CN105018732B - A kind of method of etching waste liquor waste residue synthetical recovery - Google Patents
A kind of method of etching waste liquor waste residue synthetical recovery Download PDFInfo
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- CN105018732B CN105018732B CN201510376017.1A CN201510376017A CN105018732B CN 105018732 B CN105018732 B CN 105018732B CN 201510376017 A CN201510376017 A CN 201510376017A CN 105018732 B CN105018732 B CN 105018732B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses the new method of a kind of etching waste liquor, waste residue synthetical recovery, it relates generally to the circular regeneration of iron chloride etching waste liquor, waste residue.In etching waste liquor, in addition to chloride containing iron and hydrochloric acid, the metal such as nickel, copper, chromium also produced containing other etchings；And then containing precipitated metals such as iron, nickel, copper, chromium in waste residue.It is an industry problem for the regeneration of iron chloride etching solution and heavy metal recovery now in etching industry.The invention provides a kind of new process, the iron chloride and hydrochloric acid circular regeneration that can not only allow in etching waste liquor waste residue can also will be etched the metal recoveries such as nickel, copper, chromium for producing, and be realized that comprehensive utilization of resources will be turned waste into wealth using outer.
Description
Technical field
The present invention separates the new method with reclaiming for metals such as iron, chromium, nickel, copper under chlorine root system, specifically a kind of
The iron chloride extractant extract and separate iron chloride can be utilized, then iron chloride extractant is reclaimed by heating evaporation, is recycled
The method that HBL110 extract and separates go out chromium chloride, relates generally to the iron chloride circular regeneration and other chlorine of etching waste liquor, waste residue
The metal separation of root system is with reclaiming.
Background technology
In etching industry, the processing for iron chloride etching waste liquor, waste residue is an industry problem.Remained in its waste liquid
Iron chloride and hydrochloric acid content are big, and also containing metals such as nickel, the copper for etching generation, and waste residue (mostlys come from product surface cleaning
Water neutralization precipitation process) in containing the precipitated metal such as iron, nickel, copper, chromium, have serious pollution for environment.It is right in existing process
In the processing of waste liquid, mainly there are evaporating, concentrating and crystallizing method, neutralization precipitation method, iron powder reducing method etc..And wherein equal Shortcomings, steam
Send out condensing crystallizing method energy consumption big, neutralization precipitation method cost is high and waste residue amount is big, iron powder reducing method cost is high and the gold such as other nickel, copper
Belong to further cost recovery also high, and the problem of chromium is separated and extracted with other metal can not be solved.
And utilize extraction method processing, also someone refers to, such as CN200810065306.X, but wherein exist it is various not
Foot.CN200810065306.X disclose it is a kind of handle ferric trichloride etching solution method, it by two-section extraction iron chloride, then
Iron chloride strip liquor is reclaimed to obtain with alkali back extraction.Iron chloride strip liquor concentration obtained by the method is low, it is necessary to by evaporation and concentration to institute
Ferric chloride concn is needed, required energy consumption is big；And in the acid and technical process in etching waste liquor the acid that is added can not reuse, one need to be entered
Step processing, not only acid consumption is big and produces the acid pickle of a large amount of secondary pollutions.
The content of the invention
For above-mentioned deficiency, the invention provides a kind of etching waste liquor, the new technology of waste residue synthetical recovery processing, containing one kind
The metal such as new iron chloride extracting process and a kind of chromium, nickel, copper separates the method with reclaiming, and not only realizes iron chloride
Circular regeneration is used, and metals resources in etching solution can be reclaimed.
Detailed process is：In etching process, the precipitated metal waste residue such as processing gained iron content, nickel, copper, chromium, by adding salt
After acid acid is molten, obtains solution and mixed with etching waste liquor.After oxidant is oxidation of ferrous iron to ferric iron, hydrochloric acid acid adjustment is added extremely
Suitable concn.Then, with iron chloride extractant hybrid extraction, split-phase is carried out after having extracted, the first oil phase and the first aqueous phase is obtained.
First oil phase and back extraction water mix be evaporated in proportion, obtain the first gas phase and the first liquid phase.Liquid phase is after evaporation
Gained high concentration high-purity iron chloride, is to etch stoste after acid adjustment, return is used.
After iron chloride extraction the first aqueous phase of gained is equally evaporated, the second gas phase and second liquid phase are obtained.
First oil phase and the first aqueous phase evaporate the first gas phase of gained and the second gas phase, and liquid is obtained after condensation and is divided
Phase.Split-phase obtains oil phase for iron chloride extractant, returns to extraction cycle and uses；It is hydrochloric acid to obtain aqueous phase, then is back to sour molten and acid adjustment
Use, it is not enough then supplemented with technical hydrochloric acid.
Second liquid phase is liquid after extraction iron, and nickeliferous, copper, chromium etc. etches the metal produced, after being extracted by HBL110 extractants,
Obtain the second aqueous phase and the second oil phase.Wherein, the second aqueous phase is then raffinate chromium chloride solution, is to be sold outside chromium product.And the second oil
Phase is then nickel-loaded, the HBL110 of copper extraction oil phases, after being stripped by sulfuric acid, obtains nickel sulfate and copper-bath, you can sell outside.
HBL110 extractants are extracted by being returned after backwash, saponification again.
In technique of the present invention, the etching waste liquor waste residue for realizing the metal chlorides such as iron content, nickel, copper, chromium, iron chloride
The circular regeneration of etching solution, the comprehensive utilization of the metal such as nickel, copper, chromium, and the entirety recycled of extractant and hydrochloric acid are followed
The environment-protective process that ring regeneration comprehensive is reclaimed.
The iron chloride extractant of the present invention is for ether, diisopropyl ether, methyl tertiary butyl ether(MTBE) etc., its extraction energy to iron chloride
Power is strong, and low boiling point, can be easy to fall extractant progress reuse by heating evaporation.
Before an extraction procedure, etching waste liquor need to again be extracted the present invention after persalt acid adjustment, and acid adjustment acidity is because of institute
Different, the generally 4-8mol/L with extractant difference.
The present invention is in evaporation process, and oil phase and aqueous phase evaporating temperature be able to can divide as the case may be at 50-110 DEG C
Section evaporation.
The present invention is needed plus back extraction water in stripping process before oil phase evaporation, can be according to gained iron chloride after evaporation agent
Depending on the concentration of liquid phase requirement.And gained iron chloride liquid phase chloride containing weight of iron fraction is up to more than 50%.
It present invention can be suitably applied to iron oxide concentration and reach as high as water after more than 40% (mass fraction) solution system, and extraction
Contained ferric iron concentration can as little as below 0.1g/L in phase.
The present invention mainly uses the iron chloride extractant to extract and makes the method application of extractant reuse by evaporation
Iron chloride separation and recovery is carried out, and the overall circulation and recovery process for carrying out chromium separation is extracted using HBL110.Also include steel
The metals such as iron, chromium, nickel, copper under other chlorine root systems such as the acid washing liquid for stainless steel of industry, hydrochloric acid Leaching Systems of metallurgy industry
Separation and recovery process, and other variant of the invention use.
The invention has the advantages that：(1) gained iron chloride is high-purity high-concentration chlorination iron liquid, reuse or can be gone out
Sell；(2) iron chloride extractant need not use soda acid saponification and back extraction；(3) iron chloride extracting power is strong, and raffinate iron content is low；(4) it is each
Metal is planted effectively to be reclaimed；(5) strong applicability, cost is low.
Brief description of the drawings
Fig. 1 is process flow diagram of the invention.
Embodiment
With reference to specific embodiment, the present invention is described in further detail, and protection scope of the present invention is included but not
It is limited to following examples.
The nickeliferous iron chloride etching waste liquor composition of certain etching factory is as shown in table 1 below：
The etching waste liquor cost statement of table 1
| Composition | Fe3+ | Fe2+ | Ni | Cr | HCl |
| Concentration | 200g/L | 10g/L | 18g/L | 20g/L | 2mol/L |
Waste residue is incorporated to etching waste liquor directly with after dissolving with hydrochloric acid.
Etching waste liquor adds hydrochloric acid acid adjustment to containing acid after adding sodium chlorate oxidant oxidation of ferrous iron to ferric iron
4-8mol/L.Then, hybrid extraction is carried out with extractant ether, is 2 compared to O/A, carried out split-phase after having extracted, obtain the first aqueous phase
With the first oil phase.
First oil phase and back extraction water are evaporated after being mixed in O/A for 8 ratio at 80 DEG C, after oil phase is evaporated,
Obtain the first gas phase and the first liquid phase.The first liquid phase of gained is high concentration high-purity iron chloride, chloride containing weight of iron concentration after evaporation
It is to etch stoste after acid adjustment, return is used more than 50%.
After extraction the first aqueous phase of gained is equally evaporated 30min at 80 DEG C, the second gas phase and second liquid phase, second are obtained
Liquid phase is then liquid after extraction iron.
First oil phase and the first aqueous phase evaporation the first gas phase of gained and the second gas phase, by obtaining liquid after 10 DEG C of condensed absorbents
Carry out split-phase.Split-phase obtains oil phase for extractant ether, returns to extraction cycle and uses；Aqueous phase be hydrochloric acid, then be back to acid it is molten and
Acid adjustment is used, not enough then supplemented with technical hydrochloric acid.
And liquid is nickeliferous metallic solution for waiting etching to produce after second liquid phase extraction iron, 2.0- is modulated by adding hydrochloric acid by pH
After 2.5, it is 4 to carry out after 5 grades of extractions to be pressed with 45%HBL110 and 55% sulfonated kerosene extractant compared to O/A, obtain the second aqueous phase with
Second oil phase.Wherein, the second aqueous phase is then raffinate chromium chloride solution, is to be sold outside chromium product.And the second oil phase is then nickel-loaded
HBL110 extraction oil phase, by using 1mol/L sulfuric acid press compared to O/A be 1 carry out 4 grades back extraction after, obtain nickel sulfate solution, i.e.,
It can sell outside.HBL110 extractants are extracted by being returned after backwash, saponification again.
Claims (8)
1. a kind of method of etching waste liquor waste residue synthetical recovery, it is characterised in that：
In etching process, processing gained iron content, nickel, copper and chromium precipitated metal waste residue, after adding hydrochloric acid acid molten, what is obtained is molten
Liquid is mixed with etching waste liquor；Again by add oxidant by it is ferrous oxidising be ferric iron after, then through hydrochloric acid acid adjustment to appropriate acid
Degree, with iron chloride extractant hybrid extraction, extracts and the first oil phase and the first aqueous phase is obtained after split-phase；
It is organic that its first oil phase is that iron chloride is loaded, and is evaporated again through proper temperature after adding appropriate back extraction water, obtain the first gas phase and
First liquid phase；First liquid phase is remaining high concentration high-purity chlorination iron liquid, is etched back to after being adjusted to concentration needed for etching and acidity
With；
Its first aqueous phase obtains the second gas phase and second liquid phase after also being evaporated through proper temperature；
And the first oil phase and the first aqueous phase evaporation the first gas phase of gained and the second gas phase are iron chloride extractant and mixed in hydrochloric acid gas
Body, after condensed absorbent again after split-phase iron chloride extractant liquid and hydrochloric acid liquid；Iron chloride extractant returns to iron chloride
Extraction is used, and hydrochloric acid returns to sour molten and acid adjustment and used；
Its second liquid phase is liquid after extraction iron, and the metal that nickeliferous, copper and chromium etching are produced after being extracted by HBL110 extractants, is obtained
Second aqueous phase and the second oil phase；Wherein, the second aqueous phase is then raffinate chromium chloride solution, is to be sold outside chromium product；And the second oil phase
Be then nickel-loaded, the HBL110 extraction oil phases of copper, after being stripped by sulfuric acid, obtain nickel sulfate and copper-bath, i.e., it is outer to sell；
HBL110 extractants are extracted by being returned after backwash, saponification again.
2. according to the method described in claim 1, it is characterised in that it realizes the etching waste liquor of iron content, nickel, copper and chromium metal
And in waste residue, the circular regeneration of iron chloride etching solution, the comprehensive utilization of nickel, copper and chromium metal, and extractant and hydrochloric acid are followed
The environment-protective process for the overall circular regeneration synthetical recovery that ring is utilized.
3. according to the method described in claim 1, it is characterised in that iron chloride extractant is ether, diisopropyl ether, methyl- tert fourth
Base ether, its extracting power to iron chloride is strong, and low boiling point, it is easy to falls extractant by heating evaporation and carries out reuse.
4. the method according to claim 1 or 3, it is characterised in that waste liquid need to carry out iron chloride again after persalt acid adjustment
Extraction, and acid adjustment acidity is different because of iron chloride extractant used difference, the scope of acidity is 4-8mol/L.
5. according to the method described in claim 1, it is characterised in that the first oil phase and the first aqueous phase evaporating temperature are in 50-110
DEG C, stage evaporation as the case may be.
6. according to the method described in claim 1, it is characterised in that needed before the evaporation of the first oil phase plus back extraction water, water is according to steaming
Send out after iron chloride extractant depending on the concentration of gained iron chloride liquid phase requirement；And gained iron chloride liquid phase chloride containing weight of iron fraction
Up to more than 50%.
7. according to the method described in claim 1, it is characterised in that the method is up to mass fraction suitable for iron oxide concentration
Contained ferric iron concentration as little as below 0.1g/L in liquid after more than 40% solution system, and extraction iron.
8. method according to claim 1 or 2, it is characterised in that extracted using the iron chloride extractant and by steaming
Hair makes the method for extractant reuse be applied to the separation and recovery of iron chloride, and carries out the whole of chromium separation using HBL110 extractants
Body circulation recovery process；Also including the acid washing liquid for stainless steel of steel industry, the iron under the hydrochloric acid Leaching Systems of metallurgy industry, chromium,
The separation of nickel and copper metal and recovery process.
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| CN106756043A (en) * | 2016-12-20 | 2017-05-31 | 中成致远有限公司 | The separation method of chromium and iron in a kind of hydrochloric acid system |
| CN106929686B (en) * | 2017-04-10 | 2020-06-23 | 惠州Tcl环境科技有限公司 | Method for cooperatively recovering copper in ferric trichloride etching waste liquid by utilizing metal sludge |
| 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 |
| CN115283422B (en) * | 2022-07-21 | 2023-10-31 | 上海市政工程设计研究总院（集团）有限公司 | Treatment method of glass etching waste residues |
| CN115261865A (en) * | 2022-07-28 | 2022-11-01 | 深圳市祺鑫环保科技有限公司 | Treatment method of ferric trichloride etching waste liquid |
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| JP3536787B2 (en) * | 2000-06-12 | 2004-06-14 | 東亞合成株式会社 | Method for recovering copper in aqueous solution containing hydrochloric acid and copper chloride |
| JP5158665B2 (en) * | 2006-04-05 | 2013-03-06 | 鶴見曹達株式会社 | Copper salt solution purification method, purification apparatus, and copper salt solution |
| CN102965667B (en) * | 2012-12-10 | 2015-06-17 | 南通南京大学材料工程技术研究院 | Method for regenerating and recycling waste etching solution in stainless steel etching production line |
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Inventor after: Hu Lei Inventor before: Xia Dong |
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Effective date of registration: 20170620 Address after: Jiaxing City, Zhejiang province 314599 Tongxiang City Indus Street Ring Road Fusheng heights 29 Building 2 unit 1201 room Applicant after: Hu Lei Address before: 414400, No. ten, No. 13, Zhenlong village, Miluo, Miluo, Hunan, Yueyang Applicant before: Xia Dong |
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