CN101445262B - Comprehensive utilization process of waste ITO etching liquid - Google Patents
Comprehensive utilization process of waste ITO etching liquid Download PDFInfo
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- CN101445262B CN101445262B CN2008102466405A CN200810246640A CN101445262B CN 101445262 B CN101445262 B CN 101445262B CN 2008102466405 A CN2008102466405 A CN 2008102466405A CN 200810246640 A CN200810246640 A CN 200810246640A CN 101445262 B CN101445262 B CN 101445262B
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- calcium chloride
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- etching liquid
- acetic acid
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Abstract
The invention relates to a comprehensive utilization process of a waste ITO etching liquid. The process takes the waste ITO etching liquid and calcspar as a reaction material, and obtains a clarifying solution containing calcium chloride and calcium acetate after reaction; then the clarifying solution which is obtained after the reaction is distilled, the double decompositionreaction is performed between a spot of unreacted hydrochloric acid and calcium acetate in a reaction solution during the heating distillation process, and calcium chloride and acetic acid are obtained; the solution containing acetic acid and calcium chloride is separated through distillation, the solution containing calcium chloride is injected into a pH value regulating kettle with stirring function, and various metallic ions in the solution are separated out in the form of hydroxide precipitations which is then processed through settling and obviation by filtration; after the purified calcium chloride solution is processed through concentration, crystallization, separation and dehumidification, calcium chloride products are obtained; and sodium hydroxide is added to the separated solution containing diluted acetic acid for neutralization reaction to obtain sodium acetate products. The comprehensive utilization process can recycle a mixed acid waste liquid containing two acids, and obtain multiple new industrial chemicals therefrom.
Description
Technical field
The present invention relates to the comprehensive utilization process of a kind of comprehensive utilization process of spent acid solution, particularly a kind of waste ITO etching liquid.
Technical background
The useless ITO liquid of industry is not pure material, belongs to mixture, is mixed by two or more material.Because composition, content difference do not have unified pattern and constant technology,, adopt treatment process to be burning so prior art can not be recycled.
Summary of the invention
Purpose of the present invention provides a kind of technology that waste ITO etching liquid is fully utilized, thereby the waste ITO etching liquid that contains two kinds of acid is reclaimed, and therefrom obtains Calcium dichloride dihydrate and two kinds of Industrial products of sodium-acetate.
To achieve these goals, it is that reaction raw materials reacts the clear liquor that obtains containing calcium chloride and calcium acetate that the present invention adopts waste ITO etching liquid and calcite, then reacted clear liquor is distilled, the intact small amount of hydrochloric acid of unreacted in the heating still-process with reaction solution in calcium acetate carry out replacement(metathesis)reaction and obtain calcium chloride and acetic acid, by distillation acetic acid is separated with calcium chloride solution, the solution that will contain calcium chloride is squeezed in the pH value adjusting still of stirring, each metal ion species in the solution is precipitation of hydroxide and separates out, through heavy clear, remove by filter, calcium chloride solution after the purification is through concentrating, crystallization, separate, after the drying, promptly get product calcium chloride; In the isolated solution that contains dilute acetic acid, add sodium hydroxide and carry out neutralization reaction, promptly get the product sodium-acetate.
Be not used in that restriction protects, the comprehensive utilization process of described waste ITO etching liquid can be undertaken by following concrete steps:
(1) waste ITO etching liquid and calcite are added in the retort, under agitation carry out following reaction:
CaCO
3+2HCl+H
2O＝CaCl
2·2H
2O+CO
2
Part acetic acid in the waste liquid also reacts with calcite simultaneously:
CaCO
3+2CH
3COOH＝Ca(CH
3COO)
2+CO
2↑+H
2O
(2) the reacted clear liquor of step (1) is distilled, the intact small amount of hydrochloric acid of unreacted in the heating still-process with reaction solution in calcium acetate carry out replacement(metathesis)reaction:
Ca(CH
3COO)
2+2HCl＝CaCl
2+2CH
3COOH
(3) reaction solution that obtains of distilation steps (2) separates acetic acid with calcium chloride solution, the isolated solution that contains calcium chloride is squeezed into the pH value of stirring and is regulated in the still, adds milk of lime, with the Fe in the solution
3+, Mg
2+, ln
3+, Sn
2+Be precipitation of hydroxide and separate out, through sinking clearly, removing by filter, the calcium chloride solution after the purification promptly gets product calcium chloride after concentrated, crystallization, separation, drying, also the calcium chloride solution after purifying directly can be sent into one step of rotary drum scraper plate drying machine and be finished;
(4) the isolated solution that contains dilute acetic acid is sent in the reactor, hydro-oxidation sodium, under agitation carry out neutralization reaction:
CH
3COOH+NaOH+2H
2O＝CH
3COONa·3H
2O
(5) reaction solution after step (4) is purified again through crystallization, separation, drying, promptly get the product sodium-acetate after vaporizer concentrates, and also the solution after concentrating directly can be sent into drying machine one and be gone on foot and finish.
The waste ITO etching liquid that is numbered HW34 that adopts the Jingdongfang Photoelectric Science ﹠ Technology Co., Ltd., Beijing to produce in the above-mentioned technology, the composition and the content of described waste ITO etching liquid are as follows: HCl:17-22% (wt); CH
3COOH:4-6% (wt); H
2O:72-79% (wt); Also contain the impurity of minute quantity in addition, comprise In
2O
3, SnO etc., and described waste ITO etching liquid all components weight content and be 100%; The CaCO of the calcite that uses in the technology
3Weight content＞98%, and contain impurity element iron, magnesium.The reaction unit that uses in the technology of the present invention all is the conventional equipment of this area, and each material rate can be calculated according to reaction formula and forming of each raw material by persons skilled in the art.
The comprehensive utilization of carrying out waste ITO etching liquid by above-mentioned technology has following beneficial effect:
1). treatment facility throughput is huge:
Design scale: the ability by existing utility and technology of the present invention recycling waste ITO etching liquid is 5000 tons/year.
Reality: year recycles 2500 tons of (or 2300m of waste ITO etching liquid now
3);
2). by recycling, can access two kinds of Industrial products: 1m of a large amount of Calcium dichloride dihydrates and sodium-acetate
30.443 ton of the useless recyclable Calcium dichloride dihydrate of ITO liquid (proportion 1.4), sodium-acetate 82kg is to handle waste ITO etching liquid 2300m every year
3Meter can be produced 1020.7 tons of Calcium dichloride dihydrates every year, 188.9 tons of sodium-acetates (above data all are according to the actual production gained).Industry Calcium dichloride dihydrate (CaCl
22H
2O), can be used as refrigerant (as used for refrigerator chilled brine, refrigeration and ice making rod time use chilled brine), frostproofer, automobile antifreeze solution, fire-fighting medium; Be used for molten ice and molten snow, the arrangement of cotton fabric and accurately machined fire retardant; As tackiness agent and wood preservative; Be used to make Calcium Chloride Powder Anhydrous; Be used for wall plastering and plastered work, increase coagulability; Be used as the condensation agent in rubber production; Can mix with starch paste as cementing agent; Also be used for non-ferrous metal metallurgy or be used as pharmaceuticals.Sodium-acetate (CH
3COONa) be a kind of industrial chemicals, be applied to printing and dyeing (mordant), medicine (benzyl penicillin sodium) and industrial sector such as take pictures, can be used for producing various Chemicals, as Glacial acetic acid, acetone, furfuracrylic acid, acetic ester and Mono Chloro Acetic Acid etc.; Also can be used as preservative for meat and chemical reagent.
Description of drawings
The process flow sheet of Fig. 1 for waste ITO etching liquid is fully utilized
Embodiment
Following example only is to further specify the present invention, is not the restriction the scope of protection of the invention.
Embodiment 1:
Waste ITO etching liquid is squeezed in the retort, adding calcite reacts, reacted saturated solution hydro-oxidation sodium stirring reaction, squeeze into graphite after filtering or thin-film evaporator distills concentrated, 125 ℃ of temperature, reach 28-30 and moor U.S. degree, (dilute acetic acid that distillation obtains) hydro-oxidation sodium cooling crystallization in the vaporizer air outlet, centrifuge dehydration, product sodium-acetate; Liquid outlet is obtained calcium chloride solution add to regulate still, precipitate and separate is squeezed into graphite evaporator and is distilled concentratedly, and 125 ℃ of temperature are moored U.S. degree 50-52, crystallisation by cooling, and centrifuge dehydration, packing obtain the Calcium dichloride dihydrate product.
Wherein:
The Chemical Composition of waste ITO etching liquid, content and refuse generation
Produce with above-mentioned composition:
1 ton of CaCO
3The calcite raw material of content＞98% and 23 tons of waste ITO etching liquids can be produced 4 tons of Calcium dichloride dihydrates, 200 kilograms of calcium acetates.
Claims (2)
1. technology that waste ITO etching liquid is fully utilized, described technology comprises: adopting waste ITO etching liquid and calcite is that reaction raw materials reacts, the clear liquor that reaction is obtained distills then, the intact small amount of hydrochloric acid of unreacted in the heating still-process with reaction solution in calcium acetate carry out replacement(metathesis)reaction and obtain calcium chloride and acetic acid mixing solutions, by distillation acetic acid is separated with calcium chloride solution, calcium chloride solution is squeezed into the pH value of stirring and is regulated in the still, each metal ion species in the solution is precipitation of hydroxide and separates out, through heavy clear, remove by filter, calcium chloride solution after the purification is through concentrating, crystallization, separate, after the drying, promptly get product calcium chloride; Add sodium hydroxide at isolated dilute acetic acid solution and carry out neutralization reaction, after concentrated, crystallization, separation and drying, promptly get the product sodium-acetate.
2. the technology that waste ITO etching liquid is fully utilized of claim 1 may further comprise the steps:
(1) waste ITO etching liquid and calcite are added in the retort, under agitation carry out following reaction:
CaCO
3+2HCl+H
2O＝CaCl
2·2H
2O+CO
2
Part acetic acid in the waste liquid also reacts with calcite simultaneously:
CaCO
3+2CH
3COOH＝Ca(CH
3COO)
2+CO
2+H
2O
(2) the reacted clear liquor of step (1) is distilled, the intact small amount of hydrochloric acid of unreacted in the heating still-process with reaction solution in calcium acetate carry out replacement(metathesis)reaction:
Ca(CH
3COO)
2+2HCl＝CaCl
2+2CH
3COOH
(3) reaction solution that obtains of distilation steps (2) separates acetic acid with calcium chloride solution, isolated calcium chloride solution is squeezed into the pH value of stirring and is regulated in the still, adds milk of lime, with the Fe in etching liquid in the solution and the calcite
3+, Mg
2+, ln
3+, Sn
2+Be precipitation of hydroxide and separate out, through sinking clearly, removing by filter, the calcium chloride solution after the purification promptly gets product calcium chloride after concentrated, crystallization, separation, drying;
(4) isolated dilute acetic acid solution is sent in the reactor, hydro-oxidation sodium, under agitation carry out neutralization reaction:
CH
3COOH+NaOH+2H
2O＝CH
3COONa·3H
2O
(5) reaction solution after step (4) is purified again through crystallization, separation, drying, promptly gets the product sodium-acetate after vaporizer concentrates;
The waste ITO etching liquid that is numbered HW34 that wherein said waste ITO etching liquid adopts the Jingdongfang Photoelectric Science ﹠ Technology Co., Ltd., Beijing to produce, its composition and weight content are as follows: HCl:17-22%; CH
3COOH:4-6%; H
2O:72-79%; Also contain the impurity of minute quantity in addition, be In
2O
3And SnO, and described waste ITO etching liquid all components weight content and be 100%; The CaCO of described calcite
3Content＞98%, and contain impurity element iron and magnesium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102466405A CN101445262B (en) | 2008-12-31 | 2008-12-31 | Comprehensive utilization process of waste ITO etching liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102466405A CN101445262B (en) | 2008-12-31 | 2008-12-31 | Comprehensive utilization process of waste ITO etching liquid |
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| Publication Number | Publication Date |
|---|---|
| CN101445262A CN101445262A (en) | 2009-06-03 |
| CN101445262B true CN101445262B (en) | 2010-11-17 |
Family
ID=40741194
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102466405A Active CN101445262B (en) | 2008-12-31 | 2008-12-31 | Comprehensive utilization process of waste ITO etching liquid |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102286288B (en) * | 2011-05-23 | 2014-06-11 | 江阴润玛电子材料股份有限公司 | Acetic acid ITO (Indium Tin Oxide) etching liquid and preparation process thereof |
| CN106676579B (en) * | 2017-01-05 | 2018-10-23 | 京东方科技集团股份有限公司 | The method for handling indium tin oxide target etching waste liquid |
| CN108299189A (en) * | 2018-02-06 | 2018-07-20 | 北京凯瑞英科技有限公司 | Nitromethane hydrolysis prepares hydroxylamine hydrochloride by-product recovery and utilizes device and method |
| CN110590010A (en) * | 2019-09-10 | 2019-12-20 | 新中天环保股份有限公司 | Environment-friendly treatment method for waste etching liquid of electronic material |
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