
Fig. 7 represents an example of electrolyzer (B) configuration in parallel, and Fig. 8 represents an example of electrolyzer (B) configured in series.In the described configuration in parallel, as required with independent electric supply installation or with whole electrolyzers or each electrolyzer in the electric supply installation that is connected in series to power on of at least two electrolyzers carry out power supply to each electrolyzer (B), on the other hand, can make the feed flow of each electrolyzer (B) is cut apart the feed flow 15 that the back provides respectively the anolyte compartment and the cathode compartment of each electrolyzer for the etching waste liquor that will contain iron(ic) chloride.Therefore, have quantity that reduces supply unit and the advantage that is easy to control.And then can take when all device is all moving, to keep in repair, adjust specific measures such as electrolyzer successively by stopping to specific electrolyzer with electricity.
In addition, by guaranteeing space between electrolyzer and the electrolyzer about 1～5cm, can prevent from sultry in the electrolyzer from can suppress the rising of liquid temperature in the described configuration in parallel.That is, etching waste liquor is low because of the specific conductivity of solution, and worries that bath voltage uprises, makes power cost to rise, and thermal value increases, makes the too much rising of liquid temperature, but it can be suppressed.
What more than the electrolytic oxidation method of Shuo Ming etching waste liquor related to is that iron is etching waste liquor, and also can be used to contain cupric chloride is etching waste liquor as the copper of main component.Copper is cupric chloride and the dissolved metal that contains divalent and 1 valency in the etching waste liquor.
At this moment, the management value of redox potential (is benchmark with silver/silver chloride electrode) is 400～800mV, is preferably 450～700mV.That is, as management value from the redox potential (is benchmark with silver/silver chloride electrode) of the discharge opeing of anolyte compartment, based on iron be the same reason of occasion of etching waste liquor, be limited to 800mV on it, be preferably 700mV.On the other hand, the not enough 400mV of redox potential (is benchmark with silver/silver chloride electrode), according to the mensuration of the dissolution rate of copper coin, it is better almost not having dissolving power, particularly 450mV above.
(embodiment)
Below, the present invention will be described in more detail by embodiments of the invention and comparative example, but the present invention is not subjected to any restriction of these embodiment.Also have, the analysis of the metal that uses in embodiment and comparative example is carried out with the ICP luminescence analysis.
(embodiment 1, comparative example 1)
Use following electrolyzer, anode and negative electrode and etching waste liquor, relatively (a) do not carry out occasion of controlling by the ORP that the adjustment electrical current carries out (comparative example 1) and the occasion (embodiment 1) of (b) carrying out the control of ORP by the adjustment electrical current.Implement the discharge opeing circulation of anolyte compartment in addition.
(electrolyzer)
The vinylchlorid system of being made into box electrolyzer (A).Its size is, the length of electrode wide cut direction is 90mm, and the length of the anode of facing mutually and the direction of negative electrode is 70mm, and the degree of depth of electrolyzer is 160mm.In addition, be that 30mm and cathode side are on the position of 40mm in anode side, use and to wash Telon system filter cloth and separate the long side direction of electrolyzer as barrier film, anolyte compartment and cathode compartment are set.In addition, leakage fluid dram from electrolyzer is installed downwards in 15mm and the cathode compartment downwards on the position of 10mm from the electrolyzer upper end from electrolyzer upper end in the anolyte compartment.In addition, count the variation of record redox potential with the ORP of the relief outlet that is arranged on the anolyte compartment.
(anode and negative electrode)
As anode, use chlorine generation type insoluble anode (mesh-shape) to make that with being with to shelter electrode area is the anode of 70 * 135mm with PERMELEC ELECTRODE (strain) system; As negative electrode, use the titanium plate of thick 1mm sheltered in the same mode of electrode area and anode and must negative electrode.Here, use each one on anode and negative electrode, its desired location is that 20mm and the distance from the barrier film to the negative electrode are that the mode of 40mm is fixed with distance from the barrier film to the anodic.The described anodic back side maintains the original state, and the back side of negative electrode is for sheltering all surfaces.
(etching waste liquor)
Consistent with the composition substantially of etching waste liquor in the actually operating, it is 107g/L that dissolving iron trichloride reagent makes concentration of iron, it is 53g/L that dissolving chlorination phenanthroline makes concentration of iron, and dissolving dichloride Tong Shiji makes that copper concentration is 60g/L, and adjusting pH with hydrochloric acid is about-0.3.Also have, the feed flow temperature of electrolytic solution is 60 ℃.
Logical liquid condition is based on above-mentioned (1) formula, circulates to feed flow from the ratio of discharge opeing with 1.6mL/min with the fixing logical flow quantity feed flow of 3.1mL/min flow in the anode chamber.The discharge opeing of this moment is 50% to the internal circulating load of feed flow, and solution is with the proportional flow of 4.7mL/min in the anolyte compartment.In addition, to the fixing logical flow quantity feed flow of cathode compartment with the 3.1mL/min flow, discharge opeing does not circulate.
At first,, do not carry out by adjusting the ORP control that electrical current carries out, corresponding to current density 500A/m as the occasion of (a)
2Electric current 4.73A under switch on, make ORP fix.Also have, the ORP of the initial liquid of electrolysis (is benchmark with silver/silver chloride electrode) is 560mV.
Here, be determined at the energising under bath voltage and the ORP of anolyte compartment.In addition, measure the chlorine gas concentration of the upper gaseous phase part of anolyte compartment with detector tube.The result is illustrated among Fig. 9.Fig. 9 represents the relation of the ORP (is benchmark with silver/silver chloride electrode) of electrical current amount and bath voltage and anolyte compartment.As shown in Figure 9, along with the increase of electrical current amount, bath voltage slowly rises, and ORP becomes rapid from surpassing the 750mV rising.At this moment, detect chlorine later on from 1000mV.Also having, is that 700mV does not detect chlorine until ORP (is benchmark with silver/silver chloride electrode), confirms not produce chlorine from anode.Also have, in the moment of the ORP of anolyte compartment (is benchmark with silver/silver chloride electrode) above 1000mV, after the solution of forming together with initial liquid phase was added in the anode chamber, chlorine stopped to atmospheric discharging, confirmed that the measure when this method conduct is urgent is effective.
Then,, will be set at 580～700mV, with corresponding to current density 500A/m from the management value of the ORP (is benchmark with silver/silver chloride electrode) of the discharge opeing of anolyte compartment as the occasion of (b)
2Electric current 4.73A be the basis, the increase and decrease electrical current carry out the control of ORP.Thus, the divalent iron in the discharge opeing after the processing that obtains is oxidized to 3 valencys, obtains the dissolving metal ability and obtains the regenerated etching solution, and proceed not produce the stable electrolytic oxidation of chlorine.
(embodiment 2)
Use electrolyzer shown in Figure 6 and anode similarly to Example 1, negative electrode and etching waste liquor.Also have, described electrolyzer is provided with baffle plate in the anolyte compartment, improves getting in the mode of liquid stream by the anodic mesh.
As logical liquid condition, the anode chamber is with the fixing flow quantity feed flow again that leads to of 3.1mL/min flow, and the discharge opeing of anolyte compartment is via reservoir, and 50% of lifting rate is recycled to feed flow, and solution is with the proportional flow of 4.7mL/min in the anolyte compartment.In addition, to the fixing logical flow quantity feed flow of cathode compartment with the 3.1mL/min flow, discharge opeing does not circulate.
Power on condition is as follows: will be set at 580～700mV from the management value of the ORP (is benchmark with silver/silver chloride electrode) of the discharge opeing of anolyte compartment, with corresponding to current density 500A/m
2Electric current 4.73A be the basis, the increase and decrease electrical current carry out the control of ORP.Also have, the ORP of the initial liquid of electrolysis (is benchmark with silver/silver chloride electrode) is 560mV.
Its result, through after the energising initial stage, the management value is stably kept in the indication of ORP meter, and acceptance is handled the new soln of the part a great deal of of back solution discharge with conduct, and proceeds electrolytic oxidation and handle.Thus, the divalent iron after the processing that obtains in the solution is oxidized to 3 valencys, obtains the dissolving metal ability and obtains the regenerated etching solution, and proceed not produce the stable electrolytic oxidation of chlorine.
(embodiment 3)
The power supply unit of the adjusting electrical current of electrolyzer (B) is regulated electrical current to each electrode pair, and is as shown in table 1, electrical current is made as high value at the electrode pair of feed flow side, electrode pair in the discharge opeing side is made as low value on the other hand, in addition, carries out similarly to Example 2.
Its result, through after the energising initial stage, the management value is stably kept in the indication of ORP meter, and acceptance is handled the new soln of the part a great deal of of back solution discharge with conduct, and proceeds electrolytic oxidation and handle.Thus, the divalent iron after the processing that obtains in the solution is oxidized to 3 valencys, obtains the dissolving metal ability and obtains the regenerated etching solution, and proceed not produce the stable electrolytic oxidation of chlorine.
Table 1
| Electrode pair NO. | 1 (feed flow side) | 2 | 3 | 4 (discharge opeing sides) |
| Current density (A/m 2) | 500 | 500 | 250 | 250 |
(embodiment 4)
As etching waste liquor, use with actually operating in etching waste liquor form substantially consistent and dissolving dichloride Tong Shiji make copper concentration as 60g/L, dissolving chlorination cuproine make copper concentration as 20g/L, to adjust pH with hydrochloric acid be about-0.3 solution, and the management value of ORP (is benchmark with silver/silver chloride electrode) is set at 450～700mV, in addition, carry out similarly to Example 2.
Its result, through after the energising initial stage, the management value is stably kept in the indication of ORP meter, and acceptance is handled the new soln of the part a great deal of of back solution discharge with conduct, and proceeds electrolytic oxidation and handle.Thus, 1 valency copper after the processing that obtains in the solution is oxidized to divalent, obtains the dissolving metal ability and obtains the regenerated etching solution, and proceed not produce the stable electrolytic oxidation of chlorine.
As known from the above, in embodiment 1～4, the specification of electrolyzer, the feed liquid method to electrolyzer, the cycling condition of anolyte compartment's discharge opeing and the control condition of redox potential are carried out according to method of the present invention, so the low price ion electrolysis in the etching waste liquor is being oxidized in the method for high valence ion, can be suppressed at the peroxidation of the etching waste liquor of anode surface, can prevent that chlorine from producing from electrolyzer, and electrolytic oxidation etching waste liquor effectively.Also know, relative therewith, in comparative example 1, because the control condition of redox potential does not meet these conditions, so preventing to can not get gratifying result aspect the chlorine generation.
Utilizability on the industry
As known from the above, the electrolytic oxidation method of etching waste liquor of the present invention, as the regeneration treating method of etching waste liquor, particularly being suitable as the method that the etching solution that is formed as the acidic aqueous solution of main component by the high valence ion that contains copper chloride and/or iron chloride of in the manufacturing of the lead frame that becomes the semiconductor integrated circuit base stage etc. use is processed in regeneration.
Claims (12)
1, a kind of electrolytic oxidation method of etching waste liquor, the etching waste liquor that will contain iron(ic) chloride feeds in the electrolyzer that is formed by anolyte compartment that separates with barrier film and cathode compartment as electrolytic solution the low price ion electrolysis in this etching waste liquor is oxidized to high valence ion, it is characterized in that
Use following electrolyzer (A) or electrolyzer (B), supply with described etching waste liquor to electrolyzer, to circulate as feed flow from 15～50% of anolyte compartment's lifting rate, and will be controlled at 550～800mV from the management value of the redox potential of anolyte compartment's discharge opeing, described redox potential is a benchmark with silver/silver chloride electrode
Electrolyzer (A) is to be made of with anolyte compartment and the cathode compartment that filter cloth system barrier film separates the electrode pair that anode that is provided with in the case and negative electrode form, possess: this anolyte compartment and this cathode compartment be separately individually for row's electrolytic solution, and the discharge opeing of anolyte compartment is returned to the adjusting of the feed flow unit for discharge opeing; Discharge opeing side in this anolyte compartment detects redox potential, and by increasing and decreasing the unit of the management value that the feed flow flow or the electrical current of electrolyzer are controlled this redox potential, this redox potential is a benchmark with silver/silver chloride electrode; And the power supply unit of regulating electrical current;
Electrolyzer (B) is to be made of with anolyte compartment and the cathode compartment that filter cloth system barrier film separates at least 2 above electrode pairs that anode column that is provided with in the OBL case and cathode columns form, described anode column long side direction is provided with the anode more than at least 2, this anode is arranged in series on electrode wide cut direction, described cathode columns is at the one-sided negative electrode that equates with this anode quantity that is provided with of anode column, and this negative electrode is the relative mode arranged in series of single face with the electrode surface of anode and negative electrode; This electrolyzer (B) possesses: this anolyte compartment and this cathode compartment are supplied with electrolytic solution and discharge from opposition side from being listed as a vertical side individually separately with each, and the discharge opeing of anolyte compartment is returned to the unit that supplies discharge opeing to the adjusting of feed flow; The unit that discharge opeing side in this anolyte compartment detects redox potential and controls; Set the unit of the pole span of this anode column and this cathode columns; And the power supply unit of each electrode pair being regulated electrical current.
2, the electrolytic oxidation method of etching waste liquor according to claim 1, it is characterized in that, the adjusting of described electrolyzer (B) is carried out following control for the unit of discharge opeing: can carry out circulation and self the round-robin reservoir of solution to electrolyzer by discharge opeing and the solution of accepting described anolyte compartment, continuing to carry out this discharge opeing fixes until the redox potential of the solution of anolyte compartment and reservoir to the circulation of feed flow, thereafter, in order to continue electrolytic oxidation, the solution that electrolytic oxidation is finished is expelled to from reservoir outside the system, the new etching waste liquor of the solution a great deal of that the electrolytic oxidation of accepting and being discharged finishes.
3, the electrolytic oxidation method of etching waste liquor according to claim 1 and 2 is characterized in that, the electrode pair of described electrolyzer (B) is 2～6.
4, according to the electrolytic oxidation method of any described etching waste liquor in the claim 1～3, it is characterized in that, described electrolyzer (B) uses and to be shaped as cancellous anode, and further possesses to make along the electrolyte flow of electrode surface in the anolyte compartment and become the baffle plate that crosses this anode mesh.
5, according to the electrolytic oxidation method of any described etching waste liquor in the claim 1～3, it is characterized in that the detection of described electrolyzer (B) and the unit of controlled oxidation reduction potential are controlled management value from the redox potential of anolyte compartment's discharge opeing by increase and decrease to the electrical current of electrolyzer.
According to the electrolytic oxidation method of any described etching waste liquor in the claim 1～3, it is characterized in that 6, the power supply unit of the adjusting electrical current of described electrolyzer (B) is regulated electrical current to each electrode pair.
7, the electrolytic oxidation method of etching waste liquor according to claim 6 is characterized in that, described electrical current is set at high value at the electrode place of feed flow side, be set at low value at the electrode place of discharge opeing side on the other hand.
According to the electrolytic oxidation method of any described etching waste liquor in the claim 1～3, it is characterized in that 8, the unit of the setting pole span of described electrolyzer (B) is according to the set(ting)value of the selected pole span of specific conductivity of etching waste liquor.
According to the electrolytic oxidation method of any described etching waste liquor in the claim 1～3, it is characterized in that 9, configuration in parallel of described electrolyzer or configured in series have plural at least electrolyzer (B).
10, the electrolytic oxidation method of etching waste liquor according to claim 9, it is characterized in that, in the described configuration in parallel, with independent electric supply installation or with whole electrolyzers or each electrolyzer in the electric supply installation that is connected in series of at least two above electrolyzer electricity carry out power supply to each electrolyzer (B), on the other hand, the feed flow to each electrolyzer (B) is the etching waste liquor that contains iron(ic) chloride to be cut apart the back anolyte compartment and the cathode compartment of each electrolyzer are supplied with respectively.
11, according to the electrolytic oxidation method of any described etching waste liquor in the claim 1～3, it is characterized in that, further possesses urgent unit, this unit is according to the alarm value of the indicator value of the redox potential of electrolyzer (A) or electrolyzer (B) or set chlorine gas concentration meter, will be from the discharge opeing of the cathode compartment anolyte compartment of packing into, the redox potential of regulating this anolyte compartment is to described management value.
12, according to the electrolytic oxidation method of any described etching waste liquor in the claim 1～11, it is characterized in that, etching waste liquor contains cupric chloride and replaces iron(ic) chloride, and redox potential is 400～800mV, and described redox potential is a benchmark with silver/silver chloride electrode.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102321908A (en) * | 2011-09-02 | 2012-01-18 | 广州市天承化工有限公司 | Recycling and regenerating process method and metal copper recovery system of acid chloride etching solution |
| CN106007114A (en) * | 2016-07-29 | 2016-10-12 | 陈铭 | Electronic factory waste liquid treatment system |
| CN108866572A (en) * | 2018-08-27 | 2018-11-23 | 苏碧云 | A kind of iron displacement copper electrolysis cells |
| CN111945178A (en) * | 2020-08-07 | 2020-11-17 | 涓ュ己 | Off-grid type electrolytic cell structure and electrode control method |
| CN111962092A (en) * | 2020-08-17 | 2020-11-20 | 涓ュ己 | Off-grid independent electrolytic cell structure and electrode control method |
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| EP2927347A1 (en) * | 2014-04-01 | 2015-10-07 | Sigma Engineering Ab | Oxidation of copper in a copper etching solution by the use of oxygen and/or air as an oxidizing agent |
| CN112939055A (en) * | 2021-01-25 | 2021-06-11 | 湖北林泰环境科技有限公司 | Method for producing copper chloride by using waste acidic etching solution |
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| JPS526349A (en) * | 1975-07-07 | 1977-01-18 | Yotsuwa Sangiyou Kk | Method of regenerating etching liquid on surfaces of metals |
| JP3478947B2 (en) * | 1997-05-19 | 2003-12-15 | 鶴見曹達株式会社 | Regeneration method of ferric chloride solution |
| JPH1161445A (en) * | 1997-08-06 | 1999-03-05 | Astec Irie:Kk | Electrolytic treatment of iron chloride aqueous solution |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102321908A (en) * | 2011-09-02 | 2012-01-18 | 广州市天承化工有限公司 | Recycling and regenerating process method and metal copper recovery system of acid chloride etching solution |
| CN106007114A (en) * | 2016-07-29 | 2016-10-12 | 陈铭 | Electronic factory waste liquid treatment system |
| CN108866572A (en) * | 2018-08-27 | 2018-11-23 | 苏碧云 | A kind of iron displacement copper electrolysis cells |
| CN111945178A (en) * | 2020-08-07 | 2020-11-17 | 涓ュ己 | Off-grid type electrolytic cell structure and electrode control method |
| CN111962092A (en) * | 2020-08-17 | 2020-11-20 | 涓ュ己 | Off-grid independent electrolytic cell structure and electrode control method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5125278B2 (en) | 2013-01-23 |
| JP2009024216A (en) | 2009-02-05 |
| CN101348916B (en) | 2011-06-08 |
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