CN106086460A - A kind of from acid CuCl2the method reclaiming copper by-product polymerizing aluminum chloride in etching waste liquor - Google Patents
A kind of from acid CuCl2the method reclaiming copper by-product polymerizing aluminum chloride in etching waste liquor Download PDFInfo
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- CN106086460A CN106086460A CN201610571670.8A CN201610571670A CN106086460A CN 106086460 A CN106086460 A CN 106086460A CN 201610571670 A CN201610571670 A CN 201610571670A CN 106086460 A CN106086460 A CN 106086460A
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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
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/04—Halides
- C01G3/05—Chlorides
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
A kind of from acid CuCl2The method reclaiming copper by-product polymerizing aluminum chloride in etching waste liquor, it is characterised in that directly at acid CuCl2Etching waste liquor adds the material containing metallic aluminium, replaces copper therein, or first by acidity CuCl2Free hydrochloric acid heating evaporation in etching waste liquor, adds material containing metallic aluminium and replaces copper therein, filters to obtain copper powder or copper sponge and displaced liquid.Sell after gained copper powder washing, drying；After the washing of gained copper sponge, electrorefining obtains tough cathode；Gained displaced liquid adds alkaline matter, and after adjusting pH value, evaporation and concentration obtains aluminium polychlorid product, makes acid CuCl2Copper and chlorine in etching waste liquor are fully used, it is achieved the zero-emission of copper process for separating and recovering process, have the advantages such as technique is simple, synthetical recovery low cost, good in economic efficiency.
Description
Technical field
The invention belongs to chemical industry metallurgical field, be specifically related to a kind of from acid CuCl2Etching waste liquor reclaims copper by-product gather
The method closing aluminum chloride.
Background technology
Acid copper chloride etching liquid (HCl-CuCl2-NaCl) because of its etching speed easy to control, molten copper amount is big, and etching solution exists
High etching quality can be reached under steady statue, and be widely used in producing multiple-plate internal layer and printing-etched plate, and figure
The etching of printed panel.The acidic etching processes of copper is with NaClO3Make oxidant, make dissolution agent and the acidity adjustment of copper with hydrochloric acid
Agent, product is CuCl2And NaCl.Along with the carrying out of etching reaction, CuCl2Constantly accumulate in etching solution with NaCl, thus cause
The etching speed of copper is with CuCl2The rising of concentration and reduce, when in solution, the concentration of Cu is increased to the most just be difficult to continue
Use, thus become acidic etching waste liquid.The acidic etching waste liquid discharged on production line has the highest comprehensive utilization value.
Acidic etching waste liquid mainly reclaims copper therein at present, and its method has electrolysis, solvent extraction, chemical precipitation
Method and crystallization process etc..Although effective ingredient therein can be reclaimed by electrolysis, but because electrolytic process discharges Cl2And make it answer
With being restricted.Solvent extraction is high because of etching solution acidity, it is difficult to find suitable extractant the most still to stagnate.Chemistry
The sedimentation method and crystallization process also can only reclaim copper therein, and the most substantial amounts of Cl has but become garbage, brings the biggest to environmental conservation
Pressure.
Aluminium polychlorid (PAC) is inorganic polymer coagulant the most most widely used, that sales volume is maximum and water treatment agent.
The preparation of PAC currently mainly with aluminum-containing mineral material or aluminium hydroxide or aluminium salt or metallic aluminium as raw material, first pass through salt Ore Leaching or
Alkali dissolution prepares the solution containing aluminum, then obtains aluminium polychlorid product by regulation basicity, concentration polymerization.Technique mistake
Journey consumes substantial amounts of salt bronsted lowry acids and bases bronsted lowry, and production cost is high.
Summary of the invention
The present invention is aiming at the deficiencies in the prior art, and the one of proposition is from acid CuCl2Etching waste liquor reclaims copper secondary
The method producing aluminium polychlorid.
The present invention is a kind of from acid CuCl2The method reclaiming copper by-product polymerizing aluminum chloride in etching waste liquor, including following step
Rapid:
Step one: copper is reclaimed in displacement
Toward acid CuCl2Etching waste liquor is directly added into the material containing metallic aluminium, by Cu therein2+Cement out, or add
Heat adds the material containing metallic aluminium, by Cu therein after being evaporated by free hydrochloric acid therein2+Cement out, filter extra large
Continuous copper or copper powder and chloride containing aluminum, or/and the displaced liquid of aluminium polychlorid, are sold after the drying of gained copper powder washing, gained sponge
Resaling after copper electrolyzing refining, displaced liquid is then used as to produce the raw material of aluminium polychlorid；Acid CuCl2In etching waste liquor, Cu contains
Amount is: 80-150g/L；
Step 2: by-product polymerizing aluminum chloride
Step one gained displaced liquid is directly concentrated to give aluminium polychlorid product, or first toward in step one gained displaced liquid
Adding alkaline matter, adjust pH value of solution to be polymerized to 3.5-5.0, reconcentration obtains aluminium polychlorid product.
The present invention is a kind of from acid CuCl2The method reclaiming copper by-product polymerizing aluminum chloride in etching waste liquor, it is characterised in that:
At least one in aluminum bits, aluminum ash, aluminum slag and aluminum profile extrusion leftover bits and pieces of the material containing metallic aluminium added in step one.
The present invention is a kind of from acid CuCl2The method reclaiming copper by-product polymerizing aluminum chloride in etching waste liquor, it is characterised in that:
In step one, the material containing metallic aluminium is to change into AlCl by the Cl in solution31-3.5 times of stoichiometric number adds, containing metal
After the material of aluminum adds, 0-125 DEG C of reaction 1-6h, make the Cu in solution with the form Precipitation of copper powder or copper sponge, reaction
The H that process produces2Collect after derivation to light after recycling or deriving and carry out harmless treatment.
The present invention is a kind of from acid CuCl2The method reclaiming copper by-product polymerizing aluminum chloride in etching waste liquor, it is characterised in that:
Acid CuCl in step one2Etching solution is through 75-115 DEG C of normal pressure or 0.5-2.5h is evaporated under reduced pressure so that it is in the concentration of free HCl
It is down to 0.5-0.05mol/L.
The present invention is a kind of from acid CuCl2The method reclaiming copper by-product polymerizing aluminum chloride in etching waste liquor, it is characterised in that:
The alkaline matter added in step 2 is selected from CaO, Ca (OH)2、Al(OH)3、Al2O3、NaOH、Na2CO3、NaHCO3In at least
A kind of.
The present invention is a kind of from acid CuCl2The method reclaiming copper by-product polymerizing aluminum chloride in etching waste liquor, it is characterised in that:
The aluminium polychlorid product obtained in step 2 is: containing Al2O3The aluminium polychlorid liquid of >=10% or containing Al2O3>=27%
Aluminium polychlorid solid.
Acid CuCl2The ultimate principle of etching waste liquor recovering copper and by-product polymerizing aluminum chloride can use formulas below table
Show:
2Al+3CuCl2=2AlCl3+3Cu↓ (1)
2Al+6HCl=2AlCl3+3H2↑ (2)
2Al+6H2O=2Al (OH)3+3H2↑ (3)
aAlCl3+bAl(OH)3=Al(a+b)Oa(OH)(3b-2a)Cl3a+aH2O↑ (4)
The present invention has the following advantages and effect compared with existing technology:
The present invention utilizes the material containing metallic aluminium as acid CuCl dexterously2The displacer of copper in etching waste liquor, not only
Can be by CuCl2In copper separation and recovery, and can by aluminium polychlorid product qualified for chlorine by-product therein, become give up into
Precious.Additionally, due to the technical process very exothermic of metallic aluminium displacement copper, accelerate the reaction of metallic aluminium and water, be remarkably improved molten
The basicity of liquid, promotes a large amount of evaporations of water, significantly alleviates the burden that product concentrates.Again set by the entirety of present invention process
Meter, cooperating between each step, thus acid CuCl can be made2Cu and Cl in etching waste liquor is fully used, real
The zero-emission of existing technical process, significantly alleviates the environmental protection pressure of copper acid etching technique, also complies with China's energy-conserving and emission-cutting technology and change
The development trend made.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, and it is right that following example are intended to illustrate rather than
The further restriction of the present invention.
Embodiment 1
Take containing Cu 154.2g/L, the etching waste liquor 3m of HCl 1.8mol/L3, first by wherein Cl-Change into AlCl3Theory
1.2 times of amount, are stirred at room temperature and are dividedly in some parts the aluminum ash that metal aluminum content is about 90%, continue stirring after aluminum ash all adds
1h, carries out filtering for the first time, obtains copper powder and first-time filtrate.First-time filtrate is warming up to more than 85 DEG C continue to be dividedly in some parts aluminum ash,
Aluminum ash to be added do not continue to dissolve, change add calcium oxide adjust pH value of solution to 3.6, carry out second time filter, obtain secondary filtering residue
With secondary filtrate.Gained secondary filtering residue returns copper displacement operation and is continuing with；Gained secondary filtrate obtains density through evaporation and concentration
1.2g/cm3Containing Al2O3Reach the aluminium polychlorid liquid of 11%；Gained copper powder is scrubbed, dry after purity reach 99.6% copper
Powder, the response rate of whole technical process copper reaches 99.8%.
Embodiment 2
Take containing Cu 151.5g/L, the etching waste liquor 2m of HCl 1.9mol/L3, stirring adds the aluminum slag of-40 mesh and replaces wherein
Copper, treat solution is down to 1g/L containing Cu, be filtrated to get copper sponge and the filtrate of chloride containing aluminum.Filtrate is heated to 95 DEG C, continues
Stirring add aluminum slag, after pH rises to 2.5 stop add aluminum, 110 DEG C continue stirring 1h, filter secondary filtering residue and displacement after
Liquid.After gained copper sponge washing dehydration, being squeezed into anode block, electrorefining obtains purity and reaches the tough cathode of 99.99%；Gained is replaced
Rear liquid first heats up to stir and adds Al (OH)3Adjust pH value of solution to 3.3, then add CaO adjust pH value of solution to 4.3, filter, filtrate be spray-dried
Obtain Al2O3Content reaches the aluminium polychlorid product of 28%.
Embodiment 3
Take containing Cu 99.6g/L, the etching waste liquor 2.5L of HCl 2.1mol/L, 106 DEG C of atmospheric evaporation 45min so that it is in
HCl concentration is down to 0.12mol/L, and stirring first liquid-solid ratio 2:1ml/g stirring adds the secondary filtering residue that embodiment 2 obtains, and adds
Aluminum is considered to be worth doing, stops adding aluminum after pH value of solution rises to 2.0, and 90 DEG C are continued stirring 1.5h, filter to obtain copper powder and displaced liquid.Gained copper powder
First with acid CuCl2Etching solution wash, then with clear water washing, dry purity reach 99.8% copper powder；Gained displaced liquid is first
The stirring that heats up adds sodium bicarbonate and adjusts pH value of solution to 3.8, and it is 1.19g/cm that evaporation and concentration obtains density3Containing Al2O3Reach 10.6% poly-
Close aluminum chloride liquid.
Claims (7)
1. one kind from acid CuCl2The method reclaiming copper by-product polymerizing aluminum chloride in etching waste liquor, it is characterised in that include following
Step:
Step one: copper is reclaimed in displacement
Toward acid CuCl2Etching waste liquor is directly added into the material containing metallic aluminium, by Cu therein2+Cement out, or heating will
Free hydrochloric acid therein adds the material containing metallic aluminium after being evaporated, by Cu therein2+Cement out, filter copper powder or
Copper sponge and chloride containing aluminum are or/and the displaced liquid of aluminium polychlorid；
Step 2: by-product polymerizing aluminum chloride
Step one gained displaced liquid is directly concentrated to give aluminium polychlorid product, or first adds in step one gained displaced liquid
Alkaline matter, adjusts pH value of solution to be polymerized to 3.5-5.0, and reconcentration obtains aluminium polychlorid product.
One the most according to claim 1 is from acid CuCl2The method reclaiming copper by-product polymerizing aluminum chloride in etching waste liquor,
It is characterized in that: in step one, acid CuCl2Etching solution is through 75-115 DEG C of normal pressure or 0.5-2.5h is evaporated under reduced pressure so that it is in
The concentration of free HCl is down to 0.5-0.05mol/L.
One the most according to claim 1 and 2 is from acid CuCl2Etching waste liquor reclaims the side of copper by-product polymerizing aluminum chloride
Method, it is characterised in that: in step one, the added material containing metallic aluminium is selected from aluminum bits, aluminum ash, aluminum slag and aluminum profile extrusion leftover bits and pieces
In at least one.
One the most according to claim 3 is from acid CuCl2The method reclaiming copper by-product polymerizing aluminum chloride in etching waste liquor,
It is characterized in that: in step one, the material containing metallic aluminium is to change into AlCl by the Cl in solution3The 1-3.5 of stoichiometric number
Add again, after the material containing metallic aluminium adds, 0-125 DEG C of reaction 1-6h, make the Cu in solution2+With copper powder or the form of copper sponge
Precipitation, the H that course of reaction produces2Collect after derivation to light after recycling or deriving and carry out harmless treatment.
One the most according to claim 4 is from acid CuCl2The method reclaiming copper by-product polymerizing aluminum chloride in etching waste liquor,
It is characterized in that: in step one, gained copper powder washing is sold after drying, and resales after gained copper sponge electrorefining.
A kind of method reclaiming copper by-product polymerizing aluminum chloride from acid CuCl2 etching waste liquor the most according to claim 4,
It is characterized in that: in step 2, the alkaline matter of addition is selected from CaO, Ca (OH)2、Al(OH)3、Al2O3、NaOH、Na2CO3、
NaHCO3In at least one.
A kind of method reclaiming copper by-product polymerizing aluminum chloride from acid CuCl2 etching waste liquor the most according to claim 6,
It is characterized in that: the aluminium polychlorid product being concentrated to give is: containing Al2O3The aluminium polychlorid liquid of >=10% or containing Al2O3≥
The aluminium polychlorid solid of 27%.
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| CN201610571670.8A CN106086460A (en) | 2016-07-20 | 2016-07-20 | A kind of from acid CuCl2the method reclaiming copper by-product polymerizing aluminum chloride in etching waste liquor |
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| CN201610571670.8A CN106086460A (en) | 2016-07-20 | 2016-07-20 | A kind of from acid CuCl2the method reclaiming copper by-product polymerizing aluminum chloride in etching waste liquor |
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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 |
| CN111945002A (en) * | 2020-07-06 | 2020-11-17 | 广东邦普循环科技有限公司 | Method for removing copper from waste lithium batteries by recovery wet process |
| KR20200142295A (en) * | 2019-06-12 | 2020-12-22 | 한국건설기술연구원 | Method for preparing high basicity aluminum chlorohydrate with high aluminum content |
| CN113046570A (en) * | 2021-03-12 | 2021-06-29 | 深圳市星河环境技术有限公司 | Production method of high-grade copper powder and high-quality polyaluminium chloride easy for solid-liquid separation |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200142295A (en) * | 2019-06-12 | 2020-12-22 | 한국건설기술연구원 | Method for preparing high basicity aluminum chlorohydrate with high aluminum content |
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| 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 |
| CN111945002A (en) * | 2020-07-06 | 2020-11-17 | 广东邦普循环科技有限公司 | Method for removing copper from waste lithium batteries by recovery wet process |
| CN111945002B (en) * | 2020-07-06 | 2022-06-14 | 广东邦普循环科技有限公司 | Method for removing copper from waste lithium batteries by recovery wet process |
| CN113046570A (en) * | 2021-03-12 | 2021-06-29 | 深圳市星河环境技术有限公司 | Production method of high-grade copper powder and high-quality polyaluminium chloride easy for solid-liquid separation |
| CN113046570B (en) * | 2021-03-12 | 2021-11-16 | 深圳星河环境股份有限公司 | Production method of high-grade copper powder and high-quality polyaluminium chloride easy for solid-liquid separation |
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