CN1540036A - Method for regenerating etching waste fluid of iron protochloride of containing nickel - Google Patents
Method for regenerating etching waste fluid of iron protochloride of containing nickel Download PDFInfo
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- CN1540036A CN1540036A CNA2003101200878A CN200310120087A CN1540036A CN 1540036 A CN1540036 A CN 1540036A CN A2003101200878 A CNA2003101200878 A CN A2003101200878A CN 200310120087 A CN200310120087 A CN 200310120087A CN 1540036 A CN1540036 A CN 1540036A
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- fecl
- solution containing
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- etching
- waste etching
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Abstract
A process for regenerating the used etching FeCl3 solution containing Ni includes concentrating, cooling to 40-45 deg.C, adding said used solution, crystallizing at temp lower than 17 deg.C for 24-60 hrs to obtain FeCl3.6H2O crystal, separating FeCl3.6H2O crystal from mother liquid, and adding water to the crystal for reusing it.
Description
Technical field
The present invention relates to a kind of renovation process of etch combination, particularly relate to a kind of ferric trichloride etching waste liquor that contains bivalent nickel ion and ferrous ion that makes and reduce the method that nickel content is able to regeneration.
Background technology
Planar mask is one of key part of colour picture tube, is an important color component that selects.The picture tube of 18 inch the small screen colour television sets or indicating meter generally adopts AK steel (iron content 99.95%) to produce shadow mask, because it is not nickeliferous in the raw material, so the ferric trichloride etching waste liquor that produces in the shadow mask production process only contains ferrous ion, replenishing an amount of this ferric trichloride etching waste liquor of chlorine element is reproducible utilization.Along with colour television set trend giant-screen, digitizing, full graduation, high definition development, shadow mask mostly adopts the manufacturing of INVER steel, it contains the nickel of iron and 35.5%～36.5% to INVER steel Chinese for " invar ", invar has that thermal expansivity is little, the intensity advantages of higher, use invar to produce shadow mask and can make cathode tube obtain optimum color purity, therefore the application of invar is very extensive in the large size shadow mask is produced.Adopt invar to produce shadow mask, iron trichloride is present the most frequently used etching reagent.In etch process, iron trichloride is reduced to ferrous ion by metallic iron and nickel, and metallic iron and nickel then are separately converted to ferrous ion and bivalent nickel ion is dissolved in the etching solution.Carrying out along with etching process, nickel concentration can be more and more higher in the iron trichloride etching solution, causes the mask surface roughness to raise, and etching quality descends, nickel concentration can not surpass 2% in the iron trichloride etching solution in general, otherwise just must change etching solution.In large size shadow mask production process, can produce a large amount of Ni from waste etching FeCl 3 solution containing,, then must reduce the content (concentration) of nickel ion in the etching waste liquor if make above-mentioned etching waste liquor regeneration.
Present most of manufacturer adopts the pure iron reduction method to handle to Ni from waste etching FeCl 3 solution containing, this method comprises excessive pure iron put into carries out reduction reaction in the Ni from waste etching FeCl 3 solution containing, make whole iron trichlorides be reduced into ferrous chloride, bivalent nickel ion is reduced into metallic nickel, and with the nickel sorption-coprecipitation in excessive iron, method with solid-liquid separation makes ferro-nickel mixed powder end and ferrous chloride solution separating, again ferrous chloride solution is annotated oxychlorination again and becomes the iron trichloride etching solution.Remove the method for nickel as the iron replacement reaction that proposes among the Japanese Patent JP5140667.In the method, mix with the iron trichloride waste liquid with iron powder, iron trichloride is reduced into ferrous chloride, and the excessive iron powder bivalent nickel ion in the substitutional solution again precipitates metallic nickel.Except that the ferrous chloride behind the nickel becomes iron trichloride with chlorine oxidation, again as etching solution.The iron powder amount that adds in this method must be excessive, and therefore, the grade that reclaims nickel is quite low, does not have further use value, and drops into pure iron in a large number and increased production cost.Propose a kind of first condensing crystal among the Japanese Patent JP8269745, again the mother liquor electrolytic separation has been reclaimed the method for nickel.In the method, earlier with nickeliferous iron trichloride waste liquid condensing crystal, crystallization goes out nickeliferous lower iron trichloride crystal, then the iron trichloride mother liquor after the crystallization is carried out electrolysis, has iron-nickel alloy to separate out at negative electrode, has chlorine to separate out at anode.The rate of recovery of this method nickel is higher, but owing to have chlorine to separate out in the electrolytic process, bigger to equipment corrosion, running cost is higher.The method of condensing crystal separating nickel has been proposed among the Japanese Patent JP10046370.In the method, contain the ferric trichloride etching waste liquor elder generation condensing crystal of nickel, isolate the lower iron trichloride crystal of nickel content, its mother liquor is through periodic crystallisation, and nickel ion is reached the purpose of separating nickel by enrichment.But this method steps is many, and waste is big, and efficient is very low.Chinese invention patent application number 02116014.7, publication number is 1386906, name is called the nickel method of removing that " the nickel method of removing of Ni from waste etching FeCl 3 solution containing " discloses a kind of Ni from waste etching FeCl 3 solution containing, step comprises: (1) adds iron powder or squamous iron sheet in etching waste liquor, carry out reduction reaction, (2) reacting by heating mixture to 55 is ℃-95 ℃, again toward wherein adding iron powder and SULPHUR POWDER, carry out the precipitin reaction of nickelous, (3) perhaps continue to add iron powder and SULPHUR POWDER in 55 ℃-95 ℃ reaction mixture, perhaps add iron powder and arsenic compound, perhaps add iron powder and antimony compounds, further carry out the precipitin reaction of nickelous, filter then.The Chinese invention patent application number is 00127588.7, publication number is 1309194, name is called " Ni from waste etching FeCl 3 solution containing regeneration and nickel recovery method " and discloses a kind of nickeliferous iron trichloride etching waste liquid regeneration and nickel recovery method, and this invention is precipitation agent with the hydrogen sulfide, with Ni
2+From the iron trichloride etching waste liquid, be precipitated out, make Ni with NiS
2+With Fe
2+Separate.Fe
2+Become Fe through chlorine oxidation again
3+, except that the liquor ferri trichloridi behind the nickel can be used as etching liquid again.Above-mentioned Chinese patent disclosed method all can be separated nickel effectively and make the regeneration of iron trichloride etching waste liquid from the iron trichloride etching waste liquid, but above-mentioned patented method all need be added a large amount of highly purified iron and sulfur-bearing or be contained arsenic, stibiated industrial chemicals in nickeliferous iron trichloride etching waste liquid, the input of a large amount of pure iron has increased production cost, and iron trichloride changes into ferrous chloride and mends iron trichloride total amount behind the chlorine and increase nearly 1/3rd and increased trouble for the content of iron trichloride in the accurate control etching liquid in the treating processes simultaneously; On the other hand sulfur-bearing, contain arsenic, the use that contains the antimony industrial chemicals both caused environmental pollution to have inevitably to give the iron trichloride etching liquid to introduce the difficulty that impurity has increased quality control after the regeneration of iron trichloride etching liquid easily.
Summary of the invention
The deficiency that the objective of the invention is to overcome existing Ni from waste etching FeCl 3 solution containing renovation process production cost height, complicated operation and introduce aspect existence such as new impurity easily provides the Ni from waste etching FeCl 3 solution containing renovation process that a kind of production cost is low, operation steps simply, is not introduced new impurity.
For the purpose that realizes inventing, the present invention by the following technical solutions: a kind of renovation process of Ni from waste etching FeCl 3 solution containing in turn includes the following steps:
(a) waste liquid concentrates: make the stoste of Ni from waste etching FeCl 3 solution containing be concentrated to 70%～80% of original volume under the certain pressure temperature condition;
(b) crystallisation by cooling: the Ni from waste etching FeCl 3 solution containing after above-mentioned the concentrating is cooled to 40 ℃～45 ℃, in described concentrated solution, replenish the Ni from waste etching FeCl 3 solution containing stoste of 1.5 times～2 times of volumes then, and the temperature of this mixing solutions is controlled at≤17 ℃ of crystallisation by cooling 24 hours～60 hours, obtain containing the FeCl of micro-nickel
36H
2The O crystal;
(c) solid-liquid separation: with above-mentioned FeCl
36H
2The O crystal separates from mother liquor;
Separate the FeCl that obtains
36H
2The O crystal adds a certain amount of water according to the etching solution processing requirement can redistribution become the iron trichloride etching solution.
It is 0.006MPa～normal pressure that waste liquid described in the step (a) concentrates pressure control range, and temperature controlling range is 95 ℃～128 ℃.
66 ℃ of proportions of Ni from waste etching FeCl 3 solution containing after concentrating described in the step (a) are 1.60g/cm
3～1.62g/cm
3
The crystallisation by cooling temperature is controlled at 17 ℃ described in the step (b).
The FeCl that crystallisation by cooling obtains described in the step (b)
36H
2The O crystal wherein content of nickel is controlled at weight ratio 0.09%～0.12%.
Solid-liquid separation described in the step (c) adopts the whizzer centrifugation 20min of rotating speed 1450r/min.
The invention has the beneficial effects as follows, described invention concentrates, crystallisation by cooling, solid-liquid separation, adds physical and chemical process such as water allotment by waste liquid, under the prerequisite of not adding industrial chemicals, iron trichloride in the Ni from waste etching FeCl 3 solution containing is separated out with Iron(III) chloride hexahydrate crystalline form, reached the purpose that reduces Ni from waste etching FeCl 3 solution containing nickel content.The Iron(III) chloride hexahydrate crystal that obtains separates with the mother liquor that contains nickelous chloride through centrifugation, still can make satisfactory iron trichloride etching solution for large-sized solor shadow mask etching production use through adding the water allotment.The renovation process of Ni from waste etching FeCl 3 solution containing described in the invention, production cost is low, simple to operate, is the method that a kind of environmental protection and economy type is handled Ni from waste etching FeCl 3 solution containing.
Description of drawings
Fig. 1 is the process flow sheet of Ni from waste etching FeCl 3 solution containing renovation process.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail: a kind of renovation process of Ni from waste etching FeCl 3 solution containing in turn includes the following steps: (a) waste liquid concentrates: make the stoste of Ni from waste etching FeCl 3 solution containing be concentrated to 70%～80% of original volume under the certain pressure temperature condition; (b) crystallisation by cooling: the Ni from waste etching FeCl 3 solution containing after above-mentioned the concentrating is cooled to 40 ℃～45 ℃, in described concentrated solution, replenish the Ni from waste etching FeCl 3 solution containing stoste of 1.5 times～2 times of volumes then, and the temperature of this mixing solutions is controlled at≤17 ℃ of crystallisation by cooling 24 hours～60 hours, obtain containing the FeCl of micro-nickel
36H
2The O crystal; (c) solid-liquid separation: with above-mentioned FeCl
36H
2The O crystal separates from mother liquor; Separate the FeCl that obtains
36H
2The O crystal adds a certain amount of water according to the etching solution processing requirement can redistribution become the iron trichloride etching solution, as shown in Figure 1.It is 0.006MPa～normal pressure that waste liquid described in the step (a) concentrates pressure control range, and temperature controlling range is 95 ℃～128 ℃.66 ℃ of proportions of Ni from waste etching FeCl 3 solution containing after concentrating described in the step (a) are 1.60g/cm
3～1.62g/cm
3The crystallisation by cooling temperature is controlled at 17 ℃ described in the step (b).The FeCl that crystallisation by cooling obtains described in the step (b)
36H
2The O crystal wherein content of nickel is controlled at weight ratio 0.09%～0.12%.Solid-liquid separation described in the step (c) adopts the whizzer centrifugation 20min of rotating speed 1450r/min.
Embodiment 1
A certain amount of Ni from waste etching FeCl 3 solution containing heating is concentrated, the former liquid measure of Ni from waste etching FeCl 3 solution containing (volume): Ni from waste etching FeCl 3 solution containing (volume) after concentrating=1: 0.8, thickening temperature is controlled to be 128 ℃ under the normal pressure, and the proportion that concentrates the back Ni from waste etching FeCl 3 solution containing is 1.62g/cm
3(66 ℃).Ni from waste etching FeCl 3 solution containing after above-mentioned the concentrating is cooled to 40 ℃～45 ℃, in described concentrated solution, replenish Ni from waste etching FeCl 3 solution containing stoste then, the volume of concentrated solution: the volume of stoste=1: 2, with this mixing solutions crystallisation by cooling 24 hours, recording Tc was 17 ℃.Use whizzer to above-mentioned crystallization solution centrifugation then, adopt 1450 rev/mins tripod pendulum type batch centrifugal centrifugation 20 minutes, obtain containing the Iron(III) chloride hexahydrate crystal of micro-nickel, the percent crystallization in massecuite that calculates iron trichloride in the Ni from waste etching FeCl 3 solution containing is 60%, in the Iron(III) chloride hexahydrate crystal nickeliferous 0.09%.The Iron(III) chloride hexahydrate crystal that obtains adds water by the processing requirement of etching solution and can redistribution become the iron trichloride etching solution to be used for producing use for large-sized solor picture tube and the etching of indicating meter shadow mask.
Embodiment 2
A certain amount of Ni from waste etching FeCl 3 solution containing heating is concentrated, the former liquid measure of Ni from waste etching FeCl 3 solution containing (volume): Ni from waste etching FeCl 3 solution containing (volume) after concentrating=1: 0.7, decompression 0.06MPa thickening temperature is controlled to be 95 ℃, and the proportion that concentrates the back Ni from waste etching FeCl 3 solution containing is 1.60g/cm
3(66 ℃).Ni from waste etching FeCl 3 solution containing after above-mentioned the concentrating is cooled to 40 ℃～45 ℃, in described concentrated solution, replenish Ni from waste etching FeCl 3 solution containing stoste then, the volume of concentrated solution: the volume of stoste=1: 1.5, with this mixing solutions crystallisation by cooling 60 hours, recording Tc was 10 ℃.Use whizzer to above-mentioned crystallization solution centrifugation then, adopt 1450 rev/mins tripod pendulum type batch centrifugal centrifugation 20 minutes, obtain containing the Iron(III) chloride hexahydrate crystal of micro-nickel, the percent crystallization in massecuite that calculates iron trichloride in the Ni from waste etching FeCl 3 solution containing is 65%, in the Iron(III) chloride hexahydrate crystal nickeliferous 0.12%.The Iron(III) chloride hexahydrate crystal that obtains adds water by the processing requirement of etching solution and can redistribution become the iron trichloride etching solution to be used for showing and use is produced in the etching of indicating meter image tube shadow mask for large-sized solor.
Claims (6)
1. the renovation process of a Ni from waste etching FeCl 3 solution containing is characterized in that in turn including the following steps:
(a) waste liquid concentrates: make the stoste of Ni from waste etching FeCl 3 solution containing be concentrated to 70%～80% of original volume under the certain pressure temperature condition;
(b) crystallisation by cooling: the Ni from waste etching FeCl 3 solution containing after above-mentioned the concentrating is cooled to 40 ℃～45 ℃, then to the Ni from waste etching FeCl 3 solution containing stoste of wherein adding 1.5 times～2 times of volumes, and the temperature of this mixing solutions is controlled at≤17 ℃ of crystallisation by cooling 24 hours～60 hours, obtain containing the FeCl of micro-nickel
36H
2The O crystal;
(c) solid-liquid separation: with above-mentioned FeCl
36H
2The O crystal separates from mother liquor;
The FeCl that the process above-mentioned steps obtains
36H
2The O crystal adds a certain amount of water according to the etching solution processing requirement can redistribution become the iron trichloride etching solution.
2. the renovation process of a kind of Ni from waste etching FeCl 3 solution containing according to claim 1 is characterized in that it is 0.006MPa～normal pressure that waste liquid described in the step (a) concentrates pressure control range, and temperature controlling range is 95 ℃～128 ℃.
3. the renovation process of a kind of Ni from waste etching FeCl 3 solution containing according to claim 1, the 66 ℃ of proportions of Ni from waste etching FeCl 3 solution containing after it is characterized in that concentrating described in the step (a) are 1.60g/cm
3～1.62g/cm
3
4. the renovation process of a kind of Ni from waste etching FeCl 3 solution containing according to claim 1 is characterized in that the crystallisation by cooling temperature is controlled at 17 ℃ described in the step (b).
5. the renovation process of a kind of Ni from waste etching FeCl 3 solution containing according to claim 1 is characterized in that the FeCl that crystallisation by cooling obtains described in the step (b)
36H
2The O crystal wherein content of nickel is controlled at weight ratio 0.09%～0.12%.
6. the renovation process of a kind of Ni from waste etching FeCl 3 solution containing according to claim 1 is characterized in that solid-liquid separation described in the step (c) adopts the whizzer centrifugation 20min of rotating speed 1450r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2003101200878A CN1540036A (en) | 2003-04-23 | 2003-12-06 | Method for regenerating etching waste fluid of iron protochloride of containing nickel |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN03116559.1 | 2003-04-23 | ||
| CN03116559 | 2003-04-23 | ||
| CNA2003101200878A CN1540036A (en) | 2003-04-23 | 2003-12-06 | Method for regenerating etching waste fluid of iron protochloride of containing nickel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1540036A true CN1540036A (en) | 2004-10-27 |
Family
ID=34378691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2003101200878A Pending CN1540036A (en) | 2003-04-23 | 2003-12-06 | Method for regenerating etching waste fluid of iron protochloride of containing nickel |
Country Status (1)
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|---|---|
| CN (1) | CN1540036A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102992513A (en) * | 2012-11-19 | 2013-03-27 | 天津市聚鑫源水处理技术开发有限公司 | Method for producing ferric salt-series purifiers by recycling and comprehensive utilizing stainless steel waste etching solution |
| CN109987589A (en) * | 2019-04-24 | 2019-07-09 | 成都先进金属材料产业技术研究院有限公司 | Utilize the method for ferric trichloride concentration titanium white waste acid |
| CN112028129A (en) * | 2020-08-18 | 2020-12-04 | 杭州逐真科技有限公司 | Recycling treatment device and process for ferric trichloride etching solution |
-
2003
- 2003-12-06 CN CNA2003101200878A patent/CN1540036A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102992513A (en) * | 2012-11-19 | 2013-03-27 | 天津市聚鑫源水处理技术开发有限公司 | Method for producing ferric salt-series purifiers by recycling and comprehensive utilizing stainless steel waste etching solution |
| CN109987589A (en) * | 2019-04-24 | 2019-07-09 | 成都先进金属材料产业技术研究院有限公司 | Utilize the method for ferric trichloride concentration titanium white waste acid |
| CN112028129A (en) * | 2020-08-18 | 2020-12-04 | 杭州逐真科技有限公司 | Recycling treatment device and process for ferric trichloride etching solution |
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