CN110218878A - A kind of method of acidic etching liquid displacement production frerrous chloride - Google Patents
A kind of method of acidic etching liquid displacement production frerrous chloride Download PDFInfo
- Publication number
- CN110218878A CN110218878A CN201910584325.1A CN201910584325A CN110218878A CN 110218878 A CN110218878 A CN 110218878A CN 201910584325 A CN201910584325 A CN 201910584325A CN 110218878 A CN110218878 A CN 110218878A
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- Prior art keywords
- copper
- iron
- etching liquid
- acidic etching
- iron powder
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- ing And Chemical Polishing (AREA)
Abstract
The invention discloses a kind of methods that acidic etching liquid replaces production frerrous chloride, and the method includes the steps of: step 1: being filtered processing to acidic etching liquid, impurity screening send dangerous waste to handle；Step 2: oxytropism is uniformly slowly added to iron powder containing addition in copper etchant solution, and it is stirred, copper in acidic etching liquid is once replaced, iron powder additional amount is the theoretical consumption of copper powder displacement in solution, iron content is greater than 99%, iron particle size is less than 100 mesh, it controls reaction temperature and is no more than 90 DEG C, step 3: the reaction was continued 2h after iron powder adds, solid-liquor separation is carried out to solution, it is washed after output copper sponge, wash water returns to primary displacement, washing slag is copper sponge, after the present invention by replacing twice, using evaporation and concentration, it realizes containing frerrous chloride recycling in liquid after recycling copper in copper etchant solution, production cost is low, high financial profit, waste water realizes zero-emission, environmental benefit is high.
Description
Technical field
The present invention relates to a kind of method, in particular to a kind of method of acidic etching liquid displacement production frerrous chloride belongs to
Contained waste liquid processing technology field.
Background technique
With the opening and economic development of China in recent years, the demand of electronic product is constantly increased, me is promoted
The printed wiring board of state, referred to as (PCB) production rapidly develops, driven local economic development, at the same also to environment bring compared with
Big pollution.
Etched circuit board generates a large amount of etching solution.Etching solution is divided into acidic etching liquid and two kinds of alkaline etching liquid.Generally
In the case of, acidic etching liquid cupric is 5~15%, (the mainly presence in the form of copper chloride).
China Patent No. (CN106884185A) discloses a kind of technique and system and device for recycling copper in acidic etching liquid.
Wherein, iron displacement copper electrolysis cells include anode titanium frame and cathode copper sheet, scrap iron are put into anode frame, cathode copper sheet is in electrolytic cell
In, under the conditions of applying direct current electric field, induce cathode plate of the copper ion directional migration in acidic etching waste liquid into electrolytic cell
Upper generation reduction reaction is electrolysed as copper sheet and sponge copper products；And scrap iron is oxidized to divalent ferrous ion in anode titanium frame；Place
Polymerization stabilizer is added thereto and polymerization reaction occurs for polymeric oxygen agent, most after diaphragm cell aoxidizes for waste liquid after reason
The basicity for adjusting polymer in mixed liquor with hydrochloric acid or alkali afterwards, finally prepares byproduct condensation chlorination ferric flocculant
Acidic etching liquid is replaced using iron powder, sponge copper powder can be produced, liquid still contains a small amount of copper after neutralization.Also
It needs to be further processed.The purpose of the present invention is to provide a kind of at low cost, environmental-friendly acidic etching liquid iron replacements, set
Change the method that rear liquid prepares frerrous chloride.
Summary of the invention
The purpose of the present invention is to provide a kind of methods that acidic etching liquid replaces production frerrous chloride, to solve above-mentioned back
Containing after copper etchant solution recycles copper for proposing in scape technology integrates the problem of liquid recycles.
To achieve the above object, the invention provides the following technical scheme: a kind of acidic etching liquid displacement production frerrous chloride
Method, the method includes the steps of:
Step 1: processing is filtered to acidic etching liquid, impurity screening send dangerous waste to handle；
Step 2: oxytropism is uniformly slowly added to iron powder containing addition in copper etchant solution, and is stirred, to acidic etching liquid
In copper once replaced, iron powder additional amount be solution in copper powder displacement theoretical consumption, iron content be greater than 99%, iron
Powder Particle Size controls reaction temperature and is no more than 90 DEG C less than 100 mesh；
Step 3: the reaction was continued after iron powder adds, and 2h washes solution progress solid-liquor separation after output copper sponge,
Wash water returns to primary displacement, and washing slag is copper sponge, and purity is greater than 80%；
Step 4: iron powder is continuously added in the solution after primary displacement and carries out twice replaced, iron powder additional amount is in solution
1.15~1.2 times of the theoretical consumption of hydrochloric acid and residual copper content, control reaction temperature is 70 DEG C or more, controls reaction end
PH value is 4~5, after the reaction was completed solid-liquor separation, and output slag returns to primary displacement, and production fluid carries out secondary filter；
Step 5: twice replaced secondary filter clear liquid is evaporated concentration, and control frerrous chloride content is greater than 20%, concentration
Exhaust gas washing tower (for removing CO2) absorbs, and concentrate is that industrial chlorinations are ferrous.
As a preferred technical solution of the present invention, the iron powder being added in the step 2 is by scrap iron skin, iron filings and iron
Wood shavings crushed material is made, iron powder by middle scrap iron skin, iron filings and iron plane pollen any one or any two or more mixing.
As a preferred technical solution of the present invention, the reaction condition of the step 3 is room temperature, stirring, reaction process
After neutralization reaction, control solution ph is no more than 2, and the copper to prevent displacing is dissolved again by free acid.
As a preferred technical solution of the present invention, the production fluid in the step 4 carries out secondary filter, filtering
500~600 mesh of precision.
Compared with prior art, the beneficial effects of the present invention are: a kind of acidic etching liquid displacement production protochloride of the present invention
The method of iron, using evaporation and concentration, is realized containing frerrous chloride returns in liquid after recycling copper in copper etchant solution after replacing twice
It receives, recovery efficiency is high, and production cost is low, high financial profit, and waste water realizes zero-emission, and environmental benefit is high.
Detailed description of the invention
Fig. 1 is present invention process flow diagram.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Referring to Fig. 1, the present invention provides a kind of method that acidic etching liquid replaces production frerrous chloride, 1. this method packets
Containing following steps:
Step 1: processing is filtered to acidic etching liquid, impurity screening send dangerous waste to handle；
Step 2: oxytropism is uniformly slowly added to iron powder containing addition in copper etchant solution, and is stirred, to acidic etching liquid
In copper once replaced, iron powder additional amount be solution in copper powder displacement theoretical consumption, iron content be greater than 99%, iron
Powder Particle Size controls reaction temperature and is no more than 90 DEG C less than 100 mesh；
Step 3: the reaction was continued after iron powder adds, and 2h washes solution progress solid-liquor separation after output copper sponge,
Wash water returns to primary displacement, and washing slag is copper sponge, and purity is greater than 80%；
Step 4: iron powder is continuously added in the solution after primary displacement and carries out twice replaced, iron powder additional amount is in solution
1.15~1.2 times of the theoretical consumption of hydrochloric acid and residual copper content, control reaction temperature is 70 DEG C or more, controls reaction end
PH value is 4~5, after the reaction was completed solid-liquor separation, and output slag returns to primary displacement, and production fluid carries out secondary filter；
Step 5: twice replaced secondary filter clear liquid is evaporated concentration, and control frerrous chloride content is greater than 20%, concentration
Exhaust gas washing tower (for removing CO2) absorbs, and concentrate is that industrial chlorinations are ferrous.
Preferably, the iron powder being added in step 2 is minced and is made by scrap iron skin, iron filings and iron plane pollen, and iron powder is by middle scrap iron
Any one or any two or more mixing of skin, iron filings and iron plane pollen, materials approach are simple.
Preferably, the reaction condition of step 3 is room temperature, stirring, after reaction process neutralization reaction, controls pH value of solution
Value is no more than 2, and the copper to prevent displacing is dissolved again by free acid, and the production fluid in step 4 carries out secondary filter, filtering
500~600 mesh of precision, displacement efficiency are high.
When specifically used, a kind of method of acidic etching liquid displacement production frerrous chloride of the present invention, filtered acid erosion
Carve and iron powder be uniformly slowly added in liquid, and be slowly stirred, be sufficiently mixed the filtered fluid of iron powder and acidic etching liquid, to copper into
Row is once replaced, and is washed after output copper sponge, and wash water returns to primary displacement, continuously adds iron in the solution after once replacing
Powder progress is twice replaced, after the reaction was completed solid-liquor separation, and output slag returns to primary displacement, and production fluid carries out secondary filter, secondary
Displacement secondary filter clear liquid is evaporated concentration, and concentration exhaust gas washing tower (for removing CO2) absorbs, and concentrate is that industrial chlorinations are ferrous, and frerrous chloride returns
It receives, recovery efficiency is high, and production cost is low, high financial profit, and waste water realizes zero-emission, and environmental benefit is high.
In the description of the present invention, it is to be understood that, the orientation or positional relationship of instruction is side based on the figure
Position or positional relationship, are merely for convenience of description of the present invention and simplification of the description, rather than the device or member of indication or suggestion meaning
Part must have a particular orientation, be constructed and operated in a specific orientation, therefore be not considered as limiting the invention.
In the present invention unless specifically defined or limited otherwise, for example, it may be being fixedly connected, be also possible to removable
Connection is unloaded, or integral；It can be mechanical connection, be also possible to be electrically connected；It can be directly connected, intermediate matchmaker can also be passed through
Jie is indirectly connected, and can be the connection inside two elements or the interaction relationship of two elements, unless otherwise specific limit
It is fixed, for the ordinary skill in the art, above-mentioned term in the present invention specific can be understood as the case may be
Meaning.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (4)
1. a kind of method of acidic etching liquid displacement production frerrous chloride, which is characterized in that the method includes the steps of:
Step 1: processing is filtered to acidic etching liquid, impurity screening send dangerous waste to handle；
Step 2: oxytropism is uniformly slowly added to iron powder containing addition in copper etchant solution, and is stirred, in acidic etching liquid
Copper is once replaced, and iron powder additional amount is the theoretical consumption of copper powder displacement in solution, and iron content is greater than 99%, iron powder grain
Degree controls reaction temperature and is no more than 90 DEG C less than 100 mesh；
Step 3: the reaction was continued after iron powder adds, and 2h washes, wash water solution progress solid-liquor separation after output copper sponge
Primary displacement is returned to, washing slag is copper sponge, and purity is greater than 80%；
Step 4: iron powder is continuously added in the solution after primary displacement and carries out twice replaced, iron powder additional amount is hydrochloric acid in solution
And 1.15~1.2 times of the theoretical consumption of residual copper content, control reaction temperature are 70 DEG C or more, control reaction end pH value
It is 4~5, solid-liquor separation, output slag return to primary displacement after the reaction was completed, and production fluid carries out secondary filter；
Step 5: twice replaced secondary filter clear liquid is evaporated concentration, and control frerrous chloride content is greater than 20%, exhaust gas is concentrated
Washing tower (for removing CO2) absorbs, and concentrate is that industrial chlorinations are ferrous.
2. a kind of method of acidic etching liquid displacement production frerrous chloride according to claim 1, it is characterised in that: described
The iron powder being added in step 2 is minced and is made by scrap iron skin, iron filings and iron plane pollen, and iron powder is by middle scrap iron skin, iron filings and iron plane flower
Any one or any two or more mixing of powder.
3. a kind of method of acidic etching liquid displacement production frerrous chloride according to claim 1, it is characterised in that: described
The reaction condition of step 3 is room temperature, stirring, and after reaction process neutralization reaction, control solution ph is no more than 2, to prevent setting
The copper to swap out is dissolved again by free acid.
4. a kind of method of acidic etching liquid displacement production frerrous chloride according to claim 1, it is characterised in that: described
Production fluid in step 4 carries out secondary filter, 500~600 mesh of filtering accuracy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201910584325.1A CN110218878A (en) | 2019-07-01 | 2019-07-01 | A kind of method of acidic etching liquid displacement production frerrous chloride |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910584325.1A CN110218878A (en) | 2019-07-01 | 2019-07-01 | A kind of method of acidic etching liquid displacement production frerrous chloride |
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| CN110218878A true CN110218878A (en) | 2019-09-10 |
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| CN201910584325.1A Pending CN110218878A (en) | 2019-07-01 | 2019-07-01 | A kind of method of acidic etching liquid displacement production frerrous chloride |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111001823A (en) * | 2019-12-31 | 2020-04-14 | 江西粤鹏环保高新技术开发有限公司 | Method and equipment for preparing nano-grade copper powder by using etching waste liquid and waste aluminum sheets |
| CN113549773A (en) * | 2021-07-19 | 2021-10-26 | 上海新禹固废处理有限公司 | Process for producing high-purity sponge copper by using copper chloride acidic etching waste liquid |
| CN115353255A (en) * | 2022-08-22 | 2022-11-18 | 昆明理工大学 | Circuit board industry wastewater comprehensive treatment method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1183006A (en) * | 1968-04-05 | 1970-03-04 | David Henry Thomas | Regeneration of Etchant. |
| EP0601276A1 (en) * | 1992-12-05 | 1994-06-15 | Gütling Gmbh | Process for the transformation of copper from wastewater containing copper in the spent copper chloride etching solution from printed circuit board fabrication |
| CN102912352A (en) * | 2012-11-08 | 2013-02-06 | 上海绿澄环保科技有限公司 | Method for recycling acidic copper-etching waste solution |
| CN103864153A (en) * | 2014-03-12 | 2014-06-18 | 红板（江西）有限公司 | Method for extracting copper and preparing polymerization ferric chloride by replacement of acidic etching liquid of PCB (printed circuit board) factory |
| 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 |
-
2019
- 2019-07-01 CN CN201910584325.1A patent/CN110218878A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1183006A (en) * | 1968-04-05 | 1970-03-04 | David Henry Thomas | Regeneration of Etchant. |
| EP0601276A1 (en) * | 1992-12-05 | 1994-06-15 | Gütling Gmbh | Process for the transformation of copper from wastewater containing copper in the spent copper chloride etching solution from printed circuit board fabrication |
| CN102912352A (en) * | 2012-11-08 | 2013-02-06 | 上海绿澄环保科技有限公司 | Method for recycling acidic copper-etching waste solution |
| CN103864153A (en) * | 2014-03-12 | 2014-06-18 | 红板（江西）有限公司 | Method for extracting copper and preparing polymerization ferric chloride by replacement of acidic etching liquid of PCB (printed circuit board) factory |
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111001823A (en) * | 2019-12-31 | 2020-04-14 | 江西粤鹏环保高新技术开发有限公司 | Method and equipment for preparing nano-grade copper powder by using etching waste liquid and waste aluminum sheets |
| CN113549773A (en) * | 2021-07-19 | 2021-10-26 | 上海新禹固废处理有限公司 | Process for producing high-purity sponge copper by using copper chloride acidic etching waste liquid |
| CN115353255A (en) * | 2022-08-22 | 2022-11-18 | 昆明理工大学 | Circuit board industry wastewater comprehensive treatment method |
| CN115353255B (en) * | 2022-08-22 | 2023-12-22 | 昆明理工大学 | Comprehensive treatment method for wastewater in circuit board industry |
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Application publication date: 20190910 |