CN104451688B - A kind of method of electrolytic regeneration Ni from waste etching FeCl 3 solution containing co-production iron oxide yellow - Google Patents
A kind of method of electrolytic regeneration Ni from waste etching FeCl 3 solution containing co-production iron oxide yellow Download PDFInfo
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- CN104451688B CN104451688B CN201410764425.XA CN201410764425A CN104451688B CN 104451688 B CN104451688 B CN 104451688B CN 201410764425 A CN201410764425 A CN 201410764425A CN 104451688 B CN104451688 B CN 104451688B
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Abstract
The invention discloses a kind of method of electrolytic regeneration Ni from waste etching FeCl 3 solution containing co-production iron oxide yellow, comprise the following steps：Etching waste liquor is electrolysed using anionic membrane electrolysis, anolyte and catholyte are obtained respectively；To adding alkali lye and dispersant in catholyte, and it is passed through air and is reacted, be centrifuged after the completion of reaction, Nanoscale Iron bloom body and iron oxide yellow filtered fluid is obtained respectively；To adding precipitating reagent to be reacted in iron oxide yellow filtered fluid, filtered after the completion of reaction, iron nickel co-precipitate and filtrate are obtained respectively, filtrate is discharged after charcoal absorption.The namely regenerated ferric trichloride etching solution of anolyte that the present invention is obtained through electrolysis, composition meets the quality requirement to ferric trichloride etching solution in etch process, can directly recycle；Nanoscale Iron bloom body is prepared using catholyte by alkaline process, iron resource is further recycled；Ni2+Iron oxide yellow filtered fluid mainly is enriched in, the filtrate after being precipitated through precipitating reagent can press electroplating industry standard qualified discharge after simple absorption.
Description
Technical field
The present invention relates to the processing method of Ni from waste etching FeCl 3 solution containing, and in particular to a kind of nickeliferous trichlorine of electrolytic regeneration
The method for changing iron etching waste liquor co-production iron oxide yellow.
Background technology
Liquor ferri trichloridi due to certain oxidisability and acidity, there is good corrosiveness to iron, nickel, thus
Metal etch is applied to by substantial amounts of, it is stainless in ferric trichloride etching nickel such as in the etching of fine circuit pattern, microelectronics Packaging
Steel shadow mask process.In etching process, FeCl3FeC1 is reduced into by nickel and stainless steel2, while a small amount of metallic nickel can be oxidized with Ni2+
Form enters etching solution.In etching process, with FeC1 in etching solution3The reduction of concentration and Ni2+The rising of concentration, the effect of etching
Rate can decline.Additionally, Ni in etching solution2+The rising of concentration is also easy to cause product to etch the excessively coarse tendency in surface.
According to etch process quality requirement, the constituent content of ferric trichloride etching solution should reach claimed below:Ferric trichloride content >=
35%th, frerrous chloride content≤0.4%.Therefore a large amount of used FeCl3Etching solution due to etch process requirement can not be met and
Discharged in waste liquid form from etch system.Waste liquid composition is ferric trichloride 28~34%, also frerrous chloride 2.5~8%, chlorine
Change nickel 2.5~6%, if this waste liquid is discharged as danger wastes without treatment, not only result in the pollution of environment, Er Qiezao
Into the significant wastage of resource, thus Ni from waste etching FeCl 3 solution containing how highly efficient regeneration is using being common concern both at home and abroad at present
Problem.
Current most of manufacturers are processed Ni from waste etching FeCl 3 solution containing using pure iron reducing process, are such as announced
Number for the A of JP 5140667 Japanese documentation in propose iron replacement reaction except nickel method, the method iron powder and three
Iron chloride waste liquid mixes, and ferric trichloride is reduced into ferrous chloride, and the bivalent nickel ion in excessive iron powder and substitutional solution makes
Metallic nickel precipitates；Except the ferrous chloride chlorinated with chlorine after nickel is into ferric trichloride, etching solution is re-used as.Add in the method
The iron powder amount for entering must be excessive, therefore, the grade for reclaiming nickel is at a fairly low, does not have further use value, and largely
Input pure iron increased production cost.
Notification number discloses a kind of first condensing crystallizing for the Chinese patent literature of CN 1540036A, then to mother liquor electrolysis point
Method from nickel is reclaimed.In the method, nickeliferous ferric trichloride waste liquid condensing crystallizing is first crystallized out into nickeliferous relatively low trichlorine
Change iron crystal, then the ferric trichloride mother liquor after crystallization is electrolysed, there is iron-nickel alloy to separate out in negative electrode, have chlorine in anode
Separate out.The rate of recovery of the method nickel is higher, but due to there is chlorine to separate out in electrolytic process, to equipment corrosion than larger, operates into
This is higher.
Notification number discloses the method that condensing crystallizing separates nickel for the Japanese documentation of JP10046370.In the method
In, the ferric trichloride etching waste liquor elder generation condensing crystallizing containing nickel isolates the relatively low ferric trichloride crystal of nickel content, its mother liquor warp
Repeated crystallization, nickel ion is enriched with, and reaches the purpose for separating nickel.But the method step is more, waste big, efficiency is very low.
The Chinese patent literature of Publication No. CN1386906 disclose Ni from waste etching FeCl 3 solution containing except nickel method,
The method includes：(1) iron powder or squamous iron sheet are added in etching waste liquor, reduction reaction is carried out, (2) heating response mixture is extremely
55 DEG C -95 DEG C, recommend and be charged with iron powder and Cosan, carry out the precipitation reaction of nickelous, (3) past 55 DEG C -95 DEG C reaction
In mixture, or iron powder and Cosan are continuously added, or add iron powder and arsenic compound, or add iron powder and antimony chemical combination
Thing, further carries out the precipitation reaction of nickelous, then filters.
The method needs to add the iron and sulfur-bearing of a large amount of high-purities in nickeliferous ferric trichloride etching waste liquid or containing arsenic, containing antimony
Industrial chemicals, the input of a large amount of pure iron increased production cost, and ferric trichloride changes into ferrous chloride and mends chlorine in processing procedure
Ferric trichloride total amount increase nearly 1/3rd afterwards increased trouble to the content of ferric trichloride in precise control etching liquid；The opposing party
Face sulfur-bearing, environmental pollution had both been easily caused containing arsenic, the use containing antimony industrial chemicals had inevitably to ferric trichloride etching liquid
Introduce the difficulty that impurity increased quality control after ferric trichloride etching liquid regeneration.
The content of the invention
The invention provides a kind of method of electrolytic regeneration Ni from waste etching FeCl 3 solution containing co-production iron oxide yellow, the method behaviour
Make simple, low cost, recovery utilization rate is high.
A kind of method of electrolytic regeneration Ni from waste etching FeCl 3 solution containing co-production iron oxide yellow, comprises the following steps：
(1) Ni from waste etching FeCl 3 solution containing is electrolysed using anionic membrane electrolysis, respectively obtain anolyte and
Catholyte, the anolyte is regeneration ferric trichloride etching solution；
(2) to adding alkali lye and dispersant in the catholyte, and it is passed through air and is reacted, is centrifuged after the completion of reaction,
Nanoscale Iron bloom body and iron oxide yellow filtered fluid are obtained respectively；
(3) to adding Fe in the iron oxide yellow filtered fluid2+And Ni2+Precipitating reagent reacted, after the completion of reaction filter, point
Not Huo get iron nickel co-precipitate and filtrate, filtrate discharges after charcoal absorption.
The chlorion that anion-exchange membrane can allow in etching waste liquor is selectively passed through, and with the carrying out of electrolysis time, Fe3+
In anode enrichment, Fe2+In cathodic enrichment, so that the Fe in anolyte3+Concentration can reach 3.5108mol/L, Fe2+Concentration
Less than 0.0023mol/L, meet the quality requirement to ferric trichloride etching solution in etch process, can directly recycle；Together
Shi Caiyong alkaline process is using rich in Fe2+Catholyte prepare Nanoscale Iron bloom body, further recycle iron resource；In etching waste liquor
Ni2+Iron oxide yellow filtered fluid mainly is enriched in, the filtrate after being precipitated through precipitating reagent can press electroplating industry standard after simple absorption
Qualified discharge.Whole process is simple to operate, with low cost, and the recovery utilization rate to etching waste liquor is high, and three-waste free discharge.
Specifically, the described method comprises the following steps：
(1) Ni from waste etching FeCl 3 solution containing is electrolysed using anionic membrane electrolysis, respectively obtain anolyte and
Catholyte, the anolyte is regeneration ferric trichloride etching solution；
Space in cell body is divided into sun by the electrolytic cell that anionic membrane electrolysis is used, including cell body, anion-exchange membrane
Pole room and cathode chamber, anode chamber are communicated with anode hopper, and cathode chamber is communicated with negative electrode hopper.
In electrolytic process, the Ni from waste etching FeCl 3 solution containing of anode side is circulated between anode chamber and anode hopper
Flowing, the Ni from waste etching FeCl 3 solution containing of negative electrode side is circulated between cathode chamber and negative electrode hopper, and cathode chamber
Interior Cl—Anion-exchange membrane is selectively passed through to enter in anode chamber.The main reaction for occurring is as follows in electrolytic process：
Anode reaction：2Cl—→Cl2↑+2e—(Ⅰ)；
Fe2+→Fe3++e—(Ⅱ)；
Cathode reaction：Fe3++e—→Fe2+ (Ⅲ)。
Preferably, the anion-exchange membrane is homogeneous cavity block, homogeneous cavity block has more preferable electro-chemical activity.
Preferably, the voltage for using that is electrolysed is 6.0~7.0V.During using this voltage, negative and positive the two poles of the earth are enabled to
Electrode reaction required for occurring, while reducing other side reactions.As further preferred, it is described be electrolysed the voltage that uses for
6.0V.Under this voltage, current efficiency η highests reach 95.82%.
Preferably, the current density of electrolytic process Anodic electrode is 90~150A/m2.Now Fe in anode chamber2+Oxygen
Turn to Fe3+Efficiency highest.
Preferably, the anode electrode is metal Ti electrode.Metal Ti electrode cannot participate in anode reaction, and electrolysis effect
Rate is higher.
After the completion of electrolysis, the namely regenerated ferric trichloride etching solution of anolyte regenerates the Fe of ferric trichloride etching solution3+Concentration can
To reach 3.5108mol/L, Fe2+Concentration is less than 0.0023mol/L.
(2) to adding alkali lye and dispersant in the catholyte, and it is passed through air and is reacted, is centrifuged after the completion of reaction,
Nanoscale Iron bloom body and iron oxide yellow filtered fluid are obtained respectively；
Being added to of dispersant makes the Fe in catholyte2+Ion spreads out, so as to Fe2+Can respectively with addition
OH—Reacted, the iron oxide yellow powder of generation is not formed reunion.Preferably, the dispersant is cetyl trimethyl
Ammonium bromide, the addition of cetyl trimethylammonium bromide is the 1~2% of catholyte, and preferred addition is catholyte
1%.
The reaction occurred in this step is mainly：
Fe2++2OH-→Fe(OH)2(Ⅳ)；
4Fe(OH)2+O2→4FeOOH+2H2O (Ⅴ)。
During alkaline process prepares iron oxide yellow, temperature, pH value and air velocity needed for reaction are iron oxide yellow morphosis
Major control factors.
In the present invention, step (2) reaction is carried out under the conditions of room temperature, pH 2~4, and the reaction time is no less than 40h.Temperature
Degree is too low to make reaction rate slack-off, and the too high Nanoscale Iron bloom body lattice that can make generation of temperature is converted into Fe3O4, work as temperature
During more than 80 DEG C, product is pure phase Fe3O4Black solid.
When pH is 2~4, Fe (OH)2Gradate as FeOOH precipitates, when pH is more than 6.5, Ni2+Start with altogether
Precipitation or the form into lattice precipitate, and cause Nanoscale Iron Huang powder purity not high.
Used as further preferred, step (2) reaction is carried out under the conditions of 25 DEG C, pH 4.0.
Preferably, the intake of air is 6~7L/ (Lmin)；More preferably 6.45L/ (Lmin) (oxygen now
Change speed most fast).The effect for being passed through air is to make the Fe (OH) of generation2Constantly it is oxidized to FeOOH and discharges H+, it is therefore desirable to
Constantly adding alkali during the course of the reaction makes reaction solution pH be maintained between 2~4, more preferably keeps reaction solution pH to 4.
After the completion of reaction, it is centrifuged, iron oxide yellow crude product and filtrate is obtained respectively；Iron oxide yellow crude product through washing 3 times after, again
Carry out alcohol and wash 3 acquisition Nanoscale Iron bloom bodies.The Nanoscale Iron bloom body for obtaining can further use neopelex bag
Cover, carry out surface and be modified, to reduce the oil absorption of Nanoscale Iron bloom body.
(3) to adding Fe in the iron oxide yellow filtered fluid2+And Ni2+Precipitating reagent reacted, after the completion of reaction filter, point
Not Huo get iron nickel co-precipitate and filtrate, filtrate discharges after charcoal absorption.
Preferably, the precipitating reagent is vulcanized sodium.Vulcanized sodium can be with Fe2+And Ni2+Reaction, makes Fe2+And Ni2+With sulphur
The form precipitation of compound.
Preferably, adding excessive sulphurizing salt so that Fe2+、Ni2+Precipitate completely.Experiment finds, when sodium sulfide content is
10%, when excess coefficient is 3.57, Fe in iron oxide yellow filtered fluid2+、Ni2+Basic precipitation is complete.
Preferably, first adjusting the pH of the iron oxide yellow filtered fluid to 6~6.5, precipitating reagent reaction is added.Do not adjust pH it
Before, the pH of the iron oxide yellow filtered fluid is about 3.5, and in acidity, now adding sulphurizing salt can produce poisonous hydrogen sulfide gas.
Preferably, the precipitation reaction is also carried out at ambient temperature.Temperature too low reaction speed is slack-off, and temperature is raised
Adding vulcanized sodium can produce poisonous hydrogen sulfide gas, and increase Fe2+、Ni2+Removal cost.
Reaction time is generally 30min, now the Ni in iron oxide yellow filtered fluid2+Basic precipitation is complete.Filtered after the completion of reaction,
On the one hand the ferrous sulfide and nickel sulfide co-precipitate of black are obtained, the filtrate that pH is 10~12, filtrate warp is on the other hand obtained
Can be by electroplating industry standard qualified discharge after charcoal absorption.
Compared with prior art, beneficial effects of the present invention are：
The present invention is electrolysed using anionic membrane electrolysis to Ni from waste etching FeCl 3 solution containing first, the anode of acquisition
The namely regenerated ferric trichloride etching solution of liquid, Fe3+Concentration can reach 3.5108mol/L, Fe2+Concentration is less than 0.0023mol/L,
Meet the quality requirement to ferric trichloride etching solution in etch process, can directly recycle；Utilized by alkaline process again and be rich in
Fe2+Catholyte prepare Nanoscale Iron bloom body, further recycle iron resource；Ni in etching waste liquor2+Mainly it is enriched in iron
Yellow filtered fluid, the filtrate after being precipitated through precipitating reagent can press electroplating industry standard qualified discharge after simple absorption.Whole process
Simple to operate, with low cost, the recovery utilization rate to etching waste liquor is high, and three-waste free discharge.
Brief description of the drawings
Fig. 1 is the process chart of electrolytic regeneration Ni from waste etching FeCl 3 solution containing co-production iron oxide yellow of the present invention；
The structural representation of the electrolytic cell that Fig. 2 is used by anionic membrane electrolysis.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and detailed description.
Embodiment 1
(its technological process is such as a kind of method of electrolytic regeneration Ni from waste etching FeCl 3 solution containing co-production iron oxide yellow of the present embodiment
Shown in Fig. 1), comprise the following steps：
(1) Ni from waste etching FeCl 3 solution containing is electrolysed using anionic membrane electrolysis：
The composition of the present embodiment Ni from waste etching FeCl 3 solution containing is：Iron chloride 32%, frerrous chloride 4.6%, nickel chloride
2.9%th, free acid 2.1%, proportion 1474g/L.
The electrolytic cell that anionic membrane electrolysis is used is as shown in Figure 2.From Figure 2 it can be seen that the electrolytic cell includes using polychlorostyrene
The rectangle cell body that vinyl plastics plate is made, is provided with anion-exchange membrane 5 (material is perfluoro sulfonic acid membrane) in rectangular slot body, cloudy
Rectangle cell body is divided into anode chamber 1 and cathode chamber 2 by amberplex 5, and sun is inserted with respectively in anode chamber 1 and cathode chamber 2
Pole electrode 3 and cathode electrode 4, in the present embodiment, anode electrode 3 and cathode electrode 4 are metal Ti electrode.
Rectangular slot external body is provided with the anode hopper 6 and negative electrode hopper for being connected with anode chamber 1 and cathode chamber 2 respectively
7, noncorrosive pump 8, noncorrosive pump are provided between anode chamber 1 and anode fluid injection groove 6, and between cathode chamber 2 and negative electrode hopper 7
Etching waste liquor in anode fluid injection groove 6 and negative electrode hopper 7 is mainly squeezed into anode chamber 1 and cathode chamber 2 by 8 effect respectively.
Before electrolysis, respectively to injecting Ni from waste etching FeCl 3 solution containing in anode hopper 6 and negative electrode hopper 7, and lead to
Noncorrosive pump 8 is crossed to be input into anode chamber 1 and cathode chamber 2 respectively.
In electrolytic process, the electrolyte in anode chamber 1 is made between anode chamber 1 and anode hopper 6 by noncorrosive pump 8
Circulate, the electrolyte in cathode chamber 2 is circulated between cathode chamber 2 and negative electrode hopper 6；Bath voltage is
The current density of 6.0V, anode electrode 3 and cathode electrode 4 is 102A/m2, it is electrolysed 1.5h.
(2) regeneration ferric trichloride etching solution is prepared：
After electrolysis terminates, anolyte is imported into etching solution adjustment tank (being omitted in figure), the Fe in detection solution3+、Fe2+With
The concentration of free acid, is the sodium hydroxide solution that 20%, volume is 20ml by calculating to concentration is added in every liter of anolyte, is adjusted
Whole etching liquid acidity, obtains regenerating ferric trichloride etching solution.Regeneration ferric trichloride etching solution meets：Free acid≤0.5%, chlorination
Iron ＞ 35%, frerrous chloride ＜ 0.2%, than the ferric trichloride etching solution requirement for weighing about 1400g/L or so.
(3) Nanoscale Iron bloom body is prepared：
After electrolysis terminates, catholyte is imported in reactor (being omitted in figure), be Fe to every liter of composition3+：Fe2+=1:5
It is cetyl trimethylammonium bromide 200ml, the catholyte volume 170- of 0.4g/L that concentration is added in the catholyte of (amount of substance)
180 times of sodium hydroxide solution (0.4mol/L), carries out oxidation reaction at 25 DEG C.
In course of reaction, the pH of constantly regulate reaction solution is 4.0, and it is 6.45L/ (Lmin) to accelerate to be passed through air mass flow
Oxidation, after oxidation reaction about 40h, by centrifugation, obtains iron oxide yellow crude product and filtrate respectively；Iron oxide yellow crude product through washing 3 times after,
Nanoscale Iron bloom body is obtained after washing 3 times through alcohol again.
The yield of Nanoscale Iron bloom body (FeOOH) reaches 88.9%, Fe2O3Content for 80.8%, n be 2.11.
Under the conditions of 30 DEG C, pH 3.5, Nanoscale Iron bloom body is coated using neopelex, wherein ten
Dialkyl benzene sulfonic acids sodium is the 7% of Nanoscale Iron bloom weight, and the cladding time is 30min.The now oil suction of Nanoscale Iron bloom body
Measure the 34.7g/100g after the 65.1g/100g from before cladding is down to cladding.
(4) nickel is separated：
At room temperature, to 10ml sodium carbonate (0.2mol/L) is added in every 500mL iron oxide yellows filtered fluid, iron oxide yellow filtered fluid is adjusted
PH is 6~6.5；Then add 10% vulcanized sodium, excess coefficient 3.57, natural filtration after reaction 30min, now ferrous sulfide and
Nickel sulfide co-precipitate is black, and co-precipitate is 1.6752g.
The separation nickel filtrate for obtaining can be electroplated with after 2g/L charcoal absorptions 30min per 500ml by GB21900-2008
Pollutant emission standard qualified discharge.
Embodiment 2
(its technological process is such as a kind of method of electrolytic regeneration Ni from waste etching FeCl 3 solution containing co-production iron oxide yellow of the present embodiment
Shown in Fig. 1), comprise the following steps：
(1) Ni from waste etching FeCl 3 solution containing is electrolysed using anionic membrane electrolysis：
The Ni from waste etching FeCl 3 solution containing of use, electrolytic cell are same as Example 1.But keep anode electrolytic cell electrode 3
Current density with cathode electrode 4 is 90A/m2, constant-current electrolysis 3.5h.
(2) regeneration ferric trichloride etching solution is prepared：
With embodiment 1.
(3) Nanoscale Iron bloom body is prepared：
With embodiment 1, but oxidation time is 32h, and Nanoscale Iron bloom body yield reaches 90%, Fe2O3The content of % is
80.9%, n are 2.10.
Nanoscale Iron bloom body is coated using same method, the oil absorption of Nanoscale Iron bloom body is from before cladding
The 33.5g/100g that 64.8g/100g is down to after cladding.
(4) nickel is separated：
The method of nickel is separated with embodiment 1, co-precipitate 1.6679g is obtained, it is 12.15 to separate nickel filtrate pH.Obtain
Nickel filtrate is separated per 500ml, pollutant emission mark is electroplated with GB 21900-2008 can be pressed after 2g/L charcoal absorptions 30min
Quasi- qualified discharge.
Claims (5)
1. a kind of method of electrolytic regeneration Ni from waste etching FeCl 3 solution containing co-production iron oxide yellow, it is characterised in that including following step
Suddenly：
(1) Ni from waste etching FeCl 3 solution containing is electrolysed using anionic membrane electrolysis, anolyte and negative electrode is obtained respectively
Liquid, the anolyte is regeneration ferric trichloride etching solution；
(2) to adding alkali lye and dispersant in the catholyte, and it is passed through air and is reacted, the reaction is in room temperature, pH 2
Carried out under the conditions of~4, the reaction time is no less than 40h, be centrifuged after the completion of reaction, Nanoscale Iron bloom body and iron oxide yellow filtering are obtained respectively
Liquid；The dispersant is cetyl trimethylammonium bromide, and the addition of cetyl trimethylammonium bromide is Nanoscale Iron bloom
The 1~2% of body weight；
(3) to adding Fe in the iron oxide yellow filtered fluid2+And Ni2+Precipitating reagent reacted, after the completion of reaction filter, obtain respectively
Iron nickel co-precipitate and filtrate, filtrate are discharged after charcoal absorption；
In step (3), the pH of the iron oxide yellow filtered fluid is first adjusted to 6~6.5, add precipitating reagent reaction.
2. the method for claim 1, it is characterised in that in step (1), it is described be electrolysed the voltage that uses for 6.0~
7.0V。
3. the method for claim 1, it is characterised in that in step (1), the current density of electrolytic process Anodic electrode
It is 90~150A/m2。
4. the method for claim 1, it is characterised in that in step (2), the intake of air is 6~7L/ (L
min)。
5. the method as described in Claims 1 to 4 is any, it is characterised in that in step (3), the precipitating reagent is vulcanized sodium.
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| CN106958021A (en) * | 2017-05-03 | 2017-07-18 | 中南大学 | A kind of regeneration treating method of highly acidity Ni from waste etching FeCl 3 solution containing |
| CN107699694B (en) * | 2017-09-29 | 2019-07-16 | 成都程德化工科技有限责任公司 | A method of processing containing copper chloride acidity etching waste liquid and obtained iron negative electrode material |
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| CN1053645C (en) * | 1994-08-05 | 2000-06-21 | 郑隆鳌 | Method for production of iron oxide from ferrous chloride solution |
| JP2000264640A (en) * | 1999-03-17 | 2000-09-26 | Tsurumi Soda Co Ltd | Treatment of waste liquor of hydrochloric acid |
| CN102677062B (en) * | 2012-05-21 | 2014-01-22 | 嘉兴学院 | Method for electrolyzing and regenerating alkaline etching liquid |
| CN104131285B (en) * | 2013-05-03 | 2016-08-31 | 宁波东盛集成电路元件有限公司 | The recovery method of ferric trichloride etching waste liquor |
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